Catalyst systems and methods for cyclic poly alpha-olefins

Abstract

The present disclosure relates to cyclic poly alpha-olefin (PAO) materials prepared from alpha-olefins and processes for preparing the same.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 407,608, filed Sep. 16, 2022, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure relates to cyclic polyalphaolefin (PAO) materials prepared from alpha - olefins and methods for preparing the same. Specifically, the present disclosure relates to ethylenically unsaturated cyclic PAO materials and saturated cyclic PAO materials derived from the polymerization of alpha - olefins in the presence of a catalyst system comprising a metallocene - compound specifically designed to yield a cyclic PAO composition with a high dimer content. Background Art

[0004] Polyalphaolefins (PAOs) are typically produced by the oligomerization of linear alpha - olefins. Due to the reactivity of the C═C double bonds present in the molecular structure of the oligomer molecules, these unsaturated polyalphaolefins (uPAOs) can be used as intermediates for the preparation of various specialty chemicals. For example, when a uPAO is contacted with a chemical reagent that is reactive with the C═C bond, various chemical functional groups can be bonded to the carbon backbone of the uPAO molecule. The functional groups thus introduced onto the PAO structure can impart unique properties to the functionalized and saturated PAO molecules. Hydrogenated uPAOs can be used as lubricating oil compositions, such as those used in internal combustion engines, automotive greases, industrial lubricating oils, gearbox oils, etc. Summary of the Invention

[0005] One aspect of the present disclosure relates to a method for preparing polyalphaolefin (PAO) from two or more different alpha - olefins, wherein at least one of the alpha - olefins is a cyclic alpha - olefin and at least one of the alpha - olefins is a linear or branched alpha - olefin. The method can include the steps of: contacting a composition comprising one or more C6 - C 32 cyclic alpha - olefins and one or more C4 - C 32A feed of linear and / or branched α-olefins is contacted with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions to effect a polymerization reaction to obtain a polymerization reaction mixture comprising a mixture of PAO molecules having ethylidene, trisubstituted vinylidene, disubstituted vinylidene, and optionally vinyl unsaturation. The method may further comprise the step of obtaining an unsaturated PAO product from the polymerization reaction mixture, wherein the unsaturated PAO product comprises a mixture of PAO molecules having ethylidene, trisubstituted vinylidene, disubstituted vinylidene, optionally vinyl unsaturation, and, optionally, is substantially free of the α-olefin feed. When a cyclic α-olefin having ring unsaturation such as 4-vinylcyclohex-1-ene is used as the cyclic α-olefin, the PAO product may further contain an internal ring disubstituted vinylidene. This type of unsaturation is referred to as a cyclic disubstituted vinylidene.

[0006] Another aspect of the present disclosure relates to a method for preparing α-olefin dimers and trimers from two or more α-olefins, wherein at least one α-olefin is a cyclic α-olefin and at least one α-olefin is a linear or branched α-olefin. The method may comprise the steps of: contacting a feed of a cyclic α-olefin and one or more C4-C 32 cyclic α-olefins and one or more C4-C 32 A feed of linear and / or branched α-olefins is contacted with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions to effect a polymerization reaction to obtain a polymerization reaction mixture comprising a mixture of dimer and / or trimer molecules having ethylidene, trisubstituted vinylidene, disubstituted vinylidene, and optionally vinyl unsaturation. The method may further comprise the step of obtaining an unsaturated dimer and / or trimer product from the polymerization reaction mixture, wherein the unsaturated dimer and / or trimer product has ethylidene, trisubstituted vinylidene, disubstituted vinylidene, optionally vinyl unsaturation, and, optionally, is substantially free of the α-olefin feed. When a cyclic α-olefin having ring unsaturation such as 4-vinylcyclohex-1-ene is used as the cyclic α-olefin, the dimer and / or trimer product may contain an internal ring disubstituted vinylidene. This type of unsaturation is referred to as a cyclic disubstituted vinylidene.

[0007] Another aspect of the present disclosure relates to a method for preparing α-olefin dimers and / or trimers from two or more different α-olefins, wherein at least one α-olefin is a cyclic α-olefin and at least one second α-olefin is a linear or branched α-olefin, and the products respectively comprise unsaturated dimers and / or trimers.

[0008] Another aspect of the present disclosure relates to a method for preparing α-olefin dimers and / or trimers (preferably dimers) from two or more different α-olefins, wherein at least one of the α-olefins is a cyclic α-olefin and at least one second α-olefin is a linear or branched α-olefin, and the product prepared has a selectivity of at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, or at least about 95% of the total product mixture for the preparation of dimers.

[0009] The present disclosure also relates to a method for dimerizing a cyclic α-olefin to prepare a cyclic dimer. Specifically, the present disclosure relates to ethylenically unsaturated cyclic dimers and saturated cyclic dimers derived from the dimerization of a cyclic α-olefin in the presence of a catalyst system comprising a metallocene compound specifically designed to obtain a cyclic dimer composition having vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturation.

[0010] In any of the embodiments herein, the method may include using a metallocene compound (e.g., any of those described herein). In some embodiments, the metallocene compound is represented by formula (I), (II), (III), (IV), or (V) as described herein. In some embodiments, in formula (I) or (II), R 1 and R 3 in which at least one is not hydrogen.

[0011] Details of one or more embodiments of the subject matter of the present disclosure are set forth in the accompanying drawings and the specification. Other features, aspects, and advantages of the subject matter will be apparent from the specification, the drawings, and the claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 Two reaction pathways are depicted in which 4-vinylcyclohex-1-ene (VCH) undergoes a chain transfer process and gives a bicyclic product.

[0013] Figure 2 Two reaction pathways are depicted in which VCH undergoes a chain transfer process with an α-olefin represented as CH2=CHR, where R can be a linear, branched, or cyclic aliphatic group.

[0014] DETAILED DESCRIPTION

[0015] DEFINITIONS

[0016] The term "alkyl" or "alkyl group" is interchangeably meant to refer to a saturated hydrocarbon group consisting of carbon and hydrogen atoms. The alkyl group can be straight-chain, branched-chain, cyclic, or substituted cyclic, or a combination thereof. In any case of using "straight-chain, branched-chain, or cyclic", the combination thereof is included. For example, methylcyclohexyl is a combination and is included in the definition of alkyl.

[0017] The term "branched-chain" is defined to mean not dendritic (i.e., a branched group on a branch or a crosslinked branched-chain group). Typically, a branched-chain group is a straight-chain group having one or more branches, including but not limited to those compounds represented by the following formula F-V.

[0018] The term "cyclic dimer" is defined to mean a dimer formed by the dimerization of one or more C6-C 32 cyclic α-olefins. The cyclic dimer is usually also referred to as "dimer".

[0019] The term "cycloalkyl" or "cycloalkyl group" is interchangeably meant to refer to a saturated hydrocarbon group in which carbon atoms form one or more ring structures.

[0020] The term "alkenyl" or "alkenyl group" is interchangeably meant to refer to a straight-chain unsaturated hydrocarbon group containing a C═C bond.

[0021] The term "cycloalkenyl" or "cycloalkenyl group" is interchangeably meant to refer to a cyclic hydrocarbon group containing a C═C bond in the ring.

[0022] The term "aryl" or "aryl group" is interchangeably meant to refer to a hydrocarbon group containing an aromatic ring structure.

[0023] The terms "aryloxy" and "aryloxide" mean an aryl group bonded to an oxygen atom, such as an aryl ether group / radical connected to an oxygen atom, and can include those in which the aryl group is a C6 to C 20 hydrocarbon group. Examples of suitable aryloxy can include phenoxy, biphenyloxy, naphthoxy, etc.

[0024] The terms "alkoxy" and "alkoxide" mean an alkyl group bonded to an oxygen atom, such as an alkyl ether group / radical connected to an oxygen atom, and can include those in which the alkyl group is a C1 to C 20 hydrocarbon group. The alkyl group can be straight-chain, branched-chain, or cyclic. The alkyl group can be saturated and / or partially unsaturated. Examples of suitable alkoxy can include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc.

[0025] The term "hydrocarbyl radical", "hydrocarbyl group", or "hydrocarbyl" is interchangeably used to refer to a group consisting solely of hydrogen and carbon atoms. The hydrocarbyl group can be saturated and / or unsaturated, straight-chain or branched-chain, cyclic or acyclic, aromatic or non-aromatic.

[0026] Unless otherwise specified, a substituted group (such as a substituted hydrocarbyl) means such a group in which at least one atom has been replaced by a different atom or group. For example, a substituted alkyl can be an alkyl in which at least one hydrogen atom has been replaced by a hydrocarbyl group, a halogen, any other non-hydrogen group, and / or at least one carbon atom and the hydrogen atom bonded thereto have been replaced by a different group. A substituted group can be a group in which at least one hydrogen atom has been replaced by a heteroatom or a heteroatom-containing group, preferably by at least one functional group (e.g., halogen (Cl, Br, I, F), NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, etc.) or in which at least one heteroatom has been inserted into the hydrocarbyl group (such as O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*2, GeR*2, SnR*2, PbR*2, etc.), where R* is independently hydrogen, a hydrocarbyl group, or a halocarbyl.

[0027] As used herein, aromatic refers to a cyclic compound, ligand, or substituent ("ring") that contains a cyclic cloud of delocalized π electrons above and below the plane of the "ring", and the π cloud must contain a total of 4n + 2 π electrons, where n is an integer. As used herein, the term "aromatic" also refers to a pseudo-aromatic heterocycle, which is a heterocyclic substituent having properties and a structure (nearly planar) similar to those of an aromatic heterocyclic ligand but which is not aromatic by definition.

[0028] A substituted hydrocarbyl is a group in which at least one hydrogen atom has been replaced by a heteroatom or a heteroatom-containing group, preferably by at least one functional group (such as halogen (Cl, Br, I, F), NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, etc.) or in which at least one heteroatom has been inserted into the hydrocarbyl group (such as halogen (Cl, Br, I, F), O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*2, GeR*2, SnR*2, PbR*2, etc.), where R* is independently hydrogen or a hydrocarbyl group.

[0029] In some embodiments, the hydrocarbyl groups are independently selected from methyl, ethyl, vinyl, and isomers of the following: propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, and triacontynyl. Also included are isomers of saturated, partially unsaturated, and aromatic cyclic structures, where the groups can also be subjected to substitution of the types described above. Examples include phenyl, methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, etc. The alkyl, alkenyl, and alkynyl groups listed include all isomers, including cyclic isomers where appropriate, e.g., butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (and similarly substituted cyclopropyl); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, and neopentyl (and similarly substituted cyclobutyl and cyclopropyl); and butenyl includes the E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl (as well as cyclobutenyl and cyclopropenyl). Substituted cyclic compounds include all isomeric forms, e.g., methylphenyl includes o-methylphenyl, m-methylphenyl, and p-methylphenyl; dimethylphenyl includes 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl.

[0030] Silyl groups (also known as silyl, silyl radicals, and silyl substituents) are defined as SiR*3, where R* is independently hydrogen, a hydrocarbyl group, or a halohydrocarbyl group, and two or more R* may be joined together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic structure. The silyl group is bonded via the silicon atom.

[0031] Silylcarbyl radicals (e.g., hydrocarbyl groups, silylcarbyls, silylcarbyl groups, or silylcarbyl substituents) are groups in which one or more hydrocarbyl hydrogen atoms have been replaced by at least one group containing SiR*3 or in which at least one -Si(R*)2- has been inserted into the hydrocarbyl group, where R* is independently hydrogen, a hydrocarbyl group, or a halohydrocarbyl group, and two or more R* may be joined together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic structure. The silylcarbyl group may be bonded via the silicon atom or a carbon atom.

[0032] A substituted silylcarbyl group is a silylcarbyl group in which at least one hydrogen atom has been replaced by at least one functional group (such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, GeR*3, SnR*3, PbR3, etc.) or in which at least one non-hydrocarbon atom or group has been inserted into the silylcarbyl group (such as --O--, --S--, --Se--, --Te--, --N(R*)--, =N--, --P(R*)--, =P--, --As(R*)--, =As--, --Sb(R*)--, =Sb--, --B(R*)--, =B--, --Ge(R*)2--, --Sn(R*)2--, --Pb(R*)2--, etc.), where R* is independently hydrogen, a hydrocarbyl group, or a halohydrocarbyl group, and two or more R* may be joined together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic structure.

[0033] A halohydrocarbyl group is a group in which one or more hydrocarbyl hydrogen atoms have been replaced by at least one halogen (e.g., F, Cl, Br, I) or a halogen-containing group (e.g., CF3).

[0034] A substituted haloalkyl group is a group in which at least one haloalkyl hydrogen or halogen atom has been replaced by at least one functional group (such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, etc.) or in which at least one non-carbon atom or group has been inserted into the haloalkyl group (such as --O--, --S--, --Se--, --Te--, --N(R*)--, =N--, --P(R*)--, =P--, --As(R*)--, =As--, --Sb(R*)--, =Sb--, --B(R*)--, =B--, --Si(R*)2--, --Ge(R*)2--, --Sn(R*)2--, --Pb(R*)2--, etc.), where R* is independently hydrogen, a hydrocarbon group, or a haloalkyl group, provided that at least one halogen atom remains on the original haloalkyl group. In addition, two or more R* groups can be linked together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic structure.

[0035] The term "substituted phenyl" or "substituted phenyl group" means a phenyl group having one or more hydrogen groups replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a heteroatom-containing group (such as a halogen (such as Br, Cl, F, or I)) or at least one functional group (such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*, -SiR*3, -GeR*, -GeR*3, -SnR*, -SnR*3, -PbR*3, etc., where each R* is independently a hydrocarbon group, a halogen, or a haloalkyl group). Preferably, "substituted phenyl" is represented by the following formula:

[0036]

[0037] where R 17 、R 18 、R 19 、R 20 and R 21 each independently selected from hydrogen, a C1-C 40 hydrocarbon group or a C1-C 40 substituted hydrocarbon group, a heteroatom (such as a halogen), or a heteroatom-containing group (provided that at least one of R 17 、R 18 、R 19 、R 20 and R 21 is not H), or a combination thereof.

[0038] "Fluorophenyl" or "fluorophenyl group" means a phenyl group substituted with one, two, three, four or five fluorine atoms.

[0039] The term "arylalkyl" means an aryl group in which hydrogen has been replaced by an alkyl or substituted alkyl group. For example, 3,5'-di-tert-butyl-phenylindenyl is an indene substituted with an arylalkyl group. When an arylalkyl group is a substituent on another group, it is attached to that group via the aryl.

[0040] The term "alkylaryl" means an alkyl group in which hydrogen has been replaced by an aryl or substituted aryl group. For example, phenethylindenyl is an indene substituted with an ethyl group attached to a benzene group. When an alkylaryl group is a substituent on another group, it is attached to that group via the alkyl.

[0041] Unless otherwise specified, a reference to an alkyl, alkenyl, alkoxy, or aryl group without specifying a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0042] The term "ring atom" means an atom that is part of a cyclic ring structure. Thus, benzyl has six ring atoms, and tetrahydrofuran has five ring atoms.

[0043] Unless otherwise specified, a reference to an alkyl, alkenyl, alkoxy, or aryl group without specifying a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0044] The term "Cn" group or compound refers to a group or compound containing a total of n carbon atoms. A "Cm-Cn" group or compound refers to a group or compound containing a total number of carbon atoms in the range of m to n. Thus, C1-C 50 Alkyl means an alkyl group containing a total number of carbon atoms in the range of 1 to 50.

[0045] The term "olefin", alternatively referred to as "alkene", refers to a substituted or unsubstituted aliphatic hydrocarbon compound having a hydrocarbon chain with at least one carbon-carbon double bond in its structure. In some non-limiting embodiments, the olefin is an unsaturated hydrocarbon compound. In other non-limiting embodiments, the carbon-carbon double bond does not form part of an aromatic ring. The olefin can be straight-chain, branched-chain, cyclic, or a combination thereof. For the purposes of this specification and the appended claims, when a polymer or copolymer is said to comprise an olefin (including but not limited to ethylene, propylene, and butane), the olefin present in such polymer or copolymer is the polymeric form of the olefin (e.g., as a dimer, trimer, oligomer). For example, when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and the derived units are present at 35 wt% to 55 wt% based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having identical monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. A "terpolymer" is a polymer having three monomer units that are different from each other. As used to refer to monomer units, "different" indicates that the monomer units differ from each other by at least one atom or are isomerically different. Thus, "olefin" is intended to include all structural isomeric forms of olefins, unless it is specified to mean a single isomer or the context clearly indicates otherwise. An oligomer is a polymer having a low molecular weight (such as an Mn of 2,000 g / mol or less (preferably 1,000 g / mol or less)) and / or a low number of monomer units (such as 100 monomer units or less, e.g., 50 monomer units or less). A dimer is a polymer having two monomer units that can be the same or different. A trimer is a polymer having three monomer units that can be the same or different. A tetramer is a polymer having four monomer units that can be the same or different. Dimers, trimers, and tetramers are sometimes referred to as oligomers.

[0046] The process of preparing polymers and oligomers (including dimers, trimers, and tetramers) is called polymerization. In some cases, polymerization and oligomerization may be used interchangeably in this document.

[0047] The term "α-olefin" refers to an olefin having a terminal carbon-carbon double bond in its structure ((R a R b )-C=CH2, where R a and R b can independently be hydrogen or any hydrocarbon group; preferably R a is hydrogen and R b is an alkyl group). A "linear α-olefin" is an α-olefin as defined in this paragraph, where R a is hydrogen, and Rb is hydrogen or a straight-chain alkyl group.

[0048] Non-limiting examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene, 3,5,5-trimethyl-1-hexene, vinylcyclohexane, and vinylnorbornane.

[0049] Cyclic olefins contain carbon-carbon double bonds within the ring structure. Non-limiting examples of cyclic olefins and dienes include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene, 2-methylcyclopentene, 4-methylcyclopentene, norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, vinylcyclohexene, and 5-vinyl-2-norbornene.

[0050] Non-limiting examples of branched-chain α-olefins include 4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene, and 3,5,5-trimethyl-1-hexene.

[0051] Non-limiting examples of cyclic α-olefins include vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, 4-vinylcyclohex-1-ene (also known as vinylcyclohexene), vinylcycloheptane, vinylcyclooctane, vinylcyclononane, vinylcyclodecane, vinylcycloundecane, vinylcyclododecane, 5-vinylnorbornane, 5-vinyl-2-norbornene, allylcyclohexane, and allylcyclooctane.

[0052] Non-limiting examples of aromatic cyclic α-olefins include styrene, p-methylstyrene, m-methylstyrene, p-ethylstyrene, p-propylstyrene, p-butylstyrene, 3,5-dimethylstyrene, vinylnaphthylene, and the like.

[0053] Non-limiting examples of cyclic olefins that are not α-olefins include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene, 3-methylcyclopentene, 4-methylcyclopentene, 5-ethylidene-2-norbornene, and the like.

[0054] In unsaturated PAO, the unsaturated end groups can include different types of unsaturation, such as vinyl, vinylidene, disubstituted vinylene, and trisubstituted vinylene.

[0055] The term "vinyl" means an olefin represented by the following formula:

[0056]

[0057] wherein R is a hydrocarbon group, preferably a saturated hydrocarbon group such as an alkyl group.

[0058] The term "vinylidene" means an olefin represented by the following formula:

[0059]

[0060] wherein R 1 and R 2 are each independently a hydrocarbon group, preferably a saturated hydrocarbon group such as an alkyl group. Vinylidene is a 1,1-disubstituted vinylene.

[0061] The term "disubstituted vinylene" means:

[0062] (i) an olefin represented by the following formula:

[0063] or

[0064] (ii) an olefin represented by the following formula:

[0065] or

[0066] (iii) a mixture of (i) and (ii) in any ratio, wherein R 1 and R 2 are the same or different each time they appear, and are each independently a hydrocarbon group, preferably a saturated hydrocarbon group such as an alkyl group. Disubstituted vinylene only represents 1,2-disubstituted vinylene and does not include vinylidene which can also be referred to as 1,1-disubstituted vinylene. As used herein, the term "vinylene" is only an alternative term for "disubstituted vinylene" and not a superordinate class for various vinylene species. In some non-limiting embodiments, vinylene or disubstituted vinylene does not include cyclic disubstituted vinylene.

[0067] The term "trisubstituted vinylene" means an olefin represented by the following formula:

[0068]

[0069] wherein R 1 , R 2 and R3 each independently is a hydrocarbyl group (e.g., a saturated hydrocarbyl group such as an alkyl group), or alternatively R 1 and R 2 can together form a non-aryl ring structure, wherein R 3 is a pendant hydrocarbyl group. As used herein, the term "trisub" is an alternative term for "trisubstituted vinylidene".

[0070] "Cyclic disubstituted vinylidene" is found in cyclic olefins such as cyclopentene, or in some cyclic α-olefins such as 4-vinylcyclohex-1-ene, which contains both a vinyl group and the "cyclic disubstituted vinylidene" unsaturation.

[0071] As used herein, "one or more polyalphaolefins" (one or more PAOs) are polymers of one or more alpha-olefin monomers, particularly oligomers of one or more alpha-olefins. PAOs are polymers, typically oligomer molecules, prepared by the polymerization of alpha-olefin monomer molecules in the presence of a catalyst system, which are optionally further partially or fully hydrogenated to remove residual carbon-carbon double bonds therein or optionally further functionalized by reaction with some or all of the residual carbon-carbon bonds. Thus, PAOs can be dimers, trimers, tetramers, or any other oligomers or polymers containing two or more structural units derived from one or more alpha-olefin monomers. PAO molecules can be highly regioregular (stereoregular), such that when measured by 13 13C NMR, the overall material can exhibit isotacticity or syndiotacticity. PAO molecules can be highly regiodefective (stereodefective), such that when measured by 13 13C NMR, the overall material can be substantially atactic.

[0072] PAO materials prepared by using a metallocene-based catalyst system can be referred to as metallocene-PAO (mPAO), and PAO materials prepared by using a conventional non-metallocene-based catalyst (e.g., Lewis acid, supported chromium oxide, etc.) can be referred to as conventional PAO (cPAO).

[0073] The term "carbon backbone" refers to the longest straight carbon chain in the molecule of the compound or group under discussion. "Branches" or "side groups" are interchangeably any non-hydrogen groups attached to the carbon backbone other than those attached to the carbon atoms at the very end of the carbon backbone. As used herein, the term "length" of a side group is defined as the total number of carbon atoms in the longest carbon chain in the side group, counted starting from the first carbon atom attached to the carbon backbone and ending with the last carbon atom therein, without regard to any substituents or side groups on the chain. In some embodiments, the side group does not contain substituents having more than 2 carbon atoms (or more than 1 carbon atom), or does not contain any substituents. The side group may contain a cyclic group or a portion thereof in the longest carbon chain, in which case half of the carbon atoms in the cyclic group are counted towards the length of the side group. Thus, for example, a straight-chain C8 side group has a length of 8; each of the side groups PG-1 (cyclohexylmethylene) and PG-2 (phenylmethylene) has a length of 4; and each of the side groups PG-3 (o-heptyl-phenylmethylene) and PG-4 (p-heptylphenylmethylene) has a length of 11. In the case where a PAO molecule contains multiple side groups, the arithmetic mean of the lengths of all such side groups is calculated as the average length of all side groups in the PAO molecule.

[0074]

[0075] For nomenclature purposes, the following numbering scheme is used for cyclopentadienyl, indenyl, tetrahydro-s-indacenyl, tetrahydro-as-indacenyl, benzo[f]indenyl, benzo[e]indenyl ligands. Indenyl, tetrahydro-s-indacenyl, tetrahydro-as-indacenyl, benzo[f]indenyl, benzo[e]indenyl ligands are by definition substituted cyclopentadienyl ligands. Tetrahydro-s-indacenyl, tetrahydro-as-indacenyl, benzo[f]indenyl, benzo[e]indenyl ligands are by definition substituted indenyl ligands. The numbering scheme is used to specify the position of substituents and, where applicable, the position of bridges. For example, a cyclopentadienyl ligand substituted with methyl groups at the 1 and 3 positions will be named 1,3-dimethylcyclopentadienyl. And similarly, two indenyl ligands bridged by a dimethylsilylene group at the 1 position of each indenyl will be named dimethylsilylene-bis(inden-1-yl).

[0076]

[0077]

[0078] As described herein, metallocene compounds can have one or more optical isomers. Metallocene compounds designated by name or structure herein shall include all possible optical isomers thereof and mixtures of any such optical isomers. For example, the metallocene compound Me2Si(Me4Cp)(3-PrInd)ZrMe2 includes the following two optical isomers and mixtures thereof, even when only one structure is given when it is described:

[0079]

[0080] A "metallocene" catalyst compound is a transition metal catalyst compound having one, two, or three, typically one or two, substituted or unsubstituted cyclopentadienyl ligands bonded to a transition metal. Typically, a metallocene catalyst is an organometallic compound containing at least one π-bonded cyclopentadienyl moiety (or substituted cyclopentadienyl moiety). Substituted cyclopentadienyl ligands include substituted or unsubstituted indenyl, fluorenyl, tetrahydro-s-indacenyl, tetrahydro-as-indacenyl, benzo[f]indenyl, benzo[e]indenyl, tetrahydrocyclopenta[b]naphthalene, tetrahydrocyclopenta[a]naphthalene, etc.

[0081] The substituted cyclopentadienyl ligands are bridged or unbridged, for example, by a dimethylsilylene bridge as shown above. If no bridge is specifically disclosed, the cyclopentadienyl ligand is unbridged. Similarly, if no bridge of the metallocene (also known as a pre-catalyst) is specifically disclosed, the metallocene is unbridged.

[0082] An asymmetric metallocene compound is a metallocene compound having two π-bonded cyclopentadienyl moieties that differ in ring type, such as by having a monocyclic aryl ligand and a polycyclic aryl ligand. For example, (cyclopentadienyl)(indenyl)zirconium dichloride would be considered asymmetric because it has a monocyclic aryl ligand and a polycyclic aryl ligand, while bis(indenyl)zirconium dichloride would be considered symmetric because it has two polycyclic aryl ligands.

[0083] As used herein, the term "monocyclic aryl ligand" is used herein to mean a substituted or unsubstituted monoanionic C5 to C 100 hydrocarbyl ligand containing an aromatic five-membered monohydrocarbyl ring structure (also known as a cyclopentadienyl ring).

[0084] As used herein, the term "polycyclic aryl ligand" is used herein to mean a substituted or unsubstituted monoanionic C8 to C 103 hydrocarbyl ligand containing an aromatic five-membered hydrocarbyl ring (also referred to as a cyclopentadienyl ring) fused to a partially unsaturated or aromatic hydrocarbyl ring structure which may be fused to additional saturated, partially unsaturated, or aromatic hydrocarbyl rings.

[0085] Mono-cyclic aryl ligands include substituted or unsubstituted cyclopentadienyls. Polycyclic aryl ligands include substituted or unsubstituted, partially unsaturated or aromatic indenyls, fluorenyls, benzo[f]indenyls, benzo[e]indenyls, 5,6,7,8-tetrahydro-1H-cyclopentadieno[b]naphthalenyls, 6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalenyls, 1,5,6,7-tetrahydro-s-indacenyls, 3,6,7,8-tetrahydro-as-indacenyls, and the like.

[0086] Non-limiting examples of polycyclic aromatic hydrocarbon ligands (also referred to as monoanionic ligands) include indenyl, 4,5-dihydroindenyl, 4,7-dihydroindenyl, 4,5,6,7-tetrahydroindenyl, benzo[f]indenyl, benzo[e]indenyl, 5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalenyl, 6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalenyl, 1,5,6,7-tetrahydro-s-indacenyl, 3,6,7,8-tetrahydro-as-indacenyl, 5,6-trimethylenylindenyl, 4,5-trimethylenylindenyl, 5,6-pentamethylenylindenyl, 4,5-pentamethylenylindenyl, 5,6-hexamethylenylindenyl, 4,5-hexamethylenylindenyl, 5,6-heptamethylenylindenyl, 4,5-heptamethylenylindenyl, 5,6-octamethylenylindenyl, 4,5-octamethylenylindenyl, 5,6-nonamethylenylindenyl, 4,5-nonamethylenylindenyl, 5,6-decamethylenylindenyl, 4,5-decamethylenylindenyl, 5,6-undecamethylenylindenyl, 4,5-undecamethylenylindenyl, 5,6-dodecamethylenylindenyl, 4,5-dodecamethylenylindenyl, 5,6-tridecamethylenylindenyl, 4,5-tridecamethylenylindenyl, 5,6-tetradecamethylenylindenyl, 4,5-tetradecamethylenylindenyl, 5,6-pentadecamethylenylindenyl, 4,5-pentadecamethylenylindenyl, 5,6-hexadecamethylenylindenyl, 4,5-hexadecamethylenylindenyl, 5,6-heptadecamethylenylindenyl, 4,5-heptadecamethylenylindenyl, 5,6-octadecamethylenylindenyl, 4,5-octadecamethylenylindenyl, 5,6-nonadecamethylenylindenyl, 4,5-nonadecamethylenylindenyl, 5,6-icosamethylenylindenyl, 4,5-icosamethylenylindenyl, (6Z,8Z,10Z)-cycloocta[e]indenyl ((6Z,8Z,10Z)-cycloocta[e]indenyl), (5Z,7Z,9Z)-cycloocta[f]indenyl ((5Z,7Z,9Z)-cycloocta[f]indenyl), (5E,7Z,9E,11Z,13E)-cyclododeca[f]indenyl ((5E,7Z,9E,11Z,13E)-cyclododeca[f]indenyl), (6E,8Z,10E,12Z,14E)-cyclododeca[e]indenyl ((6E,8Z,10E,12Z,14E)-cyclododeca[e]indenyl).

[0087] Partially hydrogenated polycyclic aromatic hydrocarbon ligands retain the numbering scheme of the parent polycyclic aromatic hydrocarbon ligand, i.e., the numbering scheme defined for indenyl, benzo[f]indenyl, benzo[e]indenyl, 5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalenyl, 6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalenyl, 1,5,6,7-tetrahydro-s-indacenyl, 3,6,7,8-tetrahydro-as-indacenyl.

[0088] Unless otherwise specified, the term "substantially all" with respect to PAO molecules means at least 90 mol% (such as at least 95 mol%, at least 98 mol%, at least 99 mol%, or even 100 mol%).

[0089] Unless otherwise specified, the term "substantially free of" with respect to a particular component means that the concentration of that component in the relevant composition is not more than about 10 mol% based on the total amount of the relevant composition (e.g., within the limits of the relevant measurement method, at most 5 mol%, at most 3 mol%, at most 1 mol%, or about 0%). Preferably, "substantially free of" means not more than 10 mol% based on the total amount of the relevant composition (such as not more than 5 mol%, not more than 3 mol%, not more than 1 mol%, or about 0%).

[0090] The terms "catalyst" and "catalyst compound" are defined to mean a compound that can initiate catalysis and / or promote a chemical reaction with little or no poisoning / consumption. In the description herein, a catalyst may be described as a catalyst precursor, a precatalyst compound, a transition metal complex, or a transition metal compound, and these terms may be used interchangeably. A catalyst compound can be used alone to initiate catalysis or can be used in combination with an activator to initiate catalysis. When a catalyst compound is combined with an activator to initiate catalysis, the catalyst compound is typically referred to as a precatalyst or a catalyst precursor. A "catalyst system" includes at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material, wherein the system can polymerize monomers to form a polymer.

[0091] A scavenger is a compound that is typically added to promote oligomerization / polymerization by scavenging impurities. Some scavengers can also act as activators and can be referred to as co-activators. A non-scavenger co-activator can be used in combination with an activator to form an active catalyst. In some embodiments, a co-activator can be premixed with a catalyst compound to form an alkylated catalyst compound.

[0092] As used herein, "lubricant" refers to a substance that can be introduced between two or more moving surfaces and reduces the level of frictional force between two adjacent surfaces moving relative to each other. A lubricant "base stock" is a material that is typically fluid at the operating temperature of the lubricant and is used to formulate the lubricant by blending it with other components. Non-limiting examples of base stocks suitable for use in lubricants include API Group I, Group II, Group III, Group IV, Group V, and Group VI base stocks. Fluids derived from the Fischer-Tropsch process or the Gas-to-Liquid ("GTL") process are examples of synthetic base stocks that can be used to prepare modern lubricants. GTL base stocks and methods for preparing them can be found, for example, in PCT Publication No. WO 2005 / 121280 and in U.S. Patent Nos. 7,344,631; 6,846,778; 7,241,375; and 7,053,254, which are hereby incorporated by reference in their entirety.

[0093] All numerical values within the detailed description and claims of this application are indicative values that are modified by "about" or "approximately" and take into account the experimental errors and deviations that would be expected by a person of ordinary skill in the art.

[0094] In the present disclosure, unless otherwise specified, all percentages of side groups, terminal carbon chains, and side chain groups are in mole percent. Mole percent is expressed as "mol%", and weight percent is expressed as "wt%".

[0095] In the present disclosure, unless otherwise specified, all molecular weight data are in g / mol (e.g., g·mol -1 ) units.

[0096] NMR spectroscopy provides key structural information about synthetic polymers. Proton NMR ( 1 H-NMR) analysis can be used to determine the molecular weight of oligomeric or polymeric materials, including functionalized, hydrogenated, and uPAO materials. However, the molecular weight of oligomeric or polymeric materials measured by 1 H-NMR in this application represents the number average molecular weight (Mn). In addition, 1 H-NMR analysis of unsaturated PAO products can give a quantitative breakdown of the olefinic structural types (i.e., vinyl, disubstituted vinylidene, trisubstituted vinylidene, and ethylidene). In some embodiments, the composition of an olefin mixture containing terminal olefins (vinyl and ethylidene) and internal olefins (disubstituted vinylidene and trisubstituted vinylidene) is determined using 1 H-NMR as described in the experimental section.

[0097] As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, and Mz is the z average molecular weight, wt% is weight percentage, and mol% is mole percentage. The molecular weight distribution (MWD), also known as the polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol (g mol -1 ).

[0098] Throughout this specification, the following abbreviations may be used: Cp is cyclopentadiene or cyclopentadienyl; Ind is indene or indenyl, Flu is fluorene or fluorenyl, Me is methyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is n-propyl, cPr is cyclopropyl, Bu is butyl, nBu is n-butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, MeCy is methylcyclohexane, and Cy is cyclohexyl, Ph is phenyl, p-tBu is p-tert-butyl, p-Me is p-methyl, o-biphenyl is the o-biphenyl structural moiety represented by the structure The o-biphenyl structure part, Cbz is carbazole, Cy is cyclohexyl, Oct is octyl, Ar* is 2,6-diisopropylphenyl, pMe is p-methyl, Bz or Bn is interchangeably benzyl (i.e., CH2Ph), TMS is trimethylsilyl, TIBAL or TiBAl is triisobutylaluminum, TNOAL or TNOA or TnOAl is tri-n-octylaluminum, MAO is methylaluminoxane, THF or thf is tetrahydrofuran, tol or Tol is toluene, dme is 1,2-dimethoxyethane, EtOAc is ethyl acetate, MCH is methylcyclohexane, VCH is 4-vinylcyclohex-1-ene, tol is toluene, and RT is room temperature (and is about 23 °C unless otherwise stated).

[0099] The term "continuous" means a system that operates without interruption or cessation for a certain period of time, such as a system in which reactants are continuously fed into a reaction zone and products are continuously or periodically withdrawn without stopping the reaction in the reaction zone. For example, a continuous process for preparing a polymer would be one in which reactants are continuously introduced into one or more reactors and the polymer product is continuously withdrawn.

[0100] "Solution polymerization" means a polymerization process in which the polymerization is carried out in a liquid polymerization medium such as an inert solvent or one or more monomers or blends thereof. Solution polymerization is typically homogeneous. Homogeneous polymerization is a polymerization in which the polymer product is dissolved in the polymerization medium. Such systems are typically not turbid, as described in Oliveira, J.V. et al. (2000) "High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems," Ind. Eng. Chem. Res., Vol. 39(12), pp. 4627-4633.

[0101] "Bulk polymerization" means a polymerization process in which the monomers and / or comonomers being polymerized are used as the solvent or diluent, with little or no use of an inert solvent or diluent. A small amount of an inert solvent may be used as a carrier for the catalyst and scavenger. The bulk polymerization system contains less than about 25 wt% of an inert solvent or diluent, such as less than about 10 wt%, such as less than about 1 wt%, such as 0 wt%.

[0102] Description

[0103] The present disclosure provides a process for preparing polyalphaolefins (PAOs) from two or more different alpha-olefins, wherein at least one alpha-olefin is a cyclic alpha-olefin and at least one second alpha-olefin is a linear or branched alpha-olefin. The process may comprise the steps of contacting a feed comprising one or more C6-C 32 cyclic alpha-olefins and one or more C4-C 32 linear and / or branched alpha-olefins with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions to effect a polymerization reaction to obtain a polymerization reaction mixture comprising a mixture of PAO molecules having ethylidene, trisubstituted vinylidene, disubstituted vinylidene, and optionally vinyl unsaturation.

[0104] The process may further comprise obtaining an unsaturated PAO product from the polymerization reaction mixture, wherein the unsaturated PAO product comprises a mixture of PAO molecules having ethylidene, trisubstituted vinylidene, disubstituted vinylidene, optionally vinyl unsaturation, and is optionally substantially free of the alpha-olefin feed. When a cyclic alpha-olefin having ring unsaturation such as 4-vinylcyclohex-1-ene is used as the cyclic alpha-olefin, then the PAO product will also contain internal ring disubstituted vinylidene. This type of unsaturation is referred to as cyclic disubstituted vinylidene.

[0105] The present disclosure also provides a method for preparing α-olefin dimers and trimers (preferably dimers) from two or more α-olefins, wherein at least one α-olefin is a cyclic α-olefin and at least one α-olefin is a linear or branched α-olefin. The method may include the steps of: contacting a feed containing one or more C6-C 32 cyclic α-olefins and one or more C4-C 32 linear and / or branched α-olefins with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions to effect a polymerization reaction to obtain a polymerization reaction mixture comprising dimer and / or trimer molecules having ethylidene, trisubstituted vinylidene, disubstituted vinylidene, and optionally vinyl unsaturation. The method may further include the steps of: obtaining an unsaturated dimer and / or trimer product from the polymerization reaction mixture, wherein the unsaturated dimer and / or trimer product has ethylidene, trisubstituted vinylidene, disubstituted vinylidene, optionally vinyl unsaturation, and, optionally, is substantially free of the α-olefin feed. When a cyclic α-olefin having ring unsaturation such as 4-vinylcyclohex-1-ene is used as the cyclic α-olefin, the dimer and / or trimer product will also contain an internal ring disubstituted vinylidene. This type of unsaturation is referred to as a cyclic disubstituted vinylidene.

[0106] Another aspect of the present disclosure relates to a method for preparing α-olefin dimers and / or trimers (preferably dimers) from two or more different α-olefins, wherein at least one α-olefin is a cyclic α-olefin and at least one second α-olefin is a linear or branched α-olefin, and the product prepared comprises molecules selected from the following:

[0107]

[0108]

[0109] wherein the cyclic monomeric segments (A) and (B) can independently be saturated (if the cyclic α-olefin has a saturated ring structure), or partially unsaturated (if the cyclic α-olefin has a partially unsaturated ring structure); wherein n and m independently indicate the number of additional carbon atoms in the ring structure and can be integers from 1 to 20 (alternatively 1-12, alternatively 1-9, alternatively 1-5, alternatively 1-3), R is a C2-C 30 hydrocarbyl group, R' is a C1-C 29 hydrocarbyl group, and wherein at least one of the structures CL-v or LC-v is present in the product mixture.

[0110] The present disclosure also provides a method for preparing an α-olefin dimer and / or trimer (preferably a dimer) from two or more different α-olefins, wherein at least one of the α-olefins is a cyclic α-olefin and at least one second α-olefin is a linear or branched α-olefin, and the product prepared has a selectivity of more than 50%, alternatively more than 60%, alternatively greater than 70%, alternatively greater than 80%, alternatively greater than 90%, alternatively greater than 90% of the total product mixture for preparing the dimer.

