Process for producing low viscosity polyalphaolefins using an activator soluble in non-aromatic hydrocarbons

Abstract

A process for preparing a polyalpha-olefin (PAO) having a high vinylidene content (or total vinylidene and tri-substituted vinylene content) and a low vinyl and / or di-substituted vinylene content and a relatively low molecular weight, comprising contacting a feed containing C6-C 32 The feed of alpha-olefins is contacted with a catalyst system comprising an activator soluble in the non-aromatic hydrocarbon and a metallocene compound, typically a cyclopentadienyl-tetrahydro-s-indacenyl Group 4 transition metal compound.

Description

[0001] Inventors: Jo Ann M. Canich, Jian Yang, Jennifer L. Rapp, Catherine A. Faler, Margaret T. Whalley

[0002] Related Applications

[0003] This application claims priority benefit of provisional application number 62 / 885,103, filed August 9, 2019, the disclosure of which is incorporated herein by reference.

[0004] This application is related to USSN 15 / 706,088, filed September 15, 2017, the disclosure of which is US 2018 / 0094088.

[0005] This application is also related to USSN 15 / 921,757, filed March 15, 2018, the disclosure of which is WO 2018 / 182982.

[0006] This application is also related to USSN 16 / 270,085, filed February 7, 2019, which claims priority and benefit of USSN 62 / 629,200, filed February 12, 2018, and USSN 62 / 732,311, filed September 17, 2018.

[0007] This application is also related to USSN 16 / 394,197, filed April 25, 2019, and USSN 16 / 394,166, filed April 25, 2019, which both claim priority and benefit of USSN 62 / 662,972, filed April 26, 2018, and USSN 62 / 769,208, filed November 19, 2018. TECHNICAL FIELD

[0008] The present invention relates to a process for making polyalphaolefin (PAO) materials using a catalyst system comprising a hydrocarbon-soluble activator and a metallocene-compound selected to produce a high vinylidene content. BACKGROUND

[0010] Alpha-olefins, especially those containing from about 6 to about 20 carbon atoms, and their oligomers have been used as intermediates in the manufacture of detergents, lubricants, or other types of commercial products. Longer chain alpha-olefins such as vinylidene terminated polydecenes are also known and can be used as building blocks after functionalization or as macromonomers.

[0011] Metallocene catalyst systems can be used to polymerize and oligomerize alpha-olefin polymers. For example, U.S. Patent Publication No. 2005 / 0159299 discloses polymerization using a dimethylsilyl bis(2-methyl-4-phenyl-indenyl) zirconium dimethyl catalyst compound on a closed (capped) support to produce about 50% vinyl and about 50% vinylidene terminal unsaturation. Another example includes U.S. Patent No. 8,318,998, which discloses cyclopentadienyl-benzindenyl metallocene compounds that can be used to make alpha-olefin polymers such as ethylene and or propylene polymers having a high allyl chain end content. The examples in this disclosure show that the alpha-olefin polymers / oligomers produced have a low proportion of vinylidene content and a high proportion of vinyl content. U.S. Patent Publication No. 2013 / 0023633 also discloses metallocene compounds and their use in making polyolefins having a high proportion of vinyl content.

[0012] Another example U.S. Patent No. 8,748,361 discloses a mixture comprising unsaturated polyalpha-olefin (uPAO) materials, such as made from the oligomerization of alpha-olefins in the presence of a metallocene catalyst. The uPAO is disclosed in this reference to comprise, among other things, vinyl, vinylene, disubstituted vinylene, and trisubstituted vinylene groups. In this disclosure, the mixture of uPAO produced from the polymerization step is subsequently hydrogenated and then separated by distillation to obtain hydrogenated PAO materials particularly suitable as lubricating oil composition base stocks for use in various applications.

[0013] Olefinically unsaturated PAO materials made from the oligomerization of linear alpha-olefins can be used as intermediates to make various specialty chemicals due to the reactivity of the C=C double bonds. For example, when a chemical reagent that is reactive with C=C bonds is contacted with the uPAO material, various chemical functional groups can be incorporated into the carbon backbone of the uPAO molecule. The functional groups so incorporated into the PAO structure can impart unique properties to the functionalized and saturated PAO molecules.

[0014] It has been found that the reactivity of the C=C bonds in vinyl, vinylidene, disubstituted vinylene, and trisubstituted vinylene groups is different for many chemical functionalization reagents. For a particular type of functionalization reagent, one or more particular types of olefin can be more desirable than the other type(s). In addition, for making different derivatives comprising different functional groups thereon, it can be desirable to have uPAO with various molecular weights and molecular weight distributions and different reactivities. Vinylidene and trisubstituted vinylene groups are generally more reactive than disubstituted vinylene groups with many common reagents that are reactive with C=C double bonds.

[0015] WO 2017 / 188602 discloses in paragraph

[117] Me2Si(Me4Cp)(2-Me- benzindenyl)MCl2, wherein the 2-position of the benzindenyl group is methyl.

[0016] WO 2012 / 134720, compound G, discloses 1,3-dimethylbenz[e]indenyl)(Me5Cp)HfMe2.

[0017] US Patent Publication No. 2018 / 0094088 discloses benzindenyl compounds such as (1,3-dimethylbenz[e]indenyl)(CpMe5)ZrMe2 and (1,3-dimethylbenz[e]indenyl)(CpMe4)ZrMe2.

[0018] US 5,919,983 discloses the use of catalyst systems comprising [(C 18 )2MeN)] + [B(PhF5)4] - Ethylene and octene polymerization with catalyst systems of activators having four fluorophenyl groups bound to boron atoms and two linear C 18 groups bound to nitrogen, and other linear groups are described in column 3, line 51 and following.

[0019] US 2003 / 0013913 (granted as US 7,101,940) discloses various activators such as N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate

[0070] and N,N-diethylbenzylammonium tetrakis(pentafluorophenyl)borate

[0124] .

[0020] US 2002 / 0062011 discloses di(octadecyl)ammonium (hydroxyphenyl)tris(pentafluorophenyl)borate in paragraph

[0200] and (pentafluorophenyl)di(octadecyl)ammonium tetrakis(pentafluorophenyl)borate in paragraph

[0209] .

[0021] US 7,799,879, US 7,985,816, US 8,580,902, US 8,835,587 and WO 2010 / 014344 describe ammonium borate activators, including some that use the tetrakis(septfluoro-naphth-2-yl)borate anion.

[0022] Other publications of interest include, but are not necessarily limited to: U.S. Application Serial No. 12 / 642,453, filed December 18, 2009; U.S. Application Serial No. 12 / 533,465, filed July 31, 2009; U.S. Application Serial No. 61 / 136,172, filed August 15, 2008; U.S. Application Serial No. 62 / 477,683, filed March 28, 2017; U.S. Application Serial No. 62 / 477,706, filed March 28, 2017; PCT Publication Nos. WO 1995 / 027717, WO 2009 / 155471, WO 2009 / 155472, WO 2009 / 155510, WO 2009 / 155517, WO 2017 / 155149, WO 2012 / 133717, WO 2018 / 0094088, WO 2018 / 182982, U.S. Patent Nos. 3,367,987, 7,214,745, 8,816,027, 8,669,326, 8,940,839, 8,754,170, 8,426,659, 8,841,397, 8,501,894, 8,669,330, 8,835,563, 8,841,394, 8,399,724, 8,623,974, 8,981,029, 6,403,732, 6,818,585, 7,199,072; U.S. Patent Publication Nos. 2018 / 0094088, 2009 / 0318644, 2004 / 0102590, 2017 / 0233516; Japanese Publication Nos. JP 2005-336092, JP 2011-037164A; Chinese Publication No. CN 105622807; EP Publication Nos. EP 0659756, EP 0610851, EP 0283739; Korean Publication No. KR 17250040000; Rulhoff, S. et al. (2006) “Synthesis and Characterization of Defined Branched Poly(propylene)s with Different Microstructures by Copolymerization of Propylene and Linear Ethylene Oligomers (C n= 26-28) with Metallocenes / MAO Catalysts,” Macromolecules, Vol. 207(16), pp. 1450-1460; Kaneyoshi, H. et al. (2005) “Synthesis of Block and Graft Copolymers with Linear Polyethylene Segments by Combination of Degenerative Transfer Coordination Polymerization and Atom Transfer Radical Polymerization,” Macromolecules, Vol. 38(13), pp. 5425-5435; Teuben et al. (Journal Molecular Catalysis, Vol. 62, 1990, pp. 277-287); X. Yang et al. (1992) Angew. Chem. Int’l Edition., Engl., Vol. 31, pp. 1375-1377; Small, B. L. et al. (1999) Macromolecules, Vol. 32(7), pp. 2120-2130; Weng, W. et al. (2000) Macromolecular Rapid Comm., Vol. 21(16), pp. 1103-1107; Markel, E. J. et al. (2000) Macromolecules, Vol. 33(23), pp. 8541-8548; Moscardi, G. et al. (2001) Organometallics, Vol. 20(10), pp. 1918-1931; Zhu, S. et al. (2002) Macromolecules, Vol. 35(27), pp. 10062-10070 and (2003) Macromolecular Rapid Commun., Vol. 24(4), pp. 311-315; Coates, G. W. et al. (2005) Macromolecules, Vol. 38(15), pp. 6259-6268; Rose, J. M. et al. (2008) Macromolecules, Vol. 41(03), pp. 559-567; Janiak, C.WO 2002 / 002577, US 7,087,602, US 8,642,497, US 6,121,185, US 8,642,497, US 2015 / 0203602, USSN 16 / 394,166 filed April 25, 2019, CAS No. 909721-53-5, CAS No. 943521-08-2, and US 8,642,497.

[0023] There remains a need for uPAO materials having high concentrations of vinylidene groups (and / or combined vinylidene and tri-substituted vinylene groups), as well as processes for making such uPAO materials and catalyst systems specifically tailored for making such uPAO materials. SUMMARY

[0025] The present invention relates to a process for making a polyalpha-olefin PAO, comprising: contacting a feed comprising C6-C 32 an alpha-olefin with a catalyst system comprising an asymmetric metallocene compound, a hydrocarbon-soluble activator compound, and a non-aromatic hydrocarbon solvent; and obtaining an unsaturated PAO product comprising vinylidene groups, optionally tri-substituted vinylene groups, optionally di-substituted vinylene groups, and optionally vinyl groups.

[0026] DETAILED DESCRIPTION

[0027] DEFINITIONS

[0028] The term "alkyl" or "alkyl group" interchangeably refers to a saturated hydrocarbon group consisting of carbon and hydrogen atoms. The alkyl group can be linear, branched, cyclic, or a combination thereof. Whenever "linear, branched, or cyclic" is used, including combinations thereof. For example, methylcyclohexyl is a combination and is included in the definition of alkyl group.

[0029] The term "cycloalkyl" or "cycloalkyl group" interchangeably refers to a saturated hydrocarbon group in which the carbon atoms form one or more ring structures.

[0030] The term "alkenyl" or "alkenyl group" interchangeably refers to a linear unsaturated hydrocarbon group containing a C=C bond.

[0031] The term "cycloalkenyl" or "cycloalkenyl group" interchangeably refers to a cyclic hydrocarbon group containing a C=C bond in the ring.

[0032] The term "aryl" or "aryl group" interchangeably refers to a hydrocarbon group containing an aromatic ring structure.

[0033] The terms "aryloxy" and "aryloxide" mean an aryl group bonded to an oxygen atom, e.g., an aryl ether group / residue connected to an oxygen atom and can include where the aryl group is a C6-Ci8 20 Examples of suitable aryl groups can include phenyl, biphenyl, naphthyl, etc. Examples of suitable aryl groups can include phenyl, biphenyl, naphthyl, etc.

[0034] The terms "alkoxy" and "alkoxide" mean an alkyl group bonded to an oxygen atom, e.g., an alkyl ether group / residue connected to an oxygen atom and can include where the alkyl group is a Ci-Ci8 20 Examples of suitable aryl groups can include phenyl, biphenyl, naphthyl, etc. Examples of suitable aryl groups can include phenyl, biphenyl, naphthyl, etc.

[0035] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" refer interchangeably to a group consisting solely of hydrogen and carbon atoms. A hydrocarbyl radical can be saturated or unsaturated, linear, branched, cyclic, or aromatic.

[0036] Unless otherwise indicated (e.g., for substituted hydrocarbyl groups, etc.), a substituted group means a group in which at least one atom has been replaced by 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 by 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 by a different group. Preferably, a substituted group is one in which at least one hydrogen atom has been replaced by a heteroatom or a group containing a heteroatom, preferably by at least one functional group such as a halogen (CI, Br, I, F), NR*2, OR*, SR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, etc., or in which at least one heteroatom such as O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*2, GeR*2, SnR*2, PbR*2, etc., has been inserted into a hydrocarbyl group, where R* is independently hydrogen, a hydrocarbyl group, or a halogenated hydrocarbyl group.

[0037] As used herein, aromatic refers to a cyclic compound, ligand, or substituent ("ring") that contains a cyclically delocalized pi electron cloud above or below the plane of the "ring," and the pi cloud must contain a total of 4n + 2 pi electrons, where n is an integer. As used herein, the term "aromatic" also refers to pseudoaromatic heterocyclic rings, which are heterocyclic substituents that have similar properties and structure (nearly planar) to aromatic heterocyclic ligands, but are not aromatic by definition.

[0038] A substituted hydrocarbyl group is one in which at least one hydrogen atom has been replaced by a heteroatom or a group containing a heteroatom, preferably by at least one functional group such as halogen (CI, Br, I, F), NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, and the like, or in which at least one heteroatom such as halogen (CI, Br, I, F), O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR*2, GeR*2, SnR*2, PbR*2, and the like has been inserted into the hydrocarbyl group, where R* is independently hydrogen or a hydrocarbyl group.

[0039] In some embodiments, the hydrocarbyl groups are independently selected from the group consisting of isomers of methyl, ethyl, ethenyl, and 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, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and tricosyl. Also included are isomers having saturated, partially unsaturated, and aromatic cyclic structures, where the groups can additionally be subject to substitution of the types described above. Examples include phenyl, methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and the like. The listed alkyl, alkenyl, and alkynyl groups include all isomers (including cyclic isomers where appropriate), for example butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, and cyclobutyl (and similarly substituted cyclobutyl and cyclopropyl groups); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, and neopentyl (and similarly substituted cyclobutyl and cyclopropyl groups); butenyl includes 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl in both E and Z forms (and cyclobutenyl and cyclopropenyl). Cyclic compounds with substituents include all isomeric forms, for example methylphenyl will include o-methylphenyl, m-methylphenyl, and p-methylphenyl; dimethylphenyl will include 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl.

[0040] Silyl groups (also silyl, silyl groups, and silyl substituents) are defined as SiR*3, where R* is independently hydrogen, a hydrocarbyl or halocarbyl group, and two or more R* can join together to form a substituted or unsubstituted saturated, partially saturated, or aromatic cyclic or polycyclic ring structure. Silyl groups are bonded through a silicon atom.

[0041] Silylcarbyl radicals (also hydrocarbylsilyl groups, also silylcarbyl, silylcarbyl groups, or silylcarbyl substituents) are radicals in which one or more hydrocarbyl hydrogen atoms have been replaced by at least one group containing SiR*3, or in which at least one -Si(R*)2- has been inserted within a hydrocarbyl group, where R* is independently a hydrocarbyl or halocarbyl group, and two or more R* can join together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure. Silylcarbyl radicals can be bonded through a silicon or carbon atom.

[0042] Substituted silylcarbyl radicals are silylcarbyl radicals in which at least one hydrogen atom has been replaced by at least one functional group such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, GeR*3, SnR*3, PbR3, and the like, or in which at least one non-hydrogen atom or group such as --O--, --S--, --Se--, --Te--, --N(R*)--, =N--, --P(R*)--, =P--, --As(R*)--, =As--, --Sb(R*)--, =Sb--, --B(R*)--, =B--, --Ge(R*)2--, --Sn(R*)2--, --Pb(R*)2--, and the like has been inserted within the silylcarbyl radical, where R* is independently a hydrocarbyl or halocarbyl group, and two or more R* can join together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure.

[0043] Halocarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms have been replaced with at least one halogen (e.g., F, Cl, Br, I) or halogen-containing group (e.g., CF3).

[0044] A substituted haloalkyl group is one in which at least one haloalkyl hydrogen or halogen atom has been replaced by at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*, -SiR*3, -GeR*, -GeR*3, -SnR*, -SnR*3, -PbR*3, and the like, or in which at least one non-carbon atom or group such as -0-, -S-, -Se-, -Te-, -N(R*)-, =N-, -P(R*)-, =P-, -As(R*)-, =As-, -Sb(R*)-, =Sb-, -B(R*)-, =B-, -Si(R*)2-, -Ge(R*)2-, -Sn(R*)2-, -Pb(R*)2-, and the like has been inserted into the haloalkyl group, with the proviso that at least one halogen atom remains on the original haloalkyl group. Additionally, two or more R* can be joined together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure.

[0045] The term "substituted phenyl" or "substituted phenyl group" means a phenyl group in which one or more of the hydrogen groups have been replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing group, such as a halogen (e.g., Br, CI, F, or I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*, -SiR*3, -GeR*, -GeR*3, -SnR*, -SnR*3, -PbR*3, and the like, where each R* is independently a hydrocarbyl, halide, or haloalkyl group. Preferably, a "substituted phenyl" group is represented by the formula:

[0046]

[0047] wherein each of R 17 , R 18 , R 19 , R 20 , and R 21 is independently selected from hydrogen, C1-C 40 hydrocarbyl, or C1-C 40 substituted hydrocarbyl, a heteroatom such as a halogen, or a heteroatom-containing group (with the proviso that at least one of R 17 , R 18 , R 19 , R 20 , and R 21 is not H), or a combination thereof.

[0048] "Fluorophenyl" or "fluorophenyl group" is a phenyl group substituted with one, two, three, four, or five fluorine atoms.

[0049] The term "arylalkyl" means an aryl group in which the hydrogens have been replaced by an alkyl or substituted alkyl group. For example, 3,5'-di-tert-butyl-phenyl-indenyl is an indenyl substituted with an aralkyl group. When the aralkyl group is a substituent on another group, it is bonded to the group through the aryl.

[0050] The term "arylalkyl" means an aryl group in which the hydrogens have been replaced by an alkyl or substituted alkyl group. For example, 3,5'-di-tert-butyl-phenyl-indenyl is an indenyl substituted with an aralkyl group. When the aralkyl group is a substituent on another group, it is bonded to the group through the aryl.

[0051] Unless otherwise indicated, reference to an alkyl, alkenyl, alkoxy, or aryl group (e.g., butyl) without any modifier, expressly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and t-butyl) unless otherwise specified.

[0052] The term "ring atom" means an atom that is part of a cyclic ring structure. Thus, a benzyl group has six ring atoms and tetrahydrofuran has 5 ring atoms.

[0053] Unless otherwise indicated, reference to an alkyl, alkenyl, alkoxy, or aryl group (e.g., butyl) without any modifier, expressly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and t-butyl) unless otherwise specified.

[0054] The term "Cn" group or compound means a group or compound that contains carbon atoms whose total number is n. Thus, a "Cm-Cn" group or compound means a group or compound that contains carbon atoms whose total number is in the range of m to n. Thus, a C1-C50 group or compound is a group or compound that contains carbon atoms whose total number is in the range of 1 to 50. 50 Alkyl groups mean alkyl groups containing carbon atoms whose total number is in the range of 1-50.

[0055] The term "olefin" or "alkene" refers to a saturated or unsaturated aliphatic hydrocarbon compound having a hydrocarbon chain containing at least one carbon-to-carbon double bond in its structure. The olefin can be linear, branched, or cyclic, or a combination thereof. For the purposes of the present specification and the accompanying claims, 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. For example, when a copolymer is recited as having a "ethylene" content of 35 to 55 weight percent, it is understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and that the derived units are present at 35 to 55 weight percent based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having identical monomer units. A "copolymer" is a polymer having two or more different monomer units from each other. A "terpolymer" is a polymer having three monomer units different from each other. "Different" as used to refer to monomer units means that the monomer units differ from each other by at least one atom or are isomerically different. Thus, "olefin" is intended to include all structural isomer forms of the olefin, unless it is specified to mean a single isomer or the context otherwise clearly indicates. An oligomer is a polymer having a low molecular weight, for example, Mn of 21,000 g / mol or less (preferably 10,000 g / mol or less), and / or a low number of monomer units, for example, 100 monomer units or less (preferably 75 monomer units or less).

[0056] The term "alpha-olefin" refers to an olefin having a terminal carbon-to-carbon double bond in its structure (R'HC=CH2, where R ' may be independently hydrogen or any hydrocarbyl group. Non-limiting examples of alpha-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 vinyl norbornane.

[0057] Cycloalkenes contain carbon-to-carbon double bonds within the ring structure. Non-limiting examples of cycloalkenes and dienes include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene, 2-methylcyclopentene, 4-methylcyclopentene, norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, vinylcyclohexene, and 5-vinyl-2-norbornene

[0058] The term "vinyl" means an alkene represented by the formula:

[0059]

[0060] where R is a hydrocarbyl group, preferably a saturated hydrocarbyl group such as an alkyl group.

[0061] The term "vinylidene" means an alkene represented by the formula:

[0062]

[0063] where R 1 and R 2 each independently is a hydrocarbyl group, preferably a saturated hydrocarbyl group such as an alkyl group. Vinylidene is a 1,1-disubstituted vinylene group.

[0064] The term "disubstituted vinylene" means:

[0065] (i) an alkene represented by the formula:

[0066] or

[0067] (ii) an alkene represented by the formula:

[0068] or

[0069] (iii) a mixture of (i) and (ii) in any ratio, where R 1 and R 2 each occurrence is the same or different, each independently is a hydrocarbyl group, preferably a saturated hydrocarbyl group such as an alkyl group. Disubstituted vinylene represents only 1,2-disubstituted vinylene groups and does not include vinylidene or 1,1-disubstituted vinylene. The term "vinylene" as used herein is only a substitute term for "disubstituted vinylene" and does not serve as a general category for the various vinylene species.

[0070] The term "trisubstituted vinylene" means an alkene represented by the formula:

[0071]

[0072] where R 1, R 2 and R 3 each independently is a hydrocarbyl group, preferably a saturated hydrocarbyl group such as an alkyl group, or alternatively R 1 and R 2 may together form a non-aromatic ring structure, wherein R 3 is a pendant hydrocarbyl group.

[0073] As used herein, "polyalphaolefin(s)" (PAO(s)) is a polymer, particularly an oligomer, of alpha-olefin monomer(s). A PAO is a polymer (typically an oligomer) molecule resulting from a polymerization reaction of alpha-olefin monomer molecules in the presence of a catalyst system, which is optionally further partially or completely hydrogenated to remove residual carbon-carbon double bonds therein, or optionally further functionalized by reaction with some or all of the residual carbon-carbon bonds therein. Thus, a PAO can be a dimer, a trimer, a tetramer, or any other oligomer or polymer comprising two or more structural units derived from alpha-olefin monomer(s). A PAO molecule can be highly stereoregular, such that when measured by13C NMR, the bulk material can exhibit isotactic or syndiotactic regularity. A PAO molecule can be highly stereorandom, such that when measured by13C NMR, the bulk material can be substantially atactic. Typically, stereoregularity is only relevant to higher viscosity (higher molecular weight) PAO molecules, wherein at least triad distributions can be measured by13C NMR. 13 C NMR. A PAO molecule can be highly stereorandom, such that when measured by13C NMR, the bulk material can be substantially atactic. Typically, stereoregularity is only relevant to higher viscosity (higher molecular weight) PAO molecules, wherein at least triad distributions can be measured by13C NMR. 13 C NMR. A PAO molecule can be highly stereorandom, such that when measured by13C NMR, the bulk material can be substantially atactic. Typically, stereoregularity is only relevant to higher viscosity (higher molecular weight) PAO molecules, wherein at least triad distributions can be measured by13C NMR. 13 C NMR. A PAO molecule can be highly stereorandom, such that when measured by13C NMR, the bulk material can be substantially atactic. Typically, stereoregularity is only relevant to higher viscosity (higher molecular weight) PAO molecules, wherein at least triad distributions can be measured by13C NMR.

[0074] PAO materials made by using metallocene-based catalyst systems are commonly referred to as metallocene-PAOs (mPAOs), and PAO materials made by using traditional, non-metallocene-based catalysts (e.g., Lewis acids, supported chromium oxide, etc.) are commonly referred to as conventional PAOs (cPAOs).

[0075] The term "carbon backbone" refers to the longest straight carbon chain in a molecule or group of the compound in question. "Branches" or "pendant groups" refer interchangeably to any non-hydrogen group attached to the carbon backbone other than those attached to carbon atoms at the very end of the carbon backbone. As used herein, the "length" of a pendant group is defined as the total number of carbon atoms in the longest carbon chain in the pendant group, counting from the first carbon atom attached to the carbon backbone and ending with the last carbon atom, without regard to any substituents or pendant groups on the chain. In some embodiments, the pendant group does not contain a substituent comprising more than 2 carbon atoms (or more than 1 carbon atom) or does not contain any substituents. A pendant group can contain a cyclic group or a portion of a cyclic group in the longest carbon chain, in which case half of the carbon atoms in the cyclic group are counted toward the length of the pendant group. Thus, by way of example, a linear C8pendant group has a length of 8; each of the pendant groups PG-1 (cyclohexylmethyl) and PG-2 (phenylmethyl) has a length of 4; and each of the pendant groups PG-3 (o-heptylphenylmethyl) and PG-4 (p-heptylphenylmethyl) has a length of 11. In the case of a PAO molecule containing multiple pendant groups, the arithmetic average of the lengths of all such pendant groups is calculated as the average length of all pendant groups in the PAO molecule.

[0076]

[0077] For nomenclature purposes, the following numbering scheme is used for cyclopentadienyl, indenyl, tetrahydro-s-indacenyl, tetrahydro-as-indacenyl, benzo[f]indenyl, benzo[e]indenyl ligands.

[0078]

[0079]

[0080] In the present invention, any metallocene compound can have one or more optical isomers. All metallocene compounds specified herein by name or structure shall include all possible optical isomers thereof and mixtures of any such optical isomers. For example, the metallocene compound Me2Si(Me4Cp)(3-PrInd)ZrMe2 shall include the following two optical isomers and mixtures thereof, even when only one structure is given when described:

[0081]

[0082] "Metallocene" catalyst compounds are transition metal catalyst compounds having one, two, or three, usually one or two, substituted or unsubstituted cyclopentadienyl ligands bound to the transition metal, usually metallocene catalysts are organometallic compounds containing at least one π-bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety). Substituted or unsubstituted cyclopentadienyl ligands include substituted or unsubstituted indenyl, fluorenyl, tetrahydro-s-indacenyl, tetrahydro-as-indacenyl, benzo[f]indenyl, benzo[e]indenyl, tetrahydrocyclopenta[b]naphthalene, tetrahydrocyclopenta[a]naphthalene, and the like.

[0083] Asymmetric metallocene compounds are metallocene compounds having two π-bound cyclopentadienyl moieties that are different in ring type, for example having one monocyclic arenyl ligand and one polycyclic arenyl ligand. For example, (cyclopentadienyl)(indenyl)zirconium dichloride would be considered asymmetric because it has one monocyclic arenyl ligand and one polycyclic arenyl ligand, while bis(indenyl)zirconium dichloride would be considered symmetric because it has two polycyclic arenyl ligands.

[0084] As used herein, the term "monocyclic arenyl ligand" is used herein to mean a substituted or unsubstituted, monoanionic C5-Ci2hydrocarbyl ring structure containing one monocyclic hydrocarbyl ring structure (also referred to as a cyclopentadienyl ring). 100 hydrocarbyl ligand containing an aromatic five-membered hydrocarbyl ring structure (also referred to as a cyclopentadienyl ring) fused to a partially unsaturated, or aromatic, hydrocarbyl ring structure which can be fused to additional saturated, partially unsaturated, or aromatic, hydrocarbyl rings.

[0085] As used herein, the term "polycyclic arenyl ligand" is used herein to mean a substituted or unsubstituted, monoanionic C8-Ci2hydrocarbyl ring structure 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 can be fused to additional saturated, partially unsaturated, or aromatic, hydrocarbyl rings. 103 hydrocarbyl ligand containing an aromatic five-membered hydrocarbyl ring structure (also referred to as a cyclopentadienyl ring) fused to a partially unsaturated, or aromatic, hydrocarbyl ring structure which can be fused to additional saturated, partially unsaturated, or aromatic, hydrocarbyl rings.

[0086] Monocyclic arenyl ligands include substituted or unsubstituted cyclopentadienyl. Polycyclic arenyl ligands include substituted or unsubstituted, partially unsaturated or aromatic indenyl, fluorenyl, benzo[f]indenyl, benzo[e]indenyl, 5,6,7,8-tetrahydro-lH-cyclopenta[b]naphthalenyl, 6,7,8,9-tetrahydro-lH-cyclopenta[a]naphthalenyl, 1,5,6,7-tetrahydro-s-indacenyl, 3,6,7,8-tetrahydro-as-indacenyl, and the like.

[0087] Non-limiting examples of polycyclic arene ligands (also referred to as monoanionic ligands) include indenyl, 4,5-dihydroindenyl, 4,7-dihydroindenyl, 4,5,6,7- tetrahydroindenyl, benzo[f]indenyl, benzo[e]indenyl, 5,6,7,8-tetrahydro-lH- cyclopenta[b]naphthyl, 6,7,8,9-tetrahydro-lH-cyclopenta[a]naphthyl, 1,5,6,7- tetrahydro-s-indacenyl, 3,6,7,8-tetrahydro-as-indacenyl, 5,6-trimethyleneindenyl, 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, 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, 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, (6E,8Z,10E,12Z,14E)-cyclododeca[e]indenyl.

[0088] 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-lH-cyclopenta[b]naphthyl, 6,7,8,9-tetrahydro-lH- cyclopenta[a]naphthyl, 1,5,6,7-tetrahydro-s-indacenyl, 3,6,7,8-tetrahydro-as-indacenyl.

[0089] The term "substantially all" with respect to PAO molecules means at least 90 mol% (e.g., at least 95 mol%, at least 98 mol%, at least 99 mol%, or even 100 mol%) unless otherwise specified.

[0090] The term "substantially free of" with respect to a particular component means that the concentration of that component in the relevant composition is no greater than 10 mol% (e.g., no greater than 5 mol%, no greater than 3 mol%, no greater than 1 mol%, or about 0%, within the range of the relevant measurement method), based on the total amount of the relevant composition, unless otherwise specified. Preferably, "substantially free of" means no greater than 10 mol% (e.g., no greater than 5 mol%, no greater than 3 mol%, no greater than 1 mol%, or about 0%, based on the total amount of the relevant composition.

