Catalyst systems and processes for cyclic polyalpha-olefins

Abstract

FIELD OF THE DISCLOSURE The present disclosure relates to cyclic polyalphaolefin (PAO) materials prepared from alpha-olefins and methods for making the same.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 407,608, filed September 16, 2022, which is incorporated herein by reference in its entirety. This disclosure relates to cyclic polyalphaolefin (PAO) materials prepared from alpha-olefins and methods for making same. In particular, this disclosure relates to ethylenically unsaturated 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 result in cyclic PAO compositions with a high dimer content. [Background technology]

[0002] Polyalphaolefins (PAOs) are typically produced from the oligomerization of linear alphaolefins. These unsaturated polyalphaolefins (uPAOs) can be used as intermediates for preparing various specialty chemicals due to the reactivity of the C=C double bonds present in the molecular structure of the oligomer molecules. For example, various chemical functional groups can be attached to the carbon backbone of the uPAO molecule when the uPAO is exposed to chemicals reactive to the C=C bond. The functional groups thus introduced onto the PAO structure can impart unique properties to functionalized and saturated PAO molecules. Hydrogenated uPAOs are useful in lubricating oil compositions, such as those used in internal combustion engines, automotive greases, industrial greases, and gearbox oils. Summary of the Invention

[0003] One aspect of the present disclosure relates to a process for making 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 of the alpha-olefins is a linear or branched alpha-olefin. The process comprises:32 Cyclic alpha-olefin and one or more C4-C 32 The method may include contacting a feedstock containing linear and / or branched alpha-olefins with a catalyst system containing a metallocene compound in a polymerization reactor under polymerization conditions to produce a polymerization reaction mixture containing a mixture of PAO molecules having vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturation. The method may also include obtaining an unsaturated PAO product from the polymerization reaction mixture, wherein the unsaturated PAO product contains a mixture of PAO molecules having vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturation, and may be substantially free of the alpha-olefin feedstock. When a cyclic alpha-olefin having ring unsaturation, such as 4-vinylcyclohex-1-ene, is used as the cyclic alpha-olefin, the PAO product may also contain a ring-disubstituted vinylene. This type of unsaturation is referred to as a ring-disubstituted vinylene.

[0004] Another aspect of the present disclosure relates to a process for making alpha-olefin dimers and trimers from two or more alpha-olefins, wherein at least one alpha-olefin is a cyclic alpha-olefin and at least one alpha-olefin is a linear or branched alpha-olefin. The process comprises: 32 Cyclic alpha-olefin and one or more C4-C 32The method may include contacting a feedstock containing linear and / or branched alpha-olefins with a catalyst system containing a metallocene compound in a polymerization reactor under polymerization conditions to produce a polymerization reaction mixture containing vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturated dimer and / or trimer molecules. The method may also include obtaining unsaturated dimer and / or trimer products from the polymerization reaction mixture, wherein the unsaturated dimer and / or trimer products contain vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturation and may be substantially free of the alpha-olefin feedstock. When a cyclic alpha-olefin having ring unsaturation, such as 4-vinylcyclohex-1-ene, is used as the cyclic alpha-olefin, the dimer and / or trimer products may contain endocyclic disubstituted vinylenes. This type of unsaturation is referred to as cyclic disubstituted vinylenes.

[0005] Another aspect of the present disclosure relates to a process for making alpha-olefin dimers and / or trimers from two or more different alpha-olefins, wherein at least one alpha-olefin is a cyclic alpha-olefin and at least a second alpha-olefin is a linear or branched alpha-olefin, and the product comprises unsaturated dimers and / or trimers, respectively. Another aspect of the present disclosure relates to a process for making alpha-olefin dimers and / or trimers (preferably dimers) from two or more different alpha-olefins, wherein at least one of the alpha-olefins is a cyclic alpha-olefin and at least a second alpha-olefin is a linear or branched alpha-olefin, and wherein the products produced have a selectivity for producing dimers of at least about 50% of the total product mixture, at least about 60% of the total product mixture, at least about 70% of the total product mixture, at least about 80% of the total product mixture, at least about 90% of the total product mixture, or at least about 95% of the total product mixture. The present disclosure also relates to a process for the dimerization of cyclic alpha-olefins to produce cyclic dimers. In particular, the present disclosure relates to ethylenically unsaturated and saturated cyclic dimers derived from the dimerization of cyclic alpha-olefins in the presence of a catalyst system comprising a metallocene compound specifically designed to provide cyclic dimer compositions having vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturation.

[0006] In any embodiment herein, the method can include the use of a metallocene compound (e.g., any described herein). In some embodiments, the metallocene compound is represented by formula (I), (II), (III), (IV), or (V) as described herein. In some embodiments, R 1 and R 3 At least one of is not hydrogen in formula (I) or (II). The details of one or more embodiments of the presently disclosed subject matter are set forth in the accompanying drawings and the description. Other features, aspects, and advantages of the subject matter will become apparent from the description, drawings, and claims. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 shows two reaction pathways in which 4-vinylcyclohex-1-ene (VCH) undergoes a chain transfer process to yield bicyclic products. [Figure 2] FIG. 1 is a diagram showing two reaction pathways by which VCH undergoes a chain transfer process with an alpha-olefin represented as CH═CHR, where R can be a linear, branched, or cyclic aliphatic group. DETAILED DESCRIPTION OF THE INVENTION

[0008] definition The terms "alkyl" or "alkyl group" refer interchangeably to saturated hydrocarbyl groups composed of carbon and hydrogen atoms. Alkyl groups can be linear, branched, cyclic, or substituted cyclic, or combinations thereof. Whenever "linear, branched, or cyclic" is used, these combinations are included. For example, methylcyclohexyl is a combination and is included in the definition of an alkyl group. The term "branched" is defined to mean a branched group that is not dendritic (i.e., branch-on-branch) or crosslinked. Typically, branched groups are linear groups having one or more branches, including, but not limited to, compounds represented by Formulas F through V below.

[0009] The term "cyclic dimer" refers to one or more C6-C 32 It is defined to mean a dimer formed from the dimerization of a cyclic alpha-olefin. Cyclic dimers are also commonly referred to as "dimers." The terms "cycloalkyl" or "cycloalkyl group" refer interchangeably to saturated hydrocarbyl groups in which carbon atoms form one or more ring structures. The terms "alkenyl" or "alkenyl group" refer interchangeably to a straight-chain unsaturated hydrocarbyl group containing an internal C=C bond. The terms "cycloalkenyl" or "cycloalkenyl group" refer interchangeably to a cyclic hydrocarbyl group that contains a C=C bond within the ring.

[0010] The terms "aryl" or "aryl group" refer interchangeably to a hydrocarbyl group that contains an aromatic ring structure therein. The terms "aryloxy" and "aryloxide" refer to an aryl group attached to an oxygen atom, such as an aryl ether group / radical attached to an oxygen atom, where the aryl group is C6-C 20 Examples of suitable aryloxy radicals include phenoxy, biphenoxy, naththoxy, and the like. The terms "alkoxy" and "alkoxide" refer to an alkyl group attached to an oxygen atom, such as an alkyl ether group / radical attached to an oxygen atom, where the alkyl group is C1-C 20 The alkyl group may be linear, branched, or cyclic. The alkyl group may be saturated or partially unsaturated. Examples of suitable alkoxy radicals include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and the like. The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" refer interchangeably to a group consisting solely of hydrogen and carbon atoms. Hydrocarbyl groups can be saturated or unsaturated, straight-chained or branched, cyclic or acyclic, aromatic or non-aromatic.

[0011] Unless otherwise indicated, a substituted group (such as a substituted hydrocarbyl) refers to a group in which at least one atom has been replaced with a different atom or group. For example, a substituted alkyl group can be an alkyl group in which at least one hydrogen atom has been replaced with a hydrocarbyl group, a halogen, any other non-hydrogen group, and / or at least one carbon atom, and the hydrogen atoms bonded thereto have been replaced with a different group. A substituted group is one in which at least one hydrogen atom has been replaced with a heteroatom or heteroatom-containing group, preferably with at least one functional group (e.g., halogens (Cl, Br, I, F), NR * 2, OR * , SeR * , TeR * , PR * 2. AsR * 2. SbR * 2. SR * , B.R. * 2. SiR * 3. GeR * 3. SnR * 3, and PbR * 3, etc.), or at least one heteroatom is, for example, O, S, Se, Te, NR * , PR *, AsR * , SbR * , B.R. * , SiR * 2. GeR * 2. SnR * 2, and PbR * 2, which can be a radical that is inserted within a hydrocarbyl radical, such as R * is independently hydrogen, hydrocarbyl, or halocarbyl.

[0012] Aromatic, as used herein, refers to a cyclic compound, ligand, or substituent ("ring") that contains a cyclic electron cloud of delocalized pi electrons above and below the plane of the "ring," and the pi electron cloud must contain a total of 4n+2 pi electrons, where n is an integer. As used herein, the term "aromatic" also refers to pseudo-heteroaromatic rings, which are heterocyclic substituents with properties and structure (nearly planar) similar to aromatic heterocyclic ligands, but which are not, by definition, aromatic.

[0013] Substituted hydrocarbyl radicals are those in which at least one hydrogen atom is replaced with a heteroatom or heteroatom-containing group, preferably with at least one functional group, such as a halogen (Cl, Br, I, F), NR * 2, OR * , SeR * , TeR * , PR * 2. AsR * 2. SbR * 2. SR * , B.R. * 2. SiR * 3. GeR * 3. SnR * 3, and PbR * 3, etc.), or at least one heteroatom is substituted with a hydrocarbyl radical, such as halogen (Cl, Br, I, F), O, S, Se, Te, NR * , PR * , AsR * , SbR * , B.R. * , SiR * 2. GeR * 2. SnR *2, and PbR * 2, etc., is an internally inserted radical, R * is independently hydrogen or hydrocarbyl.

[0014] In some embodiments, the hydrocarbyl radicals are independently selected from methyl, ethyl, ethenyl, 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, and is selected from the isomers of 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, eicosinyl, heneicosinyl, docosinyl, tricosinyl, tetracosinyl, pentacosinyl, hexacosinyl, heptacosinyl, octacosinyl, nonacosinyl, and triacontinyl. Also included are isomers of saturated, partially unsaturated, and aromatic ring structures, where the radicals may be further subjected to substitution of the types described above. Examples include phenyl, methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and the like.The alkyl, alkenyl, and alkynyl radicals listed include all isomers, including cyclic isomers where appropriate, for example, 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); 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, for example, methylphenyl includes ortho-methylphenyl, meta-methylphenyl, and para-methylphenyl; dimethylphenyl includes 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl.

[0015] Silyl groups (also called silyl, silyl radicals, and silyl substituents) are represented by the formula: SiR * 3 (wherein, R * are independently hydrogen, hydrocarbyl, or halocarbyl radicals, and two or more R * may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. The silyl group is bonded through the silicon atom.

[0016] A silylcarbyl radical (e.g., a hydrocarbyl group, silylcarbyl, silylcarbyl group, or silylcarbyl substituent) is a radical in which one or more hydrocarbyl hydrogen atoms are bonded to at least one SiR * 3-containing group or at least one -Si(R * )2- is inserted within the hydrocarbyl radical, where R *are independently hydrogen, hydrocarbyl, or halocarbyl radicals, and two or more R * may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. The silylcarbyl radical can be attached via a silicon atom or a carbon atom. A substituted silylcarbyl radical is one in which at least one hydrogen atom is substituted with at least one functional group, e.g., NR * 2, OR * , SeR * , TeR * , PR * 2. AsR * 2. SbR * 2. SR * , B.R. * 2. GeR * 3. SnR * 3, and PbR * 3, or at least one non-hydrocarbon atom or group is substituted with a silylcarbyl radical, 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--, and --Pb(R * )2—, where R * are independently hydrogen, hydrocarbyl, or halocarbyl radicals, and two or more R * may be joined together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

[0017] Halocarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms are replaced with at least one halogen (e.g., F, Cl, Br, I) or halogen-containing group (e.g., CF3). A substituted halocarbyl radical is one in which at least one halocarbyl hydrogen or halogen atom is substituted with at least one functional group, e.g., NR * 2, OR * , SeR * , TeR * , PR * 2. AsR * 2. SbR * 2. SR * , B.R. * 2. SiR * 3. GeR * 3. SnR * 3, and PbR * 3, or at least one non-carbon atom or group is substituted with a halocarbyl radical, 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--, and --Pb(R * )2—, where R * are independently hydrogen, hydrocarbyl, or halocarbyl radicals, provided that at least one halogen atom remains on the original halocarbyl radical. * may be joined together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

[0018] The term "substituted phenyl" or "substituted phenyl group" refers to a group that contains a hydrocarbyl, substituted hydrocarbyl, heteroatom, or 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, and -PbR * 3, etc., wherein each R * are independently a hydrocarbyl, halogen, or halocarbyl radical. Preferably, the "substituted phenyl" group has the formula: [ka] (In the formula, R 17 , R 18 , R 19 , R 20 , and R 21 each independently represents hydrogen, C1-C 40 Hydrocarbyl or C1-C 40 Substituted hydrocarbyl, heteroatom, e.g., halogen, or heteroatom-containing group (where R 17 , R 18 , R 19 , R 20 , and R 21 provided that at least one of is not H), or a combination thereof) is expressed by

[0019] A "fluorophenyl" or "flurophenyl group" is a phenyl group substituted with one, two, three, four, or five fluorine atoms. The term "arylalkyl" refers to an aryl group in which a hydrogen has been replaced with 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. The term "alkylaryl" refers to an alkyl group in which a hydrogen has been replaced with 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.

[0020] Reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl) unless otherwise indicated. The term "ring atom" means an atom that is part of a cyclic ring structure. Thus, a benzyl group has 6 ring atoms and tetrahydrofuran has 5 ring atoms. Reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl) unless otherwise indicated. The term "Cn" group or compound refers to a group or compound containing n carbon atoms in total. A "Cm-Cn" group or compound refers to a group or compound containing a total number of carbon atoms ranging from m to n. Thus, C1-C 50 Alkyl refers to alkyl groups containing a total of between 1 and 50 carbon atoms.

[0021] The term "olefin," alternatively referred to as "alkene," refers to a substituted or unsubstituted aliphatic hydrocarbon compound having a hydrocarbon chain containing at least one carbon-carbon double bond within its structure. In some non-limiting embodiments, alkenes are unsaturated hydrocarbon compounds. In other non-limiting embodiments, the carbon-carbon double bond does not form part of an aromatic ring. The olefin may be linear, branched, cyclic, or a combination thereof. For purposes of this specification and the claims appended hereto, when a polymer or copolymer is referred to as comprising an olefin, including, but not limited to, ethylene, propylene, and butene, the olefin present in such polymer or copolymer is the polymerized form of the olefin (e.g., as a dimer, trimer, or oligomer). For example, when a copolymer is said to have an "ethylene" content of 35% to 55% by weight, it is understood that the mer units in the copolymer are derived from ethylene in the polymerization reaction, and that the derived units are present in an amount of 35% to 55% by weight, based on the weight of the copolymer. A "polymer" has two or more of the same or different mer units. A "homopolymer" is a polymer with mer units that are the same. A "copolymer" is a polymer with two or more mer units that are different from each other. A "terpolymer" is a polymer with three mer units that are different from each other. "Different" when used to refer to mer units indicates that the mer units differ from each other by at least one atom or are isomerically different. Thus, "olefin" is intended to encompass all structural isomeric forms of olefins unless specified to mean a single isomer or unless 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 mer units, such as 100 mer units or less, e.g., 50 mer units or less. A dimer is a polymer having two mer units that may be the same or different. A trimer is a polymer with three mer units that may be the same or different. A tetramer is a polymer with four mer units that may be the same or different.Dimers, trimers, and tetramers are sometimes referred to as oligomers. The process of making polymers and oligomers, including dimers, trimers, and tetramers, is referred to as polymerization. In some cases, polymerization and oligomerization are used interchangeably in this document.

[0022] The term "alpha-olefin" refers to an olefin having a terminal carbon-carbon double bond within its structure (R a R b )-C=CH2, where R a and R b can independently be hydrogen or any hydrocarbyl group; preferably R a is hydrogen and R b is an alkyl group). A "linear alpha-olefin" is an alpha-olefin as defined in this paragraph, where R a is hydrogen and R b is hydrogen or a straight chain alkyl group.

[0023] 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.

[0024] Cyclic olefins contain a carbon-carbon double bond within the ring structure. Non-limiting examples of cyclic olefins and diolefins 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.

[0025] Non-limiting examples of branched α-olefins include 4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene, and 3,5,5-trimethyl-1-hexene. Non-limiting examples of cyclic α-olefins include vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, 4-vinylcyclohex-1-ene (also called vinylcyclohexene), vinylcycloheptane, vinylcyclooctane, vinylcyclononane, vinylcyclodecane, vinylcycloundecane, vinylcyclododecane, 5-vinylnorbornane, 5-vinyl-2-norbornene, allylcyclohexane, and allylcyclooctane. Non-limiting examples of aromatic cyclic α-olefins include styrene, para-methylstyrene, meta-methylstyrene, para-ethylstyrene, para-propylstyrene, para-butylstyrene, 3,5-diemethylstyrene, and vinylnaphthylene. Non-limiting examples of cyclic olefins that are not alpha-olefins include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene, 3-methylcyclopentene, 4-methylcyclopentene, and 5-ethylidene-2-norbornene. In unsaturated PAOs, the unsaturated end groups can include different types of unsaturation, such as vinyl, vinylidene, disubstituted vinylene, and trisubstituted vinylene. The term "vinyl" refers to a group having the formula: [ka] wherein R is a hydrocarbyl group, preferably a saturated hydrocarbyl group, such as an alkyl group. The olefin is represented by the formula: The term "vinylidene" refers to the compound of the formula: [ka] (In the formula, R 1 and R 2 are each independently a hydrocarbyl group, preferably a saturated hydrocarbyl group, e.g., an alkyl group. Vinylidene is a 1,1-disubstituted vinylene group. The term "disubstituted vinylene" refers to: (i) the formula: [ka] an olefin represented by: (ii) the formula: [ka] an olefin represented by: (iii) A mixture of (i) and (ii) in any proportion thereof. where R 1 and R 2 are the same or different at each occurrence and are each independently a hydrocarbyl group, preferably a saturated hydrocarbyl group, such as an alkyl group. Disubstituted vinylene refers only to 1,2-disubstituted vinylene groups and does not include vinylidene, which may also be referred to as 1,1-disubstituted vinylene. As used herein, the term "vinylene" is an alternative term for "disubstituted vinylene" only, and not as a general class of many vinylene species. In some non-limiting embodiments, vinylene or disubstituted vinylene does not include cyclic disubstituted vinylene. The term "trisubstituted vinylene" refers to a group having the formula: [ka] (In the formula, R 1 , R 2 , and R 3 are each independently a hydrocarbyl group (e.g., a saturated hydrocarbyl group such as an alkyl group), or R 1 and R 2 can together form a non-aryl ring structure, where R 3 is a hydrocarbyl side group) As used herein, the term "trisub" is an alternative name for "tri-substituted vinylene." "Cyclic disubstituted vinylenes" are found in cyclic olefins such as cyclopentene, and in some cyclic α-olefins such as 4-vinylcyclohex-1-ene, which contains both vinyl and "cyclic disubstituted vinylene" unsaturation.

[0026] As used herein, "polyalphaolefin" (PAO) refers to a polymer of one or more alpha-olefin monomers, particularly an oligomer of one or more alpha-olefins. PAOs are polymeric, typically oligomeric, molecules produced from the polymerization reaction of alpha-olefin monomer molecules in the presence of a catalyst system, which may be further partially or fully hydrogenated to remove residual internal carbon-carbon double bonds, or further functionalized by reaction with some or all of the residual internal carbon-carbon double bonds. Thus, PAOs can be dimers, trimers, tetramers, or any other oligomer or polymer containing two or more structural units derived from one or more alpha-olefin monomers. PAO molecules can be highly regioregular (stereoregular), so that the bulk material is 13 They can exhibit isotacticity or syndiotacticity as measured by C NMR. PAO molecules can be highly regioirregular (stereoirregular), and therefore the bulk material 13It can be substantially atactic as determined by C NMR.

[0027] PAO materials made by using metallocene-based catalyst systems can be referred to as metallocene-PAOs (mPAOs), while PAOs made by using traditional non-metallocene-based catalysts (e.g., Lewis acids, supported chromium oxides, etc.) can be referred to as conventional PAOs (cPAOs).

[0028] The term "carbon backbone" refers to the longest linear carbon chain within the molecule or group of the compound in question. "Branch" or "side group" refers, synonymously, to any non-hydrogen group attached to the carbon backbone other than that attached to the carbon backbone 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, counting from the first carbon atom attached to the carbon backbone and terminating at the final carbon atom within it, not taking into account any substituents or side groups on the chain. In some embodiments, the side group does not contain a substituent containing more than two carbon atoms (or more than one carbon atom), or does not contain any substituents at all. The side group may contain a cyclic group or portion thereof in the longest carbon chain, in which case half of the carbon atoms in the cyclic group count toward the length of the side group. Thus, by way of example, a linear C8 side group has a length of 8; side groups PG-1 (cyclohexylmethylene) and PG-2 (phenylmethylene) each have a length of 4; and side groups PG-3 (o-heptylphenylmethylene) and PG-4 (p-heptylphenylmethylene) each have a length of 11. When 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. [ka]

[0029] For purposes of nomenclature, the following numbering scheme is used for cyclopentadienyl, indenyl, tetrahydro-s-indacenyl, tetrahydro-as-indacenyl, benzo[f]indenyl, and benzo[e]indenyl ligands. Indenyl, tetrahydro-s-indacenyl, tetrahydro-as-indacenyl, benzo[f]indenyl, and benzo[e]indenyl ligands are, by definition, substituted cyclopentadienyl ligands. Tetrahydro-s-indacenyl, tetrahydro-as-indacenyl, benzo[f]indenyl, and benzo[e]indenyl ligands are, by definition, substituted indenyl ligands. The numbering scheme is used to indicate the position of substituents, and where applicable, a cyclopentadienyl ligand substituted with bridges, e.g., methyl groups at the 1- and 3-positions, may be named 1,3-dimethylcyclopentadienyl. Similarly, two indenyl ligands bridged by a dimethylsilylene group at the 1-position of each indenyl may be named dimethylsilylene-bis(inden-1-yl). [ka]

[0030] The metallocene compounds described herein may have one or more optical isomers. A metallocene compound identified herein by name or structure is intended to include all possible optical isomers thereof and any mixtures of such optical isomers. For example, the metallocene compound Me2Si(Me4Cp)(3-PrInd)ZrMe2 includes the following two optical isomers and mixtures thereof, even though only one structure is given when described: [ka]

[0031] 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 the transition metal; typically, metallocene catalysts are organometallic compounds containing at least one π-bonded cyclopentadienyl moiety (or a 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, and tetrahydrocyclopenta[a]naphthalene, and the like.

[0032] The substituted cyclopentadienyl ligand may be bridged or unbridged, e.g., by a dimethylsilylene bridge as described above. If no bridge is specifically disclosed, the cyclopentadienyl ligand is unbridged. Similarly, if no bridge is specifically disclosed with respect to the metallocene (also known as the precatalyst), the metallocene is unbridged. Asymmetric metallocene compounds are those that have two π-bonded cyclopentadienyl moieties that differ in ring type, such as by having one monocyclic allenyl ligand and one polycyclic allenyl ligand. For example, (cyclopentadienyl)(indenyl)zirconium dichloride would be considered asymmetric because it has one monocyclic allenyl ligand and one polycyclic allenyl ligand, while bis(indenyl)zirconium dichloride would be considered symmetric because it has two polycyclic allenyl ligands.

[0033] As used herein, the term "monocyclic allenyl ligand" refers to a substituted or unsubstituted monoanionic C5-C6 ligand containing an aromatic five-membered single hydrocarbyl ring structure (also referred to as a cyclopentadienyl ring). 100 Used to mean a hydrocarbyl ligand. As used herein, the term "polycyclic allenyl ligand" refers herein to a substituted or unsubstituted monoanionic C-C 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. 103 Used to mean a hydrocarbyl ligand. Monocyclic allenyl ligands include substituted or unsubstituted cyclopentadienyl. Polycyclic allenyl ligands include substituted or unsubstituted partially unsaturated or aromatic indenyl, fluorenyl, 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, and 3,6,7,8-tetrahydro-as-indacenyl.

[0034] Non-limiting examples of polycyclic arene ligands, also termed 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-trimethylinden ... 4,5-trimethyleneindenyl, 5,6-pentamethyleneindenyl, 4,5-pentamethyleneindenyl, 5,6-hexamethyleneindenyl, 4,5-hexamethyleneindenyl, 5,6-heptamethyleneindenyl, 4,5-heptamethyleneindenyl, 5,6-octamethyleneindenyl, 4,5-octamethyleneindenyl, 5,6-nonamethyleneindenyl, 4,5-nonamethyleneindenyl, 5,6-decamethyleneindenyl, 4,5-decamethyleneindenyl, 5,6-undecamethyleneindenyl nyl, 4,5-undecamethyleneindenyl, 5,6-dodecamethyleneindenyl, 4,5-dodecamethyleneindenyl, 5,6-tridecamethyleneindenyl, 4,5-tridecamethyleneindenyl, 5,6-tetradecamethyleneindenyl, 4,5-tetradecamethyleneindenyl, 5,6-pentadecamethyleneindenyl, 4,5-pentadecamethyleneindenyl, 5,6-hexadecamethyleneindenyl, 4,5-hexadecamethyleneindenyl, 5,6-heptadecamethyleneindenyl, 4,5-heptadecamethyleneindenyl Indenyl, 5,6-octadecamethyleneindenyl, 4,5-octadecamethyleneindenyl, 5,6-nonadecamethyleneindenyl, 4,5-nonadecamethyleneindenyl, 5,6-eicosamethyleneindenyl, 4,5-eicosamethyleneindenyl, (6Z,8Z,10Z)-cycloocta[e]indenyl, (5Z,7Z,9Z)-cycloocta[f]indenyl, (5E,7Z,9E,11Z,13E)-cyclododeca[f]indenyl, and (6E,8Z,10E,12Z,14E)-cyclododeca[e]indenyl.

[0035] The partially hydrogenated polycyclic arene ligands retain the numbering scheme of the parent polycyclic arene 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.

[0036] 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 %).

[0037] 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 about 10 mol% or less (e.g., up to 5 mol%, up to 3 mol%, up to 1 mol%, or about 0%, within the range of the relevant method of measurement), based on the total amount of the relevant composition. Preferably, "substantially free of" means 10 mol% or less (5 mol% or less, 3 mol% or less, 1 mol% or less, or about 0%), etc., based on the total amount of the relevant composition.

[0038] The terms "catalyst" and "catalyst compound" are defined to mean a compound capable of initiating catalysis and / or facilitating a chemical reaction with little or no poisoning / consumption. In this description, a catalyst may also be described as a catalyst precursor, pre-catalyst compound, transition metal complex, or transition metal compound, and these terms are used interchangeably. A catalyst compound may be used by itself to initiate catalysis, or may 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 often referred to as a pre-catalyst or catalyst precursor. A "catalyst system" includes at least one catalyst compound, at least one activator, optional co-activators, and optional support materials, and the system is capable of polymerizing monomers to form a polymer. Scavengers are compounds that are typically added to facilitate oligomerization / polymerization by scavenging impurities. Some scavengers may also act as activators and may also be referred to as co-activators. Co-activators that are not scavengers may be used in conjunction with activators to form active catalysts. In some embodiments, the co-activator may be premixed with the catalyst compound to form the alkylation catalyst compound.

[0039] As used herein, a "lubricant" refers to a substance that can be introduced between two or more moving surfaces to reduce the level of friction between the two adjacent surfaces moving relative to one another. A lubricant "base stock" is a material, typically fluid at the operating temperature of the lubricant, used to formulate a lubricant by blending with other components. Non-limiting examples of base stocks suitable for 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 gas-to-liquid ("GTL") process are examples of synthetic base stocks useful in making modern lubricants. GTL base stocks and processes for making them can be found, for example, in PCT Publication No. WO2005 / 121280, and in U.S. Pat. Nos. 7,344,631; 6,846,778; 7,241,375; and 7,053,254, which are incorporated by reference in their entireties.

[0040] All numerical values ​​within the detailed description and claims herein are modified by the term "about" or "approximately" the indicated value to account for experimental error and variations that can be expected by one of ordinary skill in the art. In this disclosure, all percentages of side groups, terminal carbon chains, and side groups are by mole unless otherwise specified. Molar percentages are expressed as "mol %" and weight percentages are expressed as "% by weight." In this disclosure, all molecular weight data are in g / mol (e.g., g mol) unless otherwise specified. -1 ) is used as the unit.

[0041] NMR spectroscopy provides important structural information about the synthesized polymers. 1 H-NMR analysis can be used to determine the molecular weight of oligomeric or polymeric materials (including functionalized, hydrogenated, and uPAO materials). 1The molecular weight of the oligomeric or polymeric material measured by H-NMR represents the number average molecular weight (Mn). 1 H-NMR analysis can provide quantitative analysis of olefin structural types (i.e., vinyl, disubstituted vinylene, trisubstituted vinylene, and vinylidene). In some embodiments, the composition of a mixture of olefins containing terminal olefins (vinyl and vinylidene) and internal olefins (disubstituted vinylene and trisubstituted vinylene) can be determined by the H-NMR analysis as described in the experimental section. 1 Determined by using H-NMR.

[0042] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, Mz is z-average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol (g mol -1 ) The following abbreviations may be used throughout the specification: 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 normal propyl, cPr is cyclopropyl, Bu is butyl, nBu is normal butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, MeCy is methylcyclohexane, Cy is cyclohexyl, Ph is phenyl, p-tBu is para-tert-butyl, p-Me is para-methyl, and o-biphenyl is the structure [ka] where Cbz is carbazole, Cy is cyclohexyl, Oct is octyl, and Ar is an ortho-biphenyl moiety represented by *is 2,6-diisopropylphenyl, pMe is para-methyl, Bz or Bn are equivalently benzyl (i.e., CHPh), TMS is trimethylsilyl, TIBAL or TiBAl is triisobutylaluminum, TNOAL or TNOA or TnOAl is tri-n-octylaluminum, MAO is methylalumoxane, 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 (which is about 23° C. unless otherwise indicated).

[0043] The term "continuous" refers to a system that operates without interruption or cessation over a period of time, e.g., reactants are continuously fed to a reaction zone and product is continuously or regularly withdrawn without stopping the reaction in the reaction zone. For example, a continuous process for producing a polymer would be considered one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

[0044] "Solution polymerization" refers to a polymerization process in which polymerization is carried out in a liquid polymerization medium, such as an inert solvent or monomer or a blend thereof. Solution polymerizations are typically homogeneous. Homogeneous polymerizations are those in which the polymer product is dissolved in the polymerization medium. Such systems are typically not turbid, as described in Oliveira, JV et al. (2000) "High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems," Ind. Eng. Chem. Res., v. 39(12), pp. 4627-4633. "Bulk polymerization" refers to a polymerization process in which the polymerizing monomers and / or comonomers are used as solvents or diluents with little or no inert solvent or diluent. A small amount of inert solvent may be used as a carrier for catalysts and scavengers. A bulk polymerization system contains less than about 25% by weight of inert solvent or diluent, for example, less than about 10% by weight, for example, less than about 1% by weight, for example, 0% by weight.

[0045] explanation Provided herein is a process for making polyalphaolefins (PAOs) from two or more different alphaolefins, wherein at least one alphaolefin is a cyclic alphaolefin and at least a second alphaolefin is a linear or branched alphaolefin. 32 Cyclic alpha-olefin and one or more C4-C 32 The method can include contacting a feedstock comprising 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, the catalyst system comprising a metallocene compound, to obtain a polymerization reaction mixture comprising a mixture of vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturated PAO molecules.