[0111] Functionalization of Unsaturated PAO Products

[0112] The unsaturated PAO products of the present disclosure, as described above and desirably prepared by polymerization of α-olefins and / or olefin monomers in the presence of a metallocene-compound-based catalyst system, can advantageously be used as chemical intermediates for preparing many products, especially those containing a PAO molecular structure moiety and one or more functional groups. Hydrocarbon molecules in the unsaturated PAO products (if prepared by polymerization of olefins / α-olefins containing only one C═C double bond in their prepolymerized molecules) can tend to each contain no more than one C═C bond, and the remainder of the molecular structure typically consists of C-C bonds and C-H bonds.

[0113] The C═C bonds present in the molecules of the unsaturated PAO products of the present disclosure are highly reactive and can thus react with a variety of different types of chemical reagents having available functional groups, resulting in PAO molecules further containing functional groups bonded thereto. The functional groups in turn can contain other functional groups that can react with additional chemical reagents, introducing additional or different functional groups to the final molecule. The hydrocarbon substrate of the thus-functionalized PAO (i.e., the PAO structure) can impart desired properties to the functionalized material, such as solubility in organic media or hydrophobicity, and the functional groups can impart other desired properties to the final material, such as polarity, hydrophilicity (and thus solubility in aqueous media), etc., making the final material particularly useful in situations where such dual properties are desired (e.g., detergents, adhesives, etc.).

[0114] U.S. Publication No. 2014 / 0087986 discloses various methods for preparing functionalized PAO from unsaturated PAO products prepared by polymerization of α-olefin monomers in the presence of a metallocene-compound-based catalyst system. The entire disclosure of US2014 / 0087986 is incorporated herein by reference.

[0115] It is highly desirable that after the functionalization of unsaturated PAO products, the C=C double bonds in the reacted uPAO molecules become saturated (i.e., each carbon atom in the original C=C bond is then bonded to four atoms). This can be achieved by using a functionalizing agent that is substantially only reactive towards the C=C bonds in uPAO olefin molecules under the functionalization conditions but is substantially inert towards C-C bonds and C-H bonds. Considering that each uPAO olefin molecule typically contains only one C=C bond, the uPAO olefin will then become saturated after such a functionalization reaction.

[0116] After the functionalization of the C=C bonds in uPAO olefin molecules, the overall structure of the functionalized PAO molecules will be substantially similar to the overall structure of hydrogenated PAO molecules in which the C=C bonds have been saturated by hydrogenation as described above. Under the use conditions, assuming that the robustness of the bonds between one or more functional groups and one or more carbon atoms is not significantly lower than that of C-C and C-H bonds, and assuming that the robustness of one or more functional groups themselves is not significantly lower than that of the pendant groups on the PAO molecule, it can be expected that the stable oligomer / polymer structure retains at least some of the properties of interest and utility of the saturated PAO molecules, such as one or more of viscosity index, oxidation stability, shear stability, bromine number, etc. The retained properties can make the functionalized PAO material particularly useful in typical applications of saturated PAO materials, such as lubricating oil compositions, etc.

[0117] It is desirable that the functionalizing agent used to functionalize the unsaturated PAO product is highly selective only towards reacting with C=C bonds and is substantially inert with respect to the C-C bonds and C-H bonds on the uPAO molecule. This can ensure the preparation of functionalized PAO molecules each containing only one or two functional groups, and if desired, can ensure the complete functionalization of substantially all uPAO molecules. In applications such as lubricating oil compositions, due to the high reactivity of the C=C bonds in uPAO molecules, it can be expected that substantially all of the C=C bonds in the uPAO molecules are saturated before the functionalized PAO material is introduced into the oil composition as a base stock or as an additive.

[0118] Additionally or alternatively, the uPAO molecules can also be functionalized by replacing one or more of the hydrogen atoms on the carbon backbone or one of the pendant groups with a functional group by using a chemical reagent known to be reactive towards C-H bonds. Since uPAO molecules typically contain many C-H bonds at multiple positions, such a reaction will be less selective than the selective functionalization of C=C bonds by using a functionalizing agent that is inert towards C-H bonds, and can produce a very large number of very different molecules, and is therefore less desirable than the functionalization that is selective only towards C=C bonds.

[0119] Additionally or alternatively, the uPAO products of the present disclosure can be functionalized by the reaction between the unsaturated C═C bonds of the uPAO molecules and chemical reagents. The chemical reagents can contain structural moieties that react directly or indirectly with one or more reactive moieties of the uPAO, optionally in the presence of a suitable catalyst or promoter. Alternatively, the chemical reagent can be a precursor that reacts directly or indirectly with one or more reactive moieties of the uPAO, optionally in the presence of a suitable catalyst or promoter, and is subsequently also optionally subjected to at least one other treatment and / or chemical reagent reaction, optionally in the presence of the same or a different suitable catalyst or promoter, in order to achieve the desired final functionality at one or more reactive moieties of the uPAO. Additionally alternatively, the chemical reagent can be a co-reactant that reacts pre or simultaneously with another chemical reagent that is used to react directly or indirectly with one or more reactive moieties of the uPAO, optionally in the presence of a suitable catalyst or promoter.

[0120] Optionally, it may be desirable to have more than one type of functionality, such that the functionalization can occur simultaneously (achieving multiple functionalities in a single outcome), in series, in parallel (provided that the two parallel reactions do not cancel each other out), or some combination thereof. Whether one or more functionalities are desired, the reaction can be of any kind that is capable of effectively achieving the functionalization, e.g., liquid-phase chemistry, gas-liquid interface chemistry, solid-liquid surface chemistry, gas oxidation, gas oxidation followed by some other functionalization mechanism, plasma oxidation, plasma oxidation followed by some other functionalization mechanism, free radical formation, free radical formation followed by some other functionalization mechanism, etc. The one or more final desired functional groups can be customized for a particular end-use application, e.g., including but not limited to structural moieties containing oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, boron atoms, silicon atoms, halogen atoms, or combinations thereof. The degree to which the functionalization can be achieved is another variable that can be customized for a particular end-use application. The functionalization(s) can be partial or substantially complete (i.e., where substantially all of the unsaturations of the uPAO can be converted into functional structural moieties, such as heteroatom-containing structural moieties).

[0121] The PAO prepared herein can be functionalized by reacting a heteroatom-containing group with the PAO in the presence or absence of a catalyst. Examples include catalytic hydrosilylation, ozonolysis, hydroformylation, hydroamination, sulfonation, halogenation, hydrohalogenation, hydroboration, epoxidation, or the Diels-Alder reaction with a polar diene, the Friedel-Crafts reaction with a polar aromatic compound, maleation with an activator such as a free radical generator (e.g., peroxide). The functionalized PAO can be used in oil additives such as anti-fog or anti-humidity additives, surfactants, for soaps, detergents, fabric softeners, antistatic agents, adhesion promoters, and many other applications. Preferred uses include additives for lubricants and / or fuels, preferably where the heteroatom-containing group comprises one or more of the following: amine, aldehyde, alcohol, acid, acid anhydride, sulfonate / ester, particularly succinic acid, maleic acid, and maleic anhydride.

[0122] In some embodiments, the PAO prepared herein is functionalized as described in U.S. Patent No. 6,022,929; Toyota, A. et al. (2002) Polymer Bulletin, Vol. 48(3), pp. 213-219; and Kropp, P.J. (1990) Journal Am. Chem. Soc., Vol. 112, pp. 7433-7434. In some embodiments, the functionalized PAO prepared herein is further functionalized (derivatized) as described in U.S. Patent No. 6,022,929; Toyota, A. et al. (2002) Polymer Bulletin, Vol. 48(3), pp. 213-219; Kropp, P.J. (1990) Journal Am. Chem. Soc., Vol. 112, pp. 7433-7434; and PCT Publication No. WO 2009 / 155472.

[0123] In a preferred embodiment, the PAO of the present disclosure can be functionalized (e.g., chemically modified by one or more functional groups typically containing heteroatoms such as P, O, S, N, Br, Cl, F, I, and / or Br (preferably N, O, Cl, and / or Br, preferably N and / or O), also referred to as heteroatom-containing groups). Preferred functional groups are selected from the group consisting of acids, esters, acid anhydrides, acid-esters, oxycarbonyls, carbonyls, formyls, formyl carbonyls, hydroxyls, and acetyl halides. Particularly preferred functional groups include those represented by the following formulas: -C(O)-X, where O is double-bonded to C and X is hydrogen, nitrogen, hydroxyl, oxyhydrocarbyl (e.g., ester), oxygen; salt moiety -OM, where M is a metal, such as an alkali metal, alkaline earth metal, transition metal, copper, zinc, etc.; oxyhetero, e.g., -O-Z, where Z represents a heteroatom, such as phosphorus, boron, sulfur, and the heteroatom can be substituted by a hydrocarbyl or oxyhydrocarbyl group, or two acyl groups can be linked through (X).

[0124] Preferred heteroatom-containing groups include acyl groups derived from mono-unsaturated mono- or dicarboxylic acids and their derivatives, such as esters and salts.

[0125] More specifically, PAO functionalized with a mono- or dicarboxylic acid material (i.e., acid, acid anhydride, salt, or acid ester) is preferred, including the reaction product of PAO with a mono-unsaturated carboxylic acid reactant, the mono-unsaturated carboxyl reactant comprising at least one member selected from the group consisting of: (i) mono-unsaturated C4 to C 10 dicarboxylic acids (preferably where (a) the carboxyl groups are vicinyl (i.e., located on adjacent carbon atoms) and (b) at least one, preferably two, of the adjacent carbon atoms are part of the mono-unsaturation); (ii) derivatives of (i), such as acid anhydrides or C1 to C5 alcohol-derived monoesters or diesters of (i); (iii) mono-unsaturated C3 to C 10 monocarboxylic acids where the carbon-carbon double bond is conjugated to the carboxyl group, i.e., the structure -C=C-C(O)- (where O is double-bonded to C), and (iv) derivatives of (iii), such as C1 to C5 alcohol-derived monoesters of (iii). After reaction with PAO, the double bond of the mono-unsaturated carboxylic acid reactant becomes saturated. Thus, for example, maleic anhydride becomes succinic anhydride upon reaction with PAO, and acrylic acid becomes propionic acid.

[0126] Suitable unsaturated acid materials for use as the functional compound include acrylic acid, crotonic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, pentenedioic acid, chloromaleic acid, aconitic acid, crotonic acid, methylcrotonic acid, sorbic acid, 3 - hexenoic acid, 10 - decenoic acid, 2 - pentene - 1,3,5 - tricarboxylic acid, cinnamic acid, and lower alkyl (e.g., C1 to C4 alkyl) acid esters of the foregoing items, such as methyl maleate, ethyl fumarate, methyl fumarate, etc. Particularly preferred are unsaturated dicarboxylic acids and their derivatives, especially maleic acid, fumaric acid, and maleic anhydride.

[0127] Typically, per mole of the PAO charged, about 0.7 to about 4.0 (e.g., 0.8 to 2.6), preferably about 1.0 to about 2.0, and most preferably about 1.1 to about 1.7 moles of the monounsaturated carboxylic acid reactant are charged to the reactor.

[0128] Functionalization can be achieved by any suitable method. Available methods include the reaction of the olefinic bond of the PAO with an unsaturated, preferably monounsaturated, carboxylic acid reactant. Alternatively, an oligomer can be halogenated using a chlorine - or bromine - containing compound. Then the halogenated PAO can be reacted with a monounsaturated carboxylic acid. The PAO and the monounsaturated carboxylic acid reactant can also be contacted at an elevated temperature to cause a thermal "ene" reaction to occur. Alternatively, the monounsaturated carboxylic acid can be reacted with the PAO by free - radical - induced grafting. The PAO of the present disclosure can be functionalized by contacting it with a hydroxyaromatic compound in the presence of a catalytically effective amount of at least one acidic alkylation catalyst. Then, the alkylated hydroxyaromatic compound can be further reacted by Mannich base condensation with aldehyde and amine reagents to obtain a Mannich base condensate to form a derivative. In yet another means of functionalizing the PAO, the PAO can be contacted with carbon monoxide under Koch reaction conditions in the presence of an acid catalyst to obtain a PAO substituted with a carboxylic acid group. In addition to the above functionalization methods, the PAO of the present disclosure can also be functionalized by methods such as air oxidation, ozonolysis, hydroformylation, epoxidation, and chloramination (e.g., U.S. Patent No. 6,022,929, column 21, line 16 to column 33, line 27).

[0129] The polyalpha - olefins prepared herein contain one or more unsaturated double bonds, are rich in vinylidene content, with some 1,2 - disubstituted olefins. These unsaturated polymers are particularly suitable for further functionalization reactions. Examples of such functionalization include alkylation with aromatic compounds such as benzene, toluene, xylene, naphthalene, phenol, or alkylphenol. The PAO can also be reacted with maleic anhydride to obtain PAO - succinic anhydride, which can be further converted to the corresponding succinimide or succinate with an amine or an alcohol. These imides and esters are excellent dispersants.

[0130] The functionalized PAO can in turn be derivatized by a derivatizing compound. (For the purposes of this disclosure and its claims, the term functionalized PAO encompasses derivatized PAO.) The derivatizing compound can react with the functional groups of the functionalized PAO by means such as nucleophilic substitution, Mannich base condensation, etc. The derivatizing compound can be polar and / or contain reactive derivative groups. Preferred derivatizing compounds are selected from compounds containing hydroxyl groups, amines, metal salts, compounds containing acid anhydrides, and compounds containing acetyl halides. The derivatizing compound can contain at least one nucleophilic group and preferably at least two nucleophilic groups. Typical derivatized PAO is prepared by contacting a functionalized PAO (i.e., substituted with carboxylic acid / acid anhydride or ester) with a nucleophile (e.g., amine, alcohol, including polyols, amino alcohols, reactive metal compounds, etc.) (e.g., U.S. Patent No. 6,022,929, column 33, line 27 to column 74, line 63). Alternatively, derivatized PAO can be prepared as follows: by contacting a functionalized PAO substituted with carboxylic acid / acid anhydride or ester with a nucleophile (e.g., amine) to prepare a quaternary ammonium compound or amine oxide.

[0131] The functionalized PAO and / or derivatized PAO has use as a lubricating additive, which can act as a dispersant, viscosity index improver, or multifunctional viscosity index improver. In addition, they can be used as disinfectants (functionalized amines) and / or wetting agents.

[0132] The functionalized PAO prepared herein can be used in oil additives, lubricants, fuels, and many other applications. Preferred uses include additives for lubricants and / or fuels.

[0133] In the specific embodiments herein, the PAO disclosed herein or its functionalized / derivatized analogs can be used as additives, preferably in lubricants.

[0134] The functionalized PAO and / or derivatized PAO prepared herein has use as a lubricating additive, which can act as a dispersant, viscosity index improver, or multifunctional viscosity index improver. In addition, they can be used as disinfectants (functionalized amines) and / or wetting agents.

[0135] The functionalized PAO and / or derivatized PAO described herein can be used as viscosity index improvers for lubricating oil compositions, adhesive additives, anti-fogging agents and wetting agents, ink and coating adhesion promoters, coatings, tackifiers, and sealants, etc. In addition, such PAO can be functionalized and derivatized to prepare multifunctional viscosity index improvers that also have dispersant properties (e.g., US 6,022,929).

[0136] The functionalized PAO and / or derivatized PAO described herein can be combined with other additives (such as viscosity index improvers, corrosion inhibitors, oxidation inhibitors, dispersants, lubricant flow improvers, detergents, demulsifiers, rust inhibitors, pour point depressants, antifoaming agents, antiwear agents, seal swell agents, friction modifiers, etc. (described, for example, in U.S. Patent No. 6,022,929, column 60, line 42 - column 78, line 54 and the references cited therein)) to form compositions for many applications, including but not limited to lubricant additive packages, lubricating oils, etc.

[0137] Compositions containing these additives are typically blended into a base oil in amounts effective to provide their normal attendant functions. Representative effective amounts of such additives are shown below:

[0138]

[0139] *Wt% is based on the active ingredient content of the additive and / or on the total weight of any additive package or formulation, which will be the sum of the A.I. weight of each additive plus the weight of the total oil or diluent.

[0140] When other additives are employed, it may be desirable (although not necessary) for the preparation of additive concentrates containing: a concentrated solution or dispersion of the subject additives of the present disclosure (in the amounts of concentrates described above) and one or more of said other additives (when constituting the concentrate of the additive mixture referred to herein as an additive package), whereby several additives can be added simultaneously to a base oil to form a lubricating oil composition. Dissolution of the additive concentrate into the lubricating oil can be facilitated by solvents and by mixing with mild heating, but this is not required. The subject functionalized or derivatized PAO of the present disclosure can be added together with other desired additives to at least a small amount of a base oil or other compatible solvent to form an additive package, which contains active ingredients in an overall amount of typically about 2.5% to about 90% and preferably about 15% to about 75% and most preferably about 25% to about 60% (by weight) of the additives, the balance being the base oil.

[0141] The final formulation can typically employ about 10 wt% of the additive package, the balance being the base oil.

[0142] In another embodiment, the PAO described herein can be used in any method, blend, or product disclosed in PCT Publication No. WO 2009 / 0155472 or U.S. Patent No. 6,022,929 (which is incorporated herein by reference).

[0143] In a preferred embodiment, the present disclosure relates to fuels comprising any of the PAOs prepared herein. In a preferred embodiment, the present disclosure relates to lubricants comprising any of the PAOs prepared herein.

[0144] Catalyst system

[0145] Catalyst systems useful herein comprise an asymmetric metallocene catalyst compound activated by one or more non-aromatic hydrocarbon soluble activators and may further include a solvent, a support, one or more scavengers, and / or the like.

[0146] Typical activator to catalyst ratios, e.g., all NCA activator to catalyst ratios, are about 1:1 molar ratio. Alternative preferred ranges include 0.1:1 to 100:1, alternatively 0.5:1 to 200:1, alternatively 1:1 to 500:1, alternatively 1:1 to 1000:1, e.g., 0.5:1 to 10:1, preferably 1:1 to 5:1.

[0147] Solvents useful for combining the catalyst compound and the activator and / or for introducing the catalyst system into the reactor include, but are not limited to, aliphatic solvents such as butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or combinations thereof; preferred solvents may include normal paraffins (such as those available from ExxonMobil Chemical Company, Houston, Texas) isoparaffinic solvents (such as those available from

[0148] ExxonMobil Chemical Company, Houston, Texas) 10 and combinations thereof. These solvents or diluents can typically be pretreated in the same manner as the feed olefins.

[0149] Preferably, the solvent is selected from C4 to C 10 linear, branched or cyclic alkanes.

[0149] Preferably, the solvent is substantially free of all aromatic solvents.

[0150] Preferably, the solvent is substantially free of toluene.

[0151] Preferably, the solvent is selected from one or more C6 to C 32 alpha-olefins, such as one or more C8 to C 16 alpha-olefins.

[0152] Preferably, the solvent is substantially free of all non-alpha-olefin solvents.

[0153] Aliphatic hydrocarbon solvents can include, but are not limited to, isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In some embodiments, based on the weight of the solvent, aromatic compounds are present in the solvent in less than 1 wt%, such as less than 0.5 wt%, such as 0 wt%.

[0154] The activator of the present disclosure can be dissolved in one or more additional solvents, provided that such solvents are non-aromatic. Additional solvents include halogenated or partially halogenated hydrocarbon solvents.

[0155] In some embodiments, the aliphatic solvent is isohexane and / or methylcyclohexane.

[0156] In some embodiments, the solvent is one or more C6 to C 32 α-olefins, such as one or more C8 to C 16 α-olefins, and no additional solvent is used.

[0157] In some embodiments, the solvent is 1-octene, 1-decene, 1-dodecene, or 1-tetradecene, or any combination of two or more thereof.

[0158] Processes using metallocene compounds

[0159] Also provided herein is a process for preparing polyalphaolefins (PAOs) from two or more different alpha-olefins, wherein at least one of the alpha-olefins is a cyclic alpha-olefin and at least one second alpha-olefin is a linear or branched alpha-olefin. The process can include the steps of contacting a feed comprising one or more C6-C 32 cyclic alpha-olefins and one or more C4-C 32 linear and / or branched alpha-olefins with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions to effect a polymerization reaction to obtain a polymerization reaction mixture comprising a mixture of PAO molecules having ethylidene, trisubstituted vinylidene, disubstituted vinylidene, and optionally vinyl unsaturation, and obtaining an unsaturated PAO product from the polymerization reaction mixture, wherein the unsaturated PAO product comprises a mixture of PAO molecules having ethylidene, trisubstituted vinylidene, disubstituted vinylidene, and optionally vinyl unsaturation, wherein the metallocene compound is represented by formula (I):

[0160]

[0161] Wherein:

[0162] R 1 、R 2 and R3 Each independently is hydrogen or a substituted or unsubstituted linear, branched, or cyclic C1-C 20 hydrocarbyl or silylhydrocarbyl;

[0163] R 4 and R 5 Each independently is a substituted or unsubstituted linear, branched, or cyclic C1-C 30 hydrocarbyl or silylhydrocarbyl, wherein R 4 and R 5 together with the carbon atoms in the first cyclopentadienyl ring to which they are directly attached, jointly form one or more substituted or unsubstituted rings fused to the first cyclopentadienyl ring;

[0164] R 12 , R 13 , R 14 , R 15 and R 16 Each independently is hydrogen or a substituted or unsubstituted linear, branched, or cyclic C1-C 20 hydrocarbyl, silylhydrocarbyl, or germanyl group, and at least four of R 12 , R 13 , R 14 , R 15 and R 16 are not hydrogen;

[0165] M is a Group 3, 4, or 5 transition metal having an integer coordination number of v, where v is 3, 4, or 5;

[0166] Each X independently is halogen, hydride, amide, alkoxide, sulfide, phosphide, diene, amine, phosphine, ether, or a C1-C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl, or optionally two or more X moieties can together form a fused ring or ring system; and

[0167] m is an integer equal to v - 2, e.g., 1, 2, or 3.

[0168] In some embodiments, the metallocene compound has a structure represented by formula (II):

[0169]

[0170] Wherein:

[0171] R 1 , R 2 and R 3Each is independently hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group;

[0172] R 6 、R 7 、R 17 and R 18 are each independently hydrogen, a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 30 hydrocarbyl group, or R 6 and R 7 、R 7 and R 17 、or R 17 and R 18 together with the carbon atoms in the indenyl ring directly connected to them jointly form one or more substituted or unsubstituted rings fused to the indenyl ring;

[0173] R 12 、R 13 、R 14 and R 15 are each independently a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group;

[0174] R 16 is hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group or a silylhydrocarbyl group;

[0175] Each X is independently halogen, a hydrogen group, an amino group, an alkoxy group, a thio group, a phosphino group, a diene, an amine, a phosphine, an ether, a C1-C 20 substituted or unsubstituted straight-chain, branched-chain, or cyclic hydrocarbyl group, or two or more X moieties together form a fused ring or a ring system;

[0176] M is a transition metal having an integer coordination number v, preferably a Group 3, 4, or 5 transition metal, for example, v is 3, 4, or 5; and

[0177] m is an integer equal to v - 2, for example, m is 1, 2, or 3.

[0178] In some embodiments, the metallocene compound is represented by formula (III):

[0179]

[0180] Wherein:

[0181] R 1 and R 2 are hydrogen;

[0182] R 23 and R 19Comprising a Group 14 atom, such as C, Ge, or Si (e.g., R 23 is C and R 19 is C or Si);

[0183] R 20 、R 21 and R 22 are independently hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group, and at least two of R 20 、R 21 and R 22 are independently a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group;

[0184] R 6 、R 7 、R 17 and R 18 are each independently hydrogen, a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 30 hydrocarbyl group, or R 6 and R 7 、R 7 and R 17 、or R 17 and R 18 together with the carbon atoms in the indenyl ring to which they are directly attached jointly form one or more substituted or unsubstituted rings fused to the indenyl ring;

[0185] R 12 、R 13 、R 14 、R 15 and R 16 are each independently a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group;

[0186] Each X is independently a halogen, a hydrogen group, an amino group, an alkoxy group, a thio group, a phosphino group, a diene, an amine, a phosphine, an ether, or a C1-C 20 substituted or unsubstituted straight-chain, branched-chain, or cyclic hydrocarbyl group, or two or more X moieties together form a fused ring or a ring system;

[0187] M is a Group 3, 4, or 5 transition metal having an integer coordination number of v, e.g., v is 3, 4, or 5; and

[0188] m is an integer equal to v - 2, e.g., 1, 2, or 3.

[0189] In some embodiments, the metallocene compound is represented by formula (IV):

[0190]

[0191] Wherein:

[0192] R 1 and R 2 is hydrogen;

[0193] R 3 is a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group;

[0194] R 6 and R 18 are each independently hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 30 hydrocarbyl group;

[0195] R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are each independently hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C8 hydrocarbyl group;

[0196] R 12 , R 13 , R 14 , R 15 and R 16 are each independently a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group;

[0197] Each X is independently a halogen, a hydrogen group, an amino group, an alkoxy group, a thio group, a phosphino group, a diene, an amine, a phosphine, an ether, or a C1-C 20 substituted or unsubstituted straight-chain, branched-chain, or cyclic hydrocarbyl group, or two or more X moieties together form a fused ring or ring system;

[0198] M is a Group 3, 4, or 5 transition metal having an integer coordination number of v, e.g., v is 3, 4, or 5; and

[0199] m is an integer equal to v - 2, e.g., m is 1, 2, or 3.

[0200] In some embodiments, the metallocene compound is represented by formula (V):

[0201]

[0202] Wherein:

[0203] R 1 and R 2 is hydrogen;

[0204] R 23 and R19 Each is independently a Group 14 atom, for example, C, Ge, or Si (e.g., R 23 is C and R 19 is C or Si);

[0205] R 20 、R 21 and R 22 are each independently hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group, and at least two of R 20 、R 21 and R 22 are independently a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group;

[0206] R 6 and R 18 are each independently hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 30 hydrocarbyl group;

[0207] R 24 、R 25 、R 26 、R 27 、R 28 and R 29 are each independently hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C8 hydrocarbyl group;

[0208] R 12 、R 13 、R 14 、R 15 and R 16 are each independently a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group;

[0209] Each X is independently a halogen, a hydrogen group, an amino group, an alkoxy group, a thio group, a phosphino group, a diene, an amine, a phosphine, an ether, or a C1-C 20 substituted or unsubstituted straight-chain, branched-chain, or cyclic hydrocarbyl group, or two or more X moieties together form a fused ring or a ring system;

[0210] M is a Group 3, 4, or 5 transition metal having an integer coordination number v, for example, v is 3, 4, or 5; and

[0211] m is an integer equal to v - 2, for example, m is 1, 2, or 3.

[0212] In some embodiments of Formulas (I), (II), (III), (IV), and (V), M is Zr, Hf, or a combination thereof.

[0213] In some embodiments of formulas (I), (II), (III), (IV), and (V), M is Hf.

[0214] In some embodiments of formulas (I), (II), (III), (IV), and (V), X is independently a halogen or a substituted or unsubstituted linear, branched, or cyclic C1-C6 hydrocarbyl.

[0215] In some embodiments of formulas (I), (II), (III), (IV), and (V), X is independently methyl, ethyl, benzyl, or trimethylsilylmethylene.

[0216] In some embodiments of formulas (I), (II), (III), (IV), and (V), R 12 , R 13 , R 14 , R 15 , and R 16 in at least four of them are each independently a substituted or unsubstituted linear, branched, or cyclic C1-C8 hydrocarbyl (e.g., methyl or ethyl).

[0217] In some embodiments of formulas (I), (II), (III), (IV), and (V), R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a substituted or unsubstituted linear, branched, or cyclic C1-C4 hydrocarbyl (e.g., methyl or ethyl).

[0218] In some embodiments of formulas (I) and (II), the first of R 1 , R 2 , and R 3 is a substituted or unsubstituted linear, branched, or cyclic C1-C 20 hydrocarbyl; the second of R 1 , R 2 , and R 3 is hydrogen; and the third of R 1 , R 2 , and R 3 is hydrogen, a substituted or unsubstituted linear, branched, or cyclic C1-C 20 hydrocarbyl.

[0219] In some embodiments of formulas (I) and (II), R 2 is hydrogen, and one of R 1 and R 3 is a substituted or unsubstituted linear, branched, or cyclic C1-C6 hydrocarbyl, and R 1 and R 3Another one in it is hydrogen.

[0220] In some embodiments of formulas (I) and (II), R 1 and R 3 One or both of them are substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C6 hydrocarbon groups, and R 2 is hydrogen.

[0221] In some embodiments of formulas (I) and (II), R 1 and R 3 One of them contains a Group 14 atom directly attached to the indenyl ring, a Group 14 atom attached to the α atom, and two or more (e.g., three) substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C8 hydrocarbon groups attached to the β atom.

[0222] In some embodiments of formulas (I), (II), and (IV), R 1 and R 2 are hydrogen, and R 3 is a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C8 hydrocarbon group (e.g., methyl, ethyl, n-propyl, isobutyl, trimethylsilylmethylene, or neopentyl).

[0223] In some embodiments of formula (II), R 1 、R 2 and R 3 are hydrogen; R 12 、R 13 、R 14 and R 15 are independently methyl or ethyl; and R 16 is hydrogen, methyl, ethyl, propyl, or butyl.

[0224] In some embodiments of formula (II) or (III), R 6 and R 7 、R 7 and R 17 、or R 17 and R 18 Together with the corresponding carbon atoms in the indenyl ring to which they are directly attached, form a ring fused to the indenyl ring. In some embodiments, the ring fused to the indenyl ring contains one or more saturated carbon atoms.

[0225] In some embodiments of formula (II) or (III), R 6 and R 18 are hydrogen and R 7 and R 17 Together with the corresponding carbon atoms in the indenyl ring to which they are directly connected, form a 5-membered or 6-membered ring fused to the indenyl ring.

[0226] In some embodiments of formula (II), (III), (IV), or (V), R 6 and R 18 are hydrogen.

[0227] In some embodiments of formula (III) or (V), R 23 is CH2 (methylene), R 19 is C or Si (preferably C), and R 20 , R 21 and R 22 are independently hydrogen or a C1-C 10 hydrocarbyl group, and at least two of R 20 , R 21 and R 22 are not hydrogen.

[0228] In some embodiments of formula (III) or (V), R 23 is CH2 (methylene); R 19 is C; and R 20 , R 21 and R 22 are independently selected from hydrogen, methyl, ethyl, propyl, or butyl, and at least two of R 20 , R 21 and R 22 are not hydrogen.

[0229] In some embodiments of formula (IV) or (V), R 24 , R 27 , R 28 and R 29 are hydrogen; and R 25 and R 26 are independently hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C8 hydrocarbyl group.

[0230] In some embodiments of formula (IV) or (V), R 24 , R 27 , R 28 and R 29 are hydrogen; and R 25 and R 26 are independently hydrogen, methyl, or ethyl.

[0231] In some embodiments of formula (IV) or (V), R 24 , R 27 , R 28 and R 29 are independently hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C8 hydrocarbyl group; and R 25 and R 26 are hydrogen.

[0232] In some embodiments of formula (IV) or (V), R 24 , R 27 , R 28 and R 29 are methyl and R 25 and R 26 are hydrogen.

[0233] In some embodiments, the metallocene compound is selected from structures A to E depicted below. In some embodiments, the metallocene compound is selected from structures A to D.

[0234]

[0235] Catalyst compounds particularly useful in the present disclosure include one or more of the following:

[0236] (Pentamethylcyclopentadienyl)(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0237] (Pentamethylcyclopentadienyl)(1-ethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0238] (Pentamethylcyclopentadienyl)(1-n-propyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0239] (Pentamethylcyclopentadienyl)(1-isopropyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0240] (Pentamethylcyclopentadienyl)(1-n-butyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0241] (Pentamethylcyclopentadienyl)(1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0242] (Pentamethylcyclopentadienyl)(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0243] (Pentamethylcyclopentadienyl)(1-isobutyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0244] (Pentamethylcyclopentadienyl)(1-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0245] (Pentamethylcyclopentadienyl)(1,6,6-triethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0246] (Pentamethylcyclopentadienyl)(1-isobutyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0247] (Pentamethylcyclopentadienyl)(1-methylindenyl)dimethylhafnium,

[0248] (Pentamethylcyclopentadienyl)(1-isobutylindeneyl)dimethylhafnium,

[0249] (Pentamethylcyclopentadienyl)(1-methyl-3,6,7,8-tetrahydro-as-indacenyl)dimethylhafnium,

[0250] (Pentamethylcyclopentadienyl)(1-isobutyl-3,6,7,8-tetrahydro-as-indacenyl)dimethylhafnium,

[0251] (Pentamethylcyclopentadienyl)(1-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene)dimethylhafnium,

[0252] (Pentamethylcyclopentadienyl)(1-isobutyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene)dimethylhafnium,

[0253] (Pentamethylcyclopentadienyl)(1-methyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene)dimethylhafnium,

[0254] (Pentamethylcyclopentadienyl)(1-isobutyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene)dimethylhafnium,

[0255] (Pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)dimethylhafnium, and

[0256] (Pentamethylcyclopentadienyl)(1-isobutyl-5,6-dimethylindenyl)dimethylhafnium.

[0257] In some embodiments of the present disclosure involving the dimerization of cyclic α-olefins, the metallocene is selected from any of formulas (I), (II), (III), (IV), or (V); provided that in formulas (I) and (II), at least one of R 1 and R 3 is not hydrogen. In formulas (I), (II), and (IV), R 1 and R 2 are preferably hydrogen; and R 3 is preferably methyl, ethyl, and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and isobutyl.

[0258] Activation of Activators and Metallocene Compounds

[0259] Non-Coordinating Anion (NCA) Activators

[0260] Non-coordinating anion (NCA) means an anion that does not coordinate with the catalyst metal cation or coordinates with the metal cation but only weakly. The term NCA is also defined to include multi-component NCA-containing activators containing acidic cationic groups and non-coordinating anions, such as N,N-di-octadecylbenzylammonium tetrakis(pentafluorophenyl)borate. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, which can react with the catalyst to form an activating species by abstracting an anionic group. The NCA coordinates weakly enough that a neutral Lewis base (such as an ethylenic or acetylenic unsaturated monomer) can displace it from the catalyst center. Any metal or metalloid that can form a compatible weakly coordinating complex can be used or included in the non-coordinating anion. Suitable metals can include aluminum, gold, and platinum. Suitable metalloids can include boron, aluminum, phosphorus, and silicon. The term non-coordinating anion activator includes neutral activators, ionic activators, and Lewis acid activators.

[0261] A "compatible" non-coordinating anion can be those that do not degrade to neutral when the initially formed complex decomposes. Additionally, the anion will not transfer an anionic substituent or fragment to the cation, causing it to form a neutral transition metal compound and a neutral by-product from the anion. The non-coordinating anions available according to the present disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge with +1, and still remain sufficiently labile to allow displacement during polymerization.

[0262] In some embodiments, the activator comprises a non-coordinating anion.

[0263] Advantageously, the activators of the present disclosure are soluble in non-aromatic hydrocarbon solvents such as aliphatic solvents.

[0264] In some embodiments, a 20 wt% mixture of the activator compound in n-hexane, iso-hexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25 °C, preferably a 30 wt% mixture of the activator compound in n-hexane, iso-hexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25 °C.

[0265] In some embodiments, the activators described herein have a solubility greater than 10 mM (or greater than 20 mM, or greater than 50 mM) in methylcyclohexane at 25 °C (with stirring for 2 hours).

[0266] In some embodiments, the activator described herein has a solubility greater than 1 mM (or greater than 10 mM, or greater than 20 mM) in isohexane at 25 °C (with stirring for 2 hours).

[0267] In some embodiments, the activator described herein has a solubility greater than 10 mM (or greater than 20 mM, or greater than 50 mM) in methylcyclohexane at 25 °C (with stirring for 2 hours) and a solubility greater than 1 mM (or greater than 10 mM, or greater than 20 mM) in isohexane at 25 °C (with stirring for 2 hours).

[0268] The present disclosure relates to a catalyst system comprising an activator compound and a metallocene transition metal compound as described herein, the use of such activator compounds for activating transition metal compounds in a catalyst system for olefin polymerization, and a method for olefin polymerization, the method comprising contacting one or more olefins with a catalyst system comprising a metallocene transition metal compound and such activator compounds under polymerization conditions, wherein there is no aromatic solvent, such as toluene (e.g., present at 0 mol%, alternatively present at less than 1 mol%), preferably the catalyst system, the polymerization reaction, and / or the polymer produced does not contain a "detectable aromatic hydrocarbon solvent", such as toluene. For the purposes of the present disclosure, "detectable aromatic hydrocarbon solvent" means 0.1 mg / m 2 or greater as determined by gas chromatography. For the purposes of the present disclosure, "detectable toluene" means 0.1 mg / m 2 or greater as determined by gas chromatography.

[0269] The poly-α-olefins prepared herein preferably contain 0 ppm (alternatively less than 1 ppm) of aromatic hydrocarbons. Preferably, the poly-α-olefins prepared herein contain 0 ppm (alternatively less than 1 ppm) of toluene.

[0270] The catalyst system used herein preferably contains 0 ppm (alternatively less than 1 ppm) of aromatic hydrocarbons. Preferably, the catalyst system used herein contains 0 ppm (alternatively less than 1 ppm) of toluene.

[0271] Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (VI):

[0272] [R 1′ R 2′ R 3′ EH] d+ [Mt k+ Q n d- (VI)

[0273] Wherein: ​

[0274] E is nitrogen or phosphorus;

[0275] d is 1, 2 or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6; n - k = d (preferably d is 1, 2 or 3; k is 3; n is 4, 5, or 6);

[0276] R 1′ 、R 2′ and R 3′ are independently C1 - C 50 hydrocarbyl groups optionally substituted by one or more alkoxy groups, silyl groups, halogen atoms, or halogen - containing groups,

[0277] wherein R 1′ 、R 2′ and R 3′ together contain 15 or more carbon atoms;

[0278] Mt is an element selected from Group 13 of the Periodic Table, such as B or P; and

[0279] each Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, or halogen - substituted hydrocarbyl.

[0280] Non - aromatic hydrocarbon - soluble activator compounds useful herein include those represented by formula (VII):

[0281] [R 1′ R 2′ R 3′ EH] + [BR 4′ R 5′ R 6′ R 7′ | - (VII)

[0282] wherein:

[0283] E is nitrogen or phosphorus;

[0284] R 1′ is methyl;

[0285] R 2′ and R 3′ are independently C4 - C 50 hydrocarbyl groups optionally substituted by one or more alkoxy groups, silyl groups, halogen atoms, or halogen - containing groups, wherein R 2′ and R 3′ together contain 14 or more carbon atoms;

[0286] B is boron;

[0287] and R 4′ 、R 5′ 、R 6′ and R 7′ are independently a hydrogen group, a bridging or non-bridging dialkylamido group, a halogen group, an alkoxy group, an aryloxy group, a hydrocarbon group, a substituted hydrocarbon group, a halogenated hydrocarbon group, a substituted halogenated hydrocarbon group, or a halogen-substituted hydrocarbon group.

[0288] Non-aromatic hydrocarbon-soluble activator compounds useful herein include those represented by formula (VIII) or formula (IX):

[0289] and

[0290]

[0291] wherein:

[0292] N is nitrogen;

[0293] R 2′ and R 3′ are independently a C6-C 40 hydrocarbon group optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups, wherein R 2′ and R 3′ (if present) together contain 14 or more carbon atoms;

[0294] R 8′ 、R 9′ and R 10′ are independently a C4-C 30 hydrocarbon group or a substituted C4-C 30 hydrocarbon group;

[0295] B is boron;

[0296] and R4′, R 5′ 、R 6′ and R 7′ are independently a hydrogen group, a bridging or non-bridging dialkylamido group, a halogen group, an alkoxy group, an aryloxy group, a hydrocarbon group, a substituted hydrocarbon group, a halogenated hydrocarbon group, a substituted halogenated hydrocarbon group, or a halogen-substituted hydrocarbon group.

