JP2014511912A - Vinyl-terminated higher olefin polymer and process for producing the same - Google Patents

Abstract

The present invention is a higher olefin vinyl-terminated polymer having at least 200 g / mol of Mn (measured by ¹ H NMR) and comprising one or more C _{4 to} C ₄₀ higher olefin derived units, wherein the higher olefin polymer is The present invention relates to a higher olefin vinyl-terminated polymer which is substantially free of propylene-derived units; These vinyl terminated higher olefin polymers may optionally contain ethylene derived units.
[Selection] Figure 1

Description

This application claims the benefit of USSN 13 / 072,288 filed March 25, 2011 and EP 11167033.7 filed March 23, 2011, and priority to the application. This application is also a continuation-in-part of USSN 13 / 072,288, filed on March 25, 2011.
FIELD OF THE INVENTION This invention relates to olefin polymerization, particularly for producing vinyl terminated higher olefin polymers.

BACKGROUND OF THE INVENTION Alpha olefins, particularly alpha olefins containing from about 6 to about 20 carbon atoms, are used as intermediates in the manufacture of detergents or other types of commercial products. The α-olefin is also used as a comonomer for linear low density polyethylene. Commercially produced alpha olefins are typically made by ethylene oligomerization. Longer chain alpha olefins are also known, such as vinyl-terminated polyethylene, which can serve as components after functionalization or as macromonomers.
Allyl-terminated low molecular weight solids and liquids of ethylene or propylene are also typically produced for use as a branch in polymerization reactions. For example, Rulhoff, Sascha and Kaminsky, (“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, 16 , 2006, pp. 1450-1460) and Kaneyoshi, Hiromu et al. (“Synthesis of Block and Graft Copolymers with Linear Polyethylene Segments by Combination of Degenerative Transfer Coordination Polymerization and Atom Transfer Radical Polymerization,” Macromolecules, 38, 2005, pp. See 5425-5435).
In addition, U.S. Pat. Disclosed are dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride and bis (tetramethyl n-butylcyclopentedienyl) hafnium dichloride and methylalumoxane. These oligomers do not have high Mn and at least 93% allylic vinyl unsaturation. Similarly, these oligomers lack comonomer and are produced at low productivity using a large excess of alumoxane (molar ratio ≧ 600 Al / M; M = Zr, Hf). Furthermore, in all the examples, 60 wt% or more of the solvent (solvent + propylene base material) is present.

Teuben et al. (J. Mol. Catal., 62, 1990, pp. 277-287), [Cp ^* ₂ MMe (THT)] + [BPh ₄ ] (M = Zr and Hf; Cp ^* = pentamethylcyclopentadienyl; Me = methyl, Ph = phenyl; THT = tetrahydrothiophene). For M = Zr, a broad product distribution (number average molecular weight (Mn) of 336) with oligomers up to C ₂₄ was obtained at room temperature. On the other hand, at M = Hf, only dimer 4-methyl-1-pentene and trimer 4,6-dimethyl-1-heptene were formed. A prominent termination mechanism was believed to be β-methyl transfer from the growing chain back to the metal center, as demonstrated by the deuterium labeling test.
X. Yang et al. (Angew. Chem. Intl Ed. Engl., 31, 1992, pp. 1375) discloses amorphous low molecular weight polypropylene produced at low temperatures, and this reaction is less active. The product has 90% allylic vinyl based on total unsaturation by ¹ H NMR. Resconi et al. (J. Am. Chem. Soc., 114, 1992, pp. 1025-1032) then bis (pentamethylcyclopentadienyl) zirconium and bis (pentamethylcyclohexane) for polymerizing propylene. Oligomers and low molecular weight polymers with “mainly allyl and isobutyl terminated” chains resulting from the use of (pentadienyl) hafnium and the resulting β-methyl termination are disclosed. As in U.S. Pat.No. 4,814,540, the oligomer produced has at least 93% allyl chain ends, no Mn from about 500 to about 20,000 g / mol (as measured by ¹ H NMR), and the catalyst is Has low productivity (1-12,620 g / mmol metallocene / hour;> Al in 3000 wppm product).
Similarly, Small and Brookhart (Macromolecules, 32, 1999, pp. 2322) describes apparently main or exclusive 2,1 chain growth, chain termination by β-hydride elimination, and high vinyl end. Disclosed is the use of a pyridylbisamidoiron catalyst in low temperature polymerization to produce low molecular weight amorphous propylene materials having groups.
Weng et al. (Macromol Rapid Comm. 2000, 21, 1103-1107) is produced using dimethylsilylbis (2-methyl, 4-phenyl-indenyl) zirconium dichloride and methylalumoxane at about 120 ° C. in toluene. Discloses materials having up to about 81 percent vinyl ends. This material has a Mn of about 12,300 (determined by ¹ H NMR) and a melting point of about 143 ° C.