[0091] The terms "catalyst" and "catalyst compound" are defined to mean a compound capable of initiating catalysis and / or facilitating a chemical reaction. In the description herein, a catalyst can be described as a catalyst precursor, a procatalyst compound, or a transition metal compound, and these terms can be used interchangeably. A catalyst compound is often referred to as a procatalyst or catalyst precursor when the catalyst compound is combined with an activator to initiate catalysis. A "catalyst system" is a combination of at least one catalyst compound, at least one activator, and optionally a co-activator, wherein the system can polymerize monomers to form a polymer (e.g., an oligomer as described herein).

[0092] A scavenger is a compound that is typically added to facilitate oligomerization / polymerization by scavenging impurities. Some scavengers can also act as activators and can be referred to as co-activators. A co-activator (which is not a scavenger) can be used in conjunction with an activator to form an active catalyst. In some embodiments, a co-activator can be premixed with a catalyst compound to form an alkylated catalyst compound.

[0093] As used herein, a "lubricant" refers to a substance that can be introduced between two or more moving surfaces and reduce the level of friction between two adjacent surfaces moving relative to each other. A "base stock" of a lubricant is a material that is typically fluid at the operating temperature of the lubricant, which is used to formulate a lubricant by mixing with other components. Non-limiting examples of base stocks suitable for use in lubricants include API Group I, Group II, Group III, Group IV, Group V, and Group VI base stocks. Fluids derived from a Fischer-Tropsch process or a gas-to-liquid ("GTL") process are examples of synthetic base stocks that can be used to make modern lubricants. GTL base stocks and methods for making them can be found, for example, in PCT Publication No. WO 2005 / 121280 and U.S. Patent Nos. 7,344,631, 6,846,778, 7,241,375, and 7,053,254.

[0094] In this invention, unless otherwise specified, all percentages of side groups, terminal carbon chains and side chain groups are in molar terms.

[0095] Mole percentage is expressed as “mole%”, and weight percentage is expressed as “weight%”.

[0096] In this invention, all molecular weight data are expressed in g / mol (also written as g·mol). -1 (in units of )

[0097] Unless otherwise specified, use proton NMR ( 1 The number-average molecular weight (Mn) of the polymer materials (including functionalized, hydrogenated, and non-hydrogenated PAO materials) prepared in this paper was determined by 1H-NMR analysis. Additionally, the unsaturated PAO products... 1 H-NMR analysis can provide a quantitative decomposition of the olefinic structure type (i.e., vinyl, disubstituted vinylene, trisubstituted vinylene, and vinylidene). In this invention, by using as described in the experimental section... 1 H-NMR determination of the composition of an olefin mixture containing terminal olefins (vinyl and vinylidene groups) and internal olefins (disubstituted vinylidene and trisubstituted vinylidene groups).

[0098] As used herein, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, and Mz is the z-average molecular weight. wt% is the weight percentage, and mol% is the mole percentage. Molecular weight distribution (MWD), also known as the polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol (g mol) -1 ).

[0099] The following abbreviations may be used throughout the instruction manual: Cp for cyclopentadiene or cyclopentadienyl, Ind for indene or indyl, Flu for fluorene or fluorenyl, Me for methyl, Et for ethyl, Pr for propyl, iPr for isopropyl, n-Pr for n-propyl, cPr for cyclopropyl, Bu for butyl, nBu for n-propyl, iBu for isobutyl, sBu for sec-butyl, tBu for tert-butyl, MeCy for methylcyclohexene, and Cy for cyclohexyl, Ph for phenyl, p-tBu for p-tert-butyl, p-Me for p-methyl, and o-biphenyl is a structure... , Cbz is carbazole, Cy is cyclohexyl, Oct is octyl, Ar* is 2,6-diisopropylphenyl, Bz or Bn are interchangeable with benzyl (i.e., CH2Ph), TMS is trimethylsilyl, TIBAL or TiBAl is triisobutylaluminum, TNOAL or TNOA or TnOAl is tri-n-octylaluminum, MAO is methylaluminoxane, THF or thf is tetrahydrofuran, tol or Tol is toluene, dme is 1,2-dimethoxyethane, EtOAc is ethyl acetate, and RT is room temperature (and unless otherwise indicated is 23 °C). The term "continuous" means a system that operates for a period of time without interruption or stoppage, e.g., where reactants are continuously fed to a reaction zone and products are continuously or periodically withdrawn without stopping the reaction in the reaction zone. For example, a continuous process to make a polymer would be one where reactants are continuously introduced into one or more reactors and the polymer product is continuously removed.

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

[0101] Bulk polymerization means a polymerization process in which the polymerized monomer and / or comonomer is used as a solvent or diluent, with little or no use of an inert solvent or diluent. A small amount of inert solvent can be used as a carrier for the catalyst and scavenger. A bulk polymerization system contains less than about 25 wt% of an inert solvent or diluent, e.g., less than about 10 wt%, e.g., less than about 1 wt%, e.g., 0 wt%.

[0102] Description

[0103] The present invention relates to a process for making a polyalphaolefin PAO, comprising: polymerizing in a polymerization reactor under polymerization conditions a C6-C 32The feed of alpha-olefins is contacted with a catalyst system comprising an asymmetric metallocene compound and an activator soluble in non-aromatic hydrocarbons to obtain a PAO comprising ethylene groups, tri-substituted vinylidene groups, optionally di-substituted vinylidene groups, and optionally vinyl groups; wherein the polymerization reaction preferably exhibits a selectivity for greater than or equal to about 80 mol% ethylene groups, preferably 90 mol% ethylene groups, preferably 95 mol% ethylene groups, more preferably 96.5 mol% ethylene groups, based on the total moles of ethylene groups, ethylene groups, di-substituted vinylidene groups, and tri-substituted vinylidene groups in the unsaturated PAO product.

[0104] In some embodiments of the process, the polymerization reaction exhibits a selectivity for the combination of greater than or equal to about 90 mol% ethylene groups, 0.5 mol% to 6 mol% tri-substituted vinylidene groups, less than or equal to about 2.5 mol% di-substituted vinylidene groups, and less than or equal to about 1.5 mol% vinyl groups, based on the total moles of ethylene groups, ethylene groups, di-substituted vinylidene groups, and tri-substituted vinylidene groups in the unsaturated PAO product.

[0105] In particular embodiments of the process, the polymerization reaction exhibits a selectivity for the combination of equal to or greater than 95.0 mol% ethylene groups, preferably equal to or greater than 96 mol%, preferably equal to or greater than 97 mol%, less than 2.5 mol% tri-substituted vinylidene groups, 1.0 mol% or less di-substituted vinylidene groups, and 1.5 mol% or less vinyl groups, based on the total moles of ethylene groups, ethylene groups, di-substituted vinylidene groups, and tri-substituted vinylidene groups in the unsaturated PAO product. In particular embodiments of the process, the polymerization reaction exhibits a selectivity for the combination of greater than 95.0 mol% ethylene groups and tri-substituted vinylidene groups, preferably greater than 98 mol%, and the combination of less than 5.0 mol%, preferably less than 2.0 mol% di-substituted vinylidene groups and vinyl groups, based on the total moles of ethylene groups, ethylene groups, di-substituted vinylidene groups, and tri-substituted vinylidene groups in the unsaturated PAO product.

[0106] Preferably, the polymerization reaction exhibits a selectivity for greater than or equal to about 80 mol% ethylene groups (alternatively greater than or equal to 85 mol% ethylene groups, preferably greater than or equal to 90 mol% ethylene groups), based on the total moles of ethylene groups, ethylene groups, di-substituted vinylidene groups, and tri-substituted vinylidene groups in the unsaturated PAO product.

[0107] Preferably, the conversion is about 10% or greater and the polymerization reaction exhibits selectivity to a combination of greater than or equal to about 80 mol% vinylidene (alternatively greater than or equal to 85 mol% vinylidene, preferably greater than or equal to 90 mol% vinylidene) based on the total moles of vinyl, vinylidene, disubstituted vinylene, and trisubstituted vinylene in the unsaturated PAO product.

[0108] Preferably, the polymerization reaction exhibits selectivity to a combination of greater than or equal to about 96.5 mol% vinylidene, 0.5 mol% to 3.5 mol% trisubstituted vinylene, less than or equal to about 1.5 mol% disubstituted vinylene, and less than or equal to about 1.5 mol% vinyl based on the total moles of vinyl, vinylidene, disubstituted vinylene, and trisubstituted vinylene in the unsaturated PAO product.

[0109] Preferably, the polymerization reaction exhibits selectivity to a combination of greater than or equal to about 96.5 mol% vinylidene, 0.5 mol% to 3.5 mol% trisubstituted vinylene, less than or equal to about 1.5 mol% disubstituted vinylene, and less than or equal to about 1.5 mol% vinyl based on the total moles of vinyl, vinylidene, disubstituted vinylene, and trisubstituted vinylene in the unsaturated PAO product.

[0110] Preferably, the polymerization reaction exhibits selectivity to a combination of greater than or equal to about 96.5 mol% vinylidene, 0.5 mol% to 3.5 mol% trisubstituted vinylene, less than or equal to about 1.5 mol% disubstituted vinylene, and less than or equal to about 1.5 mol% vinyl based on the total moles of vinyl, vinylidene, disubstituted vinylene, and trisubstituted vinylene in the unsaturated PAO product.

[0111] In some embodiments, when the only solvent used is the monomer itself, e.g., an alpha-olefin monomer, the conversion is about 20% or greater and the polymerization reaction exhibits selectivity to greater than or equal to about 80 mol% vinylidene (preferably about 85% or greater, more preferably about 90% or greater, most preferably about 95% or greater) based on the total moles of vinyl, vinylidene, disubstituted vinylene, and trisubstituted vinylene in the unsaturated PAO product.

[0112] In some embodiments of the present application, when the polymerization temperature is greater than 100°C, preferably greater than 110°C, the conversion is 50% or greater and the polymerization reaction exhibits selectivity to greater than or equal to about 80 mol% vinylidene (preferably about 85% or greater, more preferably about 90% or greater, most preferably about 95% or greater) based on the total moles of vinyl, vinylidene, disubstituted vinylene, and trisubstituted vinylene in the unsaturated PAO product.

[0113] The number average molecular weight (Mn) of the PAO is highly dependent on the molecular weight of the alpha-olefin or mixture of alpha-olefins used. Because of this, in some embodiments, the degree of polymerization (DP) is more suitable to represent the preferred range of PAO molecular weight. DP is defined as the Mn of the PAO divided by the molecular weight of the alpha-olefin used, where the PAO Mn is measured by 1 H NMR. For the purposes of the present invention, the alpha-olefin molecular weight is calculated as the number of carbons in the alpha-olefin times 14 (the molecular weight of a CH2 unit). For example, for decene (which is a C 10 alpha-olefin), the molecular weight is 140 g / mole. When a mixture of alpha-olefins is used, the DP is calculated by dividing the Mn of the PAO by the average molecular weight of the alpha-olefins used, where the PAO Mn is measured by 1 H NMR, and the average molecular weight of the alpha-olefins is calculated by the sum of the molecular weight of each alpha-olefin times the mole fraction of the alpha-olefin used in the polymerization. For example, if 50% octene and 50% tetradecene are used in the polymerization, the average molecular weight of the alpha-olefins used would be (0.5 x 112 g / mole) + (0.5 x 196 g / mole), which equals 154 g / mole. In some embodiments of the invention, the PAO product has a degree of polymerization of 10-2, preferably 7-2, more preferably 4-2. In some embodiments of the invention, the DP is 2, for example when a dimer product is preferred. In other embodiments of the invention, the DP is 3, when a trimer product is preferred.

[0114] In some embodiments of the process, the polymerization reaction results in an unsaturated PAO product having a number average molecular weight (Mn) of 2500 g / mole or less, preferably 1500 g / mole or less, preferably 1000 g / mole or less, preferably from about 150 to about 1000 g / mole, preferably from about 200 to about 800 g / mole, as measured by 1 H NMR.

[0115] In particular embodiments of the process, the polymerization conditions include a reaction temperature of 40°C to 180°C; an average activity level of at least 1500 g / mole-hr; the polymerization reaction mixture exhibits an oligomer yield of at least 10%; or a combination thereof.

[0116] In some embodiments, the process further comprises: a) contacting the unsaturated PAO product with hydrogen to thereby convert at least a portion of the unsaturated PAO product to a hydrogenated PAO product; or b) contacting the unsaturated PAO product with a chemical reagent to thereby convert at least a portion of the unsaturated PAO product to a functionalized PAO product; or a combination thereof.

[0117] In some embodiments, the method further comprises: a) contacting the unsaturated PAO product with hydrogen thereby converting at least a portion of the unsaturated PAO product to a partially hydrogenated PAO product and contacting the unsaturated PAO product with a chemical reagent thereby converting at least a portion of the unsaturated PAO product to a functionalized PAO product; or a combination thereof.

[0118] In some embodiments, the method further comprises contacting the unsaturated PAO product with a chemical reagent thereby converting at least a portion of the unsaturated PAO product to a functionalized PAO product.

[0119] In particular embodiments of the method, the feed comprises C6-C 24 C2-C5 alpha-olefins; or a combination thereof are collectively present in the alpha-olefin feed in no more than 25 mol% based on the total moles of alpha-olefins supplied to the polymerization reactor, preferably wherein the alpha-olefin feed is substantially free of ethylene, propylene, C4alpha-olefins, and C5alpha-olefins; or a combination thereof. Preferably, the alpha-olefin feed is substantially free of (preferably absent, 0 mol%) propylene, C4alpha-olefins, and C5alpha-olefins, or a combination thereof. Optionally, the alpha-olefin feed comprises less than 25 mol%, preferably less than 15 mol%, preferably less than 5 mol% of propylene, C4alpha-olefins, and C5alpha-olefins, or a combination thereof.

[0120] Optionally, the alpha-olefin feed comprises less than 25 mol%, preferably less than 0.1 to 15 mol%, preferably 1 to 5 mol% of ethylene.

[0121] Optionally, the alpha-olefin feed comprises octene. Optionally, the alpha-olefin feed comprises decene. Optionally, the alpha-olefin feed comprises octene, decene, and dodecene. Optionally, the alpha-olefin feed comprises octene and dodecene. Optionally, the alpha-olefin feed comprises a single alpha-olefin monomer or a combination of two or more alpha-olefin monomers. Optionally, the alpha-olefin feed comprises a single alpha-olefin monomer selected from the group consisting of hexene, heptene, octene, nonene, decene, dodecene, tetradecene, and hexadecene. Optionally, the alpha-olefin feed comprises two or more alpha-olefin monomers selected from the group consisting of hexene, heptene, octene, nonene, decene, dodecene, tetradecene, and hexadecene.

[0122] In embodiments of the invention, the unsaturated polyalpha-olefin product comprises greater than or equal to about 80 mol% vinylidene, preferably 90 mol% vinylidene, more preferably 96.5 mol% vinylidene, based on the total moles of vinyl, vinylidene, disubstituted vinylene, and trisubstituted vinylene contained therein. In particular embodiments, the unsaturated polyalpha-olefin product comprises 96.5 mol% to 99.9 mol% vinylidene, 0.1 mol% to 3.5 mol% trisubstituted vinylene, 3.0 mol% or less disubstituted vinylene, 3.0 mol% or less vinyl groups, based on the total moles of vinylidene, trisubstituted vinylene, disubstituted vinylene, and vinyl groups contained therein; and has a number average molecular weight (Mn) of 1500 g / mol or less as measured by H NMR. 1 HNMR.

[0123] In particular embodiments, the unsaturated polyalpha-olefin product comprises 96.5 mol% to 99.9 mol% vinylidene, 0.1 mol% to 3.5 mol% trisubstituted vinylene, disubstituted vinylene, and vinyl groups, based on the total moles of vinylidene, trisubstituted vinylene, disubstituted vinylene, and vinyl groups contained therein; and has a number average molecular weight (Mn) of 1500 g / mol or less as measured by H NMR. 1 HNMR.

[0124] In some embodiments, the unsaturated polyalpha-olefin product comprises less than or equal to about 1.0 mol% disubstituted vinylene, less than or equal to about 1.0 mol% vinyl groups, and has a number average molecular weight (Mn) of 1000 g / mol or less as measured by H NMR. 1 HNMR.

[0125] In particular embodiments, the unsaturated polyalpha-olefin product comprises 98 mol% to 99.5 mol% of the combination of vinylidene and trisubstituted vinylene; and 0.5 mol% to 2 mol% of the combination of disubstituted vinylene and vinyl groups, and has a number average molecular weight (Mn) of 800 g / mol or less as measured by H NMR. 1 HNMR.

[0126] In embodiments of the invention, the catalyst compounds useful herein have a selectivity for greater than or equal to about 80 mol% vinylidene, preferably 90 mol% vinylidene, more preferably 96.5 mol% vinylidene, based on the total moles of vinyl, vinylidene, disubstituted vinylene, and trisubstituted vinylene in the unsaturated PAO product.

[0127] In certain embodiments, the catalyst compound comprises a polymerization selectivity suitable for forming an unsaturated PAO product comprising 96.5 mol% to 99.9 mol% vinylidene groups, 0.1 mol% to 3.5 mol% tri-substituted vinylene groups, 2.0 mol% or less di-substituted vinylene groups, 2.0 mol% or less vinyl groups, based on the total moles of vinyl, vinylidene, di-substituted vinylene, and tri-substituted vinylene groups in the unsaturated PAO product; and a number average molecular weight (Mn) of 1500 g / mol or less as measured by H NMR. 1 H NMR measured number average molecular weight (Mn) of 1500 g / mol or less.

[0128] I. Unsaturated PAO Product

[0129] A PAO is a polymer, typically an oligomer molecule, produced from the polymerization reaction of alpha-olefin monomer molecules in the presence of a catalyst system. The unsaturated polyalpha-olefin (uPAO) molecules in the material of the present invention contain a C=C bond therein. Each uPAO molecule has a carbon chain of maximum number of carbon atoms, which is designated as the carbon backbone of the molecule. Any non-hydrogen group attached to the carbon backbone other than that attached to the carbon atom at the very end of the carbon backbone is defined as a side group. The number of carbon atoms in the longest carbon chain in each side group defines the length of the side group. The backbone typically includes carbon atoms derived from the C=C bond in the monomer molecules that participated in the polymerization reaction, and additional carbon atoms from the molecules and / or monomer molecules in the catalyst system that form the two ends of the backbone. Typically, an unsaturated polyalpha-olefin (uPAO) molecule can be represented by the following formula (F-1):

[0130]

[0131] wherein R 1 , R 2a , R 2b , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different at each occurrence and independently represent hydrogen or a substituted or unsubstituted hydrocarbyl (preferably alkyl) group, and n is 0 or a non-negative integer corresponding to the degree of polymerization, e.g., 1 or greater, e.g., 1, 2, 3, 4, or 5. In the case where R 1 , R 2a and R 2b are all hydrogen, (F-1) represents a vinyl uPAO; in the case where R 1 is not hydrogen and R 2a and R 2b are both hydrogen, (F-1) represents a vinylidene uPAO; in the case where R 1 is hydrogen and R 2a and R 2b(F-1) represents a disubstituted vinylidene uPAO, in the case where only one of R 1 is not hydrogen and R 2a is not hydrogen. 2b (F-1) represents a trisubstituted vinylidene uPAO, in the case where only one of R

[0132] Preferably, R 1 is not hydrogen, R 2a is not hydrogen, and R 2b is hydrogen and n is 0.

[0133] Preferably, the unsaturated PAO product is represented by the following formula (F-1):

[0134]

[0135] wherein R 1 , R 3 , R 4 , R 5 , R 6 , and R 7 are the same or different at each occurrence and each independently represents hydrogen or a substituted or unsubstituted hydrocarbyl group, R 2a and R 2b are hydrogen, n is 0, wherein R 1 is not hydrogen.

[0136] When n = 0, (F-1) represents a uPAO dimer resulting from the reaction of two monomer molecules after a single addition reaction between two C=C bonds.

[0137] Thus, when n = 1, (F-1) represents a trimer resulting from the reaction of three monomer molecules after two steps of linear addition reactions between two C=C bonds.

[0138] Assuming that the carbon chain starting with R 1 and ending with R 7 has the largest number of carbon atoms among all the straight carbon chains present in (F-1), the carbon chain starting with R 1 and ending with R 7 has the largest number of carbon atoms among all the straight carbon chains present in (F-1), the carbon chain starting with R 1 and ending with R 7 forms the carbon backbone of the unsaturated PAO product molecule (F-1). R 2 , R 3 , R 4 , and R 5 , each of which and R 6 , which can be a substituted or unsubstituted hydrocarbyl (preferably alkyl) group, are pendant groups (if not hydrogen).

[0139] If only alpha-olefin monomers are used in the polymerization process, and isomerization of monomers and oligomers never occurs in the reaction system during the polymerization process, R1 2a 2b 3 4 5 6 7 1 2a 2b 6 7 1 2a 2b 3 4 5 6 7 about one-half, and often less than one-half, of the R groups will be hydrocarbyl groups introduced from the a-olefin monomer molecules. In a specific example of such a case, assuming R 2a 2b 3 5 6 1 4 7 in which the longest carbon chain contained therein has 8 carbon atoms, and n = 8, then the carbon backbone of the (F-l) PAO molecule will contain 35 carbon atoms, and the average pendant group length of the pendant groups (initially = CR 2a 2b 4 such a uPAO molecule, which can be made by polymerizing 1-decene using certain metallocene catalyst systems described in more detail below, for example, can be represented by the following formula (F-2):

[0140]

[0141] In such a molecule, the longest 5%, 10%, 20%, 40%, 50%, and 100% of the pendant groups have average pendant group lengths of Lpg(5%) = 8, Lpg(10%) = 8, Lpg(20%) = 8, Lpg(50%) = 8, and Lpg(100%) = 7.22, respectively.

[0142] However, depending on the polymerization catalyst system used, varying degrees of isomerization of monomers and / or oligomers can occur in the reaction system during the polymerization process, resulting in varying degrees of substitution on the carbon backbone. In a specific example of such a case, assuming R​​​​​​​​​​​​​​​​​​​​​​​​​​​​​2a and R 2b both are hydrogen, R 3 and all R 5 are methyl, R 6 is hydrogen, R 1 has 8 carbon atoms in the longest carbon chain contained therein, all R 4 and R 7 has 7 carbon atoms in the longest carbon chain contained therein, and n = 8, then the carbon backbone of the (F-1) uPAO molecule will contain 34 carbon atoms, and the average side group length of the R 2a R 2b groups, all R 4 and R 5 ) will be ~ 3.7 (i.e. (1 + 1 + 7*8 + 8*1) / 18). Such a uPAO molecule can be represented by the following formula (F-3), which can be prepared by polymerizing 1-decene with a given isomerization level and pattern, or by polymerizing a combination of 1-decene and 2-decene, using certain non-metallocene catalyst systems described in more detail below:

[0143]

[0144] In this molecule, the longest 5%, 10%, 20%, 40%, 50%, and 100% of the side groups have an average side group length Lpg(5%) of 7, Lpg(10%) of 7, Lpg(20%) of 7, Lpg(50%) of 6.3, and Lpg(100%) of 3.7, respectively.

[0145] The skilled person, especially with knowledge of the molecular structure of the monomer(s) used in the polymerization step to make the unsaturated PAO product, the process conditions (catalyst used, reaction conditions, etc.), and especially the polymerization reaction mechanism, can make a rough estimate of the molecular structure of the uPAO molecule, and thus the side groups attached to the carbon backbone, and thus the approximate values of Lpg(5%), Lpg(10%), Lpg(20%), Lpg(50%), and Lpg(100%), respectively.

[0146] The skilled person can determine the Lpg(5%), Lpg(10%), Lpg(20%), Lpg(50%), and Lpg(100%) values for a given unsaturated PAO product by using separation and characterization techniques available to polymer chemists. For example, a gas chromatography / mass spectrometry machine equipped with a boiling point column separator can be used to separate and identify individual chemical species and fractions; and standard characterization methods such as NMR, IR, and UV spectroscopy can be used to further confirm the structures.

[0147] In some embodiments of the application, the uPAO is represented by formula (F-4):

[0148]

[0149] where C is a hydrocarbon chain having a length of m'-2, each m' is independently an integer from 4-16 and is the number of carbons of the monomer(s) used in polymerization, for example m' is 8 for octene, 10 for decene and 12 for dodecene, and n' is an integer from 0-10, preferably 0-2, and more preferably 0-1, and most preferably 0. When n' is 0, the product is a dimer. When n' is 1, the product is a trimer.

[0150] The unsaturated PAO product of the present application can be a homopolymer made from a single alpha-olefin monomer or a copolymer made from a combination of two or more alpha-olefin monomers. In some embodiments, the alpha-olefin monomer(s) can include (consist essentially of, or be) 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or combinations thereof, for example 1-octene, 1-decene, and 1-dodecene. Preferably, the PAO is a homopolymer of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, or 1-tetradecene. Alternatively, the PAO is a copolymer of decene and one or more of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, or 1-tetradecene.

[0151] The unsaturated PAO product of the present application can be prepared by using a catalyst system comprising, for example, a particular type of metallocene compound as described in detail herein. The unsaturated PAO product can be substantially free of the alpha-olefin monomer(s) and can advantageously contain a high concentration of vinylidene groups, desirably totaling in the range of c1-c2 mol%, where c1 and c2 can independently be 80, 85, 90, 91, 92, 93, 94, 95, 96, 96.5, 97, 98, 99, 99.5, or 99.9, based on the total moles of ethylene groups, vinylidene groups, disubstituted vinylene groups, and trisubstituted vinylene groups, so long as c1 < c2. In particular embodiments, c1 = 90 and c2 = 99, c1 = 91 and c2 = 99, c1 = 92 and c2 = 98, c1 = 93 and c2 = 97, c1 = 96.5 and c2 = 99.9, or c1 = 98 and c2 = 99.5. Without intending to be bound by a particular theory, it is believed that the high concentration of vinylidene groups can be achieved in part by the unique structure of the metallocene compound used in the catalyst system.

[0152] Between the vinylidene groups and the tri-substituted vinylene groups in the unsaturated PAO products of the present application, the tri-substituted vinylene groups tend to have a substantially lower concentration than the vinylidene groups. In some embodiments, the unsaturated PAO products of the present application can contain a tri-substituted vinylene concentration in the range of c3-c4 mol%, based on the total moles of vinyl, vinylidene, di-substituted vinylene, and tri-substituted vinylene groups, where c3and c4may independently be 0, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, or 6.0, as long as c3< c4. In particular embodiments, c3= 0.5 and c4= 5.5, c3= 1.0 and c4= 5.0, c3= 0.5 and c4= 4.0, c3= 0 and c4= 4.0, c3= 0.1 and c4= 3.5, or c3= 0.5 and c4= 2.

[0153] In some embodiments, the unsaturated PAO products of the present application can desirably contain a high combined concentration of vinylidene and tri-substituted vinylene groups in the range of c5-c6mol%, based on the total moles of vinyl, vinylidene, di-substituted vinylene, and tri-substituted vinylene groups, where c5and c6may independently be 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.5, based on the total moles of vinyl, vinylidene, di-substituted vinylene, and tri-substituted vinylene groups, as long as c5< c6. In particular embodiments, c5= 90 and c6= 99.5, c5= 92 and c6= 99.5, c5= 94 and c6= 99, c5= 95 and c6= 99, or c5= 98 and c6= 99.5.

[0154] Without intending to be bound by a particular theory, it is believed that vinylidene and tri-substituted vinylene groups are more reactive than di-substituted vinylene groups when reacted with many functionalizing agents. Thus, if the unsaturated PAO products are to be used as intermediates for making functionalized PAO products, a high concentration of vinylidene groups and a high total concentration of vinylidene plus tri-substituted vinylene groups in the unsaturated PAO products of the present application can be particularly advantageous.

[0155] The unsaturated PAO product of the present invention desirably contains a low concentration of disubstituted vinylidene in the range of c7-c8 mol%, based on the total moles of vinyl, vinylidene, disubstituted vinylidene, and trisubstituted vinylidene, where c7and c8may be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, or 5.0, as long as c7

[0156] Depending on the metallocene compound used in the catalyst system, the unsaturated PAO product of the present invention can contain a low concentration of vinyl groups, for example, c9-c10 mol%, based on the total moles of vinyl, vinylidene, disubstituted vinylidene, and trisubstituted vinylidene, where c9and c10may be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, or 5.0, as long as c9

[0157] In some embodiments, the unsaturated PAO product of the present application desirably contains a low combined concentration of vinyl and disubstituted vinylidene groups in the range of c11-c12 mol%, based on the total moles of vinyl, vinylidene, disubstituted vinylidene, and trisubstituted vinylidene groups, where c11and c12may independently be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, or 6.0, as long as c11

[0158] Thus, the unsaturated PAO product of the present application can typically comprise a plurality of PAO molecules, which can be the same or different. Each uPAO molecule can comprise a plurality of pendant groups, which can be the same or different, and the longest 5%, 10%, 20%, 40%, 50%, and 100% of the pendant groups of all the olefin molecules of the unsaturated PAO product have an average pendant group length of Lpg(5%), Lpg(10%), Lpg(20%), Lpg(40%), Lpg(50%), and Lpg(100%), respectively. It is preferred that at least one of the following conditions is met:

[0159] (i) a1≤ Lpg(5%) ≤ a2, where a1and a2may independently be 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, 15.5, or 16.0, as long as a1< a2;

[0160] (ii) b1≤ Lpg(10%) ≤ b2, where b1and b2may independently be 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, or 15.0, as long as b1< b2;

[0161] (iii) c1 < Lpg(20%) < c2, where c1 and c2 can independently be 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, or 15.0, as long as c1 < c2;

[0162] (iv) d1 < Lpg(40%) < d2, where d1 and d2 can independently be 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, or 15.0, as long as d1 < d2;

[0163] (v) e1 < Lpg(50%) < e2, where e1 and e2 can independently be 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, or 14.0, as long as e1 < e2; and

[0164] (vi) f1 < Lpg(100%) < f2, where f1 and f2 can independently be 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, or 13.0, as long as f1 < f2.

[0165] In some embodiments, at least 60% of the pendant groups on the olefin molecules in the unsaturated PAO product are linear alkyl groups having at least 4 (e.g., at least 6, at least 8, or at least 10) carbon atoms. In particular embodiments, at least 90% of the pendant groups on the olefin molecules in the unsaturated PAO product are linear alkyl groups having at least 4 (e.g., at least 6, at least 8, or at least 10) carbon atoms.

[0166] The unsaturated PAO products of the present application can have viscosities that vary over a wide range. For example, the unsaturated PAO products can have a KV100 in the range of 1-5000 cSt, for example, 1 to 3,000 cSt, 2 to 2,000 cSt, 2 to 1,000 cSt, 2 to 800 cSt, 2 to 600 cSt, 2 to 500 cSt, 2 to 400 cSt, 2 to 300 cSt, 2 to 200 cSt, or 5 to 100 cSt, as determined according to ASTM D445 (100°C). The exact viscosity of the unsaturated PAO products can be controlled by, for example, the monomers used, the polymerization temperature, the polymerization reactor residence time, the catalyst used, the concentration of the catalyst used, the distillation and isolation conditions, and mixing of multiple unsaturated PAO products having different viscosities.