[0046] The method can further include obtaining an unsaturated PAO product from the polymerization reaction mixture, wherein the unsaturated PAO product comprises a mixture of PAO molecules having vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturation, and can be substantially free of alpha-olefin feedstock. When a cyclic alpha-olefin with ring unsaturation, such as 4-vinylcyclohex-1-ene, is used as the cyclic alpha-olefin, the PAO product will also contain an endocyclic disubstituted vinylene. This type of unsaturation is referred to as a cyclic disubstituted vinylene.

[0047] Also provided herein is a process for making alpha-olefin dimers and trimers (preferably dimers) from two or more alpha-olefins, wherein at least one alpha-olefin is a cyclic alpha-olefin and at least one alpha-olefin is a linear or branched alpha-olefin. 32 Cyclic alpha-olefin and one or more C4-C 32 The method may include contacting a feedstock containing linear and / or branched alpha-olefins with a catalyst system containing a metallocene compound in a polymerization reactor under polymerization conditions to produce a polymerization reaction mixture containing vinylidene, trisubstituted vinylene, disubstituted vinylene, and dimer and / or trimer molecules, optionally having vinyl unsaturation. The method may also include obtaining unsaturated dimer and / or trimer products from the polymerization reaction mixture, wherein the unsaturated dimer and / or trimer products contain vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturation, and may be substantially free of the alpha-olefin feedstock. When a cyclic alpha-olefin having ring unsaturation, such as 4-vinylcyclohex-1-ene, is used as the cyclic alpha-olefin, the dimer and / or trimer products will also contain endocyclic disubstituted vinylenes. This type of unsaturation is referred to as cyclic disubstituted vinylenes.

[0048] Another aspect of the present disclosure is a process for making alpha-olefin dimers and / or trimers (preferably dimers) from two or more different alpha-olefins, wherein at least one alpha-olefin is a cyclic alpha-olefin and at least a second alpha-olefin is a linear or branched alpha-olefin, and the product produced comprises:

[0049] [ka] and The cyclic monomer fragments (A) and (B) may independently be saturated when the cyclic alpha-olefin has a saturated ring structure, or when the cyclic alpha-olefin has a partially unsaturated ring structure; [ka] wherein n and m independently represent the number of additional carbon atoms in the ring structure and can be an integer from 1 to 20 (alternatively, 1 to 12, alternatively, 1 to 9, alternatively, 1 to 5, alternatively, 1 to 3), and R is a C2-C 30 is a hydrocarbyl group, and R' is C-C 29 is a hydrocarbyl group, and at least one of structure CL-v or LC-v is present in the product mixture.

[0050] Also provided herein is a process for making alpha-olefin dimers and / or trimers (preferably dimers) from two or more different alpha-olefins, wherein at least one of the alpha-olefins is a cyclic alpha-olefin and at least a second alpha-olefin is a linear or branched alpha-olefin, and wherein the products produced have a selectivity for producing dimers of greater than 50% of the total product mixture, alternatively greater than 60% of the total product mixture, alternatively greater than 70% of the total product mixture, alternatively greater than 80% of the total product mixture, alternatively greater than 90% of the total product mixture, alternatively greater than 90% of the total product mixture.

[0051] Functionalization of unsaturated PAO products The unsaturated PAO products of the present disclosure, preferably produced by the polymerization of alpha-olefins and / or olefinic monomers in the presence of a metallocene-based catalyst system as described above, can be advantageously used as chemical intermediates for making many products, particularly those containing a PAO molecular moiety and one or more functional groups. The hydrocarbon molecules in the unsaturated PAO products, when prepared from the polymerization of olefins / alpha-olefins containing only one C=C double bond in their prepolymerized molecules, tend to contain no more than one C=C bond each, with the remainder of the molecular structure typically consisting of C-C and C-H bonds.

[0052] The C=C bonds present in the molecules of the unsaturated PAO products of the present disclosure are highly reactive and can therefore react with many different types of chemical agents bearing useful functional groups, thereby creating PAO molecules that further contain functional groups attached thereto. Here, the functional groups can include other functional groups that can react with additional chemical agents, resulting in additional or different functionalities in the final molecule. The hydrocarbon substrate (i.e., the PAO structure) of such functionalized PAOs can impart desired properties, such as solubility or hydrophobicity in organic media, to the functionalized material, and the functional groups can impart other desired properties, such as polarity and hydrophilicity (and thus solubility in aqueous media), to the final material, making it particularly useful where such dual properties are desired (e.g., detergents, adhesives, etc.). U.S. Publication No. 2014 / 0087986 discloses a number of methods for making functionalized PAOs from unsaturated PAO products produced by polymerization of alpha-olefin monomers in the presence of a metallocene compound-based catalyst system. The entire disclosure of U.S. Publication No. 2014 / 0087986 is incorporated herein by reference.

[0053] It is highly desirable that functionalization of the unsaturated PAO product result in saturation of the C=C double bonds in the reacted uPAO molecule (i.e., each carbon atom in the original C=C bond is subsequently bonded to four atoms). This can be achieved by using a functionalizing agent that is substantially reactive only toward C=C bonds but is substantially inert toward C-C and C-H bonds in the uPAO olefin molecule under the functionalization conditions. Given that each uPAO olefin molecule typically contains only one C=C bond, the uPAO olefin molecule is considered to be saturated by such a functionalization reaction. By functionalizing the C=C bonds in the uPAO olefin molecules, the overall structure of the functionalized PAO molecule is expected to be substantially similar to that of a hydrogenated PAO molecule in which the C=C bonds have been saturated by hydrogenation as described above. Assuming that the bond between the functional group and the carbon atom is not significantly less robust than a C-C and C-H bond, and assuming that the functional group itself is not significantly less robust than the side groups on the PAO molecule under use conditions, one can predict a stable oligomeric / polymeric structure that retains at least some of the interesting and useful properties of saturated PAO molecules, such as one or more of viscosity index, oxidation stability, shear stability, and bromine number. The retained properties may make the functionalized PAO material particularly useful in typical applications of saturated PAO materials, such as lubricating oil compositions.

[0054] It is desirable that the functionalizing agent used to functionalize the unsaturated PAO product be highly selective for reaction with only C=C bonds and substantially inert toward C-C and C-H bonds on the uPAO molecule. This can ensure the production of functionalized PAO molecules containing only one or two functional groups, respectively, and, if desired, complete functionalization of substantially all of the uPAO molecules. In applications such as lubricating oil compositions, due to the high reactivity of the C=C bonds in the uPAO molecules, it may be desirable to saturate substantially all of the C=C bonds in the uPAO molecules before the functionalized PAO material is incorporated into an oil composition, either as a base stock or an additive. Additionally, or alternatively, uPAO molecules can be functionalized by replacing one or more of the hydrogen atoms on the carbon backbone or one of the side groups with a functional group using chemical agents known to be reactive toward C-H bonds. Because uPAO molecules typically contain many C-H bonds at multiple locations, such reactions are less selective than selective functionalization of C=C bonds using functionalizing agents inert to C-H bonds, can lead to a large number of very different molecules, and are therefore considered less desirable than selective functionalization of only C=C bonds.

[0055] Additionally or alternatively, the uPAO products of the present disclosure can be functionalized by reaction between an unsaturated C═C bond of the uPAO molecule and a chemical reagent. The chemical reagent can contain a moiety that reacts directly or indirectly with the reactive portion of the uPAO, optionally in the presence of a suitable catalyst or accelerator. Alternatively, the chemical reagent may be a precursor that reacts directly or indirectly with the reactive portion of the uPAO, optionally in the presence of a suitable catalyst or accelerator, and then undergoes at least one other treatment and / or chemical reagent reaction, also optionally in the presence of the same or a different suitable catalyst or accelerator, to achieve the desired final functionality on the reactive portion of the uPAO. As a further alternative, the chemical reagent may be a co-reactant that pre-reacts or simultaneously reacts with another chemical reagent, optionally in the presence of a suitable catalyst or accelerator, for direct or indirect reaction with the reactive portion of the uPAO.

[0056] Optionally, more than one type of functionality can be desired, and thus functionalization can occur simultaneously (achieving various functionalities in a single result), sequentially, in parallel (provided that the two parallel reactions do not cancel each other out), or some combination thereof. Even if one or more functionalities are desired, the reactions can be any of a variety of methods that can effectively achieve functionalization, such as liquid-phase chemistry, gas-liquid interfacial chemistry, solid-liquid surface chemistry, vapor-phase oxidation, vapor-phase oxidation followed by some other functionalization mechanism, plasma oxidation, plasma oxidation followed by some other functionalization mechanism, radical formation, or radical formation followed by some other functionalization mechanism. The final desired functional group can be tailored to the particular end-use application, including, but not limited to, moieties containing, for example, oxygen, nitrogen, sulfur, phosphorus, boron, silicon, halogen atoms, or combinations thereof. The degree to which functionalization can be achieved is another variable that can be tailored to the particular end-use application. The functionalization (single or multiple) can be partial or substantially complete (i.e., substantially all of the unsaturation of the uPAO can be converted to a functional moiety, such as a heteroatom-containing moiety).

[0057] The PAOs prepared herein may be functionalized by reacting a heteroatom-containing group with the PAO, with or without a catalyst. Examples include catalytic hydrosilylation, ozonolysis, hydroformylation, hydroamination, sulfonation, halogenation, hydrohalogenation, hydroboration, epoxidation, or Diels-Alder reactions with polar dienes, Friedel-Crafts reactions with polar aromatics, and maleation with activators such as free-radical generators (e.g., peroxides). Functionalized PAOs can be used in oil additives as anti-fog or wetting additives, surfactants for soaps, detergents, and 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 amines, aldehydes, alcohols, acids, anhydrides, sulfonates, especially succinic acid, maleic acid, and maleic anhydride.

[0058] In some embodiments, the PAOs produced herein are functionalized as described in U.S. Pat. No. 6,022,929; Toyota, A. et al. (2002) Polymer Bulletin, v. 48(3), pp. 213-219; and Kropp, PJ (1990) Journal Am. Chem. Soc., v. 112, pp. 7433-7434. In some embodiments, the functionalized PAOs produced herein are further functionalized (derivatized) as described in U.S. Pat. No. 6,022,929; Toyota, A. et al. (2002) Polymer Bulletin, v. 48(3), pp. 213-219; Kropp, PJ (1990) Journal Am. Chem. Soc., v. 112, pp. 7433-7434; and PCT Publication No. WO 2009 / 155472.

[0059] In preferred embodiments, the PAOs of the present disclosure can be functionalized (e.g., chemically modified with one or more functional groups (also referred to as heteroatom-containing groups) that typically contain 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). Preferred functional groups are selected from the group consisting of acid, ester, anhydride, acid ester, oxycarbonyl, carbonyl, formyl, formylcarbonyl, hydroxyl, and acetyl halide. Particularly preferred functional groups include those represented by the formula: -C(O)-X, where O is double bonded to C and X is hydrogen, nitrogen, hydroxy, oxyhydrocarbyl (e.g., ester), oxygen, a salt moiety -OM (where M is a metal such as alkali, alkaline earth, transition metal, copper, and zinc), oxyhetero, such as -OZ (where Z represents a heteroatom such as phosphorus, boron, sulfur, etc., which heteroatom may be substituted with a hydrocarbyl or oxyhydrocarbyl group, or two acyl groups may be joined through (X)). Preferred heteroatom-containing groups include acyl groups derived from monounsaturated mono- or dicarboxylic acids, and derivatives thereof, such as esters and salts.

[0060] More specifically, PAO and (i) monounsaturated C4-C 10 Dicarboxylic acids (preferably, (a) the carboxyl groups are vicinyl (i.e., located on adjacent carbon atoms), and (b) at least one, preferably both, of said adjacent carbon atoms is said monounsaturated moiety); (ii) derivatives of (i), such as anhydrides, or C1-C5 alcohol-derived mono- or diesters of (i); (iii) monounsaturated C3-C5 dicarboxylic acids in which the carbon-carbon double bond is conjugated to the carboxyl group, i.e., of the structure -C=CC(O)- (where O is double bonded to C). 10 Preferred are PAOs functionalized with mono- or dicarboxylic acid materials, i.e., acids, anhydrides, salts, or acid esters, including the reaction product with a monounsaturated carboxylic reactant containing at least one member selected from the group consisting of monocarboxylic acids and (iv) derivatives of (iii), such as C1-C5 alcohol-derived monoesters of (iii). Upon reaction with the PAO, the double bond of the monounsaturated carboxylic reactant is saturated. Thus, for example, maleic anhydride reacted with a PAO becomes succinic anhydride, and acrylic acid becomes propionic acid.

[0061] Suitable unsaturated acid materials that are useful functional compounds include acrylic acid, crotonic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, glutaconic 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-C4 alkyl) acid esters of the foregoing, such as methyl maleate, ethyl fumarate, methyl fumarate, etc. Unsaturated dicarboxylic acids and their derivatives, particularly maleic acid, fumaric acid, and maleic anhydride, are particularly preferred. Typically, 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 per mole of PAO charged.

[0062] Functionalization can be achieved by any suitable method. Useful methods include reacting the olefinic bond of the PAO with an unsaturated, preferably monounsaturated, carboxylic acid reactant. Alternatively, the oligomer can be halogenated using a chlorine- or bromine-containing compound. The halogenated PAO can then be reacted with a monounsaturated carboxylic acid. The PAO and monounsaturated carboxylic acid reactant can also be contacted at elevated temperatures to effect a thermal "ene" reaction. 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 contact with a hydroxyaromatic compound in the presence of a catalytically effective amount of at least one acidic alkylation catalyst. The alkylated hydroxyaromatic compound can then be further reacted to form a derivative by Mannich base condensation with an aldehyde and an amine reagent to obtain a Mannich base condensation product. Yet another means of functionalizing the PAO involves contacting the PAO with carbon monoxide in the presence of an acid catalyst under Koch reaction conditions to obtain a PAO substituted with carboxylic acid groups. In addition to the above methods of functionalization, the PAOs of the present disclosure can be functionalized by air oxidation, ozonolysis, hydroformylation, epoxidation, and chloroamination methods (e.g., U.S. Pat. No. 6,002,929, column 21, line 16 to column 33, line 27).

[0063] The polyalphaolefins produced herein contain one or more unsaturated double bonds, with some 1,2-disubstituted olefins being rich in vinylidene content. 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 alkylphenols. PAOs can also be reacted with maleic anhydride to give PAO-succinic anhydrides, which can be further converted with amines or alcohols to the corresponding succinimides or succinic acid esters. These imides and esters are excellent dispersants.

[0064] Here, the functionalized PAO can be derivatized with a derivatizing compound (for purposes of this disclosure and its claims, the term functionalized PAO encompasses derivatized PAOs). The derivatizing compound can react with the functional groups of the functionalized PAO by means such as, for example, nucleophilic substitution and Mannich base condensation. The derivatizing compound can be polar and / or contain a reactive derivative group. Preferred derivatizing compounds are selected from hydroxy-containing compounds, amines, metal salts, anhydride-containing compounds, and acetyl halide-containing compounds. The derivatizing compound can contain at least one nucleophilic group, preferably at least two nucleophilic groups. Typical derivatized PAOs are prepared by contacting a functionalized PAO, i.e., a carboxylic acid / anhydride or ester, with a nucleophile, such as an amine, a polyol, an alcohol, including an aminoalcohol, and a reactive metal compound (e.g., U.S. Pat. No. 6,022,929, column 33, line 27 to column 74, line 63). Alternatively, derivatized PAOs may be made by contacting a carboxylic acid / anhydride or ester substituted functionalized PAO with a nucleophile, such as an amine, to make a quaternary ammonium compound or an amine oxide. Functionalized and / or derivatized PAOs have utility as lubricant additives that can act as dispersants, viscosity index improvers, or multifunctional viscosity index improvers. Additionally, they may be used as disinfectants (functionalized amines) and / or wetting agents.

[0065] The functionalized PAOs prepared herein may be used in oil additives, lubricants, fuels, and many other applications. Preferred uses include additives for lubricants and / or fuels. In certain embodiments herein, the PAOs disclosed herein or their functionalized / derivatized analogs are useful as additives, preferably in lubricants. The functionalized and / or derivatized PAOs produced herein have utility as lubricant additives, capable of acting as dispersants, viscosity index improvers, or multifunctional viscosity index improvers. Additionally, they can be used as disinfectants (functionalized amines) and / or wetting agents.

[0066] The functionalized and / or derivatized PAOs described herein are useful as viscosity index improvers for lubricating oil compositions, adhesion additives, anti-fog agents, and wetting agents, ink and paint adhesion promoters, coatings, and adhesives and sealants, etc. Additionally, such PAOs may be functionalized and derivatized to make multifunctional viscosity index improvers that also possess dispersant properties (e.g., U.S. Pat. No. 6,022,929). The functionalized and / or derivatized PAOs described herein may be combined with other additives (e.g., viscosity index improvers, corrosion inhibitors, antioxidants, dispersants, lubricant flow improvers, detergents, demulsifiers, rust inhibitors, pour point depressants, antifoam agents, antiwear agents, seal swell agents, and friction modifiers, etc. (e.g., as described in U.S. Pat. No. 6,022,929, column 60, lines 42-78, line 54, and references cited therein) to form lubricant additive packages and compositions for many applications, including, but not limited to, lubricating oils.

[0067] Compositions containing these additives are typically blended into the base oil in amounts effective to provide their usual incidental functions. Representative effective amounts of such additives are exemplified below: Composition (typical) (preferred) Mass%* Mass%* VI improver 1~12 1~4 Corrosion inhibitor 0.01~3 0.01~1.5 Antioxidant 0.01~5 0.01~1.5 Dispersant 0.1~10 0.1~5 Lubricant flow improver 0.01~2 0.01~1.5 Detergent and rust inhibitor 0.01~6 0.01~3 Pour point depressant 0.01~1.5 0.01~1.5 Antifoaming agent 0.001~0.1 0.001~0.01 Anti-wear agent 0.001~5 0.001~1.5 Encapsulating swelling agent 0.1~8 0.1~4 Friction modifier 0.01~3 0.01~1.5 Lubricant base oil Residue Residue * Mass % is based on the active ingredient content of the additive and / or the total mass of any additive package or formulation, where the total mass is the sum of the AI ​​mass of each additive plus the mass of the total oil or diluent.

[0068] When other additives are used, it may be desirable, but not necessary, to prepare an additive concentrate comprising a concentrated solution or dispersion of the additives of the present disclosure together with one or more of the additives (such concentrates, when constituting an additive mixture, are referred to herein as an additive package), thereby allowing the addition of several additives to a base oil simultaneously (in the concentrated amounts described above) to form a lubricating oil composition. Dissolution of the additive concentrate in the lubricating oil may be facilitated by solvents and by mixing accompanied by mild heating, but this is not required. The functionalized or derivatized PAOs of the present disclosure, along with other desired additives, can be added to a small amount of base oil or other compatible solvent to form an additive package containing the appropriate proportions, typically totaling about 2.5 to about 90%, preferably about 15 to about 75%, and most preferably about 25 to about 60% by weight of the active ingredients of the additives, with the remainder being base oil. The final formulation may typically use about 10% by weight of the additive package, with the remainder being base oil.

[0069] In another embodiment, the PAOs described herein can be used in any process, blend, or product disclosed in PCT Publication No. WO2009 / 0155472 or U.S. Pat. No. 6,022,929, which are incorporated herein by reference. In preferred embodiments, the present disclosure relates to fuels comprising any of the PAOs produced herein. In preferred embodiments, the present disclosure relates to lubricants comprising any of the PAOs produced herein.

[0070] catalyst system Catalyst systems useful herein comprise an asymmetric metallocene catalyst compound activated by one or more non-aromatic hydrocarbon-soluble activators, and may further comprise a solvent, a support, and / or one or more scavengers, etc. 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.

[0071] Solvents useful for combining the catalyst compound and 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; preferably, the solvent can include normal paraffins (e.g., NORPAR® solvents available from ExxonMobil Chemical Company, Houston, TX), isoparaffinic solvents (e.g., ISOPAR® solvents available from ExxonMobil Chemical Company, Houston, TX), and combinations thereof. These solvents or diluents may typically be pretreated in the same manner as the feed olefins. Preferably the solvent is C4-C 10 It is selected from linear, branched, or cyclic alkanes. Preferably the solvent is essentially free of all aromatic solvents. Preferably the solvent is essentially free of toluene. Preferably, the solvent is one or more C-C 32 Alpha olefins, such as one or more C-C 16 The olefins are selected from alpha olefins. Preferably the solvent is essentially free of all non-alpha-olefin solvents.

[0072] Aliphatic hydrocarbon solvents can include, but are not limited to, isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In some embodiments, aromatics are present in the solvent at less than 1% by weight, e.g., less than 0.5% by weight, e.g., 0% by weight, based on the weight of the solvent. The active agents of the present disclosure can be dissolved in one or more additional solvents, including halogenated or partially halogenated hydrocarbon solvents, provided such solvents are non-aromatic.

[0073] In some embodiments, the aliphatic solvent is isohexane and / or methylcyclohexane. In some embodiments, the solvent is one or more C-C 32 Alpha olefins, such as one or more C-C 16 It is an alpha olefin and no additional solvent is used. In some embodiments, the solvent is 1-octene, 1-decene, 1-dodecene, or 1-tetradecene, or a combination of any two or more.

[0074] Metallocene compound method Also provided herein is a process for making 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 a second alpha-olefin is a linear or branched alpha-olefin. 32 Cyclic alpha-olefin and one or more C4-C 32 and a linear and / or branched alpha-olefin, with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions to cause a polymerization reaction to occur to obtain a polymerization reaction mixture comprising a mixture of PAO molecules having vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturation; and obtaining an unsaturated PAO product from the polymerization reaction mixture, the unsaturated PAO product comprising a mixture of vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturation, the metallocene compound having a formula (I): [ka] is represented by During the ceremony: R 1 , R 2 , and R 3 are each independently hydrogen or a substituted or unsubstituted straight-chain, branched, or cyclic C-C 20 is a hydrocarbyl or silylcarbyl group; R 4 and R 5 are each independently a substituted or unsubstituted straight-chain, branched, or cyclic C-C 30 is a hydrocarbyl or silylcarbyl group, R 4 and R 5 together with the carbon atoms of the first cyclopentadienyl ring to which they are directly attached to form, in combination, one or more substituted or unsubstituted rings fused to the first cyclopentadienyl ring; R 12 , R 13 , R 14 , R 15 , and R 16 are each independently hydrogen or a substituted or unsubstituted straight-chain, branched, or cyclic C-C 20 is a hydrocarbyl, silylcarbyl, or germanyl group; R 12 , R 13 , R 14 , R 15 , and R 16 At least four of these 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, hydride, amide, alkoxide, sulfide, phosphide, diene, amine, phosphine, ether, or C-C 20 a substituted or unsubstituted straight-chain, branched, or cyclic hydrocarbyl group, or optionally, two or more X moieties may join together to form a fused ring or ring system; m is an integer equal to v-2, for example, 1, 2, or 3.

[0075] In some embodiments, the metallocene compound has the formula (II): [ka] and having a structure represented by During the ceremony: R 1 , R 2 , and R 3 are each independently hydrogen or a substituted or unsubstituted straight-chain, branched, or cyclic C-C 20 is a hydrocarbyl group; R 6 , R 7 , R 17 , and R 18 are each independently hydrogen, a substituted or unsubstituted straight-chain, branched, or cyclic C-C 30 is a hydrocarbyl group, or R 6 and R 7 , R 7 and R 17 , or R 17 and R 18 together with the carbon atoms of the indenyl ring to which they are directly attached, 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, or cyclic C-C 20 is a hydrocarbyl group; R 16 is hydrogen or a substituted or unsubstituted straight-chain, branched, or cyclic C-C 20 is a hydrocarbyl group or a silylcarbyl group; Each X is independently a halogen, hydride, amide, alkoxide, sulfide, phosphide, diene, amine, phosphine, ether, C1-C 20 a substituted or unsubstituted straight-chain, branched, or cyclic hydrocarbyl group, or two or more X moieties taken together form a fused ring or ring system; M is a transition metal, preferably a Group 3, 4, or 5 transition metal having an integer coordination number v, e.g., v is 3, 4, or 5; m is an integer equal to v-2, for example, m is 1, 2, or 3.

[0076] In some embodiments, the metallocene compound has the formula (III): [ka] is represented by During the ceremony: R 1 and R 2 is hydrogen; R 23 and R 19 contains a group 14 atom, such as C, Ge, or Si (e.g., R 23 is C and R 19 is C or Si); R 20 , R 21 , and R 22 are independently hydrogen or a substituted or unsubstituted straight-chain, branched, or cyclic C-C 20 is a hydrocarbyl group, R 20 , R 21 , and R 22 at least two of which are independently substituted or unsubstituted linear, branched, or cyclic C-C 20 is a hydrocarbyl group; R 6 , R 7 , R 17 , and R 18 are each independently hydrogen, a substituted or unsubstituted straight-chain, branched, or cyclic C-C 30 is a hydrocarbyl group, or R 6 and R 7 , R 7 and R 17 , or R 17 and R 18 together with the carbon atoms of the indenyl ring to which they are directly attached, form one or more substituted or unsubstituted rings fused to the indenyl ring; R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a substituted or unsubstituted straight-chain, branched, or cyclic C-C 20is a hydrocarbyl group; Each X is independently a halogen, hydride, amide, alkoxide, sulfide, phosphide, diene, amine, phosphine, ether, or C-C 20 a substituted or unsubstituted straight-chain, branched, or cyclic hydrocarbyl group, or two or more X moieties taken together form a fused ring or ring system; M is a Group 3, 4, or 5 transition metal having an integer coordination number v, e.g., v is 3, 4, or 5; m is an integer equal to v-2, for example 1, 2, or 3.

[0077] In some embodiments, the metallocene compound has the formula (IV): [ka] is represented by During the ceremony: R 1 and R 2 is hydrogen; R 3 is a substituted or unsubstituted straight-chain, branched, or cyclic C1-C 20 is a hydrocarbyl group; R 6 and R 18 are each independently hydrogen or a substituted or unsubstituted straight-chain, branched, or cyclic C-C 30 is a hydrocarbyl group; R 24 , R 25 , R 26 , R 27 , R 28 , and R 29 are each independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C1-C8 hydrocarbyl group; R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a substituted or unsubstituted straight-chain, branched, or cyclic C-C 20 is a hydrocarbyl group; Each X is independently a halogen, hydride, amide, alkoxide, sulfide, phosphide, diene, amine, phosphine, ether, or C-C 20 a substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or two or more X together form a fused ring or ring system; M is a Group 3, 4, or 5 transition metal having an integer coordination number v, e.g., v is 3, 4, or 5; m is an integer equal to v-2, for example, m is 1, 2, or 3.

[0078] In some embodiments, the metallocene compound has the formula (V): [ka] is represented by During the ceremony: R 1 and R 2 is hydrogen; R 23 and R 19 are each independently a Group 14 atom, such as C, Ge, or Si (e.g., R 23 is C and R 19 is C or Si); R 20 , R 21 , and R 22 are each independently hydrogen or a substituted or unsubstituted straight-chain, branched, or cyclic C-C 20 is a hydrocarbyl group, R 20 , R 21 , and R 22 at least two of which are independently substituted or unsubstituted linear, branched, or cyclic C-C 20 is a hydrocarbyl group; R 6 and R 18 are each independently hydrogen or a substituted or unsubstituted straight-chain, branched, or cyclic C-C 30 is a hydrocarbyl group; R 24 , R 25 , R 26 , R 27, R 28 , and R 29 are each independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C1-C8 hydrocarbyl group; R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a substituted or unsubstituted straight-chain, branched, or cyclic C-C 20 is a hydrocarbyl group; Each X is independently a halogen, hydride, amide, alkoxide, sulfide, phosphide, diene, amine, phosphine, ether, or C-C 20 a substituted or unsubstituted straight-chain, branched, or cyclic hydrocarbyl group, or two or more X moieties taken together form a fused ring or ring system; M is a Group 3, 4, or 5 transition metal having an integer coordination number v, e.g., v is 3, 4, or 5; m is an integer equal to v-2, for example, m is 1, 2, or 3.

[0079] In some embodiments of formulas (I), (II), (III), (IV), and (V), M is Zr, Hf, or a combination thereof. In some embodiments of formulas (I), (II), (III), (IV), and (V), M is Hf. 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 group. In some embodiments of Formulas (I), (II), (III), (IV), and (V), X is independently methyl, ethyl, benzyl, or trimethylsilylmethylene.

[0080] In some embodiments of formulas (I), (II), (III), (IV), and (V), R 12 , R 13 , R 14 , R 15 , and R 16At least four of are each independently a substituted or unsubstituted straight, branched, or cyclic C1-C8 hydrocarbyl group (eg, methyl or ethyl). 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 straight, branched, or cyclic C1-C4 hydrocarbyl group (e.g., methyl or ethyl). In some embodiments of formulas (I) and (II), R 1 , R 2 , and R 3 The first of these is a substituted or unsubstituted linear, branched, or cyclic C1-C 20 is a hydrocarbyl group; R 1 , R 2 , and R 3 The second one is hydrogen; R 1 , R 2 , and R 3 the third is hydrogen, substituted or unsubstituted straight-chain, branched, or cyclic C1-C 20 It is a hydrocarbyl group.

[0081] In some embodiments of formulas (I) and (II), R 2 is hydrogen and R 1 and R 3 is a substituted or unsubstituted linear, branched, or cyclic C-C hydrocarbyl group, and R 1 and R 3 The other is hydrogen. In some embodiments of formulas (I) and (II), R 1 and R 3 one or both of R is a substituted or unsubstituted linear, branched, or cyclic C-C hydrocarbyl group; 2 is hydrogen. In some embodiments of formulas (I) and (II), R 1 and R 3One of the groups comprises an alpha Group 14 atom attached directly to the indenyl ring, a beta Group 14 atom attached to the alpha atom, and two or more (e.g., three) substituted or unsubstituted linear, branched, or cyclic C1-C8 hydrocarbyl groups attached to the beta atom.

[0082] In some embodiments of formulas (I), (II), and (IV), R 1 and R 2 is hydrogen and R 3 is a substituted or unsubstituted straight-chain, branched, or cyclic C1-C8 hydrocarbyl group (e.g., methyl, ethyl, n-propyl, isobutyl, trimethylsilylmethylene, or neopentyl). In some embodiments of Formula (II), R 1 , R 2 , and R 3 is hydrogen; R 12 , R 13 , R 14 , and R 15 are independently methyl or ethyl; R 16 is hydrogen, methyl, ethyl, propyl, or butyl. In some embodiments of formula (II) or (III), R 6 and R 7 , R 7 and R 17 , or R 17 and R 18 taken together with the respective carbon atoms of 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. In some embodiments of formula (II) or (III), R 6 and R 18 is hydrogen and R 7 and R 17 together with the respective carbon atoms of the indenyl ring to which they are directly attached, form a 5- or 6-membered ring annulated with the indenyl ring. In some embodiments of formula (II), (III), (IV), or (V), R 6 and R 18 is hydrogen.

[0083] In some embodiments of formula (III) or (V), R 23 is CH2 (methylene), and R 19 is C or Si (preferably C), and R 20 , R 21 , and R 22 are independently hydrogen or C-C 10 is a hydrocarbyl group, R 20 , R 21 , and R 22 At least two of these are not hydrogen. In some embodiments of formula (III) or (V), R 23 is CH2 (methylene); R 19 is C;R 20 , R 21 , and R 22 are independently selected from hydrogen, methyl, ethyl, propyl, or butyl; R 20 , R 21 , and R 22 At least two of these are not hydrogen.