[0297] Optionally, in any of formulas (VI), (VII), (VIII), or (IX) herein, R 4′ 、R 5′ 、R 6′ and R 7′ are pentafluorophenyl.

[0298] Optionally, in any one of Formulas (VI), (VII), (VIII), or (IX) herein, R 4′ 、R 5′ 、R 6′ and R 7′ are pentafluoronaphthyl.

[0299] Optionally, in any embodiment of Formula (IX) herein, R 8′ and R 10′ are hydrogen atoms and R 9′ is a C4-C 30 hydrocarbyl optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups.

[0300] Optionally, in any embodiment of Formula (IX) herein, R 9′ is a C8-C 22 hydrocarbyl optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups.

[0301] Optionally, in any embodiment of Formula (VIII) or (IX) herein, R 2′ and R 3′ are independently C 12 -C 22 hydrocarbyl.

[0302] Optionally, R 1′ 、R 2′ and R 3′ together contain 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms).

[0303] Optionally, R 2′ and R 3′ together contain 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms).

[0304] Optionally, R 8′ 、R 9″ and R 10′Together contain 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms).

[0305] Optionally, when Q is a fluorophenyl, then R 2′ is not a C1-C 40 linear alkyl (optionally R 2′ is not an optionally substituted C1-C 40 linear alkyl).

[0306] Optionally, R 4′ , R 5′ , R 6′ and R 7′ each is an aryl (such as phenyl or naphthyl), wherein R 4′ , R 5′ , R 6＇ and R 7′ at least one of them is substituted by at least one fluorine atom, preferably R 4′ , R 5′ , R 6′ and R 7′ each is a perfluoroaryl (such as perfluorophenyl or perfluoronaphthyl).

[0307] Optionally, each Q is an aryl (such as phenyl or naphthyl), wherein at least one Q is substituted by at least one fluorine atom, preferably each Q is a perfluoroaryl (such as perfluorophenyl or perfluoronaphthyl).

[0308] Optionally, R 1′ is methyl; R 2′ is a C6-C 50 aryl; and R 3′ independently is a C1-C 40 linear alkyl or a C5-C 50 -aryl.

[0309] Optionally, each of R 2′ and R 3′ is independently unsubstituted or substituted by at least one of a halogen group, a C1-C 35 alkyl, a C5-C 15 aryl, a C6-C 35 arylalkyl, a C6-C 35 alkylaryl, wherein R 2 and R 3 together contain 20 or more carbon atoms.

[0310] Optionally, each Q is independently a hydrogen group, a bridged or unbridged dialkylamido group, a halogen group, an alkoxy group, an aryloxy group, a hydrocarbon group, a substituted hydrocarbon group, a halogenated hydrocarbon group, a substituted halogenated hydrocarbon group, or a halogen-substituted hydrocarbon group, provided that when Q is a fluorophenyl group, then R 2′ is not a C1-C 40 linear alkyl group, preferably R 2′ is not an optionally substituted C1-C 40 linear alkyl group (alternatively when Q is a substituted phenyl group, then R 2′ is not a C1-C 40 linear alkyl group, preferably R 2′ is not an optionally substituted C1-C 40 linear alkyl group). Optionally, when Q is a fluorophenyl group (alternatively when Q is a substituted phenyl group), then R 2′ is a meta- and / or para-substituted phenyl group, wherein the meta- and para-substituents are independently an optionally substituted C1 to C 40 hydrocarbon group (such as a C6 to C 40 aryl group or a linear alkyl group, C 12 to C 30 aryl group or a linear alkyl group, or C 10 to C 20 aryl group or a linear alkyl group), an optionally substituted alkoxy group, or an optionally substituted silyl group. Optionally, each Q is a fluorinated hydrocarbon group having 1 to 30 carbon atoms, more preferably each Q is a fluorinated aryl group (such as a phenyl group or a naphthyl group), and most preferably each Q is a perfluorinated aryl group (such as a phenyl group or a naphthyl group). Suitable [Mt k+ Q n d- Examples also include diboron compounds as disclosed in U.S. Patent No. 5,447,895, which are incorporated herein by reference in their entirety. Optionally, at least one Q is not a substituted phenyl group. Optionally, all Qs are not substituted phenyl groups. Optionally, at least one Q is not a perfluorophenyl group. Optionally, all Qs are not perfluorophenyl groups.

[0311] In some embodiments of the present disclosure, R 1′ is not methyl, R 2′ is not a C 18 alkyl group and R 3′ is not a C 18 alkyl group, alternatively R 1′ is not methyl, R 2′ is not a C 18 alkyl group and R 3′ is not a C 18 alkyl group, and at least one Q is not a substituted phenyl group, optionally all Qs are not substituted phenyl groups.

[0312] ​The cationic components available in formulas (V) to (VIII) include those represented by the following formulas:

[0313]

[0314] The cationic components available in formulas (VI) to (IX) include those represented by the following formulas: The anionic components of the activators described herein include those represented by the formula [Mt k+ Q n - where k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4), (preferably k is 3; n is 4, 5, or 6, preferably when M is B, n is 4); Mt is an element selected from Group 13 of the Periodic Table, preferably boron or aluminum, and Q is independently a hydrogen group, a bridging or non-bridging dialkylamido group, a halogen group, an alkoxy group, an aryloxy group, a hydrocarbon group, a substituted hydrocarbon group, a halogenated hydrocarbon group, a substituted halogenated hydrocarbon group, and a halogen-substituted hydrocarbon group, said Q having at most 20 carbon atoms, provided that no more than one occurrence of Q is a halogen group. Preferably, each Q is a fluorinated hydrocarbon group optionally having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a perfluorinated aryl group. Preferably at least one Q is not a substituted phenyl group, such as a perfluorophenyl group, preferably all Qs are not substituted phenyl groups, such as a perfluorophenyl group.

[0315] In one embodiment, the borate activator comprises tetrakis(heptafluoronaphthalen-2-yl)borate.

[0316] In one embodiment, the borate activator comprises tetrakis(pentafluorophenyl)borate.

[0317] Preferred anions for use in the non-coordinating anion activators described herein include those represented by the following formula 7:

[0318]

[0319] where:

[0320] M* is a Group 13 atom, preferably B or Al, preferably B;

[0321] Each R 11 is independently a halogen group, preferably fluoride;

[0322] Each R 12 is independently a halogen group, a C6 to C 20 substituted aromatic hydrocarbon group or a group of the formula –O-Si-R​a is a silyloxy group, where R a is a C1 to C 20 hydrocarbyl group or a hydrocarbylsilyl group, preferably R 12 is a fluoro group or a perfluorinated phenyl group;

[0323] Each R 13 is a halogen group, a C6 to C 20 substituted aromatic hydrocarbyl group or a silyloxy group of the formula –O-Si-R a where R a is a C1 to C 20 hydrocarbyl group or a hydrocarbylsilyl group, preferably R 13 is a fluoro group or a C6 perfluorinated aromatic hydrocarbyl group;

[0324] wherein R 12 and R 13 can form one or more saturated / or unsaturated, substituted or unsubstituted rings, preferably R 12 and R 13 form a perfluorinated phenyl ring. Preferably, the anion has a molecular weight greater than 700 g / mol, and preferably, at least three of the substituents on the M* atom each have a molecular volume greater than 180 cubic Å.

[0325] In this article, “molecular volume” is used as an approximation of the steric volume of the activator molecule in solution. Comparison of substituents with different molecular volumes makes a substituent with a smaller molecular volume considered “less bulky” compared to a substituent with a larger molecular volume. Conversely, a substituent with a larger molecular volume can be considered “more bulky” than a substituent with a smaller molecular volume.

[0326] The molecular volume can be calculated as reported in Girolami, G.S. (1994) “A Simple “Back of the Envelope” Method for Estimating the Densities and Molecular Volumes of Liquids and Solids,” Journal of Chemical Education, Vol. 71(11), pp. 962 - 964. The molecular volume (MV), in cubic Å, is calculated using the following equation: MV = 8.3V s where V s is the scaled volume. V s is the sum of the relative volumes of the constituent atoms and is calculated from the molecular formula of the substituent using Table A of the following relative volumes. For fused rings, the V of each fused rings Reduced by 7.5%. The calculated total MV of an anion is the sum of the MVs of each substituent. For example, the MV of perfluorophenyl is and the calculated total MV of tetrakis(perfluorophenyl)borate is four times that of, or

[0327] Table A

[0328] Element Relative volume H 1 The 1st short period, Li to F 2 The 2nd short period, Na to Cl 4 The 1st long period, K to Br 5 The 2nd long period, Rb to I 7.5 The 3rd long period, Cs to Bi 9

[0329] Exemplary anions available herein and their respective scaled volumes and molecular volumes are shown in Table B below. The dashed bonds indicate bonding to boron.

[0330] Table B

[0331]

[0332] The activator can be added to the polymerization in the form of an ion pair. For example, [M2HTH]+[NCA]−, where the bis(hydrogenated tallow)methylamine (“M2HTH”) cation reacts with the basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA]−. Alternatively, the transition metal complex can be reacted with a neutral NCA precursor such as B(C6F5)3, which abstracts an anionic group from the complex to form the activating species. Available activators include bis(hydrogenated tallow)methylammonium [tetrakis(pentafluorophenyl)borate] (i.e., [M2HTH]B(C6F5)4) and bis(octadecyl)toluylammonium [tetrakis(pentafluorophenyl)borate] (i.e., [DOdTH]B(C6F5)4).

[0333] Activator compounds particularly useful in the present disclosure include one or more of the following:

[0334] N,N-bis(hydrogenated tallow)methylammonium [tetrakis(perfluorophenyl)borate],

[0335] N-methyl-4-nonadecyl-N-octadecylbenzenammonium [tetrakis(perfluorophenyl)borate],

[0336] N-methyl-4-hexadecyl-N-octadecylbenzenammonium [tetrakis(perfluorophenyl)borate],

[0337] N-methyl-4-tetradecyl-N-octadecylbenzenammonium [tetrakis(perfluorophenyl)borate],

[0338] N-methyl-4-dodecyl-N-octadecylbenzenammonium [tetrakis(perfluorophenyl)borate],

[0339] N-Methyl-4-decyl-N-octadecylbenzenaminium [tetrakis (perfluorophenyl) borate],

[0340] N-Methyl-4-octyl-N-octadecylbenzenaminium [tetrakis (perfluorophenyl) borate],

[0341] N-Methyl-4-hexyl-N-octadecylbenzenaminium [tetrakis (perfluorophenyl) borate],

[0342] N-Methyl-4-butyl-N-octadecylbenzenaminium [tetrakis (perfluorophenyl) borate],

[0343] N-Methyl-4-octadecyl-N-decylbenzenaminium [tetrakis (perfluorophenyl) borate],

[0344] N-Methyl-4-nonadecyl-N-dodecylbenzenaminium [tetrakis (perfluorophenyl) borate],

[0345] N-Methyl-4-nonadecyl-N-tetradecylbenzenaminium [tetrakis (perfluorophenyl) borate],

[0346] N-Methyl-4-nonadecyl-N-hexadecylbenzenaminium [tetrakis (perfluorophenyl) borate],

[0347] N-Ethyl-4-nonadecyl-N-octadecylbenzenaminium [tetrakis (perfluorophenyl) borate],

[0348] N-Methyl-N,N-di-octadecylammonium [tetrakis (perfluorophenyl) borate],

[0349] N-Methyl-N,N-di-hexadecylammonium [tetrakis (perfluorophenyl) borate],

[0350] N-Methyl-N,N-di-tetradecylammonium [tetrakis (perfluorophenyl) borate],

[0351] N-Methyl-N,N-di-dodecylammonium [tetrakis (perfluorophenyl) borate],

[0352] N-Methyl-N,N-di-decylammonium [tetrakis (perfluorophenyl) borate],

[0353] N-Methyl-N,N-di-octylammonium [tetrakis (perfluorophenyl) borate],

[0354] N-Ethyl-N,N-di-octadecylammonium [tetrakis (perfluorophenyl) borate],

[0355] N,N-Di (octadecyl) tolylammonium [tetrakis (perfluorophenyl) borate],

[0356] N,N-Di (hexadecyl) tolylammonium [tetrakis (perfluorophenyl) borate],

[0357] N,N-bis(tetradecyl)toluidinium [tetrakis(perfluorophenyl)borate],

[0358] N,N-bis(dodecyl)toluidinium [tetrakis(perfluorophenyl)borate],

[0359] N-octadecyl-N-hexadecyl-toluidinium [tetrakis(perfluorophenyl)borate],

[0360] N-octadecyl-N-hexadecyl-toluidinium [tetrakis(perfluorophenyl)borate],

[0361] N-octadecyl-N-tetradecyl-toluidinium [tetrakis(perfluorophenyl)borate],

[0362] N-octadecyl-N-dodecyl-toluidinium [tetrakis(perfluorophenyl)borate],

[0363] N-octadecyl-N-decyl-toluidinium [tetrakis(perfluorophenyl)borate],

[0364] N-hexadecyl-N-tetradecyl-toluidinium [tetrakis(perfluorophenyl)borate],

[0365] N-hexadecyl-N-dodecyl-toluidinium [tetrakis(perfluorophenyl)borate],

[0366] N-hexadecyl-N-decyl-toluidinium [tetrakis(perfluorophenyl)borate],

[0367] N-tetradecyl-N-dodecyl-toluidinium [tetrakis(perfluorophenyl)borate],

[0368] N-tetradecyl-N-decyl-toluidinium [tetrakis(perfluorophenyl)borate],

[0369] N-dodecyl-N-decyl-toluidinium [tetrakis(perfluorophenyl)borate],

[0370] N-methyl-N-octadecylbenzylammonium [tetrakis(perfluorophenyl)borate],

[0371] N-methyl-N-hexadecylbenzylammonium [tetrakis(perfluorophenyl)borate],

[0372] N-methyl-N-tetradecylbenzylammonium [tetrakis(perfluorophenyl)borate],

[0373] N-methyl-N-dodecylbenzylammonium [tetrakis(perfluorophenyl)borate],

[0374] N-methyl-N-decylbenzylammonium [tetrakis(perfluorophenyl)borate], and

[0375] N-Methyl-N-octylbenzenammonium [tetrakis(pentafluorophenyl)borate].

[0376] Additional available activators and their syntheses are described in U.S. Patent Nos. 11,414,436 (USSN 16 / 394,166, filed April 25, 2019), 11,117,908 (USSN 16 / 394,186, filed April 25, 2019), and 11,041,031 (USSN 16 / 394,197, filed April 25, 2019), each of which is incorporated herein by reference.

[0377] In an embodiment, the activator is not (and the cationic moiety of formulas (VI), (VII), (VIII), and (IX) is not the cation of the following formula):

[0378]

[0379] In at least one embodiment, the general synthesis of the activator can be carried out using a two-step method. In the first step, the amine or phosphine is dissolved in a solvent (e.g., hexane, cyclohexane, methylcyclohexane, ether, dichloromethane, toluene) and an excess (e.g., 1.2 molar equivalents) of hydrogen chloride is added to form a chloride salt. The salt is typically separated from the reaction medium by filtration and dried under reduced pressure. The separated chloride is then heated to reflux with approximately one molar equivalent of an alkali metal metalate or metalloid (such as a borate or aluminate) in a solvent (e.g., cyclohexane, dichloromethane, methylcyclohexane) to form the desired borate or aluminate along with the by-product alkali metal chloride, which can typically be removed by filtration.

[0380] In at least one embodiment, the general synthesis of the ammonium borate activator can be carried out using a two-step method. In the first step, the amine is dissolved in a solvent (e.g., hexane, cyclohexane, methylcyclohexane, ether, dichloromethane, toluene) and an excess (e.g., 1.2 molar equivalents) of hydrogen chloride is added to form an ammonium chloride salt. The salt is typically separated from the reaction medium by filtration and dried under reduced pressure. The separated ammonium chloride is then heated to reflux with approximately one molar equivalent of an alkali metal borate in a solvent (e.g., cyclohexane, dichloromethane, methylcyclohexane) to form the ammonium borate along with the by-product alkali metal chloride, which can typically be removed by filtration.

[0381] A cocatalyst is a compound that can alkylate a transition metal complex such that when used in combination with an activator, an active catalyst is formed. Cocatalysts can include aluminoxanes such as methylaluminoxane, modified aluminoxanes such as modified methylaluminoxane, and alkylaluminums such as trimethylaluminum, triisobutylaluminum, triethylaluminum, and triisopropylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, or tri-n-dodecylaluminum. When the precatalyst is not a dihydrocarbyl or dihydrido complex, the cocatalyst is typically used in combination with a Lewis acid activator and an ionic activator. Sometimes, the cocatalyst is also used as a scavenger to deactivate impurities in the feed or reactor.

[0382] Additional available activators include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(pentafluorophenyl)borate, and tri-n-butylammonium tetrakis(pentafluorophenyl)borate.

[0383] Typical activator to catalyst compound ratios are about 1:1 molar ratio. Alternative preferred ranges include 0.1:1 to 100:1, alternatively 0.5:1 to 50:1. Particularly useful ranges are 0.5:1 to 10:1, preferably 1:1 to 5:1. A slightly excess activator is typically used, e.g., an activator to catalyst compound ratio of 1.1:1.

[0384] Examples of suitable activators and their syntheses are described in U.S. Patent Publication No. 2019 / 0330139, U.S. Patent No. 11,117,908, and U.S. Patent No. 11,041,031, which are incorporated herein by reference.

[0385] Optional scavengers and cocatalysts

[0386] In addition to the activator compound, scavengers or cocatalysts can also be used. A scavenger is a compound that is typically added to facilitate polymerization by scavenging impurities. Some scavengers can also act as activators and can be referred to as cocatalysts. Non-scavenger cocatalysts can also be used in combination with the activator to form an active catalyst. In some embodiments, the cocatalyst can be premixed with the transition metal compound to form an alkylated transition metal compound.

[0387] The cocatalyst can include aluminoxanes such as methylaluminoxane, modified aluminoxanes such as modified methylaluminoxane, and aluminum alkyls (also known as alkyl-aluminums) such as trimethylaluminum, triisobutylaluminum, triethylaluminum, and triisopropylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, or tri-n-dodecylaluminum. When the precatalyst is not a dihydrocarbyl or dihydrido complex, the cocatalyst is typically used in combination with a Lewis acid activator and an ionic activator. Sometimes, the cocatalyst is also used as a scavenger to deactivate impurities in the feed or reactor.

[0388] Aluminum alkyls or organoaluminum compounds that can be used as scavengers or cocatalysts include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and dialkylzincs such as diethylzinc.

[0389] The scavenger can be an additional component of the catalyst system described herein. A scavenger is a compound that can be added to facilitate oligomerization or polymerization by scavenging impurities. Some scavengers can also act as activators and can be referred to as cocatalysts. Cocatalysts that are not scavengers can also be used in combination with activators to form an active catalyst with a transition metal compound. In some embodiments, the cocatalyst can be premixed with the transition metal compound to form an alkylated transition metal compound, also known as an alkylated catalyst compound or an alkylated metallocene. To the extent that the scavenger facilitates the metallocene compound to perform its intended catalytic function, the scavenger (if used) is sometimes considered part of the catalyst system.

[0390] U.S. Patent No. 9,409,834 (e.g., in column 33, line 37 to column 34, line 61) provides a detailed description of the scavengers useful in the methods of the present disclosure for preparing PAO. The relevant portions of that patent regarding scavengers, their identity, amount, and manner of use are incorporated herein in their entirety.

[0391] Particularly useful scavengers include tri-n-octylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, etc.

[0392] Polymerization / oligomerization reactions and methods, and methods for preparing PAO

[0393] In some embodiments of the method, based on the total moles of vinyl, vinylidene, disubstituted vinylidene (excluding cyclic disubstituted vinylidene), and trisubstituted vinylidene in the unsaturated PAO product, the polymerization reaction exhibits selectivity for a combination of greater than or equal to about 60 mol% vinylidene and trisubstituted vinylidene (alternatively greater than 70 mol%, alternatively greater than 80 mol%) and less than or equal to about 10 mol% vinyl.

[0394] In some embodiments of the method, based on the total molar amount of vinyl, vinylidene, disubstituted vinylidene (excluding cyclic disubstituted vinylidene), and trisubstituted vinylidene in the unsaturated PAO product, the polymerization reaction exhibits selectivity for vinylidene of greater than or equal to about 50 mol% (alternatively greater than 60 mol%, alternatively greater than 70 mol%, alternatively greater than 80 mol%) and vinyl of less than or equal to about 10 mol%.

[0395] In some embodiments of the method, as measured by GC-MS, based on the total amount of dimers, trimers, tetramers, and higher oligomers, the polymerization reaction exhibits selectivity for dimer formation of greater than 50% (alternatively greater than 60%, alternatively greater than 70%, alternatively greater than 80%, alternatively greater than 90%, alternatively greater than 95%).

[0396] In some embodiments of the method, as measured by GC-MS, based on the total amount of dimers, trimers, tetramers, and higher oligomers, the polymerization reaction exhibits selectivity for dimer and trimer formation of greater than 70% (alternatively greater than 80%, alternatively greater than 85%, alternatively greater than 90%, alternatively greater than 95%, alternatively greater than 97%).

[0397] In some embodiments, the method further comprises: a) contacting the unsaturated PAO product with hydrogen to convert at least a portion of the unsaturated PAO product to a hydrogenated PAO product; b) contacting the unsaturated PAO product with a chemical reagent to convert at least a portion of the unsaturated PAO product to a functionalized PAO product; or a combination thereof.

[0398] In some embodiments of the method, the feed comprises one or more cyclic C6-C 32 α-olefins selected from vinyl cyclobutane, vinyl cyclopentane, vinyl cyclohexane, 4-vinylcyclohex-1-ene (also known as vinylcyclohexene), vinyl cycloheptane, vinyl cyclooctane, vinyl cyclononane, vinyl cyclodecane, vinyl cycloundecane, vinyl cyclododecane, 5-vinyl norbornane, 5-vinyl-2-norbornene, allyl cyclohexane, and allyl cyclooctane. Preferred cyclic C6-C 14 α-olefins include vinyl cyclobutane, vinyl cyclopentane, vinyl cyclohexane, and 4-vinylcyclohex-1-ene. Most preferred cyclic C6-C 32 α-olefins include vinyl cyclohexane and 4-vinylcyclohex-1-ene, with 4-vinylcyclohex-1-ene being the most preferred.

[0399] In some embodiments of the method, the feed comprises one or more cyclic C6-C 32α-olefins and one or more C4-C 32 linear or C5-C 32 branched α-olefins selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene, and 3,5,5-trimethyl-1-hexene. Preferred C4-C 32 linear or C5-C 32 branched α-olefins include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene, and 3,5,5-trimethyl-1-hexene. Most preferred C4-C 32 linear or C5-C 32 branched α-olefins include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, and 3-methyl-1-pentene. Even more highly preferred C4-C 32 linear or C5-C 32 branched α-olefins include 1-pentene, 4-methyl-1-pentene, and 1-hexene.

[0400] In some embodiments, the C6-C 32 cyclic α-olefin is C6-C 20 cyclic α-olefin, optionally C6-C 14 cyclic α-olefin, optionally C8-C 12 cyclic α-olefin.

[0401] In some embodiments, the C8-C 12 cyclic α-olefin is a non-conjugated diene.

[0402] In some embodiments, the linear α-olefin is C4-C 20 linear α-olefin, optionally C4-C 12 linear α-olefin, optionally C4-C8 linear α-olefin, optionally C5-C8 linear α-olefin, optionally C5-C6 linear α-olefin.

[0403] In some embodiments, the branched α-olefin is C5-C 20 branched α-olefin, optionally C5-C12 Branched α-olefins, optionally C5-C 10 Branched α-olefins, optionally C6-C9 branched α-olefins, optionally C6-C8 branched α-olefins.

[0404] The choice between preparing a dimer-rich product and preparing higher molecular weight PAO depends on the combination of catalyst choice and reactor conditions used, particularly reactor temperature. Preferred metallocenes for preparing dimers are those of formulas (III) and (V). Preferred reactor temperatures for preparing dimers are about 100 °C - 200 °C, more preferably about 110 °C - 180 °C, optionally about 120 °C - 170 °C, optionally about 130 °C - 160 °C, optionally about 140 °C - 155 °C.

[0405] In some embodiments, the reaction conditions include a reactor temperature of about 120 °C or higher (preferably 130 °C or higher, optionally 140 °C or higher) and a reactor pressure of 15 psia to 1600 psia.

[0406] In some embodiments, a method for preparing cyclic dimers from one or more cyclic α-olefins includes: contacting a feed comprising one or more C6-C 32 cyclic α-olefins with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions to effect a polymerization reaction to obtain a polymerization reaction mixture, the polymerization reaction mixture comprising cyclic dimer molecules having ethylidene, trisubstituted vinylidene, disubstituted vinylidene, and optionally vinyl unsaturation, and obtaining an unsaturated cyclic dimer product from the polymerization reaction mixture. In some embodiments, the metallocene compound is selected from formulas (I), (II), (III), (IV), or (V). In some embodiments, the metallocene compound is selected from formulas (I) or (II), wherein at least one of R 1 and R 3 is not hydrogen.

[0407] In one non-limiting embodiment, the present disclosure relates to a continuous solution and / or bulk process for preparing cyclic dimers, which includes: (a) contacting at least one C4-C 24 cyclic α-olefin with a metallocene catalyst, a non-coordinating anion activator, and optionally an alkylaluminum compound; (b) under polymerization conditions, wherein the reaction temperature is in the range of 100 °C to 160 °C, the reactor pressure is less than 50 atmospheres, and the residence time is 20 minutes to 3 hours; and optionally solvent-free, except for the solvents used for the catalyst and scavenger solutions, and wherein the olefin feed is substantially free of straight-chain and branched α-olefins; and (c) obtaining a dimer product, optionally hydrogenating the dimer.

[0408] In another non-limiting embodiment, the present disclosure relates to a solution and / or bulk process for preparing cyclic dimers in a batch or semi-batch reactor. In some embodiments, the process comprises: (a) contacting at least one C4-C 24 cyclic α-olefin with a metallocene catalyst, a non-coordinating anion activator, and an optional alkylaluminum compound; (b) under polymerization conditions, wherein the reaction temperature ranges from 100 °C to 160 °C, the reactor pressure is less than 50 atmospheres, and the residence time is from 20 minutes to 24 hours; wherein the catalyst and the activator are fed separately into the reactor; wherein all of the catalyst can be fed in a single dose at the start of the reaction or staged during the reaction, and optionally without solvent, except for the solvents used for the catalyst and scavenger solutions, and wherein the olefin feed is substantially free of linear and branched α-olefins; and (c) obtaining a dimer product, optionally hydrogenating the oligomers.

[0409] Many polymerization / oligomerization processes and reactor types for metallocene-catalyzed polymerization or oligomerization, such as bulk, solution, and slurry polymerization or oligomerization processes can be used in the present disclosure. The polymerization / oligomerization process can be carried out in a batch mode, a semi-batch mode, or a continuous polymerization process. The term "batch" refers to a process in which the entire reaction mixture is withdrawn from the reactor vessel at the end of the polymerization reaction. Semi-batch allows for the addition of more monomer feed and / or catalyst at one or more intervals during operation and, in some cases, allows for the withdrawal of a portion of the reaction mixture. In contrast, in a continuous polymerization process, one or more reactants (i.e., feed, catalyst, optional scavenger) are continuously introduced into the reactor vessel and the reactor contents containing the polymer product are withdrawn simultaneously or almost simultaneously. When using a continuous polymerization process, the polymerization / oligomerization process can be carried out in a continuous stirred tank reactor, a plug flow reactor (sometimes referred to as a continuous tubular reactor), or a reactor having any monomer concentration profile between a CSTR and a plug flow. The polymerization / oligomerization process can be carried out in a single reactor or multiple reactors. When multiple reactors are employed, the reactors can be arranged in a series or parallel configuration or any combination of series and parallel configurations. The polymerization / oligomerization reactor can be operated in a liquid full mode or a partially liquid filled mode with a gas phase headspace. If a solid or supported catalyst is used, a slurry or continuous fixed bed or plug flow process can be suitable.

[0410] The olefin feed can be treated to remove catalyst poisons, such as peroxides, oxygen, or nitrogen-containing organic compounds or acetylenic compounds, before being supplied to the polymerization reactor. For example, the feed olefin can be treated with an activated molecular sieve such as or molecular sieve, and / or in combination with activated alumina or an activated deoxygenation catalyst.

[0411] In any embodiment, a solvent or diluent may be present in the reactor. Suitable diluents / solvents for carrying out the polymerization reaction include non-coordinating inert liquids. In a specific embodiment, the reaction mixture for the polymerization reaction disclosed herein may include at least one hydrocarbon solvent. Examples include straight-chain and branched-chain hydrocarbons such as butane, isobutane, pentane, isopentane, hexane, isohexane, heptane, octane, decane, dodecane, and mixtures thereof; cyclic and cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as those that may be commercially available (Isopar TM ); halogenated and perhalogenated hydrocarbons such as perfluorinated C 4-10 alkanes, chlorobenzene, and mixtures thereof; and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, mesitylene, ethylbenzene, xylene, and mixtures thereof. Mixtures of any of the foregoing hydrocarbon solvents may also be used. Suitable solvents also include liquid olefins that may act as monomers or comonomers, and these monomers or comonomers include 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, 4-vinylcyclohex-1-ene, and mixtures thereof. Preferred solvents / diluents may include methylcyclohexane, toluene, xylene, ethylbenzene, normal paraffins (such as the solvent available from ExxonMobil Chemical Company, Houston, Texas), isoparaffin solvents (such as the solvent available from ExxonMobil Chemical Company, Houston, Texas), and combinations thereof. These solvents or diluents may typically be pretreated in the same manner as the feed olefin.

[0412] In some embodiments of the present disclosure, non-aromatic diluents / solvents are preferred. Suitable non-aromatic diluents / solvents for polymerization include non-coordinating inert liquids. Examples include straight-chain and branched-chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as those that may be commercially available (Isopar TM ); perhalogenated hydrocarbons such as perfluorinated C4 to C 10 alkanes. Suitable solvents also include liquid olefins that may act as monomers or comonomers, and these monomers or comonomers include C4 to C 32α-olefins such as 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and mixtures thereof. In a preferred embodiment, an aliphatic hydrocarbon solvent is used as the solvent, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and cycloaliphatic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In an alternative preferred embodiment, the solvent used is C5 to C 18 α-olefins, alternatively C5 to C 16 α-olefins, alternatively C6 to C 14 α-olefins, or mixtures thereof. Mixtures of any of the solvents listed above may be used.

[0413] In another embodiment, the solvent is not an aromatic compound, and preferably the aromatic compound is present in the solvent in an amount less than 3 wt%, preferably less than 2 wt%, preferably less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0.1 wt% based on the weight of the solvent. Preferably, the solvent or the mixture of solvents is free of aromatic compounds.

[0414] Preferably, the solvent is selected from C4 to C 10 linear, branched, or cyclic alkanes. Preferably, the solvent is substantially free of all aromatic solvents. In other embodiments of the present disclosure, preferably, the solvent is selected from one or more C5 to C 32 α-olefins, such as one or more C5 to C 16 α-olefins. Preferably, the solvent is substantially free of all non-α-olefin solvents.

[0415] In some embodiments, hydrogen may be added to the reactor to improve catalyst performance and affect the properties of the resulting oligomers. When present, the amount of hydrogen may be maintained at a level that increases catalyst productivity but preferably does not cause excessive (preferably any significant) hydrogenation of the olefins, especially the feed α-olefins (the reaction of α-olefins to saturated alkanes may be highly detrimental to the efficiency of the process). Therefore, the amount of hydrogen partial pressure is preferably kept low, e.g., less than 350 kPa, less than 170 kPa, less than 70 kPa, or less than 35 kPa; additionally or alternatively, the hydrogen concentration in the reactant phase in the reactor and / or the feed may be less than 10,000 ppm (by weight), e.g., less than 1000 ppm, less than 500 ppm, less than 100 ppm, less than 50 ppm, less than 25 ppm, or less than 10 ppm.

[0416] Alternatively, the polymerization / oligomerization process is free of hydrogen. Polymerization or oligomerization in the absence of hydrogen may be beneficial to provide polymers or oligomers having highly unsaturated double bonds. These double bonds can be readily converted into functionalized fluids having multiple performance characteristics. Examples of the conversion of oligomers and / or polymers can be found in the preparation of ashless dispersants, for example, by reacting the polymer with maleic anhydride to obtain PAO-succinic anhydride, which can then be reacted with amines, alcohols, and / or polyether alcohols to be converted into dispersants, such as those disclosed in the book "Lubricant Additives: Chemistry and Application" edited by Leslie R. Rudnick, pages 143-170.

[0417] Typically, one or more metallocene compounds, one or more activators, and one or more monomers are contacted to prepare the polymers or oligomers of the present invention. Preferably, the catalyst, activator, or optional co-activator is a soluble compound, and the reaction can be carried out in a solution polymerization process. Even if one of these components is not completely soluble in the reaction medium or the feed stream at the start of the reaction, during the reaction, or at a later stage of the reaction, solution-type operation can still be applicable. In any case, the catalyst system components dissolved or suspended in a solvent (such as in an aromatic solvent or in an aliphatic solvent) or in the monomer feed stream can be fed into the reactor under an inert atmosphere (usually a nitrogen or argon blanketed atmosphere) to allow polymerization or oligomerization to occur.

[0418] The catalyst and activator can be delivered separately to the reactor as a solution in a solvent or in an olefin feed stream (activated online immediately before the reactor or activated in the reactor), or pre-activated and delivered to the reactor as an activated solution. In some embodiments, the metallocene compound can be activated in the reactor in the presence of an olefin. In another alternative, the pre-catalyst metallocene can be premixed with the activator and / or co-activator, and then the activated catalyst solution can be charged into the reactor. Alternatively, the metallocene compound (such as the dichloride form of the metallocene compound) can be pretreated with an alkylaluminum reagent, especially triisobutylaluminum, tri-n-hexylaluminum, and / or tri-n-octylaluminum, and then charged into a reactor containing other catalyst system components and the feed olefin, or subsequently pre-activated with other catalyst system components to obtain a fully activated catalyst, which can then be fed into a reactor containing the feed olefin.

[0419] In a preferred embodiment, when all solvents are olefin monomers, the pre-catalyst is dissolved in the monomer feed in the first feed vessel and the activator is mixed in the monomer feed in the second feed vessel. Then the pre-catalyst solution and the activator solution are fed separately into the reactor and catalyst activation occurs in the reactor. If used, the scavenger can be fed independently or together with the activator feed, the pre-catalyst feed, or the monomer feed (if a separate monomer feed is used). Alternatively, the pre-catalyst and the activator are pre-mixed separately in an inert solvent and then the pre-mixed solution is fed into the reactor. Catalyst activation occurs in the reactor.

[0420] The metallocene compound and the activator can also be delivered in the form of a suspension or a dry powder. Most single-site catalysts and activators received from manufacturers are in the form of finely divided solids or "powders". If not initially in this form, the solid catalyst and / or activator can be milled into a fine powder. Without sacrificing the catalyst utilization efficiency, the catalyst and the activator can be delivered to a solution or slurry polymerization reactor as a slurry in an aliphatic hydrocarbon solvent, oil or wax or in the form of a dry powder. The catalyst and / or activator can be mixed with an aliphatic hydrocarbon solvent or a mixture of solvents to form a suspension, mixed with a high-viscosity material or wax to form a thick suspension or delivered as a dry powder using a powder feeder. Then the catalyst is dissolved in the polymerization medium inside the polymerization reactor and polymerization is initiated. The catalyst can be added directly to the polymerization reactor and then contacted with the activator, or it can first be contacted with the activator and then the resulting mixture added to the polymerization reactor.

[0421] In any embodiment, the catalyst, the activator and (when required) the co-activator can also be delivered as a supported catalyst. For a supported catalyst, the active components of such catalyst and / or activator are supported on a solid insoluble carrier. When a solid supported catalyst is used, the polymerization / oligomerization process generally operates within a similar range of temperature, pressure and residence time as described for the solution process. The residual catalyst can be separated from the product by filtration, centrifugation, or sedimentation. Then the fluid is distilled to remove the solvent, any unreacted components and light products. The solvent and a part or all of the unreacted components or light components can be recycled for reuse.

[0422] Any polymerization / oligomerization method and reactor type for metallocene-catalyzed polymerization or oligomerization, such as bulk, solution, and slurry polymerization or oligomerization methods, can be used in the present disclosure. Each of these methods can be carried out in a continuous stirred tank reactor or a plug flow reactor having a single reactor or more than one reactor operating in series or parallel configurations. For single reactor operation, the monomer or several monomers, catalyst / activator, optional co-activator, optional scavenger, and optional modifier are all fed into a single reactor. The operation and the properties of the resulting product are affected by the method conditions and the composition of the reactor medium. In another embodiment, these methods can be carried out in multiple reactors operating in series reactors, where the above components can be added to each of two or more reactors connected in series. The catalyst system components can be added to the first reactor in the series. Optionally, the catalyst system components can be added to two reactors. In one embodiment, the same catalyst is used in both the first reactor and the second reactor. Optionally, the catalyst used in the first reactor is different from the catalyst used in the second reactor. All the contents in the first reactor, including the prepared oligomers, one or more unreacted monomers, and the active catalyst, can be transferred to the second reactor. Optionally, only a portion of the contents in the first reactor is transferred to the second reactor. The oligomers prepared in each reactor can have different molecular weights and / or compositions. The differences in molecular weight and / or composition are determined by the end-use requirements. The molecular weight and composition can be controlled by the method conditions such as monomer concentration and polymerization temperature in each reactor. This can be achieved by controlling the method conditions such as monomer feed rate, catalyst feed rate, and heat removal mechanism. Preferably, the monomer concentration and temperature in each reactor can be independently controlled. In one embodiment, the copolymer oligomers (oligomers from two or more α-olefins) are prepared in the first reactor in a series configuration. In another embodiment, these methods can be carried out in multiple reactors having a parallel configuration. The advantage of parallel operation is the independent control of the properties of the resulting product. In one embodiment, the copolymer oligomers are prepared in each reactor operating in parallel. In another embodiment, the homopolymer oligomers are prepared in one reactor and the copolymer oligomers are prepared in another reactor operating in parallel. For example, 1-hexene / VCH copolymer oligomers are prepared in one reactor and VCH oligomers are prepared in another reactor. In one embodiment, the same catalyst is used in all reactors. Optionally, the catalyst used in one reactor is different from the catalyst used in another reactor in the parallel configuration. Parallel operation also provides additional degrees of freedom in method optimization, such as maximizing the desired product and method efficiency.

[0423] Many polymerization / oligomerization processes and reactor types for metallocene-catalyzed polymerization or oligomerization, such as bulk, solution, and slurry polymerization or oligomerization processes, can be used in the present disclosure. Each of these processes can also be operated in batch or semi-batch mode. For the batch mode of polymerization or oligomerization, all components are added to the reactor and the reaction is allowed to proceed to a pre-designed degree of conversion (partial or complete conversion). Subsequently, the catalyst can be deactivated by any possible means, such as exposure to air or water, or by adding an alcohol or a solvent containing a deactivator.

[0424] Polymerization or oligomerization can alternatively or optionally be carried out in semi-batch operation, where the feed and catalyst system components can be added continuously and / or simultaneously to the reactor in order to maintain a constant concentration ratio of the catalyst to one or more olefins. When all the feed and catalyst system components have been added, the reaction can be allowed to proceed to a predetermined stage. The reaction can then be terminated by catalyst deactivation in the same manner as described for batch operation. One or more monomers and the catalyst can also be fed in stages for controlling the properties of the oligomers prepared and for temperature control. In one embodiment, all the monomers are fed to the reactor before the start of the polymerization. The catalyst is fed in stages to the reactor, preferably less than 50% of the catalyst being fed at the start. Alternatively, one of the olefin monomers can be fed in stages, whereby oligomers with different compositions can be prepared.