[0167] Additionally, the unsaturated PAO products of the present application advantageously have a low molecular weight distribution (polydispersity index) Mw / Mn in the range of about 1.0 to about 5.0 (e.g., 1.2 to 4.0, 1.3 to 3.0, 1.4 to 2.5, 1.5 to 2.0, or 1.6 to 1.8). The narrow molecular weight distribution of the uPAO molecules can be achieved by using a catalyst system based on metallocene compounds in the polymerization step under controlled polymerization conditions (temperature fluctuations, residence time, etc.). Such a narrow PDI is desirable because it defines a material with a high degree of homogeneity in terms of molecular weight, molecular size, rheological behavior, viscosity index, and degradation behavior (e.g., shear stability and oxidative stability). From an olefin mixture with such a degree of homogeneity, a functionalized material can be made that also has a similar degree of homogeneity.

[0168] Generally, the olefin mixture in the unsaturated PAO product of the present application can have a widely variable average molecular weight (and correspondingly a widely variable KV100). In some embodiments, the uPAO olefin mixture can have a number average molecular weight of Mn, where Mn1≤ Mn≤ Mn2, where Mn1and Mn2may independently be 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1700, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 7000, 8,000, 9000, or 10000 g / mol, as long as Mn1< Mn2. In some embodiments, the uPAO olefin mixture can have a number average molecular weight of 3000 g / mol or less, such as 2500 g / mol or less, 2000 g / mol or less, 1700 g / mol or less, 1500 g / mol or less, 1400 g / mol or less, 1300 g / mol or less, 1200 g / mol or less, 1100 g / mol or less, 1000 g / mol or less, 900 g / mol or less, 800 g / mol or less, 700 g / mol or less, 650 g / mol or less, 620 g / mol or less, 600 g / mol or less, 520 g / mol or less, 500 g / mol or less, 400 g / mol or less, 380 g / mol or less, 370 g / mol or less, 360 g / mol or less, 350 g / mol or less, 340 g / mol or less, 330 g / mol or less, or 320 g / mol or less; generally, because the product preferably does not include olefin monomers but can include dimers and higher polymers, the number average molecular weight can optionally be at least 100 g / mol, such as at least 150 g / mol or at least 200 g / mol, depending on the molecular weight of the monomer feed olefin component.

[0169] The unsaturated PAO product of the present application can additionally comprise saturated hydrocarbons. The saturated hydrocarbons can be produced in situ in the polymerization step of the a-olefins used to make the unsaturated PAO product, for example when the polymerization is carried out in the presence of a hydrogen-containing atmosphere. Alternatively or additionally, the saturated hydrocarbons can be made by partially hydrogenating a portion of the unsaturated PAO product produced by the polymerization step. Further alternatively or additionally, the saturated hydrocarbons can be blended with the olefin mixture to obtain a mixture of desired properties and composition. Nonetheless, it is desirable that the unsaturated PAO product of the present application comprises vinylidene, tri-substituted vinylene, optionally vinyl, and optionally di-substituted vinylene groups in a total concentration of at least 50 wt% (e.g., at least 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, or 99.8 wt%) based on the total weight of the unsaturated PAO product.

[0170] Generally, it is desirable that the unsaturated PAO product of the present application has a Bromine Number in the range from Nb(PAO)i to Nb(PAO)2, where Nb(PAO)i and Nb(PAO)2 can independently be 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0, 7.0, 8.0, 9.0, or even 10.0, 15.0, 10.0, as long as Nb(PAO)i < Nb(PAO)2. Desirably, a substantial portion, e.g., at least 80, 85, 90, 95, 98, or even 99 mol% of the molecules in the unsaturated PAO product of the present application can be unsaturated. Desirably, each unsaturated PAO molecule can be capable of undergoing an addition reaction with one Br2 molecule to obtain its 1,2-dibromo derivative.

[0171] The molecular structure of an exemplary vinylidene uPAO made from a mixture of 1-octene and 1-dodecene a-olefin monomers in a 4:1 molar ratio can be schematically represented by formula (F-V) below, where n can be any integer.

[0172]

[0173] shows two C 10 The pendant groups are adjacent to each other. In a real molecule, they can be randomly distributed among all the pendant groups. The structure shows near 100% isotacticity, i.e., 100 mol% of (m,m)-triads in the structure. In a real molecule, a small fraction can be (m,r)- or (r,r)-triads. Nonetheless, each of the long pendant groups can extend to form a substantially linear chain and interact with other long straight carbon chains from other molecules and other uPAO molecules in its vicinity.

[0174] Because of the presence of C=C bonds in the uPAO molecules, the unsaturated PAO product can be oxidized when exposed to O2 molecules (e.g., when exposed to air) if not protected by a material that is more reactive to O2. For that purpose, in the unsaturated PAO product, an antioxidant material can be added to extend the shelf life and facilitate its handling, storage, and transportation. Such antioxidants can include, but are not limited to, those antioxidants commonly used in lubricant base stocks and lubricating oil compositions. Non-limiting examples of such antioxidants and the amounts in which they are used are given in

[0101] -

[0108] paragraphs on pages 9 and 10 of U.S. Patent Publication No. 2010 / 0087349, the contents of which are incorporated by reference herein in their entirety.

[0175] III. Hydrogenation of the unsaturated PAO product

[0176] The unsaturated PAO product made by the process of the present application can be used directly as a lubricating oil base stock and other applications because it can be provided with the desired physical properties, particularly rheological properties of interest for such applications. However, because of the presence of C=C bonds on most, if not all, of the uPAO molecules, the direct use of the uPAO molecules as a lubricating oil base stock can cause stability problems for the oil if the oil is exposed to an oxidizing environment such as air. Thus, generally, for lubricating oil applications, it can be desirable to hydrogenate the unsaturated PAO product to remove at least a portion, preferably a substantial portion, and usually all of the C=C bonds of the PAO molecules. For example, the unsaturated PAO product of the present application can be subjected to a hydrogenation step by contacting the unsaturated PAO product with a hydrogen-containing atmosphere in the presence of a hydrogenation catalyst such as one containing one or more of Fe, Co, Ni, noble metals (e.g., Ru, Rh, Pd, Os, Ir, Pt), etc. Because of the composition of the unsaturated PAO product of the present application, they can be advantageously hydrogenated to convert a substantial portion of the C=C bonds present in the olefin molecules to carbon-carbon single bonds, thereby achieving a substantially aliphatic and saturated material (e.g., which can be characterized by a low bromine number of no greater than 5.0, no greater than 4.0, no greater than 3.0, or no greater than 2.0). Such hydrogenated, predominantly aliphatic hydrocarbon materials can have one or more of a high viscosity index, a low pour point, a high oxidative stability, and a high shear stability. They can be advantageously used as, for example, base stocks for lubricant compositions, such as those used in internal combustion engines, automotive greases, industrial greases, gear box oils, etc.

[0177] The hydrogenated PAO product made from the hydrogenation of the unsaturated PAO product can generally exhibit nearly identical viscosity, molecular weight distribution, pendant group distribution, polydispersity index as those of the precursor unsaturated PAO product. Thus, the hydrogenated PAO product of the present application can have a KV100 in the range of 1-5000 cSt, e.g., 1 to 3,000 cSt, 2 to 2,000 cSt, 2 to 1,000 cSt, 2 to 800 cSt, 2 to 600 cSt, 2 to 500 cSt, 2 to 400 cSt, 2 to 300 cSt, 2 to 200 cSt, or 5 to 100 cSt, as determined according to ASTM D445 (100°C).

[0178] The hydrogenated PAO product of the present application can advantageously have a low polydispersity index (PDI, Mw / Mn) in the range of about 1.0 to about 5.0, e.g., 1.2 to 4.0, 1.3 to 3.0, 1.4 to 2.5, 1.5 to 2.0, or 1.6 to 1.8. Such a narrow PDI can be desirable because it defines a material with a high degree of homogeneity in terms of molecular weight, molecular size, rheological behavior, viscosity index, and degradation behavior (e.g., shear stability and oxidative stability).

[0179] The hydrogenated PAO product of the present application can have a number average molecular weight of Mn, where Mn1≤ Mn ≤ Mn2, where Mn1and Mn2may independently be 150, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1700, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 7000, 8,000, 9000, or 10000 g / mol, so long as Mn1< Mn2. In some embodiments, the hydrogenated PAO product can have a number average molecular weight of 3000 g / mol or less, e.g., 2500 g / mol or less, 2000 g / mol or less, 1700 g / mol or less, 1500 g / mol or less, 1400 g / mol or less, 1300 g / mol or less, 1200 g / mol or less, 1100 g / mol or less, 1000 g / mol or less, 900 g / mol or less, 800 g / mol or less, 700 g / mol or less, 600 g / mol or less, or 500 g / mol or less; generally, because the product preferably does not include olefin monomers but can include dimers and higher polymers, the number average molecular weight can optionally be at least 100 g / mol, e.g., at least 150 g / mol or at least 200 g / mol, depending on the molecular weight of the monomer feed olefin component.

[0180] Hydrogenated PAOs can be used as high quality API Group IV base stocks. Various grades of hydrogenated mPAOs having KV100s ranging from very low, e.g., 1 cSt, to very high, e.g., 5,000 cSt, can be made by using the process of the present application and used to make high quality lubricating oil formulations, e.g., internal combustion engine oils, automotive transmission oils, industrial oils, greases, etc., by blending with each other and with other API Group I, II, III, IV, or V base stocks. In addition, mPAOs can be used as heat transfer oils (e.g., transformer oils), process oils, hydraulic power transfer oils, etc.

[0181] III. Functionalization of Unsaturated PAO Products

[0182] Desirably, the unsaturated PAO products of the present application produced by polymerization of alpha-olefins and / or olefinic monomers in the presence of a metallocene compound-based catalyst system can advantageously be used as chemical intermediates for making many products, especially those containing PAO molecular moieties and one or more functional groups. If made from the polymerization of olefins / alpha-olefins containing only one C=C double bond in their prepolymer molecules, the hydrocarbon molecules in the unsaturated PAO products can tend to contain no more than one C=C bond each, the remaining molecular structure typically consisting of C-C bonds and C-H bonds.

[0183] The C=C bonds present in the molecules of the unsaturated PAO products of the present application are highly reactive and, thus, can react with a variety of different types of chemical reagents having available functional groups, thereby producing PAO molecules that also contain functional groups attached thereto. The functional groups, in turn, can contain other functional groups, which can react with additional chemical reagents to bring additional or different functional groups onto the final molecule. The hydrocarbon base (i.e., the PAO structure) of the PAO so functionalized can impart desirable properties to the functionalized material, such as solubility in organic media or hydrophobicity, and the functional groups can impart other desirable properties to the final material, such as polarity, hydrophilicity (and thus solubility in aqueous media), etc., making the final material particularly useful when such dual properties are desired (e.g., detergents, adhesives, etc.).

[0184] U.S. Publication No. 2014 / 0087986 discloses a variety of methods for making functionalized PAOs from unsaturated PAO products produced in the presence of a metallocene compound-based catalyst system by polymerization of alpha-olefin monomers. The entire disclosure of the invention of US 2014 / 0087986 is incorporated herein by reference.

[0185] It is highly desirable that after functionalization of the unsaturated PAO product, the C=C double bonds in the reacted uPAO molecules become saturated (i.e., each carbon atom in the original C=C bond is then connected to four atoms). This can be achieved by using a functionalizing reagent that is substantially only reactive toward C=C bonds under the functionalization conditions, but is substantially inert toward C-C bonds and C-H bonds in the uPAO olefin molecules. Given that each uPAO olefin molecule typically contains only one C=C bond, the uPAO olefin molecules will become saturated after such a functionalization reaction.

[0186] After functionalization of the C=C bonds in the uPAO olefin molecules, the overall structure of the functionalized PAO molecules will be substantially similar to that of the hydrogenated PAO molecules, where the C=C bonds have been saturated by hydrogenation as described above. Assuming that the bond between the functional group(s) and the carbon atom(s) is not substantially more labile than C-C bonds and C-H bonds, and assuming that the functional group(s) itself is not substantially more labile than the pendant groups on the PAO molecules under use conditions, it is expected that the stable oligomer / polymer structure retains at least some of the interesting and useful properties of the saturated PAO molecules, such as one or more of viscosity index, oxidation stability, shear stability, bromine number, etc. The retained properties can make the functionalized PAO material particularly useful in typical applications of saturated PAO materials, such as lubricating oil compositions, etc.

[0187] It is highly desirable that the functionalizing reagent used to functionalize the unsaturated PAO product be highly selective to reacting only with C=C bonds, and be substantially inert toward C-C bonds and C-H bonds on the uPAO molecules. This can ensure that functionalized PAO molecules containing only one or two functional groups per molecule are produced, and that substantially all of the uPAO molecules are fully functionalized, if desired. In applications such as lubricating oil compositions, because of the high reactivity of the C=C bonds in the uPAO molecules, it can be desirable that substantially all of the C=C bonds in the uPAO molecules be saturated before the functionalized PAO material is put into the oil composition (as a base stock or as an additive).

[0188] Additionally or alternatively, it is also possible to functionalize the uPAO molecules by using chemical reagents that are known to be reactive with C-H bonds to replace one or more of the hydrogen atoms on the carbon backbone or one of the pendant groups with a functional group. Because the uPAO molecules typically contain many C-H bonds at multiple locations, such a reaction will be less selective than selective functionalization of the C=C bonds by using a functionalizing reagent that is inert toward C-H bonds, and can result in a very large number of very different molecules, and thus is less desirable than selective functionalization of only the C=C bonds.

[0189] Additionally or alternatively, the uPAO product of the present application can be functionalized by reaction between the unsaturated C=C bond of the uPAO molecule and a chemical reagent. The chemical reagent can contain a moiety to be reacted, directly or indirectly, with the reactive moiety(ies) of the uPAO, optionally in the presence of an appropriate catalyst or promoter. Alternatively, the chemical reagent can be a precursor to be reacted, directly or indirectly, with the reactive moiety(ies) of the uPAO, optionally in the presence of an appropriate catalyst or promoter, followed by at least one other treatment and / or chemical reagent reaction, also optionally in the presence of the same or a different appropriate catalyst or promoter, in order to complete the desired final functionality at the reactive moiety(ies) of the uPAO. Still alternatively, the chemical reagent can be a co-reactant to be reacted, either prior to or concurrently with, another chemical reagent used to react, directly or indirectly, with the reactive moiety(ies) of the uPAO, optionally in the presence of an appropriate catalyst or promoter.

[0190] Optionally, more than one type of functionality can be desired, such that functionalization can occur simultaneously (various functionalities completed in a single outcome), in series, in parallel (assuming that the two parallel reactions do not interfere with each other), or in some combination thereof. Whether one or more functionalities are desired, the reaction can be any kind that can be effective to complete the functionalization, such as liquid phase chemistry, gas-liquid interface chemistry, solid-liquid surface chemistry, gaseous oxidation, some other functionalization mechanism after gaseous oxidation, plasma oxidation, some other functionalization mechanism after plasma oxidation, radical formation, some other functionalization mechanism after radical formation, etc. The final desired functionality(ies) can be customized for a particular end-use application, such as including but not limited to moieties containing oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, boron atoms, silicon atoms, halogen atoms, or combinations thereof. The extent to which functionalization can be achieved is another variable that can be customized for a particular end-use application. The functionalization(s) can be partial or substantially complete (i.e., where substantially all of the unsaturation of the uPAO can be converted to a functional moiety, such as a heteroatom-containing moiety).

[0191] The PAOs produced herein can be functionalized by reacting a group containing a heteroatom with the PAO with or without a catalyst. Examples include catalytic hydrosilylation, ozonolysis, hydroformylation, or hydroamination, sulfonation, halogenation, hydrohalogenation, hydroboration, epoxidation or Diels-Alder reaction with a polar diene, Friedel-Crafts reaction with a polar aromatic, maleation with an activating agent such as a free radical generator (e.g., peroxide). The functionalized PAOs can be used in oil additives as anti-mist or wetting additives, surfactants for soaps, detergents, fabric softeners, antistatic agents, adhesion promoters and many other applications. Preferred uses include lubricant and / or fuel additives, preferably wherein the group containing a heteroatom comprises one or more of an amine, aldehyde, alcohol, acid, anhydride, sulfonate, particularly succinic acid, maleic acid and maleic anhydride.

[0192] In some embodiments, the PAOs produced herein are functionalized as described in U.S. Patent No. 6,022,929; Toyota, A. et al. (2002) Polymer Bulletin, vol. 48(3), pp. 213-219; and Kropp, P. J. (1990) Journal Am. Chem. Soc, vol. 112, pp. 7433-7434. In some embodiments, the functionalized PAOs produced herein are further functionalized (derivatized), for example as described in U.S. Patent No. 6,022,929; Toyota, A. et al. (2002) Polymer Bulletin, vol. 48(3), pp. 213-219; Kropp, P. J. (1990) Journal Am. Chem. Soc, vol. 112, pp. 7433-7434; and WO 2009 / 155472.

[0193] In preferred embodiments, the PAOs of the present application can be functionalized (e.g., chemically modified with one or more functional groups, also referred to as heteroatom-containing groups, that typically contain a heteroatom 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 acids, esters, anhydrides, acid esters, oxycarbonyl groups, carbonyl groups, formyl groups, formylcarbonyl groups, hydroxyl groups, and acetyl halides. Particularly preferred functional groups include those represented by the formula -C(O)-X, wherein the O double bond is bonded to C and X is hydrogen, nitrogen, hydroxyl, an oxyhydrocarbyl group (e.g., an ester), oxygen, a salt moiety -OM, wherein M is a metal, such as an alkali metal, an alkaline earth metal, a transition metal, copper, zinc, and the like, an oxyhetero, such as -O-Z, wherein Z represents a heteroatom such as phosphorus, boron, sulfur, which can be substituted with a hydrocarbyl or oxyhydrocarbyl group, or two acyl groups can be joined by (X).

[0194] Preferred heteroatom-containing groups include acyl groups derived from mono-unsaturated mono- or di-carboxylic acids and their derivatives such as esters and salts.

[0195] More specifically, PAOs functionalized with mono- or di-carboxylic acid materials, i.e., acids, anhydrides, salts or acid esters, are preferred, including reaction products of PAOs with mono-unsaturated carboxyl reactants comprising at least one member selected from the group consisting of: (i) mono-unsaturated C4-C 10 di-carboxylic acids, preferably wherein (a) the carboxyl groups are vicinyl (i.e., located on adjacent carbon atoms) and (b) at least one of said adjacent carbon atoms, preferably both, are part of said mono-unsaturation; (ii) derivatives of (i) such as anhydrides or C1-C5 alcohol derived mono- or di-esters of (i); (iii) mono-unsaturated C3-C 10 mono-carboxylic acids wherein the carbon-carbon double bond is conjugated to the carboxylic acid group, i.e., having the structure -C=C-C(O)- (wherein the O double bond is bonded to C), and (iv) derivatives of (iii) such as C1-C5 alcohol derived mono-esters of (iii). Upon reaction with the PAO, the double bond of the mono-unsaturated carboxyl reactant becomes saturated. Thus, for example, maleic anhydride, upon reaction with the PAO, becomes succinic anhydride, and acrylic acid becomes propionic acid.

[0196] Suitable unsaturated acid materials that are useful as functionalizing 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, methyl crotonic acid, sorbic acid, 3-hexenoic acid, 10-decenoic acid, 2-pentene-l,3,5-tricarboxylic acid, cinnamic acid, and lower alkyl (e.g., C1-C4 alkyl) acid esters of the foregoing acids, such as methyl maleate, ethyl fumarate, methyl fumarate, and the like. Particularly preferred are the unsaturated di-carboxylic acids and their derivatives, especially maleic acid, fumaric acid, and maleic anhydride.

[0197] 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 said mono-unsaturated carboxyl reactant per mole of added PAO are added to the reactor.

[0198] Functionalization can be achieved by any suitable method. Useful methods include reaction of the olefinic bonds of the PAO with an unsaturated, preferably mono-unsaturated, carboxyl reactant. Alternatively, the oligomer can be halogenated using a chlorine or bromine containing compound. The halogenated PAO can then be reacted with a mono-unsaturated carboxylic acid. The PAO and mono-unsaturated carboxyl reactant can also be contacted at elevated temperatures to cause thermal "ene" reaction to occur. Alternatively, the mono-unsaturated carboxylic acid can be reacted with the PAO by free radical initiation grafting. The PAO of the present invention can be functionalized by contact with a hydroxy aromatic compound in the presence of a catalytically effective amount of at least one acidic alkylation catalyst. The alkylated hydroxy aromatic compound can then be further reacted to form derivatives, a Mannich base condensate by condensation with an aldehyde and an amine reagent. In yet another way of functionalizing the PAO, the PAO can be contacted with carbon monoxide in the presence of an acid catalyst under Koch reaction conditions to produce a PAO substituted with carboxylic acid groups. In addition to the above functionalization methods, the PAO of the present invention can be functionalized by air oxidation, ozonolysis, hydroformylation, epoxidation, and chloramination. (See US 6,022,929, column 21, line 16 to column 33, line 27 for more information.)

[0199] The polyalphaolefins produced herein contain one or more unsaturated double bonds, are rich in vinylidene content, and have some 1,2-disubstituted olefins. These unsaturated polymers are particularly useful for further functionalization reactions. Examples of such functionalization include alkylation with aromatic compounds such as benzene, toluene, xylene, naphthalene, phenol, or alkyl phenols. The PAO can also be reacted with maleic anhydride to produce a PAO-succinic anhydride, and can be further converted to the corresponding succinimide or succinate with an amine or alcohol. These imides and esters are excellent dispersants.

[0200] The functionalized PAO can in turn be derivatized with a derivatizing compound. (For the purposes of the present invention and its claims, the term functionalized PAO encompasses derivatized PAO.) The derivatizing compound can react with the functional group of the functionalized PAO by, for example, nucleophilic substitution, Mannich base condensation, and the like. The derivatizing compound can be polar and / or contain a reactive derivatizing group. Preferred derivatizing compounds are selected from the group consisting of hydroxyl-containing compounds, amines, metal salts, acid anhydride-containing compounds, and acetyl halide-containing compounds. The derivatizing compound can comprise at least one nucleophilic group and preferably at least two nucleophilic groups. Typical derivatized PAOs are prepared by contacting the functionalized PAO (i.e., substituted with carboxylic acid / acid anhydride or ester) with a nucleophilic reagent such as an amine, an alcohol (including a polyol, an amino alcohol), a reactive metal compound, and the like. (See US 6,022,929, column 33, line 27 to column 74, line 63, for more information.) Alternatively, the derivatized PAO can be prepared by contacting the functionalized PAO (substituted with carboxylic acid / acid anhydride or ester) with a nucleophilic reagent such as an amine to prepare a tertiary amine compound or an amine oxide.

[0201] The functionalized PAO and / or derivatized PAO are used as lubricating additives, which can act as dispersants, viscosity index improvers, or multifunctional viscosity index improvers. Additionally, they can be used as biocides (functionalized amines) and / or wetting agents.

[0202] The functionalized PAO produced herein can be used in oil additivation, lubricants, dyes, and many other applications. Preferred uses include lubricants and / or oil additives.

[0203] In particular embodiments herein, the PAO disclosed herein or its functionalized / derivatized analogs can be used as additives, preferably for lubricants.

[0204] The functionalized PAO and / or derivatized PAO produced herein are used as lubricating additives, which can act as dispersants, viscosity index improvers, or multifunctional viscosity index improvers. Additionally, they can be used as biocides (functionalized amines) and / or wetting agents.

[0205] The functionalized PAO and / or derivatized PAO described herein can be used in viscosity index improvers for lubricating oil compositions, adhesion agent additives, anti-fog and wetting agents, ink and paint adhesion promoters, paints, tackifiers, and sealants, and the like. Additionally, such PAOs can be functionalized and derivatized to produce multifunctional viscosity index improvers that also have dispersant properties. (See US 6,022,929 for more information.)

[0206] The functionalized PAOs and / or derivatized PAOs described herein can be combined with other additives (e.g., viscosity index improvers, corrosion inhibitors, oxidation inhibitors, dispersants, lube oil flow improvers, detergents, demulsifiers, rust inhibitors, pour point depressants, antifoams, antiwear agents, seal swell agents, friction modifiers, etc. (e.g., described in US 6,022,929 at col. 60, line 42 - col. 78, line 54 and references cited therein)) to form compositions for many applications, including but not limited to lube oil additive packages, lube oils, etc.

[0207] Compositions containing these additives are typically blended into base oils in amounts effective to provide their normal additional functions. Representative effective amounts of such additives are described below:

[0208]

[0209] * wt% based on the active ingredient content of the additive and / or the total weight of any additive package or formulation, which will be the sum of the A.I. weight of each additive plus the weight of the total oil or diluent.

[0210] When other additives are used, it can be desirable, but not necessary, to prepare an additive concentrate comprising a concentrated solution or dispersion of the subject additive (in the amounts of concentrate described herein) along with one or more of the other additives (the concentrate when constituting an additive mixture is referred to herein as an additive package), whereby several additives can be added simultaneously to a base oil to form a lube oil composition. Dissolution of the additive concentrate into the lube oil can be facilitated by solvent and by mixing with mild heating, although this is not necessary. The subject functionalized or derivatized PAO can be added to at least an amount of base oil or other compatible solvent along with other desired additives to form an additive package containing active ingredients in a total amount of typically about 2.5 to about 90 wt%, and preferably about 15 to about 75 wt%, and most preferably about 25 to about 60 wt% of the appropriate proportion of additives, with the balance being base oil.

[0211] The final formulation can use typically about 10 wt% of the additive package, with the balance being base oil.

[0212] In another embodiment, the PAOs described herein can be used using any of the methods, blends, or products disclosed in WO 2009 / 0155472 or US 6,022,929, which are incorporated herein by reference.

[0213] In preferred embodiments, the present invention relates to a fuel comprising any of the PAOs produced herein. In preferred embodiments, the present invention relates to a lubricant comprising any of the PAOs produced herein.

[0214] IV. Catalyst System

[0215] The catalyst system useful herein comprises an asymmetric metallocene catalyst compound activated by one or more activators that are soluble in non-aromatic hydrocarbons and can also include a solvent, a support, one or more scavengers, and the like.

[0216] A typical activator to catalyst ratio is, for example, about 1 : 1 molar ratio of all NCA activators to catalyst. 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. Particularly useful ranges are 0.5: 1 to 10: 1, preferably 1 : 1 to 5: 1.

[0217] Solvents that can be used to combine the catalyst compound and activator and / or introduce the catalyst system into the reactor include, but are not limited to, aliphatic solvents such as butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or combinations thereof; preferred solvents can include n-paraffins (such as Isopar® solvents available from ExxonMobil Chemical Company, Houston, Texas), isoparaffin solvents (such as Solvesso® solvents available from ExxonMobil Chemical Company, Houston, Texas), and combinations thereof. These solvents or diluents can typically be pre-treated in the same manner as the feed olefins. Solvents that can be used to combine the catalyst compound and activator and / or introduce the catalyst system into the reactor include, but are not limited to, aliphatic solvents such as butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or combinations thereof; preferred solvents can include n-paraffins (such as Isopar® solvents available from ExxonMobil Chemical Company, Houston, Texas), isoparaffin solvents (such as Solvesso® solvents available from ExxonMobil Chemical Company, Houston, Texas), and combinations thereof. These solvents or diluents can typically be pre-treated in the same manner as the feed olefins. Solvents that can be used to combine the catalyst compound and activator and / or introduce the catalyst system into the reactor include, but are not limited to, aliphatic solvents such as butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or combinations thereof; preferred solvents can include n-paraffins (such as Isopar® solvents available from ExxonMobil Chemical Company, Houston, Texas), isoparaffin solvents (such as Solvesso® solvents available from ExxonMobil Chemical Company, Houston, Texas), and combinations thereof. These solvents or diluents can typically be pre-treated in the same manner as the feed olefins.

[0218] Preferably, the solvent is selected from C4-C 10 linear, branched, or cyclic alkanes.

[0219] Preferably, the solvent is substantially free of per-aromatic solvents.

[0220] Preferably, the solvent is substantially free of toluene.

[0221] Preferably, the solvent is selected from one or more C6-C 32 a-olefins, such as one or more C8-C 16 a-olefins.

[0222] Preferably, the solvent is substantially free of per-non-a-olefin solvents.

[0223] Useful aliphatic hydrocarbon solvents can be isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methyl cyclohexane, methyl cycloheptane, and mixtures thereof. In at least one embodiment, aromatic compounds are present in the solvent at less than 1 wt%, for example, less than 0.5 wt%, for example, at 0 wt%, based on the weight of the solvent.

[0224] The activators of the present disclosure can be dissolved in one or more additional solvents, provided that such solvents are non-aromatic. Additional solvents include halogenated or partially halogenated hydrocarbon solvents.

[0225] In at least one embodiment, the aliphatic solvent is isohexane and / or methylcyclohexane.

[0226] In at least one embodiment, the solvent is one or more C6-C 32 alpha-olefins, such as one or more C8-C 16 alpha-olefins, and no additional solvent is used.

[0227] In at least one embodiment, the solvent is 1-octene, 1-decene, 1-dodecene, or 1-tetradecene, or a combination of any two or more thereof.

[0228] IV.1 Metallocene Compounds

[0229] The metallocene compounds useful herein are asymmetric, such as metallocene compounds having two π-bound cyclopentadienyl moieties of different ring types, such as one monocyclic arene ligand and one polycyclic arene ligand.

[0230] The asymmetric metallocene compounds useful herein include those represented by formula (I):

[0231]

[0232] wherein:

[0233] each R 1 , R 2 , and R 3 is independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C1-C 20 hydrocarbyl group, preferably wherein at least one of R 1 , R 2 , and R 3 is not hydrogen and at least one of R 1 , R 2 , and R 3 is hydrogen;

[0234] R 6 , R 7 , R 17 , and R 18 each is independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C1-C 30 hydrocarbyl group, or R 6 and R 7 , R 7 , and R17 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;

[0235] R 12 , R 13 , R 14 and R 15 each independently is a substituted or unsubstituted linear, branched, or cyclic Ci-C 20 hydrocarbyl group;

[0236] R 16 is a substituted or unsubstituted linear, branched, or cyclic Ci-C 20 hydrocarbyl group or a silylhydrocarbyl group;

[0237] each X independently is a halogen, hydrocarbyl, hydride, alkoxy, silyl, germyl, phosphino, diene, amino, phosphino, ether, C1-C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or two or more X moieties together form a fused ring or ring system;

[0238] M is a transition metal having an integer coordination number v, e.g., 3, 4, or 5, preferably Groups 3, 4, or 5; and

[0239] m is an integer equal to v-2, e.g., 1, 2, or 3.