[0084] In some embodiments of formula (IV) or (V), R 24 , R 27 , R 28 , and R 29 is hydrogen; R 25 and R 26 are independently hydrogen or a substituted or unsubstituted straight, branched, or cyclic C1-C8 hydrocarbyl group. In some embodiments of formula (IV) or (V), R 24 , R 27 , R 28 , and R 29 is hydrogen; R 25 and R 26 are independently hydrogen, methyl, or ethyl. In some embodiments of formula (IV) or (V), R 24 , R 27 , R 28 , and R 29are independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C-C hydrocarbyl group; R 25 and R 26 is hydrogen. In some embodiments of formula (IV) or (V), R 24 , R 27 , R 28 , and R 29 is methyl and R 25 and R 26 is hydrogen. In some embodiments, the metallocene compound is selected from structures A through E shown below: In some embodiments, the metallocene compound is selected from structures A through D. [ka]

[0085] Catalyst compounds that are particularly useful in this disclosure include: (pentamethylcyclopentadienyl)(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-ethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-n-propyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isopropyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-n-butyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1,6,6-triethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methylindenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutylindenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methyl-3,6,7,8-tetrahydro-as-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-3,6,7,8-tetrahydro-as-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene)hafnium dimethyl, (pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)hafnium dimethyl, and (Pentamethylcyclopentadienyl)(1-isobutyl-5,6-dimethyllindenyl)hafnium dimethyl It includes one or more of the following.

[0086] In some embodiments of the present disclosure related to dimerizing cyclic alpha-olefins, the metallocene is selected from any of formulas (I), (II), (III), (IV), or (V); where R 1 and R 3 In formulas (I), (II), and (IV), it is provided that at least one of R 1 and R 2 is preferably hydrogen; R 3 is preferably methyl, ethyl, and the 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.

[0087] Activators and activation of metallocene compounds. Non-coordinating anion (NCA) activators Noncoordinating anion (NCA) refers to either an anion that does not coordinate to the catalyst metal cation or that coordinates to the metal cation but very weakly. The term NCA is also defined to include multicomponent NCA-containing activators, such as N,N-dioctadecylanilinium tetrakis(perfluoronaphthyl)borate, which contain an acidic cationic group and a noncoordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluoronaphthyl)boron, that can react with the catalyst to form an activated species by abstraction of the anionic group. NCAs coordinate weakly enough so that neutral Lewis bases, such as olefinic or acetylenically unsaturated monomers, can displace the catalyst center. Any metal or metalloid capable of forming a compatible, weakly coordinating complex can be used or contained in the noncoordinating anion. Suitable metals include aluminum, gold, and platinum. Suitable metalloids include boron, aluminum, phosphorus, and silicon. The term non-coordinating anionic activators includes neutral activators, ionic activators, and Lewis acid activators.

[0088] A "compatible" non-coordinating anion may be one that does not decompose neutrally when the initially formed complex decomposes. Furthermore, the anion does not transfer anionic substituents or fragments to the cation such that a neutral transition metal compound and neutral by-products are formed from the anion. Non-coordinating anions useful according to the present disclosure are those that are compatible and stabilize the transition metal cation in the sense of balancing its ionic charge with +1, yet remain sufficiently unstable to allow displacement during polymerization. In some embodiments, the activator comprises a non-coordinating anion. Advantageously, the active agents of the present disclosure are soluble in non-aromatic hydrocarbon solvents, such as aliphatic solvents.

[0089] In some embodiments, a 20% by weight mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25°C, and preferably a 30% by weight mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25°C. In some embodiments, an active agent described herein has a solubility in methylcyclohexane at 25° C. (stirring for 2 hours) greater than 10 mM (or greater than 20 mM, or greater than 50 mM). In some embodiments, an active agent described herein has a solubility in isohexane at 25° C. (stirring for 2 hours) greater than 1 mM (or greater than 10 mM, or greater than 20 mM).

[0090] In some embodiments, the active agents described herein have a solubility in methylcyclohexane at 25° C. (stirring for 2 hours) greater than 10 mM (or greater than 20 mM, or greater than 50 mM), and a solubility in isohexane at 25° C. (stirring for 2 hours) greater than 1 mM (or greater than 10 mM, or greater than 20 mM). The present disclosure relates to catalyst systems comprising a metallocene transition metal compound and an activator compound as described herein, the use of such activator compounds to activate the transition metal compound in a catalyst system for polymerizing olefins, and methods for polymerizing olefins, the methods comprising contacting one or more olefins with a catalyst system comprising a metallocene transition metal compound and such activator compound under polymerization conditions, wherein aromatic solvents such as toluene are absent (e.g., present at zero mol % or present at less than 1 mol %); preferably, the catalyst system, polymerization reaction, and / or produced polymer are free of "detectable aromatic hydrocarbon solvents" such as toluene. For purposes of this disclosure, "detectable aromatic hydrocarbon solvents" means 0.1 mg / m or less of an aromatic hydrocarbon solvent as determined by gas phase chromatography. 2For purposes of this disclosure, "detectable toluene" means 0.1 mg / m toluene or more, as determined by gas phase chromatography. 2 Or it could mean more than that. The polyalphaolefins produced herein preferably contain 0 ppm (alternatively, less than 1 ppm) aromatic hydrocarbons. Preferably, the polyalphaolefins produced herein contain 0 ppm (alternatively, less than 1 ppm) toluene. The catalyst systems used herein preferably contain 0 ppm (alternatively, less than 1 ppm) of aromatic hydrocarbons. Preferably, the catalyst systems used herein contain 0 ppm (alternatively, less than 1 ppm) of toluene.

[0091] Non-aromatic hydrocarbon soluble activator compounds useful herein include those of formula (VI):

number

number

number

[0092] Non-aromatic hydrocarbon soluble activator compounds useful herein include those of formula (VII):

number

number

number

number

number

[0093] Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (VIII) or formula (IX): [ka] and During the ceremony: N is nitrogen;

number

number

number

number

number

[0094] In any of formulas (VI), (VII), (VIII), or (IX) herein:

number

number

number

number

[0095] In any embodiment of formula (VIII) or (IX) herein,

number

number

number

number

[0096] When Q is a fluorophenyl group,

number

number

number

number

number

[0097] Each Q may be an aryl group (such as phenyl or naphthyl), and at least one Q is substituted with at least one fluorine atom, preferably each Q is a perfluoroaryl group (such as perfluorophenyl or perfluoronaphthyl).

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[0098] Each Q may independently be a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halo-substituted hydrocarbyl radical, except that when Q is a fluorophenyl group:

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[0099] In some embodiments of the present disclosure,

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[0100] Useful cationic components in formulas (V)-(VIII) include those of the formula: [ka] This includes those represented by:

[0101] Useful cationic components in formulas (VI)-(IX) include those of the formula: [ka] The anionic components of the active agents described herein include those represented by the formula [Mt k+ Q n ] - wherein 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 of the Elements, preferably boron or aluminum; and Q is independently a hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halo-substituted-hydroxycarbyl radical, provided that Q is a halide in not more than one occurrence. Preferably, each Q is a fluorinated hydrocarbyl group, which may have from 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 such as perfluorophenyl, and preferably all Q are not substituted phenyl such as perfluorophenyl.

[0102] In one embodiment, the borate activator comprises tetrakis(heptafluoronaphth-2-yl)borate. In one embodiment, the borate activator comprises tetrakis(pentafluorophenyl)borate.

[0103] Preferred anions for use in the non-coordinating anion activators described herein include those of Formula 7: [ka] formula 7 and During the ceremony: M * is a group 13 atom, preferably B or Al, preferably B; Each R 11 are independently a halide, preferably a fluoride; Each R 12 are independently halides, C6-C 20 Substituted aromatic hydrocarbyl groups, or groups of the formula -O-Si-R a (In the formula, R a is C1-C 20 a siloxy group, preferably R 12 is a fluorinated or perfluorinated phenyl group; Each R 13 is a halide, C6-C 20 Substituted aromatic hydrocarbyl groups, or groups of the formula -O-Si-R a (In the formula, R a is C1-C 20 a siloxy group, preferably R 13 is a fluoride or C6 perfluorinated aromatic hydrocarbyl group; R 12 and R 13 can form one or more saturated or unsaturated, substituted or unsubstituted rings, preferably R 12 and R 13 forms a perfluorinated phenyl ring. Preferably the anion has a molecular weight greater than 700 g / mol, and preferably M * At least three of the substituents on the atom each have a molecular volume greater than 180 cubic Angstroms.

[0104] "Molecular volume" is used herein as an approximation of the spatial steric bulk of an active agent molecule in solution. By comparing substituents with different molecular volumes, a substituent with a smaller molecular volume can be considered "less bulky" compared to a substituent with a larger molecular volume. Conversely, a substituent with a larger molecular volume can be considered "bulkier" than a substituent with a smaller molecular volume.

[0105] Molecular volume can be calculated as reported in Girolami, GS (1994) "A Simple "Back of the Envelope" Method for Estimating the Densities and Molecular Volumes of Liquids and Solids," Journal of Chemical Education, v. 71(11), pp. 962-964. Molar volume (MV) in cubic Å is calculated using the formula: MV = 8.3V s (In the formula, V s is the scaled volume). s is the sum of the relative volumes of the constituent atoms and is calculated from the molecular formula of the substituents using the following Table A of relative volumes. s The calculated total MV of the anion is the sum of the MVs per substituent, e.g., the MV of perfluorophenyl is 183 Å, and the calculated total MV for tetrakis(perfluorophenyl)borate is 183 Å. 3 4 times or 732Å 3 is. [Table 1]

[0106] Exemplary anions useful herein and their respective scaled volumes and molar volumes are shown below in Table B. The dashed bond indicates the bond to boron. [Table 2]

[0107] The activator may be added to the polymerization in the form of an ion pair, for example, using [MHTH] + [NCA] -, where the di(hydrogenated tallow)methylamine ("MHTH") cation reacts with a basic leaving group on the transition metal complex to form the transition metal complex cation and [NCA] -. Alternatively, the transition metal complex may be reacted with a neutral NCA precursor, such as B(CF) , which abstracts an anionic group from the complex to form the activated species. Useful activators include di(hydrogenated tallow)methylammonium [tetrakis(pentafluorophenyl)borate] (i.e., [MHTH]B(CF) ) and di(octadecyl)tolylammonium [tetrakis(pentafluorophenyl)borate] (i.e., [DOdTH]B(CF) ).

[0108] Particularly useful activator compounds of the present disclosure include: N,N-di(hydrogenated tallow)methylammonium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-hexadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-tetradecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-dodecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-decyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-octyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-hexyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-butyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-octadecyl-N-decylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-4-nonadecyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate], N-ethyl-4-nonadecyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dihexadecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-ditetradecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-didodecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-didecylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N,N-dioctylammonium [tetrakis(perfluorophenyl)borate], N-ethyl-N,N-dioctadecylammonium [tetrakis(perfluorophenyl)borate], N,N-di(octadecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(hexadecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(tetradecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N,N-di(dodecyl)tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-hexadecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-octadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-tetradecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-hexadecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-tetradecyl-N-dodecyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-tetradecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-dodecyl-N-decyl-tolylammonium [tetrakis(perfluorophenyl)borate], N-methyl-N-octadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-hexadecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-tetradecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-dodecylanilinium [tetrakis(perfluorophenyl)borate], N-methyl-N-decylanilinium [tetrakis(perfluorophenyl)borate], and N-Methyl-N-octylanilinium [tetrakis(perfluorophenyl)borate] It includes one or more of the following.

[0109] Additional useful activators and their syntheses are described in U.S. Patent Nos. 11,414,436 (U.S. Ser. No. 16 / 394,166, filed April 25, 2019), 11,117,908 (U.S. Ser. No. 16 / 394,186, filed April 25, 2019), and 11,041,031 (U.S. Ser. No. 16 / 394,197, filed April 25, 2019), each of which is incorporated herein by reference.

[0110] In embodiments, the active agent is: [ka] (the cationic moieties of formulas (VI), (VII), (VIII), and (IX) are not the cations in the above formulas).

[0111] In at least one embodiment, the general synthesis of the activator can be carried out using a two-step process. In the first step, an 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 the chloride salt. This salt is typically isolated by filtration from the reaction medium and dried under reduced pressure. The isolated chloride is then heated to reflux with about 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 a by-product alkali metal chloride, which can then be removed, typically by filtration.

[0112] In at least one embodiment, the general synthesis of ammonium borate activators can be carried out using a two-step process. In the first step, an 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 the ammonium chloride salt. This salt is typically isolated by filtration from the reaction medium and dried under reduced pressure. The isolated ammonium chloride is then heated to reflux with about 1 molar equivalent of an alkali metal borate in a solvent (e.g., cyclohexane, dichloromethane, methylcyclohexane) to form ammonium borate along with the by-product alkali metal chloride, which can typically be removed by filtration.

[0113] A co-activator is a compound capable of alkylating a transition metal complex, and thus, when used in combination with an activator, forms an active catalyst. Co-activators can include alumoxanes, such as methylalumoxane, modified alumoxanes, such as modified methylalumoxane, and aluminum alkyls, such as trimethylaluminum, triisobutylaluminum, triethylaluminum, and tri-isopropylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, or tri-n-dodecylaluminum. Co-activators are typically used in combination with Lewis acid activators and ionic activators when the precatalyst is not a dihydrocarbyl or dihydride complex. Co-activators can also be used as scavengers to deactivate impurities in the feed or reactor.

[0114] Additional useful activators include N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, trimethylammonium tetrakis(perfluorophenyl)borate, and tri-n-butylammonium tetrakis(perfluorophenyl)borate. Typical activator to catalyst compound ratios range from about a 1:1 molar ratio. Alternative preferred ranges include 0.1:1 to 100:1, or 0.5:1 to 50:1. Particularly useful ranges are 0.5:1 to 10:1, preferably 1:1 to 5:1. Often, a slight excess of activator is used, for example, an activator to catalyst compound ratio of 1.1:1. Examples of suitable activators and their syntheses are described in U.S. Patent Publication No. 2019 / 0330139, U.S. Pat. No. 11,117,908, and U.S. Pat. No. 11,041,031, which are incorporated herein by reference.

[0115] Optional Scavenger and Co-activator In addition to the activator compound, a scavenger or co-activator may be used. Scavengers are compounds typically added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. Co-activators that are not scavengers may be used in conjunction with an activator to form an active catalyst. In some embodiments, the co-activator may be premixed with the transition metal compound to form an alkylated transition metal compound. Co-activators can include alumoxanes, such as methylalumoxane, modified alumoxanes, such as modified methylalumoxane, and aluminum alkyls (also called alkyl-aluminums), such as trimethylaluminum, tri-isobutylaluminum, triethylaluminum, and tri-isopropylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, or tri-n-dodecylaluminum. Co-activators are typically used in combination with Lewis acid activators and ionic activators when the precatalyst is not a dihydrocarbyl or dihydride complex. Co-activators may also be used as scavengers to deactivate impurities in the feed or reactor.

[0116] Aluminum alkyl or organoaluminum compounds which can be utilized as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and dialkylzincs such as diethylzinc. Scavengers can be additional components of the catalyst systems described herein. Scavengers are compounds that can be added to facilitate oligomerization or polymerization by scavenging impurities. Some scavengers may also act as activators and may also be referred to as co-activators. Co-activators that are not scavengers may also be used in conjunction with an activator to form an active catalyst with a transition metal compound. In some embodiments, the co-activator can be premixed with the transition metal compound to form an alkylated transition metal compound, also referred to as an alkylated catalyst compound or alkylated metallocene. As long as the scavenger promotes the metallocene compound to perform its intended catalytic function, the scavenger may be considered part of the catalyst system when used.

[0117] U.S. Patent No. 9,409,834 (e.g., line 37, column 33 to line 61, column 34) provides a detailed description of scavengers useful in the disclosed methods for making PAOs. The relevant portions of this patent regarding scavengers, their names, amounts, and methods of use are incorporated herein in their entirety. Particularly useful scavengers include tri-n-octylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-hexylaluminum, and the like.

[0118] Polymerization / oligomerization reactions and processes and methods for preparing PAOs In some embodiments of the process, the polymerization reaction exhibits a selectivity for a combination of greater than or equal to about 60 mol % vinylidene and trisubstituted vinylene (alternatively, greater than 70 mol %, or greater than 80 mol %) and less than or equal to about 10 mol % vinyl, based on the total moles of vinyl, vinylidene, disubstituted vinylene (excluding cyclic disubstituted vinylene), and trisubstituted vinylene in the unsaturated PAO product. In some embodiments of the process, the polymerization reaction exhibits a selectivity for greater than or equal to about 50 mol % vinylidene (alternatively, greater than 60 mol %, alternatively, greater than 70 mol %, alternatively, greater than 80 mol %) and less than or equal to about 10 mol % vinyl, based on the total moles of vinyl, vinylidene, disubstituted vinylene (excluding cyclic disubstituted vinylene), and trisubstituted vinylene in the unsaturated PAO product.

[0119] In some embodiments of the method, the polymerization reaction exhibits a 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%) relative to the total amount of dimers, trimers, tetramers, and higher oligomers, as measured by GC-MS. In some embodiments of the method, the polymerization reaction exhibits a 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%) relative to the total amount of dimers, trimers, tetramers, and higher oligomers, as measured by GC-MS.

[0120] 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.

[0121] In some embodiments of the process, the feedstock comprises one or more cyclic C-C cyclohexanes 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. 32 Alpha-olefins are preferred. 14 Alpha-olefins include vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, and 4-vinylcyclohex-1-ene. Most preferred are cyclic C-C 32 Alpha-olefins include vinylcyclohexane and 4-vinylcyclohex-1-ene, with 4-vinylcyclohex-1-ene being most preferred.

[0122] In some embodiments of the process, the feedstock comprises one or more cyclic C-C 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. 32 Alpha-olefins and one or more C4-C 32 Linear or C5-C 32 Branched alpha-olefins are preferred. 32 Linear or C5-C 32 Branched alpha-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. 32 Linear or C5-C 32 Branched alpha-olefins include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, and 3-methyl-1-pentene. 32 Linear or C5-C 32 Branched alpha-olefins include 1-pentene, 4-methyl-1-pentene, and 1-hexene.

[0123] In some embodiments, C6-C 32 Cyclic alpha-olefins are C6-C 20 Cyclic alpha-olefins, or C6-C 14 Cyclic alpha-olefins, or C8-C 12 It is a cyclic alpha-olefin. In some embodiments, C8-C 12 Cyclic alpha-olefins are non-conjugated dienes. In some embodiments, the linear alpha olefin is a C-C 20 Linear alpha-olefins, or C4-C 12 Linear alpha-olefins, alternatively C4-C8 linear alpha-olefins, alternatively C5-C8 linear alpha-olefins, alternatively C5-C6 linear alpha-olefins. In some embodiments, the branched alpha-olefin is a C5-C 20 Branched alpha-olefins, or C5-C 12 Branched alpha-olefins, or C5-C 10 Branched alpha-olefins, alternatively C6-C9 branched alpha-olefins, alternatively C6-C8 branched alpha-olefins.

[0124] The choice between producing a dimer-rich product and producing a higher molecular weight PAO depends on the combination of catalyst selection and the reaction conditions used, particularly the reactor temperature. Preferred metallocenes for producing dimers are those of formulas (III) and (V). Preferred reactor temperatures for producing dimers are about 100-200°C, more preferably about 110-180°C, alternatively about 120-170°C, alternatively about 130-160°C, or alternatively about 140-155°C. In some embodiments, the reaction conditions include a reactor temperature of about 120° C. or higher (preferably 130° C. or higher, or 140° C. or higher), and a reactor pressure of 15 psia to 1600 psia.

[0125] In some embodiments, the process for producing cyclic dimers from one or more cyclic alpha-olefins comprises: one or more C-C 32The method includes contacting a feedstock comprising cyclic 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 vinylidene, trisubstituted vinylene, disubstituted vinylene, and cyclic dimer molecules having optional vinyl unsaturation, and obtaining an unsaturated cyclic dimer product from the polymerization reaction mixture. In some embodiments, the metallocene compound is selected from Formula (I), (II), (III), (IV), or (V). In some embodiments, the metallocene compound is selected from Formula (I) or (II), wherein R 1 and R 3 At least one of these is not hydrogen. In one non-limiting embodiment, the present disclosure provides a continuous solution and / or bulk process for producing cyclic dimers, comprising: (a) at least one C4-C 24 (b) contacting a cyclic alpha-olefin with a metallocene catalyst, a non-coordinating anion activator, and optionally an alkyl-aluminum compound; under polymerization conditions in which 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 from 20 minutes to 3 hours; the olefin feed may be solvent-free other than the solvents used for the catalyst and scavenger solution, and the olefin feed is substantially free of linear and branched alpha-olefins; and (c) obtaining a dimer product, and optionally hydrogenating the dimer.

[0126] In another non-limiting embodiment, the present disclosure relates to a solution and / or bulk process in a batch or semi-batch reactor for producing cyclic dimers. In some embodiments, the process comprises: (a) at least one C4-C 24(b) contacting cyclic alpha-olefins with a metallocene catalyst, a non-coordinating anion activator, and optionally an alkyl-aluminum compound; (b) under polymerization conditions where 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 24 hours; the catalyst and activator are fed separately to the reactor; all catalysts can be fed in a single dose at the start of the reaction or in stages during the reaction, and do not contain any solvent other than those used for the catalyst and scavenger solutions, and the olefin feed is substantially free of linear and branched alpha-olefins; and (c) obtaining a dimer product, and optionally hydrogenating the oligomers.

[0127] Many polymerization / oligomerization processes and reactor types used in 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 may be conducted in batch mode, semi-batch mode, or as a continuous polymerization process. The term "batch" refers to a process in which the complete reaction mixture is withdrawn from the reactor vessel as a result of the polymerization reaction. Semi-batch allows for the addition of more monomer feed and / or catalyst at one or more intervals during the run, 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, including the polymer product, are withdrawn simultaneously or nearly simultaneously. When a continuous polymerization process is used, the polymerization / oligomerization process may be conducted in a continuous stirred tank reactor, a plug flow reactor (sometimes called a continuous tubular reactor), or a reactor with any monomer concentration distribution pattern between a CSTR and a plug flow reactor. The polymerization / oligomerization process may be carried out in a single reactor or multiple reactors. When multiple reactors are used, the reactors can be configured in either series or parallel configuration, or any combination of series and parallel configurations. The polymerization / oligomerization reactor can be operated in either liquid-full mode or partial liquid-filled mode with a gas phase headspace. When solid or supported catalysts are used, slurry or continuous fixed bed or plug flow processes may be appropriate.

[0128] The olefin feedstock may be treated to remove catalyst poisons such as peroxides, oxygen or nitrogen-containing organic compounds, or acetylenic compounds before being fed to the polymerization reactor. For example, the feedstock olefin may be treated with activated molecular sieves such as 3 Å, 4 Å, 8 Å, or 13 Å molecular sieves and / or in combination with activated alumina or an activated deoxygenation catalyst.

[0129] 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 certain embodiments, the reaction mixture for the polymerization reaction disclosed herein may contain 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 alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as those commercially available (Isopar™); halogenated and perhalogenated hydrocarbons, such as perfluorinated C 4-10 These include 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 aforementioned hydrocarbon solvents may also be used. Suitable solvents also include liquid olefins that can serve as monomers or comonomers, including 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 include methylcyclohexane, toluene, xylene, ethylbenzene, normal paraffins (e.g., NORPAR® solvents available from ExxonMobil Chemical Company, Houston, TX), isoparaffin solvents (e.g., ISOPAR® solvents available from ExxonMobil Chemical Company, Houston, TX), and combinations thereof. These solvents or diluents may typically be pretreated in the same manner as the feed olefins.

[0130] 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 alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as those commercially available (Isopar™); perhalogenated hydrocarbons such as perfluorinated C4-C 10 Suitable solvents include alkanes, C4-C 32 Also included are liquid olefins that can act as monomers or comonomers, including alpha-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, aliphatic hydrocarbon solvents are used as solvents, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In an alternative preferred embodiment, the solvent used is a C5-C 18 Alpha-olefins, or C5-C 16 Alpha-olefins, or C6-C 14 alpha-olefins, or mixtures thereof. Mixtures of any of the solvents listed above may be used.

[0131] In another embodiment, the solvent is not aromatic, and preferably aromatics are present in the solvent at less than 3% by weight, preferably less than 2% by weight, preferably less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0.1% by weight, based on the weight of the solvent. Preferably, the solvent or mixture of solvents is free of aromatics. Preferably, the solvent is a C4-C 10Preferably, the solvent is essentially free of all aromatic solvents. In another embodiment of the present disclosure, the solvent is preferably selected from one or more C5-C 32 Alpha olefins, such as one or more C5-C 16 Preferably, the solvent is essentially free of all non-alpha-olefin solvents.

[0132] 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 can be maintained at a level that improves catalyst productivity but preferably does not induce excessive (preferably any significant) hydrogenation of olefins, particularly feed alpha-olefins (the reaction of alpha-olefins with saturated paraffins can be very detrimental to the efficiency of the process). Therefore, the amount of hydrogen partial pressure is preferably maintained low, for example, less than 350 kPa, less than 170 kPa, less than 70 kPa, or less than 35 kPa; additionally or alternatively, the concentration of hydrogen in the reactant phase, reactor, and / or feed can be less than 10,000 ppm (by mass), for example, 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.

[0133] Alternatively, the polymerization / oligomerization process does not involve hydrogen. Polymerization or oligomerization in the absence of hydrogen can be advantageous in providing polymers or oligomers with a high degree of unsaturated double bonds. These double bonds can be easily converted into functionalized fluids with numerous performance properties. An example of the conversion of oligomers and / or polymers can be found, for example, in the preparation of ashless dispersions, as disclosed in the book "Lubricant Additives: Chemistry and Application," ed. By Leslie R. Rudnick, pp. 143-170, where, for example, a polymer is reacted with maleic anhydride to obtain a PAO-succinic anhydride, which can then be converted into a dispersion by reacting with an amine, alcohol, and / or polyether alcohol. Typically, one or more metallocene compounds, one or more activators, and one or more monomers are contacted to produce the polymers or oligomers of the present invention. Preferably, the catalyst, activator, or any co-activator are soluble compounds, and the reaction can be carried out in a solution polymerization process. Even if one of the components is not completely soluble in the reaction medium or in the feed stream, solution-type operation may still be applicable, either at the beginning of the reaction or during or at a later stage of the reaction. In either case, the catalyst system components dissolved or suspended in a solvent, such as an aromatic or aliphatic solvent, or in a monomer feed stream can be fed into a reactor under an inert atmosphere (usually a nitrogen or argon blanket atmosphere) to allow polymerization or oligomerization to occur.

[0134] The catalyst and activator may be delivered to the reactor separately (activated in-line immediately before the reactor or activated in the reactor) as solutions in a solvent or in the olefin feed stream, or may be preactivated and delivered to the reactor as an activated solution. In some embodiments, the metallocene compound may be activated in the reactor in the presence of the olefin. In another alternative, the pre-catalyst metallocene may be premixed with the activator and / or co-activator, and then this activated catalyst solution may be charged into the reactor. Alternatively, the metallocene compound (such as the dichloride form of the metallocene compound) may be pretreated with an alkylaluminum reagent, particularly triisobutylaluminum, tri-n-hexylaluminum, and / or tri-n-octylaluminum, and then charged into the reactor containing the other catalyst system components and the feed olefin, or may then be preactivated with the other catalyst system components to obtain a fully activated catalyst, which may then be fed into the reactor containing the feed olefin.

[0135] In a preferred embodiment where all solvents are olefin monomers, the pre-catalyst is dissolved in the monomer feed in the first feed tank, and the activator is mixed with the monomer feed in the second feed tank. The pre-catalyst and activator solutions are then fed separately into the reactor, and catalyst activation occurs in the reactor. If used, a scavenger can be fed independently or with the activator feed, pre-catalyst feed, or monomer feed if a separate monomer feed is used. Alternatively, the pre-catalyst and activator are pre-mixed separately in an inert solvent, and the pre-mixed solutions are then fed into the reactor. Catalyst activation occurs in the reactor.

[0136] Metallocene compounds and activators can also be delivered in suspension or dry powder form. Most single-site catalysts and activators received from manufacturers are in finely divided solid or "powder" form. Solid catalysts and / or activators can be milled into fine powders if not initially in such form. Catalysts and activators can be delivered to solution or slurry polymerization reactors as slurries in aliphatic hydrocarbon solvents, oils, or waxes, or in dry powder form, without sacrificing catalyst utilization. The catalyst and / or activator can be mixed with an aliphatic hydrocarbon solvent or 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. The catalyst is then dissolved in the polymerization medium in the polymerization reactor to initiate polymerization. The catalyst can be added directly to the polymerization reactor and then contacted with the activator, or it can be first contacted with the activator, and the resulting mixture can then be added to the polymerization reactor.

[0137] In any embodiment, the catalyst, activator, and, if necessary, co-activator may also be delivered as a supported catalyst. In a supported catalyst, the active component and / or activator of such a catalyst are supported on a solid, insoluble support. When a solid, supported catalyst is used, the polymerization / oligomerization process generally operates at temperature, pressure, and residence time ranges similar to those described for the solution process. Residual catalyst can be separated from the product by filtration, centrifugation, or settling. The fluid is then distilled to remove the solvent, any unreacted components, and light products. Some or all of the solvent and unreacted or light components can be recycled for reuse.

[0138] Any of the reactor types used in polymerization / oligomerization processes and metallocene-catalyzed polymerization or oligomerization, such as bulk, solution, and slurry polymerization or oligomerization processes, can be used in the present disclosure. Any of these processes can be carried out in a single reactor, or in a continuous stirred tank reactor or plug flow reactor with more than one reactor operating in a series or parallel configuration. In a single reactor operation, the monomer or monomers, catalyst / activator, optional coactivator, optional scavenger, and optional modifier are all fed into a single reactor. The behavior and properties of the resulting product are affected by the process conditions and the composition of the reactor medium. In another embodiment, these processes can be carried out in multiple reactors in a series reactor operation, with the components added to each of two or more reactors connected in series. Catalyst system components can be added to the first reactor in the series. Alternatively, catalyst system components may be added to both reactors. In one embodiment, the same catalyst is used in both the first and second reactors. Alternatively, the catalyst used in the first reactor is different from that used in the second reactor. The entire contents of the first reactor, including the oligomer product, unreacted monomer, and active catalyst, can be transferred to the second reactor. Alternatively, only a portion of the contents of the first reactor can be transferred to the second reactor. The oligomers produced in each reactor can have different molecular weights and / or compositions. The differences in molecular weight and / or composition are determined by end-use requirements. The molecular weight and composition can be controlled through the process conditions of each reactor, such as the monomer concentration and polymerization temperature. This can be achieved by controlling process conditions such as the 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, co-oligomers (oligomers from two or more alpha-olefins) are produced in a first reactor in a series configuration. In another embodiment, these processes can be carried out in multiple reactors in a parallel configuration. The advantage of parallel operation is independent control of the properties of the resulting products.In one embodiment, a cooligomer is produced in each reactor operating in parallel. In another embodiment, homo-oligomers are produced in one reactor and cooligomers are produced in another reactor operating in parallel. For example, 1-hexene / VCH cooligomers are produced in one reactor and VCH oligomers are produced in another reactor. In one embodiment, the same catalyst is used in all reactors. Alternatively, the catalyst used in one reactor is different from that used in another reactor in a parallel configuration. Parallel operation also provides additional freedom in process optimization, such as maximizing desired products and process efficiency.

[0139] Many of the polymerization / oligomerization processes and reactor types used in metallocene-catalyzed polymerization or oligomerization, including bulk, solution, and slurry polymerization or oligomerization processes, can be used in the present disclosure. Each of these processes may also be used in batch or semi-batch mode operation. In batch mode polymerization or oligomerization, all components are added to the reactor and reacted to a pre-designed degree of conversion, either partial or complete. The catalyst can then be deactivated by any possible means, such as exposure to air or water, or by adding an alcohol or solvent containing a deactivator.

[0140] Polymerization or oligomerization can also or alternatively be carried out in semi-batch operation, with the feed and catalyst system components being added to the reactor continuously and / or simultaneously to maintain a constant catalyst to olefin concentration ratio. When all feed and catalyst system components have been added, the reaction may proceed to a predetermined stage. The reaction can then be interrupted by catalyst deactivation in the same manner as described for batch operation. The monomer and catalyst can also be fed in stages to manipulate the properties of the produced oligomers and to control the temperature. In one embodiment, all of the monomers are fed into the reactor before the start of polymerization. The catalyst is fed into the reactor in stages, preferably with less than 50% of the catalyst fed at the start. Alternatively, one of the olefin monomers can be fed in stages to produce oligomers with different compositions.