[0425] Any polymerization / oligomerization process and reactor type for metallocene-catalyzed polymerization or oligomerization, such as bulk, solution, and slurry polymerization or oligomerization processes, can be used in the present disclosure. In any embodiment, the temperature in any reactor used herein can be from -10 °C to 250 °C, for example, from 30 °C to 220 °C, preferably from 50 °C to 200 °C, 60 °C to 200 °C, 70 °C to 200 °C, 100 °C to 200 °C, 110 °C to 180 °C, 120 °C to 170 °C, 130 °C to 160 °C, or 140 °C to 155 °C. Alternatively, the polymerization reaction conditions include a temperature of 80 °C or higher, 100 °C or higher, 120 °C or higher, 130 °C or higher, 140 °C or higher. Temperature control in the reactor can generally be achieved by balancing the heat of polymerization with reactor cooling achieved by: cooling the contents of the reactor through a reactor jacket or cooling coil or a cooling sidestream of the reactants, auto-refrigeration, pre-cooling the feed, vaporization of a liquid medium (diluent, monomer, or solvent), or a combination of the above. An adiabatic reactor with pre-cooled feed can alternatively or optionally be used. Stirring of the reactor contents is generally carried out to reduce or avoid concentration or temperature gradients.

[0426] In any embodiment, the pressure in any reactor used herein can be from 0.1 to 120 atmospheres, for example, from 0.5 to 75 atmospheres or from 1 to 50 atmospheres. One or more monomers, one or more metallocenes, and one or more activators can be contacted in the reactor for a residence time of from 1 second to 100 hours, for example, from 30 seconds to 50 hours, from 2 minutes to 24 hours, or from 10 minutes to 24 hours, or from 10 minutes to 12 hours, or from 10 minutes to 6 hours, or from 10 minutes to 3 hours or from 10 minutes to 2 hours.

[0427] The molecular weight distribution or polydispersity of the oligomers prepared is important for some applications. For most metallocene catalysts, the molecular weight of the oligomers is sensitive to process conditions such as reactor temperature and monomer concentration. To prepare a product with a narrow molecular weight distribution, good temperature control and intense mixing are recommended to minimize fluctuations in temperature and monomer concentration. A process with a low monomer conversion (high monomer concentration) in the reactor can also reduce the dependence of the molecular weight on the monomer concentration, thereby narrowing the molecular weight distribution.

[0428] Depending on the catalyst type and chain termination mechanism, the oligomers described in the present disclosure can have vinyl, or ethylidene, or disubstituted vinylidene, or trisubstituted vinylidene chain ends. For some applications, the type of unsaturated chain ends of the oligomers is important. Process conditions such as reaction temperature and H2 concentration can be used to adjust the level of unsaturated chain ends of a given catalyst system. For example, in the case of some catalyst systems, a high reaction temperature is favorable for preparing oligomers having ethylidene and trisubstituted vinylidene chain ends.

[0429] When the polymerization or oligomerization reaction proceeds to a predetermined stage (such as an olefin conversion of higher than 20% or higher than 30% or higher than 40% or higher than 50% or higher than 60% or higher than 70% or higher than 80% or higher than 90%), the reactor effluent is withdrawn from the reactor. The reaction effluent contains active catalyst. These active components can preferably be deactivated and / or removed. Typically, the reaction can be deactivated by adding a stoichiometric amount or an excess of air, water, alcohol, isopropyl alcohol, etc. Any conventional catalyst deactivation method or aqueous washing method can be used to remove the catalyst system components. Then the mixture can be washed with dilute sodium hydroxide or with water to remove the catalyst system components. Then the residual organic layer can be subjected to distillation to remove the solvent and unreacted monomers, and can optionally be recycled for reuse.

[0430] The reactor products prepared herein are typically mixtures of many different oligomers. Extraction or fractionation can be carried out to separate the products into multiple fractions with different boiling ranges, corresponding to different molecular weight ranges and different degrees of polymerization. Unreacted monomers can be recycled back to the reactor. Depending on the application, the oligomer fractions can also be hydrogenated.

[0431] In a preferred embodiment, the present disclosure relates to a continuous solution and / or bulk process for preparing oligomers, which comprises: (a) contacting at least one α-olefin monomer and at least one cyclic α-olefin having 4 to 24 carbon atoms with a metallocene catalyst, a non-coordinating anion activator, and optionally an alkylaluminum compound; (b) under polymerization conditions, wherein the reaction temperature is in the range of 70 °C to 160 °C, and the reactor pressure is less than 50 atmospheres, and the residence time is from 20 minutes to 3 hours; and optionally solvent-free, except for the solvents used for the catalyst and scavenger solutions; (c) obtaining an oligomer product (unsaturated PAO), optionally fractionating the oligomers and hydrogenating the oligomers.

[0432] In another preferred embodiment, the present disclosure relates to a solution and / or bulk process for preparing oligomers in a batch or semi-batch reactor, which comprises: (a) contacting at least one α-olefin monomer and at least one cyclic α-olefin having 4 to 24 carbon atoms with a metallocene catalyst, a non-coordinating anion activator, and optionally an alkylaluminum compound; (b) under polymerization conditions, wherein the reaction temperature is in the range of 70 °C to 160 °C, and the reactor pressure is less than 50 atmospheres, and the residence time is from 20 minutes to 24 hours; feeding the catalyst and the activator separately into the reactor; all the catalyst can be fed in a single dose at the start of the reaction or staged during the reaction, and optionally solvent-free, except for the solvents used for the catalyst and scavenger solutions; (c) obtaining an oligomer product (unsaturated PAO), optionally fractionating the oligomers and hydrogenating the oligomers.

[0433] Although long or short residence times can be used, the choice depends on the choice of catalyst, the concentration of the monomer, the reaction temperature, and the desired conversion level. Although residence times as short as 1 minute and as long as 48 hours can be used, the preferred residence time range in the continuous process is from 20 minutes to 2 hours, and in the batch or semi-batch process is from 20 minutes to 12 hours.

[0434] Feed

[0435] In some embodiments of the process, the feed comprises one or more cyclic C6-C 32α-olefins selected from vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, 4-vinylcyclohex-1-ene (also known as vinylcyclohexene), vinylcycloheptane, vinylcyclooctane, vinylcyclononane, vinylcyclodecane, vinylcycloundecane, vinylcyclododecane, 5-vinylnorbornane, 5-vinyl-2-norbornene, allylcyclohexane, and allylcyclooctane. In some embodiments of the method, the feed comprises one or more cyclic C6-C 14 α-olefins. In some embodiments of the method, the feed comprises one or more C6-C 32 α-olefins selected from vinylcyclohexane and 4-vinylcyclohex-1-ene.

[0436] In some embodiments of the method, the feed comprises one or more cyclic C6-C 32 α-olefins and one or more C4-C 32 linear or C5-C 32 branched α-olefins selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-henicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene, and 3,5,5-trimethyl-1-hexene. In some embodiments of the method, the feed comprises one or more C4-C 32 linear α-olefins or C5-C 32 branched α-olefins selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene, and 3,5,5-trimethyl-1-hexene. In some embodiments of the method, the feed comprises one or more C4-C 32 linear α-olefins or C5-C 32 branched α-olefins selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, and 3-methyl-1-pentene. In some embodiments of the method, the feed comprises one or more C4-C 32 linear α-olefins or C5-C 32Branched α-olefins selected from 1-pentene, 4-methyl-1-pentene, and 1-hexene.

[0437] In some embodiments, C6-C 32 The cyclic α-olefin is C6-C 20 Cyclic α-olefins (e.g., C6-C 14 Cyclic α-olefins or C8-C 12 Cyclic α-olefins).

[0438] In some embodiments, C8-C 12 The cyclic α-olefin is a non-conjugated diene.

[0439] In some embodiments, the linear α-olefin is C4-C 20 Linear α-olefins (e.g., C4-C 12 Linear α-olefins, C4-C8 linear α-olefins, C5-C8 linear α-olefins, or C5-C6 linear α-olefins).

[0440] In some embodiments, the branched α-olefin includes C5-C 20 Branched α-olefins (e.g., C5-C 12 Branched α-olefins, C5-C 10 Branched α-olefins, C6-C9 branched α-olefins, or C6-C8 branched α-olefins).

[0441] uPAO products and products obtained by the method

[0442] In some embodiments of the method, based on the total moles of vinyl, vinylidene, disubstituted vinylidene (excluding cyclic disubstituted vinylidene), and trisubstituted vinylidene in the unsaturated PAO product, the polymerization reaction exhibits selectivity for a combination of at least about 60 mol% vinylidene and trisubstituted vinylidene (e.g., at least about 70 mol% or at least about 80 mol%) and at most about 10 mol% vinyl.

[0443] In some embodiments of the method, based on the total moles of vinyl, vinylidene, disubstituted vinylidene (excluding cyclic disubstituted vinylidene), and trisubstituted vinylidene in the unsaturated PAO product, the polymerization reaction exhibits selectivity for at least about 50 mol% vinylidene (e.g., at least about 60 mol%, at least about 70 mol%, or at least about 80 mol%) and less than or equal to about 10 mol% vinyl.

[0444] In some embodiments of the method, as measured by GC-MS, based on the total amount of dimers, trimers, tetramers, and higher oligomers, the polymerization reaction exhibits at least about 50% selectivity for dimer formation (e.g., at least about 60%, at least about 70%, at least about 80%, at least about 90%, or at least about 95%).

[0445] In some embodiments of the method, as measured by GC-MS, based on the total amount of dimers, trimers, tetramers, and higher oligomers, the polymerization reaction exhibits at least about 70% selectivity for dimer and trimer formation (e.g., at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 97%).

[0446] In some embodiments, the method further comprises: a) contacting the unsaturated PAO product with hydrogen to convert at least some of the unsaturated PAO product to a hydrogenated PAO product; b) contacting the unsaturated PAO product with a chemical reagent to convert at least some of the unsaturated PAO product to a functionalized PAO product; or both a) and b).

[0447] The choice between preparing a dimer-rich product and preparing a higher molecular weight PAO depends at least in part on the combination of catalyst selection and reactor conditions (e.g., reactor temperature). In some embodiments, the metallocenes used to prepare dimers include metallocene compounds represented by formula (III) and formula (V). Suitable reactor temperatures for preparing dimers can range from about 100 °C to about 200 °C (e.g., about 110 °C to about 180 °C, about 120 °C to about 170 °C, about 130 °C to about 160 °C, or about 140 °C to about 155 °C).

[0448] In some embodiments, the reaction conditions include a reactor temperature of at least about 120 °C (e.g., at least about 130 °C or at least about 140 °C) and a reactor pressure in the range of about 15 psia to about 1600 psia.

[0449] In some embodiments, 4-vinylcyclohex-1-ene (VCH) is used together with other cyclic α-olefins or other linear or branched α-olefins. VCH (diene) is capable of undergoing a chain transfer process that results in bicyclic products. Figure 1Depicts two reaction pathways in which VCH undergoes a chain transfer process and a bicyclic product is obtained. Pathway A shows a β-hydrogen chain termination pathway, where M represents the catalyst active site. Transfer of β-H (dark gray) to M gives a dimer product containing vinylidene unsaturation. In pathway B, M interacts with the double bond of the last inserted VCH monomer, resulting in the close proximity of the ε-hydrogen (light gray). Transfer of the ε-hydrogen to the metal gives a bicyclic ring structure. This latter chain transfer pathway does not occur in the case of cyclic saturated α-olefins such as vinylcyclohexane. A similar pathway is shown in Figure 2 where the first inserted α-olefin is represented as CH2=CHR, where R can be a straight-chain, branched-chain, or cyclic aliphatic group.

[0450] In some embodiments of the present disclosure, the PAO product comprises a mixture of unsaturated dimers selected from the compounds depicted below.

[0451]

[0452]

[0453] wherein if the cyclic α-olefin has a saturated ring structure, the cyclic monomeric fragments (A) and (B) are independently saturated, or if the cyclic α-olefin has a partially unsaturated ring structure, the cyclic monomeric fragments (A) and (B) are independently partially unsaturated; and

[0454]

[0455] wherein n and m independently indicate the number of additional carbon atoms in the ring structure and can be integers from 1 to 20 (e.g., 1-12, 1-9, 1-5, or 1-3), R is a C2-C 30 hydrocarbyl group, R' is a C1-C 29 hydrocarbyl group, and at least one of the structures CL-v or LC-v is present in the PAO product mixture. It should be noted that the wavy bonds in the structure indicate the inclusion of both E and Z isomers.

[0456] In some embodiments, independently, n and m are preferably 1-5, more preferably 2-4, and most preferably 3. In some embodiments, R is preferably a C2-C8 hydrocarbyl group, more preferably a C2-C6 hydrocarbyl group, alternatively a C2-C4 hydrocarbyl group, alternatively a C3-C4 hydrocarbyl group. In some embodiments, R' is preferably a C1-C7 hydrocarbyl group, more preferably a C1-C5 hydrocarbyl group, alternatively a C1-C3 hydrocarbyl group, alternatively a C2-C3 hydrocarbyl group. In some embodiments of the present disclosure, n and m independently represent integers from 1 to 5, R is a C2-C8 hydrocarbyl group, and R' is a C1-C7 hydrocarbyl group. In some embodiments of the present disclosure, n and m are 3, R is a C3-C8 hydrocarbyl group, and R' is a C2-C7 hydrocarbyl group, and the cyclic monomer fragments (A) and (B) have a partially unsaturated ring structure.

[0457] In some embodiments of the present disclosure, CC-v and CL-v and / or LC-v are present in the PAO product. In some embodiments of the present disclosure, LL-v and CL-v and / or LC-v are present in the PAO product. In some embodiments of the present disclosure, CC-v, LL-v, and CL-v and / or LC-v are present in the PAO product.

[0458] In some embodiments of the present disclosure, CC-v is selected from the following structures, where each q is independently an integer:

[0459]

[0460] In some embodiments of the present disclosure, CC-t 1 is selected from the following structures, where each q is independently an integer:

[0461]

[0462] In some embodiments of the present disclosure, in the CC-t 1 structures shown above, q is preferably 1-5, more preferably 2-3.

[0463] In some embodiments of the present disclosure, CC-t2 is selected from the following structures, where each q is independently an integer:

[0464]

[0465] In some embodiments of the present disclosure, in the CC-t2 structures shown above, q is preferably 1-5, more preferably 2-3.

[0466] In some embodiments of the present disclosure, LC-v is selected from the following structures, where p is an integer:

[0467]

[0468] In some embodiments of the present disclosure, in the LC-v structure shown above, where p = 3 - 19, p is preferably 3 - 11, more preferably 4 - 7, most preferably 4 - 5, where 5 is the most preferred. For structures where p = 5 - 19, p is preferably 5. For structures where p = 3 - 4 and 6 - 19, p is preferably 3 - 4 and 6 - 7, most preferably 4.

[0469] In some embodiments of the present disclosure, LC-t 1 is selected from the following structures, where p is an integer:

[0470]

[0471] In some embodiments of the present disclosure, in the LC-t 1 structure shown above, where p = 2 - 18, p is preferably 2 - 10, more preferably 3 - 6, most preferably 3 - 4, where 4 is the most preferred. For structures where p = 2 and 5 - 20, p is preferably 2 and 5 - 10, most preferably 2, 5, and 6.

[0472] In some embodiments of the present disclosure, LC-t2 is selected from the following structures, where p is an integer:

[0473]

[0474] In some embodiments of the present disclosure, in the LC-t2 structure shown above, where p = 3 - 19, p is preferably 3 - 11, more preferably 4 - 7, most preferably 4 - 5, where 5 is the most preferred. For structures where p = 4 - 5 and 6 - 19, p is preferably 3 and 6 - 7, most preferably 3 and 7.

[0475] In some embodiments of the present disclosure, CL-v is selected from the following structures, where p is an integer:

[0476]

[0477]

[0478] In some embodiments of the present disclosure, in the CL-v structure shown above, p is preferably 1 - 9, more preferably 2 - 5, most preferably 2 - 3, where 3 is the most preferred.

[0479] In some embodiments of the present disclosure, CL-t 1 is selected from the following structures, where p is an integer:

[0480]

[0481] In some embodiments of the present disclosure, in the CL-t 1 structure shown above, p is preferably 1-9, more preferably 2-5, and most preferably 2-3, where 3 is the most preferred.

[0482] In some embodiments of the present disclosure, CL-t2 is selected from the following structures, where p is an integer:

[0483]

[0484]

[0485] In some embodiments of the present disclosure, in the CL-t2 structure shown above, p is preferably 1-8, more preferably 1-4, and most preferably 1-2, where 2 is the most preferred.

[0486] In some embodiments of the present disclosure, the following structures are preferred, where p is an integer:

[0487]

[0488] In some embodiments of the present disclosure, in the structure shown above, p is preferably 2-8, more preferably 3-6, and most preferably 3-4, where 4 is the most preferred.

[0489] In an embodiment of the present disclosure, the PAO product contains 7-(2-(cyclohex-3-en-1-yl)ethyl)bicyclo[3.2.1]oct-2-ene.

[0490] In an embodiment of the present disclosure, the PAO product contains 7-hexylbicyclo[3.2.1]oct-2-ene.

[0491] In an embodiment of the present disclosure, the PAO product contains 7-pentylbicyclo[3.2.1]oct-2-ene.

[0492] In an embodiment of the present disclosure, the PAO product contains 4,4'-(but-3-ene-1,3-diyl)dicyclohex-1-ene.

[0493] In an embodiment of the present disclosure, the PAO product contains 4-(oct-1-en-2-yl)cyclohex-1-ene.

[0494] In an embodiment of the present disclosure, the PAO product contains oct-1-en-2-ylcyclohexane.

[0495] In an embodiment of the present disclosure, the PAO product contains 4-(hept-1-en-2-yl)cyclohex-1-ene.

[0496] In an embodiment of the present disclosure, the PAO product contains hept-1-en-2-ylcyclohexane.

[0497] In embodiments of the present disclosure, the PAO product comprises 4-(non-1-en-2-yl)cyclohex-1-ene.

[0498] In embodiments of the present disclosure, the PAO product comprises non-1-en-2-ylcyclohexane.

[0499] In embodiments of the present disclosure, the PAO product comprises 4-(hex-1-en-2-yl)cyclohex-1-ene.

[0500] In embodiments of the present disclosure, the PAO product comprises 4-(6-methylhept-1-en-2-yl)cyclohex-1-ene.

[0501] In embodiments of the present disclosure, the PAO product comprises (6-methylhept-1-en-2-yl)cyclohexane.

[0502] In some embodiments, the PAO is a mixture of unsaturated dimers prepared from two different α-olefins, wherein at least one α-olefin is a cyclic α-olefin (C) and at least one second α-olefin is a linear or branched α-olefin (L). The unsaturated dimers prepared are represented by the formulas CC, CL, and LL. The dimer product distribution can vary and depends at least in part on the molar ratio of C and L used in the oligomerization reaction. In some embodiments, the ratio of C and L used in the method is selected such that the percentage of CL prepared (based on CC + CL + LL equal to 100%) is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on CC + CL + LL equal to 100%, the percentage of CC prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on CC + CL + LL equal to 100%, the percentage of LL prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages related to the CC, CL, and LL ratios are based on GC-MS as described in the experimental section.

[0503] In an embodiment of the present disclosure, the PAO product comprises 4,4'-(but-3-ene-1,3-diyl)dicyclohex-1-ene (VCHx2), 4-(oct-1-en-2-yl)cyclohex-1-ene (VCH-hex), and 5-methyleneundecane (2-butyl-1-octene) (hex-hex). In some embodiments, based on the total moles of VCHx2 + VCH-hex + hex-hex equal to 100%, the mole percentage of VCH-hex is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on VCHx2 + VCH-hex + hex-hex equal to 100%, the mole percentage of VCHx2 prepared is at least about 0%, more typically at least 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on VCHx2 + VCH-hex + hex-hex equal to 100%, the mole percentage of hex-hex prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0504] In embodiments of the present disclosure, the PAO product comprises but-3-ene-1,3-diyl dicyclohexane (VCH’x2), oct-1-ene-2-yl cyclohexane (VCH’-hex), and 5-methyleneundecane (2-butyl-1-octene) (hex-hex). In some embodiments, based on the total moles of VCH’x2 + VCH’-hex + hex-hex equal to 100%, the mole percentage of VCH’-hex is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on VCH’x2 + VCH’-hex + hex-hex equal to 100%, the mole percentage of VCH’x2 prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on VCH’x2 + VCH’-hex + hex-hex equal to 100%, the mole percentage of hex-hex prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0505] In an embodiment of the present disclosure, the PAO product comprises 4,4'-(but-3-ene-1,3-diyl)dicyclohex-1-ene (VCHx2), 4-(hept-1-en-2-yl)cyclohex-1-ene (VCH-pent), and 4-methylenenonane (2-propyl-1-octene) (pent-pent). In some embodiments, based on the total molar amount of VCHx2 + VCH-pent + pent-pent equal to 100%, the molar percentage of VCH-pent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on VCHx2 + VCH-pent + pent-pent being equal to 100%, the molar percentage of VCHx2 prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on VCHx2 + VCH-pent + pent-pent being equal to 100%, the molar percentage of pent-pent prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0506] In embodiments of the present disclosure, the PAO product comprises but-3-ene-1,3-diyl dicyclohexane (VCH’x2), hept-1-en-2-yl cyclohexane (VCH’-pent), and 4-methylenenonane (2-propyl-1-octene) (pent-pent). In some embodiments, based on the total mole number of VCH’x2 + VCH’-pent + pent-pent equal to 100%, the mole percentage of VCH’-pent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on VCH’x2 + VCH’-pent + pent-pent being equal to 100%, the mole percentage of VCH’x2 prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on VCH’x2 + VCH’-pent + pent-pent being equal to 100%, the mole percentage of pent-pent prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0507] In embodiments of the present disclosure, the PAO product comprises 4,4'-(but-3-ene-1,3-diyl)dicyclohex-1-ene (VCHx2), 4-(non-1-en-2-yl)cyclohex-1-ene (VCH-hept), and 6-methylenetridecane (hept-hept). In some embodiments, based on the total moles of VCHx2 + VCH-hept + hept-hept being equal to 100%, the mole percentage of VCH-hept is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on VCHx2 + VCH-hept + hept-hept being equal to 100%, the mole percentage of VCHx2 prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on VCHx2 + VCH-hept + hept-hept being equal to 100%, the mole percentage of hept-hept prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0508] In embodiments of the present disclosure, the PAO product comprises but-3-ene-1,3-diyl dicyclohexane (VCH’x2), non-1-en-2-yl cyclohexane (VCH’-hept), and 6-methylenetridecane (6-hexyl-1-octene) (hept-hept). In some embodiments, based on the total moles of VCH’x2 + VCH’-hept + hept-hept being equal to 100%, the mole percentage of VCH’-hept is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on VCH’x2 + VCH’-hept + hept-hept being equal to 100%, the mole percentage of VCH’x2 prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on VCH’x2 + VCH’-hept + hept-hept being equal to 100%, the mole percentage of hept-hept prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0509] In embodiments of the present disclosure, the PAO product comprises 4,4'-(but-3-ene-1,3-diyl)dicyclohex-1-ene (VCHx2), 4-(hex-1-en-2-yl)cyclohex-1-ene (VCH-but), and 3-methylideneheptane (2-ethyl-1-hexene) (3-methyleneheptane) (but-but). In some embodiments, based on the total moles of VCHx2 + VCH-but + but-but equal to 100%, the mole percentage of VCH-but is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on VCHx2 + VCH-but + but-but equal to 100%, the mole percentage of VCHx2 prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on VCHx2 + VCH-but + but-but equal to 100%, the mole percentage of but-but prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0510] In embodiments of the present disclosure, the PAO product comprises but-3-ene-1,3-diyl dicyclohexane (VCH’x2), hex-1-ene-2-yl cyclohexane (VCH’-but), and 3-methylideneheptane (2-ethyl-1-hexene) (3-methyleneheptane) (but-but). In some embodiments, based on the total moles of VCH’x2 + VCH’-but + but-but being equal to 100%, the mole percentage of VCH’-but is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on VCH’x2 + VCH’-but + but-but being equal to 100%, the mole percentage of VCH’x2 prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on VCH’x2 + VCH’-but + but-but being equal to 100%, the mole percentage of but-but prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0511] In embodiments of the present disclosure, the PAO product comprises 4,4'-(but-3-ene-1,3-diyl)dicyclohex-1-ene (VCHx2), 4-(6-methylhept-1-en-2-yl)cyclohex-1-ene (VCH-MePent), and 2,8-dimethyl-4-methylenenonane (2-isobutyl-6-methyl-heptene) (MePent-MePent). In some embodiments, based on the total moles of VCHx2 + VCH-MePent + MePent-MePent being equal to 100%, the mole percentage of VCH-MePent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on VCHx2 + VCH-MePent + MePent-MePent being equal to 100%, the mole percentage of VCHx2 prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on VCHx2 + VCH-MePent + MePent-MePent being equal to 100%, the mole percentage of MePent-MePent prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0512] In embodiments of the present disclosure, the PAO product comprises but-3-ene-1,3-diyl dicyclohexane (VCH’x2), (6-methylhept-1-en-2-yl) cyclohexane (VCH’-MePent), and 2,8-dimethyl-4-methylenenonane (2-isobutyl-6-methyl-heptene) (MePent-MePent). In some embodiments, based on the total moles of VCH’x2 + VCH’-MePent + MePent-MePent equal to 100%, the mole percentage of VCH’-MePent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on VCH’x2 + VCH’-MePent + MePent-MePent equal to 100%, the mole percentage of VCH’x2 prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on VCH’x2 + VCH’-MePent + MePent-MePent equal to 100%, the mole percentage of MePent-MePent prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0513] In some embodiments of the present disclosure, when only cyclic α-olefins are in the feed, the conversion of cyclic α-olefins to dimers is 30% or greater, alternatively 40% or greater, alternatively 50% or greater, alternatively 60% or greater, alternatively 70% or greater, alternatively 80% or greater, alternatively 86% or greater, alternatively 90% or greater, alternatively 92% or greater, alternatively 94% or greater, alternatively 95% or greater, alternatively 96% or greater, or alternatively 98% or greater, based on the total amount of monomer feed, dimers, trimers, tetramers, and higher oligomers including isomerization or hydrogenation, as measured by GC-MS.

[0514] In some embodiments of the present disclosure, when only cyclic α-olefins are in the feed, the selectivity to form dimers is 80% or greater, alternatively 90% or greater, alternatively 94% or greater, alternatively 98% or greater, with 99% or greater being most preferred, based on the total amount of dimers, trimers, tetramers, and higher oligomers, as measured by GC-MS.

[0515] In some embodiments of the present disclosure, when only cyclic α-olefins are in the feed, the selectivity for forming a dimer species (an isomer) is 80% or greater, alternatively 85% or greater, alternatively 90% or greater, alternatively 95% or greater, alternatively 98% or greater, based on the total amount of dimers, as measured by GC-MS.

[0516] In some embodiments of the present disclosure, when only cyclic α-olefins are in the feed, the conversion of the cyclic α-olefin monomer to form a dimer species (an isomer) is 30% or greater, alternatively 40% or greater, alternatively 50% or greater, alternatively 60% or greater, alternatively 70% or greater, alternatively 80% or greater, alternatively 86% or greater, alternatively 90% or greater, alternatively 92% or greater, alternatively 94% or greater, alternatively 95% or greater, alternatively 96% or greater, or alternatively 98% or greater, based on the amount of the major dimer isomer relative to the total amount of the feed monomers, dimers, trimers, tetramers, and higher oligomers including isomerized or hydrogenated monomers, as measured by GC-MS.

[0517] Hydrogenation

[0518] Some of the unsaturated PAO product can be hydrogenated to obtain an at least partially saturated PAO product. In some embodiments, the treated product is contacted with hydrogen and a hydrogenation catalyst at a temperature of about 25 °C to about 350 °C (e.g., about 100 °C to about 300 °C) and a hydrogen pressure of about 25 psig to about 2500 psig (i.e., about 170 kPag to about 17 MPag) (e.g., about 100 psig to about 2000 psig (i.e., about 690 kPag to about 14 MPag)) for about 5 minutes to about 100 h (e.g., about 5 minutes to about 24 h) to prepare an at least partially saturated hydrogenated PAO product. Additional information regarding the hydrogenation of unsaturated PAO products can be found in U.S. Patent No. 5,573,657 and “Lubricant Base Oil Hydrogen Refining Processes” (pages 119 to 152 of Lubricant Base Oil and Wax Processing, Avilino Sequeira, Jr., Marcel Dekker, Inc., NY, 1994), which are incorporated herein by reference.

[0519] This hydrogenation process can be carried out, for example, in a slurry reactor, in a batch operation, or in a continuous stirred tank reactor (CSTR), where the catalyst is 0.001 wt% to 20 wt% (e.g., 0.01 wt% to 10 wt%) of the unsaturated PAO feed, and hydrogen and uPAO can be continuously added to the reactor to allow a certain residence time (e.g., 5 minutes to 10 h) to allow the desired (e.g., substantially complete) hydrogenation of the unsaturated olefins. The amount of catalyst added is typically very small, only to compensate for catalyst deactivation. The catalyst and hydrogenated PAO can be continuously withdrawn from the reactor. The product mixture can be filtered, centrifuged, or sedimented to remove the solid hydrogenation catalyst. If desired, the catalyst can be regenerated and reused. The hydrogenated PAO can be used as is or further distilled or fractionated to the desired level. In some cases, when the hydrogenation catalyst shows little or no catalyst deactivation after long-term operation, the stirred tank hydrogenation process can be carried out in the following manner: a fixed amount of catalyst (e.g., about 0.1 wt% to about 10% of the total reactants) is maintained in the reactor, most (or only) hydrogen and PAO feed are continuously added at a certain feed rate, and mainly (or only) hydrogenated PAO is withdrawn from the reactor.

[0520] The hydrogenation process can additionally or alternatively be carried out by a fixed bed process, where a solid catalyst can be loaded in a tubular reactor and heated to the reactor temperature. Hydrogen and PAO feeds can be fed through the reactor simultaneously from the top or bottom or countercurrently, e.g., to maximize the contact between hydrogen, PAO, and the catalyst and to allow heat management. The feed rates of PAO and hydrogen can be adjusted to give an appropriate residence time, e.g., to allow the desired (typically substantially complete) hydrogenation of the unsaturated PAO in the feed. The hydrogenated PAO fluid can be used as is or further distilled or fractionated to the desired level. Generally, the hydrogenated PAO product can have a bromine value of at most about 2.

[0521] In some embodiments, the hydrogenated PAO (hPAO) product comprises a mixture of dimers selected from the following:

[0522]

[0523] wherein the cyclic monomeric fragments (A) and (B) are saturated ring structures:

[0524] and wherein: n and m independently indicate the number of additional carbon atoms in the ring structure and can be integers from 1 to 20 (e.g., 1 - 12, 1 - 9, 1 - 5, 1 - 3), R is a C2 - C 30 hydrocarbyl group, R' is a C1 - C 29 hydrocarbyl group, and wherein the structure hCL 1,2 or hLC1,2 At least one of them is present in the hydrogenated PAO product mixture.

[0525] In some embodiments, independently, n and m are preferably 1 - 5, more preferably 2 - 4, and most preferably 3. In some embodiments, R is preferably a C2 - C8 hydrocarbyl group, more preferably a C2 - C6 hydrocarbyl group, alternatively a C2 - C4 hydrocarbyl group, alternatively a C3 - C4 hydrocarbyl group. In some embodiments, R' is preferably a C1 - C7 hydrocarbyl group, more preferably a C1 - C5 hydrocarbyl group, alternatively a C1 - C3 hydrocarbyl group, alternatively a C2 - C3 hydrocarbyl group.

[0526] In some embodiments of the present disclosure, n and m independently represent integers from 1 to 5, R is a C2 - C8 hydrocarbyl group, and R' is a C1 - C7 hydrocarbyl group. In some embodiments of the present disclosure, n and m are 3, R is a C3 - C8 hydrocarbyl group, and R' is a C2 - C7 hydrocarbyl group.

[0527] In some embodiments of the present disclosure, hCC 1,2 and hLC 1,2 and / or hCL 1,2 are present in the hPAO product. In some embodiments of the present disclosure, hLL 1,2 and hLC 1,2 and / or hCL 1,2 are present in the hPAO product. In some embodiments of the present disclosure, hCC 1,2 、hLL 1,2 and hLC 1,2 and / or hCL 1,2 are present in the hPAO product.

[0528] In some embodiments of the present disclosure, hCC 1,2 is selected from the following structures, where each q is independently an integer:

[0529]

[0530] In some embodiments of the present disclosure, hLC 1,2 is selected from the following structures, where each p is an integer:

[0531]

[0532] In some embodiments of the present disclosure, hCL 1,2 is selected from the following structures, where each p is an integer:

[0533]

[0534] In some embodiments of the present disclosure, in the hCL shown above 1,2In the structure, when p is from 1 to 9, p is preferably from 1 to 9, more preferably from 2 to 5, and most preferably from 2 to 3, where 3 is the most preferred. For the structure where p = 2 - 3 and 5 - 19, p is preferably 2 - 3 and 6 - 7, and most preferably 2 and 3. For the structure where p = 2 - 6 and 8 - 19, p is preferably 2 - 6, and most preferably 2 and 3.

[0535] In some embodiments of the present disclosure, the following structure is preferred, where p is an integer:

[0536]

[0537] In some embodiments of the present disclosure, in the structure shown above, p is preferably from 2 to 8, more preferably from 3 to 6, and most preferably from 3 to 4, where 4 is the most preferred.

[0538] In an embodiment of the present disclosure, the hPAO product contains 6-(2-cyclohexylethyl)bicyclo[3.2.1]octane.

[0539] In an embodiment of the present disclosure, the hPAO product contains 6-hexylbicyclo[3.2.1]octane.

[0540] In an embodiment of the present disclosure, the hPAO product contains 6-pentylbicyclo[3.2.1]octane.

[0541] In an embodiment of the present disclosure, the hPAO product contains nonan-2-ylcyclohexane.

[0542] In an embodiment of the present disclosure, the hPAO product contains (6-methylheptan-2-yl)cyclohexane.

[0543] In some embodiments, the hydrogenated PAO is a mixture of saturated dimers prepared from two different α-olefins, wherein at least one α-olefin is a cyclic α-olefin (C) and at least one α-olefin is a linear or branched α-olefin (L), and wherein the saturated dimers prepared after hydrogenation are represented by the formulas hCC, hCL, and hLL. The saturated dimer product distribution can vary and depends at least in part on the molar ratio of C and L used in the oligomerization reaction. In some embodiments, the ratio of C and L used in the method is selected such that the percentage of hCL prepared after hydrogenation (based on hCC + hCL + hLL being equal to 100%) is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on hCC + hCL + hLL being equal to 100%, the percentage of hCC prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on hCC + hCL + hLL being equal to 100%, the percentage of hLL prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages related to the ratios of hCC, hCL, and hLL are based on GC-MS as described in the experimental section.

[0544] In embodiments of the present disclosure, the hPAO product comprises butane-1,3-diyl dicyclohexane (hVCHx2), oct-2-yl cyclohexane (hVCH-hex), and 5-methylundecane (hHex-hex). In some embodiments, based on the total molar amount of hVCHx2 + hVCH-hex + hHex-hex equal to 100%, the molar percentage of hVCH-hex is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on hVCHx2 + hVCH-hex + hHex-hex equal to 100%, the molar percentage of the prepared hVCHx2 is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on hVCHx2 + hVCH-hex + hHex-hex equal to 100%, the molar percentage of the prepared hHex-hex is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0545] In embodiments of the present disclosure, the hPAO product comprises butane-1,3-diyl dicyclohexane (hVCHx2), 4-non-2-yl cyclohexane (hVCH-pent), and 4-methylnonane (hPent-pent). In some embodiments, based on the total molar amount of hVCHx2 + hVCH-pent + hPent-pent equal to 100%, the molar percentage of hVCH-pent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on hVCHx2 + hVCH-pent + hPent-pent equal to 100%, the molar percentage of the prepared hVCHx2 is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on hVCHx2 + hVCH-pent + hPent-pent equal to 100%, the molar percentage of the prepared hPent-pent is at least about 110% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0546] In embodiments of the present disclosure, the hPAO product comprises butane-1,3-diyl dicyclohexane (hVCHx2), 4-hept-2-yl cyclohexane (hVCH-hept), and 6-methyltridecane (hHept-hept). In some embodiments, based on the total molar amount of hVCHx2 + hVCH-hept + hHept-hept being equal to 100%, the molar percentage of hVCH-pent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on hVCHx2 + hVCH-hept + hHept-hept being equal to 100%, the molar percentage of hVCHx2 prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on hVCHx2 + hVCH-hept + hHept-hept being equal to 100%, the molar percentage of hHept-hept prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0547] In embodiments of the present disclosure, the hPAO product comprises butane-1,3-diyl dicyclohexane (hVCHx2), hex-2-yl cyclohexane (hVCH-but), and 3-methylheptane (hbut-but). In some embodiments, based on the total molar amount of hVCHx2 + hVCH-but + hbut-but being equal to 100%, the molar percentage of hVCH-but is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on hVCHx2 + hVCH-but + hbut-but being equal to 100%, the molar percentage of hVCHx2 prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on hVCHx2 + hVCH-but + hbut-but being equal to 100%, the molar percentage of hbut-but prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0548] In embodiments of the present disclosure, the hPAO product comprises butane-1,3-diyl dicyclohexane (hVCHx2), (6-methylheptan-2-yl) cyclohexane (hVCH-MePent), and 4-methylnonane (hMePent-MePent). In some embodiments, based on the total molar amount of hVCHx2 + hVCH-MePent + hMePent-MePent being equal to 100%, the molar percentage of hVCH-MePent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. In some embodiments, based on hVCHx2 + hVCH-MePent + hMePent-MePent being equal to 100%, the molar percentage of hVCHx2 prepared is 0%, more typically at least about 1% and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. In some embodiments, based on hVCHx2 + hVCH-MePent + hMePent-MePent being equal to 100%, the molar percentage of hMePent-MePent prepared is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%. All percentages and relative ratios are based on GC-MS as described in the experimental section.

[0549] Functionalization

[0550] Some of the unsaturated PAO product can be reacted with chemical reagents to obtain an at least partially functionalized PAO product. However, due to the individual nature of the functionalization reactions, the potential by-products or by-product specificities to be avoided, the breadth of potentially desired functionalities, and thus the breadth of potential reaction conditions available or sufficient to obtain the desired functionality, it may be difficult to specify a suitable set of conditions, reactors, chemical reagents, and / or catalysts / additives, etc. to cover them all. However, conventional functionalization techniques and their reaction parameters are known to those skilled in the art of chemistry, allowing PAO products that are partially or fully functionalized with any one or more of a variety of functional groups to be readily obtainable. In the case of a substantially or fully functionalized PAO product, in some embodiments, the bromine value can be at most about 2.

[0551] Lubricant base oil

[0552] The unsaturated PAO products and hydrogenated PAO products described herein can be used as base stocks for lubricating oil compositions. In some embodiments, a hydrogenated PAO having a bromine number of at most about 2, or not greater than 2.0, is used as a lubricating oil base stock. The base stocks can be in any viscosity grade suitable for any particular lubricating oil composition. The base stocks of the present disclosure can be blended with each other, and with other Group I, Group II, Group III, Group IV, or Group V base stocks, lubricant additive packages, and / or the like, to form lubricating oil compositions. "Lubricating oil", "lubricating oil composition", and "lubricant" are used interchangeably herein. The lubricants can include internal combustion engine oils, gas turbine oils, automotive driveline fluids, power transmission fluids (e.g., hydraulic oils), process oils, heat transfer oils (e.g., transformer oils), industrial lubricants, gearbox lubricants, etc., and combinations thereof.