[0240] Asymmetric metallocene compounds useful herein include those represented by formula (II):

[0241]

[0242] wherein:

[0243] R 1 and R 2 are hydrogen;

[0244] R 23 and R 19 contain a Group 14 atom, preferably C, Ge, or Si (preferably R 23 is C and R 19 is C or Si);

[0245] R 20 , R 21 and R 22 independently are hydrogen or a substituted or unsubstituted linear, branched, or cyclic Ci-C 20 hydrocarbyl group, and at least two of R 20 , R 21 and R 22 are not hydrogen;

[0246] R 6 R 7 R 17 and R 18 Each is independently hydrogen, substituted or unsubstituted, linear, branched or cyclic C1-C 30 hydrocarbon group, or R 6 and R 7 R 7 and R 17 Or R 17 and R 18 Together with the carbon atoms in the indenyl ring directly connected to them, they form one or more substituted or unsubstituted rings fused with the indenyl ring;

[0247] R 12 R 13 R 14 R 15 and R 16 Each is independently a substituted or unsubstituted linear, branched or cyclic C1-C8 hydrocarbon group;

[0248] Each X is independently a halogen, hydrogen, amino, alkoxy, thio, phosphorus, diene, amine, phosphine, ether, or C1-C. 20 Substituted or unsubstituted linear, branched, or cyclic hydrocarbon groups, or two or more X structural moieties together forming a fused ring or cyclic system;

[0249] M is a group 3, 4 or 5 transition metal with an integer coordination number v, such as 3, 4 or 5;

[0250] m is an integer equal to v-2, such as 1, 2, or 3.

[0251] The asymmetric metallocene compounds available in this paper include those represented by formula (III):

[0252]

[0253] Where R 1 and R 3 One of them is a substituted or unsubstituted linear, branched or cyclic C1-C 20 hydrocarbon group;

[0254] R 1 R 2 and R 3 Each of the two is hydrogen;

[0255] R 6 R 18 R 29 R 24 R 25 R26 27 28 each independently is hydrogen, a substituted or unsubstituted linear, branched, or cyclic Ci-Ci8alkyl group, or R 30 6 18 29 24 25 26 27 and R 28 two of R

[0256] R 12 13 14 15 16 each independently is a substituted or unsubstituted linear, branched, or cyclic Ci-Ci8alkyl group; 20

[0257] each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, a Ci-Ci8substituted or unsubstituted linear, branched, or cyclic alkyl group, or two or more X moieties together form a fused ring or ring system; 20

[0258] M is a Group 3, 4, or 5 transition metal having an integer coordination number v, such as 3, 4, or 5;

[0259] and m is an integer equal to v-2, such as 1, 2, or 3.

[0260] Asymmetric metallocene compounds useful herein include those represented by formula (IV):

[0261]

[0262] wherein:

[0263] R 1 and R 2 are hydrogen;

[0264] R 23 and R 19 comprise a Group 14 atom, preferably C, Ge, or Si (preferably R 23 is C and R 19 is C or Si);

[0265] R 20 , R 21 , and R 22 ​​​​​​​​​​​​​​​Independently hydrogen or substituted or unsubstituted linear, branched or cyclic C1-C 20 Hydrocarbon group, and R 20 R 21 and R 22 At least two of them are not hydrogen;

[0266] R 6 R 18 R 29 R 24 R 25 R 26 R 27 and R 28 Each is independently hydrogen, substituted or unsubstituted, linear, branched or cyclic C1-C 30 hydrocarbon group, or R 6 R 18 R 29 R 24 R 25 R 26 R 27 and R 28 The carbon atoms in the two cyclopentane-indenyl rings that are directly connected to them together form one or more substituted or unsubstituted rings fused with the cyclopentane-indenyl ring;

[0267] R 12 R 13 R 14 R 15 and R 16 Each is independently a substituted or unsubstituted linear, branched, or cyclic C1-C 20 hydrocarbon group;

[0268] Each X is independently a halogen, hydrogen group, amino group, alkoxy group, thio group, phosphoro group, diene group, amine group, phosphine group, ether group, C1-C group. 20 Substituted or unsubstituted linear, branched, or cyclic hydrocarbon groups, or two or more X structural moieties together forming a fused ring or cyclic system;

[0269] M is a group 3, 4 or 5 transition metal with an integer coordination number v, such as 3, 4 or 5;

[0270] m is an integer equal to v-2, such as 1, 2, or 3.

[0271] Optionally, in any embodiment of formula (I) or (III) of this document, R 2 It is hydrogen and R 1 and R 3 One of them is a substituted or unsubstituted linear, branched or cyclic C1-C6 hydrocarbon group, and R 1 and R 3 The other is hydrogen.

[0272] Optionally, in any embodiment of formula (I) or (II) herein, R 6 and R 7 , or R 7 and R 17 , or R 17 and R 18 together with the corresponding carbon atoms in the indenyl ring to which they are directly attached form a ring fused to the indenyl ring comprising one or more saturated carbon atoms.

[0273] Optionally, in any embodiment of formula (I) or (II) herein, R 6 and R 7 , or R 7 and R 17 , or R 17 and R 18 together with the corresponding carbon atoms in the indenyl ring to which they are directly attached form a ring fused to the indenyl ring comprising one or more saturated carbon atoms.

[0274] Optionally, in any embodiment of formula (I), (II), (III), or (IV) herein, M is a Group 4 metal, preferably Zr or Hf, preferably Hf.

[0275] Optionally, in any embodiment of formula (I), (II), (III), or (IV) herein, M is a Group 4 metal, preferably Zr or Hf, preferably Hf and m is 2.

[0276] Optionally, in any embodiment of formula (II) and (IV) herein, R 23 is carbon and R 20 , R 21 , and R 22 are not hydrogen.

[0277] Non-linear examples of polycyclic arene ligands include:

[0278] 1 -methyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0279] 1 -ethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0280] 1 -n-propyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0281] 1 -isopropyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0282] 1 -isopropyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0283] 1 -n-butyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0284] 1-Isobutyl-1,5,6,7-Tetrahydro-S-indarose,

[0285] 1-sec-butyl-1,5,6,7-tetrahydro-s-indarene,

[0286] 1-n-pentyl-1,5,6,7-tetrahydro-s-indaraben,

[0287] 1-Neopentyl-1,5,6,7-tetrahydro-s-indarene,

[0288] 1-n-hexyl-1,5,6,7-tetrahydro-s-indaraben,

[0289] 1-n-heptyl-1,5,6,7-tetrahydro-s-indausendiol,

[0290] 1-n-octyl-1,5,6,7-tetrahydro-s-indaragelyl

[0291] 1-Benzyl-1,5,6,7-Tetrahydro-S-indarase,

[0292] 1-Phenylacetyl-1,5,6,7-Tetrahydro-S-indaraben,

[0293] 1-(2-phenylpropyl)-1,5,6,7-tetrahydro-s-indaraben,

[0294] 1,6,6-Trimethyl-1,5,6,7-Tetrahydro-S-indarogeneous

[0295] 1-Ethyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indaraben,

[0296] 1-n-propyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indaracan,

[0297] 1-Isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indaracanyl group,

[0298] 1-n-Butyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indaracan,

[0299] 1-Isobutyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indaracan,

[0300] 1-sec-butyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indaracanyl group,

[0301] 1-n-pentyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indaracan,

[0302] 1 -n-Hexyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0303] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0304] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0305] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0306] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0307] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0308] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0309] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0310] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0311] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0312] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0313] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0314] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0315] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0316] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0317] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0318] 1 -n-Heptyl-6,6-dimethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0319] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0320] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0321] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0322] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0323] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0324] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0325] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0326] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0327] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0328] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0329] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0330] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0331] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0332] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0333] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0334] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0335] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0336] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0337] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0338] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0339] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0340] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0341] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0342] 1 -n-octyl-6,6-diethyl- 1,5,6,7-tetrahydro-s-indacenyl,

[0343] 1 -n-pentyl-3, 6, 7, 8-tetrahydro-as-indacenyl,

[0344] 1 -neopentyl-3, 6, 7, 8-tetrahydro-as-indacenyl,

[0345] 1 -n-hexyl-3, 6, 7, 8-tetrahydro-as-indacenyl,

[0346] 1 -n-heptyl-3, 6, 7, 8-tetrahydro-as-indacenyl,

[0347] 1 -n-octyl-3, 6, 7, 8-tetrahydro-as-indacenyl,

[0348] 1 -benzyl-3, 6, 7, 8-tetrahydro-as-indacenyl,

[0349] 1 -phenethyl-3, 6, 7, 8-tetrahydro-as-indacenyl,

[0350] 1 -(2-phenylpropyl)-3, 6, 7, 8-tetrahydro-as-indacenyl,

[0351] 1 -methyl-benzo [f] indenyl,

[0352] 1 -ethyl-benzo [f] indenyl,

[0353] 1 -n-propyl-benzo [f] indenyl,

[0354] 1 -isopropyl-benzo [f] indenyl,

[0355] 1 -n-butyl-benzo [f] indenyl,

[0356] 1 -isobutyl-benzo [f] indenyl,

[0357] 1 -sec-butyl-benzo [f] indenyl,

[0358] 1 -tert-butyl-benzo [f] indenyl,

[0359] 1 -n-pentyl-benzo [f] indenyl,

[0360] 1 -neopentyl-benzo [f] indenyl,

[0361] 1 -n-hexyl-benzo [f] indenyl,

[0362] 1 -n-heptyl-benzo [f] indenyl,

[0363] 1 -n-octyl-benzo [f] indenyl,

[0364] 1 -benzyl-benzo [f] indenyl,

[0365] 1 -n-hexyl-phenalene- 1 -yl,

[0366] 1 -(2-phenylpropyl)-phenalene- 1 -yl,

[0367] 1 -methyl-phenalene- 1 -yl,

[0368] 1 -ethyl-phenalene- 1 -yl,

[0369] 1 -n-propyl-phenalene- 1 -yl,

[0370] 1 -isopropyl-phenalene- 1 -yl,

[0371] 1 -n-butyl-phenalene- 1 -yl,

[0372] 1 -isobutyl-phenalene- 1 -yl,

[0373] 1 -n-pentyl-phenalene- 1 -yl,

[0374] 1 -neopentyl-phenalene- 1 -yl,

[0375] 1 -n-hexyl-phenalene- 1 -yl,

[0376] 1 -n-heptyl-phenalene- 1 -yl,

[0377] 1 -n-octyl-phenalene- 1 -yl,

[0378] 1 -benzyl-phenalene- 1 -yl,

[0379] 1 -phenethyl-phenalene- 1 -yl,

[0380] 1 -(2-phenylpropyl)-phenalene- 1 -yl, 1 -methyl-5,6,7,8-tetrahydro- 1 H-cyclopenta[b]naphthalen-yl,

[0381] 1 -ethyl-5,6,7,8-tetrahydro- 1 H-cyclopenta[b]naphthalen-yl,

[0382] 1 -n-propyl-5,6,7,8-tetrahydro- 1 H-cyclopenta[b]naphthalen-yl,

[0383] 1 -isopropyl-5,6,7,8-tetrahydro- 1 H-cyclopenta[b]naphthalen-yl,

[0384] 1 -n-butyl-5,6,7,8-tetrahydro- 1 H-cyclopenta[b]naphthalen-yl,

[0385] 1 -isobutyl-5,6,7,8-tetrahydro- 1 H-cyclopenta[b]naphthalen-yl,

[0386] 1 -sec-butyl-5,6,7,8-tetrahydro- 1 H-cyclopenta[b]naphthalen-yl,

[0387] 1 -n-hexyl-5, 6, 7, 8-tetrahydro-1 H-cyclopenta[b]naphthalenyl,

[0388] 1 -n-hexyl-5, 6, 7, 8-tetrahydro-1 H-cyclopenta[b]naphthalenyl,

[0389] 1 -n-hexyl-5, 6, 7, 8-tetrahydro-1 H-cyclopenta[b]naphthalenyl,

[0390] 1 -n-hexyl-5, 6, 7, 8-tetrahydro-1 H-cyclopenta[b]naphthalenyl,

[0391] 1 -n-hexyl-5, 6, 7, 8-tetrahydro-1 H-cyclopenta[b]naphthalenyl,

[0392] 1 -n-hexyl-5, 6, 7, 8-tetrahydro-1 H-cyclopenta[b]naphthalenyl,

[0393] 1 -n-hexyl-5, 6, 7, 8-tetrahydro-1 H-cyclopenta[b]naphthalenyl,

[0394] 1 -n-hexyl-5, 6, 7, 8-tetrahydro-1 H-cyclopenta[b]naphthalenyl,

[0395] 1 -n-hexyl-5, 6, 7, 8-tetrahydro-1 H-cyclopenta[b]naphthalenyl,

[0396] Catalyst compounds particularly useful in the present application include those represented by formula (I-B), (III-B), (IV-B), (VI), (VIII), (IX), (X), (XI), (XII), (XV), (XVII), (XVIII), (XIX), or (XX):

[0397]

[0398]

[0399]

[0400] wherein each X is independently halogen, hydride, amide, alkoxide, sulfide, phosphide, diene, amine, phosphine, ether, or Ci-C6alkyl; M is Hf or Zr, preferably Hf; and m is 2. Optionally, the metallocene is not represented by formula (I-B). 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl radical, or two or more X moieties can together form a fused ring or ring system; M is Hf or Zr, preferably Hf; and m is 2. Optionally, the metallocene is not represented by formula (I-B).

[0401] Catalyst compounds useful in the present application include one or more of:

[0402] Pentamethylcyclopentadienyl (1 -methyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0403] Pentamethylcyclopentadienyl (1 -n-propyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0404] Pentamethylcyclopentadienyl (1 -isopropyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0405] Pentamethylcyclopentadienyl (1 -n-butyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0406] Pentamethylcyclopentadienyl (1 -isobutyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0407] Pentamethylcyclopentadienyl (1 -sec-butyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0408] Pentamethylcyclopentadienyl (1 -t-butyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0409] Pentamethylcyclopentadienyl (1 -pentyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0410] Pentamethylcyclopentadienyl (1 -neopentyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0411] Pentamethylcyclopentadienyl (1 -n-hexyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0412] Pentamethylcyclopentadienyl (1 -n-heptyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0413] Pentamethylcyclopentadienyl (1 -n-octyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0414] Pentamethylcyclopentadienyl (1 -benzyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0415] Pentamethylcyclopentadienyl (1 -phenethyl- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0416] Pentamethylcyclopentadienyl (1 -(2-phenylpropyl)- 1, 5, 6, 7-tetrahydro-s-indacenyl) dimethyl hafnium,

[0417] Pentamethylcyclopentadienyl(1 -ethyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0418] Pentamethylcyclopentadienyl(1 -isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0419] Pentamethylcyclopentadienyl(1 -isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0420] Pentamethylcyclopentadienyl(1 -isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0421] Pentamethylcyclopentadienyl(1 -isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0422] Pentamethylcyclopentadienyl(1 -isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0423] Pentamethylcyclopentadienyl(1 -isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0424] Pentamethylcyclopentadienyl(1 -isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0425] Pentamethylcyclopentadienyl(1 -isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0426] Pentamethylcyclopentadienyl(1 -isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0427] Pentamethylcyclopentadienyl(1 -isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0428] Pentamethylcyclopentadienyl(1 -isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0429] Pentamethylcyclopentadienyl(1 -isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0430] Pentamethylcyclopentadienyl(1 -isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indacenyl)dimethylhafnium,

[0431] Pentamethylcyclopentadienyl(1-phenylethyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium,

[0432] Pentamethylcyclopentadienyl(1-(2-phenylpropyl)-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsyl)dimethylhafnium,

[0433] Pentamethylcyclopentadienyl(1-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium,

[0434] Pentamethylcyclopentadienyl(1,6,6-triethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium,

[0435] Pentamethylcyclopentadienyl(1-n-propyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium,

[0436] Pentamethylcyclopentadienyl(1-isopropyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium,

[0437] Pentamethylcyclopentadienyl(1-n-butyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsyl)dimethylhafnium

[0438] Pentamethylcyclopentadienyl(1-isobutyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium,

[0439] Pentamethylcyclopentadienyl(1-sec-butyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium,

[0440] Pentamethylcyclopentadienyl(1-tert-butyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium,

[0441] Pentamethylcyclopentadienyl(1-pentyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium,

[0442] Pentamethylcyclopentadienyl(1-neopentyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium,

[0443] Pentamethylcyclopentadienyl(1-benzyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium,

[0444] Pentamethylcyclopentadienyl(1-phenylethyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium,

[0445] Pentamethylcyclopentadienyl(1-(2-phenylpropyl)-6,6-dimethyl-1,5,6,7- tetrahydro-s-indacenyl)hafnium dimethyl,

[0446] Pentamethylcyclopentadienyl(1-methylindenyl)hafnium dimethyl,

[0447] Pentamethylcyclopentadienyl(1-ethylindenyl)hafnium dimethyl,

[0448] Pentamethylcyclopentadienyl(1-n-propylindenyl)hafnium dimethyl,

[0449] Pentamethylcyclopentadienyl(1-isopropylindenyl)hafnium dimethyl,

[0450] Pentamethylcyclopentadienyl(1-n-butylindenyl)hafnium dimethyl,

[0451] Pentamethylcyclopentadienyl(1-isobutylindenyl)hafnium dimethyl,

[0452] Pentamethylcyclopentadienyl(1-sec-butylindenyl)hafnium dimethyl,

[0453] Pentamethylcyclopentadienyl(1-t-butylindenyl)hafnium dimethyl,

[0454] Pentamethylcyclopentadienyl(1-pentylindenyl)hafnium dimethyl,

[0455] Pentamethylcyclopentadienyl(1-neopentylindenyl)hafnium dimethyl,

[0456] Pentamethylcyclopentadienyl(1-n-hexylindenyl)hafnium dimethyl,

[0457] Pentamethylcyclopentadienyl(1-n-heptylindenyl)hafnium dimethyl,

[0458] Pentamethylcyclopentadienyl(1-n-octylindenyl)hafnium dimethyl,

[0459] Pentamethylcyclopentadienyl(1-benzylindenyl)hafnium dimethyl,

[0460] Pentamethylcyclopentadienyl(1-phenethylindenyl)hafnium dimethyl,

[0461] Pentamethylcyclopentadienyl(1-(2-phenylpropyl)indenyl)hafnium dimethyl,

[0462] Pentamethylcyclopentadienyl(1-methyl-3,6,7,8-tetrahydro-as-indacenyl)hafnium dimethyl,

[0463] Pentamethylcyclopentadienyl(1-ethyl-3,6,7,8-tetrahydro-as-indacenyl)hafnium dimethyl,

[0464] Pentamethylcyclopentadienyl (1 -n-propyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl,

[0465] Pentamethylcyclopentadienyl (1 -i-propyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl,

[0466] Pentamethylcyclopentadienyl (1 -n-butyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl,

[0467] Pentamethylcyclopentadienyl (1 -i-butyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl,

[0468] Pentamethylcyclopentadienyl (1 -s-butyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl,

[0469] Pentamethylcyclopentadienyl (1 -t-butyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl,

[0470] Pentamethylcyclopentadienyl (1 -pentyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl,

[0471] Pentamethylcyclopentadienyl (1 -neopentyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl,

[0472] Pentamethylcyclopentadienyl (1 -benzyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl,

[0473] Pentamethylcyclopentadienyl (1 -phenethyl-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl,

[0474] Pentamethylcyclopentadienyl (1 -(2-phenylpropyl)-3,6,7,8-tetrahydro-as-indacenyl) hafnium dimethyl,

[0475] Pentamethylcyclopentadienyl (1 -methyl-benzo[f]indenyl) hafnium dimethyl,

[0476] Pentamethylcyclopentadienyl (1 -ethyl-benzo[f]indenyl) hafnium dimethyl,

[0477] Pentamethylcyclopentadienyl (1 -n-propyl-benzo[f]indenyl) hafnium dimethyl,

[0478] Pentamethylcyclopentadienyl (1 -i-propyl-benzo[f]indenyl) hafnium dimethyl,

[0479] Pentamethylcyclopentadienyl (1 -n-butyl-benzo[f]indenyl) hafnium dimethyl,

[0480] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0481] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0482] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0483] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0484] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0485] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0486] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0487] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0488] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0489] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0490] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0491] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0492] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0493] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0494] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0495] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0496] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0497] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0498] Pentamethylcyclopentadienyl(1-ethyl-9H-carbazol-5-yl)hafnium dimethyl,

[0499] Pentamethylcyclopentadienyl(1-phenylethyl-benzo[e]indenyl)dimethylhafnium,

[0500] Pentamethylcyclopentadienyl(1-(2-phenylpropyl)-benzo[f]indenyl)dimethylhafnium,

[0501] Pentamethylcyclopentadienyl(1-methyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium,

[0502] Pentamethylcyclopentadienyl(1-ethyl-5,6,7,8-tetrahydro-1H-cyclopentadieno[b]naphthalene)dimethylhafnium,

[0503] Pentamethylcyclopentadienyl(1-n-propyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium,

[0504] Pentamethylcyclopentadienyl(1-isopropyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium,

[0505] Pentamethylcyclopentadienyl(1-n-butyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium,

[0506] Pentamethylcyclopentadienyl(1-isobutyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium,

[0507] Pentamethylcyclopentadienyl(1-sec-butyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium,

[0508] Pentamethylcyclopentadienyl(1-tert-butyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium,

[0509] Pentamethylcyclopentadienyl(1-pentyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium,

[0510] Pentamethylcyclopentadienyl(1-neopentyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium,

[0511] Pentamethylcyclopentadienyl(1-benzyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium,

[0512] Pentamethylcyclopentadienyl(1-phenylethyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium,

[0513] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0514] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0515] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0516] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0517] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0518] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0519] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0520] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0521] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0522] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0523] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0524] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0525] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0526] Pentamethylcyclopentadienyl(1 -methyl-6,7,8,9-tetrahydro-1 H-cyclopenta[ c]chrysen)dimethylhafnium,

[0527] Pentamethylcyclopentadienyl(1 -ethyl-5,6-dimethylindenyl)dimethylhafnium,

[0528] Pentamethylcyclopentadienyl(1 -isopropyl-5,6-dimethylindenyl)dimethylhafnium,

[0529] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0530] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0531] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0532] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0533] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0534] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0535] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0536] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0537] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0538] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0539] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0540] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0541] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0542] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0543] Pentamethylcyclopentadienyl(1 -isobutyl-5,6-dimethylindenyl)dimethylhafnium,

[0544] tetramethylcyclopentadienyl (1-isobutyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dimethyl,

[0545] tetramethylcyclopentadienyl (1, 6, 6-trimethyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dimethyl,

[0546] pentamethylcyclopentadienyl (1-methyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dibenzyl,

[0547] pentamethylcyclopentadienyl (1-isobutyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dibenzyl, and

[0548] pentamethylcyclopentadienyl (1, 6, 6-trimethyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dibenzyl.

[0549] Catalyst compounds particularly useful in the present application include one or more of the following:

[0550] pentamethylcyclopentadienyl (1-methyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dimethyl, pentamethylcyclopentadienyl (1-ethyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dimethyl,

[0551] pentamethylcyclopentadienyl (1-n-propyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dimethyl,

[0552] pentamethylcyclopentadienyl (1-isopropyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dimethyl,

[0553] pentamethylcyclopentadienyl (1-n-butyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dimethyl,

[0554] pentamethylcyclopentadienyl (1-isobutyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dimethyl,

[0555] pentamethylcyclopentadienyl (1, 6, 6-trimethyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dimethyl,

[0556] pentamethylcyclopentadienyl (1-isobutyl-6, 6-dimethyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dimethyl,

[0557] pentamethylcyclopentadienyl (1-methyl-6, 6-diethyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dimethyl,

[0558] pentamethylcyclopentadienyl (1, 6, 6-triethyl-1, 5, 6, 7-tetrahydro-s-indacenyl) hafnium dimethyl,

[0559] Pentamethylcyclopentadienyl(1-isobutyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium,

[0560] Pentamethylcyclopentadienyl(1-methylindenyl)dimethylhafnium,

[0561] Pentamethylcyclopentadienyl(1-isobutylindenyl)dimethylhafnium,

[0562] Pentamethylcyclopentadienyl(1-methyl-3,6,7,8-tetrahydro-as-indarsenyl)dimethylhafnium,

[0563] Pentamethylcyclopentadienyl(1-isobutyl-3,6,7,8-tetrahydro-as-indarsenyl)dimethylhafnium,

[0564] Pentamethylcyclopentadienyl(1-methyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium,

[0565] Pentamethylcyclopentadienyl(1-isobutyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium,

[0566] Pentamethylcyclopentadienyl(1-methyl-6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalene)dimethylhafnium,

[0567] Pentamethylcyclopentadienyl(1-isobutyl-6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalene)dimethylhafnium,

[0568] Pentamethylcyclopentadienyl(1,5,6-trimethylindenyl)dimethylhafnium, and

[0569] Pentamethylcyclopentadienyl(1-isobutyl-5,6-dimethylindenyl)dimethylhafnium.

[0570] Particularly desirable metallocene compounds for use in the methods of the present invention include the following compounds and their optical isomers (if applicable (not shown)):

[0571]

[0572]

[0573]

[0574]

[0575] Metallocene compounds can generally be synthesized using commercially available, common chemical reagents (e.g., halides of hafnium, zirconium, titanium) and intermediates (e.g., ligands containing one or two substituted or unsubstituted Cp rings, substituted or unsubstituted fused Cp rings such as indenyl or benzindenyl rings, etc.) and following common reaction mechanisms exemplified in various synthetic descriptions, e.g., see USSN 16 / 394,197 filed April 25, 2019 and USSN 16 / 394,166 filed April 25, 2019, which describe catalyst compounds useful herein and are incorporated by reference herein. See also USSN 16 / 270,085 filed February 7, 2019, which claims priority and benefit of USSN 62 / 629,200 filed February 12, 2018, and USSN 62 / 732,311 filed September 17, 2018, which describe catalyst compounds useful herein and are incorporated by reference herein.

[0576] III.2 Activation of Activators and Metallocene Compounds

[0577] Non-coordinating anion (NCA) activators

[0578] A non-coordinating anion (NCA) is one which forms, without further reaction, a stable complexed species which does not transfer an anionic group to the catalyst metal center. The term "non-coordinating" means that the NCA is not bonded to the catalyst metal center. An NCA is typically an anion of an element from Group 13 to 17 of the Periodic Table of the Elements, preferably from Group 17. The NCA is not capable of donating an electron pair to the catalyst metal center or of donating an electron cloud to the catalyst metal center to form a dative bond. The NCA is further defined as an anion which does not, upon contact with a catalyst metal center, exchange anions with said center, thereby causing deactivation of the catalyst center. This is distinguished from an exchange that may occur, for example, upon contact with a material such as Lewis bases. The term "neutral" is used to describe Lewis acid activators which are not anions. The term "compatible" non-coordinating anion is used to describe those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful according to the present disclosure are those which are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge, and also remain sufficiently unstable to allow displacement during polymerization.

[0579] A "compatible" non-coordinating anion can be one which is not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful according to the present disclosure are those which are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge, and also remain sufficiently unstable to allow displacement during polymerization.

[0580] The activators of the present invention comprise a non-coordinating anion.

[0581] Activators

[0582] Advantageously, the activators of the present disclosure can be used in non-aromatic hydrocarbon solvents, such as aliphatic solvents.

[0583] In one or more embodiments, a 20 wt% mixture of the activator compound in n-hexane, i-hexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear, homogeneous solution at 25°C, preferably a 30 wt% mixture of the activator compound in n-hexane, i-hexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear, homogeneous solution at 25°C.

[0584] In embodiments of the present application, the activators described herein have a solubility in methylcyclohexane at 25°C (with stirring for 2 hours) of greater than 10 mM (or greater than 20 mM or greater than 50 mM).

[0585] In embodiments of the present application, the activators described herein have a solubility in i-hexane at 25°C (with stirring for 2 hours) of greater than 1 mM (or greater than 10 mM or greater than 20 mM).

[0586] In embodiments of the present application, the activators described herein have a solubility in methylcyclohexane at 25°C (with stirring for 2 hours) of greater than 10 mM (or greater than 20 mM or greater than 50 mM) and a solubility in i-hexane at 25°C (with stirring for 2 hours) of greater than 1 mM (or greater than 10 mM or greater than 20 mM).

[0587] The present disclosure relates to catalyst systems comprising a metallocene transition metal compound as described herein and an activator compound, to the use of such activator compounds for activating transition metal compounds in catalyst systems for polymerizing olefins, and to processes for polymerizing olefins, which processes comprise contacting one or more olefins under polymerization conditions with a catalyst system comprising a metallocene transition metal compound and such an activator compound, wherein no aromatic solvent, such as toluene, is present (e.g. is present at 0 mol%, alternatively is present at less than 1 mol%, preferably the catalyst system, the polymerization reaction, and / or the produced polymer is free of "detectable aromatic hydrocarbon solvent", such as toluene. For the purposes of the present disclosure, "detectable aromatic hydrocarbon solvent" means 0.1 mg / m 2 or more. For the purposes of the present disclosure, "detectable toluene" means 0.1 mg / m 2 or more.

[0588] The polyalpha-olefins produced herein preferably contain 0 ppm (or less than 1 ppm) of aromatic hydrocarbons. Preferably, the polyalpha-olefins produced herein contain 0 ppm (or less than 1 ppm) of toluene.

[0589] The catalyst system used herein preferably contains 0 ppm (or less than 1 ppm) of aromatic hydrocarbons. Preferably, the catalyst system used herein contains 0 ppm (or less than 1 ppm) of toluene.

[0590] The non- aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (V):

[0591]

[0592] wherein:

[0593] E is nitrogen or phosphorus;

[0594] d is 1, 2, or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6; n-k = d (preferably d is 1, 2, or 3; k is 3; n is 4, 5, or 6);

[0595] R 1′ , R 2′ , and R 3′ are independently a C1-C 50 hydrocarbyl group, optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen containing groups,

[0596] wherein R 1′ , R 2′ , and R 3′ together comprise 15 or more carbon atoms;

[0597] Mt is an element selected from Group 13 of the Periodic Table of the Elements, e.g., B or P; and

[0598] each Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halogenated hydrocarbyl, substituted halogenated hydrocarbyl, or halogen substituted hydrocarbyl group.

[0599] The non- aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (V):

[0600] [R 1′ R 2′ R 3′ EH] + [BR 4′ R 5′ R 6′ R 7′ ] - (VI)

[0601] wherein:

[0602] E is nitrogen or phosphorus;

[0603] R1′ is a methyl group;

[0604] R 2′ and R 3′ are independently C4-C 50 hydrocarbyl groups, optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen containing groups, wherein R 2′ and R 3′ together comprise 14 or more carbon atoms;

[0605] B is boron;

[0606] and R 4′ , R 5′ , R 6′ and R 7′ are independently a hydrogen radical, a bridged or unbridged dialkylamino radical, a halo radical, an alkoxy radical, an aryloxy radical, a hydrocarbyl radical, a substituted hydrocarbyl radical, a halogenated hydrocarbyl radical, a substituted halogenated hydrocarbyl radical, or a halogen substituted hydrocarbyl radical.