[0141] Any of the polymerization / oligomerization processes and reactor types used in metallocene-catalyzed polymerization or oligomerization, such as bulk, solution, and slurry polymerization or oligomerization processes, can be used in the present disclosure. In all embodiments, the temperature of any reactor used herein can be from -10°C to 250°C, e.g., 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, polymerization reaction conditions include temperatures of 80°C or higher, 100°C or higher, 120°C or higher, 130°C or higher, or 140°C or higher. Temperature control within the reactor is generally achieved by balancing the heat of polymerization and reactor cooling via the reactor jacket or cooling coils, or by a cooled tributary stream of reactants to cool the reactor contents, autorefrigeration, pre-cooled feed, vaporization of the liquid medium (diluent, monomer, or solvent), or a combination of the above. Adiabatic reactors with pre-cooled feed may additionally or alternatively be used. Agitation of the reactor contents is generally performed to reduce or avoid concentration or temperature gradients.

[0142] In all embodiments, the pressure of 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. The monomer, metallocene, and activator 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.

[0143] The molecular weight distribution, or polydispersity, of the oligomers produced is important in some applications. With most metallocene catalysts, the molecular weight of the oligomers is sensitive to process conditions such as reactor temperature and monomer concentration. To produce products with narrow molecular weight distributions, good temperature control and intensive mixing are recommended to minimize temperature and monomer concentration fluctuations. Processes with low monomer conversion (high monomer concentration) in the reactor can also reduce the dependence of molecular weight on monomer concentration, thereby narrowing the molecular weight distribution. The oligomers described in this disclosure can have vinyl, vinylidene, disubstituted vinylene, or trisubstituted vinylene chain ends, depending on the catalyst type and chain termination mechanism. For some applications, the type of unsaturated chain end of the oligomer is important. Process conditions such as reaction temperature and H concentration can be used to adjust the level of unsaturated chain ends for a given catalyst system. For example, for some catalyst systems, higher reaction temperatures favor the production of oligomers with vinylidene and trisubstituted vinylene chain ends.

[0144] When the polymerization or oligomerization reaction has progressed to a predetermined stage, such as greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, or greater than 90% olefin conversion, a reactor effluent is withdrawn from the reactor. The reaction effluent contains active catalyst; these active components can be preferably deactivated and / or removed. Typically, the reaction can be deactivated by adding stoichiometric or excess amounts of air, water, alcohol, isopropanol, or the like. Catalyst system components can be removed using either conventional catalyst deactivation methods or aqueous washing methods. The mixture can then be washed with dilute sodium hydroxide or water to remove catalyst system components. The remaining organic layer can then be subjected to distillation to remove the solvent and unreacted monomer, which can then be recycled for reuse. The reactor product produced herein is typically a mixture of many different oligomers. Extraction or fractionation may be performed to separate the product into multiple fractions with different boiling ranges corresponding to different molecular weight ranges and degrees of polymerization. Unreacted monomers can be recycled to the original reactor. The oligomer fractions can also be hydrogenated depending on the application.

[0145] In a preferred embodiment, the present disclosure relates to a continuous solution and bulk process for producing oligomers, comprising: (a) contacting at least one alpha-olefin monomer having 4 to 24 carbon atoms and at least one cyclic alpha-olefin with a metallocene catalyst, a non-coordinating anion activator, and optionally an alkyl-aluminum compound; (b) under polymerization conditions in which the reaction temperature is in the range of 70° C. to 160° C., the reactor pressure is less than 50 atmospheres, and the residence time is 20 minutes to 3 hours, and which may contain no solvent other than that used for the catalyst and scavenger solution; and (c) obtaining an oligomer product (unsaturated PAO), optionally fractionating the oligomer, and hydrogenating the oligomer.

[0146] In another preferred embodiment, the present disclosure relates to a solution and / or bulk process in a batch or semi-batch reactor for producing oligomers, comprising: (a) contacting at least one alpha-olefin monomer having 4 to 24 carbon atoms and at least one cyclic alpha-olefin with a metallocene catalyst, a non-coordinating anion activator, and optionally an alkyl-aluminum compound; (b) under polymerization conditions where the reaction temperature is in the range of 70° C. to 160° C., the reactor pressure is less than 50 atmospheres, and the residence time is 20 minutes to 24 hours; the catalyst and activator are fed separately in the reactor; all catalysts can be fed in a single dose at the start of the reaction or in stages during the reaction, and may be free of solvents other than those used for the catalyst and scavenger solutions; and (c) obtaining an oligomer product (unsaturated PAO), optionally fractionating the oligomers, and hydrogenating the oligomers. Longer or shorter residence times can be used, the choice depending on the catalyst choice, monomer concentration, reaction temperature, and desired conversion level. Residence times as short as 1 minute but as long as 48 hours may be used, with preferred residence times ranging from 20 minutes to 2 hours for continuous processes and 20 minutes to 12 hours for batch or semi-batch processes.

[0147] supply material In some embodiments of the process, the feedstock comprises one or more cyclic C-C cyclohexanes selected from vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, 4-vinylcyclohex-1-ene (also referred to as vinylcyclohexane), vinylcycloheptane, vinylcyclooctane, vinylcyclononane, vinylcyclodecane, vinylcycloundecane, vinylcyclododecane, 5-vinylnorbornane, 5-vinyl-2-norbornene, allylcyclohexane, and allylcyclooctane. 32 In some embodiments of the process, the feedstock comprises one or more cyclic C-C alpha-olefins selected from vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, and 4-vinylcyclohex-1-ene. 14In some embodiments of the process, the feedstock comprises one or more C-C alpha-olefins selected from vinylcyclohexane and 4-vinylcyclohex-1-ene. 32 In some embodiments of the process, the feedstock comprises 4-vinylcyclohex-1-ene.

[0148] In some embodiments of the process, the feedstock comprises one or more cyclic C6-C 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. 32 Alpha-olefins and one or more C4-C 32 Linear or C5-C 32 In some embodiments of the process, the feedstock comprises one or more C4-C 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. 32 Linear alpha-olefins or C5-C 32 In some embodiments of the process, the feedstock comprises one or more C4-C olefins selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, and 3-methyl-1-pentene. 32 Linear alpha-olefins or C5-C 32In some embodiments of the process, the feedstock comprises one or more C4-C olefins selected from 1-pentene, 4-methyl-1-pentene, and 1-hexene. 32 Linear alpha-olefins or C5-C 32 Contains branched alpha-olefins.

[0149] In some embodiments, C6-C 32 Cyclic alpha-olefins are C6-C 20 Cyclic alpha-olefins (e.g., C6-C 14 Cyclic alpha-olefins or C8-C 12 cyclic alpha-olefins). In some embodiments, C8-C 12 Cyclic alpha-olefins are non-conjugated dienes. In some embodiments, the linear alpha-olefin is a C-C 20 Linear alpha-olefins (e.g., C4-C 12 linear alpha-olefin, C4-C8 linear alpha-olefin, C5-C8 linear alpha-olefin, or C5-C6 linear alpha-olefin). In some embodiments, the branched alpha-olefin is a C5-C 20 Branched alpha-olefins (e.g., C5-C 12 Branched Alpha-Olefins, C5-C 10 branched alpha-olefins, C6-C9 branched alpha-olefins, or C6-C8 branched alpha-olefins).

[0150] uPAO Products and Methods In some embodiments of the process, the polymerization reaction exhibits a selectivity for a combination of at least about 60 mol % vinylidene and trisubstituted vinylene (e.g., at least about 70 mol % or at least about 80 mol %), and up to about 10 mol % vinyl, based on the total moles of vinyl, vinylidene, disubstituted vinylene (excluding cyclic disubstituted vinylene), and trisubstituted vinylene in the unsaturated PAO product.

[0151] In some embodiments of the process, the polymerization reaction exhibits a 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, based on the total moles of vinyl, vinylidene, disubstituted vinylene (excluding cyclic disubstituted vinylene), and trisubstituted vinylene in the unsaturated PAO product.

[0152] In some embodiments of the method, the polymerization reaction exhibits a selectivity for dimer formation of at least about 50% (e.g., at least about 60%, at least about 70%, at least about 80%, at least about 90%, or at least about 95%) relative to the total amount of dimers, trimers, tetramers, and higher oligomers, as measured by GC-MS.

[0153] In some embodiments of the method, the polymerization reaction exhibits a selectivity for dimer and trimer formation of at least about 70% (e.g., at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 97%) relative to the total amount of dimers, trimers, tetramers, and higher oligomers, as measured by GC-MS. 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 both a) and b).

[0154] The choice between producing a dimer-rich product and producing a higher molecular weight PAO depends, at least in part, on a combination of catalyst selection and reactor conditions (e.g., reactor temperature). In some embodiments, the metallocene for producing the dimer comprises a metallocene compound represented by Formula (III) and Formula (V). Suitable reactor temperatures for producing the dimer can range from about 100°C to about 200°C (e.g., from about 110°C to about 180°C, from about 120°C to about 170°C, from about 130°C to about 160°C, or from about 140°C to about 155°C). In some embodiments, the reaction conditions include a reactor temperature of at least about 120° C. (eg, 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.

[0155] In some embodiments, 4-vinylcyclohex-1-ene (VCH) is used with other cyclic alpha-olefins or other linear or branched alpha-olefins. VCH, a diene, can undergo a chain transfer process to yield a bicyclic product. Figure 1 shows two reaction pathways by which VCH undergoes a chain transfer process to yield a bicyclic product. Pathway A shows the beta-hydride chain termination pathway, where M represents a catalytically active site. The beta-H (dark gray) transfers to M, resulting in a dimeric product containing vinylidene unsaturation. In Pathway B, M interacts with the double bond of the last inserted VCH monomer, providing access to the epsilon-hydride (light gray). The epsilon-hydride transfers to the metal, resulting in a bicyclic ring structure. This latter chain transfer pathway does not occur with ring-saturated alpha-olefins such as vinylcyclohexane. A similar route is shown in Figure 2, where the initially inserted alpha-olefin is represented as CH2=CHR, where R can be a linear, branched, or cyclic aliphatic group.

[0156] In some embodiments of the present disclosure, the PAO product comprises a mixture of unsaturated dimers selected from the compounds shown below. [ka] TIFF2025530375000068.tif74156

[0157] cyclic monomer fragments (A) and (B) are independently saturated when the cyclic alpha-olefin has a saturated ring structure, or partially unsaturated when the cyclic alpha-olefin has a partially unsaturated ring structure; [ka] where n and m independently represent the number of additional carbon atoms in the ring structure and can be an integer from 1 to 20 (e.g., 1 to 12, 1 to 9, 1 to 5, or 1 to 3), and R is a C-C 30 is a hydrocarbyl group, and R' is C-C 29 is a hydrocarbyl group, and at least one of structure CL-v or LC-v is present in the PAO product mixture. Note that the wavy bond in the structure indicates that both E and Z isomers are included.

[0158] In some embodiments, n and m are preferably 1 to 5, more preferably 2 to 4, and most preferably 3, independently. In some embodiments, R is preferably a C2-C8 hydrocarbyl group, more preferably a C2-C6 hydrocarbyl group, alternatively a C2-C4 hydrocarbyl group, or 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, or alternatively a C2-C3 hydrocarbyl group. In some embodiments of the present disclosure, 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. 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 partially unsaturated ring structures.

[0159] In some embodiments of the present disclosure, CC-v and CL-v and / or LC-v are present in the PAO structure. 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.

[0160] In some embodiments of the present disclosure, CC-v is selected from the following structures, where each q is independently an integer: [ka]

[0161] In some embodiments of the present disclosure, CC-t1 is selected from the following structures, wherein each q is independently an integer: [ka] In some embodiments of the present disclosure, in the CC-t1 structure shown above, q is preferably 1-5, more preferably 2-3.

[0162] In some embodiments of the present disclosure, CC-t2 is selected from the following structures, wherein each q is independently an integer: [ka] In some embodiments of the present disclosure, in the CC-t2 structure shown above, q is preferably 1-5, more preferably 2-3.

[0163] In some embodiments of the present disclosure, LC-v is selected from the following structures, where p is an integer: [ka] In some embodiments of the present disclosure, in the LC-v structures shown above, p=3-19, and p is preferably 3-11, more preferably 4-7, most preferably 4-5, with 5 being 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.

[0164] In some embodiments of the present disclosure, LC-t1 is selected from the following structures, where p is an integer: [ka] In some embodiments of the present disclosure, in the LC-t1 structure shown above, p=2-18, and p is preferably 2-10, more preferably 3-6, most preferably 3-4, and most preferably 4. For structures where p=2 and 5-20, p is preferably 2 and 5-10, and most preferably 2, 5, and 6.

[0165] In some embodiments of the present disclosure, LC-t2 is selected from the following structures, where p is an integer: [ka]

[0166] In some embodiments of the present disclosure, in the LC-t2 structure shown above, p=3-19, and p is preferably 3-11, more preferably 4-7, most preferably 4-5, and most preferably 5. For the structures where p=4-5 and 6-19, p is preferably 3 and 6-7, and most preferably 3 and 7.

[0167] In some embodiments of the present disclosure, CL-v is selected from the following structures, where p is an integer: [ka] In some embodiments of the present disclosure, in the CL-v structure shown above, p is preferably 1 to 9, more preferably 2 to 5, most preferably 2 to 3, with 3 being most preferred.

[0168] In some embodiments of the present disclosure, CL-t1 is selected from the following structures, where p is an integer: [ka] In some embodiments of the present disclosure, in the CL-t1 structure shown above, p is preferably 1 to 9, more preferably 2 to 5, most preferably 2 to 3, with 3 being most preferred.

[0169] In some embodiments of the present disclosure, CL-t2 is selected from the following structures, where p is an integer: [ka] In some embodiments of the present disclosure, in the CL-t2 structure shown above, p is preferably 1 to 8, more preferably 1 to 4, most preferably 1 to 2, with 2 being most preferred.

[0170] In some embodiments of the present disclosure, the following structures are preferred, where p is an integer: [ka]

[0171] In some embodiments of the present disclosure, in the structure shown above, p is preferably 2 to 8, more preferably 3 to 6, and most preferably 3 to 4, with 4 being most preferred. In an embodiment of the present disclosure, the PAO product comprises 7-(2-(cyclohex-3-en-1-yl)ethyl)bicyclo[3.2.1]oct-2-ene. In an embodiment of the present disclosure, the PAO product comprises 7-hexylbicyclo[3.2.1]oct-2-ene. In an embodiment of the present disclosure, the PAO product comprises 7-pentylbicyclo[3.2.1]oct-2-ene. In an embodiment of the present disclosure, the PAO product comprises 4,4'-(but-3-ene-1,3-diyl)dicyclohex-1-ene. In an embodiment of the present disclosure, the PAO product comprises 4-(oct-1-en-2-yl)cyclohex-1-ene. In an embodiment of the present disclosure, the PAO product comprises oct-1-en-2-ylcyclohexane.

[0172] In an embodiment of the present disclosure, the PAO product comprises 4-(hept-1-en-2-yl)cyclohex-1-ene.

[0173] In an embodiment of the present disclosure, the PAO product comprises hept-1-en-2-ylcyclohexane. In an embodiment of the present disclosure, the PAO product comprises 4-(non-1-en-2-yl)cyclohex-1-ene. In an embodiment of the present disclosure, the PAO product comprises non-1-en-2-ylcyclohexane. In an embodiment of the present disclosure, the PAO product comprises 4-(hex-1-en-2-yl)cyclohex-1-ene. In an embodiment of the present disclosure, the PAO product comprises 4-(6-methylhept-1-en-2-yl)cyclohex-1-ene. In an embodiment of the present disclosure, the PAO product comprises (6-methylhept-1-en-2-yl)cyclohexane.

[0174] In some embodiments, the PAO is a mixture of unsaturated dimers produced from two different alpha-olefins, where at least one alpha-olefin is a cyclic alpha-olefin (C) and at least a second alpha-olefin is a linear or branched alpha-olefin (L). The unsaturated dimers produced are represented by the formulas CC, CL, and LL. The dimer product distribution may vary and depends, at least in part, on the molar ratio of C to L used in the oligomerization reaction. In some embodiments, the ratio of C to L used in the process is selected so that the percentage of CL produced relative to CC + CL + LL equaling 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, the percentage of CC produced relative to 100% CC+CL+LL is 0%, more typically at least 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the percentage of LL produced relative to 100% CC+CL+LL is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages for CC, CL, and LL ratios are based on GC-MS as described in the experimental section.

[0175] In embodiments 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 (hex-hex). In some embodiments, the mole percentage of VCH-hex relative to the total moles of VCHx2 + VCH-hex + hex-hex equals 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, the molar percentage of VCHx2 produced relative to 100% VCHx2 + VCH-hex + hex-hex 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, the molar percentage of hex-hex produced relative to 100% VCHx2 + VCH-hex + 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%. All percentages and relative ratios are based on GC-MS as described in the Experimental Section.

[0176] In embodiments of the present disclosure, the PAO product comprises but-3-ene-1,3-diyldicyclohexane (VCH'x2), oct-1-en-2-ylcyclohexane (VCH'-hex), and 5-methyleneundecane (hex-hex). In some embodiments, the mole percentage of VCH'-hex relative to the total number of moles of VCH'x2 + VCH'-hex + hex-hex equals 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, the molar percentage of VCH'x2 produced relative to 100% VCH'x2 + VCH'-hex + hex-hex is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of hex-hex produced relative to 100% VCH'x2 + VCH'-hex + hex-hex is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS as described in the Experimental Section.

[0177] In embodiments 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 (pent-pent). In some embodiments, the mole percentage of VCH-pent relative to the total moles of VCHx2 + VCH-pent + pent-pent equals 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, the molar percentage of VCHx2 produced relative to 100% VCHx2 + VCH-pent + pent-pent is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of pent-pent produced relative to 100% VCHx2 + VCH-pent + pent-pent is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS as described in the Experimental Section.

[0178] In embodiments of the present disclosure, the PAO product comprises but-3-ene-1,3-diyldicyclohexane (VCH'x2), hept-1-en-2-ylcyclohexane (VCH'-pent), and 4-methylenenonane (pent-pent). In some embodiments, the mole percentage of VCH'-pent relative to the total number of moles of VCH'x2 + VCH'-pent + pent-pent equals 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, the molar percentage of VCH'x2 produced relative to 100% VCH'x2 + VCH'-pent + pent-pent is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of pent-pent produced relative to 100% VCH'x2 + VCH'-pent + pent-pent is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS as described in the Experimental Section.

[0179] 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, the mole percentage of VCH-hept relative to the total moles of VCHx2 + VCH-hept + hept-hept equals 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, the molar percentage of VCHx2 produced relative to 100% VCHx2 + VCH-hept + hept-hept is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of hept-hept produced relative to 100% VCHx2 + VCH-hept + hept-hept is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS as described in the Experimental Section.

[0180] In embodiments of the present disclosure, the PAO product comprises but-3-ene-1,3-diyldicyclohexane (VCH'x2), non-1-en-2-ylcyclohexane (VCH'-hept), and 6-methylenetridecane (hept-hept). In some embodiments, the mole percentage of VCH'x2 + VCH'-hept + hept-hept, relative to the total moles of VCH'x2 + VCH'-hept + hept-hept equaling 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, the molar percentage of VCH'x2 produced relative to 100% VCH'x2 + VCH'-hept + hept-hept is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of hept-hept produced relative to 100% VCH'x2 + VCH'-hept + hept-hept is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS as described in the Experimental Section.

[0181] 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-methyleneheptane (but-but). In some embodiments, the mole percentage of VCH-but relative to the total moles of VCHx2 + VCH-but + but-but equals 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, the molar percentage of VCHx2 produced relative to 100% VCHx2 + VCH-but + but-but is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of but-but produced relative to 100% VCHx2 + VCH-but + but-but is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS as described in the Experimental Section.

[0182] In embodiments of the present disclosure, the PAO product comprises but-3-ene-1,3-diyldicyclohexane (VCH'x2), hex-1-en-2-ylcyclohexane (VCH'-but), and 3-methyleneheptane (but-but). In some embodiments, the mole percentage of VCH'-but relative to the total moles of VCH'x2 + VCH'-but + but-but equals 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, the molar percentage of VCH'x2 produced relative to 100% VCH'x2 + VCH'-but + but-but is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of but-but produced relative to 100% VCH'x2 + VCH'-but + but-but is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS as described in the Experimental Section.

[0183] 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 (MePent-MePent). In some embodiments, the mole percentage of VCH-MePent relative to the total moles of VCHx2 + VCH-MePent + MePent-MePent equals 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, the molar percentage of VCHx2 produced relative to 100% VCHx2 + VCH-MePent + MePent-MePent is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of MePent-MePent produced relative to 100% VCHx2 + VCH-MePent + MePent-MePent is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS as described in the Experimental Section.

[0184] In embodiments of the present disclosure, the PAO product comprises but-3-ene-1,3-diyldicyclohexane (VCH'x2), (6-methylhept-1-en-2-yl)cyclohexane (VCH'-MePent), and 2,8-dimethyl-4-methylenenonane (MePent-MePent). In some embodiments, the mole percentage of VCH'x2 + VCH'-MePent + MePent-MePent relative to the total moles of VCH'x2 + VCH'-MePent + MePent-MePent equals 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, the molar percentage of VCH'x2 produced relative to 100% VCH'x2 + VCH'-MePent + MePent-MePent is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of MePent-MePent produced relative to 100% VCH'x2 + VCH'-MePent + MePent-MePent is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS as described in the Experimental Section.

[0185] In some embodiments of the present disclosure, when only cyclic alpha-olefins are in the feed, the conversion of cyclic alpha-olefins to dimers, as measured by GC-MS, based on the total amount of feed monomers, including isomerized or hydrogenated monomers, dimers, trimers, tetramers, and higher oligomers, 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. In some embodiments of the present disclosure, when only cyclic alpha-olefins are present in the feed, the selectivity to form dimers, as measured by GC-MS, relative to the total amount of dimers, trimers, tetramers, and higher oligomers, is 80% or greater, alternatively 90% or greater, alternatively 94% or greater, alternatively 98% or greater, with 99% or greater being most preferred. In some embodiments of the present disclosure, when only cyclic alpha-olefins are present in the feed, the selectivity to form one dimer species (one isomer) relative to the total amount of dimers is 80% or greater, alternatively 85% or greater, alternatively 90% or greater, alternatively 95% or greater, or alternatively 98% or greater, as measured by GC-MS.

[0186] In some embodiments of the present disclosure, when only cyclic alpha-olefins are present in the feed, the conversion of cyclic alpha-olefin monomer to the formation of one dimeric species (one isomer) is, as measured by GC-MS, 30% or more, alternatively 40% or more, alternatively 50% or more, alternatively 60% or more, alternatively 70% or more, alternatively 80% or more, alternatively 86% or more, alternatively 90% or more, alternatively 92% or more, alternatively 94% or more, alternatively 95% or more, alternatively 96% or more, alternatively 98% or more, based on the amount of the predominant dimeric isomer relative to the total amount of feed monomer, including isomerized or hydrogenated monomer, dimers, trimers, tetramers, and higher oligomers.

[0187] Hydrogenation A portion of the unsaturated PAO product can be hydrogenated to produce an at least partially saturated PAO product. In some embodiments, the treated product is contacted with hydrogen and a hydrogenation catalyst to produce an at least partially saturated hydrogenated PAO product, for example, at a temperature of about 25°C to about 350°C (e.g., about 100°C to about 300°C), for about 5 minutes to about 100 hours (e.g., about 5 minutes to about 24 hours), and at a hydrogen pressure of about 25 psig to about 2500 psig (i.e., about 170 kPa g to about 17 MPa g) (e.g., about 100 psig to about 2000 psig (i.e., about 690 kPa g to about 14 MPa g)). Further information regarding the hydrogenation of unsaturated PAO products can be found in U.S. Pat. No. 5,573,657 and in "Lubricant Base Oil Hydrogen Refining Processes" (pages 119 to 152 of Lubricant Base Oil and Wax Processing, by Avilino Sequeira, Jr., Marcel Dekker, Inc., NY, 1994), which are incorporated herein by reference.

[0188] This hydrogenation process can be achieved, for example, in a slurry reactor, batch operation, or continuous stirred tank reactor (CSTR), with the catalyst present at 0.001% to 20% by weight (e.g., 0.01% to 10% by weight) of the unsaturated PAO feed. Hydrogen and uPAO can be continuously added to the reactor for a specific residence time (e.g., 5 minutes to 10 hours) to achieve the desired (e.g., substantially complete) hydrogenation of the unsaturated olefins. The amount of catalyst added is typically very small, merely sufficient 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 settled to remove the solid hydrogenation catalyst. The catalyst can be regenerated and reused, if desired. The hydrogenated PAO can be used as is or further distilled or fractionated to the desired level. In some cases, when the hydrogenation catalyst exhibits little or no catalyst deactivation over extended periods of operation, a stirred-tank hydrogenation process can be carried out in such a manner that a fixed amount of catalyst is maintained in the reactor (e.g., about 0.1% to about 10% by weight of the total reactants), most (or only) the hydrogen and PAO feed is added continuously at a particular feed rate, and most (or only) the hydrogenated PAO is withdrawn from the reactor.

[0189] The hydrogenation process can also or alternatively be achieved by a fixed-bed process, in which the solid catalyst is packed into a tubular reactor and heated to reactor temperature. The hydrogen and PAO feed can be fed simultaneously or countercurrently through the reactor from the top or bottom, e.g., to maximize contact between the hydrogen, PAO, and catalyst, and to allow for heat management. The PAO and hydrogen feed rates can be adjusted to provide adequate residence time, e.g., to allow for the desired (typically substantially complete) hydrogenation of the unsaturated PAO in the feed. The hydrogenated PAO stream can be used as is or can be further distilled or fractionated to the desired level. Typically, the hydrogenated PAO product can have a Bromine Number of up to about 2.

[0190] In some embodiments, the hydrogenated PAO (hPAO) product is [ka] and a mixture of dimers selected from The cyclic monomer fragments (A) and (B) are saturated ring structures: [ka] and; where n and m independently represent the number of additional carbon atoms in the ring structure and can be an integer from 1 to 20 (e.g., 1 to 12, 1 to 9, 1 to 5, 1 to 3), and R is a C-C 30 is a hydrocarbyl group, and R' is a C-C 29 is a hydrocarbyl group having the structure hCL 1,2 or hLC 1,2 At least one of these is present in the hydrogenated PAO product mixture.

[0191] In some embodiments, n and m are preferably 1 to 5, more preferably 2 to 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, or 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, or 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. In some embodiments of the present disclosure, hCC 1,2 and hLC 1,2 and / or hCL 1,2is present in the hPAO product. In some embodiments of the present disclosure, hLL 1,2 and hLC 1,2 and / or hCL 1,2 In some embodiments of the present disclosure, hCC is present in the hPAO product. 1,2 , hLL 1,2 , and hLC 1,2 , and / or hCL 1,2 is present in the hPAO product.

[0192] In some embodiments of the present disclosure, hCC 1,2 is selected from the following structures, where each q is independently an integer: [ka]

[0193] In some embodiments of the present disclosure, hLC 1,2 is selected from the following structures, where each q is an integer: [ka]

[0194] In some embodiments of the present disclosure, hCL 1,2 is selected from the following structures, where each p is an integer: [ka]

[0195] In some embodiments of the present disclosure, the hCL 1,2 In the structures, when p is 1 to 9, p is preferably 1 to 9, more preferably 2 to 5, most preferably 2 to 3, and most preferably 3. For structures where p=2 to 3 and 5 to 19, p is preferably 2 to 3 and 6 to 7, and most preferably 2 and 3. For structures where p=2 to 6 and 8 to 19, p is preferably 2 to 6, and most preferably 2 and 3.

[0196] In some embodiments of the present disclosure, the following structures are preferred, where p is an integer: [ka]

[0197] In some embodiments of the present disclosure, in the structure shown above, p is preferably 2 to 8, more preferably 3 to 6, most preferably 3 to 4, with 4 being most preferred. In an embodiment of the present disclosure, the hPAO product comprises 6-(2-cyclohexylethyl)bicyclo[3.2.1]octane. In an embodiment of the present disclosure, the hPAO product comprises 6-hexylbicyclo[3.2.1]octane. In an embodiment of the present disclosure, the hPAO product comprises 6-pentylbicyclo[3.2.1]octane. In an embodiment of the present disclosure, the hPAO product comprises nonan-2-ylcyclohexane. In an embodiment of the present disclosure, the hPAO product comprises (6-methylheptan-2-yl)cyclohexane.

[0198] In some embodiments, the hydrogenated PAO is a mixture of saturated dimers formed from two different alpha-olefins, at least one alpha-olefin being a cyclic alpha-olefin (C) and at least one alpha-olefin being a linear or branched alpha-olefin (L), and the saturated dimers formed after hydrogenation are represented by the formulas hCC, hCL, and hLL. The saturated dimer product distribution may vary and depends, at least in part, on the molar ratio of C to L used in the oligomerization reaction. In some embodiments, the ratio of C to L used in the process is selected such that the percentage of hCL formed after hydrogenation, relative to hCC + hCL + hLL 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, the percentage of hCC produced relative to 100% hCC + hCL + hLL is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the percentage of hLL produced relative to 100% hCC + hCL + hLL is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages for the ratios of hCC, hCL, and hLL are based on GC-MS, as described in the experimental section.

[0199] In embodiments of the present disclosure, the hPAO product comprises butane-1,3-diyldicyclohexane (hVCHx2), octan-2-ylcyclohexane (hVCH-hex), and 5-methylundecane (hHex-hex). In some embodiments, the mole percentage of hVCH-hex relative to the total moles of hVCHx2 + hVCH-hex + hHex-hex equals 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, the molar percentage of hVCHx2 produced relative to 100% hVCHx2 + hVCH-hex + hHex-hex is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of hHex-hex produced relative to 100% hVCHx2 + hVCH-hex + hHex-hex is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS as described in the Experimental Section.

[0200] In embodiments of the present disclosure, the hPAO product comprises butane-1,3-diyldicyclohexane (hVCHx2), 4-nonan-2-ylcyclohexane (hVCH-pent), and 4-methylnonane (hPent-pent). In some embodiments, the mole percentage of hVCH-pent relative to the total moles of hVCHx2 + hVCH-pent + hPent-pent equals 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, the molar percentage of hVCHx2 produced relative to 100% hVCHx2 + hVCH-pent + hPent-pent is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of hPent-pent produced relative to 100% hVCHx2 + hVCH-pent + hPent-pent is at least about 110%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS, as described in the Experimental Section.

[0201] In embodiments of the present disclosure, the hPAO product comprises butane-1,3-diyldicyclohexane (hVCHx2), 4-heptan-2-ylcyclohexane (hVCH-hept), and 6-methyltridecane (hHept-hept). In some embodiments, the mole percentage of hVCH-pent relative to the total moles of hVCHx2 + hVCH-hept + hHept-hept equals 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, the molar percentage of hVCHx2 produced relative to 100% hVCHx2 + hVCH-hept + hHept-hept is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of hHept-hept produced relative to 100% hVCHx2 + hVCH-hept + hHept-hept is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS, as described in the Experimental Section.

[0202] In embodiments of the present disclosure, the hPAO product comprises butane-1,3-diyldicyclohexane (hVCHx2), hexan-2-ylcyclohexane (hVCH-but), and 3-methylheptane (hbut-but). In some embodiments, the mole percentage of hVCH-but relative to the total moles of hVCHx2 + hVCH-but + hbut-but equals 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, the molar percentage of hVCHx2 produced relative to 100% hVCHx2 + hVCH-but + hbut-but is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of hbut-but produced relative to 100% hVCHx2 + hVCH-but + hbut-but is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS, as described in the Experimental Section.