Macromolecules, 33, 2000, 8541-8548) discloses the preparation of a branched block ethylene-butene polymer made by reuptake of vinyl-terminated polyethylene, which was activated with methylalumoxane. Manufactured by a combination of Cp ₂ ZrCL ₂ and (C ₅ Me ₄ SiMe ₂ NC ₁₂ H ₂₃ ) TiCl ₂ .
Moscardi et al. (Organometallics, 20, 2001, pp. 1918) describes the batch polymerization of propylene to produce a material “… all allylic end groups always outperform any other end groups in any [propene]”. Discloses the use of rac-dimethylsilylmethylenebis (3-t-butylindenyl) zirconium dichloride and methylalumoxane. In these reactions, morphology control is limited and about 60% of the chain ends are allylic.
Coates et al. (Macromolecules, 38, 2005, pp. 6259) was activated with modified methylalumoxane (MMAO; Al / Ti molar ratio = 200) in a batch polymerization experiment at −20 to + 20 ° C. for 4 hours. The preparation of low molecular weight syndiotactic polypropylene ([rrrr] = 0.46-0.93) with about 100% allyl end groups using bis (phenoxyimine) titanium dichloride ((PHI) ₂ TiCl ₂ ) is disclosed. In these polymerizations, propylene was dissolved in toluene to give a 1.65M toluene solution. The catalyst productivity was very low (0.95-1.14 g / mmol Ti / hr).
JP 2005-336092 A2 discloses the production of a vinyl-terminated propylene polymer using materials such as H ₂ SO ₄ treated montmorillonite, triethylaluminum, triisopropylaluminum, in which case liquid propylene is made into a catalyst slurry in toluene. Supply. This process produces substantially isotactic macromonomers that do not have significant amounts of amorphous material.

Rose et al. (Macromolecules, 41, 2008, pp. 559-567) discloses poly (ethylene-co-propylene) macromonomers that do not have significant amounts of isobutyl chain ends. They were prepared using bis (phenoxyimine) titanium dichloride ((PHI) ₂ TiCl ₂ ) activated with modified methylalumoxane (MMAO; Al / Ti molar ratio range 150-292) in a semi-batch polymerization (30 psi). (207 kPa) of propylene was added to toluene at 0 ° C. for 30 minutes, followed by a polymerization time of 2.3 to 4 hours at about 0 ° C. and an ethylene gas stream at an excess pressure of 32 psi (221 kPa) to give about 4,800 to 23,300 Mn. Produced an EP copolymer). For the four reported copolymers, the following formula:
% Allyl chain end (total unsaturation) = -0.95 (incorporated mol% ethylene) + 100
Thus, therefore, the allylic chain ends decreased with increasing ethylene incorporation.
For example, 65% allyl (compared to total unsaturation) was reported for an EP copolymer containing 29 mol% ethylene. This is the best allyl population achieved. In ethylene incorporated at 64 mol%, only 42% of the unsaturated portion is allylic. The productivity of these polymerizations ranged from 0.78 × 10 ² g / mmol Ti / hour to 4.62 × 10 ² g / mmol Ti / hour.
Prior to this study, Zhu et al. Used a constrained metallocene catalyst [C ₅ Me ₄ (SiMe ₂ N-tert-butyl) TiMe ₂ activated with B (C ₆ F ₅ ) ₃ and MMAO. Only low (about 38%) vinyl-terminated ethylene-propylene copolymers produced were reported (Macromolecules, 35, 2002, pp. 10062-10070 and Macromolecules Rap. Commun., 24, 2003, pp. 311-315).
Janiak and Blank summarize various studies on olefin oligomerization (Macromol. Symp., 236, 2006, pp. 14-22).