[0607] The activator compounds useful herein that are soluble in non-aromatic hydrocarbons include those represented by formula (VII) or formula (VIII):

[0608]

[0609] wherein:

[0610] N is nitrogen:

[0611] R 2′ and R 3′ are independently C6-C 40 hydrocarbyl groups, optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen containing groups, wherein R 2′ and R 3′ together comprise 14 or more carbon atoms, if present;

[0612] R 8′ , R 9′ and R 10′ are independently C4-C 30 hydrocarbyl or substituted C4-C 30 hydrocarbyl groups;

[0613] B is boron;

[0614] and R 4′ , R 5′ , R 6′ and R 7′ are independently a hydrogen radical, a bridged or unbridged dialkylamino radical, a halo radical, an alkoxy radical, an aryloxy radical, a hydrocarbyl radical, a substituted hydrocarbyl radical, a halogenated hydrocarbyl radical, a substituted halogenated hydrocarbyl radical, or a halogen substituted hydrocarbyl radical.

[0615] Optionally, in any of Formula (V), (VI), (VII), or (VIII) herein, R 4′ , R 5′ , R 6′ , and R 7′ are pentafluorophenyl.

[0616] Optionally, in any of Formula (V), (VI), (VII), or (VIII) herein, R 4′ , R 5′ , R 6′ , and R 7′ are pentafluoronaphthyl.

[0617] Optionally, in any embodiment of Formula (VIII) herein, R 8′ and R 10′ are hydrogen atoms and R 9′ is a C4-C 30 hydrocarbyl group optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups.

[0618] Optionally, in any embodiment of Formula (VIII) herein, R 9′ is a C8-C 22 hydrocarbyl group optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups.

[0619] Optionally, in any embodiment of Formula (VII) or (VIII) herein, R 2′ and R 3′ are independently C 12 -C 22 hydrocarbyl groups.

[0620] Optionally, R 1′ , R 2′ , and R 3′ together comprise 15 or more carbon atoms (e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 38 or more carbon atoms, e.g., 40 or more carbon atoms, e.g., 15 to 100 carbon atoms, e.g., 25 to 75 carbon atoms).

[0621] Optionally, R 2′ and R 3′comprise 15 or more carbon atoms (e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 38 or more carbon atoms, e.g., 40 or more carbon atoms, e.g., 15 to 100 carbon atoms, e.g., 25 to 75 carbon atoms).

[0622] optionally, R 8′ , R 9″ , and R 10′ comprise 15 or more carbon atoms (e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 38 or more carbon atoms, e.g., 40 or more carbon atoms, e.g., 15 to 100 carbon atoms, e.g., 25 to 75 carbon atoms).

[0623] optionally, when Q is a fluorophenyl group, then R 2′ is not a C1-C 40 linear alkyl group (alternatively, R 2′ is not an optionally substituted C1-C 40 linear alkyl group).

[0624] optionally, each of R 4′ , R 5′ , R 6′ , and R 7′ is an aryl group (e.g., phenyl or naphthyl), wherein at least one of R 4′ , R 5′ , R 6′ , and R 7′ is substituted with at least one fluorine atom, preferably each of R 4′ , R 5′ , R 6′ , and R 7′ is a perfluoroaryl group (e.g., perfluorophenyl or perfluoronaphthyl).

[0625] optionally, each Q is an aryl group (e.g., phenyl or naphthyl), wherein at least one Q is substituted with at least one fluorine atom, preferably each Q is a perfluoroaryl group (e.g., perfluorophenyl or perfluoronaphthyl).

[0626] optionally, R 1′ is a methyl group R 2′ is a C6-C 50 aryl group; and R 3′ is independently a C1-C 40 linear alkyl or C5-C 50 -aryl group.

[0627] Optionally, R 2′ and R 3′ each independently is unsubstituted or substituted with halo, C1-C 35 alkyl, C5-C 15 aryl, C6-C 35 aralkyl, C6-C 35 alkaryl, wherein R 2 and R 3 together comprise 20 or more carbon atoms.

[0628] Optionally, each Q is independently a hydrogen radical, a bridged or unbridged dialkylamino radical, a halo radical, an alkoxy radical, an aryloxy radical, a hydrocarbyl radical, a substituted hydrocarbyl radical, a halogenated hydrocarbyl radical, a substituted halogenated hydrocarbyl radical, or a halogen-substituted hydrocarbyl radical, with the proviso that when Q is a fluorophenyl radical, then R 2′ is not a C1-C 40 linear alkyl radical, preferably R 2′ is not an optionally substituted C1-C 40 linear alkyl radical (alternatively when Q is a substituted phenyl radical, then R 2′ is not a C1-C 40 linear alkyl radical, preferably R 2′ is not an optionally substituted C1-C 40 linear alkyl radical). Optionally, when Q is a fluorophenyl radical (alternatively when Q is a substituted phenyl radical), then R 2′ is a meta- and / or para-substituted phenyl radical, with the meta and para substituents independently being an optionally substituted C1-C 40 hydrocarbyl radical (e.g., a C6-C 40 aryl radical or a linear alkyl radical, C 12 -C 30 aryl radical or a linear alkyl radical, or C 10 -C 20 aryl radical or a linear alkyl radical), an optionally substituted alkoxy radical, or an optionally substituted silyl radical. Optionally, each Q is a fluorinated hydrocarbyl radical having 1-30 carbon atoms, more preferably each Q is a fluorinated aryl (e.g., phenyl or naphthyl) radical, and most preferably each Q is a perfluorinated aryl (e.g., phenyl or naphthyl) radical. Examples of suitable [Mt k+ Q n ] d- include the diboron compounds as disclosed in U.S. Patent No. 5,447,895, which is incorporated by reference herein in its entirety. Optionally, at least one Q is not a substituted phenyl. Optionally, all Qs are not substituted phenyl. Optionally, at least one Q is not a perfluorophenyl. Optionally, all Qs are not perfluorophenyl.

[0629] In some embodiments of the invention, R1′ R is not methyl 2′ R is not C 18 R is not alkyl and R 3′ R is not C 18 R is not alkyl, alternatively R 1′ R is not methyl 2′ R is not C 18 R is not alkyl and R 3′ R is not C 18 R is not alkyl and at least one Q is not substituted phenyl, preferably all Q are not substituted phenyl.

[0630] Cationic components useful in the formula (V) through (VIII) include those represented by the formula:

[0631]

[0632]

[0633] Cationic components useful in the formula (V) through (VIII) include those represented by the formula:

[0634]

[0635] Anionic components of the activators 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 and 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 dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halogenated hydrocarbyl, substituted halogenated hydrocarbyl, and halogen-substituted-hydrocarbyl radical, said Q having up to 20 carbon atoms with the proviso that Q is halide only when not more than one occurrence. Preferably, each Q is a fluorinated hydrocarbyl radical, optionally having from 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl radical, and most preferably each Q is a perfluorinated aryl radical. Preferably at least one Q is not a substituted phenyl, such as a perfluorophenyl, preferably all Q are not substituted phenyl, such as a perfluorophenyl.

[0636] In one embodiment, the borate activator comprises tetrakis(pentafluorophenyl)borate.

[0637] In one embodiment, the borate activator comprises tetrakis(pentafluorophenyl)borate.

[0638] Preferred anions for use in the non-coordinating anion activators described herein include those represented by the following formula 7:

[0639]

[0640] wherein:

[0641] M* is a group 13 atom, preferably B or Al, preferably B;

[0642] each R 11 independently is halo, preferably fluoro;

[0643] each R 12 independently is halo, C6-C 20 substituted aromatic hydrocarbyl group or a siloxy group having the formula -O-Si-R a wherein R a is a C1-C 20 hydrocarbyl or hydrocarbylsilyl group, preferably R 12 is fluoro or a perfluorophenyl group;

[0644] each R 13 is halo, C6-C 20 substituted aromatic hydrocarbyl group or a siloxy group having the formula -O-Si-R a wherein R a is a C1-C 20 hydrocarbyl or hydrocarbylsilyl group, preferably R 13 is fluoro or a C6perfluorinated aromatic hydrocarbyl group;

[0645] wherein R 12 and R 13 may form one or more saturated or unsaturated, substituted or unsubstituted rings, preferably R 12 and R 13 form a perfluorophenyl ring. Preferably, the anion has a molecular weight greater than 700 g / mol, and preferably at least three of the substituents on the M* atom each have a molecular volume greater than .

[0646] "Molecular volume" is used herein as an approximation of the spatial steric bulk of an activated agent molecule in solution. Comparing substituents having different molecular volumes, a substituent having a smaller molecular volume is considered "sterically smaller" than a substituent having a larger molecular volume. Conversely, a substituent having a larger molecular volume can be considered "sterically larger" than a substituent having a smaller molecular volume.

[0647] Molecular volumes can be calculated as reported in Girolami, G. S. (1994) "A Simple 'Back of the Envelope' Method for Estimating the Densities and Molecular Volumes of Liquids and Solids," Journal of Chemical Education, Vol. 71(11), pp. 962-964. Molecular volumes (MV) in units of 8.3 V s where V s is the scaled volume. V s is the sum of the relative volumes of the constituent atoms and is calculated from the molecular formula of the substituent using the relative volumes of Table A below. For fused rings, each fused ring V S is reduced by 7.5%. The calculated total MV of an anion is the sum of the MV of each substituent, for example the MV of a perfluorophenyl group is and the calculated total MV of a tetra(perfluorophenyl)borate salt is four times or

[0648] Table A

[0649] Element Relative Volume H 1 First short period, Li to F 2 Second short period, Na to Cl 4 First long period, K to Br 5 Second long period, Rb to I 7.5 Third long period, Cs to Bi 9

[0650] Exemplary anions useful herein and their respective scaled volumes and molecular volumes are shown in Table B below. The dashed bond indicates bonding to boron.

[0651] Table B

[0652]

[0653]

[0654] Activators can be added to the polymerization in the form of an ion pair using, for example, [M2HTH]+[NCA]~where the di(hydrogenated tallow) methylamine ("M2HTH") cation reacts with the basic leaving group on the transition metal complex to form the transition metal complex cation and [NCA]~. Alternatively, the transition metal complex can be reacted with a neutral NCA precursor such as B(C6F5)3which abstracts the anionic group from the complex to form the activated species. Useful activators include [tetra(pentafluorophenyl)borate] di(hydrogenated tallow) methylammonium (i.e., [M2HTH]B(C6F5)4) and [tetra(pentafluorophenyl)borate] di(octadecyl) tolylammonium (i.e., [DOdTH]B(C6F5)4).

[0655] Activator compounds particularly useful in the present application include one or more of the following: [tetrakis(perfluorophenyl)borate] N,N-di(hydrogenated tallow) methyl ammonium,

[0656] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0657] [tetrakis(perfluorophenyl)borate] N-methyl-4-hexyl-N- octadecyl anilinium,

[0658] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0659] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0660] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0661] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0662] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0663] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0664] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0665] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0666] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0667] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0668] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0669] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0670] [tetrakis(perfluorophenyl)borate] N-methyl-4-nonyl-N- octadecyl anilinium,

[0671] [Tetra(perfluorophenyl)boronic acid]N-methyl-N,N-dioctylammonium,

[0672] [Tetra(perfluorophenyl)boronic acid]N-ethyl-N,N-di(octadecyl)ammonium

[0673] [Tetrafluorophenyl]boronic acid]N,N-Di(octadecyl)tolylammonium

[0674] [Tetrafluorophenyl]boronic acid]N,N-di(hexadecyl)tolylammonium,

[0675] [Tetra(perfluorophenyl)boronic acid]N,N-di(tetradecyl)tolylammonium,

[0676] [Tetra(perfluorophenyl)boronic acid]N,N-di(dodecyl)tolylammonium,

[0677] [Tetra(perfluorophenyl)boronic acid]N-octadecyl-N-hexadecyl-tolylammonium, [Tetra(perfluorophenyl)boronic acid]N-octadecyl-N-hexadecyl-tolylammonium, [Tetra(perfluorophenyl)boronic acid]N-octadecyl-N-tetradecyl-tolylammonium, [Tetra(perfluorophenyl)boronic acid]N-octadecyl-N-dodecyl-tolylammonium, [Tetra(perfluorophenyl)boronic acid]N-octadecyl-N-decyl-tolylammonium

[0678] [Tetra(perfluorophenyl)boronic acid]N-hexadecyl-N-tetradecyl-tolylammonium, [Tetra(perfluorophenyl)boronic acid]N-hexadecyl-N-dodecyl-tolylammonium, [Tetra(perfluorophenyl)boronic acid]N-hexadecyl-N-decyl-tolylammonium

[0679] [Tetra(perfluorophenyl)boronic acid]N-Tetradecyl-N-dodecyl-tolylammonium, [Tetra(perfluorophenyl)boronic acid]N-Tetradecyl-N-decyl-tolylammonium,

[0680] [Tetrafluorophenyl]boronic acid]N-dodecyl-N-decyl-tolylammonium

[0681] [Tetra(perfluorophenyl)boronic acid]N-methyl-N-octadecylphenylammonium

[0682] [Tetra(perfluorophenyl)boronic acid]N-methyl-N-hexadecylphenylammonium

[0683] [Tetra(perfluorophenyl)boronic acid]N-methyl-N-tetradecylphenylammonium

[0684] [Tetra(perfluorophenyl)boronic acid]N-methyl-N-dodecylphenylammonium

[0685] [Tetra(perfluorophenyl)boronic acid]N-methyl-N-decylphenylammonium, and

[0686] [Tetrakis(perfluorophenyl)borate] N-methyl-N-octylphenanamine.

[0687] Additional activators and their synthesis are described in USSN 16 / 394,166 filed April 25, 2019, USSN 16 / 394,186 filed April 25, 2019, and USSN 16 / 394,197 filed April 25, 2019, which are incorporated herein by reference.

[0688] In embodiments, the activator is not (and the cationic portion of formula (V), (VI), (VII), and (VII) is not a cation in) the following formula:

[0689]

[0690] Synthesis

[0691] In at least one embodiment, the general synthesis of activators can be performed using a two-step process. In the first step, the amine or phosphine is dissolved in a solvent (e.g., hexanes, cyclohexane, methylcyclohexane, diethyl ether, dichloromethane, toluene) and an excess (e.g., 1.2 molar equivalents) of hydrogen chloride is added to form a chloride salt. This salt is typically isolated from the reaction medium by filtration and dried under reduced pressure. The isolated chloride is then heated to reflux with about 1 molar equivalent of an alkali metal metalate or metalloidate (e.g., borate or aluminate) in a solvent (e.g., cyclohexane, dichloromethane, methylcyclohexane) to form the desired borate or aluminate and a byproduct alkali metal chloride, which can typically be removed by filtration.

[0692] In at least one embodiment, the general synthesis of ammonium borate activators can be performed using a two-step process. In the first step, the amine is dissolved in a solvent (e.g., hexanes, cyclohexane, methylcyclohexane, diethyl ether, dichloromethane, toluene) and an excess (e.g., 1.2 molar equivalents) of hydrogen chloride is added to form an ammonium chloride salt. This salt is typically isolated from the reaction medium by filtration 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 the ammonium borate and a byproduct alkali metal chloride, which can typically be removed by filtration.

[0693] Co-activators are compounds that are capable of alkylating a transition metal complex such that, when used with an activator, an active catalyst is formed. Co-activators can include aluminoxanes such as methyl aluminoxane, modified aluminoxanes such as modified methyl aluminoxane and alkylaluminum such as trimethylaluminum, triisobutylaluminum, triethylaluminum, and triisopropylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, or tri-n-dodecylaluminum. Co-activators are often used in conjunction with Lewis acid activators and ionic activators when the current catalyst is not a dihydrocarbyl or dihydrogen complex. Sometimes co-activators also act as scavengers to deactivate impurities in the feed or reactor.

[0694] III.3 Scavengers

[0695] Scavengers can be additional components of the catalyst system described herein. Scavengers are compounds that are typically added to facilitate oligomerization or polymerization by scavenging impurities. Some scavengers can also act as activators and can be referred to as co-activators. Co-activators (which are not scavengers) can also be used in conjunction with activators in order to form an active catalyst with a transition metal compound. In some embodiments, co-activators can be pre-mixed with a transition metal compound to form an alkylated transition metal compound, which is also referred to as an alkylated catalyst compound or an alkylated metallocene. To some extent, scavengers facilitate the intended catalytic function of the metallocene compound, and if used, are sometimes considered part of the catalyst system.

[0696] U.S. Patent No. 9,409,834 (e.g., at column 33, line 37 to column 34, line 61) provides a detailed description of scavengers that can be used in the inventive process for making PAO. The corresponding section in this patent regarding scavengers, their properties, amounts, and manner of use are fully incorporated herein.

[0697] Particularly useful scavengers include tri-n-octylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and the like.

[0698] IV. Process for making PAO

[0699] The inventive process for making PAO includes polymerizing in a polymerization reactor under polymerization conditions a C6-C 32 α-olefins (preferably C6-C 30 , especially C6-C 24 , C6-C 18 , C8-C 18 , or C6-C 12) with the catalyst system comprising the metallocene compound described above to perform a polymerization reaction to obtain a polymerization reaction mixture comprising ethenylidene, trisubstituted vinylene, optionally disubstituted vinylene, and optionally vinyl groups; and obtaining an unsaturated PAO product from the polymerization reaction mixture, wherein the unsaturated PAO product comprises ethenylidene, trisubstituted vinylene, optionally disubstituted vinylene, and optionally vinyl groups.

[0700] IV.1 Monomer(s)

[0701] The alpha-olefin feed for making the PAO material of the present application comprises one or more of C6-C 32 alpha-olefins (preferably C6-C 24 , in particular C6-C 18 , C8-C 18 , or C6-C 12 . The feed can also comprise ethylene, propylene, C4alpha-olefins, and C5alpha-olefins, however each of ethylene, propylene, C4alpha-olefins (1-butene and 2-methyl-1 -propene), and C5alpha-olefins (1-pentene and the various isomers of methyl-1 -butene) is supplied to the polymerization reactor at no more than ci mol% each independently, based on the total moles of alpha-olefins supplied to the polymerization reactor, where ci can be 25, 20, 10, 5, 4, 3, 2, 1, 0.5, 0.1, or 0.01 for each monomer. Additionally or alternatively, any combination of C2-C5alpha-olefins (including two or more, three or more, or all four of ethylene, propylene, C4alpha-olefins, and C5alpha-olefins) are collectively supplied to the polymerization reactor at no more than ci mol%, based on the total moles of alpha-olefins supplied to the polymerization reactor. Preferably, the alpha-olefin feed is substantially free of ethylene, propylene, C4alpha-olefins, and C5alpha-olefins (or completely free of C2-C5alpha-olefins intentionally added, considering impurities present in other feed components). In preferred embodiments, substantially all of the alpha-olefins in the feed are C6-C 30 (eg. C6-C 24 , in particular C6-C 18 , C8-C 18 , or C6-C 12) alpha-olefins. By "substantially all" is meant at least 90 mol% (e.g., at least 92 mol%, at least 94 mol%, at least 95 mol%, at least 96 mol%, at least 98 mol%, at least 99%, at least 99.5 mol%, or all of, taking into account some impurities present in the feed components), based on the total number of moles of alpha-olefins present in the feed. Preferably, any combination of C2-C5 alpha-olefins collectively is present in the alpha-olefin feed in no more than c1 mol% (where c1 can be 25, 20, 10, 5, 4, 3, 2, 1, 0.5, 0.1, or 0.01), based on the total number of moles of alpha-olefins supplied to the polymerization reactor.

[0702] In some preferred embodiments, at least a portion (e.g., at least 80 mol%, at least 85 mol%, at least 90 mol%, at least 95 mol%, at least 96 mol%, at least 98 mol%, at least 99%, at least 99.5 mol%, or all of, taking into account some impurities present in the feed components) of the alpha-olefins present in the feed are linear alpha-olefins (LAOs), i.e., those alpha-olefins that have no branches attached to their carbon backbone. Non-limiting examples of LAOs are 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, C 22 , C 24 , C 26 , C 28 , C 30 , and C 32 LAOs. Without being bound by theory, PAO products made from such LAOs by using the processes of the present application tend to have fewer branches and side groups, resulting in generally more uniform PAO molecular structures, and thus generally better performance for applications such as lubricant base stocks, lubricant additives, and the like.

[0703] In the case where a single alpha-olefin is fed to the polymerization reactor, the PAO so obtained is a homopolymer. Homopolymers can have a substantially uniform molecular structure, and thus desirable physical and rheological properties such as viscosity index. Homopolymers can tend to have side groups attached to the carbon backbone in highly uniform lengths.

[0704] In certain cases, it can be desirable to feed a mixture of two, three, or even more alpha-olefins in the feed to produce a copolymer PAO product. For that purpose, alpha-olefins having the following combinations can be particularly advantageous: C6 / C8, C6 / C 10 , C6 / C 12 , C6 / C 14 , C6 / C 16 , C8 / C 10 , C8 / C12 , C8 / C 14 , C8 / C 16 , C 10 / C 12 , C 10 / C 14 , C 10 / C 16 , C 10 / C 18 , C 12 / C 14 , C 12 / C 16 , C 12 / C 18 , C 12 / C 20 , C6 / C8 / C 10 , C6 / C8 / C 12 , C6 / C8 / C 14 , C6 / C 10 / C 12 , C6 / C 10 / C 14 , C8 / C 10 / C 12 , C8 / C 10 / C 14 , C8 / C 12 / C 14 , C 10 / C 12 / C 16 , C 10 / C 12 / C 18 , C 10 / C 14 / C 16 , C 10 / C 14 / C 18 and the like. Desirably, at least one of the alpha-olefins in the mixture feed can be LAO. In particular, substantially all of the alpha-olefins in the mixture feed can be LAO.

[0705] Preferred alpha-olefin monomers are mono-olefins containing one C=C bond per monomer molecule, although those containing two or more C=C bonds per monomer molecule can also be used.

[0706] Preferred monomers useful herein include substituted or unsubstituted C6-C 32 alpha-olefins, or C6-C 20 alpha-olefins, or C6-C 14a-olefins, or hexene, heptene, octene, nonene, decene, undecene, dodecene, tetradecene, and isomers thereof. Preferably, the poly-a-olefins produced herein comprise 50 mol% or more (preferably 60 mol% or more, preferably 70 mol% or more, preferably 80 mol% or more, preferably 90 mol% or more, preferably 99 mol% or more) of one or more C6-C 32 (preferably C6-C 20 , preferably C8-C 18 ) a-olefin monomers.

[0707] Useful C6-C 32 a-olefin monomers include hexene, heptene, octene, nonene, decene, undecene, dodecene, tetradecene, substituted derivatives thereof, and isomers thereof.

[0708] Preferably, the monomers comprise C6-C 20 a-olefins, or C6-C 14 a-olefins and / or C8-C 12 a-olefins.

[0709] Preferred olefin monomers include one (alternatively two, alternatively three) or more of hexene, heptene, octene, nonene, decene, dodecene, and tetradecene.

[0710] In embodiments, the PAO is a homopolymer of any C8-C 12 a-olefin, i.e., the PAO is a homopolymer of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, or 1-tetradecene. Preferably, the PAO is a homopolymer of decene. In another embodiment, the PAO is a copolymer comprising decene and one or more of any of the monomers listed above.

[0711] In embodiments, the PAO comprises two or more monomers, or three or more monomers, or four or more monomers, or five or more monomers. For example, a C8, C 10 , C 12 -linear a-olefin mixture, or a C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 -linear a-olefin mixture, or a C6, C8, C 10 , C 12 , C 14 , C 16 , C 18 -linear a-olefin mixture can be used as a feed.

[0712] In alternative embodiments, the PAO comprises less than 50 mol% C2, C3, and C4 monomers, or less than 40 mol%, or less than 30 mol%, or less than 20 mol%, or less than 10 mol%, or less than 5 mol%, or less than 3 mol%, or 0 mol%. Specifically, in alternative embodiments, the PAO comprises less than 50 mol% ethylene, propylene, and butylene, or less than 40 mol%, or less than 30 mol%, or less than 20 mol%, or less than 10 mol%, or less than 5 mol%, or less than 3 mol%, or 0 mol%. In another embodiment, the PAO comprises less than 40 mol%, or less than 20 mol%, or less than 10 mol%, or less than 5 mol%, or less than 3 mol%, or 0 mol% ethylene.

[0713] In alternative embodiments, the PAO comprises less than 25 mol% C2, C3, and C4 monomers, or less than 20 mol%, or less than 15 mol%, or less than 10 mol%, or less than 5 mol%, or less than 1 mol%, or 0 mol%. Specifically, in alternative embodiments, the PAO comprises less than 25 mol% ethylene, propylene, and butylene, or less than 20 mol%, or less than 15 mol%, or less than 10 mol%, or less than 5 mol%, or less than 1 mol%, or 0 mol%. In another embodiment, the PAO comprises less than 25 mol%, or less than 20 mol%, or less than 10 mol%, or less than 5 mol%, or less than 1 mol%, or 0 mol% ethylene.

[0714] In another embodiment, the PAO comprises less than 40 mol% propylene. In another embodiment, the PAO comprises less than 40 mol% butylene. In another embodiment, the PAO comprises less than 10 mol% ethylene. In another embodiment, the PAO comprises less than 10 mol% propylene. In another embodiment, the PAO comprises less than 10 mol% butylene.

[0715] In another embodiment, the PAO comprises less than 25 mol% propylene. In another embodiment, the PAO comprises less than 25 mol% butylene. In another embodiment, the PAO comprises less than 5 mol% ethylene. In another embodiment, the PAO comprises less than 5 mol% propylene. In another embodiment, the PAO comprises less than 5 mol% butylene. In another embodiment, the PAO comprises less than 1 mol% ethylene. In another embodiment, the PAO comprises less than 1 mol% propylene. In another embodiment, the PAO comprises less than 1 mol% butylene.

[0716] The alpha-olefins used herein can be produced directly by ethylene growth processes such as several commercial production processes, or they can be produced from CO / H2 synthesis gas by Fischer-Tropsch hydrocarbon synthesis, or from the displacement of internal olefins with ethylene, or from the cracking of petroleum or Fischer-Tropsch waxes at elevated temperatures, or from any other alpha-olefin synthesis route. Exemplary feeds for use in the present application can be at least 80 wt% alpha-olefins (preferably linear alpha-olefins), preferably at least 90 wt% alpha-olefins (preferably linear alpha-olefins), or about 100% alpha-olefins (preferably linear alpha-olefins). However, mixtures of alpha-olefins can also be used as the feed in the present application, especially if other components are internal olefins, branched olefins, paraffins, naphthenes, aromatics (such as toluene and or xylenes). These components can have a diluent effect and are believed to have no substantial deleterious effect on the polymerization of alpha-olefins. In other words, the processes described herein can selectively convert the alpha-olefins in the mixture and leave the other components largely, if not completely, unreacted. This can be particularly useful when ethylene is not present in the mixture. This technique can be used to separate alpha-olefins from mixtures by selectively reacting them with a polymerization or oligomerization catalyst system, effectively, if not completely, removing the need to separate the alpha-olefins from the remaining components in the mixed feed stream. This can be economically advantageous, for example, in processes using Fischer-Tropsch synthesis olefin product streams containing alpha-olefins, internal olefins, and branched olefins. Such mixtures can be fed to the oligomerization techniques as described herein and the alpha-olefins selectively reacted away. There can be no need for a separate step to isolate the alpha-olefins. Another example of using this approach includes alpha-olefins produced by the displacement of internal olefins with ethylene, which can contain some internal olefins. This mixed olefin base stock feed can be reacted as is in the polymerization / oligomerization process of the present application, which selectively converts the alpha-olefins to lube products. Thus, alpha-olefins can be used for base stock synthesis without having to isolate the alpha-olefins from the internal olefins. This can result in a significant improvement in process economics. The feed olefins can be C4-C2o alpha-olefins produced from other linear alpha-olefin processes. 20 Alpha-olefin mixtures, as described in Chapter 3, "Routes to Alpha-Olefins", in the book Alpha Olefins Applications Handbook, edited by G. R. Lappin and J. D. Sauer, Marcel Dekker, Inc. N. Y., 1989.

[0717] IV.2 Feed Purification

[0718] The olefin feed and / or solvent can be treated to remove catalyst poisons, such as peroxides, oxygen or nitrogen containing organic compounds, or acetylenic compounds, prior to being supplied to the polymerization reactor. For example, the feed can be treated with activated Treatment of linear alpha-olefins with molecular sieves and deoxygenated catalysts (i.e., reduced copper catalysts) can increase catalyst productivity (expressed in terms of the amount of PAO produced per micromole of metallocene compound used) by greater than ten-fold. Alternatively, the feed olefins and or solvents can be treated with activated molecular sieves, such as or molecular sieves and / or in combination with activated alumina or activated deoxygenated catalysts. Such treatment desirably increases catalyst productivity by a factor of two to ten or greater.

[0719] IV.3 Polymerization Reaction

[0720] A number of polymerization / oligomerization processes and reactor types can be used in the present application for metallocene catalyzed polymerization or oligomerization, such as solution, slurry, and bulk polymerization or oligomerization processes. If a solid or supported catalyst is used, a slurry or continuous fixed bed or plug flow process can be suitable. Preferably, the monomer(s) are contacted with the metallocene compound and activator in a solution phase, bulk phase, or slurry phase, such as in a continuous stirred tank reactor or a continuous tubular reactor. In some embodiments, the temperature in any reactor used herein can be from -10°C to 250°C, such as from 30°C to 220°C, preferably from 50°C to 180°C, from 60°C to 170°C, or from 70°C to 150°C. In some embodiments, the pressure in any reactor used herein can be from 0.1 to 100 atmospheres, such as from 0.5 to 75 atmospheres or from 1 to 50 atmospheres. Alternatively, the pressure in any reactor used herein can be from 1 to 50,000 atmospheres, such as from 1 to 25,000 atmospheres. Additionally or alternatively, the monomer(s), metallocene, and activator can be contacted for a residence time of from 1 second to 100 hours, such as from 30 seconds to 50 hours, from 2 minutes to 6 hours, or from 1 minute to 4 hours. Additionally or alternatively, a solvent or diluent can be present in the reactor and can include aliphatic solvents such as butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or combinations thereof; preferred solvents can include n-paraffins (such as Isopar® solvents available from ExxonMobil Chemical Company, Houston, Texas), isoparaffin solvents (such as Solvesso® solvents available from ExxonMobil Chemical Company, Houston, Texas), and combinations thereof. These solvents or diluents can be typically pre-treated in the same manner as the feed olefins. These solvents or diluents can be typically pre-treated in the same manner as the feed olefins.

[0721] ​Suitable non-aromatic diluents / solvents for polymerization include noncoordinate inert liquids. Examples include straight-chain and branched 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 commercially available (Isopar) TM ); perhalogenated hydrocarbons, such as perfluorinated C4-C 10 Alkanes. Suitable solvents also include liquid olefins, which can act as monomers or comonomers, including C3-C... 32 α-olefins, such as propylene, 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 a preferred embodiment, the solvent used is C6-C. 18 α-olefins, with C8-C as a selectable alternative 16 α-olefins, with C8-C as a selectable alternative 14 α-olefins or mixtures thereof. Mixtures of any of the solvents listed above may be used.