[0203] In embodiments of the present disclosure, the hPAO product comprises butane-1,3-diyldicyclohexane (hVCHx2), (6-methylheptan-2-yl)cyclohexane (hVCH-MePent), and 4-methylnonane (hMePent-MePent). In some embodiments, the mole percentage of hVCH-MePent relative to the total moles of hVCHx2 + hVCH-MePent + hMePent-MePent equals 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, the molar percentage of hVCHx2 produced relative to 100% hVCHx2 + hVCH-MePent + hMePent-MePent is 0%, more typically at least about 1%, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%. In some embodiments, the molar percentage of hMePent-MePent produced relative to 100% hVCHx2 + hVCH-MePent + hMePent-MePent is at least about 10%, and up to about 80%, up to about 70%, up to about 60%, up to about 50%, up to about 40%, up to about 30%, or up to about 20%. All percentages and relative ratios are based on GC-MS, as described in the Experimental Section.

[0204] sensualization A portion of the unsaturated PAO product can be reacted with a chemical reagent to yield an at least partially functionalized PAO product. However, due to the individual nature of the functionalization reaction, the potential by-products or specificity of by-products to be avoided, the wide range of potentially desired functionality, and therefore the wide range of potential reaction conditions available or sufficient to obtain the desired functionality, it can be difficult to define an appropriate set of conditions, reactors, chemical reagents, and / or catalysts / additives, etc., to encompass them all. Nevertheless, conventional functionalization techniques and their reaction parameters are known to those skilled in the chemical arts, and can readily yield partially or fully functionalized PAO products with any one or more of a variety of functional groups. For substantially or fully functionalized PAO products, in some embodiments, the Bromine Number can be up to about 2.

[0205] Lubricant Base Stocks The unsaturated PAO products and hydrogenated PAO products described herein can be used as base stocks for lubricating oil compositions. In some embodiments, hydrogenated PAOs having a Bromine Number of up to about 2 or 2.0 or less are used as lubricating oil base stocks. The base stocks can be of any viscosity grade useful for any particular lubricating oil composition. The base stocks of this disclosure can be blended with each other, other API Group I, II, III, IV, or V base stocks, and / or lubricant additive packages to form lubricating oil compositions. The terms "lubricant," "lubricant composition," and "lubricant" are used interchangeably herein. 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, and the like, as well as combinations thereof.

[0206] In some embodiments, the method of producing the PAO dimer further comprises reacting the PAO dimer with a reactant to form a functionalized PAO product, followed by hydrogenation. In some embodiments, the method of producing a PAO dimer and / or trimer further comprises hydrogenating the product. Some embodiments include fuels comprising hydrogenated PAO dimers and / or trimers. Some embodiments include driveline or electric vehicle fluids comprising hydrogenated or functionalized or hydrogenated functionalized derivatives of PAO dimers and / or trimers.

[0207] Some embodiments include engine oils comprising hydrogenated or functionalized derivatives or hydrogenated functionalized derivatives of PAO dimers and / or trimers. Some embodiments include gear oils comprising hydrogenated or functionalized derivatives or hydrogenated functionalized derivatives of PAO dimers and / or trimers. Some embodiments include coolants comprising hydrogenated or functionalized derivatives or hydrogenated functionalized derivatives of PAO dimers and / or trimers. Some embodiments include compressor oils comprising hydrogenated or functionalized derivatives or hydrogenated functionalized derivatives of PAO dimers and / or trimers. Some embodiments include hydraulic fluids comprising hydrogenated or functionalized derivatives or hydrogenated functionalized derivatives of PAO dimers and / or trimers. [Example]

[0208] catalyst complex Catalyst complexes A-E were 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. [ka] Complex A, (1-isobutyl-3,5,6,7-tetrahydro-s-indacenyl)(pentamethylcyclopentadienyl)hafnium dimethyl, and Complex B, (1-methyl-3,5,6,7-tetrahydro-s-indacenyl)(pentamethylcyclopentadienyl)hafnium dimethyl), used in the oligomerization experiments below, can be synthesized according to PCT Publication No. WO 21 / 030045, which is incorporated herein by reference for its synthetic methodology. Complex D, (1-methylindenyl)(pentamethylcyclopentadienyl)hafnium dimethyl, used below, can be synthesized according to PCT Publication No. WO 2019 / 157169, which is incorporated herein by reference for its synthetic methodology.

[0209] Catalytic synthesis reactions were carried out under inert and oxygen-free conditions (under dinitrogen or similar), using anhydrous solvents, and using commercially available reagents. Synthesis of Complex C, (1,5,6-trimethylindenyl)(pentamethylcyclopentadienyl)hafnium dimethyl Synthesis of (5,6-dimethyl-1H-inden-1-yl)lithium [ka] To a pale yellow solution of 5,6-dimethylindene (8.94 g, 62.0 mmol, purchased from Boulder Scientific) in diethyl ether (300 mL) at −35° C. was added n-BuLi in hexanes (25.0 mL, 2.48 M, 62.0 mmol, 1.00 equiv.). The initial amber solution quickly turned cloudy manila with a precipitate after the addition. The reaction turned cloudy peach with a white precipitate after 30 minutes of stirring. The reaction was concentrated in vacuo to leave a peach-colored solid. The solid was washed with pentane (40 mL) and dried under vacuum as a peach-colored powder. Yield: 9.06 g (97%). 1 H 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).

[0210] Synthesis of 1,5,6-trimethyl-1H-indene [ka] To a colorless solution of iodomethane (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 cloudy, thick, light manila mixture. The reaction warmed, turned cloudy, light manila, and became less thick after stirring for 20 minutes. After stirring for 45 minutes, the reaction turned a warm, clear amber color. After stirring at room temperature for 3 hours, the reaction was clear. Dimethoxyethane (11.0 g, 122 mmol, 2.06 equiv.) was added, giving a cloudy manila mixture along with a precipitate. The reaction was evaporated in vacuo to leave a wet manila solid. This 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 to leave an amber liquid. Yield: 8.90 g (95%). 1 H 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).

[0211] Synthesis of (3,5,6-trimethyl-1H-inden-1-yl)lithium [ka] To an amber solution of 1,5,6-trimethyl-1H-indene (8.87 g, 56.1 mmol) in diethyl ether (120 mL) at −35° C. was added n-BuLi in hexanes (23.0 mL, 2.48 M, 57.0 mmol, 1.02 equiv.) to give a hazy amber solution that quickly thickened due to a manila precipitate after the addition was complete. The reaction mixture was stirred for 30 minutes and then evaporated in vacuo to leave a manila-colored solid. The solid was washed with pentane (2×40 mL) and dried under vacuum to give a light manila-colored powder. Yield: 9.20 g (100%). 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).

[0212] Tri(dimethylamido)hafnium iodide, Hf(NMe 2 ) 3 Synthesis of I Hafnium tetrakisdimethylamide (24.92 g, 70.2 mmol) in pentane (150 mL) was added dropwise slowly over 20 minutes to trimethylsilyl iodide (10.00 mL, 1.41 g / mL, 70.3 mmol) to give a cloudy white mixture. After 1 hour, the reaction was white with a lot of precipitate. The reaction was filtered, and the solid was washed with pentane (2 x 40 mL) and dried under vacuum as a white powder. This yielded 29.45 g (96%) of tri(dimethylamido)hafnium iodide as a white powder. 1 H NMR (400 MHz, benzene-d6): δ 2.82 (s, 13H), 2.59 (s, 6H).

[0213] (Pentamethylcyclopentyldienyl)hafnium tri(dimethylamide), (Me 5 Cp)Hf(NMe 2 ) 3 Synthesis of [ka] 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.). The reaction became a cloudy white mixture, with a white precipitate after 1 h. After 5 h, the reaction was evaporated in vacuo to leave 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%). 1 H NMR (400 MHz, benzene-d6): δ 2.97 (s, 15H), 2.00 (s, 12H).

[0214] (Pentamethylcyclopentyldienyl)hafnium trichloride dimethoxyethane adduct, (Me 5 Cp)HfCl 3 Synthesis of (dme) [ka]

[0215] To a pale yellow solution of (Me5Cp)Hf(NMe2)3 (20.32 g, 45.6 mmol) in 1,2-dimethoxyethane (75 mL) was added trimethylsilyl chloride (30.00 g, 276 mmol, 6.06 equiv.). The reaction was mildly exothermic and turned nearly colorless after the addition of trimethylsilyl chloride. After 1 minute, the reaction became cloudy with the formation of a white precipitate. After 1 hour, the reaction turned cloudy and pale manila-colored after stirring. After 2.5 hours, the reaction was evaporated in vacuo to leave a manila-colored solid. The solid was washed with pentane (30 mL) and dried under vacuum to give a yield of 22.86 g (98%) as a pale peach-colored powder. 1 H NMR (400 MHz, methylene chloride-d): δ 3.81 (s, 4H), 3.56 (s, 6H), 2.23 (s, 15H).

[0216] (pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)hafnium dichloride, (Me 5 Cp)(1,5,6-Me 3 Ind)HfCl 2 Synthesis of [ka]

[0217] (Me5Cp)HfCl3(dme) (2.50 g, 4.90 mmol) was slurried in diethyl ether (35 mL). The slurry was charged with Li[1,5,6-Me3Ind] (0.81 g, 4.93 mmol, 1.01 equiv.) to give a cloudy, manila-yellow mixture and stirred overnight. After 20 h, the reaction was evaporated in vacuo to leave 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 leave a pale yellow solid. The solid was washed with chilled pentane (15 mL) and dried under vacuum to give a pale yellow powder in 2.30 g (87%) yield. 1 H NMR (400 MHz, methylene chloride-d): 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).

[0218] (pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)hafnium dimethyl, (Me 5 Cp)(1,5,6-Me 3 Ind)HfMe 2 Synthesis of [ka]

[0219] 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.) to produce a cloudy yellow mixture. The reaction was allowed to warm slightly and after 1 minute of stirring became cloudy. After 1 hour, the solution was cloudy yellow and allowed to stir overnight. After 20 hours, the mixture was cloudy pale yellow-white. The reaction was then evaporated in vacuo to leave 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 to leave a pale yellow solid. Yield: 2.07 g, (99%). 1 H 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).

[0220] Synthesis of Complex E, (indenyl)(tetramethylcyclopentadienyl)hafnium dimethyl Tri(dimethylamido)hafnium chloride, Hf(NMe 2 ) 3 Synthesis of Cl To a colorless solution of Hf(NMe2)4 (50.00 g, 141 mmol, 3.01 equiv.) in dichloromethane (250 mL) was added HfCl4 (15.0 g, 46.8 mmol) to give a warm, slightly hazy, colorless solution. After 1 h, the reaction was filtered. The filtrate was evaporated in vacuo to leave a white solid. The solid was dried in vacuo overnight, washed with pentane (2 x 40 mL), and dried again in vacuo. Yield: 61.98 g (96%) as a white powder. 1 H NMR (400 MHz, benzene-d6): 2.82 (s, 18H)

[0221] (Tetramethylcyclopentadienyl)hafnium tri(dimethylamide), (Me 4 Cp)Hf(NMe 2 ) 3 Synthesis of [ka] To a white suspension of Hf(NMe2)3Cl (15.00 g, 43.3 mmol, 1.02 equiv.) in diethyl ether (90 mL) was added sodium tetramethylcyclopentadienide (6.15 g, 42.7 mmol) to give a cloudy white mixture. The reaction mixture was stirred as a cloudy pale yellow-white mixture for 3.5 hours. It was then evaporated in vacuo to leave 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 pale manila-colored solid. Yield: 17.59 g (95%). 1 H NMR (400 MHz, benzene-d6): δ 6.87 (s, 1H), 2.69 (s, 18H), 1.78 (s, 6H), 1.64 (s, 6H).

[0222] (Tetramethylcyclopentyldienyl)hafnium trichloride dimethoxyethane adduct, (Me 4 Cp)HfCl 3 Synthesis of (dme) [ka]

[0223] To a pale yellow solution of (Me4Cp)Hf(NMe2)3 (17.55 g, 40.6 mmol) in 1,2-dimethoxyethane (50 mL) was added trimethylsilyl chloride (27.00 g, 249 mmol, 6.12 equiv.). The reaction became slightly warm and lightened in color upon completion of the addition. After 3.5 hours, the reaction was a cloudy amber-white mixture. It was then evaporated in vacuo to leave a manila-colored solid. The solid was washed with pentane (2 x 20 mL) and dried under vacuum to give a light manila-colored powder. Yield: 19.88 g (99%) 1H NMR (400 MHz, methylene chloride-d): δ 5.62 (s, 1H), 4.04 (s, 4H), 3.80 (s, 6H), 2.28 (s, 6H), 2.17 (s, 6H).

[0224] (Indenyl)(tetramethylcyclopentadienyl)hafnium dichloride, (Ind)(Me 4 Cp)HfCl 2 Synthesis of [ka] A pale peach 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 cloudy, manila-yellow mixture. The reaction was stirred for 18 hours and turned cloudy and pale yellow with a precipitate. The reaction was evaporated in vacuo to give a pale yellow solid. The solid was extracted with dichloromethane (30 mL, then 3 × 5 mL) and filtered to give a pale yellow filtrate and a gray solid. The filtrate was evaporated in vacuo to leave a pale yellow solid. The solid was washed with pentane (20 mL) and dried in vacuo to give a pale yellow powder. Yield: 2.32 g (95%).

[0225] 1 H NMR (400 MHz, methylene chloride-d): 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).

[0226] (Indenyl)(tetramethylcyclopentadienyl)hafnium dimethyl, (Ind)(Me 4 Cp)HfMe 2 Synthesis of [ka]

[0227] To a cloudy yellow suspension of (Ind)(MeCp)HfCl (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.) to give a cloudy yellow mixture. The reaction was hazy yellow and slightly warm and stirred overnight. After 18 h, the reaction mixture was cloudy and pale yellow-white. The reaction was evaporated in vacuo to leave a pale yellow-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 to leave a pale yellow solid. Yield: 2.10 g (100%). 1 H 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).

[0228] activator For catalyst activation, N,N-di(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate (M2HTH-D4) can be purchased from Boulder Chemical Company as a 10 wt % solution in methylcyclohexane. Scavenger Regarding scavengers, tri-n-octylaluminum (untreated) can be purchased as Azko Nobel Part # K52296 or similar.

[0229] monomer Unless otherwise stated, monomers were sparged with dry nitrogen to remove air and placed over molesieves (3 Å) to remove moisture before use. Monomers were sourced as indicated: 1-Butene - Airgas Product # B1 CPLP5, chemically pure grade or similar; 1-Pentene - GFS Item # 3396, 98% purity or higher; 4-Methyl-1-pentene - Sigma Aldrich Part # M67400, or similar; 1-Hexene - sourced from Pilot Plant - Chevron Phillips AlphaPlus® 1-Hexene or similar; 1-Heptene - TCI America Product # H0042 - 98% or greater by GC; 1-Octene - sourced from Pilot Plant - Chevron Phillips AlphaPlus® 1-octene or similar; 1-Nonene - TCI America Product # N0613 - 95% or greater by GC; 1-Decene - Sourced from Pilot Plant - Chevron Philips AlphaPlus® 1-Decene or similar; 4-Vinylcyclohex-1-ene - Gelest Product Code ENEV4520 - 97% purity, contains 100-200 ppm BHT (2,6-di-tert-butyl-4-methylphenol) stabilizer, purified by passage through basic alumina, sparged with nitrogen, and treated with a drying agent (3 Å mole sieves with any Q5); 4-vinylcyclohexane was purchased from TCI chemicals, purified by sparging with nitrogen, and stored over activated molecular sieves (4 Å) and AZ300 as described above; 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 February 8, 2022, and U.S. Patent Publication No. 2023 / 0250200.

[0230] Additional Reagents Additional reagents were obtained as described below. Aluminum oxide, basic, Brockmann I - Sigma Aldrich Part # 199443 or similar; Aluminum oxide, acidic, Brockmann I - Sigma Aldrich Part # 199966 or similar; Silica gel - Sigma Aldrich Part # 288624 high purity grade, pore size 60 Å, 70-230 mesh or similar; Molecular sieves 3Å - Sigma Aldrich Part # 208582 beads, 8-12 mesh, or similar; Q-5 Reactant BASF CU-0226 S - from BASF Product Identifier: CU 0226 S 8x14 MESH or similar; AZ300 - UOP; and Celite® 545 - Sigma Aldrich # 419931.

[0231] solvent Unless otherwise stated, solvents were sparged with dry nitrogen to remove air and placed over molesieves (3 Å) to remove moisture before use. Methylcyclohexane (abbreviated as MCH) - Sigma Aldrich # 300306-2L; and Toluene - Sigma Aldrich # 244511-1L

[0232] Oligomerization Experimental Procedure Batch oligomerization reactions for Examples 1-16 were carried out in 1- or 2-L stainless steel autoclave reactors equipped with a paddle stirrer, an external water / steam jacket for temperature control, a regulated supply of dry nitrogen, and inlets for the introduction of other solvents, monomers, precatalysts, scavengers, and activators. The reactor body was dried by heating the reactor at 110-120°C under a stream of dry nitrogen for approximately 1 hour before use. Typically, 500-1000 mL of monomer was measured through the sight glass, either as a premixed mixture of two monomers or as a single monomer addition.

[0233] The following abbreviations are used for the olefin monomers: VCH: Also known as 4-vinylcyclohex-1-ene, 4-vinylcyclohexene, 4-vinyl-1-cyclohexene, and vinylcyclohexene VCB: vinylcyclobutane C4: 1-butene, also called butene C5: 1-pentene, also known as pentene C6: 1-Hexene, also known as hexene iC6: 4-methylpent-1-ene, also known as 4-methylpentene, 4-methyl-1-pentene, and isohexene C7: 1-heptene, also called heptene C8: 1-octene, also known as octene C9: 1-Nonene, also known as nonene C10: 1-Decene, also known as Decene

[0234] Oligomerization Examples 1-10 For catalyst addition in Examples 1-10, a dual cylinder (also called a dual addition tube) consisting of two 25 mL SS Swagelok cylinders with three SS Swagelok ball valves (one in the middle and one at each end) was typically used. All catalysts, activators, and scavengers were handled inside a nitrogen-purged dry box. All catalyst and activator solutions were prepared separately and loaded into different ends of the dual cylinder while inside the nitrogen-purged dry box. After removal from the dry box, the dual addition tube was attached to the reactor so that the activator / scavenger solution entered the reactor before the catalyst solution.

[0235] Oligomerization Example 1: Typical Co-oligomerization of C6 and VCH Using Catalyst A In 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 the dual addition tube. In the front section, M2HTH-D4 (10 wt.% in MCH, 3.0–4.0 mL) was combined with untreated tri-n-octylaluminum (scavenger, 0.3–0.5 mL) and an additional 5–10 mL of MCH. Dry dinitrogen was used to push 1000 mL of the monomer mixture (approximately 50:50 by volume) into the reactor, and the dual addition tube was then attached to the reactor and nitrogen source. Agitation was initiated (approximately 500 rpm), and the reactor was then heated to 90°C. Once the monomer and reactor temperatures reached 90°C, approximately 80 psi of dry dinitrogen was used to inject the catalyst, scavenger, and activator solution, and the reactor was then heated to 110°C. Timing began with the addition of the catalyst to the reactor and was allowed to proceed for 30 to 90 minutes. After this period, heating and stirring were stopped. Upon cooling to ambient temperature, the high pressure within the reactor was reduced and the reactor was opened. The contents were then filtered through approximately 200 mL of a 1:1 volume ratio of silica and alumina to yield a clear liquid in a volume of approximately 1000 mL.

[0236] Oligomerization Example 2: Typical co-oligomerization of C7 and VCH using catalyst A In 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 the dual addition tube. In the front section, M2HTH-D4 (10 wt.% in MCH, 3.6–4.0 mL) was combined with untreated tri-n-octylaluminum (0.3–0.4 mL) and an additional 7 mL of MCH. 1000 mL of the monomer mixture (approximately 50:50 by volume) was forced into the reactor using 80 psi of dry dinitrogen, and the dual addition tube was then attached to the reactor and nitrogen source. Agitation was initiated (approximately 500 rpm), and the reactor was then heated to 90°C. Once the monomer and reactor temperatures reached 90°C, the catalyst, scavenger, and activator solutions were injected into the reactor using approximately 80 psi of dry dinitrogen, and the reactor was then heated to 110°C. Timing began with the addition of the catalyst to the reactor and was allowed to proceed for 30 to 90 minutes. After this period, heating and stirring were stopped. Upon cooling to ambient temperature, the high pressure within the reactor was reduced and the reactor was opened. The contents were then filtered through approximately 200 mL of a 1:1 volume ratio of silica and alumina to yield a clear liquid in a volume of approximately 1000 mL.

[0237] Oligomerization Example 3: Typical co-oligomerization of C5 and VCH using catalyst A In 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 the dual addition tube. In the front section, M2HTH-D4 (10 wt.% in MCH, 3.6–4.0 mL) was combined with untreated tri-n-octylaluminum (0.3–0.4 mL) and an additional 7 mL of MCH. 1000 mL of the monomer mixture (approximately 50:50 by volume) was forced into the reactor using 80 psi of dry dinitrogen; the dual addition tube was then attached to the reactor and nitrogen source. Agitation was initiated (approximately 500 rpm), and the reactor was then heated to 90°C. Once the monomer and reactor temperatures reached 90°C, the catalyst, scavenger, and activator solutions were injected using approximately 80 psi of dry dinitrogen, followed by heating to 110°C. Timing began with the addition of the catalyst to the reactor and was allowed to proceed for 30 to 90 minutes. After this period, heating and stirring were stopped. Upon cooling to ambient temperature, the high pressure within the reactor was reduced and the reactor was opened. The contents were then filtered through approximately 200 mL of a 1:1 volume ratio of silica and alumina to yield a clear liquid in a volume of approximately 1000 mL.

[0238] Oligomerization Example 4: Typical Oligomerization of iC6 Using Catalyst D In 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 the dual-addition tube. In the front section, M2HTH-D4 (10 wt.% in MCH, 0.8 mL), tri-n-octylaluminum (100 μL), and MCH (8 mL) were combined and added. Using high-pressure dry dinitrogen, 1 L of 4-methylpent-1-ene was added to the reactor; the dual-addition tube was then attached to the reactor and a nitrogen source. The stirrer was then turned to 900-1000 rpm. The heat was set to reach 110°C. After the reactor contents reached between 100-110°C, high-pressure dry nitrogen was used to push in the catalyst and activator solution. Timing began with the addition of the catalyst to the reactor and was allowed to proceed for 1 hour. After this period, the heating and stirring were stopped, the pressure was vented from the reactor, and the reactor was opened. After combining the products from several runs of this type, the product was filtered through Celite® to remove catalyst residues.

[0239] Oligomerization Example 5: Typical C5 and C4 Co-oligomerization Using Catalyst A In 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 addition tube. In the front section, M2HTH-D4 (10 wt% in MCH, 0.8 mL), tri-n-octylaluminum (100 μL), and MCH (8 mL) were combined and added. Using high-pressure nitrogen, 300 mL of 1-pentene was added to the reactor, followed by 250 mL of 1-butene; the dual addition tube was then attached to the reactor and nitrogen source. The stirrer was then turned to 900-1000 rpm. The heat was set to reach 110°C. After the reactor reached between 100-110°C, high-pressure dry dinitrogen was used to push in the catalyst and activator solutions. Timing began with the addition of the catalyst to the reactor and was allowed to proceed for 1 hour. After this period, heating and stirring were stopped, the pressure was vented from the reactor, and the reactor was opened and let down to expose the contents to air. The contents were poured into a pre-weighed container and the mass of the product was recorded. After combining the product from several runs of this type, the product was filtered through Celite® to remove catalyst residues.

[0240] Oligomerization Example 6: Typical co-oligomerization of VCH and C4 using catalyst A In 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 addition tube. In the front section, M2HTH-D4 (1.60 mL of 10% by weight in MCH), tri-n-octylaluminum (200 μL), and MCH (7 mL) were combined and added. Using high-pressure dry dinitrogen, 600 mL of VCH was added to the reactor, followed by 200 mL of 1-butene (passed through a dryer as described above); the dual addition tube was then attached to the reactor and nitrogen source. The stirrer was then turned to 900-1000 rpm. The heat was set to reach 110°C. After the reactor reached between 100-110°C, high-pressure dry nitrogen was used to push in the catalyst and activator solutions. Timing began with the addition of the catalyst to the reactor and was allowed to proceed for 1 hour. After this period, heating and stirring were stopped, the pressure was vented from the reactor, and the reactor was opened and let down to expose the contents to air. The contents were poured into a pre-weighed container and the mass of the product was recorded. After combining the product from several runs of this type, the product was filtered through Celite® to remove catalyst residues.

[0241] Oligomerization Example 7: Typical co-oligomerization of VCH and iC6 using catalyst A In 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 addition tube. In the front section, M2HTH-D4 (1.60 mL of 10% by weight in MCH), tri-n-octylaluminum (200 μL), and MCH (7 mL) were combined and added. Using high-pressure nitrogen, 500 mL of VCH was added to the reactor, followed by 500 mL of 4-methylpent-1-ene; the dual addition tube was then attached to the reactor and nitrogen source. The stirrer was then turned to 900-1000 rpm. The heat was set to reach 110°C. After the reactor reached between 100-110°C, high-pressure dry dinitrogen was used to push in the catalyst and activator solutions. Timing began with the addition of the catalyst to the reactor and was allowed to proceed for 1 hour. After this period, the heating and stirring were stopped. The high pressure was vented from the reactor and the reactor was opened. The contents were poured into a pre-weighed container and the mass of the product was recorded. After the addition of several runs, the product was filtered through Celite® to remove catalyst residues.

[0242] Oligomerization Example 8: Typical Oligomerization of C5 Using Catalyst A In 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-addition tube. In the front section, M2HTH-D4 (10 wt.% in MCH, 0.8 mL) was combined with untreated tri-n-octylaluminum (100 μL) and an additional 8 mL of MCH. Using high-pressure dry dinitrogen, 500 mL of 1-pentene was added to the reactor; the dual-addition tube was then attached to the reactor and a nitrogen source. The stirrer was then turned to 900-1000 rpm, and the temperature was set to 110°C. After the reactor reached a temperature between 100-110°C, high-pressure dry dinitrogen was used to push in the catalyst and activator solutions. Timing began with the addition of the catalyst to the reactor and was allowed to proceed for 1 hour. After this period, the heating and stirring were stopped, the pressure was vented from the reactor, and the reactor was opened. After combining the products from several runs of this type, the product was filtered through Celite® to remove catalyst residues.

[0243] Oligomerization Example 9: Typical Oligomerization of C4 Using Catalyst A In 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 addition tube. In the front section, M2HTH-D4 (10 wt.% in MCH, 0.8 mL) was combined with untreated tri-n-octylaluminum (200 μL) and an additional 7 mL of MCH. The 1-butene cylinder was attached to the reactor via a desiccator containing a mixture of desiccants including Q5 and 3 Å molecular sieves. 1 L of 1-butene from the cylinder was charged into the reactor using high-pressure dry dinitrogen, and the dual addition tube was then attached to the reactor and a nitrogen source. After 1 L was added, the stirrer was turned on to 900-1000 rpm. The heat was set to reach 110 °C. After the reactor reached temperature (between 100 °C and 110 °C), high-pressure nitrogen was used to push in the catalyst and activator solution. Timing began with the addition of the catalyst to the reactor and was allowed to proceed for 1 hour. After this period, heating and stirring were stopped, excess pressure was vented from the reactor, and the reactor was opened. The contents were poured into a pre-weighed container and the mass of the product was recorded. After combining the product from several runs of this type, the product was filtered through Celite® to remove catalyst residues.

[0244] Oligomerization Example 10: Typical Oligomerization of C4 Using Catalyst C In this example, 1-butene was used. Catalyst C (52 mg) was dissolved in 9 mL of MCH and added to the rear section of the dual addition tube. In the front section, M2HTH-D4 (10 wt.% in MCH, 1.6 mL) was combined with untreated tri-n-octylaluminum (200 μL) and an additional 7 mL of MCH. The 1-butene cylinder was attached to the reactor via a desiccator containing a mixture of desiccants including Q5 and 3 Å molecular sieves. 1 L of 1-butene from the cylinder was charged into the reactor using high-pressure dry dinitrogen; the dual addition tube was then attached to the reactor and a nitrogen source. After 1 L was added, the stirrer was turned on to 900-1000 rpm. The heat was set to reach 90°C. After the reactor contents reached between 80-90°C, high-pressure dry dinitrogen was used to push the catalyst and activator solution into the reactor. Timing began with the addition of the catalyst to the reactor and was allowed to proceed for 1 hour. After this period, heating and stirring were stopped. The high pressure was vented from the reactor and the reactor was opened. The contents were poured into a pre-weighed container and the mass of the product was recorded. After combining the product from several runs of this type, the product was filtered through Celite® to remove catalyst residues.

[0245] Oligomerization Examples 11-15 For catalyst addition in Examples 11-15, a dual cylinder (also called a dual addition tube) consisting of two 25 mL SS Swagelok cylinders with three SS Swagelok ball valves (one in the middle and one at each end) was typically used. All catalysts, activators, and scavengers were handled inside a nitrogen-purged dry box. In these examples, the catalyst and activator were premixed as a solution in MCH and added to the front section of the addition tube. The rear section of the dual addition tube typically contained 10 mL of MCH to aid in flushing the catalyst into the reactor. The orientation of the addition tube when attached to the reactor was such that, during injection, the catalyst solution was injected into the reactor first, followed by the solvent chaser. Scavenger solutions were also prepared inside the dry box and placed in septum-sealed vials for cannula delivery of the solutions into the reactor.

[0246] Oligomerization Example 11: Typical Oligomerization of C6 Using Catalyst A In 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. The activated catalyst solution was then transferred to one side of a dual-addition tube. 10 mL of MCH was added to the other side of the dual-addition tube. A scavenger solution was prepared by adding tri-n-octylaluminum (175 μL) to 15 mL of 1-hexene in a 60 mL vial, which was then sealed with a septum.

[0247] For a 2 L reactor, 1500 mL of dry 1-hexene was pushed into the reactor with high-pressure nitrogen. The reactor was evacuated. The scavenger solution was cannulated into the reactor using low-pressure nitrogen (2-5 psi). A dual addition tube was then connected to the reactor and to the high-pressure nitrogen line. The stirrer was turned on to 400 rpm. The heat was set to reach 120°C. After the reactor reached 110°C, the catalyst solution and solvent chaser were pushed into the reactor using high-pressure dry nitrogen. Timing began with the injection of the catalyst and was allowed to proceed for 1 hour. After this period, the heating and stirring were stopped, and the reactor was cooled to approximately 60°C. The reactor was evacuated and then opened. The contents were poured into a tared container, and the mass was recorded (e.g., typically approximately 1200 g). The product was then suction filtered through Celite® to remove catalyst residues.

[0248] Oligomerization Example 12: Typical Oligomerization of C8 Using Catalyst A In 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% by weight in MCH) was added to the vial. The activated catalyst solution was then transferred to one side of a dual-addition tube. 10 mL of MCH was added to the other side of the dual-addition tube. A scavenger solution was prepared by adding tri-n-octylaluminum (120 μL) to 15 mL of 1-octene in a 60 mL vial, which was then sealed with a septum. Additionally, while in the drybox, 1400 mL of 1-octene was transferred to a 2 L bottle and sealed with a septum. In a 2 L reactor, 1-octene was cannulated into the reactor using low-pressure nitrogen (2-5 psi). The scavenger solution was then cannulated into the reactor using low-pressure nitrogen (2-5 psi). A dual addition tube was then connected to the reactor and to the high-pressure nitrogen line. The stirrer was turned on to 400 rpm. The heat was set to reach 120°C. After the reactor reached 110°C, high-pressure dry nitrogen was used to push the catalyst solution and solvent chaser into the reactor. Timing began with the catalyst injection and was allowed to proceed for 1 hour. After this period, the heating and stirring were stopped, and the reactor was cooled to approximately 60°C. The reactor was vented and then opened. The contents were poured into a tared container, and the mass was recorded (e.g., typically approximately 900 g). The product was then suction filtered through Celite® to remove catalyst residues.

[0249] Oligomerization Example 13: Typical co-oligomerization of C6 (25%) and C8 (75%) using catalyst A In 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. The activated catalyst solution was then transferred to one side of a dual-addition tube. 10 mL of MCH was added to the other side of the dual-addition 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.