[0553] In some embodiments, the method of preparing a PAO dimer further comprises reacting the PAO dimer with a reactant to form a functionalized PAO product, followed by hydrogenation.

[0554] In some embodiments, the method of preparing a PAO dimer and / or trimer further comprises hydrogenating the product.

[0555] Some embodiments include fuels that comprise a hydrogenated PAO dimer and / or trimer.

[0556] Some embodiments include driveline or electric vehicle fluids that comprise a hydrogenated or functionalized derivative of a PAO dimer and / or trimer, or a hydrogenated functionalized derivative.

[0557] Some embodiments include engine oils that comprise a hydrogenated or functionalized derivative of a PAO dimer and / or trimer, or a hydrogenated functionalized derivative.

[0558] Some embodiments include gear oils that comprise a hydrogenated or functionalized derivative of a PAO dimer and / or trimer, or a hydrogenated functionalized derivative.

[0559] Some embodiments include cooling fluids that comprise a hydrogenated or functionalized derivative of a PAO dimer and / or trimer, or a hydrogenated functionalized derivative.

[0560] Some embodiments include compressor oils that comprise a hydrogenated or functionalized derivative of a PAO dimer and / or trimer, or a hydrogenated functionalized derivative.

[0561] Some embodiments include hydraulic fluids that comprise a hydrogenated or functionalized derivative of a PAO dimer and / or trimer, or a hydrogenated functionalized derivative. Examples

[0562] Catalyst complex

[0563] Catalyst complexes A - E are prepared as described below. Complex F is commercially available. The terms "catalyst complex", "complex", "transition metal complex", "transition metal compound", "pre - catalyst", and "catalyst" are used interchangeably in this document.

[0564]

[0565] The complexes A (1 - isobutyl - 3,5,6,7 - tetrahydro - s - indacenyl)(pentamethylcyclopentadienyl)dimethylhafnium and B (1 - methyl - 3,5,6,7 - tetrahydro - s - indacenyl)(pentamethylcyclopentadienyl)dimethylhafnium used in the following oligomerization runs can be synthesized according to PCT publication number WO2021 / 030045, the synthesis method of which is incorporated herein by reference. The complex D (1 - methylindenyl)(pentamethylcyclopentadienyl)dimethylhafnium used below can be synthesized according to PCT publication number WO2019 / 157169, the synthesis method of which is incorporated herein by reference.

[0566] The catalyst synthesis reaction is carried out under inert and anaerobic conditions (under dinitrogen or the like) using anhydrous solvents and commercially available reagents.

[0567] Synthesis of complex C (1,5,6 - trimethylindenyl)(pentamethylcyclopentadienyl)dimethylhafnium Synthesis of (5,6 - dimethyl - 1H - inden - 1 - yl)lithium

[0568]

[0569] At - 35 °C, n - BuLi (25.0 mL, 2.48 M, 62.0 mmol, 1.00 equivalent) in hexane was added to a pale yellow solution of 5,6 - dimethylindene (8.94 g, 62.0 mmol, purchased from Boulder Scientific) in diethyl ether (300 mL). Once added, the original amber solution quickly became a turbid manila color, with a precipitate. After stirring for 30 min, the reaction became a turbid pink color, with a white precipitate. The reaction was concentrated in vacuo, leaving a pink solid. The solid was washed with pentane (40 mL) and dried in vacuo to a pink powder. Yield: 9.06 g (97%).

[0570] 11H NMR (400 MHz, THF-d8): δ 7.10 (s, 2H), 6.39 (t, J = 3.3 Hz, 1H), 5.78 (d, J = 3.3 Hz, 2H), 2.24 (s, 6H).

[0571] Synthesis of 1,5,6-Trimethyl-1H-indene

[0572]

[0573] To a colorless solution of methyl iodide (17.50 g, 0.123 mmol, 2.08 equiv) in diethyl ether (100 mL) was added (5,6-dimethyl-1H-inden-1-yl)lithium (8.90 g, 59.3 mmol), producing a turbid, thick, light Manila-colored mixture. After stirring for 20 min, the reaction warmed and became a turbid light Manila color and less thick. After stirring for 45 min, the reaction became warm and clear amber. After stirring at room temperature for 3 h, the reaction was clear. Dimethoxyethane (11.0 g, 122 mmol, 2.06 equiv) was added to give a turbid Manila-colored mixture with a precipitate. The reaction was evaporated in vacuo, leaving a moist Manila-colored solid. The solid was extracted with pentane (100 mL, then 3 × 20 mL) to give an amber filtrate and a white solid. The filtrate was evaporated in vacuo, leaving an amber liquid. Yield: 8.90 g (95%).

[0574] 1 1H NMR (400 MHz, benzene-d6): δ 7.08 (d, J = 7.6 Hz, 2H), 6.69 (ddd, J = 5.5, 2.0, 0.7 Hz, 1H), 6.24 (dd, J = 5.5, 2.0 Hz, 1H), 3.36–3.24 (m, 1H), 2.15 (d, J = 8.3 Hz, 6H), 1.16 (d, J = 7.6 Hz, 3H).

[0575] Synthesis of (3,5,6-Trimethyl-1H-inden-1-yl)lithium

[0576]

[0577] At -35 °C, n-BuLi (23.0 mL, 2.48 M, 57.0 mmol, 1.02 equiv) in hexane was added to a amber solution of 1,5,6-trimethyl-1H-indene (8.87 g, 56.1 mmol) in diethyl ether (120 mL) to give a turbid amber solution which thickened rapidly upon completion of the addition, accompanied by a manila-colored precipitate. The reaction mixture was stirred for 30 min and then evaporated in vacuo, leaving a manila-colored solid. The solid was washed with pentane (2 × 40 mL) and dried in vacuo to give a pale manila-colored powder. Yield: 9.20 g (100%).

[0578] 1 H NMR (400 MHz, THF-d8): δ 7.04 (s, 2H), 6.20 (dd, J = 3.1, 0.8 Hz, 1H), 5.59 (dd, J = 3.1, 0.8 Hz, 1H), 2.38 (d, J = 0.8 Hz, 3H), 2.25 (d, J = a 13.3 Hz, 6H).

[0579] Synthesis of hafnium tris(dimethylamido) iodide Hf(NMe2)3I

[0580] Over 20 min, hafnium tetrakis(dimethylamido) (24.92 g, 70.2 mmol) in pentane (150 mL) was slowly added dropwise to trimethylsilyl iodide (10.00 mL, 1.41 g / mL, 70.3 mmol) to give a turbid white mixture. After 1 h, the reaction was white with a large amount of precipitate. The reaction was filtered, and the solid was washed with pentane (2 × 40 mL) and dried in vacuo to a white powder. This produced 29.45 g (96%) of hafnium tris(dimethylamido) iodide as a white powder.

[0581] 1 H NMR (400 MHz, benzene-d6): δ 2.82 (s, 13H), 2.59 (s, 6H). Synthesis of (pentamethylcyclopentadienyl)hafnium tris(dimethylamido) (Me5Cp)Hf(NMe2)3

[0582]

[0583] To a white suspension of Hf(NMe2)3I (20.00 g, 45.7 mmol) in diethyl ether (100 mL) was added sodium pentamethylcyclopentyldienide (7.21 g, 4.56 mmol, 0.99 equiv). After 1 h, the reaction became a turbid white mixture with a white precipitate. After 5 h, the reaction was evaporated in vacuo, leaving a white solid. The solid was extracted with pentane (100 mL, then 4 × 10 mL) to give a colorless filtrate and a white solid. The filtrate was evaporated in vacuo to leave the desired product as a white solid. Yield: 20.32 g (100%).

[0584] 1 1H NMR (400 MHz, benzene-d6): δ 2.97 (s, 15H), 2.00 (s, 12H). Synthesis of (Pentamethylcyclopentadienyl)hafnium trichloride dimethoxyethane adduct (Me5Cp)HfCl3(dme)

[0585]

[0586] To a pale yellow solution of (Me5Cp)Hf(NMe2)3 (20.32 g, 45.6 mmol) in 1,2-dimethoxyethane (75 mL) was added trimethylchlorosilane (30.00 g, 276 mmol, 6.06 equiv). The reaction was slightly exothermic and became almost colorless upon addition of trimethylchlorosilane. After 1 min, the reaction formed a white precipitate and became turbid. After 1 h, after stirring, the reaction was turbid and light Manila-colored. After 2.5 h, the reaction was evaporated in vacuo, leaving a Manila-colored solid. The solid was washed with pentane (30 mL) and dried in vacuo to give 22.86 g (98%) as a pale pink powder.

[0587] 1 1H NMR (400 MHz, dichloromethane-d2): δ 3.81 (s, 4H), 3.56 (s, 6H), 2.23 (s, 15H).

[0588] Synthesis of (Pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)hafnium dichloride (Me5Cp)(1,5,6-Me3Ind)HfCl2

[0589]

[0590] The (Me5Cp)HfCl3(dme) (2.50 g, 4.90 mmol) was slurried in diethyl ether (35 mL). The slurry received Li[1,5,6-Me3Ind] (0.81 g, 4.93 mmol, 1.01 equiv) to give a turbid Manila-yellow mixture, which was stirred overnight. After 20 h, the reaction was evaporated in vacuo, leaving a pale yellow solid. The solid was extracted with diethyl ether (2 × 30 mL) and filtered to give a yellow solution and a white solid. The filtrate was evaporated in vacuo to remove the solvent, leaving a pale yellow solid. The solid was washed with cold pentane (15 mL) and dried in vacuo to give 2.30 g (87%) yield as a pale yellow powder.

[0591] 1 1H NMR (400 MHz, dichloromethane-d2): δ 7.30 (s, 1H), 7.06 (s, 1H), 5.87 (dd, J = 2.8, 0.7 Hz, 1H), 5.66 (dd, J = 2.8, 0.8 Hz, 1H), 2.42–2.30 (m, 9H), 2.05 (s, 15H).

[0592] Synthesis of (Pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)dimethylhafnium (Me5Cp)(1,5,6-Me3Ind)HfMe2

[0593]

[0594] To a solution of (Me5Cp)(1,5,6-Me3Ind)HfCl2 (2.27 g, 4.19 mmol) in toluene (15 mL) was added potassium fluoride (1.95 g, 33.6 mmol, 8.01 equiv) and trimethylaluminum (0.84 mL, 8.76 mmol, 2.10 equiv), which produced a turbid yellow mixture. After stirring for 1 min, the reaction warmed slightly and became turbid. After one hour, the solution was turbid yellow and was stirred overnight. After 20 h, the mixture was turbid pale yellow-white. The reaction was then evaporated in vacuo, leaving a pale yellow solid. The solid was extracted with pentane (30 mL, then 4 × 5 mL), and the pale yellow filtrate was evaporated in vacuo, leaving a pale yellow solid. Yield: 2.07 g, (99%).

[0595] 11H NMR (400 MHz, benzene-d6): δ 7.45 (s, 1H), 6.99 (d, J = 1.4 Hz, 1H), 5.22 (dd, J = 2.8, 0.8 Hz, 1H), 5.10 (dd, J = 2.9, 0.6 Hz, 1H), 2.28–2.13 (m, 9H), 1.76 (s, 16H), -1.58 (s, 3H). Synthesis of Complex E (indenyl)(tetramethylcyclopentadienyl)dimethylhafnium

[0596] Synthesis of hafnium tris(dimethylamino) chloride Hf(NMe2)3Cl

[0597] To a colorless solution of Hf(NMe2)4 (50.00 g, 141 mmol, 3.01 eq) in dichloromethane (250 mL) was added HfCl4 (15.0 g, 46.8 mmol), giving a warm, slightly turbid colorless solution. After 1 h, the reaction was filtered. The filtrate was evaporated in vacuo, leaving a white solid. The solid was dried in vacuo overnight and washed with pentane (2 × 40 mL) and redried in vacuo. Yield: 61.98 g (96%), as a white powder.

[0598] 1 1H NMR (400 MHz, benzene-d6): 2.82 (s, 18H)

[0599] (Tetramethylcyclopentadienyl)tris(dimethylamino)hafnium (Me4Cp)Hf(NMe2)3 synthesis

[0600]

[0601] To a white suspension of Hf(NMe2)3Cl (15.00 g, 43.3 mmol, 1.02 eq) in diethyl ether (90 mL) was added sodium tetramethylcyclopentadienide (6.15 g, 42.7 mmol), giving a turbid white mixture. The reaction mixture was stirred for 3.5 h to give a turbid pale yellowish-white mixture. It was then evaporated in vacuo, leaving a white solid. The solid was extracted with pentane (100 mL, then 3 × 5 mL) and filtered to give a very pale yellow filtrate and a white solid. The filtrate was concentrated in vacuo to give the desired product as a light Manila-colored solid. Yield: 17.59 g (95%).

[0602] 1 1H NMR (400 MHz, benzene-d6): δ 6.87 (s, 1H), 2.69 (s, 18H), 1.78 (s, 6H), 1.64 (s, 6H).

[0603] Synthesis of (Tetramethylcyclopentadienyl)hafnium Trichloride Dimethoxyethane Adduct (Me4Cp)HfCl3(dme)

[0604]

[0605] Trimethylchlorosilane (27.00 g, 249 mmol, 6.12 equiv) was added to a pale yellow solution of (Me4Cp)Hf(NMe2)3 (17.55 g, 40.6 mmol) in 1,2-dimethoxyethane (50 mL). After the addition was complete, the reaction underwent a slight temperature increase and the color lightened. After 3.5 h, the reaction was a turbid amber-white mixture. It was then evaporated in vacuo, leaving a Manila-colored solid. The solid was washed with pentane (2 × 20 mL) and dried in vacuo to give a pale Manila-colored powder. Yield: 19.88 g (99%).

[0606] 1 1H NMR (400 MHz, dichloromethane-d2): δ 5.62 (s, 1H), 4.04 (s, 4H), 3.80 (s, 6H), 2.28 (s, 6H), 2.17 (s, 6H).

[0607] Synthesis of (Indenyl)(tetramethylcyclopentadienyl)hafnium Dichloride (Ind)(Me4Cp)HfCl2

[0608]

[0609] A pale pink suspension of (Me4Cp)HfCl3(dme) (2.50 g, 5.02 mmol) in diethyl ether (50 mL) was added to lithium indenide (0.62 g, 5.08 mmol, 1.01 equiv) to give a turbid Manila-yellow mixture. The reaction was stirred for 18 h. The reaction was turbid light yellow with a precipitate. The reaction was evaporated in vacuo to give a light yellow solid. The solid was extracted with dichloromethane (30 mL, then 3 × 5 mL) and filtered to give a light yellow filtrate and a gray solid. The filtrate was evaporated in vacuo, leaving a light yellow solid. The solid was washed with pentane (20 mL) and dried in vacuo to give a light yellow powder. Yield: 2.32 g (95%).

[0610] 1 1H NMR (400 MHz, dichloromethane-d2): δ 7.58 (dd, J = 6.5, 3.1 Hz, 2H), 7.23 (dd, J = 6.6, 3.1 Hz, 2H), 6.65 (t, J = 3.3 Hz, 1H), 6.23 (d, J = 3.0 Hz, 2H), 5.73 (s, 1H), 2.03 (s, 7H), 1.97 (s, 7H).

[0611] Synthesis of (Indenyl)(tetramethylcyclopentadienyl)dimethylhafnium (Ind)(Me4Cp)HfMe2

[0612]

[0613] To a turbid yellow suspension of (Ind)(Me4Cp)HfCl2 (2.30 g, 4.73 mmol) in toluene (25 mL) was added potassium fluoride (2.20 g, 3.79 mmol, 8.00 equiv) and trimethylaluminum (0.94 mL, 0.752 g / mL, 9.81 mmol, 2.07 equiv), giving a turbid yellow mixture. The reaction was turbid yellow and slightly warm, and was stirred overnight. After 18 h, the reaction mixture was turbid pale yellowish white. The reaction was evaporated in vacuo, leaving a pale yellowish white solid. The solid was extracted with pentane (50 mL, then 3 × 5 mL) and filtered to give a very pale yellow filtrate and a gray solid. The filtrate was evaporated in vacuo, leaving a pale yellow solid. Yield: 2.10 g (100%).

[0614] 1 1H NMR (400 MHz, benzene-d6): δ 7.38 (dd, J = 6.5, 3.2 Hz, 2H), 7.04 (dd, J = 6.5, 3.2 Hz, 2H), 5.84 (d, J = 3.2 Hz, 2H), 5.66 (t, J = 3.2 Hz, 1H), 4.83 (s, 1H), 1.76 (s, 6H), 1.70 (s, 6H), -0.91 (s, 6H).

[0615] Activator

[0616] For catalyst activation, N,N-bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate (M2HTH-D4) is available from Boulder Chemical Company as a 10 wt% solution in methylcyclohexane.

[0617] Scavenger

[0618] For scavenger, tri-n-octylaluminum (pure) is available from Azko Nobel Part# K52296 or the like.

[0619] Monomer

[0620] Unless otherwise described, the monomers were purged with dry nitrogen prior to use to remove air and placed on molecular sieves to remove moisture. Monomer sources are as follows:

[0621] 1-Butene - Airgas Product#B1 CPLP5, chemically pure grade or the like;

[0622] 1-Pentene - GFS Item#3396, 98% purity or higher;

[0623] 4-Methyl-1-pentene - Sigma Aldrich Part#M67400 or the like;

[0624] 1-Hexene – sourced from Pilot Plant – Chevron Phillips 1-Hexene or the like;

[0625] 1-Heptene – TCI America Product#H0042 – 98% or greater as determined by GC;

[0626] 1-Octene – sourced from Pilot Plant – Chevron Phillips 1-Octene or the like;

[0627] 1-Nonene – TCI America Product#N0613 – 95% or greater as determined by GC;

[0628] 1-Decene – sourced from Pilot Plant - Chevron Philips 1-Decene or the like;

[0629] 4-Vinylcyclohex-1-ene – Gelest Product Code ENEV4520 – 97% pure, with 100 - 200 ppm BHT (2,6-di-tert-butyl-4-methylphenol) stabilizer, purified by passing through basic alumina, purged with nitrogen and treated with a desiccant (molecular sieve with optional Q5) ;

[0630] 4-Vinylcyclohexane is purchased from TCI chemicals and purified by purging with nitrogen, and stored on activated molecular sieves and AZ300; and

[0631] Vinylcyclobutane can be prepared as described in Journal of the American Chemical Society (2011), 133(23), 8858 - 8861 and U.S. Provisional Application No. 63 / 307,738 filed on February 8, 2022 and U.S. Patent Publication No. 2023 / 0250200.

[0632] Additional reagents

[0633] Additional reagents are obtained as described below.

[0634] Basic alumina, Brockmann I - Sigma Aldrich Part#199443 or the like;

[0635] Acidic alumina, Brockmann I – Sigma Aldrich Part#199966 or the like;

[0636] Silica gel – Sigma Aldrich Part#288624 high purity grade, pore size 70 - 230 mesh or the like;

[0637] Molecular sieve – Sigma Aldrich Part#208582 beads, 8 - 12 mesh, or the like;

[0638] Q - 5 reactant BASF CU - 0226S – from BASF product identifier: CU 0226S 8x14MESH or the like;

[0639] AZ300 - UOP; and

[0640] 545 - Sigma Aldrich#419931.

[0641] Solvent

[0642] Unless otherwise described, the solvent is purged with dry nitrogen before use to remove air and placed on a molecular sieve to remove moisture.

[0643] Methylcyclohexane (abbreviated as MCH) – Sigma Aldrich#300306 - 2L; and

[0644] Toluene – Sigma Aldrich#244511 - 1L

[0645] Oligomerization run

[0646] The batch oligomerization reactions of Examples 1-16 were carried out in a 1 or 2 L stainless steel autoclave reactor equipped with a paddle stirrer, an external water / steam jacket for temperature control, a controlled supply of dry nitrogen, and inlets for introducing other solvents, monomers, precatalysts, scavengers, and activators. Prior to use, the reactor body was dried by heating the reactor at 110 °C - 120 °C under a dry nitrogen stream for approximately 1 hour. Typically, 500 - 1000 mL of monomer was measured through a sight glass and added as a pre-mixed mixture of two monomers or as a single monomer.

[0647] For olefin monomers, the following abbreviations were used:

[0648] VCH: 4-vinylcyclohex-1-ene, also known as 4-vinylcyclohexene, 4-vinyl-1-cyclohexene, and vinylcyclohexene

[0649] VCB: vinylcyclobutane

[0650] C4: 1-butene, also known as butene

[0651] C5: 1-pentene, also known as pentene

[0652] C6: 1-hexene, also known as hexene

[0653] iC6: 4-methylpent-1-ene, also known as 4-methylpentene, 4-methyl-1-pentene, and isohexene

[0654] C7: 1-heptene, also known as heptene

[0655] C8: 1-octene, also known as octene

[0656] C9: 1-nonene, also known as nonene

[0657] C10: 1-decene, also known as decene

[0658] Oligomerization Examples 1-10

[0659] For the catalyst addition in Examples 1-10, typically a dual cylinder (also known as a dual feed line) consisting of two 25 mL SS Swagelok cylinders (with three SS Swagelok ball valves (one valve in the middle and one valve at each end)) was used. All catalysts, activators, and scavengers were handled in a nitrogen-purged dry box. All catalyst and activator solutions were prepared separately and loaded into different ends of the dual cylinder while in the nitrogen-purged dry box. After removal from the dry box, the dual feed line was attached to the reactor such that the activator / scavenger solution entered the reactor before the catalyst solution. Oligomerization Example 1: Typical co-oligomerization of C6 and VCH using Catalyst A

[0660] For this example, 1-hexene and 4-vinyl-1-cyclohexene were used. Catalyst A (150 - 240 mg) was dissolved in 10 mL of methylcyclohexane (MCH) and added to the rear section of a dual-feed tube. In the front section, M2HTH-D4 (3.0 - 4.0 mL of 10 wt% in MCH) was combined with neat tri-n-octylaluminum (scavenger, 0.3 - 0.5 mL) and an additional 5 - 10 mL of MCH. 1000 mL of a mixed monomer (∼50:50 by volume) was pushed into the reactor using dry molecular nitrogen; then the dual-feed tube was attached to the reactor and the nitrogen source. Stirring was started (∼500 rpm), and then the reactor was heated to 90 °C. Once the temperature of the monomer and the reactor had reached 90 °C, the catalyst, scavenger, and activator solution were injected using dry molecular nitrogen at ∼80 psi, and then the reactor was heated to 110 °C. Timing was started upon addition of the catalyst to the reactor and allowed to proceed for 30 to 90 min. After this period, heating and stirring were stopped. Once cooled to ambient temperature, the elevated pressure in the reactor decreased and the reactor was opened. The contents were then filtered through ∼200 mL of silica and alumina in a 1:1 ratio by volume to obtain a clear liquid with an approximate volume of 1000 mL.

[0661] Oligomerization Example 2: Typical co-oligomerization of C7 and VCH using Catalyst A

[0662] For this example, 1-heptene and 4-vinyl-1-cyclohexene were used. Catalyst A (130 - 200 mg) was dissolved in 10 mL of MCH and added to the rear section of a dual-feed tube. In the front section, M2HTH-D4 (3.6 - 4.0 mL of 10 wt% in MCH) was combined with neat tri-n-octylaluminum (0.3 - 0.4 mL) and an additional 7 mL of MCH. 1000 mL of a monomer mixture (∼50:50 by volume) was pushed into the reactor using dry molecular nitrogen at 80 psi; then the dual-feed tube was attached to the reactor and the nitrogen source. Stirring was started (∼500 rpm), and then the reactor was heated to 90 °C. Once the temperature of the monomer and the reactor had reached 90 °C, the catalyst, scavenger, and activator solution were injected into the reactor using dry molecular nitrogen at ∼80 psi, and then it was heated to 110 °C. Timing was started upon addition of the catalyst to the reactor and allowed to proceed for 30 to 90 min. After this period, heating and stirring were stopped. Once cooled to ambient temperature, the elevated pressure in the reactor decreased and the reactor was opened. The contents were then filtered through ∼200 mL of silica and alumina in a 1:1 ratio by volume to obtain a clear liquid with an approximate volume of 1000 mL.

[0663] Oligomerization Example 3: Typical Co - oligomerization of C5 and VCH Using Catalyst A

[0664] For this example, 1 - pentene and 4 - vinylcyclohex - 1 - ene were used. Catalyst A (130 - 200 mg) was dissolved in 10 mL of MCH and added to the rear section of a dual - feed tube. In the front section, M2HTH - D4 (3.6 - 4.0 mL of 10 wt% in MCH), pure tri - n - octylaluminum (0.3 - 0.4 mL), and an additional 7 mL of MCH were combined. 1000 mL of a monomer mixture (~50:50 by volume) was pushed into the reactor using dry molecular nitrogen at 80 psi; then the dual - feed tube was attached to the reactor and the nitrogen source. Stirring (~500 rpm) was started, and then the reactor was heated to 90 °C. Once the temperature of the monomers and the reactor had reached 90 °C, the catalyst, scavenger, and activator solutions were injected using dry molecular nitrogen at ~80 psi, and then heated to 110 °C. Timing was started when the catalyst was added to the reactor and allowed to proceed for 30 to 90 min. After this period, heating and stirring were stopped. Once cooled to ambient temperature, the elevated pressure in the reactor decreased and the reactor was opened. The contents were then filtered through ~200 mL of silica and alumina in a 1:1 ratio by volume to obtain a clear liquid with an approximate volume of 1000 mL.

[0665] Oligomerization Example 4: Typical Oligomerization of iC6 Using Catalyst D

[0666] For this example, 4 - methylpent - 1 - ene was used. Catalyst D (22 mg) was dissolved in 9 mL of MCH and added to the rear section of a dual - feed tube. In the front section, M2HTH - D4 (0.8 mL of 10 wt% in MCH), tri - n - octylaluminum (100 μL), and MCH (8 mL) were combined and added. 1 L of 4 - methylpent - 1 - ene was added to the reactor using high - pressure dry molecular nitrogen; then the dual - feed tube was attached to the reactor and the nitrogen source. The stirrer was then turned on to 900 - 1000 rpm. The heating was set to reach 110 °C. After the reactor contents reached between 100 - 110 °C, the catalyst and activator solutions were pushed in using high - pressure dry nitrogen. Timing was started when the catalyst was added to the reactor and allowed to proceed for 1 hour. After this period, heating and stirring were stopped, the pressure was released from the reactor, and the reactor was opened. After combining the products from several runs of this type, the product was filtered through to remove catalyst residues.

[0667] Oligomerization Example 5: Typical Co - oligomerization of C5 and C4 Using Catalyst A

[0668] For this example, 1-pentene and 1-butene were used. Catalyst A (26 mg) was dissolved in 9 mL of MCH and added to the rear section of the dual-feed tube. In the front section, M2HTH-D4 (0.8 mL of 10 wt% in MCH), tri-n-octylaluminum (100 μL), and MCH (8 mL) were combined and added. 300 mL of 1-pentene was added to the reactor using high-pressure nitrogen, followed by 250 mL of 1-butene; then the dual-feed tube was attached to the reactor and the nitrogen source. Then the stirrer was turned on to 900 - 1000 rpm. The heating was turned on to reach 110 °C. After the reactor reached between 100 - 110 °C, the catalyst and activator solution were pushed in using high-pressure dry molecular nitrogen. Timing was started when the catalyst was added to the reactor and allowed to proceed for 1 hour. After this period, the heating and stirring were stopped, the pressure was released from the reactor, and the reactor was opened and depressurized to expose the contents to air. The contents were poured into a pre-weighed container and the weight of the product was recorded. After combining the products from several runs of this type, the product was passed through filtration to remove catalyst residues.

[0669] Oligomerization Example 6: Typical co-oligomerization of VCH and C4 using Catalyst A

[0670] For this example, 4-vinylcyclohex-1-ene and 1-butene were used. Catalyst A (52 mg) was dissolved in 9 mL of MCH and added to the rear section of the dual-feed tube. In the front section, M2HTH-D4 (1.60 mL of 10 wt% in MCH), tri-n-octylaluminum (200 μL), and MCH (7 mL) were combined and added. 600 mL of VCH was added to the reactor using high-pressure dry molecular nitrogen, followed by 200 mL of 1-butene (through a dryer, as previously described); then the dual-feed tube was attached to the reactor and the nitrogen source. Then the stirrer was turned on to 900 - 1000 rpm. The heating was turned on to reach 110 °C. After the reactor reached between 100 - 110 °C, the catalyst and activator solution were pushed in using high-pressure dry nitrogen. Timing was started when the catalyst was added to the reactor and allowed to proceed for 1 hour. After this period, the heating and stirring were stopped, the pressure was released from the reactor, and the reactor was opened and depressurized to expose the contents to air. The contents were poured into a pre-weighed container and the weight of the product was recorded. After combining the products from several runs of this type, the product was passed through filtration to remove catalyst residues.

[0671] Oligomerization Example 7: Typical co-oligomerization of VCH and iC6 using Catalyst A

[0672] For this example, 4-vinylcyclohex-1-ene and 4-methylpent-1-ene were used. Catalyst A (22 mg) was dissolved in 9 mL of MCH and added to the rear section of the dual-feed pipe. In the front section, M2HTH-D4 (1.60 mL of 10 wt% in MCH), tri-n-octylaluminum (200 μL), and MCH (7 mL) were combined and added. 500 mL of VCH was added to the reactor using high-pressure nitrogen, followed by 500 mL of 4-methylpent-1-ene; then the dual-feed pipe was attached to the reactor and the nitrogen source. Then the stirrer was turned on to 900 - 1000 rpm. Heating was turned on to reach 110 °C. After the reactor reached between 100 - 110 °C, the catalyst and activator solution were pushed in using high-pressure dry molecular nitrogen. Timing was started when the catalyst was added to the reactor and allowed to proceed for 1 hour. After this period, heating and stirring were stopped. The elevated pressure was released from the reactor and the reactor was opened. The contents were poured into a pre-weighed container and the weight of the product was recorded. After adding together several runs, the product was passed through filtration to remove catalyst residues.

[0673] Oligomerization Example 8: Typical oligomerization of C5 using Catalyst A

[0674] For this example, 1-pentene was used. Catalyst A (26 mg) was dissolved in 9 mL of MCH and added to the rear section of the dual-feed pipe. In the front section, M2HTH-D4 (0.8 mL of 10 wt% in MCH) was combined with pure tri-n-octylaluminum (100 μL) and an additional 8 mL of MCH. 500 mL of 1-pentene was added to the reactor using high-pressure dry molecular nitrogen; then the dual-feed pipe was attached to the reactor and the nitrogen source. Then the stirrer was turned on to 900 - 1000 rpm and the temperature was set to 110 °C. After the reactor reached between 100 - 110 °C, the catalyst and activator solution were pushed in using high-pressure dry molecular nitrogen. Timing was started when the catalyst was added to the reactor and allowed to proceed for 1 hour. After this period, heating and stirring were stopped, the pressure was released from the reactor and the reactor was opened. After combining the products of several runs of this type, the product was passed through filtration to remove catalyst residues.

[0675] Oligomerization Example 9: Typical oligomerization of C4 using Catalyst A

[0676] For this example, 1-butene was used. Catalyst A (26 mg) was dissolved in 9 mL of MCH and added to the rear section of the dual-feed pipe. In the front section, M2HTH-D4 (0.8 mL of 10 wt% in MCH) was combined with pure tri-n-octylaluminum (200 μL) and an additional 7 mL of MCH. The 1-butene cylinder was passed through a line equipped with Q5 and A dryer of the desiccant mixture of molecular sieve is attached to the reactor. 1 L of 1-butene is charged into the reactor from a cylinder using high-pressure dry molecular nitrogen; then a double-feeding tube is attached to the reactor and the nitrogen source. After adding 1 L, the stirrer is turned on to 900 - 1000 rpm. The heating is turned on to reach 110 °C. After the reactor reaches the temperature (between 100 °C and 110 °C), the catalyst and activator solution are pushed into the reactor using high-pressure nitrogen. The timing starts when the catalyst is added to the reactor and is allowed to proceed for 1 hour. After this period, the heating and stirring are stopped, the excess pressure is released from the reactor, and the reactor is opened. The content is poured into a pre-weighed container and the weight of the product is recorded. After combining the products of several runs of this type, the product is passed through filtration to remove catalyst residues.

[0677] Oligomerization Example 10: Typical oligomerization of C4 using Catalyst C

[0678] For this example, 1-butene is used. Catalyst C (52 mg) is dissolved in 9 mL of MCH and added to the rear section of the double-feeding tube. In the front section, M2HTH-D4 (1.6 mL of 10 wt% in MCH) is combined with pure tri-n-octylaluminum (200 μL) and an additional 7 mL of MCH. The 1-butene cylinder is attached to the reactor via a dryer equipped with a desiccant mixture including Q5 and a molecular sieve. 1 L of 1-butene is charged into the reactor from a cylinder using high-pressure dry molecular nitrogen; then a double-feeding tube is attached to the reactor and the nitrogen source. After adding 1 L, the stirrer is turned on to 900 - 1000 rpm. The heating is turned on to reach 90 °C. After the reactor content reaches between 80 °C and 90 °C, the catalyst and activator solution are pushed into the reactor using high-pressure dry molecular nitrogen. The timing starts when the catalyst is added to the reactor and is allowed to proceed for 1 hour. After this period, the heating and stirring are stopped. The elevated pressure is released from the reactor and the reactor is opened. The content is poured into a pre-weighed container and the weight of the product is recorded. After combining the products of several runs of this type, the product is passed through filtration to remove catalyst residues.

[0679] Oligomerization Examples 11 - 15

[0680] For the catalyst addition in Examples 11 - 15, typically a dual cylinder (also known as a dual feed tube) consisting of two 25 mL SS Swagelok cylinders (with three SS Swagelok ball valves (one valve in the middle and one valve at each end)) is used. All catalysts, activators, and scavengers are handled in a nitrogen - purged dry box. For these examples, the catalyst and activator are premixed as an MCH solution and added to the front section of the feed tube. The rear section of the dual feed tube is typically filled with 10 mL of MCH to help flush the catalyst into the reactor. When attached to the reactor, the feed tube is oriented such that upon injection, the catalyst solution will be injected into the reactor first, followed by the solvent chaser. The scavenger solution is also prepared in the dry box and placed in a septum - sealed vial for delivery of the solution cannula to the reactor.

[0681] Oligomerization Example 11: Typical oligomerization of C6 using Catalyst A

[0682] For this example, 1 - hexene was used. Catalyst A (240 mg) was dissolved in 10 mL of MCH in a 20 mL glass vial. M2HTH - D4 (7.4 mL of 10 wt% in MCH) was added to the vial. Then the activated catalyst solution was transferred to one side of the dual feed tube. 10 mL of MCH was added to the other side of the dual feed tube. The scavenger solution was prepared by adding tri - n - octylaluminum (175 μL) to 15 mL of 1 - hexene in a 60 mL vial and then sealing it with a septum.

[0683] In a 2 L reactor, 1500 mL of dry 1 - hexene was pushed into the reactor with high - pressure nitrogen. The reactor was vented. The scavenger solution was cannulated into the reactor using low - pressure nitrogen (2 - 5 psi). Then the dual feed tube was connected to the reactor and the high - pressure nitrogen line. The stirrer was turned on to 400 rpm. The heating was turned on to reach 120 °C. After the reactor reached 110 °C, the catalyst solution and the solvent chaser were pushed into the reactor using high - pressure dry nitrogen. Timing was started after the catalyst was injected and allowed to proceed for 1 hour. After this period, the heating and stirring were stopped and the reactor was allowed to cool to approximately 60 °C. The reactor was vented and then opened. The contents were poured into a tared container and the weight was recorded (e.g., typical ~1200 g). Then the product was filtered by suction filtration to remove catalyst residues.

[0684] Oligomerization Example 12: Typical oligomerization of C8 using Catalyst A

[0685] For this example, 1-octene was used. Catalyst A (240 mg) was dissolved in 10 mL of MCH in a 20 mL glass vial. M2HTH-D4 (7.4 mL of 10 wt% in MCH) was added to the vial. Then the activated catalyst solution was transferred to one side of a dual-feed tube. 10 mL of MCH was added to the other side of the dual-feed tube. A scavenger solution was prepared by adding tri-n-octylaluminum (120 μL) to 15 mL of 1-octene in a 60 mL vial and then sealing it with a septum. Additionally, 1400 mL of 1-octene was transferred to a 2 L bottle and sealed with a septum while in the drying oven.

[0686] Into a 2 L reactor, 1-octene was transferred to the reactor through a conduit using low-pressure nitrogen (2 - 5 psi). Next, the scavenger solution was cannulated into the reactor using low-pressure nitrogen (2 - 5 psi). Then the dual-feed tube was connected to the reactor and the high-pressure nitrogen line. The stirrer was turned on to 400 rpm. The heating was turned on to reach 120 °C. After the reactor reached 110 °C, the catalyst solution and solvent tracer were pushed into the reactor using high-pressure dry nitrogen. Timing was started after the catalyst was injected and allowed to proceed for 1 hour. After this period, the heating and stirring were stopped and the reactor was allowed to cool to approximately 60 °C. The reactor was vented and then opened. The contents were poured into a tared container and the weight was recorded (e.g., typical ~900 g). Then the product was passed through suction filtration to remove catalyst residues.

[0687] Oligomerization Example 13: Typical co-oligomerization of C6 (25%) and C8 (75%) using Catalyst A

[0688] For this example, 1-hexene and 1-octene were used. Catalyst A (240 mg) was dissolved in 10 mL of MCH in a 20 mL glass vial. M2HTH-D4 (7.4 mL of 10 wt% in MCH) was added to the vial. Then the activated catalyst solution was transferred to one side of a dual-feed tube. 10 mL of MCH was added to the other side of the dual-feed tube. 1-Octene (1000 mL) and tri-n-octylaluminum (120 μL) were added to a 2 L glass bottle and sealed with a septum. 1-Hexene (333 mL) was added to a 1 L glass bottle and sealed with a septum.

[0689] Into a 2 L reactor, 1-octene / tri-n-octylaluminum was transferred to the reactor through a conduit using low-pressure nitrogen (2 - 5 psi). Next, 1-hexene was cannulated into the reactor using low-pressure nitrogen (2 - 5 psi). Then, a dual feed tube was connected to the reactor and the high-pressure nitrogen pipeline. The stirrer was turned on to 400 rpm. The heating was turned on to reach 120 °C. After the reactor reached 110 °C, the catalyst solution and the solvent tracer were pushed into the reactor using high-pressure dry nitrogen. Timing was started after the catalyst was injected and allowed to proceed for 1 hour. After this period, the heating and stirring were stopped and the reactor was allowed to cool to approximately 60 °C. The reactor was vented and then opened. The contents were poured into a tared container, and the weight was recorded (e.g., typical ~900 g). Then the product was passed through suction filtration to remove catalyst residues.

[0690] Oligomerization Example 14: Typical co-oligomerization of C6 (50%) and C8 (50%) using Catalyst A

[0691] For this example, 1-hexene and 1-octene were used. Catalyst A (240 mg) was dissolved in 10 mL of MCH in a 20 mL glass vial. M2HTH-D4 (7.4 mL of 10 wt% in MCH) was added to the vial. Then the activated catalyst solution was transferred to one side of the dual feed tube. 10 mL of MCH was added to the other side of the dual feed tube. 1-octene (600 mL) and tri-n-octylaluminum (120 μL) were added to a 2 L glass bottle and sealed with a septum. 1-hexene (600 mL) was added to a 1 L glass bottle and sealed with a septum.