[0722] In another embodiment, the solvent is not aromatic; preferably, the aromatic compound is present in the solvent at less than 3% by weight, more preferably less than 3% by weight, more preferably less than 1% by weight, more preferably less than 0.5% by weight, more preferably less than 0.1% by weight, based on the weight of the solvent. Preferably, the solvent or mixture of solvents is aromatic-free.

[0723] Preferably, the solvent is selected from C4-C. 10 Linear, branched, or cyclic alkanes.

[0724] Preferably, the solvent is substantially free of all aromatic solvents.

[0725] Preferably, the solvent is selected from one or more C6-C solvents. 32 α-olefins, such as one or more C8-C 16 α-olefins.

[0726] Preferably, the solvent is substantially free of all-non-α-olefin solvents.

[0727] In some embodiments of the invention, where all of the solvent is an alpha-olefin feed (monomer feed), the procatalyst is dissolved in the monomer feed in a first feed tank and the activator is dissolved in the monomer feed in a second feed tank. The procatalyst solution is then added separately from the activator solution to the reactor and catalyst activation occurs in the reactor. If used, the scavenger can be added independently or the scavenger can be added with the activator feed, the procatalyst feed, or the monomer feed if separate monomer feeds are used.

[0728] In other embodiments of the invention, where all of the solvent is an alpha-olefin feed (monomer feed), the procatalyst is dissolved in the monomer feed in a first feed tank and the activator is dissolved in the monomer feed in a second feed tank and the procatalyst solution and the activator solution are pre-mixed in a zone prior to entering the reactor, typically immediately prior to entering the reactor. Alternatively the two solutions are contacted for 1 hour or less, 30 minutes or less, 10 minutes or less, 5 minutes or less, 1 minute or less prior to entering the reactor.

[0729] When C4-C 10 When linear, branched, or cyclic alkanes are used as the solvent / diluent, the procatalyst and activator can be pre-mixed in a feed tank and added together to the reactor.

[0730] Regardless of the type of reactor or process, it is generally desirable for the average activity level of the catalyst system to be maintained at or above a sufficiently high level to achieve a minimum reasonable yield of oligomer product(s) relative to the monomeric reactant(s). For example, in some embodiments, the catalytic reaction can have an average activity level of at least 800 g / mmol-hr, such as at least 900 g / mmol-hr, at least 1,000 g / mmol-hr, at least 1,100 g / mmol-hr, at least 1,200 g / mmol-hr, at least 1,300 g / mmol-hr, at least 1,400 g / mmol-hr, at least 1,500 g / mmol-hr, at least 1,700 g / mmol-hr, at least 1,900 g / mmol-hr, at least 2,100 g / mmol-hr, at least 2,500 g / mmol-hr, or at least 2,800 g / mmol-hr; while the average activity level is not generally characterized as "too high," the average activity level can theoretically be so high that control of the reaction product can be difficult to achieve in practice, such that the average catalytic reaction activity level can optionally be less than 1,000 kg / mmol-hr, such as less than 500 kg / mmol-hr in some embodiments. Additionally or alternatively, in some embodiments, the catalytic reaction can provide a minimum reasonable yield (grams of oligomer / grams of monomer feed) of at least 18%, such as at least 19%, at least 20%, at least 22%, at least 24%, at least 27%, at least 30%, at least 33%, at least 36%, at least 38%, or at least 40%, based on a reaction time of ~1 hour (~3,600 seconds); while a reasonable catalytic yield is not generally characterized as "too high," with a maximum of about 100% in a 1 hour reaction time, for relatively high yields, particularly high yields in relatively short reaction times, it is theoretically possible to adversely affect the ability to control the reaction product, such as to make the maximum reasonable yield optionally about 100% in a reaction time of ~1 minute or less, such as about 100% in a reaction time of ~10 minutes or less, about 100% in a reaction time of ~30 minutes or less, about 100% in a reaction time of ~1 hour or less, about 95% in a reaction time of ~1 hour or less, or about 90% in a reaction time of ~1 hour or less.

[0731] In some embodiments, it can be desirable to obtain a relatively low product molecular weight and a relatively high product vinylidene content. However, in many metallocene reactions where the vinylidene linkage is a significant fraction of the total moles of vinyl, vinylidene, disubstituted vinylene, and trisubstituted vinylene, increasing the reaction temperature can cause a decrease (or at least no increase) in both molecular weight and vinylidene content. Because reaction temperature can be one of the most general ways to control product property parameters for a given catalyst system, it is often a challenge in many conventional systems to obtain a product with both a relatively low molecular weight and a relatively high vinylidene content. Thus, in some preferred embodiments of the present application, the combination of reaction / polymerization / oligomerization conditions and certain metallocene catalyst systems can advantageously result in decreasing molecular weight and increasing vinylidene content as the reaction temperature is increased, thereby allowing increased control over the desired parameters without having to sacrifice one to achieve the other. In such preferred embodiments, for example, by carefully selecting the elements of the metallocene catalyst system, the average activity level of the catalyst system can further advantageously be maintained at or above a sufficiently high level to obtain a minimum reasonable yield of oligomer product relative to the monomer reactant(s).

[0732] Generally, one or more metallocene compounds, one or more activators, and one or more monomers are contacted to produce a polymer or oligomer. These catalysts can be supported and thus can be particularly useful for known slurry, solution, or bulk modes of operation, either in a single, series, or parallel reactors. If the catalyst, activator, or co-activator is a soluble compound, then a solution mode can be employed for the reaction. Solution or slurry type operation can be applicable even if one of the components is not completely soluble in the reaction medium or in the feed solution, at the beginning of the reaction or during the course of the reaction or at a later stage of the reaction. In any case, the catalyst system components, dissolved or suspended in a solvent such as toluene or other conveniently available aromatic solvent, or in an aliphatic solvent, or in the feed alpha-olefin stream, are fed to the reactor under an inert atmosphere, typically an atmosphere surrounded by nitrogen or argon, to allow polymerization or oligomerization to occur.

[0733] The polymerization or oligomerization can be carried out in a batch mode, where all components are added to the reactor and allowed to react to a predetermined degree of conversion, either partial or complete. Subsequently, the catalyst can be deactivated by any available means, such as exposure to air or water, or by addition of an alcohol or a solvent containing a deactivating agent.

[0734] Alternatively or additionally, the polymerization or oligomerization can be carried out in a semi-continuous operation, in which the feed and catalyst system components can be added continuously and / or simultaneously to the reactor, thereby maintaining a constant ratio of catalyst system components to feed olefin(s). The reaction can be allowed to proceed to a predetermined stage when all of the feed and catalyst system components are added. The reaction can then be interrupted by catalyst deactivation in the same manner as described for the batch operation.

[0735] Alternatively or additionally, the polymerization or oligomerization can be carried out in a continuous operation, in which the feed and catalyst system components can be added continuously and / or simultaneously to the reactor, thereby maintaining a constant ratio of catalyst system and feed olefins. The reaction product can be continuously withdrawn from the reactor, e.g., in the usual continuous stirred tank reactor (CSTR) operation. Preferably, the process is carried out in a continuous operation, in which the feed and catalyst system components are added continuously and / or simultaneously to the reactor, thereby maintaining a constant ratio of catalyst system and feed olefins; and the reaction mixture is continuously withdrawn from the reactor. The residence time of the reactants can be controlled by a predetermined degree of conversion. The withdrawn product can then be quenched, typically in a separate reactor, in a similar manner as for the other operations. In some embodiments, any process for making the PAO described herein is a continuous process, which can include the steps of: a) continuously introducing a feed stream comprising at least 10 mol% of one or more C6-Ci8α-olefins into a reactor, b) continuously introducing a metallocene compound and an activator into the reactor, and c) continuously withdrawing the PAO from the reactor. Preferably, the process is carried out in a continuous stirred tank reactor or a plug flow reactor. Additionally or alternatively, the continuous process can include the step of maintaining a partial pressure of hydrogen in the reactor of 200 psig (-1.4 MPag) or less, based on the total pressure in the reactor, e.g., 150 psig (-1.0 MPag) or less, 100 psig (-690 kPag) or less, 50 psig (-350 kPag) or less, 25 psig (-170 kPag) or less, or 10 psig (-69 kPag) or less. Additionally or alternatively, the hydrogen, if present in the reactor, in the feed, or in both, is at a concentration of 1,000 ppm by weight or less, e.g., 750 wppm or less, 500 wppm or less, 250 wppm or less, 100 wppm or less, 50 wppm or less, 25 wppm or less, 10 wppm or less, or 5 wppm or less. 24 The feed stream of α-olefins is continuously introduced into the reactor, b) the metallocene compound and the activator are continuously introduced into the reactor, and c) the PAO is continuously withdrawn from the reactor. Preferably, the process is carried out in a continuous stirred tank reactor or a plug flow reactor. Additionally or alternatively, the continuous process can include the step of maintaining a partial pressure of hydrogen in the reactor of 200 psig (-1.4 MPag) or less, based on the total pressure in the reactor, e.g., 150 psig (-1.0 MPag) or less, 100 psig (-690 kPag) or less, 50 psig (-350 kPag) or less, 25 psig (-170 kPag) or less, or 10 psig (-69 kPag) or less. Additionally or alternatively, the hydrogen, if present in the reactor, in the feed, or in both, is at a concentration of 1,000 ppm by weight or less, e.g., 750 wppm or less, 500 wppm or less, 250 wppm or less, 100 wppm or less, 50 wppm or less, 25 wppm or less, 10 wppm or less, or 5 wppm or less.

[0736] Preferred reactor sizes can range from 2 mL and above. Frequently, for commercial production, reactors having a volume greater than 1 liter are preferred. The production facility can have one single reactor, or several reactors arranged in series or in parallel, or both, to maximize production rate, product properties, and overall process efficiency. Frequently, the reactor and associated equipment are pretreated to ensure proper reaction rates and catalyst performance. Frequently, the reaction is conducted under an inert atmosphere, where the catalyst system and feed components can not be contacted with any catalyst deactivators or poisons such as polar oxygen, nitrogen, sulfur, and / or acetylenic compounds.

[0737] One or more reactors in series or in parallel can be used in the present application. The metallocene compound, activator, and when desired, co-activator, can be delivered to the reactor separately as a solution or slurry in a solvent or in the alpha-olefin feed stream, activated in-line prior to the reactor, or pre-activated and pumped to the reactor as an activated solution or slurry. Polymerization / oligomerization can be conducted in a single reactor, where monomer, or monomers, catalyst / activator / co-activator, optional scavenger, and optional modifier can be added continuously to the single reactor, or in series reactors, where the above components can be added to each of two or more reactors connected in series. The catalyst system components can be added to the first reactor in series. Alternatively, the catalyst system components can be added to two reactors, where one component is added to the first reactor and the other component is added to the other reactor. In some embodiments, the metallocene compound can be activated in the reactor in the presence of the olefin. Alternatively, the metallocene compound (e.g., the dichloride form of the metallocene compound) can be pre-treated with an aluminum alkyl reagent, especially triisobutylaluminum, tri-n-hexylaluminum, and / or tri-n-octylaluminum, before charging to a reactor containing the other catalyst system components and the feed olefin, or pre-activated with the other catalyst system components to produce a fully activated catalyst, which can then be fed to a reactor containing the feed olefin. In another alternative, the procatalyst metallocene can be mixed with the activator and / or co-activator, and this activated catalyst can then be added to the reactor with a feed olefin stream containing some scavenger or co-activator. In another alternative, all or part of the co-activator can be pre-mixed with the feed olefin and added to the reactor simultaneously with the other catalyst solution containing the metallocene and activator and / or co-activator.

[0738] The catalyst composition can be used alone or can be mixed with other known polymerization catalysts to produce polymer or oligomer blends. The monomer and catalyst selection can allow the production of polymer or oligomer blends under conditions similar to those using the catalyst alone. Polymers having an increased PDI can be obtained from polymers made using a mixed catalyst system and thus can be achieved. The mixed catalyst can comprise two or more metallocene compounds and / or two or more activators.

[0739] The PAOs described herein can additionally or alternatively be produced in a homogeneous solution process. Generally, this involves polymerization or oligomerization in a continuous reactor in which the forming polymer and supplied starting monomer and catalyst materials can be agitated to reduce or avoid concentration or temperature gradients. Temperature control in the reactor can generally be obtained with reactor cooling to balance the heat of polymerization, by reactor jacket or cooling coils or cooling side streams of the reactants to cool the contents of the reactor, auto refrigeration, pre-cooling of the feed, evaporation of a liquid medium (diluent, monomer or solvent) or combinations of the above. Adiabatic reactors can additionally or alternatively be used with pre-cooling of the feed. The reactor temperature can vary with the catalyst used and the desired product. Higher temperatures can tend to produce lower molecular weight, and lower temperatures can tend to produce higher molecular weight; however, this is not a fixed rule. Generally, the reactor temperature can preferably vary between about 0°C and about 300°C, for example from about 10°C to about 230°C or from about 25°C to about 200°C. Frequently, it is important to control the reaction temperature to be predetermined. To produce fluids with narrow polydispersities, for example to promote the highest possible shear stability, it can be useful to control the reaction temperature to obtain minimal temperature swings in the reactor or over the reaction time. If multiple reactors are used in series or in parallel, it can be useful to keep the temperature constant at a predetermined value, for example to minimize any broadening of the molecular weight distribution. To produce products with a broader molecular weight distribution, the reaction temperature swing or fluctuation can be adjusted, or as with series operation, the second reactor temperature can be higher than the first reactor temperature. In parallel reactor operation, the temperatures of the two reactors can be independent. Alternatively, more than one type of metallocene catalyst can be used.

[0740] The pressure in any of the reactors used herein can vary from about 0.1 atm to about 100 atm (about 1.5 psia to about 1500 psia), for example from about 0.5 atm to about 80 atm (~7 psia to ~1,200 psia) or from about 1.0 atm to about 50 atm (~15 psia to ~750 psia). The reaction can be conducted under an atmosphere of nitrogen or with some hydrogen. At times, a small amount of hydrogen can be added to the reactor to improve catalyst performance. When present, the amount of hydrogen can be maintained at such a level as to improve catalyst productivity, but preferably does not cause excessive (preferably any appreciable) hydrogenation of the olefins, especially the alpha-olefins of the feed (alpha-olefin reaction to saturated paraffins can be very detrimental to the efficiency of the process). The amount of hydrogen partial pressure is thus preferably maintained at a low value, for example less than 50 psi (350 kPa), less than 25 psi (170 kPa), less than 10 psi (69 kPa), or less than 5 psi (35 kPa); additionally or alternatively, the concentration of hydrogen in the reaction phase, in the reactor and / or in the feed can be less than 10,000 ppm by weight, for example less than 1,000 ppm, less than 500 ppm, less than 100 ppm, less than 50 ppm, less than 25 ppm, or less than 10 ppm.

[0741] The reaction time or reactor residence time can depend on the catalyst used, the amount of catalyst used, and the level of alpha-olefin conversion desired. Different metallocene compounds generally have different activities. Often, higher degrees of alkyl substitution on the Cp rings or bridging can improve catalyst productivity. Higher catalyst loadings can tend to produce higher alpha-olefin conversion in shorter reaction times. However, high catalyst usage can make the production process uneconomical and difficult to manage reaction heat or control reaction temperature. Thus, it can be useful to select a catalyst with the maximum catalyst productivity to minimize the amount of metallocene and activator required.

[0742] When the catalyst system is a metallocene plus a Lewis acid or ionic promoter with an NCA component, the amount of metallocene can range from 0.00001 micrograms per gram (mcg / g) to 500 mcg / g of the metallocene component relative to the alpha-olefin feed, for example 0.0001 mcg / g to 100 mcg / g, and / or the molar ratio of NCA activator to metallocene can range from 0.001 to 10, for example 0.01 to 5 or 0.1 to 3. If an alkyl aluminum compound co-activator is used, the molar ratio of Al to metallocene can range from 1 to 1000, for example 2 to 500 or 4 to 400.

[0743] Generally, it can be preferred to have the maximum possible conversion of the alpha-olefin (close to 100%) in the shortest possible reaction time with the feed alpha-olefin. However, in CSTR operation, it can sometimes be beneficial to run the reaction at an optimal alpha-olefin conversion, which can be less than 100% alpha-olefin conversion, but preferably close to 100%. There can also be situations where partial alpha-olefin conversion can be more desirable, for example, where a narrow product PDI (Mw / Mn) is desired, as partial conversion can avoid PDI broadening effects. If the reaction is run to less than 100% alpha-olefin conversion, the unreacted starting material can be simply removed after separation from other products and solvent / diluent, or it can be recycled to improve overall reaction efficiency. Conversion (also referred to as alpha-olefin conversion) is determined by the amount (grams) of isolated PAO recovered from the polymerization mixture (after the polymerization has stopped) divided by the amount (grams) of alpha-olefin introduced into the reactor. (When reported in %, conversion = (grams of isolated PAO / grams of alpha-olefin used) x 100). Preferably, the conversion of the polymerization reactions described herein is 20% or greater, alternatively 40% or greater, alternatively 60% or greater, alternatively 70% or greater, alternatively 80% or greater, alternatively 90% or greater, alternatively 95% or greater. The isolated PAO is the PAO product obtained after the solvent, unreacted monomer, and other volatile materials (e.g., dimers) have been removed (e.g., by vacuum flash). In some cases, the desired PAO is a dimer, and care is taken to remove the dimeric material without the untreated monomer and / or solvent.

[0744] The desired residence time for any of the methods described herein can be 1 minute to 20 hours, for example, 5 minutes to 10 hours.

[0745] Each of these methods can also be used in a single reactor, parallel or series reactor configuration. The methods can be conducted in a continuous stirred tank reactor or plug flow reactor, or more than one reactor operating in series or in parallel. These reactors can or can not have internal cooling and can or can not be refrigerated for the monomer feed. See the general invention of U.S. Patent No. 5,705,577 for general process conditions.

[0746] When using a solid-supported catalyst, the slurry polymerization / oligomerization process is generally operated at similar temperatures, pressures, and residence times as described previously. In slurry polymerization or oligomerization, a suspension of the solid catalyst, promoter, monomer, and comonomer is added. The suspension, including the diluent, is removed from the reactor intermittently or continuously. The catalyst is then separated from the product by filtration, centrifugation, or sedimentation. The fluid is then distilled to remove the solvent, any unreacted components, and light products. Some or all of the solvent and unreacted components or light components can be recycled for use again.

[0747] If the catalyst used is unsupported or a solution catalyst, the product can still contain soluble, suspended, or mixed catalyst system components when the reaction is complete or when the product is withdrawn from the reactor (e.g., in a CSTR). These components can be deactivated and / or removed, if desired. Any conventional catalyst deactivation method or water wash method can be used to remove the catalyst system components. Typically, the reaction can be deactivated by adding a stoichiometric amount or an excess of air, moisture, alcohol, isopropanol, etc. The mixture can then be washed with diluent sodium hydroxide or with water to remove the catalyst system components. The residual organic layer can then be distilled to remove the solvent, which can optionally be recycled for reuse. Distillation can also remove any light reaction products, such as from a CSTR, and the distillate can be hydrogenated to produce a high quality chain hydrocarbon solvent. 18 and lower. These light components can be used as diluents for additional reactions or can be used as olefinic feedstocks for other chemical syntheses, as these light olefin byproducts can have vinylidene unsaturation, which is most suitable for further functionalization to convert to high performance fluids. Additionally or alternatively, these light olefin products can be hydrogenated for use as high quality chain hydrocarbon solvents.

[0748] Polymerization or oligomerization in the absence of hydrogen can advantageously provide polymers or oligomers having a high degree of unsaturation. These double bonds can be readily converted to functionalized fluids having a variety of performance characteristics. Examples of converting oligomers and / or polymers can be found in the preparation of ashless dispersants, such as by reacting the polymer with maleic anhydride to produce a PAO-succinic anhydride, which can then be reacted with amines, alcohols, and / or polyether alcohols to convert to dispersants, such as disclosed in the book "Lubricant Additives: Chemistry and Application" edited by Leslie R. Rudnick, pages 143-170.

[0749] Desirably, in the process of the present application, the polymerization reaction mixture exiting the polymerization reactor can typically comprise oligomers, including vinylidene, tri-substituted vinylene, optionally di-substituted vinylene, and optionally vinyl groups, optionally residual olefin monomer feed, optionally solvent, and components derived from the catalyst system, due to the structural features of the metallocene compound.

[0750] The polymerization reaction mixture can then be quenched, such as by adding a quenching agent, such as water, CO2, methanol, ethanol, mixtures thereof, etc. Subsequently, the polymerization reaction mixture can be separated to remove residual monomer, which can be recycled to the polymerization reactor. Monomer removal can be carried out by, for example, flashing under vacuum, distillation, or extraction. The resulting mixture can comprise unsaturated PAO product, including vinylidene, tri-substituted vinylene, optionally di-substituted vinylene, and optionally vinyl groups.

[0751] Without being bound by theory, it is believed that non-coordinating anions having a small molecular size (e.g., tetra(perfluorophenyl)borate anion) can tend to result in higher selectivity for ethenyl groups and lower selectivity for ethylene groups when used as activators for the same metallocene compound of the present invention as compared to non-coordinating anions having a large molecular size (e.g., tetra(perfluoronaphthyl)borate anion).

[0752] The unsaturated PAO product obtained immediately after monomer removal can contain dimers, trimers, tetramers, pentamers, and even oligomers having higher degrees of polymerization. Extraction or fractionation can be performed to separate the product into multiple fractions having different boiling point ranges (corresponding to different molecular weight ranges and different degrees of polymerization). For example, dimers can be isolated as a low viscosity, low boiling point fraction as one grade of product, and the remaining material can be used as another grade of unsaturated PAO product, etc.

[0753] IV.6 Hydrogenation

[0754] At least a portion of the unsaturated PAO product can be hydrogenated to obtain an at least partially saturated PAO product. The unsaturated PAO product can be treated to reduce compounds containing heteroatoms to less than 600 ppm by weight. Thereafter, in some embodiments, the treated product can then be contacted with hydrogen and a hydrogenation catalyst to produce an at least partially saturated hydrogenated PAO product, for example at a temperature of 25 °C to 350 °C (e.g., 100 °C to 300 °C) for a time period of 5 minutes to 100 h (e.g., 5 minutes to 24 h) at a hydrogen pressure of 25 psig to 2500 psig (~ 170 kPag to ~ 17 MPag), for example 100 psig to 2000 psig (~ 690 kPag to ~ 14 MPag). More information regarding hydrogenation of unsaturated PAO products can be found in U.S. Patent No. 5,573,657 and “Lubricant Base Oil Hydrogen Refining Processes” (Sequeira, Avilino Jr. et al. (1994) pp. 119-152 in Lubricant Base Oil and Wax Processing, Marcel Dekker, Inc., New York).

[0755] This hydrogenation process can be accomplished, for example, in a slurry reactor, using batch operation, or in a continuous stirred tank reactor (CSTR), where 0.001 wt% to 20 wt% (e.g., 0.01 wt% - 10 wt%) of the catalyst, hydrogen, and uPAO feed can be continuously added to the reactor to allow for a residence time, for example, of 5 minutes to 10 hours, to allow for the desired (e.g., substantially complete) hydrogenation of the unsaturated olefins. The amount of catalyst added can typically be very small, to compensate only 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. If desired, the catalyst can be regenerated and reused. The hydrogenated PAO can be used as is or further distilled or fractionated to the desired level. In some cases, where the hydrogenation catalyst shows little or no catalyst deactivation over long term operation, the stirred tank hydrogenation process can be carried out in the following manner, where a fixed amount of catalyst is maintained in the reactor, for example, 0.1 wt% - 10% of the total reactants, the majority (or just) of the hydrogen and PAO feed are continuously added at a feed rate, and the primarily (or just) hydrogenated PAO is withdrawn from the reactor.

[0756] The hydrogenation process can additionally or alternatively be accomplished by a fixed bed process, where the solid catalyst can be packed inside a tubular reactor and heated to the reactor temperature. The hydrogen and PAO feed can be sent through the reactor simultaneously, either from the top or bottom, or countercurrently, for example, to maximize contact between the hydrogen, PAO, and catalyst and to allow for excellent heat management. The feed rates of the PAO and hydrogen can be adjusted to produce the appropriate residence time, for example, to allow for the desired (typically substantially complete) hydrogenation of the unsaturated PAO in the feed. The hydrogenated PAO fluid can be used as is or further distilled or fractionated to the desired level. Frequently, the hydrogenated PAO product can have a bromine value of 2.0 or less.

[0757] IV.7 Functionalization

[0758] At least a portion of the unsaturated PAO product can be reacted with a chemical reagent to obtain an at least partially functionalized PAO product. However, due to the unique nature of the functionalization reaction, the specificity of potential byproducts or side products to be avoided, the range of potential desired functionality, and thus the range of potential reaction conditions that can be obtained or sufficient to obtain the desired functionality, it can be difficult to specify a set of appropriate conditions, reactors, chemical reagents, and / or catalysts / additives, etc. to include them all. Nonetheless, conventional functionalization techniques and their reaction parameters are known to those skilled in the chemical arts, allowing for partially or fully functionalized PAO products to exhibit any one or more of a variety of functional groups to be readily obtained. In the case of substantially or fully functionalized PAO products, in some embodiments, the bromine number can be 2.0 or less. Unless otherwise indicated, the bromine number in the present application is determined according to ASTM D 1159.

[0759] Kinematic viscosity (KV40 and KV100) is determined according to ASTM D445 (at 40°C and 100°C). Viscosity Index (VI) is determined according to ASTM D2270. Noack volatility (NV) is determined according to ASTM D5800.

[0760] V. Lubricant Base Stocks

[0761] The unsaturated PAO products and hydrogenated PAO products of the present application that can be advantageously obtained by using the methods of the present application can be used as base stocks for lubricating oil compositions. Preferably, the hydrogenated PAO products having a bromine number of no greater than 2.0 are used as lubricating oil base stocks. The base stocks can be of any viscosity grade that can be used in any particular lubricating oil composition. The base stocks of the present application can be blended with each other, with other API Group I, II, III, IV, or V base stocks, lubricating additive packages, etc. to form a lubricating oil composition. "Lubricating oil," "lubricating oil composition," and "lubricant" are used interchangeably herein. Lubricants can include internal combustion engine oils, gas turbine oils, automotive transmission system oils, power transmission fluids (e.g., hydraulic fluids), process oils, heat transfer oils (e.g., transformer oils), industrial lubricants, gear box lubricants, etc., and combinations thereof.

[0762] VI. Additional Embodiments

[0763] Additionally or alternatively, the present application can include one or more of the following embodiments:

[0764] 1. A method of producing a polyalphaolefin PAO, the method comprising:

[0765] polymerizing in a polymerization reactor under polymerization conditions a C6-C 32The feedstock of an α-olefin is contacted with a catalyst system comprising an asymmetric metallocene compound, an activator compound soluble in a non-aromatic hydrocarbon solvent, and a non-aromatic hydrocarbon solvent to undergo polymerization, thereby obtaining a polymerization reaction mixture comprising vinylidenes, trisubstituted vinylides, optionally disubstituted vinylides, and optionally vinylides; and

[0766] An unsaturated PAO product is obtained from the polymerization reaction mixture, wherein the unsaturated PAO product comprises ethylene ide groups, optional trisubstituted vinylides, optional disubstituted vinylides, and optional vinyl groups.

[0767] 2. The method of paragraph 1, wherein the metallocene compound is represented by formula (I) described herein, preferably R 1 R 2 and R 3 At least one of them is not hydrogen and R 1 R 2 and R 3 At least one of them is hydrogen.

[0768] 3. The method of paragraph 1, wherein the metallocene compound is represented by formula (II) described herein.

[0769] 4. The method of paragraph 1, wherein the metallocene compound is represented by formula (III) described herein.

[0770] 5. The method of paragraph 1, wherein the metallocene compound is represented by formula (IV) described herein.

[0771] 6. The method in paragraph 2 or 4, where in equation (I) or (III), R 2 It is hydrogen and R 1 and R 3 One is a substituted or unsubstituted linear, branched or cyclic C1-C6 hydrocarbon group, and R 1 and R 3 The other one is hydrogen, and / or R 6 and R 7 、or R 7 and R 17 、or R 17 and R 18 Together with the corresponding carbon atoms in the indenyl ring directly connected to them, they form a ring fused with the indenyl ring, preferably the ring fused with the indenyl ring contains one or more saturated carbon atoms.

[0772] 7. The methods in paragraphs 2 to 6, wherein M is Hf or Zr in any of equations (I), (II), (III) or (IV).

[0773] 8. The methods in paragraphs 1 to 7, wherein the activator compound soluble in non-aromatic hydrocarbons is represented by formula (V):

[0774] [R 1′ R 2′ R 3′ EH] d+ [Mt k+ Q n ] d- (V)

[0775] Where: E is nitrogen or phosphorus; d is 1, 2, or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6; nk = d, R 1′ R 2′ and R 3′ Independently for C1-C 50 The hydrocarbon group may be optionally replaced by one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups, wherein R 1′ R 2′ and R 3′ It contains a total of 15 or more carbon atoms; Mt is an element selected from Group 13 of the periodic table; and each Q is independently a hydrogen group, a bridged or unbridged dialkylamino group, a halogen group, an alkoxy group, an aryloxy group, a hydrocarbon group, a substituted hydrocarbon group, a halohydrocarbon group, a substituted halohydrocarbon group, or a halogen-substituted hydrocarbon group.

[0776] 9. The methods in paragraphs 1 to 7, wherein the activating compound soluble in non-aromatic hydrocarbons is represented by formula (VI):

[0777] [R 1′ R 2′ R 3′ EH] + [BR 4′ R 5′ R 6′ R 7′ ] - (VI)

[0778] Where: E is nitrogen or phosphorus; R 1′ It is a methyl group; R 2′ and R 3′ Independently for C4-C 50 The hydrocarbon group may be optionally replaced by one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups, wherein R 2′ and R 3′ It contains a total of 14 or more carbon atoms; B is boron; and R 4′ R 5′ R 6′ and R 7′ It is independently a hydrogen-based, bridged or unbridged dialkylamino, halogenated, alkoxy, aryloxy, hydrocarbon, substituted hydrocarbon, haloalkyl, substituted haloalkyl, or halogen-substituted hydrocarbon group.

[0779] 10. The methods in paragraphs 1 to 7, wherein the activating compound soluble in non-aromatic hydrocarbons is represented by formula (VII) or formula (VIII):

[0780]

[0781] Where: N is nitrogen; R 2’ and R 3’ Independently for C6-C 40 The hydrocarbon group may be optionally replaced by one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups, wherein R in formula (VII) 2 and R 3 It contains a total of 14 or more carbon atoms and R in formula (VIII) 2’ Contains 13 or more carbon atoms; R 8’ R 9’ and R 10’ Independently for C4-C 30 Hydrocarbon group or substituted C4-C 30 Hydrocarbon group; B is boron; and R 4’ R 5’ R 6’ and R 7’ It is independently a hydrogen-based, bridged or unbridged dialkylamino, halogenated, alkoxy, aryloxy, hydrocarbon, substituted hydrocarbon, haloalkyl, substituted haloalkyl, or halogen-substituted hydrocarbon group.