[0250] Into a 2 L reactor, 1-octene / tri-n-octylaluminum was cannulated using low-pressure nitrogen (2-5 psi). Next, 1-hexene was cannulated into the reactor using low-pressure nitrogen (2-5 psi). A dual addition tube was then connected to the reactor and to the high-pressure nitrogen line. The stirrer was turned to 400 rpm. The heat was set to reach 120°C. After the reactor reached 110°C, high-pressure dry nitrogen was used to push the catalyst solution and solvent chaser into the reactor. Timing began with the catalyst injection and was allowed to proceed for 1 hour. After this period, the heating and stirring were stopped, and the reactor was cooled to approximately 60°C. The reactor was vented and then opened. The contents were poured into a tared container, and the mass was recorded (e.g., typically approximately 900 g). The product was then suction filtered through Celite® to remove catalyst residue.

[0251] Oligomerization Example 14: Typical co-oligomerization of C6 (50%) and C8 (50%) using catalyst A In 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. The activated catalyst solution was then transferred to one side of a dual-addition tube. 10 mL of MCH was added to the other side of the dual-addition 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. Into a 2 L reactor, 1-octene / tri-n-octylaluminum was cannulated using low-pressure nitrogen (2-5 psi). Next, 1-hexene was cannulated into the reactor using low-pressure nitrogen (2-5 psi). A dual addition tube was then connected to the reactor and to the high-pressure nitrogen line. The stirrer was turned to 400 rpm. The heat was set to reach 120°C. After the reactor reached 110°C, high-pressure dry nitrogen was used to push the catalyst solution and solvent chaser into the reactor. Timing began with the injection of the catalyst and was allowed to proceed for 1 hour. After this period, the heating and stirring were stopped, and the reactor was cooled to approximately 60°C. The reactor was vented and then opened. The contents were poured into a tared container, and the mass was recorded (e.g., typically approximately 820 g). The product was then suction filtered through Celite® to remove catalyst residue.

[0252] Oligomerization Example 15: Typical co-oligomerization of C6 (75%) and C (25%) using catalyst A In 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. The activated catalyst solution was then transferred to one side of a dual-addition tube. 10 mL of MCH was added to the other side of the dual-addition 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. Into a 2 L reactor, 1-hexene / tri-n-octylaluminum was cannulated using low-pressure nitrogen (2-5 psi). Next, 1-octene was cannulated into the reactor using low-pressure nitrogen (2-5 psi). A dual addition tube was then connected to the reactor and to the high-pressure nitrogen line. The stirrer was turned to 400 rpm. The heat was set to reach 120°C. After the reactor reached 110°C, high-pressure dry nitrogen was used to push the catalyst solution and solvent chaser into the reactor. Timing began with the catalyst injection and was allowed to proceed for 1 hour. After this period, the heating and stirring were stopped, and the reactor was cooled to approximately 60°C. The reactor was vented and then opened. The contents were poured into a tared container, and the mass was recorded (e.g., typically approximately 920 g). The product was then suction filtered through Celite® to remove catalyst residue.

[0253] Oligomerization Examples 16-20 For Examples 16-20, batch oligomerization reactions were carried out in a 2 L Ace Glass jacketed reactor equipped with a paddle stirrer, internal thermocouple, and inlets for the introduction of monomer, precatalyst, and activator in an N2-purged glovebox. Prior to use, the reactor was purged with anhydrous toluene and dried by heating at 120 °C for 1 h under a stream of dry nitrogen. Monomers and solvents were separated using activated basic alumina columns (50 g アルミナ / L モノマー ) and purified by sparging with nitrogen for 1 hour (1 L N2 / min) and dried over activated molecular sieves (3 Å) and AZ300 for at least 12 h.

[0254] Oligomerization Example 16: Typical Co-oligomerization of C8 and VCH Using Catalyst A In 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 a reactor, and the resulting mixture was heated to an internal temperature of 110 °C while stirring at 400 rpm. Tri-n-octylaluminum (0.24 mL, 0.197 g, 0.5 mmol) was then 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). The resulting mixture was stirred for 1 minute, and the solution was then added in 0.5 mL or 1 mL increments to the reactor. The exothermic reaction caused a rapid increase in temperature; therefore, each addition was delayed 5 to 30 minutes until the reaction temperature had dropped below 125 °C. To facilitate heterodimer formation, additional 1-octene (400 mL, 280 g, 2.55 mol) was added to the reactor in 50 mL increments after each injection of catalyst. All catalyst and 1-octene were added over 1.5 hours, and the reaction mixture was stirred for an additional hour. The reactor contents were collected and then filtered through a column of activated basic alumina, yielding approximately 1.6 L of a colorless liquid.

[0255] Oligomerization Example 17: Typical Co-oligomerization of C9 and VCH Using Catalyst A In 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 a reactor, and the resulting mixture was heated to an internal temperature of 120 °C while stirring at 400 rpm. Tri-n-octylaluminum (0.12 mL, 0.99 g, 0.25 mmol) was then 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). The resulting mixture was stirred for 1 minute, and the solution was then added in 0.5 mL or 1 mL increments to the reactor. The exothermic reaction caused a rapid increase in temperature; therefore, each catalyst addition was delayed 5 to 30 minutes until the reaction temperature had dropped below 125 °C. To facilitate heterodimer formation, additional aliquots of 1-nonene (750 mL, 557 g, 4.41 mol) were added to the reactor in two 200 mL portions and one 150 mL portion after each injection of catalyst. All catalyst and 1-nonene were added over 1.5 hours, and the reaction mixture was stirred for an additional hour. The reactor contents were collected and then filtered through a column of activated basic alumina, yielding approximately 1.3 L of a colorless liquid.

[0256] Oligomerization Example 18: Typical Co-oligomerization of C10 and VCH Using Catalyst A In this example, 1-decene and 4-vinylcyclohexene were used. 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. Tri-n-octylaluminum (0.24 mL, 0.197 g, 0.5 mmol) was then 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). The resulting mixture was stirred for 1 minute, and the solution was then added in 0.5 mL or 1 mL increments to the reactor. The exothermic reaction caused a rapid increase in temperature; therefore, each catalyst addition was delayed 5 to 30 minutes until the reaction temperature had dropped below 125 °C. To facilitate heterodimer formation, additional 200 mL portions of 1-decene (800 mL, 592 g, 4.22 mol) were added to the reactor after each injection of catalyst. All catalyst and 1-decene were added over 1.5 hours, and the reaction mixture was stirred for an additional hour. The reactor contents were collected and then filtered through a column of activated basic alumina, yielding approximately 1.4 L of a colorless liquid.

[0257] Oligomerization Example 19: Typical Oligomerization of VCH Using Catalyst E In this example, 4-vinylcyclohexene was used. VCH (1500 mL, 1245 g, 11.52 mol) was added to the reactor, and the resulting mixture was heated to an internal temperature of 120 °C while stirring at 400 rpm. Tri-n-octylaluminum (1.05 mL, 0.861 g, 2.30 mmol) was then 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 mol). The resulting mixture was stirred for 30 min, after which the solution was added in 1.5 mL or 3 mL increments to the reactor. The exothermic reaction caused a rapid increase in temperature; therefore, each catalyst addition was delayed for 5 to 30 min until the reaction temperature had dropped below 125 °C. All of the catalyst was added over 1.5 hours, and the reaction mixture was stirred for an additional 0.8 hours. The reactor contents were collected and then filtered through a column of activated basic alumina to yield approximately 1.5 L of a colorless liquid.

[0258] Oligomerization Example 20: Typical Oligomerization of VCH Using Catalyst A In 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. Tri-n-octylaluminum (1.1 mL, 0.902 g, 2.50 mmol) was then 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 mol). After stirring the resulting mixture for 1 minute, the first portion (approximately 3 mL) of the activated catalyst solution was injected into the reactor. The catalyst solution was then added in small portions (1.5-3.0 mL) over 2.5 hours, allowing the temperature to rise to 120°C; the next injection was delayed 10-20 minutes until the temperature reached approximately 117°C. The second catalyst portion was prepared as above and then similarly injected in small portions, slowly turning the reaction a deep orange / brown. As more catalyst was added, the exothermic response became less pronounced. After the entire second catalyst portion had been added over 2.5 hours, the reaction mixture was stirred for an additional 45 minutes. The contents were then removed from the reactor and passed through a column of activated basic alumina.

[0259] Oligomerization Example 21: Oligomerization of VCB to but-3-ene-1,3-diyldicyclobutane using catalyst E A 20 mL pressure 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. The system was then cooled to ambient temperature, and the reaction mixture was filtered through alumina to obtain a yellow liquid, which was used for hydrogenation.

[0260] Hydrogenation Example 22: Hydrogenation of but-3-ene-1,3-diylcyclobutane to butane-1,3-diyldicyclobutane The reaction mixture obtained in Example 21 above was hydrogenated in a pressure flask over Pd / C (50 mg, 10% by weight) at 125°C for 4 hours at 40 psi H. Toluene and methylcyclohexane were then removed by distillation at ambient pressure (approximately 1.5 mL), and the residue was distilled under reduced pressure (0.5-1.0 mTorr). The collected product (bp 45-50°C, 1.04 g) was further rehydrogenated at 200 psi H at 125°C for 4 hours to remove traces of unsaturation.

[0261] Oligomerization Example 23: Oligomerization of Vinylcyclohexane Using Catalyst E In this example, only one monomer was used: 4-vinylcyclohexene. 4-Vinylcyclohexane was purchased from TCI Chemicals, purified by sparging with nitrogen, and stored over activated molecular sieves (4 Å) 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 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 hour before being added to the vinylcyclohexane. The flask was then sealed and heated to 136 °C. The reaction mixture was stirred for 2 hours, then cooled and exposed to air. The contents were removed from the flask and passed through a column of activated basic alumina to give a colorless liquid.

[0262] Hydrogenation Example 24: Hydrogenation of but-3-ene-1,3-diyldicyclohexane to butane-1,3-diyldicyclohexane The reaction mixture (15 g) obtained in Example 23 above 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 N for 10 minutes. It was then heated to 232°C and pressurized with hydrogen (650 psi H). The reaction mixture was stirred at 400 rpm for 2 hours and then cooled to ambient temperature. The catalyst was then filtered off under anaerobic conditions, and the hexane and other low-boiling components were evaporated to give approximately 15 g of a fully saturated (88%) product, consisting of butane-1,3-diyldicyclohexane by GC analysis. 1 A colorless liquid (based on 1 H NMR) was obtained. 1 H 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 C 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.

[0263] Oligomerization Example 39 (Comparative): Oligomerization of VCH using Catalyst F In 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. Tri-isobutylaluminum (2.83 mL, 2.22 g, 11.2 mmol) was then added as a scavenger. Separately, in a 20 mL scintillation vial, catalyst F (225 mg, 0.770 mmol) was dissolved in toluene (4 mL), and tri-isobutylaluminum (2.0 mL, 157 g, 7.93 mmol) was slowly added, 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 minutes, 2 mL of the catalyst solution was added to the reactor, followed by approximately 2 mL increments over the next hour until the entire catalyst solution had been added. The addition was carried out such that the reactor temperature was maintained between 115-120°C. After the final catalyst addition, the reaction was stirred for an additional 4.5 hours. After this time, the mixture was quenched with a few milliliters of isopropanol and then filtered through Celite to yield approximately 0.5 L of a colorless liquid.

[0264] Oligomerization Example 40 (Comparative): Oligomerization of VCH using Catalyst F In 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. Tri-isobutylaluminum (20.0 mL, 15.7 g, 79.3 mmol) was then 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 tri-isobutylaluminum (5.0 mL, 3.93 g, 19.8 mmol) was slowly added 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 deep orange. The reactor temperature was maintained at approximately 50°C with stirring for a total of 5 hours. The reactor contents were then quenched with methanol (30 ml) by slow addition, as the reaction was exothermic and generated heat, volatiles, and precipitate. The quenched reactor product was added in batches of 50 ml 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 (a cloudy solution) was collected and dried over MgSO4. It was then passed through Celite and activated basic alumina.

[0265] Characterization of batch oligomerization reaction mixtures by GC-MS Qualitative determination of the contents of the reaction mixture by relative peak area % was obtained using an Agilent 7890 GC equipped with a 5977B Inert Plus MSD Turbo EI / CI, using the following parameters: [Table 3]

[0266] Samples were prepared by diluting 50 μL of nonane or undecane (standard) into 500 μL of reaction sample and 500 μL of isohexane. Mixtures of homodimers (AA, BB), heterodimers (AB), and in some experiments, homotrimers (AAA, BBB) and heterotrimers (A × 2 − B, B × 2 + A) were observed. In some experiments, homotetramers and heterotetramers were also observed. For heterotrimers and heterotetramers, it was not possible to distinguish between the order of monomer units, e.g., AAB vs. ABA vs. BAA. The following table represents heterotrimers in an A × 2 − B format. Heterotetramers are represented in a similar format, e.g., A × 2 − B × 2. Each peak of the separated components was identified by mass, and the amount of each component was then determined by the area of ​​each peak relative to the total area of ​​all peaks to obtain a qualitative mass % of the sample, calculated using the following formula, where "standard area" is the peak area for nonane (C9) or undecane (C11) depending on the standard used:

number

number

[0267] From the GC chromatogram, the reported retention peak is the peak retention time. This number may vary to a certain extent from sample to sample based on the column conditions. Peaks less than 1.5% were generally excluded from the calculation. The products from batch polymerization reactor runs (typically 12-16 runs) were combined in batches of the same composition to yield 3-4 gallon volumes and stored under ambient conditions until further processing. Methylcyclohexane (MCH) in the samples is from the solvent used to deliver the catalyst and / or activator to the reactor. For homo-oligomerization, the percent monomer conversion to dimer and trimer was calculated by multiplying the sum of the areas of all dimer and trimer peaks by 100 and then dividing by the sum of the areas of all non-solvent and non-GC-standard peaks (if present). The percent monomer conversion to all dimer products was calculated by multiplying the sum of the areas of all dimer peaks by 100 and then dividing by the sum of the areas of all non-solvent and non-GC-standard peaks (if present). The percent monomer conversion to a single dimer (the dimer isomer with the largest peak area) was calculated by multiplying the area of ​​the largest dimer peak by 100 and then dividing by the sum of the areas of all non-solvent and non-GC-standard peaks (if present). The percent selectivity for forming dimer relative to trimer was calculated by multiplying the sum of the areas of all dimer peaks by 100 and then dividing by the sum of the areas of all dimer and trimer peaks. The percent selectivity for forming one dimer species (one isomer) relative to the total dimers formed was calculated by multiplying the sum of the areas of the largest dimer peaks by 100 and then dividing by the sum of the areas of all dimer peaks.

[0268] GC Characterization Example 1: Co-oligomerized C6 and VCH from the Use of Catalyst A Chromatograms were obtained for the oligomerization products of 1-hexene (C6) and 4-vinyl-cyclohex-1-ene (VCH) using catalyst A. Table 1A outlines the composition of the samples, and Table 1B summarizes the composition of the products. [Table 4] [Table 5]

[0269] GC Characterization Example 2: Co-oligomerized C7 and VCH from the Use of Catalyst A Chromatograms were obtained for the oligomerization products of 1-heptene (C7) and 4-vinyl-cyclohex-1-ene (VCH) using catalyst A. Table 2A outlines the composition of the samples, and Table 2B summarizes the composition of the products. [Table 6] [Table 7]

[0270] GC Characterization Example 3: Co-oligomerized C5 and VCH from the Use of Catalyst A Chromatograms were obtained for the oligomerization products of 1-pentene (C5) and 4-vinyl-cyclohex-1-ene (VCH) using catalyst A. Table 3A outlines the composition of the samples, and Table 3B summarizes the composition of the products. [Table 8] [Table 9]

[0271] GC Characterization Example 4: Oligomerized iC6 from the Use of Catalyst D Chromatograms were obtained for the oligomerization products of 4-methyl-1-pentene (iC6) using catalyst D. Table 4A outlines the composition of the samples, and Table 4B summarizes the composition of the products. [Table 10] [Table 11]

[0272] GC Characterization Example 5: Co-oligomerized C5 and C4 from the Use of Catalyst A Chromatograms were obtained for the oligomerization products of 1-butene (C4) and 1-pentene (C5) using Catalyst A. Table 5A outlines the composition of the samples, and Table 5B summarizes the product compositions. [Table 12] [Table 13]

[0273] GC Characterization Example 6: Co-oligomerized VCH and C4 from the Use of Catalyst A Chromatograms were obtained for the oligomerization products of (1-butene) C4 and 4-vinyl-cyclohex-1-ene (VCH) using catalyst A. Table 6A outlines the composition of the samples, and Table 6B summarizes the product compositions. [Table 14] [Table 15]

[0274] GC Characterization Example 7: Co-oligomerized VCH and iC6 from the Use of Catalyst A Chromatograms were obtained for the oligomerization products of 4-methylpent-1-ene (iC6) and 4-vinyl-cyclohex-1-ene (VCH) using catalyst A. Table 7A outlines the composition of the samples, and Table 7B summarizes the product compositions. [Table 16] [Table 17]

[0275] GC Characterization Example 8: Oligomerized C5 from Use of Catalyst A Chromatograms were obtained for the oligomerization products of 1-pentene (C5) using Catalyst A. Table 8A outlines the composition of the samples, and Table 8B summarizes the composition of the products. [Table 18] [Table 19]

[0276] GC Characterization Example 9: Oligomerized C4 from Use of Catalyst A Chromatograms were obtained for the oligomerization products of 1-butene (C4) over catalyst A. Table 9A outlines the composition of the samples, and Table 9B summarizes the composition of the products. [Table 20] [Table 21]

[0277] GC Characterization Example 10: Oligomerized C4 from Use of Catalyst C Chromatograms were obtained for the oligomerization products of 1-butene (C4) over catalyst C. Table 10A outlines the composition of the samples, and Table 10B summarizes the composition of the products. [Table 22] [Table 23]

[0278] GC Characterization Example 11: Oligomerized C6 from Use of Catalyst A Chromatograms were obtained for the oligomerization products of 1-hexene (C6) over catalyst A. Table 11A outlines the composition of the samples, and Table 11B summarizes the composition of the products. [Table 24] [Table 25]

[0279] GC Characterization Example 12: Oligomerized C8 from Use of Catalyst A Chromatograms were obtained for the oligomerization products of 1-octene (C8) over Catalyst A. Table 12A outlines the composition of the samples, and Table 12B summarizes the composition of the products. [Table 26] [Table 27]

[0280] GC Characterization Example 13: Co-oligomerized C6 (25%) and C8 (75%) from the Use of Catalyst A Chromatograms were obtained for the oligomerization products of 1-hexene (C6) and 1-octene (C8) over Catalyst A. Table 13A outlines the composition of the samples, and Table 13B summarizes the product compositions. [Table 28] [Table 29]

[0281] GC Characterization Example 14: Co-oligomerized C6 (50%) and C8 (50%) from the Use of Catalyst A Chromatograms were obtained for the oligomerization products of 1-hexene (C6) and 1-octene (C8) over Catalyst A. Table 14A outlines the composition of the samples, and Table 14B summarizes the product compositions. [Table 30] [Table 31]

[0282] GC Characterization Example 15: Co-oligomerized C6 (75%) and C8 (25%) from the Use of Catalyst A Chromatograms were obtained for the oligomerization products of 1-hexene (C6) and 1-octene (C8) over Catalyst A. Table 15A outlines the composition of the samples, and Table 15B summarizes the product compositions. [Table 32] [Table 33]

[0283] GC Characterization Example 16: Co-oligomerized C8 and VCH from the Use of Catalyst A Chromatograms were obtained for the oligomerization products of 1-octene (C8) and 4-vinyl-cyclohex-1-ene (VCH) using catalyst A. Table 16A outlines the composition of the samples, and Table 16B summarizes the product compositions. [Table 34] [Table 35]

[0284] GC Characterization Example 17: Co-oligomerized C9 and VCH from the Use of Catalyst A Chromatograms were obtained for the oligomerization products of 1-nonene (C9) and 4-vinyl-cyclohex-1-ene (VCH) using catalyst A. Table 17A outlines the composition of the samples, and Table 17B summarizes the composition of the products. [Table 36] [Table 37]

[0285] GC Characterization Example 18: Co-oligomerized C10 and VCH from the Use of Catalyst A Chromatograms of the oligomerization products of 1-decene (C10) and 4-vinyl-cyclohex-1-ene (VCH) using catalyst A. Table 18A outlines the composition of the samples, and Table 18B summarizes the composition of the products. [Table 38] [Table 39]

[0286] GC Characterization Example 19: Oligomerized VCH from Use of Catalyst E Chromatograms of the oligomerization products of 4-vinyl-cyclohex-1-ene (VCH) using catalyst E were obtained. Table 19A outlines the sample composition, and Table 19B summarizes the product composition. Based on GC-MS analysis, the VCH conversion to dimer and trimer was 90.6%, the VCH conversion to all dimer products was 81.3%, and the VCH conversion to a single dimer (the dimer isomer with the largest peak area) was 65.1%. The selectivity for forming dimer relative to trimer was 89.8%, and the selectivity for forming one dimer species (one isomer) relative to the total dimers formed was 80.0%. [Table 40] [Table 41]

[0287] GC Characterization Example 20: Oligomerized VCH from Use of Catalyst A Chromatograms of the oligomerization products of 4-vinyl-cyclohex-1-ene (VCH) using Catalyst A were obtained. Table 20A outlines the sample composition, and Table 20B summarizes the product composition. Based on GC-MS analysis, the VCH conversion to dimer was 96.2% (no trimer was observed), the VCH conversion to all dimer products was 96.2%, and the VCH conversion to a single dimer (the dimer isomer with the largest peak area) was 94.5%. The selectivity for forming dimer relative to trimer was 100%, and the selectivity for forming one dimer species (one isomer) relative to the total dimers formed was 98.2%. [Table 42] [Table 43]

[0288] GC Characterization Example 21: VCB Oligomerized to But-3-ene 1,3-diyldicyclobutane from the Use of Catalyst E A chromatogram of the oligomerization products of 4-vinylcyclobutane (VCB) using catalyst E was obtained. Table 21A outlines the sample composition, and Table 21B summarizes the product composition. Based on GC-MS analysis, the VCB conversion to dimer, trimer, and higher oligomers was 98.1%, the VCB conversion to all dimer products was 50.4%, and the VCB conversion to a single dimer (the dimer isomer with the largest peak area) was 37.1%. The selectivity for forming dimers relative to trimers and higher oligomers was 51.4%, and the selectivity for forming one dimer species (one isomer) relative to the total dimers formed was 73.7%. [Table 44] [Table 45]

[0289] GC Characterization Example 22: Hydrogenation of but-3-ene-1,3-diyldicyclobutane to butane-1,3-diyldicyclobutane Chromatograms were obtained for the hydrogenation products of but-3-ene-1,3-diyldicyclobutane using catalyst E. Table 22A outlines the composition of the samples, and Table 22B summarizes the composition of the products. [Table 46] [Table 47]

[0290] GC Characterization Example 23: Vinylcyclohexane Oligomerized to But-3-ene-1,3-diyldicyclohexane from the Use of Catalyst E A chromatogram of the 4-vinylcyclohexane (vch) oligomerization product using catalyst E was obtained. Table 23A outlines the sample composition, and Table 23B summarizes the product composition. The vinylcyclohexane conversion based on the GC sample composition was 98%. Based on GC-MS analysis, the vch conversion to dimer and trimer was 92.7%, the vch conversion to all dimer products was 88.1%, and the vch conversion to a single dimer (the dimer isomer with the largest peak area) was 85.1%. The selectivity for forming dimer relative to trimer was 95.0%, and the selectivity for forming one dimer species (one isomer) relative to the total dimers formed was 96.6%. [Table 48] [Table 49]

[0291] GC Characterization Example 24: Hydrogenation of But-3-ene-1,3-diyldicyclohexane to Butane-1,3-diyldicyclohexane A chromatogram was obtained of the hydrogenation products of but-3-ene-1,3-diyldicyclohexane using catalyst E. Table 24A outlines the composition of the samples, and Table 24B summarizes the composition of the products. [Table 50] [Table 51]

[0292] GC Characterization Example 39 (Comparative): Oligomerization of VCH using Catalyst F Chromatograms of the oligomerization products of 4-vinyl-cyclohex-1-ene (VCH) using catalyst F were obtained. Table 39A outlines the sample composition, and Table 39B summarizes the product composition. Based on GC-MS analysis, the VCH conversion to dimer and trimer was 41.2%, the VCH conversion to all dimer products was 36.6%, and the VCH conversion to a single dimer (the dimer isomer with the largest peak area) was 28.1%. The selectivity for forming dimer relative to trimer was 89.0%, and the selectivity for forming one dimer species (one isomer) relative to the total dimers formed was 76.7%. [Table 52] [Table 53]

[0293] GC Characterization Example 40 (Comparative): Oligomerization of VCH using Catalyst F Chromatograms of the oligomerization products of 4-vinyl-cyclohex-1-ene (VCH) using catalyst F were obtained. Table 40A outlines the sample composition, and Table 40B summarizes the product composition. Based on GC-MS analysis, the VCH conversion to dimer and trimer was 32.4%, the VCH conversion to all dimer products was 30.0%, and the VCH conversion to a single dimer (the dimer isomer with the largest peak area) was 15.5%. The selectivity for forming dimer relative to trimer was 92.7%, and the selectivity for forming one dimer species (one isomer) relative to the total dimers formed was 51.7%. [Table 54] [Table 55]

[0294] NMR Characterization of Batch Oligomerization Examples Quantitative characterization of reaction mixtures by proton NMR Specifically, a 500 MHz NMR instrument is operated under the following conditions: approximately 30° flip angle RF pulses, 128 scans, relaxation delay of approximately 5 seconds between pulses; sample (60-100 mg) is dissolved in CDCl3 (deuterated chloroform) in a 5 mm NMR tube; and signal collection temperature is approximately 25°C. The following procedure is employed to determine the concentration of various olefins among all olefins from the NMR spectrum. First, peaks corresponding to different types of hydrogen atoms in vinyl (T1), vinylidene (T2), disubstituted vinylene (T3), and trisubstituted vinylene (T4) are identified with peak areas that vary by monomer as shown in Table 25. Second, the areas of each of the above peaks (A1, A2, A3, and A4, respectively) are then integrated. Third, the amount of each type of olefin (Q1, Q2, Q3, and Q4, respectively) in moles is calculated (as A1 / 2, A2 / 2, A3 / 2, and A4, respectively). Fourth, the total amount of all olefins (Qt) in moles is calculated as the sum of all four types combined (Qt = Q1 + Q2 + Q3 + Q4). Finally, the molar concentration of each type of olefin (C1, C2, C3, and C4, respectively, in mole %) relative to the total molar amount of all olefins is then calculated (Ci = 100 × Qi / Qt in each case). This procedure was used when end group analysis was quantified. Other conditions / solvents for proton spectra may be used for rough characterization.

[0295] [Table 56]

[0296] NMR spectra of Examples 1 to 24 Reaction mixture of 1-hexene and vinylcyclohexene cooligomerization reaction using catalyst A (Example 1) 1 H NMR spectra were obtained. Reaction mixture of 1-heptene and vinylcyclohexene cooligomerization reaction using catalyst A (Example 2) 1 H NMR spectra were obtained. Reaction mixture of 1-pentene and vinylcyclohexene co-oligomerization reaction using catalyst A (Example 3) 1 H NMR spectra were obtained. Reaction mixture of oligomerization reaction using 4-methylpent-1-ene with catalyst D (Example 4) 1 H NMR spectra were obtained.

[0297] Reaction mixture of the oligomerization reaction of the monomers 1-butene and 1-pentene using catalyst A (Example 5) 1 H NMR spectra were obtained and Table 26 shows the calculated olefin compositions. [Table 57]

[0298] Reaction mixture of 1-butene and vinylcyclohexene cooligomerization reaction using catalyst A (Example 6) 1 H NMR spectra were obtained. Reaction mixture of the oligomerization reaction of the monomer 1-pentene using catalyst A (Example 8) 1 H NMR spectra were obtained and Table 27 shows the calculated olefin compositions. [Table 58]

[0299] Reaction mixture of the oligomerization reaction of the monomer 1-butene using catalyst A (Example 9) 1H NMR spectra were obtained and Table 28 shows the calculated olefin compositions. [Table 59]

[0300] Reaction mixture of the oligomerization reaction of the monomer 1-butene using catalyst C (Example 10) 1 H NMR spectra were obtained and Table 29 shows the calculated olefin compositions. [Table 60]

[0301] Reaction mixture of 1-hexene oligomerization reaction using catalyst A (Example 11) 1 H NMR spectra were obtained and Table 30 shows the calculated olefin compositions. [Table 61]

[0302] Reaction mixture of 1-octene oligomerization reaction using catalyst A (Example 12) 1 H NMR spectra were obtained and Table 31A shows the calculated olefin compositions. [Table 62]

[0303] Reaction mixture of 1-hexene (25%) and 1-octene (75%) co-oligomerization using catalyst A (Example 13) 1 H NMR spectra were obtained and Table 31B shows the calculated olefin compositions. [Table 63]

[0304] Reaction mixture of 1-hexene (50%) and 1-octene (50%) co-oligomerization using catalyst A (Example 14) 1 H NMR spectra were obtained and Table 32 shows the calculated olefin compositions. [Table 64]

[0305] Reaction mixture of 1-hexene (75%) and 1-octene (25%) co-oligomerization using catalyst A (Example 15) 1 H NMR spectra were obtained and Table 33 shows the calculated olefin compositions. [Table 65] Reaction mixture of C8 and VCH co-oligomerization using catalyst A (Example 16) 1 H NMR spectra were obtained. Reaction mixture of C9 and VCH co-oligomerization using catalyst A (Example 17) 1 H NMR spectra were obtained. Reaction mixture of C10 and VCH co-oligomerization using catalyst A (Example 18) 1 H NMR spectra were obtained. Reaction mixture of VCH oligomerization reaction using catalyst E (Example 18) 1 H NMR spectra were obtained. Reaction mixture of VCH oligomerization reaction using catalyst A (Example 20) 1 H NMR spectrum and 13 C NMR spectra were obtained. Reaction mixture of the oligomerization reaction of VCH to but-3-ene-1,3-diyldicyclobutane using catalyst E (Example 21) 1 H NMR spectra were obtained.

[0306] Reaction mixture of hydrogenation reaction of but-3-ene-1,3-diyldicyclobutane to butane-1,3-diyldicyclobutane (Example 22) 1 H NMR and 13 C NMR spectra were obtained. Reaction mixture of the oligomerization reaction of vinylcyclohexane to but-3-ene-1,3-diyldicyclohexane using catalyst E (Example 23) 1 H NMR spectra were obtained. Reaction mixture of hydrogenation reaction of but-3-ene-1,3-diyldicyclohexane to butane-1,3-diyldicyclohexane (Example 24) 1 H NMR and 13 C NMR spectra were obtained.

[0307] Example of continuous polymerization Oligomerization was carried out in a continuous stirred tank reactor system equipped with two autoclave reactors in a series configuration. Both reactors had a volume of 1 L. The autoclave reactors were equipped with a stirrer, a pressure regulator, and a water-cooled / steam (or hot oil-heated for polymerizations above 130 °C) heating element with a temperature controller. The reactors were operated liquid-filled, with the reactor pressure exceeding the bubble point pressure of the reactant mixture, keeping the reactants in the liquid phase. Pentene, hexene, or vinylcyclohexene (VCH) was fed into a holding tank under N2 head pressure or through a metering pump. All liquid flow rates were controlled using a Coriolis mass flow controller (Quantim series, Brooks). The mixture was then fed to the reactor through a single line. A scavenger solution was added to the combined monomer stream just before entering the reactor to further reduce any catalyst poisoning. Similarly, the catalyst solution was fed to the reactor through a separate line using an ISCO syringe pump. All monomers and solvents were purified over beds of alumina and molecular sieves.