[0692] Into a 2 L reactor, 1-octene / tri-n-octylaluminum was transferred to the reactor through a conduit using low-pressure nitrogen (2 - 5 psi). Next, 1-hexene was cannulated into the reactor using low-pressure nitrogen (2 - 5 psi). Then, a dual feed tube was connected to the reactor and the high-pressure nitrogen pipeline. The stirrer was turned on to 400 rpm. The heating was turned on to reach 120 °C. After the reactor reached 110 °C, the catalyst solution and the solvent tracer were pushed into the reactor using high-pressure dry nitrogen. Timing was started after the catalyst was injected and allowed to proceed for 1 hour. After this period, the heating and stirring were stopped and the reactor was allowed to cool to approximately 60 °C. The reactor was vented and then opened. The contents were poured into a tared container, and the weight was recorded (e.g., typical ~820 g). Then the product was passed through suction filtration to remove catalyst residues.

[0693] Oligomerization Example 15: Typical co-oligomerization of C6 (75%) and C8 (25%) using Catalyst A

[0694] For this example, 1-hexene and 1-octene were used. Catalyst A (240 mg) was dissolved in 10 mL of MCH in a 20 mL glass vial. M2HTH-D4 (7.4 mL of 10 wt% in MCH) was added to the vial. Then the activated catalyst solution was transferred to one side of a dual-feed tube. 10 mL of MCH was added to the other side of the dual-feed tube. 1-Hexene (1000 mL) and tri-n-octylaluminum (120 μL) were added to a 2 L glass bottle and sealed with a septum. 1-Octene (333 mL) was added to a 1 L glass bottle and sealed with a septum.

[0695] Into a 2 L reactor, 1-hexene / tri-n-octylaluminum was transferred into the reactor through a conduit using low-pressure nitrogen (2 - 5 psi). Next, 1-octene was cannulated into the reactor using low-pressure nitrogen (2 - 5 psi). Then the dual-feed tube was connected to the reactor and the high-pressure nitrogen pipeline. The stirrer was turned on to 400 rpm. The heating was turned on to reach 120 °C. After the reactor reached 110 °C, the catalyst solution and the solvent tracer were pushed into the reactor using high-pressure dry nitrogen. Timing was started after the catalyst was injected and allowed to proceed for 1 hour. After this period, the heating and stirring were stopped and the reactor was allowed to cool to about 60 °C. The reactor was vented and then opened. The contents were poured into a tared container and the weight was recorded (e.g., typical ~920 g). Then the product was passed through suction filtration to remove catalyst residues.

[0696] Oligomerization Examples 16 - 20

[0697] For Examples 16 - 20, the batch oligomerization reaction was carried out in a N2-purged glove box in a 2 L Ace glass jacketed reactor equipped with a paddle stirrer, an internal thermocouple, and inlets for introducing monomers, precatalyst, and activator. Before use, the reactor was cleaned with anhydrous toluene and dried by heating at 120 °C under a dry nitrogen stream for 1 hour. The monomers and solvents were purified by passing through an activated basic alumina column (50 g 氧化铝 / L 单体 ), degassed by purging with nitrogen for 1 hour (1 L N2 / min), and dried over activated molecular sieves and AZ300 for at least 12 hours.

[0698] Oligomerization Example 16: Typical co-oligomerization of C8 and VCH using Catalyst A

[0699] For this example, 1-octene and 4-vinylcyclohexene were used. VCH (600 mL, 498 g, 4.61 mol) and 1-octene (600 mL, 429 g, 3.82 mol) were added to the reactor, and the resulting mixture was heated to an internal temperature of 110 °C while stirring at 400 rpm. Then tri-n-octylaluminum (0.24 mL, 0.197 g, 0.5 mmol) was added as a scavenger. Separately, in a 20 mL scintillation vial, catalyst A (240 mg, 0.432 mmol) was dissolved in MCH (3.3 mL), and then activated by adding a solution of M2HTH-D4 (10 wt% in MCH, 6.7 mL, 0.436 mmol). After stirring the resulting mixture for 1 min, the solution was added to the reactor in 0.5 mL or 1 mL increments. The exothermic reaction caused the temperature to rise rapidly, so each addition was delayed 5 - 30 min until the reaction temperature dropped below 125 °C. To promote heterodimer formation, after each injection of the catalyst, an additional portion of 1-octene (400 mL, 280 g, 2.55 mol) was added to the reactor in 50 mL increments. Over the course of 1.5 h, all of the catalyst and 1-octene were added, and the reaction mixture was stirred for an additional 1 h. The contents of the reactor were collected and then filtered through an activated basic alumina column to give approximately 1.6 L of a colorless liquid.

[0700] Oligomerization Example 17: Typical co-oligomerization of C9 and VCH using Catalyst A

[0701] For this example, 1-nonene and 4-vinylcyclohexene were used. VCH (500 mL, 415 g, 3.84 mol) and 1-nonene (50 mL, 37.17 g, 0.294 mol) were added to the reactor, and the resulting mixture was heated to an internal temperature of 120 °C while stirring at 400 rpm. Then tri-n-octylaluminum (0.12 mL, 0.99 g, 0.25 mmol) was added as a scavenger. Separately, in a 20 mL scintillation vial, catalyst A (120 mg, 0.216 mmol) was dissolved in MCH (5.0 mL), and then activated by adding a solution of M2HTH-D4 (10 wt% in MCH, 3.4 mL, 0.218 mmol). After stirring the resulting mixture for 1 min, the solution was added to the reactor in 0.5 mL or 1 mL increments. The exothermic reaction caused the temperature to rise rapidly, so each catalyst addition was delayed by 5 - 30 min until the reaction temperature dropped below 125 °C. To promote the formation of the heterodimer, after each injection of the catalyst, an additional portion of 1-nonene (750 mL, 557 g, 4.41 mol) was added to the reactor in two 200 mL increments and one 150 mL increment. Over the course of 1.5 h, all of the catalyst and 1-nonene were added, and the reaction mixture was stirred for an additional 1 h. The contents of the reactor were collected and then filtered through an activated basic alumina column to give approximately 1.3 L of a colorless liquid.

[0702] Oligomerization Example 18: Typical co-oligomerization of C10 and VCH using Catalyst A

[0703] For this example, 1-decene and 4-vinylcyclohexene. VCH (500 mL, 415 g, 3.84 mol) and 1-decene (100 mL, 74 g, 0.53 mol) were added to a reactor, and the resulting mixture was heated to an internal temperature of 120 °C while stirring at 400 rpm. Then tri-n-octylaluminum (0.24 mL, 0.197 g, 0.5 mmol) was added as a scavenger. Separately, in a 20 mL scintillation vial, catalyst A (240 mg, 0.432 mmol) was dissolved in MCH (3.3 mL), and then activated by adding a solution of M2HTH-D4 (10 wt% in MCH, 6.7 mL, 0.436 mmol). After stirring the resulting mixture for 1 min, the solution was added to the reactor in 0.5 mL or 1 mL increments. The exothermic reaction caused the temperature to rise rapidly, so each catalyst addition was delayed by 5 - 30 min until the reaction temperature dropped below 125 °C. To promote the formation of the heterodimer, after each injection of the catalyst, an additional portion of 1-decene (800 mL, 592 g, 4.22 mol) was added to the reactor in 200 mL increments. Over the course of 1.5 h, all of the catalyst and 1-decene were added, and the reaction mixture was stirred for an additional 1 h. The contents of the reactor were collected and then filtered through an activated basic alumina column to give approximately 1.4 L of a colorless liquid.

[0704] Oligomerization Example 19: Typical Oligomerization of VCH Using Catalyst E

[0705] For this example, 4-vinylcyclohexene was used. VCH (1500 mL, 1245 g, 11.52 mol) was added to a reactor, and the resulting mixture was heated to an internal temperature of 120 °C while stirring at 400 rpm. Then tri-n-octylaluminum (1.05 mL, 0.861 g, 2.30 mmol) was added as a scavenger. Separately, in a 20 mL scintillation vial, catalyst E (310 mg, 0.697 mmol) was dissolved in toluene (10 mL), and then activated by adding a solution of M2HTH-D4 (10 wt% in MCH, 11.25 mL, 0.729 mmol). After stirring the resulting mixture for 30 min, the solution was added to the reactor in 1.5 mL or 3 mL increments. The exothermic reaction caused the temperature to rise rapidly, so each catalyst addition was delayed by 5 - 30 min until the reaction temperature dropped below 125 °C. Over the course of 1.5 h, all of the catalyst was added, and the reaction mixture was stirred for an additional 0.8 h. The contents of the reactor were collected and then filtered through an activated basic alumina column to give approximately 1.5 L of a colorless liquid.

[0706] Oligomerization Example 20: Typical Oligomerization of VCH Using Catalyst A

[0707] For this example, 4-vinylcyclohexene was used. VCH (1000 mL, 830 g, 7.685 mol) was added to the reactor and the resulting mixture was heated to an internal temperature of 110 °C while stirring at 400 rpm. Then tri-n-octylaluminum (1.1 mL, 0.902 g, 2.50 mmol) was added as a scavenger. Separately, in a 20 mL scintillation vial, catalyst A (400 mg, 0.721 mmol) was dissolved in MCH (8.3 mL) and the resulting mixture was premixed with activator M2HTH-D4 (10 wt% in MCH, 11.7 mL, 0.758 mmol). The resulting mixture was stirred for 1 min and then the first portion of the activated catalyst solution (ca. 3 mL) was injected into the reactor. Then the catalyst solution was added in small increments (1.5 - 3.0 mL) over 2.5 h, causing the temperature to rise to 120 °C and delaying the next injection for 10 - 20 min until the temperature reached ~117 °C. A second catalyst portion was prepared as above and then similarly injected in increments, causing the reaction to slowly turn dark orange / brown. As more catalyst was added, the exothermic response became less pronounced. After all of the second portion of the catalyst had been added over 2.5 h, the reaction mixture was stirred for an additional 45 min. Then the contents were removed from the reactor and passed through an activated basic alumina column.

[0708] Oligomerization Example 21: Oligomerization of VCB to But-3-ene-1,3-diylbicyclobutane Using Catalyst E

[0709] A 20 mL pressure-resistant flask was charged with vinylcyclobutane (9.70 g, 118 mmol) and tri-n-octylaluminum (56 mg, 0.153 mmol). Separately, a solution of catalyst E (20 mg, 0.045 mmol) in toluene (3 mL) was mixed with activator M2HTH-D4 (10 wt% in methylcyclohexane, 0.72 mL, 0.0465 mmol). The resulting mixture was added to the vinylcyclobutane and the flask was sealed and heated to 130 °C. The reaction mixture was stirred for 3 h. Then the system was cooled to ambient temperature and the reaction mixture was filtered through alumina to give a yellow liquid which was used for hydrogenation.

[0710] Hydrogenation Example 22: Hydrogenation of But-3-ene-1,3-diylbicyclobutane to Butane-1,3-diylbicyclobutane

[0711] In a pressure-resistant flask, the reaction mixture obtained in the previous Example 21 was hydrogenated at 125 °C under 40 psi H2 over Pd / C (50 mg, 10 wt%) for 4 h. Then, toluene and methylcyclohexane were removed by distillation at ambient pressure (ca. 1.5 mL), and the residue was distilled under reduced pressure (0.5 - 1.0 mTorr). The collected product (bp 45 °C - 50 °C, 1.04 g) was further re-hydrogenated at 125 °C under 200 psi H2 for 4 h to remove trace unsaturation.

[0712] Oligomerization Example 23: Oligomerization of vinylcyclohexane using Catalyst E

[0713] For this example, only one monomer was used: 4-vinylcyclohexane. 4-Vinylcyclohexane was purchased from TCI chemicals, purified by purging with nitrogen, and stored on activated molecular sieves and AZ300. 4-Vinylcyclohexane (20.6 g, 187 mmol) and tri-n-octylaluminum (17.1 μL, 14 mg, 0.0382 mmol) were combined in a 50 mL pressure-resistant flask. Separately, in a 20 mL scintillation vial, Catalyst E (10 mg, 0.0225 mmol) was dissolved in methylcyclohexane (2 mL), and the resulting mixture was further premixed with activator M2HTH-D4 (10 wt% in MCH, 0.35 mL, 0.0232 mmol). The resulting mixture was stirred for 1 min and then added to vinylcyclohexane. The flask was then sealed and heated to 136 °C. The reaction mixture was stirred for 2 h, then cooled and exposed to air. The contents were removed from the flask and passed through an activated basic alumina column to give a colorless liquid.

[0714] Hydrogenation Example 24: Hydrogenation of but-3-ene-1,3-diyl dicyclohexane to butane-1,3-diyl dicyclohexane

[0715] The reaction mixture (15 g) obtained in the previous Example 23 was added to a Parr reactor containing a hydrogenation catalyst (NiSat, 2 wt%, 300 mg) and 50 mL of hexane. The reactor was sealed and purged with N2 for 10 min. Next, it was heated to 232 °C and pressurized with hydrogen (650 psi H2). The reaction mixture was stirred at 400 rpm for 2 h and then cooled to ambient temperature. Then, the catalyst was filtered off under anaerobic conditions, and hexane and other low-boiling components were evaporated to give ca. 15 g of a completely saturated (based on 1 1H NMR) colorless liquid, which consisted of 88% of butane-1,3-diyl dicyclohexane according to GC analysis.

[0716] 1 1H NMR (400 MHz, C6D6): δ 1.75 - 1.57 (m, 9H), 1.37 (m, 1H), 1.28 - 1.10 (m, 11H), 1.08 - 0.87 (m, 4H), 0.84 (d, J HH = 6.7 Hz, 3H). 13 13C NMR (101 MHz, C6D6): δ 42.83, 38.39, 38.16, 35.49, 33.70, 33.36, 31.34, 30.76, 28.69, 27.03, 26.94, 26.90, 26.82, 26.55, 26.52, 16.02.

[0717] Oligomerization Example 39 (Comparative): Oligomerization of VCH Using Catalyst F

[0718] For this example, 4-vinylcyclohexene was used. VCH (500 mL, 415 g, 3.84 mol) was added to the reactor, and the resulting mixture was heated to an internal temperature of 115 °C while stirring at 400 rpm. Then triisobutylaluminum (2.83 mL, 2.22 g, 11.2 mmol) was added as a scavenger. Separately, in a 20 mL scintillation vial, catalyst F (225 mg, 0.770 mmol) was dissolved in toluene (4 mL), triisobutylaluminum (2.0 mL, 1.57 g, 7.93 mmol) was added slowly, followed by a solution of M2HTH-D4 (10 wt.% in MCH, 13.1 mL, 0.849 mmol). After stirring the resulting catalyst solution for 10 min, 2 mL of the catalyst solution was added to the reactor, followed by addition in ~2 mL increments over the next hour until all of the catalyst solution was added. The addition was carried out such that the temperature of the reactor was maintained between 115 °C and 120 °C. After the final catalyst addition, the reaction was allowed to stir for an additional 4.5 hours. After this time, the mixture was quenched with several mL of isopropanol and then filtered through diatomaceous earth to give approximately 0.5 L of a colorless liquid.

[0719] Oligomerization Example 40 (Comparative): Oligomerization of VCH Using Catalyst F

[0720] For this example, 4-vinylcyclohexene was used. VCH (500 mL, 415 g, 3.84 mol) was added to the reactor and the resulting mixture was heated to an internal temperature of 50 °C while stirring at 400 rpm. Then triisobutylaluminum (20.0 mL, 15.7 g, 79.3 mmol) was added as a scavenger. Separately, in a 20 mL scintillation vial, catalyst F (560 mg, 1.92 mmol) was dissolved in toluene (3.0 mL) and triisobutylaluminum (5.0 mL, 3.93 g, 19.8 mmol) was added slowly to form a yellow solution. When the reactor reached 48 °C, the catalyst solution was added to the reactor, followed by a solution of M2HTH-D4 (10 wt.% in MCH, 30 mL, 1.94 mmol). After addition of the catalyst components, the solution was slowly warmed to 54 °C and the color changed to dark orange. With stirring, the temperature of the reactor was maintained at ~50 °C for a total of 5 hours. After that, the reactor contents were quenched with methanol (30 ml) added slowly as the reaction was exothermic and generated heat, volatiles, and precipitate. In 50 ml portions, the quenched reactor product was added to a separatory funnel and washed with 1 M HCL (3 x 25 ml), deionized water (2 x 25 ml), and brine (3 x 25 ml). After washing, the organic layer (turbid solution) was collected and dried over MgSO4. Then it was passed through diatomaceous earth and activated basic alumina.

[0721] GC-MS Characterization of the Batch Oligomerization Reaction Mixture

[0722] Qualitative measurements were obtained by the relative peak area % of the contents of the reaction mixture using an Agilent 7890 GC with a 5977B Inert Plus MSD Turbo EI / CI. The following parameters were used:

[0723]

[0724]

[0725] Samples were prepared by diluting 50 μL of nonane or undecane (standards) into 500 μL of reaction sample and 500 μL of isooctane. A mixture of homodimers (A-A, B-B), heterodimers (A-B) was observed and in some experiments, homotrimers (A-A-A, B-B-B) and heterotrimers (Ax2-B, Bx2+A) were observed. For some experiments, homotetramers and heterotetramers were also observed. For the heterotrimers and heterotetramers, the order of the monomer units could not be distinguished, e.g., A-A-B vs A-B-A vs B-A-A. The following table presents the heterotrimers in the form Ax2-B. The heterotetramers are presented in a similar form, e.g., Ax2-Bx2. Each peak of the components separated by mass discrimination was then quantified by calculating the amount of each component using the following equation based on the area of each peak relative to the total area of all peaks to obtain the qualitative wt% of the sample, where "standard area" is the peak area of nonane (C9) or undecane (C11), depending on the standard used:

[0726]

[0727] Or in embodiments where no standard was added to the sample, the following equation was used

[0728]

[0729] From the GC chromatogram, the reported retention peak is the peak retention time. This number may vary somewhat from sample to sample based on column conditions. Peaks less than 1.5% are typically excluded from the calculations.

[0730] The products from the batch polymerization reactor runs (typically 12 - 16 runs) were combined into batches of the same composition to obtain amounts of 3 - 4 gallons and stored under ambient conditions until further processing. Methylcyclohexane (MCH) in the samples originated from the solvent used to deliver the catalyst and / or activator to the reactor.

[0731] For homopolymerization oligomerization, the monomer conversion percentages to dimers and trimers are calculated as the sum of the areas of all dimer and trimer peaks multiplied by 100 and then divided by the sum of the areas of all non-solvent and non-GC standard peaks (if present). The monomer conversion percentage to all dimer products is calculated as the sum of the areas of all dimer peaks multiplied by 100 and then divided by the sum of the areas of all non-solvent and non-GC standard peaks (if present). The monomer conversion percentage to a single dimer (the dimer isomer with the largest peak area) is calculated as the area of the largest dimer peak multiplied by 100 and then divided by the sum of the areas of all non-solvent and non-GC standard peaks (if present). The selectivity percentage for dimer formation relative to trimer formation is calculated as the sum of the areas of all dimer peaks multiplied by 100 and then divided by the sum of the areas of all dimer and trimer peaks. Based on the total dimers formed, the selectivity percentage for forming one dimer species (one isomer) is calculated as the sum of the areas of the largest dimer peaks multiplied by 100 and then divided by the sum of the areas of all dimer peaks. GC Characterization Example 1: C6 and VCH co-oligomerization obtained using Catalyst A

[0732] Chromatograms of the oligomerization products of 1-hexene (C6) and 4-vinyl-cyclohex-1-ene (VCH) using Catalyst A were obtained. Table 1A outlines the composition of the samples, and Table 1B summarizes the product composition.

[0733] Table 1A.

[0734]

[0735] Table 1B.

[0736]

[0737]

[0738] GC Characterization Example 2: C7 and VCH co-oligomerization obtained using Catalyst A GC

[0739] Chromatograms of the oligomerization products of 1-heptene (C7) and 4-vinyl-cyclohex-1-ene (VCH) using Catalyst A were obtained. Table 2A outlines the composition of the samples, and Table 2B summarizes the product composition.

[0740] Table 2A.

[0741]

[0742] Table 2B.

[0743] Identification ％ C7-C7 dimer 21.1 VCH-C7 (dimer) 42.6 VCH-VCH dimer 24.31 C7-C7-C7 (trimer) 4.72 VCH-C7x2 (trimer) 7.28 All dimers 88.00 All trimers 12.00

[0744] GC Characterization Example 3: Co-oligomerized C5 and VCH Obtained Using Catalyst A

[0745] The chromatogram of the oligomerization product of 1-pentene (C5) and 4-vinyl-cyclohex-1-ene (VCH) obtained using Catalyst A was obtained. Table 3A outlines the composition of the sample, and Table 3B summarizes the product composition.

[0746] Table 3A.

[0747]

[0748] Table 3B.

[0749] Identification ％ C5 (dimer) 26.7 VCH-C5 (dimer) 54.5 VCH-VCH (dimer) 18.8 All dimers 100.0 All trimers 0.0

[0750] GC Characterization Example 4: Oligomerized iC6 Obtained Using Catalyst D

[0751] The chromatogram of the oligomerization product of 4-methyl-1-pentene (iC6) obtained using Catalyst D was obtained. Table 4A outlines the composition of the sample, and Table 4B summarizes the product composition.

[0752] Table 4A.

[0753]

[0754] Table 4B.

[0755] Identification ％ iC6-iC6 (dimer) 77.1 iC6-iC6-iC6 (trimer) 14.0 iC6-iC6-iC6-iC6 (tetramer) 8.8

[0756] GC Characterization Example 5: Co-oligomerized C5 and C4 Obtained Using Catalyst A

[0757] The chromatogram of the oligomerization product of 1-butene (C4) and 1-pentene (C5) obtained using Catalyst A was obtained. Table 5A outlines the composition of the sample, and Table 5B summarizes the product composition.

[0758] Table 5A.

[0759]

[0760] Table 5B.

[0761]

[0762]

[0763] GC Characterization Example 6: Co-oligomerized VCH and C4 Obtained Using Catalyst A

[0764] The chromatogram of the oligomerization product of (1-butene) C4 and 4-vinyl-cyclohex-1-ene (VCH) using catalyst A was obtained. Table 6A outlines the composition of the sample, and Table 6B summarizes the product composition.

[0765] Table 6A.

[0766]

[0767] Table 6B.

[0768]

[0769]

[0770] GC Characterization Example 7: Co-oligomerized VCH and iC6 obtained using catalyst A

[0771] The chromatogram of the oligomerization product of 4-methylpent-1-ene (iC6) and 4-vinyl-cyclohex-1-ene (VCH) using catalyst A was obtained. Table 7A outlines the composition of the sample, and Table 7B summarizes the product composition.

[0772] Table 7A.

[0773]

[0774] Table 7B.

[0775] Identification ％ iC6-iC6 (dimer) 28.5 VCH-iC6 (dimer) 50.4 iC6-iC6-iC6 (trimer) 4.3 VCH-VCH (dimer) 7.7 VCH-iC6x2 (trimer) 7.0 iC6-iC6-iC6-iC6 (tetramer) 2.1 All dimers 86.6 All trimers 11.3 All tetramers 2.1

[0776] GC Characterization Example 8: Oligomerized C5 obtained using catalyst A

[0777] The chromatogram of the oligomerization product of 1-pentene (C5) using catalyst A was obtained. Table 8A outlines the composition of the sample, and Table 8B summarizes the product composition.

[0778] Table 8A.

[0779]

[0780] Table 8B.

[0781] Identification ％ C5-C5 (dimer) 56.6 C5-C5-C5 (trimer) 32.6 C5-C5-C5-C5 (tetramer) 10.9

[0782] GC Characterization Example 9: Oligomerized C4 obtained using catalyst A

[0783] The chromatogram of the oligomerization product of 1-butene (C4) using catalyst A was obtained. Table 9A outlines the composition of the sample, and Table 9B summarizes the product composition.

[0784] Table 9A.

[0785]

[0786] Table 9B.

[0787] Identification ％ C4-C4 (dimer) 63.8 C4-C4-C4 (trimer) 26.6 C4-C4-C4-C4 (tetramer) 9.5

[0788] GC Characterization Example 10: Oligomeric C4 Obtained Using Catalyst C

[0789] The chromatogram of the oligomerization product of 1-butene (C4) in the case of catalyst C was obtained. Table 10A outlines the composition of the sample, and Table 10B summarizes the product composition.

[0790] Table 10A.

[0791]

[0792] Table 10B.

[0793] Identification ％ C4-C4 (dimer) 34.0 C4-C4-C4 (trimer) 28.9 C4-C4-C4-C4 (tetramer) 21.4 Other oligomers 15.8

[0794] GC Characterization Example 11: Oligomeric C6 Obtained Using Catalyst A

[0795] The chromatogram of the oligomerization product of 1-hexene (C6) using catalyst A was obtained. Table 11A outlines the composition of the sample, and Table 11B summarizes the product composition.

[0796] Table 11A.

[0797]

[0798] Table 11B.

[0799] Identification ％ C6-C6 (dimer) 72.5 C6-C6-C6 (trimer) 21.6 C6-C6-C6-C6 (tetramer) 5.8

[0800] GC Characterization Example 12: Oligomeric C8 Obtained Using Catalyst A

[0801] The chromatogram of the oligomerization product of 1-octene (C8) using catalyst A was obtained. Table 12A outlines the composition of the sample, and Table 12B summarizes the product composition.

[0802] Table 12A.

[0803]

[0804] Table 12B.

[0805] Identification ％ C8-C8 (dimer) 76.1 C8-C8-C8 (trimer) 23.9

[0806] GC Characterization Example 13: Co-oligomerized C6 (25%) and C8 (75%) Obtained Using Catalyst A

[0807] The chromatogram of the oligomerization product of 1-hexene (C6) and 1-octene (C8) obtained using Catalyst A was obtained. Table 13A outlines the composition of the sample, and Table 13B summarizes the product composition.

[0808] Table 13A.

[0809]

[0810] Table 13B.

[0811]

[0812]

[0813] GC Characterization Example 14: Co-oligomerized C6 (50%) and C8 (50%) Obtained Using Catalyst A

[0814] The chromatogram of the oligomerization product of 1-hexene (C6) and 1-octene (C8) obtained using Catalyst A was obtained. Table 14A outlines the composition of the sample, and Table 14B summarizes the product composition.

[0815] Table 14A.

[0816]

[0817] Table 14B.

[0818]

[0819]

[0820] GC Characterization Example 15: Co-oligomerized C6 (75%) and C8 (25%) Obtained Using Catalyst A

[0821] The chromatogram of the oligomerization product of 1-hexene (C6) and 1-octene (C8) obtained using Catalyst A was obtained. Table 15A outlines the composition of the sample, and Table 15B summarizes the product composition.

[0822] Table 15A.

[0823]

[0824] Table 15B.

[0825] Identification ％ C6-C6 (dimer) 34.2 C6-C8 (dimer) 32.8 C8-C8 (dimer) 6.8 C6-C6-C6 (trimer) 8.1 C8-C6x2 (trimer) 9.4 C6-C8x2 (trimer) 3.2 C6-C6-C6-C6 (tetramer) 1.6 C8-C8-C8 (trimer) 2.6 Other oligomers 1.2 All dimers 73.8 All trimers 23.3 All tetramers 1.6 All other oligomers 1.2

[0826] GC Characterization Example 16: Co - oligomerized C8 and VCH Obtained Using Catalyst A

[0827] The chromatogram of the oligomerization product of 1 - octene (C8) and 4 - vinyl - cyclohex - 1 - ene (VCH) obtained using catalyst A was obtained. Table 16A outlines the composition of the sample, and Table 16B summarizes the product composition.

[0828] Table 16A.

[0829]

[0830]

[0831] Table 16B.

[0832] Identification ％ C8-C8 (dimer) 32.1 VCH-C8 (dimer) 49.6 VCH-VCH (dimer) 1.3 C8-C8-C8 (trimer) 6.0 VCH-C8x2 (trimer) 8.3 Other oligomers 2.7 All dimers 83.0 All trimers 14.3 All other oligomers 2.7

[0833] GC Characterization Example 17: Co - oligomerized C9 and VCH Obtained Using Catalyst A

[0834] The chromatogram of the oligomerization product of 1 - nonene (C9) and 4 - vinyl - cyclohex - 1 - ene (VCH) obtained using catalyst A was obtained. Table 17A outlines the composition of the sample, and Table 17B summarizes the product composition.

[0835] Table 17A.

[0836]

[0837] Table 17B.

[0838]

[0839]

[0840] GC Characterization Example 18: Co - oligomerized C10 and VCH Obtained Using Catalyst A

[0841] The chromatogram of the oligomerization product of 1 - decene (C10) and 4 - vinyl - cyclohex - 1 - ene (VCH) using catalyst A. Table 18A outlines the composition of the sample, and Table 18B summarizes the product composition.

[0842] Table 18A.

[0843]

[0844] Table 18B.

[0845]

[0846]

[0847] GC Characterization Example 19: Oligomeric VCH Obtained Using Catalyst E

[0848] The chromatogram of the oligomeric product of 4-vinyl-cyclohex-1-ene (VCH) obtained using catalyst E was obtained. Table 19A outlines the composition of the sample, and Table 19B summarizes the product composition. Based on GC-MS analysis, the conversion of VCH to dimers and trimers was 90.6%, the conversion of VCH to all dimer products was 81.3%, and the conversion of VCH to the single dimer (the dimer isomer with the largest peak area) was 65.1%. Based on the total dimers formed, the selectivity for forming dimers relative to trimers was 89.8%, and the selectivity for forming one dimer species (one isomer) was 80.0%.

[0849] Table 19A.

[0850]

[0851] Table 19B.

[0852]

[0853]

[0854] GC Characterization Example 20: Oligomeric VCH Obtained Using Catalyst A

[0855] The chromatogram of the oligomeric product of 4-vinyl-cyclohex-1-ene (VCH) obtained using catalyst A was obtained. Table 20A outlines the composition of the sample, and Table 20B summarizes the product composition. Based on GC-MS analysis, the conversion of VCH to dimers was 96.2% (trimers were not observed), the conversion of VCH to all dimer products was 96.2%, and the conversion of VCH to the single dimer (the dimer isomer with the largest peak area) was 94.5%. Based on the total dimers formed, the selectivity for forming dimers relative to trimers was 100%, and the selectivity for forming one dimer species (one isomer) was 98.2%.

[0856] Table 20A.

[0857]

[0858] Table 20B.

[0859] Identification ％ VCH-VCH (dimer) 100.0

[0860] GC Characterization Example 21: Oligomerization of VCB to 3-butene-1,3-diylbicyclobutane using Catalyst E

[0861] The chromatogram of the oligomerization product of 4-vinylcyclobutane (VCB) using Catalyst E was obtained. Table 21A outlines the composition of the sample, and Table 21B summarizes the product composition. Based on GC-MS analysis, the conversion of VCB to dimers, trimers, and higher oligomers was 98.1%, the conversion of VCB to all dimer products was 50.4%, and the conversion of VCB to a single dimer (the dimer isomer with the largest peak area) was 37.1%. Based on the total dimers formed, the selectivity for forming dimers relative to trimers and higher oligomers was 51.4%, and the selectivity for forming one dimer species (one isomer) was 73.7%.

[0862] Table 21A.

[0863]

[0864] Table 21B.

[0865] Identification ％ VCB-VCB (dimer) 51.4 VCB-VCB-VCB (trimer) 35.1 VCB oligomers 13.5

[0866] GC Characterization Example 22: Hydrogenation of But-3-ene-1,3-diyl Dicyclobutane to Butane-1,3-diyl Dicyclobutane

[0867] The chromatogram of the hydrogenation product of 3-butene-1,3-diylbicyclobutane using Catalyst E was obtained. Table 22A outlines the composition of the sample, and Table 22B summarizes the product composition.

[0868] Table 22A.

[0869]

[0870] Table 22B.

[0871] Identification ％ Hydrogenated VCB-VCB (Dimer) 100.0

[0872] GC Characterization Example 23: Oligomerization of Vinylcyclohexane to But-3-ene-1,3-diyl Dicyclo Hexane Obtained Using Catalyst E

[0873] A chromatogram of the oligomerization product of 4-vinylcyclohexane (vch) using catalyst E was obtained. Table 23A outlines the composition of the sample, and Table 23B summarizes the product composition. Based on the GC sample composition, the vinylcyclohexane conversion was 98%. Based on GC-MS analysis, the conversion of vch to dimers and trimers was 92.7%, the conversion of vch to all dimer products was 88.1%, and the conversion of vch to the single dimer (the dimer isomer with the largest peak area) was 85.1%. Based on the total dimers formed, the selectivity for forming dimers relative to trimers was 95.0%, and the selectivity for forming one dimer species (one isomer) was 96.6%.

[0874] Table 23A.

[0875]

[0876]

[0877] Table 23B.

[0878] Identification ％ vch-vch (Dimer) 95.0 vch-vch-vch (Trimer) 5.0

[0879] GC Characterization Example 24: Hydrogenation of But-3-ene-1,3-diyl Dicyclohexane to Butane-1,3-diyl Dicyclohexane

[0880] A chromatogram of the hydrogenation product of but-3-ene-1,3-diyl dicyclohexane using catalyst E was obtained. Table 24A outlines the composition of the sample, and Table 24B summarizes the product composition.

[0881] Table 24A.

[0882]

[0883] Table 24B.

[0884] Identification ％ Hydrogenated Dimer 94.4 Hydrogenated Trimer 5.6

[0885] GC Characterization Example 39 (Comparison): Oligomerization of VCH Using Catalyst F

[0886] A chromatogram of the oligomerization product of 4-vinyl-cyclohex-1-ene (VCH) using catalyst F was obtained. Table 39A outlines the composition of the sample, and Table 39B summarizes the product composition. Based on GC-MS analysis, the conversion of VCH to dimers and trimers was 41.2%, the conversion of VCH to all dimer products was 36.6%, and the conversion of VCH to the single dimer (the dimer isomer with the largest peak area) was 28.1%. Based on the total dimers formed, the selectivity for forming dimers relative to trimers was 89.0%, and the selectivity for forming one dimer species (one isomer) was 76.7%.

[0887] Table 39A.

[0888]

[0889]

[0890] Table 39B.

[0891] Identification ％ VCH-VCH (Dimer) 89.0 VCH-VCH-VCH (Trimer) 11.0

[0892] GC Characterization Example 40 (Comparison): Oligomerization of VCH Using Catalyst F

[0893] The chromatogram of the oligomerization product of 4-vinyl-cyclohex-1-ene (VCH) using catalyst F was obtained. Table 40A outlines the composition of the sample, and Table 40B summarizes the product composition. Based on GC-MS analysis, the conversion of VCH to dimers and trimers is 32.4%, the conversion of VCH to all dimer products is 30.0%, and the conversion of VCH to the single dimer (the dimer isomer with the largest peak area) is 15.5%. Based on the total dimers formed, the selectivity for forming dimers relative to trimers is 92.7%, and the selectivity for forming one dimer species (one isomer) is 51.7%.

[0894] Table 40A.

[0895]

[0896]

[0897] Table 40B.

[0898] Identification ％ VCH-VCH (Dimer) 92.7 VCH-VCH-VCH (Trimer) 7.3

[0899] NMR Characterization of Batch Oligomerization Examples

[0900] Proton NMR Quantitative Characterization of Reaction Mixtures

[0901] Specifically, a 500 MHz NMR instrument was operated under the following conditions: a ~30° flip angle RF pulse, 128 scans, a relaxation delay of ~5 s between pulses; a sample (60 - 100 mg) dissolved in CDCl3 (deuterochloroform) in a 5 mm NMR tube; and a signal acquisition temperature of ~25 °C. When determining the concentration of various olefins in all olefins from the NMR spectrum, the following method was adopted. First, as shown in Table 25, peaks corresponding to different types of hydrogen atoms in vinyl (T1), vinylidene (T2), disubstituted vinylidene (T3), and trisubstituted vinylidene (T4) were identified at peak regions that vary depending on the monomer. Second, then the area of each of the above peaks (A1, A2, A3, and A4 respectively) was integrated. Third, the amount of each type of olefin (in moles) (Q1, Q2, Q3, and Q4 respectively) was calculated (calculated as A1 / 2, A2 / 2, A3 / 2, and A4 respectively). Fourth, the total amount of all olefins (in moles) (Qt) was calculated as the sum of all four types (Qt = Q1 + Q2 + Q3 + Q4). Finally, then the molar concentration of each type of olefin (C1, C2, C3, and C4 respectively, in mol%) was calculated (in each case, Ci = 100*Qi / Qt). This procedure was used when quantifying the end group analysis. For general characterization, other conditions / solvents for proton spectra can be used.

[0902] Table 25.

[0903]

[0904]

[0905] NMR Spectra of Examples 1 - 24

[0906] Obtained the 1 1H NMR spectrum of the reaction mixture of the co - oligomerization reaction of 1 - hexene and vinylcyclohexene using catalyst A (Example 1).

[0907] Obtained the 1 1H NMR spectrum of the reaction mixture of the co - oligomerization reaction of 1 - heptene and vinylcyclohexene using catalyst A (Example 2).

[0908] Obtained the 1 1H NMR spectrum of the reaction mixture of the co - oligomerization reaction of 1 - pentene and vinylcyclohexene using catalyst A (Example 3).

[0909] Obtained the 1 1H NMR spectrum of the reaction mixture of the oligomerization reaction of 4 - methylpent - 1 - ene using catalyst D (Example 4).

[0910] Obtained the 1 1H NMR spectrum of the reaction mixture of the oligomerization reaction of monomer 1-butene and 1-pentene using catalyst A (Example 5). Table 26 shows the calculated olefinic composition.

[0911] Table 26.

[0912]

[0913] Obtained the 1 1H NMR spectrum of the reaction mixture of the co-oligomerization reaction of 1-butene and vinylcyclohexene using catalyst A (Example 6).

[0914] Obtained the 1 1H NMR spectrum of the reaction mixture of the oligomerization reaction of monomer 1-pentene using catalyst A (Example 8). Table 27 shows the calculated olefinic composition.

[0915] Table 27.

[0916]

[0917] Obtained the 1 1H NMR spectrum of the reaction mixture of the oligomerization reaction of monomer 1-butene using catalyst A (Example 9). Table 28 shows the calculated olefinic composition.

[0918] Table 28.

[0919]

[0920] Obtained the 1 1H NMR spectrum of the reaction mixture of the oligomerization reaction of monomer 1-butene using catalyst C (Example 10). Table 29 shows the calculated olefinic composition.

[0921] Table 29.

[0922]

[0923] Obtained the 1 1H NMR spectrum of the reaction mixture of the oligomerization reaction of 1-hexene using catalyst A (Example 11). Table 30 shows the calculated olefinic composition.

[0924] Table 30.

[0925]

[0926] Reaction mixture obtained from the oligomerization of 1-octene (Example 12) using catalyst A 1 1H NMR spectrum. Table 31A shows the calculated olefinic composition.

[0927] Table 31A.

[0928]

[0929] Reaction mixture obtained from the co-oligomerization of 1-hexene (25%) and 1-octene (75%) (Example 13) using catalyst A 1 1H NMR spectrum. Table 31B shows the calculated olefinic composition.

[0930] Table 31B.

[0931]

[0932]

[0933] Reaction mixture obtained from the co-oligomerization of 1-hexene (50%) and 1-octene (50%) (Example 14) using catalyst A 1 1H NMR spectrum. Table 32 shows the calculated olefinic composition.

[0934] Table 32.

[0935]

[0936] Reaction mixture obtained from the co-oligomerization of 1-hexene (75%) and 1-octene (25%) (Example 15) using catalyst A 1 1H NMR spectrum. Table 33 shows the calculated olefinic composition.

[0937] Table 33.

[0938]

[0939]

[0940] Reaction mixture obtained from the co-oligomerization of C8 and VCH (Example 16) using catalyst A 1 1H NMR spectrum.

[0941] Reaction mixture obtained from the co-oligomerization of C9 and VCH (Example 17) using catalyst A 1 1H NMR spectrum.