[0782] 11. The method in paragraph 9 or 10, where R 4’ R 5’ R 6’ and R 7’ It is pentafluorophenyl.

[0783] 12. The method in paragraph 10, where R 8’ and R 10’ It is a hydrogen atom and R 9’ It is C4-C 30 The hydrocarbon group may be optionally replaced by one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups.

[0784] 13. The method in paragraph 11, where R 9’ It is C8-C 22 The hydrocarbon group may be optionally replaced by one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups.

[0785] 14. The method in paragraph 10, where R 2’ and R 3’ Independently for C 12 -C 22 Hydrocarbon group.

[0786] 15. The method of any one of paragraphs 1 to 14, wherein the solvent is substantially free of fully aromatic solvents, such as toluene.

[0787] 16. The method of any one of paragraphs 1 to 15, wherein the solvent is selected from C4-C 10 Linear, branched, or cyclic alkanes.

[0788] 17. The method of any one of paragraphs 1 to 16, wherein the solvent is selected from one or more C6-C solvents. 32 α-olefins, such as C8-C 16 α-olefins.

[0789] 18. The method of any one of paragraphs 1 to 15, wherein the solvent is substantially free of all-non-α-olefin solvents.

[0790] 19. The method of any one of paragraphs 1 to 18, wherein: the method comprises obtaining an unsaturated PAO product from a polymerization reaction mixture, wherein the polymerization reaction exhibits selectivity for greater than or equal to about 80 mol% vinylidene groups, based on the total molar number of vinyl, vinylidene, disubstituted vinylidene and trisubstituted vinylidene groups in the unsaturated PAO product.

[0791] 20. The method of any one of paragraphs 1 to 19, wherein the conversion is about 10% or greater and the polymerization reaction exhibits selectivity for about 80 mol% ethylene ide groups, based on the total molar number of vinyl groups, ethylene ide groups, disubstituted vinylides and trisubstituted vinylides in the unsaturated PAO product.

[0792] 21. The method of any one of paragraphs 1 to 20, wherein the polymerization reaction exhibits selectivity for combinations of more than or equal to about 90 mol% vinylidene, 0.5 mol% to 6 mol% trisubstituted vinylidene, less than or equal to about 2.5 mol% disubstituted vinylidene, and less than or equal to about 1.5 mol% vinylidene, based on the total molar number of vinylidene, vinylidene, disubstituted vinylidene, and trisubstituted vinylidene in the unsaturated PAO product.

[0793] 22. The method of paragraph 21, wherein the polymerization reaction exhibits selectivity for combinations of vinylidene groups equal to or greater than 95 mol%, trisubstituted vinylidene groups less than 2.5 mol%, disubstituted vinylidene groups 1.0 mol% or less, and vinylidene groups 1.5 mol% or less, based on the total molar number of vinylidene, vinylidene, disubstituted vinylidene, and trisubstituted vinylidene groups in the unsaturated PAO product.

[0794] 23. The method of paragraph 22, wherein the polymerization reaction exhibits selectivity for combinations of vinylidene and trisubstituted vinylidene together greater than 95.0 mol%, and combinations of disubstituted vinylidene and vinylidene together less than 5.0 mol%, based on the total molar number of vinylidene, vinylidene, disubstituted vinylidene and trisubstituted vinylidene in the unsaturated PAO product.

[0795] 24. The method of any one of paragraphs 1 to 23, wherein the polymerization reaction results in a state as described above. 1 Unsaturated PAO products with a number-average molecular weight (Mn) of 2500 g / mol or less, preferably 1000 g / mol or less, as measured by H NMR.

[0796] 25. The method of any one of paragraphs 1 to 24, wherein: the polymerization conditions include a reaction temperature of 40°C to 180°C; an average activity level of at least 1,500 g / mmol·hr; the polymerization reaction mixture exhibiting a conversion of at least 10%; or a combination thereof.

[0797] 26. The method of any one of paragraphs 1 to 25 further comprises: a) contacting the unsaturated PAO product with hydrogen to convert at least a portion of the unsaturated PAO product into 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 into a functionalized PAO product; or a combination thereof.

[0798] 27. The method of any one of paragraphs 1 to 26, wherein any combination of C2-C5 α-olefins is present in the α-olefin feed at a concentration not exceeding 25 mol%, based on the total number of α-olefins supplied to the polymerization reactor.

[0799] 28. The method of any one of paragraphs 1 to 27, wherein the unsaturated PAO product comprises a dimer.

[0800] 29. The method of any one of paragraphs 1 to 27, wherein the unsaturated PAO product is represented by the following formula (F-1):

[0801]

[0802] Where R 1 R 2a R 2b R 3 Each R 4 and R 5 R 6 and R 7 The , which may be the same or different each time it appears, independently represents hydrogen or a substituted or unsubstituted hydrocarbon group, and n is a non-negative integer corresponding to the degree of polymerization, preferably R 1 It is an unsubstituted hydrocarbon group, R2a and R 2b Both are hydrogen and n is 0.

[0803] 30. Any one of the methods in paragraphs 1 to 29, where C6-C 32 α-olefins, metallocene compounds, and activators are contacted in a continuous stirred tank reactor or a continuous tubular reactor in either the solution phase or the bulk phase.

[0804] 31. The method of any one of paragraphs 1 to 30, wherein the method is carried out in a continuous operation, wherein the feed and catalyst system components are continuously and / or simultaneously added to the reactor to maintain a constant ratio of the catalyst system to the feed olefin; and the reaction mixture is continuously withdrawn from the reactor.

[0805] 32. Any of the methods in paragraphs 1 to 30, wherein the method is a sequential method.

[0806] 33. The method of any one of paragraphs 1 to 30, wherein the method is a continuous method comprising the steps of: a) dissolving at least 10 mol% of one or more C6-C 24 a) The feed stream of α-olefin is continuously introduced into the reactor, b) the metallocene compound and activator are continuously introduced into the reactor, and c) the PAO product is continuously extracted from the reactor.

[0807] 34. The method of any one of paragraphs 1 to 30, wherein the method is carried out in a continuous stirred tank reactor or a plug flow reactor.

[0808] 35. The method of any one of paragraphs 1 to 34, wherein the feed comprises octene, decene, octene and decene, or octene, decene and dodecene.

[0809] 36. The method of any one of paragraphs 1 to 35, wherein the feed comprises a single α-olefin monomer or a combination of two or more α-olefin monomers.

[0810] 37. The method of any one of paragraphs 1 to 36, wherein the feed comprises a single α-olefin monomer selected from the group consisting of hexene, heptenene, octene, nonene, decene, dodecene, tetradecene, and hexadecane.

[0811] 38. The method of any one of paragraphs 1 to 36, wherein the feed comprises two or more α-olefin monomers selected from the group consisting of hexene, heptenene, octene, nonene, decene, dodecene, tetradecene, and hexadecene.

[0812] 39. The method of any one of paragraphs 1 to 38, wherein PAO is a homopolymer of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetracene or 1-tetradecene.

[0813] 40. The method of any one of paragraphs 1 to 38, wherein PAO is a copolymer of decene and one or more of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetracene or 1-tetradecene.

[0814] 41. Any one of the methods in paragraphs 1 to 40, where C6-C 32 α-olefins, metallocene compounds, and activators are contacted in a continuous stirred tank reactor or continuous tubular reactor in a solution phase, bulk phase, or slurry phase.

[0815] 42. The method of any one of paragraphs 1 to 41, wherein the polymerization temperature is greater than 100°C, the conversion rate is 50% or greater, and the unsaturated PAO product has about 80 mol% or more of vinylidene groups, based on the total molar number of vinyl groups, vinylidene groups, disubstituted vinylides, and trisubstituted vinylides in the unsaturated PAO product.

[0816] 43. The method of any one of paragraphs 1 to 41, wherein the polymerization temperature is greater than 110°C, the conversion rate is 50% or greater, and the unsaturated PAO product has about 90 mol% or more of vinylidene groups, based on the total molar number of vinyl groups, vinylidene groups, disubstituted vinylides, and trisubstituted vinylides in the unsaturated PAO product.

[0817] 44. The method of any one of paragraphs 1 to 43, wherein the unsaturated PAO product is represented by the following formula:

[0818]

[0819] Where C is a hydrocarbon chain with a length of m'-2, each m' being independently 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 and being the carbon number of one or more monomers used in the polymerization, and n' being 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0820] 45. Fuel or lubricant containing PAO produced according to any one of paragraphs 1 to 44.

[0821] 46. ​​A functionalized PAO comprising the following reaction products: 1) a heteroatom-containing group, and 2) a PAO produced by any one of paragraphs 1 to 44, wherein the heteroatom-containing group comprises one or more sulfonates / esters, amines, aldehydes, alcohols, or acids, preferably comprising epoxides, succinic acid, maleic acid, or maleic anhydride, or the heteroatom-containing group comprises one or more of acids, esters, anhydrides, acid esters, oxycarbonyl, carbonyl, formyl, formylcarbonyl, hydroxyl, and acetyl halide.

[0822] 47. The method of any one of paragraphs 1 to 44, the method having a productivity of at least 4,500 g / mmol / hr, wherein the method comprises: contacting at a temperature of 35°C to 150°C.

[0823] 48. The method of any one of paragraphs 1 to 44 or 47 further comprises hydrogenating at least a portion of the polyalphaolefin and then formulating a fuel or lubricating composition comprising the product of hydrogenating at least a portion of the polyalphaolefin.

[0824] 49. The method of any one of paragraphs 1 to 44 or 47 further comprises functionalizing at least a portion of the PAO and then formulating a fuel or lubricating composition comprising the product of functionalizing at least a portion of the PAO.

[0825] experiment

[0826] Preparation of pre-catalyst

[0827] All operations involving air- and moisture-sensitive compounds are performed in a thoroughly purified argon atmosphere using standard Schlenk techniques or in a controlled atmosphere glove box (VacuumAtmospheres Co.).

[0828] Tetrahydrofuran (THF, Merck = Merck KGaA, Darmstadt, Germany) and diethyl ether (Merck) used in synthesis are typically purified by distillation with LiAlH4 and stored under an inert atmosphere using sodium benzophenone ketyl; the solvent is distilled from the benzophenone carbonyl before use. Hydrocarbon solvents such as toluene (Merck) and hexane (Merck) are typically distilled with CaH2 and stored under an inert atmosphere using a Na / K alloy; the solvent is distilled from the Na / K alloy before use. Dichloromethane (and CCl2D2 used for NMR measurements) are typically distilled with CaH2 under an inert atmosphere and stored; the solvent is distilled from the CaH2 before use. Celite (Aldrich) is dried in a vacuum oven at 180 °C. Use p-toluenesulfonic acid (TsOH, Aldrich), 2-methylindan-1-one (Aldrich), n-butyllithium (1.6M in hexane, Aldrich), hexane (Aldrich anhydrous), 3-chloropropionyl chloride (Acros), potassium tert-butoxide (Acros), iodomethane (Acros), Na2SO4 (Akzo Nobel), methanol (Merck), ethylene glycol (Merck), sodium lumps (Merck), potassium hydroxide (KOH, Merck), AlCl3 (Merck), 1 and 2M HCl (dilute as needed; Reachim, Moscow, Russia), NaBH4 (Aldrich), anhydrous K2CO3 (Merck), MgSO4 (Merck), MeMgI (3M in Et2O, Sigma-Aldrich), CH3I (Sigma-Aldrich), isobutyl bromide (Sigma-Aldrich), Me5CpHfCl3 (Strem Chemicals), 1,2,3,5-tetrahydro-s-indacene (GLSyntech), hydrazine hydrate (Merck), silica gel 60 (40-63µm; Merck), and CDCl3 (Deutero GmbH).

[0829] Analytical and semi-preparative liquid chromatography was performed using a Waters Delta 600 HPLC system comprising a 996 photodiode array detector, Nova-Pack C18 or HR silica gel (60A, 6μm, 3.9 and 19×300mm) and symmetrical C18 (5μm, 4.6×250mm) columns. MPLC (medium-pressure liquid chromatography, 5–15 bar) was performed using an MPLC glass column and accessories (Ace Glass), a PD5130 pump drive equipped with a J1 gear-well pump head (Heidolph), a 996 photodiode array detector, and a Fraction Collector II (Waters Corp.). Recordings were performed using a Brucker Avance-400 spectrophotometer. 1 H and 13 C-chromatogram. Measurement of relative tetramethylsilane (TMS). 1 H and 13 Chemical shift of C. 1 The assignment of 1H NMR spectra was based on double resonance and nuclear Ofhausen effect (NOE) experiments. Trace CHN analysis was performed using a CHN-O-Rapid analyzer (Heraecus Ltd., Banau, Germany).

[0830] Synthesis of pentamethylcyclopentadienyl(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium(IV) (catalyst number = C)

[0831]

[0832] 2,2-Dimethylindan-1-one

[0833]

[0834] A solution of 176 g (1.21 mol) of 2-methylindan-1-one and 205 g (1.44 mol, 1.2 equivalent) of iodomethane in 200 mL of THF was added dropwise over 4 hours. The reaction mixture was stirred overnight at room temperature and then 2 L of water was added. The crude product was extracted with 300 mL of hexane and then 2 × 300 mL of dichloromethane. The combined organic extracts were dried by K₂CO₃, passed through a silica gel 60 short pad (40-63 μm), and the eluent was evaporated to dryness to produce a red oil. The oil was then distilled under vacuum to produce 185 g (96%) of 2,2-dimethylindan-1-one as a pale yellow oil (boiling point 76-78 °C / 5 mmHg) crystallizing at room temperature.

[0835] C 11 H 12 Analysis and calculation of O: C 82.46, H 7.55. Findings: C 82.24, H 7.61.

[0836] 1 H NMR (CDCl3): δ7.76 (d, J=7.6Hz, 1 H), 7.59(dt, J=7.6, 1.2Hz, 1 H), 7.44-7.35 (m, 2 H), 3.00(s, 2 H), 1.24(s, 6 H). 13 C{ 1 H}NMR(CDCl3): δ211.38,152.18,135.30,134.77,127.37,126.59,124.40,45.43,42.81,25.22.

[0837] 2,2-Dimethylindene

[0838]

[0839] A mixture of 129 g (~2.3 mol) KOH, 182.5 g (1.14 mol) 2,2-dimethylindan-1-one, and 144 mL of hydrazine hydrate in 850 mL of ethylene glycol was refluxed for 5 hours. Then, a Claisen distillation head with a condenser was used instead of the reflux condenser, and the mixture of H₂O, NH₂, NH₂, product, and ethylene glycol was distilled off until the distillation temperature reached 195 °C. The residue was then cooled to room temperature, and 300 mL of ethylene glycol, the second portion of 2,2-dimethylindan-1-one (182.5 g, 1.139 mol), and hydrazine hydrate (144 mL) were added, and the reduction process was repeated as described above. The upper layer (from the two consecutive reductions) of the combined distillates was separated, and the aqueous phase was diluted with 1,000 mL of water. The crude product was extracted with 3 × 300 mL of dichloromethane. The combined organic extracts were washed with 1M HCl, dried over K2CO3, passed through a short pad of silica gel 60 (40-63 μm), and the eluent was evaporated to dryness. The residue was distilled under vacuum to produce 290 g (87%) of 2,2-dimethylindene as a colorless liquid (boiling point 73.5 °C / 20 mm Hg).

[0840] C 11 H 14 Analysis and calculation: C 90.35, H 9.65. Findings: C 90.50, H 9.73.

[0841] 1 H NMR (CDCl3): δ7.19-7.08(m,4H),2.72(s,4H),1.15(s,6H). 13 C{ 1 H}NMR(CDCl3): δ143.51,125.93,124.70,47.70,40.05,28.77.

[0842] 6,6-Dimethyl-3,5,6,7-tetrahydro-s-indarsen-1(2H)-one

[0843]

[0844] A solution of 144.4 g (1.14 mol) of 3-chloropropionyl chloride and 165.6 g (1.13 mol) of 2,2-dimethylindene in 300 ml of dichloromethane was added dropwise to a stirred suspension of 165 g (1.24 mol) of AlCl3 in 900 ml of dichloromethane over 3 hours at room temperature. The mixture was stirred for an additional 3 hours at room temperature and then poured onto 1,000 g of crushed ice. The organic layer was separated, and the aqueous layer was extracted with 3 × 200 ml of dichloromethane. The combined organic extracts were washed with an aqueous solution of K2CO3, dried over K2CO3, passed through a silica gel 60 short pad (40-63 μm), and then evaporated to dryness to produce crude 3-chloro-1-(2,2-dimethyl-2,3-dihydro-1H-indene-5-yl)prop-1-one as a dark oily liquid. The liquid was added to 3,000 ml of 96% sulfuric acid at room temperature, and the mixture was stirred at room temperature. The resulting dark solution was heated to 90°C for 40 minutes and stirred at the same temperature for an additional hour. After cooling to room temperature, the reaction mixture was poured onto 6,000 g of crushed ice and 4,000 ml of cold water. Then, 2 liters of dichloromethane were added. The organic layer was separated, and the aqueous layer was extracted with dichloromethane (100 ml / 900 ml liquid phase). The combined organic extracts were washed with cold water and an aqueous K₂CO₃ solution, dried over K₂CO₃, and passed through a silica gel 60 short pad (40-63 μm). The eluent was evaporated to dryness to produce a slightly yellow solid. The latter was recrystallized from 600 ml of n-hexane (hot → room temperature) to produce 115.6 g (51%) of 6,6-dimethyl-3,5,6,7-tetrahydro-s-indane-1(2H)-one as a white crystalline material.

[0845] C 14 H 16 Analysis and calculation of O: C 83.96, H 8.05. Findings: C 84.19, H 8.22.

[0846] 1H NMR (CDCl3): δ7.52(s,1H),7.23(s,1H),3.09-3.02(m,2H),2.75(s,2H),2.73(s,2H),2.70-2.64(m,2H),1.15(s,6H). 13 C{ 1 H} NMR (CDCl3): δ206.53,154.39,152.31,143.46,135.89,122.55,119.36,47.74,46.74,40.69,36.61,28.42,25.52.

[0847] 2,2-Dimethyl-1,2,3,5-tetrahydro-s-indah

[0848]

[0849] 33 g (0.872 mol) of NaBH4 was added to a solution of 115.6 g (0.577 mol) of 6,6-dimethyl-3,5,6,7-tetrahydro-s-indargen-1(2H)-one in 600 mL of THF, cooled to 5 °C. Further, 300 mL of methanol was added dropwise to this mixture by vigorous stirring at 5 °C for approximately 5 hours. The mixture was stirred overnight at room temperature and then evaporated to dryness. 1,000 mL of dichloromethane and 1,000 mL of water were added to the resulting white substance, and the resulting mixture was acidified to pH ~4 with 2 M HCl. The organic layer was separated, and the aqueous layer was extracted with 2 × 250 mL of dichloromethane. The combined organic extracts were dried over Na2SO4 and then evaporated to dryness to produce a white solid. Add 0.4 g of TsOH to a solution of this substance in 1,500 ml of toluene, rapidly heat the mixture to reflux, reflux for 15 minutes with a Dean-Stark head, and then rapidly cool to room temperature using a water bath. Wash the resulting solution with a 10% K₂CO₃ aqueous solution. Separate the organic layer and extract the aqueous layer with 2 × 150 ml of dichloromethane. Dry the combined organic extracts with K₂CO₃ and then pass them through a short mat (40–63 μm) of silica gel 60. Wash the silica gel layer additionally with 250 ml of dichloromethane. Evaporate the combined organic eluent to dryness to produce a pale yellow liquid, which is then distilled under vacuum to produce 94.1 g (84%) of 2,2-dimethyl-1,2,3,5-tetrahydro-s-indigo (boiling point 105 °C / 7 mm Hg) as a colorless liquid.

[0850] C 14 H 16 Analysis and calculation: C 91.25, H 8.75. Findings: C 91.37, H 8.92.

[0851] 1 H NMR (CDCl3): δ7.25(s,1H),7.18(s,1H),6.81(m,1H),6.45(m,1H),3.32(s,2H),2.73(s,4H),1.15(s,6H). 13 C{ 1 H} NMR (CDCl3): δ143.34,142.13,141.64,140.27,133.14,132.13,120.35,117.32,47.65,47.61,40.48,38.66,28.95.

[0852] Solvents and Celite drying methods used in the following processes:

[0853] All synthesis was performed using standard air-sensitive procedures in an N2-purged drying oven. Celite (Sigma-Aldrich) and... were dried in a vacuum oven at 250°C. Molecular sieve (Sigma-Aldrich or Acros) for 3 days. The solvent is purged with N2 and dried. Molecular sieve storage. The NMR solvent is dried and then... Molecular sieves were stored. MeMgI (3M in Et₂O, Sigma-Aldrich), CH₃I (Sigma-Aldrich), isobutyl bromide (Sigma-Aldrich), and 1,2,3,5-tetrahydro-s-indahedron (GLSyntech) were used in the received state. Pentamethylcyclopentadienyl hafnium trichloride (Me₅CpHfCl₃) was purchased from Stem Chemicals or synthesized in a similar manner to that described in the Journal of Organometallic Chemistry, 1988, Vol. 340, pp. 37-40.

[0854] 6,6-Dimethyl-1,5,6,7-Tetrahydro-s-indahedral lithium

[0855] Approximately 13.89 mL of a 1.6 M solution (22.2 mmol) of n-BuLi in hexane was added dropwise to a solution of 2,2-dimethyl-1,2,3,5-tetrahydro-s-indane (4.095 g, 22.2 mmol) cooled to -35 °C in 60 mL of Et₂O. The reaction mixture was stirred at room temperature for two hours. After two hours, the colorless solution turned into a white slurry. Et₂O was removed under vacuum. The lithium salt was filtered and washed with pentane (4 × 20 mL). The separated white precipitate was dried under vacuum to yield 4.001 g (94.6%) of the product. 1H-NMR (d8-THF, ppm): δ1.04 (s, 6H, CH3), 2.58 (br, s, 4H, CH2), 5.72 (d, J = 3.4, 0.5Hz, 1H, Cp_H), 6.32 (t, J = 3.3Hz, 1H, Cp_H), 7.02 (S, 2H, Ar_H).

[0856] 1,6,6-Trimethyl-1,5,6,7-Tetrahydro-s-indaryl lithium

[0857] MeI (0.19 g, 1.31 mmol) was added to 6,6-dimethyl-1,5,6,7-tetrahydro-s-indarene (0.21 g, 1.09 mmol) in THF (10 mL) and stirred for 16 hours. THF was then removed by a nitrogen stream, and the crude product was slurried again in pentane for 15 minutes. The solid was removed by filtration on a Celite filter and washed with pentane. All solvent was then removed from the filtrate under vacuum, and 2,2,5-trimethyl-1,2,3,5-tetrahydro-s-indarene was separated into a clear oil (0.16 g, 0.8 mmol) dissolved in Et₂O (15 mL). nBuLi (0.074 mL, 11 M) was then slowly added, and the reagent was stirred for 30 minutes. All Et₂O was then removed under vacuum, and pentane was added and stirred for an additional 10 minutes. The product was then filtered off as a white solid (0.166 g, 100%), which was obtained by filtration. 1 ¹H NMR (500MHz, DMSO-d6) analysis showed δ 6.77 (s, 2H), 6.04 (s, 1H), 5.39 (s, 1H), 2.59 (d, J = 12.9Hz, 4H), 2.29 (s, 3H), and 1.09 (s, 6H).

[0858] Pentamethylcyclopentadienyl(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium(IV) (Catalyst No. = C)

[0859] 1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indahedral lithium (0.166 g, 0.8 mmol) was mixed with CpMe5HfCl3 (0.341 g, 0.8 mmol) in Et2O (20 ml) and stirred overnight. All Et2O was then removed by a nitrogen stream, and the crude product was slurried again in pentane for 15 min. The product was separated into a mixture of LiCl by filtration and used in the next step without further purification. Crude hafnium dichloride (0.36 g, 0.6 mmol) was slurried in toluene (15 ml), and then MeMgI (0.38 ml, 3 M in Et2O) was added, and the reaction was stirred at 70 °C for 16 h. The reaction was cooled to room temperature, and 1,4-dioxane was added. The mixture was stirred for 15 min, and the solids were removed by filtration on CELITE and washed with Et2O. All volatiles were then removed under vacuum. The final product (C 27 H 38 Hf) was separated into solids (0.29 g, 67%), which was obtained by... 1 H NMR (CD2Cl2, 400MHz) analysis: δ7.32 (s, 1H), 6.93 (d, J = 1.1Hz, 1H), 5.25 (d, J = 2.8Hz, 2H), 2.76 (d, J = 1.5Hz, 2H) ,2.72(dd,J=4.7,1.5Hz,2H),2.18(s,3H),1.87(s,15H),1.15(s,3H),1.13(s,3H),-1.07(s,3H),-2.05(s Hz,3H).

[0860] Synthesis of pentamethylcyclopentadienyl(1-methyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium(IV) (catalyst number = A)

[0861]

[0862] 1-Methyl-1,5,6,7-tetrahydro-s-indahedral lithium

[0863] 1,5,6,7-tetrahydro-s-indahedral lithium was synthesized in a manner similar to that described in USSN 16 / 192,493 (published as US 2019 / 0161560), filed November 15, 2018.

[0864] MeI (6.74 g, 47.5 mmol) was slowly added to 1,5,6,7-tetrahydro-s-indarene (7.0 g, 43.2 mmol) in Et₂O (100 ml) and THF (20 ml) and stirred for 4 hours. All solvent was then removed by a nitrogen stream, and the crude product was slurried again in pentane for 15 minutes. The solid was removed by filtration on a Celite filter and washed with pentane. All solvent was then removed from the filtrate under vacuum, and 1-methyl-1,5,6,7-tetrahydro-s-indarene was separated into a clear oil (6.95 g, 41.0 mmol), which was then dissolved in Et₂O (100 ml). nBuLi (3.7 ml, 11 M) was then slowly added and stirred for 1 hour. All Et₂O was then removed under vacuum, and pentane was added and stirred for an additional 10 minutes. The product was then collected by filtration as a white solid (6.97 g, 97%), which was obtained by... 1 ¹H NMR (500MHz, DMSO-d6) analysis showed δ 6.80 (d, J = 1.0 Hz, 2H), 6.04 (d, J = 3.2 Hz, 1H), 5.37 (d, J = 3.9 Hz, 1H), 2.74 (dt, J = 10.5, 7.0 Hz, 4H), 2.27 (s, 3H), and 1.86 (p, J = 7.1 Hz, 2H).

[0865] Pentamethylcyclopentadienyl(1-methyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium(IV)

[0866] 1-Methyl(1,5,6,7-tetrahydro-s-indaryl)lithium (6.97 g, 40 mmol) was mixed with CpMe5HfCl3 (16.1 g, 40 mmol) in Et2O (150 ml) and stirred for 3 hours. LiCl was removed by filtration. All Et2O was then removed by a nitrogen stream, and the crude product was slurried again in pentane for 15 minutes and cooled at -35 °C. The product was separated into a pale white solid (15.47 g, 26 mmol) by filtration, slurried in toluene (50 ml), and then MeMgI (17.3 ml, 3 M in Et2O) was added and the reaction was stirred at 70 °C for 16 hours. The reaction was cooled to room temperature and 1,4-dioxane was added. The mixture was stirred for 15 minutes, and the solid was removed by filtration on a Celite filter and washed with Et2O. All volatiles were then removed under vacuum. The final product (C 25 H 34 Hf) was separated into solids (12.3 g, 60%), which was obtained by... 1H NMR (CD2Cl2, 400MHz) analysis: δ7.45–7.33(m,1H),7.02–6.92(m,1H),5.32(dd,J=2.9,0.9Hz,1H),5.27(dd,J=2. 8,0.6Hz,1H),2.99–2.86(m,4H),2.19(s,3H),2.11–1.99(m,2H),1.88(s,15H),-1.08(s,3H),-2.12(s,3H).

[0867] Synthesis of pentamethylcyclopentadienyl(1-isobutyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium(IV) (catalyst number = B)

[0868]

[0869] 1-Isobutyl-1,5,6,7-Tetrahydro-S-indaryllithium

[0870] Isobutyl bromide (1.69 g, 12 mmol) was added to 1,5,6,7-tetrahydro-s-indarene (2.0 g, 12 mmol) in THF (100 ml) and stirred for 16 hours. THF was then removed by a nitrogen stream, and the crude product was slurried again in pentane for 15 minutes. The solid was removed by filtration on a celite filter and washed with pentane. All solvent was then removed from the filtrate under vacuum, and 1-isobutyl-1,5,6,7-tetrahydro-s-indarene was separated into a clear oil (2.54 g, 12 mmol) dissolved in Et₂O (50 ml). nBuLi (1.1 ml, 11 M) was then slowly added and stirred for 1 hour. All Et₂O was then removed under vacuum, and pentane was added and stirred for an additional 10 minutes. The product was then collected by filtration as a white solid (2.5 g, 96%), which was obtained by... 1 H NMR (500MHz, DMSO-d6) analysis δ6.82(d,J=9.7Hz,2H),6.06(s,1H),5.39(d,J=3.2Hz,1H),2.73(q,J=6.9Hz, 4H), 2.50 (d, J = 6.7Hz, 2H), 1.86 (p, J = 7.0Hz, 2H), 1.70 (dt, J = 13.2, 6.6Hz, 1H), 0.83 (d, J = 6.6Hz, 6H).

[0871] Pentamethylcyclopentadienyl(1-isobutyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium(IV)

[0872] 1-Isobutyl-1,5,6,7-tetrahydro-s-indahedral lithium (0.27 g, 1.2 mmol) was mixed with CpMe5HfCl3 (0.52 g, 1.2 mmol) in Et2O (20 mL) and stirred overnight. The Et2O was then removed by a nitrogen stream, and the crude product was slurried again in pentane for 15 min. The mixture was cooled at -35 °C for 1 h. The product was separated into a mixture of LiCl by filtration and used in the next step without further purification. Crude hafnium dichloride (0.68 g, 1.1 mmol) was slurried in toluene (20 mL), and then MeMgI (0.71 mL, 3 M in Et2O) was added, and the reaction was stirred at 70 °C for 16 h. The reaction was cooled to room temperature, and 1,4-dioxane (0.38 mL) was added. The mixture was stirred for 15 min, and the solids were removed by filtration on a Celite filter and washed with Et2O. Volatile substances were then removed from the filtrate under vacuum. The product slowly solidified, to which 0.5 ml of pentane was added. It was then rapidly rotated and cooled at -35°C for 3 hours, and the pentane was removed using a pipette. The final product (C2) 28 H 40 Hf) was separated into a solid (0.4 g, 60%), which was obtained by... 1 H NMR (CD2Cl2, 400MHz) analysis: δ7.38(s,1H),6.97(d,J=1.4Hz,1H),5.34(dd,J=2.9,0.8Hz,1H),5.27(d,J=2.9Hz,1H),2.99–2.88(m,4H),2.80(d d,J=13.5,5.8Hz,1H),2.04(p,J=7.3Hz,2H),1.93-1.79(m,17H),0.93(d,J=6.5Hz,3H),0.85(d,J=6.4Hz,3H),-1.08(s,3H),-2.14(s,3H).