[0308] All monomers (pentene, hexane, and VCH), catalyst solution, and scavenger solution were fed into the first reactor. The contents of the first reactor (including the produced oligomers and active catalyst) flowed directly into the second reactor. The two reactors were operated at the same temperature. The reactor effluent exited the second reactor through a backpressure control valve, which reduced the pressure to atmospheric pressure. This caused some of the unconverted monomers in solution to burst into the vapor phase and exit through the top of the vapor-liquid separator. The liquid phase, containing primarily oligomer product, solvent, and unconverted monomers, was collected for product recovery. The collected liquid samples were weighed and reported as the liquid collected in the examples listed in Tables 34-38. All reactions were conducted at a pressure of approximately 2.4 MPa / g unless otherwise noted.

[0309] Tri-n-octylaluminum (TNOA) (25 wt% in hexane, Sigma Aldrich) was used as a scavenger. The scavenger was diluted in either methylcyclohexane (MCH) or toluene to a concentration of approximately 1-4 micromoles / mL. M2HTH-D4 (Boulder Scientific Company) was used as the activator for all experiments listed in Tables 34-38. Both the catalyst and activator were dissolved in either methylcyclohexane or toluene. The catalyst solution and activator solution were fed separately into the reactor unless otherwise noted.

[0310] The molar ratio of catalyst feed rate to activator feed rate was approximately 1:1. The scavenger feed rate was adjusted to optimize catalyst efficiency, and the feed rate varied from 0 (no scavenger) to 15 μmol / min. The catalyst feed rate may be adjusted according to the impurity level in the system to reach the target conversion rates listed.

[0311] Oligomerization of 1-pentene in a continuous reactor Examples P-1 and P-2 were produced using the general procedure described above using 1-pentene as the monomer. Catalyst A was used as the catalyst. Both the catalyst and 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. Detailed polymerization process conditions and some product analyses by GC-MS are listed in Table 34A. Tables 34B and 34C summarize the compositions of the samples determined by GC-MS. [Table 66] [Table 67] [Table 68]

[0312] Oligomerization of 1-hexene in a continuous reactor The hexene oligomers in Examples H-1 to H-3 were produced using the general procedure described above. Catalyst A was used as the catalyst. Both the catalyst and activator were dissolved separately in MCH. A solution of tri-n-octylaluminum (TNOA) (25 wt% in hexane, Sigma Aldrich) in MCH was used as the scavenger solution. Examples H-4 to H-6 were produced using the general procedure described above, except that a single 1 L oil-heated autoclave reactor was used. Toluene was used as the carrier solvent for the catalyst, activator, and scavenger. Detailed polymerization process conditions and some product analyses by GC-MS are listed in Table 35. [Table 69]

[0313] Tables 35A-35C outline the compositions of Examples H1-H3, respectively, as determined by GC-MS. [Table 70] [Table 71] [Table 72]

[0314] Tables 35D-35F outline the compositions of Examples H4-H6, respectively, as determined by GC-MS. [Table 73] [Table 74] [Table 75]

[0315] Oligomerization of VCH in a continuous reactor The VCH oligomers in Examples V-1 to V-3 were produced 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 activator. Tri-n-octylaluminum (TNOA) was diluted using MCH for the scavenger solution. In Example V-3, both the catalyst and 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. Detailed polymerization process conditions and some product analyses by GC-MS are listed in Table 36A. [Table 76]

[0316] Tables 36B-36D outline the compositions of Samples V1-V-3, respectively, as determined by GC-MS. [Table 77] [Table 78] [Table 79]

[0317] Co-oligomerization of 1-pentene and VCH in a continuous reactor The pentene-VCH oligomers in Examples VP-1 to VP-3 were produced 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 followed the same procedure as used for VP-1 to VP-3, except that no scavenger was used. Example VP-5 followed the same procedure as used for VP-1 to VP-3, except that Catalyst B was used and toluene was used as the solvent for the tri-n-aluminum. Detailed polymerization process conditions and some product analyses by GC-MS are listed in Table 37A. [Table 80]

[0318] Tables 37B-37D outline the compositions of Examples VP-1, VP-2, and VP-3, as determined by GC-MS. [Table 81] [Table 82] [Table 83]

[0319] Tables 37E and 37F outline the compositions of samples VP-4 and VP-5, as determined by GC-MS. [Table 84] [Table 85]

[0320] Co-oligomerization of 1-hexene and VCH in a continuous reactor The hexene-VCH oligomers in Examples VH-1 to VH-2 were produced 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 produced 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. Detailed polymerization process conditions and some product analyses by GC-MS are listed in Table 38A. [Table 86]

[0321] Tables 38B and 38C outline the compositions of Examples VH-1 and VH-2, as determined by GC-MS. [Table 87] [Table 88]

[0322] Tables 38D and 38E outline the compositions of Examples VH-3 and VH-4, as determined by GC-MS. [Table 89] [Table 90]

[0323] Small scale oligomerization of VCH The solvents, polymerization-grade toluene and / or isohexane, were supplied by ExxonMobil Chemical Co. and purified by passage through a series of columns: two 500 cc Oxyclear cylinders in series manufactured by Labclear (Oakland, Calif.), followed by two 500 cc columns in series packed with dried 3 Å molecular sieves (8-12 mesh; Aldrich Chemical Company), and two 500 cc columns in series packed with dried 5 Å molecular sieves (8-12 mesh; Aldrich Chemical Company). 4-Vinylcyclohexane was purified as previously described.

[0324] All complexes and activators were added to the reactor as dilute solutions in isohexane. The pre-catalyst solution was 8.0 mmol / L in isohexane. The scavengers, tri-n-octylaluminum (TNOA) and triisobutylaluminum (TIBA), were purchased as neat reagents from Akzo Nobel (now Nouryon). The scavengers were diluted and used as 0.100 mol / L solutions in isohexane. 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. Reactor Details and Preparation. Polymerizations were carried out in an inert atmosphere (N2) drybox using an autoclave equipped with an external heater for temperature control, a glass insert (internal reactor volume = 23.5 mL), a septum inlet, a regulated supply of nitrogen, and a disposable polyetheretherketone mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110 or 115°C for 5 hours, then at 25°C for 5 hours.

[0325] In the experimental run for VCH oligomerization, the reactor was prepared as described above. Isohexane (enough to bring the total solution volume to a final volume of 5.0 ml) and VCH (1.0 ml) were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (110°C). The stir bar and cell, set at 800 RPM, were then pressurized to 80 PSI with N2. The scavenger solution (e.g., TNOA or TIBA) was then added via syringe to the reactor at process conditions. The exact amounts added are listed in Table 41 below. The activator solution was added via syringe to the reactor at process conditions, followed by the precatalyst solution via syringe to the reactor at process conditions. The reactor temperature was monitored and typically maintained within ±1°C. The polymerization was stopped after 120 minutes of reaction time by adding approximately 50 psi of Ultra Air gas to the autoclave for approximately 30 seconds. The reactor was then cooled and vented. In some experiments, 200 μl of product solution was removed before removing the solvent, unreacted monomer, and other volatile materials. The final product was isolated after the solvent, unreacted monomer, and other volatile materials were removed under vacuum. The reported yield includes the total mass of non-volatile products and residual catalyst. The catalytic activity is expressed as grams of product per mmol of transition metal compound per hour of reaction time ( g / mmol·h ) and are based on the mass of the isolated product. For samples with 200 μl of product solution removed for GC-MS analysis, the reported product mass and activity are not corrected for material removal (Examples 50-55, 62-67, 74-79, and 86-91). An aliquot (200 μl) of the removed solution was diluted with 500 μl of toluene for GC-MS analysis. Oligomerization results are reported in Table 41. Examples 50-73 are inventive and use Catalyst A. Examples 74-97 are comparative and use Comparative Catalyst F.

[0326] GC-MS analysis of the samples followed the protocol described previously. The GC-MS calculations reported in Table 41 are as follows: The percent monomer conversion to dimer and trimer was calculated by multiplying the sum of the areas for all dimer and trimer peaks by 100 and then dividing by the sum of the areas of all non-solvent peaks, excluding the unknown product peak (if present), and is reported as % VCH conversion in Table 41.

[0327] The percent unreacted VCH is calculated by subtracting the percent monomer conversion to dimers and trimers from 100. This value includes isomerized, hydrogenated, and / or dehydrogenated VCH. This value is reported as Unreacted VCH (%) in Table 41.

[0328] The percent monomer conversion to all dimer products was calculated by multiplying the sum of the areas for all dimer peaks by 100 and then dividing by the sum of the areas of all non-solvent peaks, excluding the unknown product peak (if present). This value is reported in Table 41 as % VCH Conversion to Dimer. The percent monomer conversion to a single dimer (the dimer isomer with the largest peak area) was calculated by multiplying the area of ​​the largest dimer peak by 100 and then dividing by the sum of the areas of all non-solvent peaks, excluding the unknown product peak (if present). This value is reported in Table 41 as % VCH conversion to a single cyclic dimer species. The percent selectivity for forming dimers relative to trimers was calculated by multiplying the sum of the areas for all dimer peaks by 100 and then dividing by the sum of the areas for all dimer and trimer peaks. This value is reported as % Dimer in Table 41. The percent selectivity for forming trimer over dimer was calculated by multiplying the sum of the areas for all trimer peaks by 100 and then dividing by the sum of the areas for all dimer and trimer peaks. This value is reported as % Trimer in Table 41. The percent selectivity for forming one dimer species (one isomer) relative to the total dimers formed was calculated by multiplying the sum of the areas of the largest dimer peaks by 100 and then dividing by the sum of the areas of all dimer peaks. This value is reported as the % selectivity for a single cyclic dimer species.

[0329] [Table 91-1] [Table 91-2] Table 41 shows that the selectivity for dimer to trimer is 100% for inventive catalyst A, while for comparative catalyst F it is typically less than 90%. Furthermore, the conversion of VCH to products is greater than 60% for catalyst A when TIBA or lower levels of TNOA are used as a scavenger. With comparative catalyst F, higher levels of TNOA or TIBA are required for higher VCH conversion to products, with the conversion never exceeding 50%. While catalyst A provides 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 about 98% for the single dimer product, which only decreases when higher levels of TNOA are used. Similarly, catalyst F requires lower scavenger levels to achieve higher selectivity for the single dimer product, but at the same time, yields and catalytic activity are substantially reduced and, in most cases, more trimer is also produced. Overall, in some non-limiting embodiments, there may be one or more benefits in using Catalyst A over Catalyst F, including, for example, achieving better selectivity of dimer relative to trimer while requiring less scavenger, as well as overall higher yield and catalytic activity.

[0330] While the present disclosure includes details of many specific embodiments, these should not be construed as limiting the scope of the subject matter or the scope that may be claimed, but rather as a description of features that may be unique to particular embodiments. Certain features described in the present disclosure in the context of individual embodiments can also be implemented in combination in a single embodiment. Conversely, various features that are described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable subcombination. Furthermore, while the foregoing features may be described as acting in certain combinations and even as originally claimed, one or more features from a claimed combination may, in some cases, be excluded from the combination, and the claimed combination may be directed to a subcombination or variations of the subcombination.

[0331] Specific embodiments of the subject matter have been described. Other embodiments, alternatives, and permutations of the described embodiments are within the scope of the following claims, as will be apparent to those skilled in the art. Although operations may be presented in a particular order in the figures or claims, this should not be understood as requiring such operations to be performed in the particular order shown, or in sequential order, or to perform all of the illustrated operations (although some operations may be considered optional), to achieve desirable results. Therefore, the foregoing exemplary embodiments do not define or constrain this disclosure. Other changes, substitutions, and alterations are also possible without departing from the spirit and scope of this disclosure.

Claims

1. 1. A process for producing polyalphaolefins (PAO) from two or more different alpha-olefins, comprising: One or more C 6 -C 32 A cyclic alpha-olefin and one or more C 4 -C 32 and a feedstock comprising linear and / or branched alpha-olefins, contacting the feedstock with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions to effect polymerization, and obtaining a polymerization reaction mixture comprising a mixture of vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturated PAOs (e.g., PAO molecules); Obtaining an unsaturated PAO product from the polymerization reaction mixture. A method comprising:

2. 10. The process of claim 1, wherein the unsaturated PAO product comprises a mixture of PAO molecules having vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturation, and may be free of alpha-olefin feedstock.

3. One or more C 6 -C 32 3. The process of claim 1 or 2, wherein one of the cyclic alpha-olefins contains ring unsaturation and the unsaturated PAO product further contains a cyclic disubstituted vinylene.

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

5. The unsaturated PAO products are 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-isomer, and / or VCHx2-isomer, cyclic monomer fragments (A) and (B) are, independently, saturated when the cyclic alpha-olefin has a saturated ring structure, or partially unsaturated when the cyclic alpha-olefin has a partially unsaturated ring structure; 【Chemical 1】 n and m represent the number of additional carbon atoms in the ring structure of the cyclic monomer fragments (A) and (B), respectively, and independently represent integers from 1 to 20; R is C 2 -C 30 is a hydrocarbyl group, R' is C 1 -C 29 is a hydrocarbyl group, At least one of CL-v and LC-v is present in the unsaturated PAO product or mixture thereof; The method according to any one of claims 1 to 4.

6. n and m independently represent an integer of 1 to 5, and R is C 2 -C 8 is a hydrocarbyl group, and R' is C 1 -C 7 The method of claim 5, wherein the alkyl group is a hydrocarbyl group.

7. n and m are 3 and R is C 3 -C 8 is a hydrocarbyl group, and R' is C 2 -C 7 The method of claim 5 , wherein the cyclic monomer fragments (A) and (B) are hydrocarbyl groups and have partially unsaturated ring structures.

8. The method of claim 5, wherein LL-v is present in an unsaturated PAO product or mixture thereof.

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

10. 10. The process of any one of claims 1 to 9, having a selectivity to produce dimers greater than 50%, 60%, 70%, 80%, 90%, 95%, or 99% of the compounds in the unsaturated PAO product.

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

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

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

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

15. One or more cyclic C 6 -C 32 15. The method of any one of claims 1 to 14, wherein the alpha-olefin is selected from vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, 4-vinylcyclohex-1-ene, vinylcycloheptane, vinylcyclooctane, vinylcyclononane, vinylcyclodecane, vinylcycloundecane, vinylcyclododecane, 5-vinylnorbornane, 5-vinyl-2-norbornene, allylcyclohexane, and allylcyclooctane.

16. One or more cyclic C 6 -C 32 16. The method of claim 15, wherein the alpha-olefin is selected from vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, and 4-vinylcyclohex-1-ene.

17. One or more C 4 -C 32 15. The process of any one of claims 1 to 14, wherein the linear and / or branched alpha-olefin is 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. One or more C 4 -C 32 18. The process of claim 17, wherein the linear and / or branched alpha-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. One or more C 4 -C 32 The linear alpha-olefin is C 4 -C 20 Linear alpha-olefins, C 4 -C 12 Linear alpha-olefins, C 4 -C 8 Linear alpha-olefins, C 5 -C 8 Linear alpha olefin, or C 5 -C 6 The method of any one of claims 1 to 14, comprising a linear alpha olefin.

20. One or more C 4 -C 32 The branched alpha-olefin is 5 -C 20 Branched alpha-olefins, C 5 -C 12 Branched alpha-olefins, C 5 -C 10 Branched alpha-olefins, C 6 -C 9 Branched alpha olefins, or C 6 -C 8 The process of any one of claims 1 to 14, comprising branched alpha olefins.

21. One or more C 6 -C 32 The cyclic alpha-olefin is C 6 -C 20 Cyclic alpha-olefins, C 6 -C 14 Cyclic alpha-olefins, or C 8 -C 12 The method of any one of claims 1 to 14, comprising a cyclic alpha-olefin.

22. C 8 -C 12 22. The method of claim 21, wherein the cyclic alpha-olefin is a non-conjugated diene.

23. The unsaturated PAO product is One or more C 6 -C 32 A first dimer (CC) formed by the reaction of two cyclic alpha-olefins, C 6 -C 32 one of cyclic alpha-olefins and C 4 -C 32 a second dimer (CL) formed by reaction with one of the linear and / or branched alpha-olefins, and C 4 -C 32 A third dimer (LL) formed by two of the linear and / or branched alpha-olefins. The method of claim 1 , comprising one or more of:

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

25. 25. The method of claim 23 or 24, wherein the percentage of CC in the unsaturated PAO product, relative to CC+CL+LL equaling 100%, is 0% or higher, and 35% or lower, 30% or lower, 25% or lower, 20% or lower, 15% or lower, 10% or lower, or 5% or lower, based on GC-MS.

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

27. 27. The method of any one of claims 1 to 26, further comprising contacting the unsaturated PAO product with a chemical reagent comprising a heteroatom-containing group to convert at least a portion of the unsaturated PAO product to a functionalized PAO product, wherein the heteroatom-containing group comprises one or more of a sulfonate, an amine, an aldehyde, an alcohol, or an acid; preferably, the heteroatom-containing group comprises an epoxide, a succinic acid, a maleic acid, or a maleic anhydride; or the heteroatom-containing group comprises one or more of an acid, an ester, anhydride, an acid-ester, an oxycarbonyl, a carbonyl, a formyl, a formylcarbonyl, a hydroxyl, and an acetyl halide.

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

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

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

31. The process of any one of claims 28 to 30, wherein the hydrogenation catalyst comprises from 0.001 to 20 wt. % or from 0.01 to 10 wt. % of the unsaturated PAO feed material.

32. The process of any one of claims 28 to 31, wherein the hydrogenated PAO product has a Bromine Number of 2.0 or less.

33. The hydrogenated PAO product is 1,2 , hLC 1,2 , hCL 1,2 , hLL 1,2 , hCC 2,1 , hLC 2,1 , hLL 2,1 , hLVCH-isomers, and hVCHx2-isomers, The cyclic monomer fragments (A) and (B) are saturated ring structures, 【Chemistry 2】 and 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 C 2 -C 30 is a hydrocarbyl group, R' is C 1 -C 29 is a hydrocarbyl group, hCL 1,2 and hLC 1,2 is present in the hydrogenated PAO product; The method according to any one of claims 28 to 32.

34. n and m independently represent an integer of 1 to 5, and R is C 2 -C 8 is a hydrocarbyl group, and R' is C 1 -C 7 34. The method of claim 33, wherein the alkyl group is a hydrocarbyl group.

35. n and m are 3 and R is C 3 -C 8 is a hydrocarbyl group, and R' is C 2 -C 7 34. The method of claim 33, wherein the alkyl group is a hydrocarbyl group.

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

37. hCC 1,2 and hLL 1,2 The process of any one of claims 33 to 35, wherein is present in the hydrogenated PAO product or mixture thereof.

38. The hydrogenated PAO product is One or more C 6 -C 32 a first hydrogenated dimer (hCC) formed by the reaction of two cyclic alpha-olefins; One or more C 6 -C 32 one or more C cyclic alpha-olefins 4 -C 32 a second hydrogenated dimer (hCL) formed by reaction with one of the linear and / or branched alpha-olefins, and C 4 -C 32 A third hydrogenated dimer (hLL) formed by two of the linear and / or branched alpha-olefins. The method of any one of claims 28 to 37, comprising:

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

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

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

42. The metallocene compound has the formula (I): 【Chemistry 3】 is represented by During the ceremony: R 1 , R 2 , and R 3 are each independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 is a hydrocarbyl or silylcarbyl group; R 4 and R 5 are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 is a hydrocarbyl or silylcarbyl group, R 4 and R 5 together with the carbon atoms of the first cyclopentadienyl ring to which they are directly attached to 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 are each independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 is a hydrocarbyl, silylcarbyl, or germanyl group; R 12 , R 13 , R 14 , R 15 , and R 16 at least four of which 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 hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or C 1 -C 20 a substituted or unsubstituted straight chain, branched, or cyclic hydrocarbyl group, or optionally, two or more X moieties may join together to form a fused ring or ring system; m is an integer equal to v-2; The method of claim 1.

43. The metallocene compound has the formula (II): 【Chemistry 4】 is represented by During the ceremony: R 1 , R 2 , and R 3 are each independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 is a hydrocarbyl group; R 6 , R 7 , R 17 , and R 18 are each independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 is a hydrocarbyl group, or R 6 and R 7 , R 7 and R 17 , or R 17 and R 18 together with the carbon atoms of the indenyl ring to which they are directly attached, 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 linear, branched, or cyclic C 1 -C 20 is a hydrocarbyl group; R 16 is hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 is a hydrocarbyl group or a silylcarbyl group; Each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, C 1 -C 20 a substituted or unsubstituted straight-chain, branched, or cyclic hydrocarbyl group, or two or more X moieties taken 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; m is an integer equal to v-2; The method of claim 1.

44. The metallocene compound has the formula (III): 【Chemistry 5】 is represented by During the ceremony: R 1 and R 2 is hydrogen; R 23 and R 19 independently contain 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 linear, branched, or cyclic C 1 -C 20 is a hydrocarbyl group, R 20 , R 21 , and R 22 At least two of are independently substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 is a hydrocarbyl group; R 6 , R 7 , R 17 , and R 18 are each independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 is a hydrocarbyl group, or R 6 and R 7 , R 7 and R 17 , or R 17 and R 18 together with the carbon atoms of the indenyl ring to which they are directly attached, form one or more substituted or unsubstituted rings fused to the indenyl ring; R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 is a hydrocarbyl group; Each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or C 1 -C 20 a substituted or unsubstituted straight-chain, branched, or cyclic hydrocarbyl group, or two or more X moieties taken 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; m is an integer equal to v-2; The method of claim 1.

45. The metallocene compound is represented by formula (IV): 【Chemistry 6】 is represented by During the ceremony: R 1 and R 2 is hydrogen; R 3 is a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 is a hydrocarbyl group; R 6 and R 18 are each independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 is a hydrocarbyl group; R 24 , R 25 , R 26 , R 27 , R 28 , and R 29 are each independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 8 is a hydrocarbyl group; R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 is a hydrocarbyl group; Each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or C 1 -C 20 a substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or two or more X 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; m is an integer equal to v-2; The method of claim 1.

46. The metallocene compound has the formula (V): 【Chemistry 7】 is represented by During the ceremony: R 1 and R 2 is hydrogen; R 23 and R 19 are independently 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 each independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 is a hydrocarbyl group, R 20 , R 21 , and R 22 At least two of are independently substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 is a hydrocarbyl group; R 6 and R 18 are each independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 is a hydrocarbyl group; R 24 , R 25 , R 26 , R 27 , R 28 , and R 29 are each independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 8 is a hydrocarbyl group; R 12 , R 13 , R 14 , R 15 , and R 16 are each independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 is a hydrocarbyl group; Each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or C 1 -C 20 a substituted or unsubstituted straight-chain, branched, or cyclic hydrocarbyl group, or two or more X moieties taken 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; m is an integer equal to v-2; The method of claim 1.

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

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

49. The metallocene compound is (pentamethylcyclopentadienyl)(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-ethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-n-propyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isopropyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-n-butyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1,6,6-triethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methylindenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutylindenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methyl-3,6,7,8-tetrahydro-as-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-3,6,7,8-tetrahydro-as-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene)hafnium dimethyl, (pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)hafnium dimethyl, and (pentamethylcyclopentadienyl)(1-isobuty-5,6-dimethyllindenyl)hafnium dimethyl The method of claim 1 , wherein the compound is selected from the group consisting of:

50. The metallocene compound is (pentamethylcyclopentadienyl)(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methylindenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutylindenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)hafnium dimethyl, and (pentamethylcyclopentadienyl)(1-isobutyl-5,6-dimethyllindenyl)hafnium dimethyl The method of claim 1 , wherein the compound is selected from the group consisting of:

51. The method of claim 1 , wherein the catalyst comprises an activator.

52. The activator is [N,N-di(hydrogenated tallow)methylammonium][tetrakis(perfluorophenyl)borate], [N-methyl-4-nonadecyl-N-octadecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-4-hexadecyl-N-octadecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-4-tetradecyl-N-octadecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-4-dodecyl-N-octadecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-4-decyl-N-octadecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-4-octyl-N-octadecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-4-hexyl-N-octadecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-4-butyl-N-octadecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-4-octadecyl-N-decylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-4-nonadecyl-N-dodecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-4-nonadecyl-N-tetradecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-4-nonadecyl-N-hexadecylanilinium][tetrakis(perfluorophenyl)borate], [N-ethyl-4-nonadecyl-N-octadecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-N,N-dioctadecylammonium][tetrakis(perfluorophenyl)borate], [N-methyl-N,N-dihexadecylammonium][tetrakis(perfluorophenyl)borate], [N-methyl-N,N-ditetradecylammonium][tetrakis(perfluorophenyl)borate], [N-methyl-N,N-didodecylammonium][tetrakis(perfluorophenyl)borate], [N-methyl-N,N-didecylammonium][tetrakis(perfluorophenyl)borate], [N-methyl-N,N-dioctylammonium][tetrakis(perfluorophenyl)borate], [N-ethyl-N,N-dioctadecylammonium][tetrakis(perfluorophenyl)borate], [N,N-di(octadecyl)tolylammonium][tetrakis(perfluorophenyl)borate], [N,N-di(hexadecyl)tolylammonium][tetrakis(perfluorophenyl)borate], [N,N-di(tetradecyl)tolylammonium][tetrakis(perfluorophenyl)borate], [N,N-di(dodecyl)tolylammonium][tetrakis(perfluorophenyl)borate], [N-octadecyl-N-hexadecyl-tolylammonium][tetrakis(perfluorophenyl)borate], [N-octadecyl-N-hexadecyl-tolylammonium][tetrakis(perfluorophenyl)borate], [N-octadecyl-N-tetradecyl-tolylammonium][tetrakis(perfluorophenyl)borate], [N-octadecyl-N-dodecyl-tolylammonium][tetrakis(perfluorophenyl)borate], [N-octadecyl-N-decyl-tolylammonium][tetrakis(perfluorophenyl)borate], [N-hexadecyl-N-tetradecyl-tolylammonium][tetrakis(perfluorophenyl)borate], [N-hexadecyl-N-dodecyl-tolylammonium][tetrakis(perfluorophenyl)borate], [N-hexadecyl-N-decyl-tolylammonium][tetrakis(perfluorophenyl)borate], [N-tetradecyl-N-dodecyl-tolylammonium][tetrakis(perfluorophenyl)borate], [N-tetradecyl-N-decyl-tolylammonium][tetrakis(perfluorophenyl)borate], [N-dodecyl-N-decyl-tolylammonium][tetrakis(perfluorophenyl)borate], [N-methyl-N-octadecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-N-hexadecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-N-tetradecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-N-dodecylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-N-decylanilinium][tetrakis(perfluorophenyl)borate], [N-methyl-N-octylanilinium][tetrakis(perfluorophenyl)borate], N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, trimethylammonium tetrakis(perfluorophenyl)borate, and Tri-n-butylammonium tetrakis(perfluorophenyl)borate 52. The method of claim 51 , wherein the

53. The activator is [N,N-di(hydrogenated tallow)methylammonium][tetrakis(perfluorophenyl)borate], [N-methyl-N,N-dioctadecylammonium][tetrakis(perfluorophenyl)borate], and [N-methyl-N,N-dihexadecylammonium][tetrakis(perfluorophenyl)borate] 53. The method of claim 51 or 52, wherein the

54. 52. The method of claim 51, wherein the activator is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate.

55. 55. The method of any one of claims 1 to 54, which is a continuous process, a batch process, or a semi-batch process.

56. continuously introducing the feedstock into a polymerization reactor; continuously introducing a catalyst system into a polymerization reactor; and continuously withdrawing the polymerization reaction mixture from the polymerization reactor.

56. The method of claim 55, which is a continuous process comprising:

57. 57. The process of claim 56, wherein the polymerization reactor comprises a continuous stirred tank reactor or a plug flow reactor.

58. at least one alpha-olefin monomer and at least one C 4 -C 24 contacting a cyclic alpha-olefin with a metallocene catalyst, a non-coordinating anion activator, and optionally an alkyl-aluminum compound, wherein the polymerization conditions comprise a reaction temperature ranging from 70° C. to 160° C., a reactor pressure less than 50 atmospheres, and a residence time ranging from 20 minutes to 3 hours; obtaining a polymerization reaction mixture (e.g., including one or more oligomeric products); and Optionally, fractionating the polymerization reaction mixture and / or hydrogenating the polymerization reaction mixture (which may, for example, include fractionating one or more oligomer products and hydrogenating one or more oligomer products).

58. The method of claim 56 or 57, comprising:

59. introducing two or more different alpha-olefins into a polymerization reactor; adding a catalyst system into a polymerization reactor; and agitating the contents of the polymerization reactor for about 10 minutes to about 24 hours, and then withdrawing the polymerization reaction mixture from the polymerization reactor.

56. The method of claim 55, which is a batch or semi-batch process comprising:

60. at least one alpha-olefin monomer and at least one C 4 -C 24 contacting a cyclic alpha-olefin with a metallocene catalyst, a non-coordinating anion activator, and optionally an alkyl-aluminum compound, wherein the polymerization conditions comprise a reaction temperature ranging from 70° C. to 160° C., a reactor pressure less than 50 atmospheres, and a residence time ranging from 20 minutes to 24 hours; obtaining a polymerization reaction mixture (e.g., including one or more oligomeric products); and Optionally, fractionating the polymerization reaction mixture and / or hydrogenating the polymerization reaction mixture (which may, for example, include fractionating one or more oligomer products and hydrogenating one or more oligomer products).

60. The method of claim 59, comprising:

61. 61. The method of claim 59 or 60, wherein the catalyst system is added to the polymerization reactor in a single dose or in multiple doses.

62. 62. The process of any one of claims 59 to 61, wherein one or more of the two or more different alpha-olefins are added to the polymerization reactor in a single dose or in multiple doses.

63. 63. The method of any one of claims 59 to 62, wherein a portion of the polymerization reaction mixture is withdrawn from the polymerization reactor.

64. 60. The method of claim 59, wherein at least one of the two or more different alpha-olefins is a solvent.

65. 64. The method of any one of claims 55 to 63, wherein the polymerization reaction conditions comprise a reaction temperature of about 100 to 200°C, 110 to 180°C, 120 to 170°C, 130 to 160°C, or 140 to 155°C.

66. 65. The process of any one of claims 55 to 64, wherein the polymerization reaction conditions comprise a temperature of 120°C or greater, 130°C or greater, or 140°C or greater, and / or a reactor pressure of 15 psia to 1600 psia.

67. The process of any one of claims 1 to 66, wherein the unsaturated PAO product is separated from unreacted monomer and solvent, hydrogenated, and fractionated by distillation.

68. The process of any one of claims 1 to 66, wherein the unsaturated PAO product is separated from unreacted monomer and solvent and fractionated by distillation.

69. A fuel or lubricant comprising an unsaturated PAO product formed by the process of any one of claims 1 to 26, or a hydrogenated PAO product formed by the process of any one of claims 28 to 41.

70. 42. A driveline or electric vehicle fluid, engine oil, gear oil, coolant, compressor oil, or hydraulic fluid comprising the hydrogenated PAO product formed by the process of any one of claims 28-41 or the functionalized PAO product formed by the process of claim 27.

71. One or more C 6 -C 32 A cyclic alpha olefin and one or more C 4 -C 32 and a feedstock comprising linear and / or branched alpha olefins, with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions to effect polymerization to obtain a polymerization reaction mixture comprising a mixture of vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally PAOs having vinyl unsaturation; Optionally, obtaining an unsaturated PAO product from the polymerization reaction mixture. A polyalphaolefin (PAO) produced from a process comprising:

72. A polyalphaolefin (PAO) produced from the method of any one of claims 1 to 70.

73. One or more C 6 -C 32 72. The PAO produced from the process of claim 71, wherein one of the cyclic alpha-olefins contains ring unsaturation and the unsaturated PAO product further contains a cyclic disubstituted vinylene.

74. 72. The PAO produced from the process of claim 71, wherein the unsaturated PAO product comprises vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally dimeric and / or trimeric molecules having vinyl unsaturation.