[0942] Reaction mixture obtained from the co-oligomerization of C10 and VCH using catalyst A (Example 18) 1 1H NMR spectrum

[0943] Reaction mixture obtained from the oligomerization of VCH using catalyst E (Example 18) 1 1H NMR spectrum

[0944] Reaction mixture obtained from the oligomerization of VCH using catalyst A (Example 20) 1 1H NMR and 13 13C NMR spectra

[0945] Reaction mixture obtained from the oligomerization of VCB to but-3-ene-1,3-diyl dicyclobutane using catalyst E (Example 21) 1 1H NMR spectrum

[0946] Reaction mixture obtained from the hydrogenation of but-3-ene-1,3-diyl dicyclobutane to butane-1,3-diyl dicyclobutane (Example 22) 1 1H NMR and 13 13C NMR spectra

[0947] Reaction mixture obtained from the oligomerization of vinylcyclohexane to but-3-ene-1,3-diyl dicyclohexane using catalyst E (Example 23) 1 1H NMR spectrum

[0948] Reaction mixture obtained from the hydrogenation of but-3-ene-1,3-diyl dicyclohexane to butane-1,3-diyl dicyclohexane (Example 24) 1 1H NMR and 13 13C NMR spectra

[0949] Continuous polymerization examples

[0950] Oligomerization is carried out in a continuous stirred tank reactor system having two autoclave reactors in series configuration. The volume of each of the two reactors is 1 L. The autoclave reactors are equipped with stirrers, pressure controllers, and water-cooling / steam (or alternatively hot oil heating for polymerization above 130 °C) heating elements with temperature controllers. The reactors are operated at a reactor pressure above the bubble point pressure of the reactant mixture under liquid filling conditions, keeping the reactants in the liquid phase. Under N2 head pressure, pentene, hexene, or vinylcyclohexene (VCH) is fed in a storage tank or via a metering pump. All liquid flow rates are controlled using Coriolis mass flow controllers (Quantim series from Brooks). The mixture is then fed to the reactor through a single line. A scavenger solution is added to the mixture before the combined monomer stream enters the reactor to further reduce any catalyst poisons. Similarly, the catalyst solution is fed to the reactor through a separate line using an ISCO injection pump. All monomers and solvents are purified through beds of alumina and molecular sieves.

[0951] All monomers (pentene, hexane, and VCH), the catalyst solution, and the scavenger solution are fed into the first reactor. The contents of the first reactor (including the prepared oligomers and the active catalyst) flow directly into the second reactor. The two reactors are operated at the same temperature. The reactor effluent leaves the second reactor through a backpressure control valve that reduces the pressure to atmospheric pressure. This causes some of the unreacted monomers in the solution to flash into the vapor phase, which is discharged from the top of the vapor-liquid separator. The liquid phase, which mainly contains the oligomer product, the solvent, and the unreacted monomers, is collected for product recovery. The collected liquid samples are weighed and reported as the collected liquids in the examples listed in Tables 34-38. Unless otherwise stated, all reactions are carried out at a pressure of about 2.4 MPa / g.

[0952] Tri-n-octylaluminum (TNOA) (25 wt% in hexane, Sigma Aldrich) is used as the scavenger. The scavenger is diluted to a concentration of about 1 - 4 μmol / mL in methylcyclohexane (MCH) or toluene. M2HTH-D4 (Boulder Scientific Company) is used as the activator for all experiments listed in Tables 34-38. Both the catalyst and the activator are dissolved in methylcyclohexane or toluene. Unless otherwise stated, the catalyst solution and the activator solution are fed into the reactor separately.

[0953] The molar ratio of the catalyst feed rate to the activator feed rate is about 1:1. The scavenger feed rate is adjusted to optimize the catalyst efficiency, and the feed rate varies from 0 (no scavenger) to 15 μmol / min. The catalyst feed rate can also be adjusted according to the level of impurities in the system to achieve the listed target conversion.

[0954] Oligomerization of 1-Pentene in a Continuous Reactor

[0955] Examples P-1 and P-2 were prepared using 1-pentene as the monomer and the general procedure described above. Catalyst A was used as the catalyst. Both the catalyst and the activator were separately dissolved in MCH. A toluene solution of tri-n-octylaluminum (TNOA) (25 wt% in hexane, Sigma Aldrich) was used as the scavenger solution. The detailed polymerization method conditions and some product analyses by GC-MS are listed in Table 34A. Tables 34B and 34C summarize the composition of the samples determined by GC-MS.

[0956] Table 34A.

[0957]

[0958] Table 34B.

[0959]

[0960] Table 34C.

[0961]

[0962]

[0963] Oligomerization of 1-Hexene in a Continuous Reactor

[0964] The hexene oligomers in Examples H-1 to H-3 were prepared using the general procedure described above. Catalyst A was used as the catalyst. Both the catalyst and the activator were separately dissolved in MCH. An MCH solution of tri-n-octylaluminum (TNOA) (25 wt% in hexane, Sigma Aldrich) was used as the scavenger solution. Examples H-4 to H-6 were prepared using the general procedure described above, except that a 1 L single oil-heated autoclave reactor was used. Toluene was used as the carrier solvent for the catalyst, activator, and scavenger. The detailed polymerization method conditions and some product analyses by GC-MS are listed in Table 35.

[0965] Table 35.

[0966]

[0967]

[0968] Tables 35A - 35C summarize the composition of Examples H1 - H3 determined by GC-MS.

[0969] Table 35A.

[0970]

[0971] Table 35B.

[0972]

[0973] Table 35C.

[0974]

[0975]

[0976] Table 35D - 35F summarize the compositions of Examples H4 - H6 as determined by GC - MS.

[0977] Table 35D.

[0978]

[0979] Table 35E.

[0980]

[0981] Table 35F.

[0982]

[0983] Oligomerization of VCH in a continuous reactor

[0984] The VCH oligomers in Examples V - 1 to V - 3 were prepared using the general procedure described above. Catalyst E was used as the catalyst. MCH was used as the carrier solvent for the catalyst, activator, and scavenger in Example V - 1. Toluene was used as the solvent for both the catalyst and the activator. For the scavenger solution, tri - n - octylaluminum (TNOA) was diluted with MCH. For Example V - 3, both the catalyst and the activator were dissolved separately in MCH. A toluene solution of tri - n - octylaluminum (TNOA) (25 wt% in hexane, Sigma Aldrich) was used as the scavenger solution. The detailed polymerization method conditions and some product analyses by GC - MS are listed in Table 36A.

[0985] Table 36A.

[0986]

[0987]

[0988] Tables 36B - 36D summarize the compositions of Samples V1 - V3 as determined by GC - MS.

[0989] Table 36B.

[0990]

[0991] Table 36C.

[0992]

[0993] Table 36D.

[0994]

[0995]

[0996] *Isomerization (isom) refers to the isomerization of the VCH monomer

[0997] Co - oligomerization of 1 - pentene and VCH in a continuous reactor

[0998] The pentene - VCH oligomers in Examples VP - 1 to VP - 3 were prepared using the general procedure described above. Catalyst A was used as the catalyst. MCH was used as the carrier solvent for all catalysts, activators, and scavengers. Example VP - 4 was prepared according to the same procedure used for VP - 1 to VP - 3, except that no scavenger was used. Example VP - 5 was prepared according to the same procedure used for Examples VP - 1 to VP - 3, except that Catalyst B was used and toluene was used as the solvent for tri - n - octylaluminum in Example VP - 5. The detailed polymerization method conditions and some product analyses by GC - MS are listed in Table 37A.

[0999] Table 37A.

[1000]

[1001]

[1002] Tables 37B - 37D summarize the compositions of Examples VP - 1, VP - 2, and VP - 3 as determined by GC - MS.

[1003] Table 37B.

[1004]

[1005] Table 37C.

[1006]

[1007] Table 37D.

[1008]

[1009] Tables 37E and 37F summarize the compositions of samples VP-4 and VP-5 as determined by GC-MS.

[1010] Table 37E.

[1011]

[1012]

[1013] Table 37F.

[1014]

[1015] Co-oligomerization of 1-hexene and VCH in a continuous reactor

[1016] The hexene-VCH oligomers in Examples VH-1 to VH-2 were prepared using the general procedure described above. Catalyst A was used as the catalyst. MCH was used as the solvent for the catalyst and activator. Toluene was used as the carrier solvent for the scavenger. The hexene-VCH oligomers in Examples VH-3 to VH-4 were prepared using the general procedure described above, except that a 1-liter single-oil heated autoclave reactor was used. Catalyst A was used as the catalyst. Toluene was used for all catalysts, activators, and scavengers. The detailed polymerization method conditions and some product analyses by GC-MS are listed in Table 38A.

[1017] Table 38A.

[1018]

[1019]

[1020] Tables 38B and 38C summarize the compositions of Examples VH-1 and VH-2 as determined by GC-MS.

[1021] Table 38B.

[1022]

[1023] Table 38C.

[1024]

[1025] Tables 38D and 38E summarize the compositions of Examples VH-3 and VH-4 as determined by GC-MS.

[1026] Table 38D.

[1027]

[1028] Table 38E.

[1029]

[1030] Small-scale oligomerization of VCH

[1031] The solvents, polymerization-grade toluene, and / or isohexane were supplied by ExxonMobil Chemical Co. and purified by passing through a series of columns: two 500 cc Oxyclear columns in series from Labclear (Oakland, CA), followed by two 500 cc columns packed with dried molecular sieves (8 - 12 mesh; Aldrich Chemical Company), and two 500 cc columns packed with dried molecular sieves (8 - 12 mesh; Aldrich Chemical Company). 4-Vinylcyclohexene was purified as previously described.

[1032] All complexes and activators were added to the reactor as dilute solutions in isohexane. The precatalyst solution was 8.0 mmol / L in isohexane. The scavengers tri-n-octylaluminum (TNOA) and triisobutylaluminum (TIBA) were purchased as pure reagents from Akzo Nobel (now Nouryon). The scavengers were diluted in isohexane and used as 0.100 mol / L solutions. The activator M2HTH-D4 was purchased from Boulder Chemical Company as a 10 wt% solution in methylcyclohexane. This solution was further diluted with isohexane to make a 5.0 wt% solution.

[1033] Reactor description and preparation. Polymerization was carried out in an inert atmosphere (N2) dry box using an autoclave equipped with an external heater for temperature control, a glass insert (internal volume of the reactor = 23.5 mL), a septum inlet, a controlled nitrogen supply, and equipped with a disposable polyether ether ketone mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110 °C or 115 °C for 5 hours and then at 25 °C for 5 hours.

[1034] For the VCH oligomerization run, the reactor was prepared as described above. Isohexane (sufficient to ultimately bring the total solution volume to 5.0 ml) and VCH (1.0 ml) were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to the process temperature (110 °C). Next, the stirrer was set to 800 RPM and the reaction cell was pressurized with N2 to 80 PSI. The scavenger solution (e.g., TNOA or TIBA) was then added to the reactor via syringe under process conditions. The exact amount added is listed in Table 41 below. The activator solution was added to the reactor via syringe under process conditions, followed by the precatalyst solution added to the reactor via syringe under process conditions. The reactor temperature was monitored and typically maintained within + / - 1 °C. After a reaction time of 120 minutes, the polymerization was stopped by adding high purity air (ultra air) gas at approximately 50 psi to the autoclave for approximately 30 seconds. The reactor was then cooled and vented. For some experiments, 200 μl of the product solution was removed before removing the solvent, unreacted monomer, and other volatiles. After vacuum removing the solvent, unreacted monomer, and other volatiles, the final product was isolated. The yields reported include the total weight of the non-volatile product and residual catalyst. The catalyst activity was reported as grams of product / mmol transition metal compound / hour of reaction time ( g / mmol·h ) and was based on the weight of the isolated product. For samples of the 200 μl of the product solution removed for GC-MS analysis, the product weights and activities reported were not corrected for the removal of the material (Examples 50 - 55, 62 - 67, 74 - 79, and 86 - 91). The aliquot (200 μl) of the removed solution was diluted with 500 μl of toluene for GC-MS analysis. The oligomerization results are reported in Table 41. Examples 50 - 73 are of the present invention and use catalyst A. Examples 74 - 97 are comparative and use comparative catalyst F.

[1035] GC-MS analysis of the samples was performed according to the protocol described previously. The GC-MS reported in Table 41 was calculated as follows:

[1036] The percentage of monomer conversion to dimers and trimers was calculated as the sum of the areas of all dimer and trimer peaks multiplied by 100, then divided by the sum of the areas of all non-solvent peaks and excluding the area of the product unknown peak (if present). This is reported in Table 41 as VCH conversion (%).

[1037] The percentage of unreacted VCH was calculated as 100 minus the percentage of monomer conversion to dimers and trimers. This value includes VCH that has been isomerized, hydrogenated, and / or dehydrogenated. This value is reported in Table 41 as unreacted VCH (%).

[1038] The monomer conversion percentage to all dimer products was calculated as the sum of the areas of all dimer peaks multiplied by 100, then divided by the sum of the areas of all non-solvent peaks and excluding the area of the product unknown peak (if present). This value was reported in Table 41 as the conversion of VCH to dimer (%).

[1039] The monomer conversion percentage to the single dimer (the dimer isomer with the largest peak area) was calculated as the area of the largest dimer peak multiplied by 100, then divided by the sum of the areas of all non-solvent peaks and excluding the area of the product unknown peak (if present). This value was reported in Table 41 as the conversion of VCH to the single cyclic dimer substance (%).

[1040] The selectivity percentage of dimer formation relative to trimer formation was calculated as the sum of the areas of all dimer peaks multiplied by 100, then divided by the sum of the areas of all dimer and trimer peaks. This value was reported in Table 41 as dimer (%).

[1041] The selectivity percentage of trimer formation relative to dimer formation was calculated as the sum of the areas of all trimer peaks multiplied by 100, then divided by the sum of the areas of all dimer and trimer peaks. This value was reported in Table 41 as trimer (%).

[1042] The selectivity percentage of forming one dimer substance (one isomer) based on the total dimers formed was calculated as the sum of the areas of the largest dimer peaks multiplied by 100, then divided by the sum of the areas of all dimer peaks. This value was reported as the selectivity to the single cyclic dimer substance (%).

[1043]

[1044]

[1045]

[1046] Table 41 shows that the selectivity of the dimer of catalyst A of the present invention relative to the trimer is 100%, while for comparative catalyst F it is typically less than 90%. Further, when using TIBA as a scavenger or when using a lower level of TNOA as a scavenger, the conversion of VCH to product over catalyst A is greater than 60%. For comparative catalyst F, higher levels of TNOA or TIBA are required for higher conversion of VCH to product, and the conversion never exceeds 50%. Although catalyst A produces higher yields and activity at lower scavenger levels, the opposite is true for catalyst F. At lower scavenger levels, catalyst A has a selectivity of approximately 98% to the single dimer product and is reduced only when using higher levels of TNOA. Similarly, catalyst F requires lower scavenger levels to achieve higher selectivity to one dimer product, but at the same time, the yield and catalyst activity are significantly reduced and, in most cases, more trimers are also produced. Overall, in some non-limiting embodiments, there can be one or more benefits to using catalyst A compared to using catalyst F, including, for example, the need to use less scavenger while achieving better selectivity of dimer relative to trimer, and generally higher yields and catalyst activity.

[1047] Although this disclosure contains many specific implementation details, these should not be construed as limitations on the scope of the subject matter or on the scope of what can be claimed, but rather as descriptions of features that may be specific to particular implementations. Certain features described in the context of separate implementations in this disclosure can also be implemented in combination in a single implementation. Conversely, the various features described in the context of a single implementation can also be implemented separately or in any suitable sub-combination in multiple implementations. Additionally, although the previously described features may be described as acting in certain combinations or even as initially claimed per se, in some cases, one or more features from a claimed combination can be deleted from the combination, and the claimed combination can be directed to a sub-combination or a variant of a sub-combination.

[1048] Specific implementations of the subject matter have been described. As will be apparent to those skilled in the art, other implementations, changes, and permutations of the described implementations are within the scope of the following claims. Although operations are depicted in the figures or claims in a particular order, this should not be construed as requiring that such operations be performed in the particular order shown or in sequential order, or that all of the operations shown be performed (some operations may be considered optional) to achieve the desired result.

[1049] Accordingly, the previously described example implementations do not define or limit this disclosure. Other changes, substitutions, and alterations are also possible without departing from the spirit and scope of this disclosure.

Claims

1. A method for preparing polyalphaolefin (PAO) from two or more different alpha-olefins, the method comprising: To make it contain one or more C6-C 32 cyclic α-olefins and one or more C4-C 32 a feed of linear and / or branched α-olefins is contacted with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions to effect a polymerization reaction to obtain a polymerization reaction mixture, said polymerization reaction mixture comprising a mixture of PAOs (e.g., PAO molecules) having ethylidene, trisubstituted vinylidene, disubstituted vinylidene and optionally vinyl unsaturation, and Obtaining an unsaturated PAO product from the polymerization reaction mixture.

2. The method according to claim 1, wherein, The unsaturated PAO product comprises a mixture of PAO molecules having vinylidene, trisubstituted vinylidene, disubstituted vinylidene, and optionally vinyl unsaturation, and is optionally substantially free of the alpha-olefin feed.

3. The method according to claim 1 or 2, wherein The one or more C6-C 32 One of the cyclic α-olefins contains ring unsaturation, and the unsaturated PAO product further contains a cyclic disubstituted vinylidene group.

4. The method according to any one of claims 1-3, wherein, The unsaturated PAO product comprises dimeric and / or trimeric molecules having vinylidene, trisubstituted vinylidene, disubstituted vinylidene, and optionally vinyl unsaturation.

5. The method according to any one of claims 1-4, wherein: The unsaturated PAO product contains one or more compounds represented by CC-v, LC-v, CL-v, CC-t1, LC-t1, CL-t1, CC-t2, LC-t2, CL-t2, LL-v, LL-t1, LL-t2, CC 2,1 -t1, CC 2,1 -vl1, CC 2,1 -vl2, CC 2,1 -vl3, CC 2,1 -vl1, LC 2,1 -vl1, LC 2,1 -vl2, LC 2,1 -vl3, LL-vd, LVCH-isomers, and / or VCHx2-isomers wherein if the cyclic alpha-olefin has a saturated ring structure, the cyclic monomeric fragments (A) and (B) are independently saturated, or if the cyclic alpha-olefin has a partially unsaturated ring structure, the cyclic monomeric fragments (A) and (B) are independently partially unsaturated, n and m respectively represent the number of additional carbon atoms in the ring structures of the cyclic monomeric fragments (A) and (B), and independently represent an integer from 1 to 20, R is a C2-C 30 hydrocarbyl group, R’ is a C1-C 29 hydrocarbyl group, and At least one of CL-v and LC-v is present in the unsaturated PAO product or a mixture thereof.

6. The method according to claim 5, wherein n and m independently represent an integer from 1 to 5, R is a C2-C8 hydrocarbyl group, and R' is a C1-C7 hydrocarbyl group.

7. The method according to claim 5, wherein n and m are 3, R is a C3-C8 hydrocarbyl group, R' is a C2-C7 hydrocarbyl group, and the cyclic monomeric fragments (A) and (B) have a partially unsaturated ring structure.

8. The method according to claim 5, wherein LL-v is present in the unsaturated PAO product or a mixture thereof.

9. The method according to claim 5, wherein CC-v and LL-v are present in the unsaturated PAO product or a mixture thereof.

10. The method according to any one of claims 1-9, wherein, The method has a selectivity for preparing greater than 50%, 60%, 70%, 80%, 90%, 95%, or 99% of the dimers in the unsaturated PAO product.

11. According to the method according to any one of claims 1-10, wherein, The unsaturated PAO product comprises vinylidene and trisubstituted vinylidene in an amount greater than or equal to 60 mol%, 70 mol%, or 80 mol% and vinyl in an amount less than or equal to 10 mol% based on the total moles of vinyl, vinylidene, acyclic disubstituted vinylidene, and trisubstituted vinylidene in the unsaturated PAO product.

12. The method according to any one of claims 1-10, wherein The unsaturated PAO product comprises vinylidene in an amount greater than or equal to 50 mol%, 60 mol%, 70 mol%, or 80 mol% and vinyl in an amount less than or equal to 10 mol% based on the total moles of vinyl, vinylidene, acyclic disubstituted vinylidene, and trisubstituted vinylidene in the unsaturated PAO product.

13. The method according to any one of claims 1-10, wherein As measured by GC-MS, the unsaturated PAO product comprises dimers in an amount greater than or equal to 50%, 60%, 70%, 80%, 90%, or 95% based on the total amount of dimers, trimers, tetramers, and higher oligomers in the unsaturated PAO product.

14. The method according to any one of claims 1-10, wherein, As measured by GC-MS, the unsaturated PAO product comprises dimers and trimers in an amount greater than or equal to 70%, 80%, 85%, 90%, 95%, or 97% based on the total amount of dimers, trimers, tetramers, and higher oligomers in the unsaturated PAO product.

15. The method according to any one of claims 1-14, wherein, The one or more cyclic C6-C 32 α-olefins are selected from vinyl cyclobutane, vinyl cyclopentane, vinyl cyclohexane, 4-vinyl cyclohex-1-ene, vinyl cycloheptane, vinyl cyclooctane, vinyl cyclononane, vinyl cyclodecane, vinyl cycloundecane, vinyl cyclododecane, 5-vinyl norbornane, 5-vinyl-2-norbornene, allyl cyclohexane and allyl cyclooctane.

16. The method according to claim 15, wherein, The one or more cyclic C6-C 32 α-olefins are selected from vinyl cyclobutane, vinyl cyclopentane, vinyl cyclohexane, and 4-vinylcyclohex-1-ene.

17. The method according to any one of claims 1-14, wherein, The one or more C4-C 32 linear and / or branched α-olefins are selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene, 4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene, and 3,5,5-trimethyl-1-hexene.

18. The method according to claim 17, wherein The one or more C4-C 32 linear and / or branched α-olefins are selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene, and 3,5,5-trimethyl-1-hexene.

19. The method according to any one of claims 1-14, wherein The one or more C4-C 32 linear α-olefins comprise C4-C 20 linear α-olefins, C4-C 12 linear α-olefins, C4-C8 linear α-olefins, C5-C8 linear α-olefins, or C5-C6 linear α-olefins.

20. The method according to any one of claims 1 - 14, wherein, The one or more C4-C 32 branched α-olefins include C5-C 20 branched α-olefins, C5-C 12 branched α-olefins, C5-C 10 branched α-olefins, C6-C9 branched α-olefins, or C6-C8 branched α-olefins.

21. The method according to any one of claims 1-14, wherein, The one or more C6-C 32 cyclic α-olefins comprise C6-C 20 cyclic α-olefins, C6-C 14 cyclic α-olefins, or C8-C 12 cyclic α-olefins.

22. The method according to claim 21, wherein, The C8-C 12 cyclic α-olefin is a non-conjugated diene.

23. The method according to claim 1, wherein The unsaturated PAO product comprises one or more of the following: The first dimer (CC) formed by the reaction of two of said one or more C6-C 32 cyclic α-olefins; formed by the reaction of one of said C6-C 32 cyclic α-olefins and one of said C4-C 32 linear and / or branched α-olefins, a second dimer (CL); and The third dimer (LL) formed by two of the C4-C 32 linear and / or branched α-olefins.

24. The method according to claim 23, wherein, Based on GC-MS, based on CC + CL + LL being equal to 100%, the percentage of CL in the unsaturated PAO product is 20% or greater, 30% or greater, 40% or greater, 50% or greater, 60% or greater, 70% or greater, or 80% or greater.

25. The method according to claim 23 or 24, wherein Based on GC-MS, based on CC + CL + LL being equal to 100%, the percentage of CC in the unsaturated PAO product is 0% or greater and 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less.

26. The method according to any one of claims 23-25, wherein, Based on GC-MS, based on CC + CL + LL being equal to 100%, the percentage of LL in the unsaturated PAO product is 10% or greater and 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or less.

27. The method according to any one of claims 1-26, further comprising contacting the unsaturated PAO product with a chemical reagent comprising a heteroatom-containing group to convert at least some of the unsaturated PAO product into a functionalized PAO product, wherein the heteroatom-containing group comprises one or more sulfonates / esters, amines, aldehydes, alcohols, or acids, preferably the heteroatom-containing group comprises epoxides, succinic acid, maleic acid, or maleic anhydride, alternatively the heteroatom-containing group comprises one or more of acids, esters, acid anhydrides, acid-esters, oxycarbonyls, carbonyls, formyls, formyl carbonyls, hydroxyls, and acetyl halides.

28. The method according to any one of claims 1-26, further comprising contacting the unsaturated PAO product with hydrogen and a hydrogenation catalyst in a hydrogenation process to convert at least some of the unsaturated PAO product into a hydrogenated PAO product.

29. The method according to claim 28, wherein The hydrogenation process occurs at a temperature of 25°C - 350°C or 100°C - 300°C and a hydrogen pressure of 25 psig to 2500 psig or 100 psig to 2000 psig for 5 minutes to 100 hours or 5 minutes to 24 hours.

30. The method according to claim 28 or 29, wherein, The hydrogenation process occurs in a slurry reactor, batch operation, fixed bed reactor, or continuous stirred tank reactor.

31. The method according to any one of claims 28 - 30, wherein, The hydrogenation catalyst accounts for 0.001 wt% - 20 wt% or 0.01 wt% - 10 wt% of the unsaturated PAO feed.

32. The method according to any one of claims 28-31, wherein, The bromine value of the hydrogenated PAO product is 2.0 or less.

33. The method according to any one of claims 28 - 32, wherein, The hydrogenated PAO product comprises a mixture of dimers selected from hCC 1,2 , hLC 1,2 , hCL 1,2 , hLL 1,2 , hCC 2,1 , hLC 2,1 , hLL 2,1 , hLVCH-isomerized and hVCHx2-isomerized dimers, wherein: The cyclic monomeric fragments (A) and (B) are saturated ring structures; n and m represent the number of additional carbon atoms in the ring structure and are each independently an integer from 1 to 20, R is a C2-C 30 hydrocarbyl group, R’ is a C1-C 29 hydrocarbyl group, and hCL 1,2 and hLC 1,2 is present in the hydrogenated PAO product.

34. The method according to claim 33, wherein, n and m independently represent an integer from 1 to 5, R is a C2-C8 hydrocarbyl group, and R' is a C1-C7 hydrocarbyl group.

35. The method according to claim 33, wherein, n and m are 3, R is a C3-C8 hydrocarbyl group, and R' is a C2-C7 hydrocarbyl group.

36. The method according to any one of claims 33-35, wherein, hCC 1,2 or hLL 1,2 is present in the hydrogenated PAO product or mixture thereof.

37. The method according to any one of claims 33-35, wherein hCC 1,2 and hLL 1,2 are present in the hydrogenated PAO product or a mixture thereof.

38. The method according to any one of claims 28 - 37, wherein, The hydrogenated PAO product comprises: The first hydrodimer (hCC) formed by the reaction of two of said one or more C6-C 32 cyclic α-olefins; formed by the reaction of one of said one or more C6-C 32 cyclic α-olefins and one of said one or more C4-C 32 linear and / or branched α-olefins; and The third hydrogenated dimer (hLL) formed by two of said C4-C 32 linear and / or branched α-olefins.

39. The method according to claim 38, wherein, Based on GC-MS, based on hCC + hCL + hLL being equal to 100%, the percentage of hCL in the hydrogenated PAO product is 20% or greater, 30% or greater, 40% or greater, 50% or greater, 60% or greater, 70% or greater, or 80% or greater.

40. The method according to claim 38 or 39, wherein Based on GC-MS, based on hCC + hCL + hLL being equal to 100%, the percentage of hCC in the hydrogenated PAO product is 0% or greater and 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less.

41. The method according to any one of claims 38 - 40, wherein, Based on GC-MS, based on hCC + hCL + hLL being equal to 100%, the percentage of hLL in the hydrogenated PAO product is 10% or greater and 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or less.

42. The method according to claim 1, wherein, The metallocene compound is represented by formula (I): Wherein: R 1 、R 2 and R 3 each independently is hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl or silylhydrocarbyl; R 4 and R 5 each independently is a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 30 hydrocarbyl or silylhydrocarbyl, wherein R 4 and R 5 together with the carbon atoms in the first cyclopentadienyl ring to which they are directly attached, jointly form one or more substituted or unsubstituted rings fused to the first cyclopentadienyl ring; R 12 、R 13 、R 14 、R 15 and R 16 each independently is hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl, silylhydrocarbyl, or germyl, and at least four of R 12 、R 13 、R 14 、R 15 and R 16 are not hydrogen; M is a Group 3, 4, or 5 transition metal having an integer coordination number v, where v is 3, 4, or 5; Each X is independently a halogen, a hydrogen group, an amino group, an alkoxy group, a sulfide group, a phosphide group, a diene, an amine, a phosphine, an ether, or a C1-C 20 substituted or unsubstituted straight-chain, branched-chain, or cyclic hydrocarbon group, or optionally two or more X structural moieties may together form a fused ring or a ring system; and m is an integer equal to v - 2.

43. The method according to claim 1, wherein, The metallocene compound is represented by formula (II): Wherein: R 1 、R 2 and R 3 each independently is hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group; R 6 、R 7 、R 17 and R 18 each independently is hydrogen, a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 30 hydrocarbyl group, or R 6 and R 7 、R 7 and R 17 、or R 17 and R 18 together with the carbon atoms in the indenyl ring directly connected to them jointly form one or more substituted or unsubstituted rings fused to the indenyl ring; R 12 、R 13 、R 14 and R 15 are each independently a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group; R 16 is hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl or silylhydrocarbyl; Each X is independently a halogen, a hydrogen group, an amino group, an alkoxy group, a sulfide group, a phosphide group, a diene, an amine, a phosphine, an ether, a C1-C 20 substituted or unsubstituted straight-chain, branched-chain, or cyclic hydrocarbon group, or two or more X structural moieties together form a fused ring or ring system; M is a Group 3, 4, or 5 transition metal having an integer coordination number v, where v is 3, 4, or 5; and m is an integer equal to v - 2.

44. The method according to claim 1, wherein, The metallocene compound is represented by formula (III): Wherein: R 1 and R 2 is hydrogen; R 23 and R 19 each independently contains a Group 14 atom, such as C, Ge, or Si (e.g., R 23 contains C and R 19 contains C or Si); R 20 , R 21 and R 22 are independently hydrogen or a substituted or unsubstituted straight chain, branched chain, or cyclic C1-C 20 Hydrocarbon, and R 20 , R 21 and R 22 At least two of them are independently substituted or unsubstituted straight chain, branched chain, or cyclic C1-C 20 Hydrocarbon; R 6 、R 7 、R 17 and R 18 each independently is hydrogen, a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 30 hydrocarbyl group, or R 6 and R 7 、R 7 and R 17 、or R 17 and R 18 together with the carbon atoms in the indenyl ring to which they are directly attached jointly form one or more substituted or unsubstituted rings fused to the indenyl ring; R 12 、R 13 、R 14 、R 15 and R 16 each independently is a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group; Each X is independently a halogen, a hydrogen group, an amino group, an alkoxy group, a sulfide group, a phosphide group, a diene, an amine, a phosphine, an ether, or a C1-C 20 substituted or unsubstituted straight-chain, branched-chain, or cyclic hydrocarbon group, or two or more X structural moieties together form a fused ring or a ring system; M is a Group 3, 4, or 5 transition metal having an integer coordination number v, where v is 3, 4 or 5; and m is an integer equal to v - 2.

45. The method according to claim 1, wherein The metallocene compound is represented by formula (IV): Wherein: R 1 and R 2 is hydrogen; R 3 is a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group; R 6 and R 18 each independently is hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 30 hydrocarbyl group; R 24 、R 25 、R 26 、R 27 、R 28 and R 29 each independently is hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C8 hydrocarbon group; R 12 、R 13 、R 14 、R 15 and R 16 each independently is a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group; Each X is independently a halogen, a hydrogen group, an amino group, an alkoxy group, a sulfide group, a phosphide group, a diene, an amine, a phosphine, an ether, or a C1-C 20 substituted or unsubstituted straight-chain, branched-chain, or cyclic hydrocarbon group, or two or more X structural moieties together form a fused ring or a ring system; M is a Group 3, 4, or 5 transition metal having an integer coordination number v, where v is 3, 4 or 5; and m is an integer equal to v - 2.

46. The method according to claim 1, wherein, The metallocene compound is represented by formula (V): Wherein: R 1 and R 2 is hydrogen; R 23 and R 19 each independently comprises C, Ge, or Si (e.g., R 23 comprises C; and R 19 comprises C or Si); R 20 、R 21 and R 22 each independently is hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group, and at least two of R 20 、R 21 and R 22 are independently a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group; R 6 and R 18 each independently is hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 30 hydrocarbyl group; R 24 、R 25 、R 26 、R 27 、R 28 and R 29 each independently is hydrogen or a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C8 hydrocarbon group; R 12 、R 13 、R 14 、R 15 and R 16 each independently is a substituted or unsubstituted straight-chain, branched-chain, or cyclic C1-C 20 hydrocarbyl group; Each X is independently a halogen, a hydrogen group, an amino group, an alkoxy group, a sulfide group, a phosphide group, a diene, an amine, a phosphine, an ether, or a C1-C 20 substituted or unsubstituted straight-chain, branched-chain, or cyclic hydrocarbon group, or two or more X structural moieties together form a fused ring or ring system; M is a Group 3, 4, or 5 transition metal having an integer coordination number v, where v is 3, 4 or 5; and m is an integer equal to v - 2.

47. The method according to any one of claims 42-46, wherein, M is Zr or Hf and v is 4.

48. The method according to any one of claims 42-46, wherein, M is Hf and v is 4.

49. The method according to claim 1, wherein The metallocene compound is selected from: (Pentamethylcyclopentadienyl)(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-ethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-n-propyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isopropyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-n-butyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1,6,6-triethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-methylindenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutylindeneyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-methyl-3,6,7,8-tetrahydro-as-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-3,6,7,8-tetrahydro-as-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-methyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene)dimethylhafnium, (Pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)dimethylhafnium, and (Pentamethylcyclopentadienyl)(1-isobutyl-5,6-dimethylindenyl)dimethylhafnium.

50. The method according to claim 1, wherein, The metallocene compound is selected from: (Pentamethylcyclopentadienyl)(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-methylindenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutylindeneyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)dimethylhafnium, and (Pentamethylcyclopentadienyl)(1-isobutyl-5,6-dimethylindenyl)dimethylhafnium.

51. The method according to claim 1, wherein, The catalyst system contains an activator.

52. The method according to claim 51, wherein, The activator is selected from: [N,N-bis(hydrogenated tallow)methylammonium][tetrakis(pentafluorophenyl)borate], [N-methyl-4-nonadecyl-N-octadecylanilinium][tetrakis(pentafluorophenyl)borate], [N-methyl-4-hexadecyl-N-octadecylanilinium][tetrakis(pentafluorophenyl)borate], [N-methyl-4-tetradecyl-N-octadecylanilinium][tetrakis(pentafluorophenyl)borate], [N-methyl-4-dodecyl-N-octadecylanilinium][tetrakis(pentafluorophenyl)borate], [N-methyl-4-decyl-N-octadecylanilinium][tetrakis(pentafluorophenyl)borate], [N-methyl-4-octyl-N-octadecylanilinium][tetrakis(pentafluorophenyl)borate], [N-methyl-4-hexyl-N-octadecylanilinium][tetrakis(pentafluorophenyl)borate], [N-methyl-4-butyl-N-octadecylanilinium][tetrakis(pentafluorophenyl)borate], [N-methyl-4-octadecyl-N-decylanilinium][tetrakis(pentafluorophenyl)borate], [N-methyl-4-nonadecyl-N-dodecylanilinium][tetrakis(pentafluorophenyl)borate], [N-methyl-4-nonadecyl-N-tetradecylanilinium][tetrakis(pentafluorophenyl)borate], [N-methyl-4-nonadecyl-N-hexadecylanilinium][tetrakis(pentafluorophenyl)borate], [N-ethyl-4-nonadecyl-N-octadecylanilinium][tetrakis(pentafluorophenyl)borate], [N-methyl-N,N-di-octadecylammonium][tetrakis(pentafluorophenyl)borate], [N-methyl-N,N-di-hexadecylammonium][tetrakis(pentafluorophenyl)borate], [N-methyl-N,N-di-tetradecylammonium][tetrakis(pentafluorophenyl)borate], [N-methyl-N,N-di-dodecylammonium][tetrakis(pentafluorophenyl)borate], [N-methyl-N,N-di-decylammonium][tetrakis(pentafluorophenyl)borate], [N-methyl-N,N-di-octylammonium][tetrakis(pentafluorophenyl)borate], [N-ethyl-N,N-di-octadecylammonium][tetrakis(pentafluorophenyl)borate], [N,N-bis(octadecyl)tolylammonium][tetrakis(pentafluorophenyl)borate], [N,N-bis(hexadecyl)tolylammonium][tetrakis(pentafluorophenyl)borate], [N,N-bis(tetradecyl)tolylammonium][tetrakis(pentafluorophenyl)borate], [N,N-bis(dodecyl)toluidinium][tetrakis(pentafluorophenyl)borate], [N-octadecyl-N-hexadecyl-toluidinium][tetrakis(pentafluorophenyl)borate], [N-octadecyl-N-hexadecyl-toluidinium][tetrakis(pentafluorophenyl)borate], [N-octadecyl-N-tetradecyl-toluidinium][tetrakis(pentafluorophenyl)borate], [N-octadecyl-N-dodecyl-toluidinium][tetrakis(pentafluorophenyl)borate], [N-octadecyl-N-decyl-toluidinium][tetrakis(pentafluorophenyl)borate], [N-hexadecyl-N-tetradecyl-toluidinium][tetrakis(pentafluorophenyl)borate],, [N-hexadecyl-N-dodecyl-tolylammonium][tetrakis(pentafluorophenyl)borate], [N-hexadecyl-N-decyl-tolylammonium][tetrakis(pentafluorophenyl)borate], [N-tetradecyl-N-dodecyl-tolylammonium][tetrakis(pentafluorophenyl)borate], [N-tetradecyl-N-decyl-tolylammonium][tetrakis(pentafluorophenyl)borate], [N-Dodecyl-N-decyl-toluenylammonium][tetrakis(pentafluorophenyl)borate], [N-Methyl-N-octadecylbenzylammonium][tetrakis(pentafluorophenyl)borate], [N-Methyl-N-hexadecylbenzylammonium][tetrakis(pentafluorophenyl)borate], [N-Methyl-N-tetradecylbenzylammonium][tetrakis(pentafluorophenyl)borate], [N-Methyl-N-dodecylbenzylammonium][tetrakis(pentafluorophenyl)borate], [N-Methyl-N-decylbenzylammonium][tetrakis(pentafluorophenyl)borate], [N-Methyl-N-octylbenzylammonium][tetrakis(pentafluorophenyl)borate], N,N-Dimethylbenzylammonium tetrakis(pentafluorophenyl)borate, N,N-Dimethylbenzylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Triphenylcarbenium tetrakis(pentafluorophenyl)borate, Trimethylammonium tetrakis(pentafluorophenyl)borate, and Tri-n-butylammonium tetrakis(pentafluorophenyl)borate.

53. The method according to claim 51 or 52, wherein The activator is selected from: [N,N-Di(hydrogenated tallow)methylammonium][tetrakis(pentafluorophenyl)borate], [N-Methyl-N,N-di-octadecylammonium][tetrakis(pentafluorophenyl)borate], and [N-Methyl-N,N-di-hexadecylammonium][tetrakis(pentafluorophenyl)borate].

54. The method according to claim 51, wherein, The activator is N,N-Dimethylbenzylammonium tetrakis(pentafluorophenyl)borate.

55. The method according to any one of claims 1-54, wherein, The method is a continuous method, a batch method, or a semi-batch method.

56. The method according to claim 55, wherein, The method is a continuous method, which includes: continuously introducing the feed into the polymerization reactor, continuously introducing the catalyst system into the polymerization reactor, and continuously withdrawing the polymerization reaction mixture from the polymerization reactor.

57. The method according to claim 56, wherein, The polymerization reactor comprises a continuous stirred tank reactor or a plug flow reactor.