[0873] Aggregate Examples

[0874] The precatalysts used in the examples can be prepared as described above. Activator A-1 is available from Boulder Chemical Company as a 10% by weight solution of methylcyclohexyl. Activator A-2 can be prepared as described in USSN 16 / 394,166, filed April 25, 2019. Activator A-3 is available from WR Grace & Company or Boulder Chemical Company.

[0875]

[0876] Supplied by ExxonMobil Chemical Company, the solvent, polymerization grade toluene, and / or isohexane were purified using the following series of columns: two tandem 500cc Oxyclear columns from Labclear (Oakland, California), followed by columns filled with dry... Two 500cc columns in series of a molecular sieve (8-12 mesh, Aldrich Chemical Company) and packed with dry... Two 500cc columns in series of a molecular sieve (8-12 mesh, Aldrich Chemical Company).

[0877] 1-Decanene monomer was available from Sigma Aldrich and purified by alkaline alumina column and subjected to [further treatment] before use. Dry on the molecular sieve. Add all the complex and activator as a diluent solution in the indicated solvent to the reactor. Select the concentration of the activator, scavenger, and complex solution added to the reactor such that a solution between 40 and 200 μL is added to the reactor to ensure accurate delivery.

[0878] Reactor Description and Preparation. Polymerization was carried out in an autoclave equipped with an external heater for temperature control, a glass insert (reactor internal volume = 23.5 mL), a diaphragm inlet, a nitrogen supply adjustment, and a disposable polyetheretherketone mechanical stirrer (800 RPM) in an inert atmosphere (N2) drying oven. The autoclave was prepared by purging with dry nitrogen at 110°C or 115°C for 5 hours and then purging at 25°C for 5 hours.

[0879] Typical decene polymerization: Prepare the reactor as described above. Add the solvent (if used) and 1-decene via syringe at room temperature and atmospheric pressure. Then bring the reactor to the method temperature (60°C, 85°C, or 110°C). Next, set the stirrer to 800 RPM and pressurize the cell to 80 psi with nitrogen. Then, add the scavenger solution (e.g., tri-n-octylaluminum TNOA) to the reactor via syringe under method conditions. Add the activator solution to the reactor via syringe under method conditions, followed by the pre-catalyst solution via syringe under method conditions. Monitor the reactor temperature and typically maintain it within + / - 1°C. Stop the polymerization by adding approximately 50 psi of O2 / Ar (5 mol% O2) gas mixture to the autoclave for approximately 30 seconds. Quench the polymerization after a 60-minute polymerization time. Cool the reactor and vent it. Separate the final PAO under vacuum after removing the solvent, unreacted monomers, and other volatiles. The reported yield includes the total weight of non-volatile PAO and residual catalyst. Catalyst activity is reported as PAO g / mmol transition metal compound / hour reaction time ( g / hr·mmol The concentration is based on the weight of the separated PAO. This represents the minimum catalyst activity because some dimerized PAO molecules can be lost during the drying process.

[0880] Characterization of isolated PAO

[0881] The unsaturated PAO products (below) were analyzed to determine the distribution of vinylidenes (“Vd”), disubstituted vinylides (“Di”), trisubstituted vinylides (“Trisub”), and vinylides (“Vi”), as well as the catalyst activity level and physical properties such as number-average molecular weight. The percentage conversion of the reaction was calculated from the yield of the separated products and the amount of α-olefin used in the reaction. Specifically, conversion = grams of separated PAO / grams of α-olefin used (when reported as a percentage, conversion = (grams of separated PAO / grams of α-olefin used) x 100).

[0882] Using proton NMR ( 1 ¹H-NMR was used to determine the number-average molecular weight and quantitative decomposition of unsaturated PAO and its olefinic structure type (e.g., vinyl, vinylidene, disubstituted vinylidene, trisubstituted vinylidene, and vinylidene).

[0883] Specifically, a 400 or 500 MHz NMR instrument was operated under the following conditions: ~30° flip angle RF pulses, 128 scans, with a ~5 second relaxation delay between pulses; a sample (60-100 mg) dissolved in CDCl3 (deuterated chloroform) in a 5 mm NMR tube; and a signal collection temperature of ~25 °C. The following method was used to determine the concentrations of various olefins in all olefins from the NMR spectra. First, peaks corresponding to different types of hydrogen atoms in vinyl (T1), vinylidene (T2), disubstituted vinylidene (T3), and trisubstituted vinylidene (T4) were designated at the peak regions in Table C below. Second, the areas of each of the above peaks (A1, A2, A3, and A4, respectively) were then integrated. Third, the quantities of each type of olefin (Q1, Q2, Q3, and Q4, respectively) were calculated in moles (A1 / 2, A2 / 2, A3 / 2, and A4, respectively). Fourth, the total amount of all olefins (Qt) is calculated in moles as the sum of all four types (Qt = Q1 + Q2 + Q3 + Q4). Finally, based on the total number of all olefins in moles, the molar concentration of each type of olefin is then calculated (C1, C2, C3, and C4, respectively, in mol%) (in each case, Ci = 100 * Qi / Qt).

[0884] Table C

[0885]

[0886] Number-average molecular weight is determined by the following:

[0887] Mn = {[saturated + (vinylene + vinylidene + vinyl + trisubstituted x2)] / (vinylene + vinylidene + vinyl + trisubstituted x2)} x 14

[0888] (In this equation, "saturated", "vinylene", "vinyl", and "trisubstituted" refer to the peak area integral.)

[0889] Table I below shows the embodiments and comparative examples (*) of the present invention, listing the reaction conditions, including the characteristics of the metallocene compound (catalyst number) and activator (activator number), polymerization temperature, yield of isolated PAO, catalyst activity, and as described above. 1 Mn, as measured by H NMR, and the distribution of olefins expressed as molar percentages of each type, based on, for example, by 1 The total molar number of the four types of olefins determined by ¹H NMR. All embodiments of the invention used non-aromatic hydrocarbon solvents, while the comparative examples required the use of toluene to dissolve activator A-3.

[0890] Standard reaction conditions for PPR were as follows: 0.08 μmol pre-catalyst, 0.088 μmol activator, 0.60 μmol TnOAl scavenger (10 mmol / L in isohexane), 2 mL decene (pure, 1.48 g), a total of 3 mL of solvent used (isohexane (iHex) alone or isohexane with methylcyclohexane (MeCy), or isohexane with toluene (Tol)), stirring speed of 800 rpm, and reaction time of 60 min. All pre-catalyst was dissolved in isohexane at 0.8 mmol / L. Activator A-2 was dissolved in isohexane at 0.8 mmol / L. Activator A-1 was supplied as a 10% solution (72.4 mM) in methylcyclohexane and was also diluted in isohexane to prepare a 0.8 mmol / L solution. Activator A-3 was slightly soluble in alkane solvents and dissolved in toluene at 0.8 mmol / L as a control. The actual amounts of solvent used, reaction temperatures, PAO yields, catalyst activity, and PAO characterization are reported in Table 1 below.

[0891] Table 1

[0892]

[0893] Table 1 (continued)

[0894]

[0895]

[0896] Table 1 (continued)

[0897]

[0898] *Comparative example using standard activator A-3 and toluene as activator diluents

[0899] Table 2 below shows embodiments of the present invention, listing reaction conditions, including the characteristics of the metallocene compound (catalyst number) and activator (activator number), polymerization temperature, yield of isolated PAO, catalyst activity, and other conditions as described above. 1 Mn and the distribution of olefins in terms of molar percentage of each type, as measured by H NMR, are based on, for example, by 1 The total molar number of four types of olefins was determined by ¹H NMR. Activator A-1, supplied as a 10% solution in methylcyclohexane, was separated as oil by removing the solvent under vacuum. 1 No residual solvent was detected by 1H NMR. The resulting oil was diluted in 1-decene to a concentration of 0.8 mmol / L. All examples further described in Table 2 are free of aromatic solvents and substantially free of non-α-olefin solvents.

[0900] The standard reaction conditions used for PPR were: 0.12 μmol of pre-catalyst (0.8 mmol / L in 1-decene), 0.158 μmol of activator (0.8 mmol / L in 1-decene), 0.60 μmol of TnOAl scavenger (10 mmol / L in 1-decene), and a total of 3 mL of decene added to the reactor, including amounts used to dilute the catalyst, activator, and scavenger (2.22 g total), a stirring rate of 800 rpm, and a reaction time of 60 minutes. The reaction temperature, PAO yield, catalyst activity, and PAO characterization are reported in Table 2 below.

[0901] Table 2

[0902]

[0903]

[0904] Table 2 (continued)

[0905]

[0906] Polymerization Example 97 was carried out in a batch polymerization reactor in a 1L autoclave equipped with a paddle stirrer, an external water jacket for temperature control, dry nitrogen, regulated supply of ethylene, propylene, and isohexane, and inlets for introducing other solvents, comonomers, pre-catalysts, and activators. The reactor was dried before use by heating it at 110-120°C under a stream of dry nitrogen for approximately 1 hour. 200 mL of dry 1-decene and 100 μL of tri-n-octylaluminum were introduced into the reactor via a tube under nitrogen. Stirring was started (400 rpm), and the reactor was then heated to 110°C. Activator A-1 (67.3 mg) was dissolved in 10 mL of 1-decene in an activator addition tube connected to the reactor. A second addition tube containing 10 mL of 1-decene was connected to the activator addition tube (chaser), and high-pressure nitrogen was connected to the end. The activator and chaser were then pushed into the reactor using high-pressure nitrogen. Catalyst A (25.8 mg) was dissolved in 10 ml of 1-decene in a catalyst addition tube connected to the reactor. A second addition tube containing 10 ml of 1-decene was connected to the catalyst addition tube (trapping device), and high-pressure nitrogen was connected to the end. The catalyst and trap were then pushed into the reactor using high-pressure nitrogen. Timing was started when catalyst A was added to the reactor and allowed to proceed for 1 hour. After this time period, heating and stirring were stopped, the pressure was vented from the reactor, and the reactor was opened and lowered to expose the contents to air. After purging the liquid with nitrogen overnight to remove any unreacted 1-decene, a total of 171 g of oligomers was separated. Additional information is available in Table 3 below.

[0907] Table 3

[0908]

[0909] For the purposes of all jurisdictions where such practice is permitted, all documents described herein are incorporated herein by reference, including any priority documents, related applications and / or test procedures, provided they do not contradict this document, provided that no priority document not named in the original application or filing is incorporated herein by reference. As should be apparent from the foregoing general description and specific embodiments, various modifications may be made without departing from the spirit and scope of the invention, although the forms of the invention have been set forth and described. Various elements or features of a particular embodiment are generally not limited to that particular embodiment, but are interchangeable where applicable and may be used in selected embodiments even if not specifically shown or described. It may also vary in many ways. Such variations are not considered a departure from the invention, and all such modifications are intended to be included within the scope of the invention. Therefore, it is not intended to limit the invention. Similarly, the term “comprising” is considered synonymous with the terms “including” and “containing”. Similarly, whenever a composition, element, or group of elements is preceded by the conjunction "comprising," it should be understood that the same composition or group of elements is preceded by the conjunction "substantially composed of," "composed of," "selected from," or "is," and vice versa.

Claims

1. A method for producing polyalphaolefin (PAO), the method comprising: In a polymerization reactor, under polymerization conditions, C6-C is contained... 32 The feedstock of an α-olefin is contacted with a catalyst system comprising an asymmetric metallocene compound, an activator compound soluble in a non-aromatic hydrocarbon solvent, and a non-aromatic hydrocarbon solvent to undergo polymerization, thereby obtaining a polymerization reaction mixture comprising vinylidenes, trisubstituted vinylides, optionally disubstituted vinylides, and optionally vinylides; and An unsaturated PAO product is obtained from the polymerization reaction mixture, wherein the unsaturated PAO product comprises vinylidene groups, optionally trisubstituted vinylides, optionally disubstituted vinylides, and optionally vinyl groups. The metallocene compounds are represented by formula (I): in: R 2 It is hydrogen and R 1 and R 3 One of them is a substituted or unsubstituted linear, branched or cyclic C1-C6 hydrocarbon group, and R 1 and R 3 The other one is hydrogen; R 6 R 7 R 17 and R 18 Each is independently hydrogen, substituted or unsubstituted, linear, branched or cyclic C1-C 30 hydrocarbon group, or R 6 and R 7 R 7 and R 17 Or R 17 and R 18 Together with the carbon atoms in the indenyl ring directly connected to them, they form one or more substituted or unsubstituted rings fused with the indenyl ring; R 12 R 13 R 14 and R 15 Each is independently a substituted or unsubstituted linear, branched, or cyclic C1-C 20 hydrocarbon group; R 16 It is a substituted or unsubstituted linear, branched or cyclic C1-C 20 Hydrocarbon group or silyl hydrocarbon group; Each X is independently a halogen, hydrogen group, amino group, alkoxy group, thio group, phosphoro group, diene group, amine group, phosphine group, ether group, C1-C group. 20 Substituted or unsubstituted linear, branched, or cyclic hydrocarbon groups, or two or more X structural moieties together forming a fused ring or cyclic system; M is a transition metal with an integer coordination number v; and m is an integer equal to v-2, or The metallocene compounds are represented by formula (II): in: R 1 and R 2 It is hydrogen; R 23 and R 19 Includes Group 14 atoms; R 20 R 21 and R 22 Independently hydrogen or substituted or unsubstituted linear, branched or cyclic C1-C 20 Hydrocarbon group, and R 20 R 21 and R 22 At least two of them are not hydrogen; R 6 R 7 R 17 and R 18 Each is independently hydrogen, substituted or unsubstituted, linear, branched or cyclic C1-C 30 hydrocarbon group, or R 6 and R 7 R 7 and R 17 Or R 17 and R 18 Together with the carbon atoms in the indenyl ring directly connected to them, they form one or more substituted or unsubstituted rings fused with the indenyl ring; R 12 R 13 R 14 R 15 and R 16 Each is independently a substituted or unsubstituted linear, branched or cyclic C1-C8 hydrocarbon group; Each X is independently a halogen, hydrogen, amino, alkoxy, thio, phosphorus, diene, amine, phosphine, ether, or C1-C. 20 Substituted or unsubstituted linear, branched, or cyclic hydrocarbon groups, or two or more X structural moieties together forming a fused ring or cyclic system; M is a group 3, 4 or 5 transition metal with an integer coordination number v; And m is an integer equal to v-2, or The metallocene compounds are represented by formula (III): Where R 2 It is hydrogen and R 1 and R 3 One of them is a substituted or unsubstituted linear, branched or cyclic C1-C6 hydrocarbon group, and R 1 and R 3 The other one is hydrogen; R 6 R 18 R 29 R 24 R 25 R 26 R 27 and R 28 Each is independently hydrogen, substituted or unsubstituted, linear, branched or cyclic C1-C 30 hydrocarbon group, or R 6 R 18 R 29 R 24 R 25 R 26 R 27 and R 28 The carbon atoms in the two cyclopentane-indenyl rings that are directly connected to them together form one or more substituted or unsubstituted rings fused with the cyclopentane-indenyl ring; R 12 R 13 R 14 R 15 and R 16 Each is independently a substituted or unsubstituted linear, branched, or cyclic C1-C 20 hydrocarbon group; Each X is independently a halogen, hydrogen group, amino group, alkoxy group, thio group, phosphoro group, diene group, amine group, phosphine group, ether group, C1-C group. 20 Substituted or unsubstituted linear, branched, or cyclic hydrocarbon groups, or two or more X structural moieties together forming a fused ring or cyclic system; M is a group 3, 4 or 5 transition metal with an integer coordination number v; And m is an integer equal to v-2, or Metallocene compounds are represented by formula (IV): in: R 1 and R 2 It is hydrogen; R 23 and R 19 Includes Group 14 atoms; R 20 R 21 and R 22 Independently hydrogen or substituted or unsubstituted linear, branched or cyclic C1-C 20 Hydrocarbon group, and R 20 R 21 and R 22 At least two of them are not hydrogen; R 6 R 18 R 29 R 24 R 25 R 26 R 27 and R 28 Each is independently hydrogen, substituted or unsubstituted, linear, branched or cyclic C1-C 30 hydrocarbon group, or R 6 R 18 R 29 R 24 R 25 R 26 R 27 and R 28 The carbon atoms in the two cyclopentane-indenyl rings that are directly connected to them together form one or more substituted or unsubstituted rings fused with the cyclopentane-indenyl ring; R 12 R 13 R 14 R 15 and R 16 Each is independently a substituted or unsubstituted linear, branched, or cyclic C1-C 20 hydrocarbon group; Each X is independently a halogen, hydrogen group, amino group, alkoxy group, thio group, phosphoro group, diene group, amine group, phosphine group, ether group, C1-C group. 20 Substituted or unsubstituted linear, branched, or cyclic hydrocarbon groups, or two or more X structural moieties together forming a fused ring or cyclic system; M is a group 3, 4 or 5 transition metal with an integer coordination number v; And m is an integer equal to v-2. The activator compounds soluble in non-aromatic hydrocarbons are represented by formula (VII) or formula (VIII): in: N is nitrogen: R 2’ and R 3’ Independently for C6-C 40 The hydrocarbon group may be optionally replaced by one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups, wherein R in formula (VII) 2’ and R 3’ It contains a total of 14 or more carbon atoms and R in formula (VIII) 2’ It contains 13 or more carbon atoms; R 8’ R 9’ and R 10’ Independently for C4-C 30 Hydrocarbon group or substituted C4-C 30 hydrocarbon group; B is boron; and R 4’ R 5’ R 6’ and R 7’ Independently, it is a hydrogen group, a bridged or unbridged dialkylamino group, a halogen group, an alkoxy group, an aryloxy group, a substituted hydrocarbon group, a haloalkyl group, a substituted haloalkyl group, or a halogen-substituted hydrocarbon group. The solvent is isohexane and / or methylcyclohexane.

2. The method according to claim 1, wherein in formula (I), M is a group 3, 4 or 5 transition metal.

3. The method according to claim 1, wherein in formula (I), v is 3, 4 or 5.

4. The method according to claim 1, wherein in formula (I), m is 1, 2 or 3.

5. The method of claim 1, wherein the metallocene is selected from... Pentamethylcyclopentadienyl(1-methyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-ethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-propyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-isopropyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-butyl-1,5,6,7-tetrahydro-s-indarsyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-isobutyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-sec-butyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-tert-butyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-pentyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-neopentyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-hexyl-1,5,6,7-tetrahydro-s-indarsyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-heptyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-octyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-benzyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-phenylethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-(2-phenylpropyl)-1,5,6,7-tetrahydro-s-indaryl)dimethylhafnium, Pentamethylcyclopentadienyl(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-ethyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-propyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-isopropyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-butyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-isobutyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-sec-butyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-tert-butyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-pentyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-neopentyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-hexyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsyl)dimethylhafnium Pentamethylcyclopentadienyl(1-n-heptyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-octyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsyl)dimethylhafnium Pentamethylcyclopentadienyl(1-benzyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-phenylethyl-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-(2-phenylpropyl)-6,6-dimethyl-1,5,6,7-tetrahydro-s-indarsyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-methyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1,6,6-triethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-propyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-isopropyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-butyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsyl)dimethylhafnium Pentamethylcyclopentadienyl(1-isobutyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-sec-butyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-tert-butyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-pentyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-neopentyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-benzyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-phenylethyl-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-(2-phenylpropyl)-6,6-diethyl-1,5,6,7-tetrahydro-s-indarsyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-methyl-3,6,7,8-tetrahydro-as-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-ethyl-3,6,7,8-tetrahydro-as-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-propyl-3,6,7,8-tetrahydro-as-indarsyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-isopropyl-3,6,7,8-tetrahydro-as-indarsyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-butyl-3,6,7,8-tetrahydro-as-indarsyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-isobutyl-3,6,7,8-tetrahydro-as-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-sec-butyl-3,6,7,8-tetrahydro-as-indarsyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-tert-butyl-3,6,7,8-tetrahydro-as-indarsyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-pentyl-3,6,7,8-tetrahydro-as-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-neopentyl-3,6,7,8-tetrahydro-as-indarsyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-benzyl-3,6,7,8-tetrahydro-as-indarsyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-phenylethyl-3,6,7,8-tetrahydro-as-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-(2-phenylpropyl)-3,6,7,8-tetrahydro-as-indaryl)dimethylhafnium, Pentamethylcyclopentadienyl(1-methyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-ethyl-5,6,7,8-tetrahydro-1H-cyclopentadieno[b]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-propyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-isopropyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-butyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-isobutyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-sec-butyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-tert-butyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-pentyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-neopentyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-benzyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-phenylethyl-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-(2-phenylpropyl)-5,6,7,8-tetrahydro-1H-cyclopentadien[b]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-methyl-6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-ethyl-6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-propyl-6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-isopropyl-6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-n-butyl-6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-isobutyl-6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-sec-butyl-6,7,8,9-tetrahydro-1H-cyclopentadien[a]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-tert-butyl-6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-pentyl-6,7,8,9-tetrahydro-1H-cyclopentadien[a]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-neopentyl-6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-benzyl-6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-phenylethyl-6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1-(2-phenylpropyl)-6,7,8,9-tetrahydro-1H-cyclopentadieno[a]naphthalene)dimethylhafnium, Pentamethylcyclopentadienyl(1,5,6-trimethylindenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-ethyl-5,6-dimethylindenyl)dimethylhafnium Pentamethylcyclopentadienyl(1-n-propyl-5,6-dimethylindenyl)dimethylhafnium Pentamethylcyclopentadienyl(1-isopropyl-5,6-dimethylindenyl)dimethylhafnium Pentamethylcyclopentadienyl(1-n-butyl-5,6-dimethylindenyl)dimethylhafnium Pentamethylcyclopentadienyl(1-isobutyl-5,6-dimethylindenyl)dimethylhafnium Pentamethylcyclopentadienyl(1-sec-butyl-5,6-dimethylindenyl)dimethylhafnium Pentamethylcyclopentadienyl(1-tert-butyl-5,6-dimethylindenyl)dimethylhafnium Pentamethylcyclopentadienyl(1-pentyl-5,6-dimethylindenyl)dimethylhafnium Pentamethylcyclopentadienyl(1-neopentyl-5,6-dimethylindenyl)dimethylhafnium Pentamethylcyclopentadienyl(1-benzyl-5,6-dimethylindenyl)dimethylhafnium Pentamethylcyclopentadienyl(1-phenylethyl-5,6-dimethylindenyl)dimethylhafnium Pentamethylcyclopentadienyl(1-(2-phenylpropyl)-5,6-dimethylindenyl)dimethylhafnium Pentamethylcyclopentadienyl(1-methyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylzirconium, Pentamethylcyclopentadienyl(1-isobutyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylzirconium, Pentamethylcyclopentadienyl(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylzirconium, Tetramethylcyclopentadienyl(1-methyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Tetramethylcyclopentadienyl(1-isobutyl-1,5,6,7-tetrahydro-s-indaryl)dimethylhafnium, Tetramethylcyclopentadienyl(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsenyl)dimethylhafnium, Pentamethylcyclopentadienyl(1-methyl-1,5,6,7-tetrahydro-s-indarsyl)dibenzylhafnium, Pentamethylcyclopentadienyl(1-isobutyl-1,5,6,7-tetrahydro-s-indarsyl)dibenzylhafnium, and Pentamethylcyclopentadienyl(1,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarsyl)dibenzylhafnium.

6. The method of claim 1, wherein R 4’ R 5’ R 6’ and R 7’ It is pentafluorophenyl.

7. The method of claim 1, wherein R 8’ and R 10’ It is a hydrogen atom and R 9’ It is C4-C 30 The hydrocarbon group may be optionally replaced by one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups.

8. The method according to claim 1, wherein R 9’ It is C8-C 22 The hydrocarbon group may be optionally replaced by one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups.

9. The method of claim 1, wherein R 2’ and R 3’ Independently for C 12 -C 22 Hydrocarbon group.

10. The method of claim 1, wherein the activator is selected from: [Tetra(perfluorophenyl)boronic acid]N,N-di(hydrogenated tallow)methylammonium [Tetra(perfluorophenyl)boronic acid]N-methyl-4-nonadecanyl-N-octadecylphenylammonium, [Tetra(perfluorophenyl)boronic acid]N-methyl-4-hexadecyl-N-octadecylphenylammonium, [Tetra(perfluorophenyl)boronic acid]N-methyl-4-tetradecyl-N-octadecylphenylammonium, [Tetra(perfluorophenyl)boronic acid]N-methyl-4-dodecyl-N-octadecylphenylammonium, [Tetra(perfluorophenyl)boronic acid]N-methyl-4-decyl-N-octadecylphenylammonium [Tetra(perfluorophenyl)boronic acid]N-methyl-4-octyl-N-octadecylphenylammonium [Tetra(perfluorophenyl)boronic acid]N-methyl-4-hexyl-N-octadecylphenylammonium [Tetra(perfluorophenyl)boronic acid]N-methyl-4-butyl-N-octadecylphenylammonium [Tetra(perfluorophenyl)boronic acid]N-methyl-4-octadecyl-N-decylphenylammonium [Tetra(perfluorophenyl)boronic acid]N-methyl-4-nonadecanyl-N-dodecylphenylammonium, [Tetra(perfluorophenyl)boronic acid]N-methyl-4-nonadecanyl-N-tetradecylphenylammonium, [Tetra(perfluorophenyl)boronic acid]N-methyl-4-nonadecanyl-N-hexadecylphenylammonium, [Tetra(perfluorophenyl)boronic acid]N-ethyl-4-nonadecanyl-N-octadecylphenylammonium, [Tetra(perfluorophenyl)boronic acid]N-methyl-N,N-di(octadecyl)ammonium, [Tetra(perfluorophenyl)boronic acid]N-methyl-N,N-di(hexadecyl)ammonium, [Tetra(perfluorophenyl)boronic acid]N-methyl-N,N-di(tetradecyl)ammonium, [Tetra(perfluorophenyl)boronic acid]N-methyl-N,N-di(dodecyl)ammonium [Tetra(perfluorophenyl)boronic acid]N-methyl-N,N-didecylammonium [Tetra(perfluorophenyl)boronic acid]N-methyl-N,N-dioctylammonium, [Tetra(perfluorophenyl)boronic acid]N-ethyl-N,N-di(octadecyl)ammonium [Tetrafluorophenyl]boronic acid]N,N-Di(octadecyl)tolylammonium [Tetrafluorophenyl]boronic acid]N,N-di(hexadecyl)tolylammonium, [Tetra(perfluorophenyl)boronic acid]N,N-di(tetradecyl)tolylammonium, [Tetra(perfluorophenyl)boronic acid]N,N-di(dodecyl)tolylammonium, [Tetrafluorophenyl]boronic acid]N-octadecyl-N-hexadecyl-tolylammonium [Tetrafluorophenyl]boronic acid]N-octadecyl-N-hexadecyl-tolylammonium [Tetrafluorophenyl]boronic acid]N-octadecyl-N-tetradecyl-tolylammonium [Tetrafluorophenyl]boronic acid]N-octadecyl-N-dodecyl-tolylammonium [Tetrafluorophenyl]boronic acid]N-octadecyl-N-decyl-tolylammonium [Tetrafluorophenyl]boronic acid]N-hexadecyl-N-tetradecyl-tolylammonium [Tetrafluorophenyl]boronic acid]N-hexadecyl-N-dodecyl-tolylammonium [Tetrafluorophenyl]boronic acid]N-hexadecyl-N-decyl-tolylammonium [Tetra(perfluorophenyl)boronic acid]N-Tetradecyl-N-dodecyl-tolylammonium [Tetrafluorophenyl]boronic acid]N-Tetradecyl-N-decyl-tolylammonium [Tetrafluorophenyl]boronic acid]N-dodecyl-N-decyl-tolylammonium [Tetra(perfluorophenyl)boronic acid]N-methyl-N-octadecylphenylammonium [Tetra(perfluorophenyl)boronic acid]N-methyl-N-hexadecylphenylammonium [Tetra(perfluorophenyl)boronic acid]N-methyl-N-tetradecylphenylammonium [Tetra(perfluorophenyl)boronic acid]N-methyl-N-dodecylphenylammonium [Tetra(perfluorophenyl)boronic acid]N-methyl-N-decylphenylammonium, and [Tetra(perfluorophenyl)boronic acid]N-methyl-N-octylphenylammonium.

11. The method of claim 1, wherein the solvent does not contain any aromatic solvents.

12. The method of claim 1, wherein the method comprises obtaining an unsaturated PAO product from a polymerization reaction mixture, wherein the polymerization reaction exhibits selectivity for ≥80 mol% vinylidene groups, based on the total molar number of vinyl groups, vinylidene groups, disubstituted vinylides, and trisubstituted vinylides in the unsaturated PAO product, and wherein the unsaturated PAO product has as described by 1 The number-average molecular weight (Mn) measured by H NMR is 2,500 g / mol or less.

13. The method according to claim 1, further comprising: a) Contacting unsaturated PAO products with hydrogen to convert at least a portion of the unsaturated PAO products into hydrogenated PAO products; b) Contacting unsaturated PAO products with chemical reagents to convert at least a portion of the unsaturated PAO products into functionalized PAO products; Or a combination thereof.

14. The method of claim 1, wherein the unsaturated PAO product comprises a dimer.

15. The method according to claim 1, wherein C6-C 32 α-olefins, metallocene compounds, and activators are contacted in a continuous stirred tank reactor or a continuous tubular reactor in either the solution phase or the bulk phase.

16. The method of claim 1, wherein the method is a continuous method comprising the following steps: a) Containing at least 10 mol% of one or more C6-C 24 a) The feed stream of α-olefin is continuously introduced into the reactor, b) the metallocene compound and activator are continuously introduced into the reactor, and c) the PAO product is continuously extracted from the reactor.

17. The method according to claim 1, wherein C6-C 32 α-olefins, metallocene compounds, and activators are contacted in a continuous stirred tank reactor or continuous tubular reactor in a solution phase, bulk phase, or slurry phase.

18. The method of claim 1, wherein the polymerization temperature is greater than 100°C, the conversion rate is 50% or greater, and the unsaturated PAO product has 80 mol% or more ethylene ide groups, based on the total molar number of vinyl groups, ethylene ide groups, disubstituted vinylides, and trisubstituted vinylides in the unsaturated PAO product.

19. The method of claim 1, wherein the unsaturated PAO product is represented by the following formula: Where C is a hydrocarbon chain with a length of m'-2, each m' being independently 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 and being the carbon number of one or more monomers used in the polymerization, and n' being 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

20. The method of claim 1, wherein the method has a productivity of at least 4,500 g / mmol / hr, wherein the method comprises: Contact at temperatures between 35℃ and 150℃.

21. The method of claim 1, further comprising hydrogenating at least a portion of the polyalphaolefin and then formulating a fuel or lubricant composition comprising the product of hydrogenating at least a portion of the polyalphaolefin.

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