75. The unsaturated PAO products are 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-isomer, and / or VCHx2-isomer, cyclic monomer fragments (A) and (B) are, independently, saturated when the cyclic alpha-olefin has a saturated ring structure, or partially unsaturated when the cyclic alpha-olefin has a partially unsaturated ring structure; 【Chemistry 8】 n and m each represent the number of additional carbon atoms in the ring structure of the cyclic monomer fragments (A) and (B), and each independently represent an integer from 1 to 20; R is C 2 -C 30 is a hydrocarbyl group, R' is C 1 -C 29 is a hydrocarbyl group, 72. The PAO produced from the process of claim 71, wherein at least one of CL-v and LC-v is present in the unsaturated PAO product or mixture thereof.

76. n and m independently represent an integer of 1 to 5, and R is C 2 -C 8 is a hydrocarbyl group, and R' is C 1 -C 7 76. The PAO produced from the process of claim 75, wherein the PAO is a hydrocarbyl group.

77. n and m are 3 and R is C 3 -C 8 is a hydrocarbyl group, and R' is C 2 -C 7 76. The PAO produced from the process of claim 75, wherein the cyclic monomer fragments (A) and (B) are hydrocarbyl groups and have partially unsaturated ring structures.

78. 76. The PAO produced from the process of claim 75, wherein LL-v is present in the unsaturated PAO product or mixture thereof.

79. 76. The PAO produced from the process of claim 75, wherein CC-v and LL-v are present in the unsaturated PAO product or mixture thereof.

80. 72. The PAO produced from the process of claim 71, wherein the unsaturated PAO product comprises greater than or equal to 60 mol%, 70 mol%, or 80 mol% vinylidene and trisubstituted vinylene, and less than or equal to 10 mol% vinyl, based on the total moles of vinyl, vinylidene, acyclic disubstituted vinylene, and trisubstituted vinylene in the unsaturated PAO product.

81. 72. The PAO produced from the process of claim 71, wherein the unsaturated PAO product comprises greater than or equal to 50%, 60%, 70%, 80%, 90%, or 95% dimers, relative to the total amount of dimers, trimers, tetramers, and higher oligomers in the unsaturated PAO product, as measured by GC-MS.

82. 72. The PAO produced from the process of claim 71, wherein the unsaturated PAO product comprises greater than or equal to 70%, 80%, 85%, 90%, 95%, or 97% dimers and trimers, based on the total amount of dimers, trimers, tetramers, and higher oligomers in the PAO product, as measured by GC-MS.

83. The unsaturated PAO product is One or more C 6 -C 32 A first dimer (CC) formed by the reaction of two cyclic alpha-olefins, C 6 -C 32 one of cyclic alpha-olefins and C 4 -C 32 a second dimer (CL) formed by reaction with one of the linear and / or branched alpha-olefins, and C 4 -C 32 A third dimer (LL) formed by two of the linear and / or branched alpha-olefins.

72. The PAO produced from the method of claim 71, comprising one or more of:

84. 84. A PAO produced from the process of claim 83, wherein the percentage of CL in the unsaturated PAO product, based on CC+CL+LL equaling 100%, is 20% or greater, 30% or greater, 40% or greater, 50% or greater, 60% or greater, 70% or greater, or 80% or greater, based on GC-MS.

85. 84. A PAO produced from the process of claim 83, wherein the percentage of CC in the unsaturated PAO product, based on CC+CL+LL equaling 100%, is equal to or greater than 0%, and equal to or less than 35%, equal to or less than 30%, equal to or less than 25%, equal to or less than 20%, equal to or less than 15%, equal to or less than 10%, or equal to or less than 5% based on GC-MS.

86. 84. A PAO produced from the process of claim 83, wherein the percentage of LL in the unsaturated PAO product, based on CC+CL+LL equaling 100%, 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, based on GC-MS.

87. 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, cyclic monomer fragments (A) and (B) are, independently, saturated when the cyclic alpha-olefin has a saturated ring structure, or partially unsaturated when the cyclic alpha-olefin has a partially unsaturated ring structure; 【Chemistry 9】 n and m represent the number of additional carbon atoms in the ring structure of the cyclic monomer fragments (A) and (B), respectively, and independently represent integers from 1 to 20; R is C 2 -C 30 is a hydrocarbyl group, R' is C 1 -C 29 is a hydrocarbyl group, A mixture, wherein at least one of CL-v and LC-v is present in the mixture.

88. n and m independently represent an integer of 1 to 5, and R is C 2 -C 8 is a hydrocarbyl group, and R' is C 1 -C 7 88. The mixture of claim 87, wherein the group is a hydrocarbyl group.

89. n and m are 3 and R is C 3 -C 8 is a hydrocarbyl group, and R' is C 2 -C 7 89. The mixture of claim 87 or 88, wherein the cyclic monomer fragments (A) and (B) are hydrocarbyl groups and have partially unsaturated ring structures.

90. 90. The mixture of any one of claims 87 to 89, wherein LL-v is present in the mixture.

91. 90. The mixture of any one of claims 87 to 89, wherein CC-v and LL-v are present in the mixture.

92. 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-en-1,3-diyl)dicyclohex-1-ene, 4-(oct-1-en-2-yl)cyclohex-1-ene, oct-1-en-2-ylcyclohexane, 4-(hept-1 and (6-methylhept-1-en-2-yl)cyclohex-1-ene, 4-(hex-1-en-2-yl)cyclohex-1-ene, 4-(6-methylhept-1-en-2-yl)cyclohex-1-ene, 4-(hex-1-en-2-yl)cyclohex-1-ene, 4-(6-methylhept-1-en-2-yl)cyclohex-1-ene, 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. PAO products including 4,4'-(but-3-en-1,3-diyl)dicyclohex-1-ene (VCHx2), 4-(oct-1-en-2-yl)cyclohex-1-ene (VCH-hex), and 5-methyleneundecane (hex-hex).

94. 94. The PAO product of claim 93, wherein 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%, based on the total number of moles of VCHx2 + VCH-hex + hex-hex equaling 100%.

95. 95. The PAO product of claim 93 or 94, wherein the mole percentage of VCHx2 is 0% or greater and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, based on the total number of moles of VCHx2 + VCH-hex + hex-hex equaling 100%.

96. 96. The PAO product of any one of claims 93-95, wherein 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%, based on the total number of moles of VCHx2 + VCH-hex + hex-hex equaling 100%.

97. PAO products including but-3-ene-1,3-diyldicyclohexane (VCH'x2), oct-1-en-2-ylcyclohexane (VCH'-hex), and 5-methyleneundecane (hex-hex).

98. 98. The PAO product of claim 97, wherein 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%, based on the total number of moles of VCH'x2 + VCH'-hex + hex-hex equaling 100%.

99. 99. The PAO product of claim 97 or 98, wherein the mole percentage of VCH'x2 is 0% or higher and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, based on the total number of moles of VCH'x2 + VCH'-hex + hex-hex equaling 100%.

100. 100. The PAO product of any one of claims 97-99, wherein 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%, based on the total number of moles of VCH'x2 + VCH'-hex + hex-hex equaling 100%.

101. PAO products including 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 (pent-pent).

102. 102. The PAO product of claim 101, wherein 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%, based on the total number of moles of VCHx2 + VCH-pent + pent-pent equaling 100%.

103. 103. The PAO product of claim 101 or 102, wherein the mole percentage of VCHx2 is 0% or higher and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, based on the total number of moles of VCHx2 + VCH-pent + pent-pent equaling 100%.

104. 104. The PAO product of any one of claims 101-103, wherein 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%, based on the total number of moles of VCHx2 + VCH-pent + pent-pent equaling 100%.

105. PAO products including but-3-ene-1,3-diyldicyclohexane (VCH'x2), hept-1-en-2-ylcyclohexane (VCH'-pent), and 4-methylenenonane (pent-pent).

106. 106. The PAO product of claim 105, wherein 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%, based on the total number of moles of VCH'x2 + VCH'-pent + pent-pent equaling 100%.

107. 107. The PAO product of claim 105 or 106, wherein the mole percentage of VCH'x2 is 0% or higher and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, based on the total number of moles of VCH'x2 + VCH'-pent + pent-pent equaling 100%.

108. 108. The PAO product of any one of claims 105-107, wherein 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%, based on the total number of moles of VCH'x2 + VCH'-pent + pent-pent equaling 100%.

109. PAO products including 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. 110. The PAO product of claim 109, wherein 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%, based on the total number of moles of VCHx2 + VCH-hept + hept-hept equaling 100%.

111. 111. The PAO product of claim 109 or 110, wherein the mole percentage of VCHx2 is 0% or higher and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, based on the total number of moles of VCHx2 + VCH-hept + hept-hept equaling 100%.

112. 112. The PAO product of any one of claims 109-111, wherein the mole 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%, relative to the total number of moles of VCHx2 + VCH-hept + hept-hept equaling 100%.

113. PAO products including but-3-ene-1,3-diyldicyclohexane (VCH'x2), non-1-en-2-ylcyclohexane (VCH'-hept), and 6-methylenetridecane (hept-hept).

114. 114. The PAO product of claim 113, wherein 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%, based on the total number of moles of VCH'x2 + VCH'-hept + hept-hept equaling 100%.

115. 115. The PAO product of claim 113 or 114, wherein the mole percentage of VCH'x2 is 0% or greater, and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, relative to the total number of moles of VCHx2' + VCH'-hept + hept-hept equaling 100%.

116. 116. The PAO product of any one of claims 113-115, wherein the mole 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%, based on the total number of moles of VCH'x2 + VCH'-hept + hept-hept equaling 100%.

117. PAO products including 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-methyleneheptane (but-but).

118. 118. The PAO product of claim 117, wherein 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%, based on the total number of moles of VCHx2 + VCH-but + but-but equaling 100%.

119. 119. The PAO product of claim 117 or 118, wherein the mole percentage of VCHx2 is 0% or greater and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, based on the total number of moles of VCHx2 + VCH-but + but-but equaling 100%.

120. 120. The PAO product of any one of claims 117-119, wherein the mole 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%, based on the total number of moles of VCHx2 + VCH-but + but-but equaling 100%.

121. PAO products including but-3-ene-1,3-diyldicyclohexane (VCH'x2), hex-1-en-2-ylcyclohexane (VCH'-but), and 3-methyleneheptane (but-but).

122. 122. The PAO product of claim 121, wherein 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%, based on the total number of moles of VCH'x2 + VCH'-but + but-but equaling 100%.

123. 123. The PAO product of claim 121 or 122, wherein the mole percentage of VCH'x2 is 0% or greater and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, based on the total number of moles of VCH'x2 + VCH'-but + but-but equaling 100%.

124. 124. The PAO product of any one of claims 121-123, wherein the mole 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%, based on the total number of moles of VCH'x2 + VCH'-but + but-but equaling 100%.

125. PAO products including 4,4'-(but-3-en-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 (MePent-MePent).

126. 126. The PAO product of claim 125, wherein 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%, based on the total number of moles of VCHx2 + VCH-MePent + MePent - MePent equaling 100%.

127. 127. The PAO product of claim 125 or 126, wherein the mole percentage of VCHx2 is 0% or higher and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, based on the total number of moles of VCHx2 + VCH-MePent + MePent-MePent equaling 100%.

128. 128. The PAO product of any one of claims 125-127, wherein the mole 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%, based on the total number of moles of VCHx2 + VCH-MePent + MePent-MePent equal to 100%.

129. PAO products including but-3-ene-1,3-diyldicyclohexane (VCH'x2), (6-methylhept-1-en-2-yl)cyclohexane (VCH'-MePent), and 2,8-dimethyl-4-methylenenonane (MePent-MePent).

130. 130. The PAO product of claim 129, wherein 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%, based on the total number of moles of VCH'x2 + VCH'-MePent + MePent-MePent equaling 100%.

131. 131. The PAO product of claim 129 or 130, wherein the mole percentage of VCH'x2 is 0% or higher and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, relative to the total number of moles of VCH'x2 + VCH'-MePent + MePent-MePent equaling 100%.

132. 132. The PAO product of any one of claims 129-131, wherein the mole 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%, based on the total number of moles of VCH'x2+VCH'-MePent+MePent-MePent equal to 100%.

133. 1. A process for hydrogenating an unsaturated polyalpha-olefin (PAO) product formed from two or more different alpha-olefins, comprising: contacting the unsaturated PAO product with hydrogen and a hydrogenation catalyst in a hydrogenation process to convert at least a portion of the unsaturated PAO product to a hydrogenated PAO product, wherein the unsaturated PAO product comprises a mixture of PAO molecules having vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturation, and wherein the unsaturated PAO product comprises one or more C 6 -C 32 A cyclic alpha-olefin and one or more C 4 -C 32 and a linear and / or branched alpha-olefin.

134. 134. The method of claim 133, wherein the hydrogenation process occurs at a temperature of about 25 to 350°C or about 100 to 300°C; for a time period ranging from about 5 minutes to 100 hours or from about 5 minutes to 24 hours; and / or a hydrogen pressure of about 25 psig to 2500 psi or about 100 psig to 2000 psig.

135. 135. The method of claim 133 or 134, wherein the hydrogenation process occurs in a slurry reactor, a batch operation, a fixed bed reactor, or in a continuous stirred tank reactor.

136. 136. The process of any one of claims 133 to 135, wherein the hydrogenation catalyst comprises about 0.001 to 20 weight percent or about 0.01 to 10 weight percent of the unsaturated PAO product or feedstock comprising the unsaturated PAO product.

137. The method of any one of claims 133 to 136, wherein the hydrogenated PAO product has a Bromine Number of 2.0 or less.

138. The hydrogenated PAO product is 1,2 , hLC 1,2 , hCL 1,2 , hLL 1,2 , hCC 2,1 , hLC 2,1 , hLL 2,1 , hLVCH-isomers, and / or hVCHx2-isomers, The cyclic monomer fragments (A) and (B) are saturated ring structures, 【Chemistry 10】 and 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 C 2 -C 30 is a hydrocarbyl group, R' is C 1 -C 29 is a hydrocarbyl group, hCL 1,2 and hLC 1,2 is present in the hydrogenated PAO product; 138. The method of any one of claims 133 to 137.

139. n and m independently represent an integer of 1 to 5, and R is C 2 -C 8 is a hydrocarbyl group, and R' is C 1 -C 7 The method of claim 138, wherein the group is a hydrocarbyl group.

140. n and m are 3 and R is C 3 -C 8 is a hydrocarbyl group, and R' is C 2 -C 7 The method of claim 138, wherein the group is a hydrocarbyl group.

141. hLL 1,2 is present in the hydrogenated PAO product or mixture thereof.

142. hCC 1,2 or hLL 1,2 is present in the hydrogenated PAO product or mixture thereof.

143. hCC 1,2 and hLL 1,2 is present in the hydrogenated PAO product or mixture thereof.

144. The hydrogenated PAO product is One or more C 6 -C 32 a first hydrogenated dimer (hCC) formed by the reaction of two cyclic alpha-olefins; One or more C 6 -C 32 one or more C cyclic alpha-olefins 4 -C 32 a second hydrogenated dimer (hCL) formed by reaction with one of the linear and / or branched alpha-olefins, and C 4 -C 32 A third hydrogenated dimer (hLL) formed by two of the linear and / or branched alpha-olefins.

144. The method of any one of claims 133 to 143, comprising:

145. 145. The method of claim 144, wherein 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 based on GC-MS, with hCC+hCL+hLL equal to 100%.

146. 145. The method of claim 144, wherein the percentage of hCC in the hydrogenated PAO product is equal to or greater than 0% and equal to or less than 35%, equal to or less than 30%, equal to or less than 25%, equal to or less than 20%, equal to or less than 15%, equal to or less than 10%, or equal to or less than 5%, based on GC-MS, with hCC+hCL+hLL equal to 100%.

147. 145. The method of claim 144, wherein the percentage of hLL in the hydrogenated PAO product is greater than or equal to 10% and less than or equal to 80%, less than or equal to 70%, less than or equal to 60%, less than or equal to 50%, less than or equal to 40%, less than or equal to 30%, or less than or equal to 20%, based on GC-MS, with hCC+hCL+hLL equal to 100%.

148. contacting the unsaturated PAO product mixture with hydrogen and a hydrogenation catalyst in a hydrogenation process to convert the unsaturated PAO mixture into a hydrogenated PAO mixture, wherein the unsaturated PAO mixture comprises PAOs having vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturation, and wherein the unsaturated PAO mixture comprises one or more C 6 -C 32 A cyclic alpha-olefin and one or more C 4 -C 32 A blend of hydrogenated polyalphaolefins (PAOs) formed by a process formed from linear and / or branched alpha-olefins.

149. 149. The mixture formed by the process of claim 148, wherein the hydrogenation process occurs at a temperature of 25 to 350°C, or 100 to 300°C, for a time of 5 minutes to 100 hours, or 5 minutes to 24 hours, and at a hydrogen pressure of 25 psig to 2500 psig, or 100 psig to 2000 psig.

150. 150. The mixture formed by the method of claim 148 or 149, wherein the hydrogenation process occurs in a slurry reactor, a batch operation, a fixed bed reactor, or in a continuous stirred tank reactor.

151. 151. The mixture formed by the process of any one of claims 148 to 150, wherein the hydrogenation catalyst comprises 0.001 to 20 wt. % or 0.01 to 10 wt. % of the unsaturated PAO feed material.

152. 152. The mixture formed by the process of any one of claims 148-151, wherein the bromine number of the hydrogenated PAO product is 2.0 or less.

153. The hydrogenated PAO product is 1,2 , hLC 1,2 , hCL 1,2 , hLL 1,2 , hCC 2,1 , hLC 2,1 , hLL 2,1 , hLVCH-isomers, and hVCHx2-isomers, The cyclic monomer fragments (A) and (B) are saturated ring structures, 【Chemistry 11】 and 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 C 2 -C 30 is a hydrocarbyl group, R' is C 1 -C 29 is a hydrocarbyl group, hCL 1,2 and hLC 1,2 is present in the hydrogenated PAO product; 153. A mixture formed by the method of any one of claims 148 to 152.

154. n and m independently represent an integer of 1 to 5, and R is C 2 -C 8 is a hydrocarbyl group, and R' is C 1 -C 7 154. The mixture formed by the method of claim 153, wherein the hydroxyl group is a hydrocarbyl group.

155. n and m are 3 and R is C 3 -C 8 is a hydrocarbyl group, and R' is C 2 -C 7 154. The mixture formed by the method of claim 153, wherein the hydroxyl group is a hydrocarbyl group.

156. hCC 1,2 is present in the hydrogenated PAO product or mixture thereof.

157. hLL 1,2 is present in the hydrogenated PAO product or mixture thereof.

158. hCC 1,2 and hLL 1,2 is present in the hydrogenated PAO product or mixture thereof.

159. The hydrogenated PAO product is One or more C 6 -C 32 a first hydrogenated dimer (hCC) formed by the reaction of two cyclic alpha-olefins; One or more C 6 -C 32 one or more C cyclic alpha-olefins 4 -C 32 a second hydrogenated dimer (hCL) formed by reaction with one of the linear and / or branched alpha-olefins, and C 4 -C 32 A third hydrogenated dimer (hLL) formed by two of the linear and / or branched alpha-olefins.

159. The mixture formed by the method of any one of claims 153 to 158, comprising:

160. 160. The mixture formed by the process of claim 159, wherein 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, based on GC-MS, of hCC+hCL+hLL equal to 100%.

161. 161. The mixture formed by the process of claim 159 or 160, wherein the percentage of hCC in the hydrogenated PAO product is equal to or greater than 0% and equal to or less than 35%, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% based on GC-MS, with hCC + hCL + hLL equal to 100%.

162. 162. The mixture formed by the process of any one of claims 159-161, wherein the percentage of hLL in the hydrogenated PAO product is greater than or equal to 10% based on GC-MS, and is less than or equal to 80%, less than or equal to 70%, less than or equal to 60%, less than or equal to 50%, less than or equal to 40%, less than or equal to 30%, or less than or equal to 20%, based on hCC+hCL+hLL equal to 100%.

163. hCC 1,2 , hLC 1,2 , hCL 1,2 , hLL 1,2 , hCC 2,1 , hLC 2,1 , hLL 2,1 , hLVCH-isomers, and / or hVCHx2-isomers, The cyclic monomer fragments (A) and (B) are saturated ring structures, 【Chemistry 12】 and 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 C 2 -C 30 is a hydrocarbyl group, R' is C 1 -C 29 is a hydrocarbyl group, hCL 1,2 and hLC 1,2 is present in the mixture.

164. n and m independently represent an integer of 1 to 5, and R is C 2 -C 8 is a hydrocarbyl group, and R' is C 1 -C 7 164. The mixture of claim 163, wherein the group is a hydrocarbyl group.

165. n and m are 3 and R is C 3 -C 8 is a hydrocarbyl group, and R' is C 2 -C 7 The mixture of claim 163, wherein the cyclic monomer fragments (A) and (B) are hydrocarbyl groups and have partially unsaturated ring structures.

166. hCC 1,2 or hLL 1,2 166. The mixture of any one of claims 163 to 165, wherein is present in the mixture.

167. hCC 1,2 and hLL 1,2 166. The mixture of any one of claims 163 to 165, wherein is present in the mixture.

168. hPAO has the following structure: 【Chemistry 13】 wherein p is an integer from 2 to 18.

169. 169. The mixture of claim 168, wherein p is 2 to 8.

170. 1. 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. Hydrogenated polyalpha-olefin (hPAO) products including butane-1,3-diyldicyclohexane (hVCHx2), octan-2-ylcyclohexane (hVCH-hex), and 5-methylundecane (hHex-hex).

172. 172. The hPAO product of claim 171, wherein the mole 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%, relative to the total moles of hVCHx2 + hVCH-hex + hHex-hex equal to 100%.

173. 173. The hPAO product of claim 171 or 172, wherein the mole percentage of hVCHx2 is 0% or greater and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, relative to the total moles of hVCHx2 + hVCH-hex + hHex-hex equaling 100%.

174. 174. The hPAO of any one of claims 171-173, wherein the mole 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%, relative to the total number of moles of hVCHx2 + hVCH-hex + hHex-hex equaling 100%.

175. Hydrogenated polyalpha-olefin (hPAO) products including butane-1,3-diyldicyclohexane (hVCHx2), 4-heptan-2-ylcyclohexane (hVCH-pent), and 4-methylnonane (hPent-pent).

176. 176. The hPAO product of claim 175, wherein 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%, relative to the total moles of hVCHx2 + hVCH-pent + hPent-pent equaling 100%.

177. 177. The hPAO product of claim 175 or 176, wherein the mole percentage of hVCHx2 is 0% or higher and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, relative to the total moles of hVCHx2 + hVCH-pent + hPent-pent equaling 100%.

178. 178. The hPAO product of any one of claims 175-177, wherein 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%, relative to the total number of moles of hVCHx2 + hVCH-pent + hPent-pent equaling 100%.

179. Hydrogenated polyalpha-olefin (hPAO) products including butane-1,3-diyldicyclohexane (hVCHx2), 4-heptan-2-ylcyclohexane (hVCH-hept), and 6-methyltridecane (hHept-hept).

180. 180. The hPAO product of claim 179, wherein 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%, relative to the total moles of hVCHx2 + hVCH-hept + hHept-hept equal to 100%.

181. 181. The hPAO product of claim 179 or 180, wherein the molar percentage of hVCHx2 is 0% or higher and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, relative to the total number of moles of hVCHx2 + hVCH-hept + hHept-hept equaling 100%.

182. 182. The hPAO product of any one of claims 179-181, wherein the molar 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%, relative to the total number of moles of hVCHx2 + hVCH-hept + hHept-hept equaling 100%.

183. Hydrogenated polyalpha-olefin (hPAO) products including butane-1,3-diyldicyclohexane (hVCHx2), hexan-2-ylcyclohexane (hVCH-but), and 3-methylheptane (hbut-but).

184. 184. The hPAO product of claim 183, wherein 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%, relative to the total moles of hVCHx2 + hVCH-but + hbut-but equaling 100%.

185. 185. The hPAO product of claim 183 or 184, wherein the mole percentage of hVCHx2 is 0% or greater and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, relative to the total moles of hVCHx2 + hVCH-but + hbut-but equaling 100%.

186. 186. The hPAO product of any one of claims 183-185, wherein the mole 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%, relative to the total moles of hVCHx2 + hVCH-but + hbut-but equaling 100%.

187. Hydrogenated polyalpha-olefins (hPAOs) including butane-1,3-diyldicyclohexane (hVCHx2), (6-methylheptan-2-yl)cyclohexane (hVCH-MePent), and 4-methylnonane (hMePent-MePent).

188. 188. The hPAO product of claim 187, wherein the mole 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%, relative to the total number of moles of hVCHx2 + hVCH-MePent + hMePent-MePent equal to 100%.

189. 189. The hPAO product of claim 187 or 188, wherein the mole percentage of hVCHx2 is 0% or higher and up to about 35%, up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, or up to about 5%, relative to the total moles of hVCHx2 + hVCH-MePent + hMePent-MePent equal to 100%.

190. 190. The hPAO product of any one of claims 187-189, wherein the mole 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%, relative to the total number of moles of hVCHx2 + hVCH-MePent + hMePent-MePent equal to 100%.

191. A functionalized polyalphaolefin (PAO) comprising the reaction product of 1) a heteroatom-containing group and 2) an unsaturated PAO product produced by a process (e.g., any process described herein, such as a process for producing a polyalphaolefin (PAO) from two or more different alpha-olefins), wherein the heteroatom-containing group comprises one or more of a sulfonate, an amine, an aldehyde, an alcohol, or an acid; preferably, the heteroatom-containing group comprises an epoxide, succinic acid, maleic acid, or maleic anhydride; or the heteroatom-containing group comprises one or more of an acid, an ester, anhydride, an acid-ester, oxycarbonyl, carbonyl, formyl, formylcarbonyl, hydroxyl, and an acetyl halide.

192. The unsaturated PAO is produced by a process for producing polyalphaolefins (PAO) from two or more different alpha-olefins, the process comprising: One or more C 6 -C 32 A cyclic alpha olefin and one or more C 4 -C 32 and a feedstock comprising linear and / or branched alpha olefins, with a catalyst system comprising a metallocene compound in a polymerization reactor under polymerization conditions to effect polymerization, to obtain a polymerization reaction mixture comprising a mixture of vinylidene, trisubstituted vinylene, disubstituted vinylene, and optionally vinyl unsaturated PAOs (e.g., PAO molecules); Obtaining an unsaturated PAO product from the polymerization reaction mixture.

192. The functionalized PAO of claim 191, comprising:

193. 192. The functionalized PAO of claim 191, wherein the unsaturated PAO is produced by the method of any one of claims 1-26.

194. 1. A process for producing cyclic dimers from one or more cyclic alpha-olefins, comprising: One or more C 6 -C 32 contacting a feedstock comprising cyclic 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 vinylidene, trisubstituted vinylene, disubstituted vinylene, and cyclic dimers (e.g., cyclic dimer molecules) optionally having vinyl unsaturation, wherein the metallocene compound is selected from Formula (I), (II), (III), (IV), or (V), wherein in Formulas (I) and (II), R 1 and R 3 is not hydrogen; and obtaining an unsaturated cyclic dimer product from the polymerization reaction mixture. A method comprising:

195. 195. The method of claim 194, which is a continuous process, a batch process, or a semi-batch process.

196. 196. The method of claim 195, which is a continuous solution and / or bulk method for producing cyclic dimers.

197. At least one type of C 4 -C 24 contacting a cyclic alpha-olefin with a metallocene catalyst, a non-coordinating anion activator, and optionally an alkyl-aluminum compound, wherein the polymerization conditions comprise 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 a cyclic dimer; and Optionally, hydrogenating the cyclic dimer.

197. The method of claim 196, comprising:

198. At least one type of C 4 -C 24 200. The method of claim 197, wherein the step of contacting the cyclic alpha-olefins is free of solvents other than those used in the catalyst and scavenger solutions, and / or the feed is substantially free of linear and branched alpha-olefins.

199. 196. The method of claim 195, which is a solution and / or bulk process in a batch or semi-batch reactor to produce the cyclic dimer.

200. At least one type of C 4 -C 24 contacting a cyclic alpha-olefin with a metallocene catalyst, a non-coordinating anion activator, and optionally an alkyl-aluminum compound, wherein the polymerization conditions comprise a reaction temperature in the range of 100°C to 160°C, a reactor pressure 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 to the reactor; obtaining a cyclic dimer; and Optionally, hydrogenating the cyclic dimer.

200. The method of claim 199, comprising:

201. 201. The method of claim 200, wherein the metallocene catalyst is added in a single dose at the beginning of the reaction or in stages (e.g., in multiple doses) during the reaction.

202. At least one type of C 4 -C 24 202. The method of claim 200 or 201, wherein the step of contacting the cyclic alpha-olefins does not include any solvent other than the solvents used in the catalyst and scavenger solutions, and / or the feed is substantially free of linear and branched alpha-olefins.

203. 203. The process of any one of claims 194 to 202, wherein the conversion of the one or more cyclic alpha-olefins to cyclic dimers, based on the total amount of feed monomers including isomerized or hydrogenated monomers, dimers, trimers, tetramers, and higher oligomers, as measured by GC-MS, is 50% or more, alternatively 60% or more, alternatively 70% or more, alternatively 80% or more, alternatively 90% or more, alternatively 95% or more.

204. 204. The process of any one of claims 194 to 203, wherein the selectivity to form cyclic dimers relative to the total amount of dimers, trimers, tetramers and higher oligomers is 80% or higher, alternatively 90% or higher, alternatively 94% or higher, alternatively 98% or higher, alternatively 99% or higher, as measured by GC-MS.

205. 205. The method of any one of claims 194 to 204, wherein the selectivity to form a single cyclic dimer species (e.g., a single isomer), relative to the total amount of cyclic dimer, as measured by GC-MS, is 80% or greater, alternatively 85% or greater, alternatively 90% or greater, alternatively 95% or greater, or alternatively 98% or greater.

206. 206. The process of any one of claims 194 to 205, wherein when only cyclic alpha-olefins are in the feed, the conversion of cyclic alpha-olefin monomer to form a single cyclic dimer species (e.g., 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 predominant dimer isomer relative to the total amount of feed monomer including isomerized or hydrogenated monomer, dimers, trimers, tetramers, and higher oligomers, as measured by GC-MS.

207. 207. A method according to any one of claims 194 to 206, wherein 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 dimers, trimers, tetramers and higher oligomers as measured by GC-MS.

208. The metallocene compound or metallocene catalyst is selected from formula (II), (III), (IV), or (V), wherein in formula (II), R 1 and R 3 The method of any one of claims 194 to 207, provided that at least one of is not hydrogen.

209. The metallocene compound or metallocene catalyst is selected from formula (I), (II), or (IV), and R 1 and R 2 is hydrogen, and R 3 is selected from the group consisting of methyl, ethyl, and the 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.

210. The metallocene compound or metallocene catalyst is (pentamethylcyclopentadienyl)(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-ethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-n-propyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isopropyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-n-butyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1,6,6-triethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methylindenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutylindenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methyl-3,6,7,8-tetrahydro-as-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-3,6,7,8-tetrahydro-as-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-5,6,7,8-tetrahydro-1H-cyclopenta[b]naphthalene)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-6,7,8,9-tetrahydro-1H-cyclopenta[a]naphthalene)hafnium dimethyl, (pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)hafnium dimethyl, and (pentamethylcyclopentadienyl)(1-isobuty-5,6-dimethyllindenyl)hafnium dimethyl 210. The method of any one of claims 194 to 209, selected from the group consisting of:

211. The metallocene compound or metallocene catalyst is (pentamethylcyclopentadienyl)(1-methyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-methylindenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1-isobutylindenyl)hafnium dimethyl, (pentamethylcyclopentadienyl)(1,5,6-trimethylindenyl)hafnium dimethyl, and (pentamethylcyclopentadienyl)(1-isobutyl-5,6-dimethyllindenyl)hafnium dimethyl 210. The method of any one of claims 194 to 209, selected from the group consisting of:

212. 212. The process of any one of claims 194 to 211, wherein the feedstock is substantially free of linear and branched alpha-olefins.

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