58. The method according to claim 56 or 57, which includes: Contact at least one α-olefin monomer and at least one C4-C 24 cyclic α-olefin with a metallocene catalyst, a non-coordinating anion activator, and optionally an alkylaluminum compound, wherein the polymerization conditions include a reaction temperature in the range of 70 °C to 160 °C, a reactor pressure of less than 50 atmospheres, and a residence time in the range of 20 minutes to 3 hours; obtaining the polymerization reaction mixture (e.g., containing one or more oligomer products); and optionally fractionating the polymerization reaction mixture and / or hydrogenating the polymerization reaction mixture (e.g., optionally including fractionating the one or more oligomer products and hydrogenating the one or more oligomer products).

59. The method according to claim 55, wherein The method is a batch method or a semi-batch method, which includes: introducing two or more different α-olefins into the polymerization reactor, adding the catalyst system to the polymerization reactor, and stirring the content of the polymerization reactor for about 10 minutes to about 24 hours, and then withdrawing the polymerization reaction mixture from the polymerization reactor.

60. The method according to claim 59, which includes: Contact at least one α-olefin monomer and at least one C4-C 24 cyclic α-olefin with a metallocene catalyst, a non-coordinating anion activator, and an optional alkylaluminum compound, wherein the polymerization conditions include a reaction temperature in the range of 70 °C to 160 °C, a reactor pressure of less than 50 atmospheres, and a residence time in the range of 20 minutes to 24 hours; obtaining the polymerization reaction mixture (e.g., containing one or more oligomer products); and optionally fractionating the polymerization reaction mixture and / or hydrogenating the polymerization reaction mixture (e.g., optionally including fractionating the one or more oligomer products and hydrogenating the one or more oligomer products).

61. The method according to claim 59 or 60, wherein, The catalyst system is added to the polymerization reactor in a single dose or in multiple doses.

62. The method according to any one of claims 59 - 61, wherein, One or more of the two or more different α-olefins are added to the polymerization reactor in a single dose or multiple doses.

63. The method according to any one of claims 59 - 62, wherein, A portion of the polymerization reaction mixture is withdrawn from the polymerization reactor.

64. The method according to claim 59, wherein, At least one of the two or more different α-olefins is the solvent.

65. The method according to any one of claims 55 - 63, wherein, The polymerization reaction conditions include a reaction temperature of about 100 °C - 200 °C, 110 °C - 180 °C, 120 °C - 170 °C, 130 °C - 160 °C, or 140 °C - 155 °C.

66. The method according to any one of claims 55 - 64, wherein, The polymerization reaction conditions include a temperature of 120 °C or higher, 130 °C or higher, or 140 °C or higher; and / or a reactor pressure of 15 psia to 1600 psia.

67. The method according to any one of claims 1-66, wherein, The unsaturated PAO product is separated from unreacted monomers and solvents, hydrogenated, and fractionated by distillation.

68. The method according to any one of claims 1-66, wherein, The unsaturated PAO product is separated from unreacted monomers and solvents and fractionated by distillation.

69. A fuel or lubricant comprising the unsaturated PAO product formed by the method according to any one of claims 1 - 26 or the hydrogenated PAO product formed by the method according to any one of claims 28 - 41.

70. A driveline or electric vehicle fluid, engine oil, gear oil, cooling fluid, compressor oil, or hydraulic fluid comprising the hydrogenated PAO product formed by the method according to any one of claims 28 - 41 or the functionalized PAO product formed by the method according to claim 27.

71. A polyalphaolefin (PAO) prepared by a method comprising: To make a feed containing one or more C6-C 32 cyclic α-olefins and one or more C4-C 32 linear and / or branched α-olefins contact a catalyst system containing a metallocene compound in a polymerization reactor under polymerization conditions to effect a polymerization reaction to obtain a polymerization reaction mixture, the polymerization reaction mixture containing a mixture of PAO having ethylidene, trisubstituted vinylidene, disubstituted vinylidene, and optionally vinyl unsaturation, and Optionally obtaining an unsaturated PAO product from the polymerization reaction mixture.

72. A polyalphaolefin (PAO) prepared by the method according to any one of claims 1 - 70. The PAO prepared by the method according to claim 71, wherein, The one or more C6-C 32 One of the cyclic α-olefins contains ring unsaturation, and wherein the unsaturated PAO product further comprises a cyclic disubstituted vinylidene.

74. The PAO prepared by the method according to claim 71, wherein, The unsaturated PAO product comprises dimer and / or trimer molecules having vinylidene, trisubstituted vinylidene, disubstituted vinylidene, and optionally vinyl unsaturation.

75. The PAO prepared by the method according to claim 71, wherein, The unsaturated PAO product contains one or more compounds represented by CC-v, LC-v, CL-v, CC-t1, LC-t1, CL-t1, CC-t2, LC-t2, CL-t2, LL-v, LL-t1, LL-t2, CC 2,1 -t1, CC 2,1 -vl1, CC 2,1 -vl2, CC 2,1 -vl 3, CC 2,1 -vl 1, LC 2,1 -vl 1, LC 2,1 -vl2, LC 2,1 -vl 3, LL-vd, LVCH-isomers, and / or VCHx2-isomers Wherein if the cyclic α-olefin has a saturated ring structure, the cyclic monomer fragments (A) and (B) are independently saturated, or if the cyclic α-olefin has a partially unsaturated ring structure, the cyclic monomer fragments (A) and (B) are independently partially unsaturated. n and m respectively represent the number of additional carbon atoms in the ring structures of the cyclic monomer fragments (A) and (B), and independently represent an integer from 1 to 20. R is a C2-C 30 hydrocarbyl group, R’ is a C1-C 29 hydrocarbyl group, and At least one of CL-v and LC-v is present in the unsaturated PAO product or a mixture thereof.

76. The PAO prepared by the method according to claim 75, wherein, n and m independently represent an integer from 1 to 5, R is a C2 - C8 hydrocarbon group, and R' is a C1 - C7 hydrocarbon group.

77. The PAO prepared by the method according to claim 75, wherein, n and m are 3, R is a C3 - C8 hydrocarbon group, R' is a C2 - C7 hydrocarbon group, and the cyclic monomer fragments (A) and (B) have a partially unsaturated ring structure. The PAO prepared by the method according to claim 75, wherein, LL-v is present in the unsaturated PAO product or a mixture thereof.

79. The PAO prepared by the method according to claim 75, wherein, CC-v and LL-v are present in the unsaturated PAO product or a mixture thereof.

80. The PAO prepared by the method according to claim 71, wherein, The unsaturated PAO product contains vinylidene and trisubstituted vinylene in a total molar amount of greater than or equal to 60 mol%, 70 mol%, or 80 mol% based on the total molar amount of vinyl, vinylidene, non-cyclic disubstituted vinylidene, and trisubstituted vinylene in the unsaturated PAO product, and vinyl in an amount less than or equal to 10 mol%.

81. The PAO prepared by the method according to claim 71, wherein, As measured by GC-MS, the unsaturated PAO product contains dimers in an amount greater than or equal to 50%, 60%, 70%, 80%, 90%, or 95% based on the total amount of dimers, trimers, tetramers, and higher oligomers in the unsaturated PAO product.

82. The PAO prepared by the method according to claim 71, wherein, As measured by GC-MS, the unsaturated PAO product contains dimers and trimers in an amount greater than or equal to 70%, 80%, 85%, 90%, 95%, or 97% based on the total amount of dimers, trimers, tetramers, and higher oligomers in the PAO product. The PAO prepared by the method according to claim 71, wherein, The unsaturated PAO product contains one or more of the following: The first dimer (CC) formed by the reaction of two of said one or more C6-C 32 cyclic α-olefins; formed by reaction of one of said C6-C 32 cyclic α-olefins and one of said C4-C 32 linear and / or branched α-olefins to form a second dimer (CL); and The third dimer (LL) formed by two of said C4-C 32 linear and / or branched α-olefins.

84. The PAO prepared by the method according to claim 83, wherein, Based on GC-MS, with CC + CL + LL equal to 100%, the percentage of CL in the unsaturated PAO product is 20% or greater, 30% or greater, 40% or greater, 50% or greater, 60% or greater, 70% or greater, or 80% or greater. The PAO prepared by the method according to claim 83, wherein, Based on GC-MS, with CC + CL + LL equal to 100%, the percentage of CC in the unsaturated PAO product is 0% or greater and 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less.

86. The PAO prepared by the method according to claim 83, wherein, Based on GC-MS, with CC + CL + LL equal to 100%, the percentage of LL in the unsaturated PAO product is 10% or greater and 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or less.

87. A mixture comprising two or more unsaturated poly-α-olefin (PAO) dimers represented by CC-v, LC-v, CL-v, CC-t1, LC-t1, CL-t1, CC-t2, LC-t2, CL-t2, LL-v, LL-t1, LL-t2, CC 2,1 -t1, CC 2,1 -vl1, CC 2,1 -vl2, CC 2,1 -vl 3, CC 2,1 -vl 1, LC 2,1 -vl 1, LC 2,1 -vl2, LC 2,1 -vl 3, LL-vd, LVCH-isomers, and / or VCHx2-isomers, Wherein: If the cyclic α-olefin has a saturated ring structure, the cyclic monomer fragments (A) and (B) are independently saturated, or if the cyclic α-olefin has a partially unsaturated ring structure, the cyclic monomer fragments (A) and (B) are independently partially unsaturated. n and m respectively represent the number of additional carbon atoms in the ring structures of the cyclic monomer fragments (A) and (B), and independently represent an integer from 1 to 20. R is a C2-C 30 hydrocarbyl group, R’ is a C1-C 29 hydrocarbyl group, and At least one of CL-v and LC-v is present in the mixture.

88. The mixture according to claim 87, wherein, n and m independently represent an integer from 1 to 5, R is a C2-C8 hydrocarbyl group, and R' is a C1-C7 hydrocarbyl group.

89. The mixture according to claim 87 or 88, wherein, n and m are 3, R is a C3-C8 hydrocarbyl group, R' is a C2-C7 hydrocarbyl group, and the cyclic monomer fragments (A) and (B) have a partially unsaturated ring structure.

90. The mixture according to any one of claims 87 - 89, wherein, LL-v is present in the mixture.

91. The mixture according to any one of claims 87 - 89, wherein, CC-v and LL-v are present in the mixture.

92. A PAO product comprising one or more of the following compounds: 7-(2-(cyclohex-3-en-1-yl)ethyl)bicyclo[3.2.1]oct-2-ene, 7-hexylbicyclo[3.2.1]oct-2-ene, 7-pentylbicyclo[3.2.1]oct-2-ene, 4,4'-(but-3-ene-1,3-diyl)dicyclohex-1-ene, 4-(oct-1-en-2-yl)cyclohex-1-ene, oct-1-en-2-ylcyclohexane, 4-(hept-1-en-2-yl)cyclohex-1-ene, hept-1-en-2-ylcyclohexane, 4-(non-1-en-2-yl)cyclohex-1-ene, non-1-en-2-ylcyclohexane, 4-(hex-1-en-2-yl)cyclohex-1-ene, 4-(6-methylhept-1-en-2-yl)cyclohex-1-ene, and (6-methylhept-1-en-2-yl)cyclohexane.

93. A PAO product comprising 4,4'-(but-3-ene-1,3-diyl)dicyclohex-1-ene (VCHx2), 4-(oct-1-en-2-yl)cyclohex-1-ene (VCH-hex), and 5-methylidenoundecane (hex-hex).

94. The PAO product according to claim 93, wherein Based on the total molar amount of VCHx2 + VCH-hex + hex-hex equal to 100%, the molar percentage of VCH-hex is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

95. The PAO product according to claim 93 or 94, wherein Based on the total molar amount of VCHx2 + VCH-hex + hex-hex equal to 100%, the molar percentage of VCHx2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%.

96. The PAO product according to any one of claims 93 - 95, wherein, Based on the total molar amount of VCHx2 + VCH-hex + hex-hex equal to 100%, the molar percentage of hex-hex is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

97. A PAO product comprising but-3-ene-1,3-dicyclohexane (VCH’x2), oct-1-en-2-ylcyclohexane (VCH’-hex), and 5-methylidenoundecane (hex-hex).

98. The PAO product according to claim 97, wherein Based on the total molar amount of VCH’x2 + VCH’-hex + hex-hex equal to 100%, the molar percentage of VCH’-hex is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

99. The PAO product according to claim 97 or 98, wherein, Based on the total molar amount of VCH’x2 + VCH’-hex + hex-hex equal to 100%, the molar percentage of VCH’x2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%.

100. The PAO product according to any one of claims 97-99, wherein, Based on a total mole number of VCH’x2 + VCH’-hex + hex-hex equal to 100%, the mole percentage of hex-hex is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

101. A PAO product comprising 4,4'-(but-3-ene-1,3-diyl)dicyclohex-1-ene (VCHx2), 4-(hept-1-en-2-yl)cyclohex-1-ene (VCH-pent), and 4-methylidenenonane (pent-pent).

102. The PAO product according to claim 101, wherein, Based on a total mole number of VCHx2 + VCH-pent + pent-pent equal to 100%, the mole percentage of VCH-pent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

103. The PAO product according to claim 101 or 102, wherein, Based on a total mole number of VCHx2 + VCH-pent + pent-pent equal to 100%, the mole percentage of VCHx2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%.

104. The PAO product according to any one of claims 101-103, wherein Based on a total mole number of VCHx2 + VCH-pent + pent-pent equal to 100%, the mole percentage of pent-pent is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

105. A PAO product comprising but-3-ene-1,3-diyl dicyclohexane (VCH’x2), hept-1-en-2-yl cyclohexane (VCH’-pent), and 4-methylidenenonane (pent-pent).

106. The PAO product according to claim 105, wherein, Based on a total mole number of VCH’x2 + VCH’-pent + pent-pent equal to 100%, the mole percentage of VCH’-pent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

107. The PAO product according to claim 105 or 106, wherein Based on a total mole number of VCH’x2 + VCH’-pent + pent-pent equal to 100%, the mole percentage of VCH’x2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%.

108. The PAO product according to any one of claims 105-107, wherein, Based on a total mole number of VCH’x2 + VCH’-pent + pent-pent equal to 100%, the mole percentage of pent-pent is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

109. A PAO product comprising 4,4'-(but-3-ene-1,3-diyl)dicyclohex-1-ene (VCHx2), 4-(non-1-en-2-yl)cyclohex-1-ene (VCH-hept), and 6-methylenetridecane (hept-hept).

110. The PAO product according to claim 109, wherein, Based on the total molar amount of VCHx2 + VCH-hept + hept-hept equal to 100%, the molar percentage of VCH-hept is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

111. The PAO product according to claim 109 or 110, wherein, Based on the total molar amount of VCHx2 + VCH-hept + hept-hept equal to 100%, the molar percentage of VCHx2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%.

112. The PAO product according to any one of claims 109 - 111, wherein, Based on the total molar amount of VCHx2 + VCH-hept + hept-hept equal to 100%, the molar percentage of hept-hept is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

113. A PAO product comprising but-3-ene-1,3-diyl dicyclohexane (VCH’x2), non-1-en-2-yl cyclohexane (VCH’-hept), and 6-methylenetridecane (hept-hept).

114. The PAO product according to claim 113, wherein Based on the total molar amount of VCH’x2 + VCH’-hept + hept-hept equal to 100%, the molar percentage of VCH’-hept is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

115. The PAO product according to claim 113 or 114, wherein, Based on the total molar amount of VCHx2’ + VCH’-hept + hept-hept equal to 100%, the molar percentage of VCH’x2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%.

116. The PAO product according to any one of claims 113 - 115, wherein, Based on the total molar amount of VCH’x2 + VCH’-hept + hept-hept equal to 100%, the molar percentage of hept-hept is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

117. A PAO product comprising 4,4'-(but-3-ene-1,3-diyl)dicyclohex-1-ene (VCHx2), 4-(hex-1-en-2-yl)cyclohex-1-ene (VCH-but), and 3-methylenheptane (but-but).

118. The PAO product according to claim 117, wherein Based on a total molar amount of VCHx2 + VCH-but + but-but equal to 100%, the molar percentage of VCH-but is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

119. The PAO product according to claim 117 or 118, wherein Based on a total molar amount of VCHx2 + VCH-but + but-but equal to 100%, the molar percentage of VCHx2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%.

120. The PAO product according to any one of claims 117 - 119, wherein, Based on a total molar amount of VCHx2 + VCH-but + but-but equal to 100%, the molar percentage of but-but is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

121. A PAO product comprising but-3-ene-1,3-diyl dicyclohexane (VCH’x2), hex-1-ene-2-yl cyclohexane (VCH’-but), and 3-methylideneheptane (but-but).

122. The PAO product according to claim 121, wherein, Based on a total molar amount of VCH’x2 + VCH’-but + but-but equal to 100%, the molar percentage of VCH’-but is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

123. The PAO product according to claim 121 or 122, wherein Based on a total molar amount of VCH’x2 + VCH’-but + but-but equal to 100%, the molar percentage of VCH’x2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%.

124. The PAO product according to any one of claims 121-123, wherein, Based on a total molar amount of VCH’x2 + VCH’-but + but-but equal to 100%, the molar percentage of but-but is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

125. A PAO product comprising 4,4'-(but-3-ene-1,3-diyl) dicyclohex-1-ene (VCHx2), 4-(6-methylhept-1-ene-2-yl) cyclohex-1-ene (VCH-MePent), and 2,8-dimethyl-4-methylidene nonane (MePent-MePent).

126. The PAO product according to claim 125, wherein, Based on a total molar amount of VCHx2 + VCH-MePent + MePent-MePent equal to 100%, the molar percentage of VCH-MePent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. The PAO product according to claim 125 or 126, wherein Based on a total molar amount of VCHx2 + VCH-MePent + MePent-MePent equal to 100%, the molar percentage of VCHx2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%.

128. The PAO product according to any one of claims 125-127, wherein Based on a total molar amount of VCHx2 + VCH-MePent + MePent-MePent equal to 100%, the molar percentage of MePent-MePent is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

129. A PAO product comprising but-3-ene-1,3-diyl dicyclohexane (VCH’x2), (6-methylhept-1-en-2-yl) cyclohexane (VCH’-MePent), and 2,8-dimethyl-4-methylidenenonane (MePent-MePent).

130. The PAO product according to claim 129, wherein, Based on a total molar amount of VCH’x2 + VCH’-MePent + MePent-MePent equal to 100%, the molar percentage of VCH’-MePent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

131. The PAO product according to claim 129 or 130, wherein, Based on a total molar amount of VCH’x2 + VCH’-MePent + MePent-MePent equal to 100%, the molar percentage of VCH’x2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%.

132. The PAO product according to any one of claims 129-131, wherein, Based on a total molar amount of VCH’x2 + VCH’-MePent + MePent-MePent equal to 100%, the molar percentage of MePent-MePent is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

133. A method for hydrogenating an unsaturated polyalphaolefin (PAO) product formed from two or more different alpha-olefins, the method comprising: Contacting the unsaturated PAO product with hydrogen and a hydrogenation catalyst in a hydrogenation process to convert at least some of the unsaturated PAO product to a hydrogenated PAO product, the unsaturated PAO product comprising PAO molecules having vinylidene, trisubstituted vinylene, disubstituted vinylene and optionally vinyl unsaturation and formed from one or more C6-C 32 cyclic alpha-olefins and one or more C4-C 32 mixture of linear and / or branched alpha-olefins.

134. The method according to claim 133, wherein, The hydrogenation process occurs at a temperature of about 25°C - 350°C or about 100°C - 300°C; a time period of about 5 minutes to 100 hours or about 5 minutes to 24 hours; and / or at a hydrogen pressure of about 25 psig to 2500 psig or about 100 psig to 2000 psig.

135. The method according to claim 133 or 134, wherein The hydrogenation process occurs in a slurry reactor, batch operation, fixed bed reactor, or continuous stirred tank reactor.

136. The method according to any one of claims 133-135, wherein, The hydrogenation catalyst comprises about 0.001 wt% - 20 wt% or about 0.01 wt% - 10 wt% of the unsaturated PAO product or a feed comprising the unsaturated PAO product.

137. The method according to any one of claims 133-136, wherein The bromine value of the hydrogenated PAO product is 2.0 or less.

138. The method according to any one of claims 133-137, wherein, The hydrogenated PAO product comprises a mixture of dimers selected from hCC 1,2 , hLC 1,2 , hCL 1,2 , hLL 1,2 , hCC 2,1 , hLC 2,1 , hLL 2,1 , hLVCH-isomerization, and / or hVCHx2-isomerization, wherein: The cyclic monomeric segments (A) and (B) are saturated ring structures; n and m represent the number of additional carbon atoms in the ring structure and are each independently an integer from 1 to 20, R is a C2-C 30 hydrocarbyl group, R’ is C1-C 29 hydrocarbyl, and hCL 1,2 and hLC 1,2 is present in the hydrogenated PAO product.

139. The method according to claim 138, wherein, n and m independently represent an integer from 1 to 5, R is a C2-C8 hydrocarbyl group, and R' is a C1-C7 hydrocarbyl group.

140. The method according to claim 138, wherein, n and m are 3, R is a C3-C8 hydrocarbyl group, and R' is a C2-C7 hydrocarbyl group.

141. The method according to any one of claims 138 - 140, wherein, hLL 1,2 is present in the hydrogenated PAO product or a mixture thereof.

142. The method according to any one of claims 138 - 141, wherein, hCC 1,2 or hLL 1,2 is present in the hydrogenated PAO product or a mixture thereof.

143. The method according to any one of claims 138 - 141, wherein hCC 1,2 and hLL 1,2 are present in the hydrogenated PAO product or a mixture thereof.

144. The method according to any one of claims 133 - 143, wherein, The hydrogenated PAO product comprises: The first hydrodimer (hCC) formed by the reaction of two of said one or more C6-C 32 cyclic α-olefins; formed by the reaction of one of said one or more C6-C 32 cyclic α-olefins and one of said one or more C4-C 32 linear and / or branched α-olefins; and The third hydrogenated dimer (hLL) formed by two of said C4-C 32 linear and / or branched α-olefins.

145. The method according to claim 144, wherein, Based on GC-MS, based on hCC + hCL + hLL being equal to 100%, the percentage of hCL in the hydrogenated PAO product is 20% or greater, 30% or greater, 40% or greater, 50% or greater, 60% or greater, 70% or greater, or 80% or greater.

146. The method according to claim 144, wherein, Based on GC-MS, based on hCC + hCL + hLL being equal to 100%, the percentage of hCC in the hydrogenated PAO product is 0% or greater and 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less.

147. The method according to claim 144, wherein, Based on GC-MS, based on hCC + hCL + hLL being equal to 100%, the percentage of hLL in the hydrogenated PAO product is 10% or greater and 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or less.

148. A mixture of hydrogenated polyalphaolefins (PAO), which is formed by a process comprising: Contact a mixture of unsaturated PAO with hydrogen and a hydrogenation catalyst in a hydrogenation process to convert the unsaturated PAO mixture into a hydrogenated PAO mixture, the unsaturated PAO mixture comprising vinylidene, trisubstituted vinylene, disubstituted vinylene and optionally vinyl unsaturation and being composed of one or more C6-C 32 cyclic α-olefins and one or more C4-C 32 PAO formed from linear and / or branched α-olefins.

149. The mixture formed by the method according to claim 148, wherein, The hydrogenation process occurs at a temperature of 25°C - 350°C or 100°C - 300°C under a hydrogen pressure of 25 psig to 2500 psig or 100 psig to 2000 psig for 5 minutes to 100 hours or 5 minutes to 24 hours.

150. The mixture formed by the method according to claim 148 or 149, wherein, The hydrogenation process occurs in a slurry reactor, batch operation, fixed bed reactor, or continuous stirred tank reactor.

151. The mixture formed by the method according to any one of claims 148 - 150, wherein, The hydrogenation catalyst accounts for 0.001 wt% - 20 wt% or 0.01 wt% - 10 wt% of the unsaturated PAO feed.

152. The mixture formed by the method according to any one of claims 148 - 151, wherein, The bromine number of the hydrogenated PAO product is 2.0 or less.

153. The mixture formed by the method according to any one of claims 148 - 152, wherein, The hydrogenated PAO product comprises a mixture of dimers selected from hCC 1,2 , hLC 1,2 , hCL 1,2 , hLL 1,2 , hCC 2,1 , hLC 2,1 , hLL 2,1 , hLVCH-isomerization and hVCHx2-isomerization, wherein: The cyclic monomer fragments (A) and (B) are saturated ring structures; n and m represent the number of additional carbon atoms in the ring structure and are each independently an integer from 1 to 20, R is a C2-C 30 hydrocarbyl group, R’ is a C1-C 29 hydrocarbyl group, and hCL 1,2 and hLC 1,2 is present in the hydrogenated PAO product.

154. The mixture formed by the method according to claim 153, wherein, n and m independently represent an integer from 1 to 5, R is a C2-C8 hydrocarbyl group, and R' is a C1-C7 hydrocarbyl group.

155. The mixture formed by the method according to claim 153, wherein, n and m are 3, R is a C3-C8 hydrocarbyl group, and R' is a C2-C7 hydrocarbyl group.

156. The mixture formed by the method according to any one of claims 153-155, wherein, hCC 1,2 is present in the hydrogenated PAO product or a mixture thereof.

157. The mixture formed by the method according to any one of claims 153-155, wherein, hLL 1,2 is present in the hydrogenated PAO product or a mixture thereof. The mixture formed by the method according to any one of claims 153 - 155, wherein, hCC 1,2 and hLL 1,2 are present in the hydrogenated PAO product or a mixture thereof.

159. The mixture formed by the method according to any one of claims 153-158, wherein, The hydrogenated PAO product comprises: The first hydrodimer (hCC) formed by the reaction of two of said one or more C6-C 32 cyclic α-olefins; formed by the reaction of one of said one or more C6-C 32 cyclic α-olefins and one of said one or more C4-C 32 linear and / or branched α-olefins; and a second hydrogenated dimer (hCL); and The third hydrogenated dimer (hLL) formed by two of said C4-C 32 linear and / or branched α-olefins.

160. The mixture formed by the method according to claim 159, wherein, Based on GC-MS, based on hCC + hCL + hLL being equal to 100%, the percentage of hCL in the hydrogenated PAO product is 20% or greater, 30% or greater, 40% or greater, 50% or greater, 60% or greater, 70% or greater, or 80% or greater.

161. The mixture formed by the method according to claim 159 or 160, wherein, Based on GC-MS, based on hCC + hCL + hLL being equal to 100%, the percentage of hCC in the hydrogenated PAO product is 0% or greater and 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less.

162. The mixture formed by the method according to any one of claims 159 - 161, wherein, Based on GC-MS, based on hCC + hCL + hLL being equal to 100%, the percentage of hLL in the hydrogenated PAO product is 10% or greater and 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or less.

163. A mixture comprising two or more hydrogenated polyalphaolefin (hPAO) dimers selected from hCC 1,2 , hLC 1,2 , hCL 1,2 , hLL 1,2 , hCC 2,1 , hLC 2,1 , hLL 2,1 , hLVCH-isomerization, and / or hVCHx2-isomerization, wherein: The cyclic monomer fragments (A) and (B) are saturated ring structures; n and m represent the number of additional carbon atoms in the ring structure and are each independently an integer from 1 to 20, R is a C2-C 30 hydrocarbyl group, R’ is C1-C 29 hydrocarbyl, and hCL 1,2 and hLC 1,2 at least one of which is present in the mixture.

164. The mixture according to claim 163, wherein, n and m independently represent an integer from 1 to 5, R is a C2-C8 hydrocarbyl group, and R' is a C1-C7 hydrocarbyl group.

165. The mixture according to claim 163, wherein, n and m are 3, R is a C3-C8 hydrocarbyl group, R' is a C2-C7 hydrocarbyl group, and the cyclic monomer fragments (A) and (B) have a partially unsaturated ring structure.

166. The mixture according to any one of claims 163 - 165, wherein, hCC 1,2 or hLL 1,2 is present in the mixture.

167. The mixture according to any one of claims 163-165, wherein, hCC 1,2 and hLL 1,2 are present in the mixture.

168. The mixture according to claim 163, wherein, The hPAO contains one or more of the following structures: where p is an integer from 2 to 18.

169. The mixture according to claim 168, wherein, p is 2 - 8.

170. A hydrogenated polyalphaolefin (hPAO) product comprising one or more of the following compounds: 6-(2-cyclohexylethyl)bicyclo[3.2.1]octane, 6-hexylbicyclo[3.2.1]octane, 6-pentylbicyclo[3.2.1]octane, (6-methylheptan-2-yl)cyclohexane, and nonan-2-ylcyclohexane.

171. A hydrogenated polyalphaolefin (hPAO) product comprising butane-1,3-diyl dicyclohexane (hVCHx2), octan-2-ylcyclohexane (hVCH-hex), and 5-methylundecane (hHex-hex).

172. The hPAO product according to claim 171, wherein, Based on the total molar amount of hVCHx2 + hVCH-hex + hHex-hex being equal to 100%, the molar percentage of hVCH-hex is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%. The hPAO product according to claim 171 or 172, wherein, Based on the total molar amount of hVCHx2 + hVCH-hex + hHex-hex being equal to 100%, the molar percentage of hVCHx2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. The hPAO product according to any one of claims 171-173, wherein, Based on the total molar amount of hVCHx2 + hVCH-hex + hHex-hex being equal to 100%, the molar percentage of hHex-hex is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

175. A hydrogenated polyalphaolefin (hPAO) product comprising butane-1,3-diyl dicyclohexane (hVCHx2), 4-heptan-2-ylcyclohexane (hVCH-pent), and 4-methylnonane (hPent-pent).

176. The hPAO product according to claim 175, wherein, Based on the total molar amount of hVCHx2 + hVCH-pent + hPent-pent being equal to 100%, the molar percentage of hVCH-pent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

177. The hPAO product according to claim 175 or 176, wherein, Based on a total mole number of hVCHx2 + hVCH-pent + hPent-pent equal to 100%, the mole percentage of hVCHx2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. The hPAO product according to any one of claims 175-177, wherein, Based on a total mole number of hVCHx2 + hVCH-pent + hPent-pent equal to 100%, the mole percentage of hPent-pent is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

179. A hydrogenated polyalphaolefin (hPAO) product comprising butane-1,3-diyl dicyclohexane (hVCHx2), 4-hept-2-yl cyclohexane (hVCH-hept), and 6-methyltridecane (hHept-hept).

180. The hPAO product according to claim 179, wherein, Based on a total mole number of hVCHx2 + hVCH-hept + hHept-hept equal to 100%, the mole percentage of hVCH-pent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

181. The hPAO product according to claim 179 or 180, wherein, Based on a total mole number of hVCHx2 + hVCH-hept + hHept-hept equal to 100%, the mole percentage of hVCHx2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%.

182. The hPAO product according to any one of claims 179-181, wherein, Based on a total mole number of hVCHx2 + hVCH-hept + hHept-hept equal to 100%, the mole percentage of hHept-hept is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

183. A hydrogenated polyalphaolefin (hPAO) product comprising butane-1,3-diyl dicyclohexane (hVCHx2), hex-2-yl cyclohexane (hVCH-but), and 3-methylheptane (hbut-but).

184. The hPAO product according to claim 183, wherein, Based on a total mole number of hVCHx2 + hVCH-but + hbut-but equal to 100%, the mole percentage of hVCH-but is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

185. The hPAO product according to claim 183 or 184, wherein, Based on a total mole number of hVCHx2 + hVCH-but + hbut-but equal to 100%, the mole percentage of hVCHx2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%.

186. The hPAO product according to any one of claims 183-185, wherein, Based on a total molar amount of hVCHx2 + hVCH-but + hbut-but equal to 100%, the molar percentage of hbut-but is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

187. A hydrogenated polyalphaolefin (hPAO) comprising butane-1,3-diyl dicyclohexane (hVCHx2), (6-methylhept-2-yl) cyclohexane (hVCH-MePent), and 4-methylnonane (hMePent-MePent).

188. The hPAO product according to claim 187, wherein, Based on a total molar amount of hVCHx2 + hVCH-MePent + hMePent-MePent equal to 100%, the molar percentage of hVCH-MePent is at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, or at least about 80%.

189. The hPAO product according to claim 187 or 188, wherein, Based on a total molar amount of hVCHx2 + hVCH-MePent + hMePent-MePent equal to 100%, the molar percentage of hVCHx2 is 0% or greater and at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, or at most about 5%. The hPAO product according to any one of claims 187-189, wherein, Based on a total molar amount of hVCHx2 + hVCH-MePent + hMePent-MePent equal to 100%, the molar percentage of hMePent-MePent is at least about 10% and at most about 80%, at most about 70%, at most about 60%, at most about 50%, at most about 40%, at most about 30%, or at most about 20%.

191. A functionalized polyalphaolefin (PAO) comprising the reaction product of: 1) a heteroatom-containing group, and 2) an unsaturated PAO prepared by a method (e.g., any method described herein, such as a method for preparing a polyalphaolefin (PAO) from two or more different alpha-olefins), wherein the heteroatom-containing group comprises one or more sulfonates / esters, amines, aldehydes, alcohols, or acids, preferably the heteroatom-containing group comprises an epoxide, succinic acid, maleic acid, or maleic anhydride, alternatively the heteroatom-containing group comprises one or more of an acid, ester, anhydride, acid-ester, oxycarbonyl, carbonyl, formyl, formylcarbonyl, hydroxyl, and acetyl halide.

192. The functionalized PAO according to claim 191, wherein, The unsaturated PAO is prepared by a method for preparing a polyalphaolefin (PAO) from two or more different alpha-olefins, wherein the method comprises: To make a feed containing one or more C6-C 32 cyclic α-olefins and one or more C4-C 32 linear and / or branched α-olefins contact a catalyst system containing a metallocene compound in a polymerization reactor under polymerization conditions to effect a polymerization reaction to obtain a polymerization reaction mixture, the polymerization reaction mixture comprising a mixture of PAOs (e.g., PAO molecules) having ethylidene, trisubstituted vinylidene, disubstituted vinylidene, and optionally vinyl unsaturation, and Obtaining an unsaturated PAO product from the polymerization reaction mixture.

193. The functionalized PAO according to claim 191, wherein, The unsaturated PAO is prepared by the method according to any one of claims 1-26.

194. A method for preparing a cyclic dimer from one or more cyclic alpha-olefins, the method comprising: Contact a feed containing one or more C6-C 32 cyclic α-olefins with a catalyst system containing a metallocene compound in a polymerization reactor under polymerization conditions to effect a polymerization reaction to obtain a polymerization reaction mixture, the polymerization reaction mixture containing cyclic dimers (e.g., cyclic dimer molecules) having ethylidene, trisubstituted vinylidene, disubstituted vinylidene, and optionally vinyl unsaturation, wherein the metallocene compound is selected from formula (I), (II), (III), (IV), or (V), provided that in formula (I) and (II) R 1 and R 3 in at least one is not hydrogen, and Obtaining an unsaturated cyclic dimer product from the polymerization reaction mixture. The method according to claim 194, wherein, The method is a continuous method, a batch method, or a semi-batch method.

196. The method according to claim 195, wherein, The method is a continuous solution and / or bulk method for preparing the cyclic dimer.

197. The method according to claim 196, comprising: Contact at least one C4-C 24 cyclic α-olefin with a metallocene catalyst, a non-coordinating anion activator, and optionally an alkylaluminum compound, wherein the polymerization conditions include a reaction temperature in the range of 100 °C to 160 °C, a reactor pressure of less than 50 atmospheres, and a residence time in the range of 20 minutes to 3 hours; obtaining the cyclic dimer; and optionally hydrogenating the cyclic dimer.

198. The method according to claim 197, wherein, contacting at least one C4-C 24 cyclic α-olefin with a solvent-free composition except for the solvents used in the catalyst and scavenger solutions; and / or wherein the feed is substantially free of linear and branched α-olefins.

199. The method according to claim 195, wherein, The method is a solution and / or bulk method for preparing the cyclic dimer in a batch or semi-batch reactor.

200. The method according to claim 199, comprising: Contact at least one C4-C 24 cyclic α-olefin with a metallocene catalyst, a non-coordinating anion activator and optionally an alkylaluminum compound, wherein the polymerization conditions include a reaction temperature in the range of 100 °C to 160 °C, a reactor pressure of less than 50 atmospheres and a residence time in the range of 20 minutes to 24 hours; and wherein the metallocene catalyst and the non-coordinating anion activator are fed separately into the reactor; obtaining the cyclic dimer; and optionally hydrogenating the cyclic dimer. The method according to claim 200, wherein, The metallocene catalyst is added in a single dose at the start of the reaction or in stages (e.g., in multiple doses) during the reaction. The method according to claim 200 or 201, wherein contacting at least one C4-C 24 cyclic α-olefin with a solvent-free composition except for the solvents used in the catalyst and scavenger solutions; and / or wherein the feed is substantially free of linear and branched α-olefins. The method according to any one of claims 194 to 202, wherein By GC-MS measurement, the conversion of the one or more cyclic α-olefins to the cyclic dimer is 50% or greater, alternatively 60% or greater, alternatively 70% or greater, alternatively 80% or greater, alternatively 90% or greater, alternatively 95% or greater, based on the total amount of the feed monomers, dimers, trimers, tetramers, and higher oligomers including isomerized or hydrogenated monomers. The method according to any one of claims 194 to 203, wherein By GC-MS measurement, the selectivity for forming the cyclic dimer is 80% or greater, alternatively 90% or greater, alternatively 94% or greater, alternatively 98% or greater, where 99% or greater, based on the total amount of the dimers, trimers, tetramers, and higher oligomers. The method according to any one of claims 194 to 204, wherein By GC-MS measurement, the selectivity for forming a single cyclic dimer species (e.g., a single isomer) is 80% or greater, alternatively 85% or greater, alternatively 90% or greater, alternatively 95% or greater, alternatively 98% or greater, based on the total amount of the cyclic dimer. The method according to any one of claims 194 to 205, wherein By GC-MS measurement, when only cyclic α-olefins are in the feed, the conversion of the cyclic α-olefin monomer to form a single cyclic dimer species (e.g., a single isomer) is 30% or greater, alternatively 40% or greater, alternatively 60% or greater, alternatively 80% or greater, alternatively 90% or greater, alternatively 94% or greater, based on the amount of the major dimer isomer relative to the total amount of the feed monomers, dimers, trimers, tetramers, and higher oligomers including isomerized or hydrogenated monomers.

207. The method according to any one of claims 194-206, wherein, By GC-MS measurement, the formation of trimers and higher oligomers is 5% or less, alternatively 4% or less, alternatively 3% or less, alternatively 2% or less, preferably 1% or less, most preferably 0.1% or less, based on the total amount of the dimers, trimers, tetramers, and higher oligomers. The method according to any one of claims 194 to 207, wherein, The metallocene compound or the metallocene catalyst is selected from formula (II), (III), (IV), or (V), provided that in formula (II), R 1 and R 3 in which at least one is not hydrogen. The method according to claim 208, wherein The metallocene compound or the metallocene catalyst is selected from formula (I), (II), or (IV); wherein R 1 and R 2 are hydrogen; and wherein R 3 is selected from the group consisting of methyl, ethyl, and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and isobutyl. The method according to any one of claims 194 to 209, wherein, The metallocene compound or the metallocene catalyst is selected from the group consisting of: (Pentamethylcyclopentadienyl)(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-ethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-n-propyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isopropyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-n-butyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1,6,6-triethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-methylindenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutylindenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-methyl-3,6,7,8-tetrahydro-as-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-3,6,7,8-tetrahydro-as-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-methyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene)dimethylhafnium, (Pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)dimethylhafnium, and (Pentamethylcyclopentadienyl)(1-isobutyl-5,6-dimethylindenyl)dimethylhafnium. The method according to any one of claims 194 to 209, wherein, The metallocene compound or the metallocene catalyst is selected from the group consisting of: (Pentamethylcyclopentadienyl)(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-methylindenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1-isobutylindenyl)dimethylhafnium, (Pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)dimethylhafnium, and (Pentamethylcyclopentadienyl)(1-isobutyl-5,6-dimethylindenyl)dimethylhafnium.

212. The method according to any one of claims 194 - 211, wherein, The feedstock is substantially free of linear and branched α-olefins.

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