  However, polymerization based on higher olefins to produce vinyl-terminated higher olefin polymers is not known. Accordingly, there is a need for new catalysts that produce vinyl terminated higher olefin polymers with a particularly high yield and a wide range of molecular weights and that have high catalytic activity. Furthermore, there is a need for vinyl-terminated higher olefin polymers with allyl ends present in high amounts that are controlled over a wide range of molecular weights that can be produced at commercial temperatures and that can be produced at commercial rates (productivity over 5,000 g / mmol / hour). ing. Furthermore, there is a need for higher olefin polymers having vinyl ends that can be functionalized and used as additives or as macromonomers for the synthesis of poly (macromonomers).

SUMMARY OF THE INVENTION The present invention is a vinyl-terminated higher olefin polymer having at least 200 g / mol Mn (measured by ¹ H NMR) and comprising one or more C ₄ -C ₄₀ higher olefin derived units, The olefin vinyl terminated polymer is substantially free of propylene derived units; and the higher olefin polymer relates to a vinyl terminated higher olefin polymer having at least 5% allyl chain ends relative to total unsaturation. The vinyl terminated higher olefin polymer may optionally contain ethylene derived units. This higher olefin vinyl terminated polymer preferably does not contain isobutyl chain ends. The isobutyl chain end is determined according to the procedure shown in WO 2009/155471.
The present invention is a process for producing a vinyl-terminated higher olefin polymer comprising the step of contacting one or more C _{4 to} C ₄₀ higher olefins (substantially free of propylene) under polymerization conditions; Is an activator and the following formula:
(i)

式I；

Formula I;

式II； Or (ii)

Formula II;

式III； Or (iii)

Formula III;

式IV； Or (iv)

Formula IV;

Wherein M is hafnium or zirconium; each X is independently a hydrocarbyl group having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halogen, diene, amine, phosphine, ether , And combinations thereof (two Xs may form part of a fused ring or ring system) and each Q is independently a carbon or heteroatom; each R ¹ is independently a C ₁ -C ₈ alkyl group, R ¹ is may be identical or different and R ^2; each R ² is independently a C ₁ -C ₈ alkyl group; each R ³ is independently , Hydrogen, or substituted or unsubstituted hydrocarbyl groups having 1 to 8 carbon atoms, provided that at least three R ³ groups are not hydrogen; each R ⁴ is independently hydrogen or substituted or unsubstituted hydrocarbyl Group, heteroatom or heteroatom-containing group ; R ⁵ is hydrogen or C ₁ -C ₈ alkyl group; R ⁶ is hydrogen or C ₁ -C ₈ alkyl group; each R ⁷ is independently hydrogen, or C ₁ -C ₈ alkyl group Yes (but at least 7 R ⁷ groups are not hydrogen); R ₂ ^a T is a bridging group, T is a group 14 element (preferably C, Si, or Ge, preferably Si), and each R ^a Are independently hydrogen, halogen, or C ₁ -C ₂₀ hydrocarbyl, and the two R ^{a form a} cyclic structure (including aromatic, partially saturated, or saturated cyclic or fused ring systems) In addition, any two adjacent R groups may form a fused ring or a multi-centered fused ring system, provided that the ring may be aromatic, partially saturated or saturated) ;
Or (v)

式V；

Formula V;

Wherein M is hafnium or zirconium; each X is independently a hydrocarbyl group having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether. Selected from the group consisting of, and combinations thereof, wherein two Xs may form part of a fused ring or ring system; each R ⁸ is independently a C ₁ -C ₁₀ alkyl group; R ⁹ is independently a C ₁ -C ₁₀ alkyl group; each R ¹⁰ is hydrogen; each R ¹¹ , R ¹² , and R ¹³ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, hetero An atom or a heteroatom-containing group; T is a bridging group (eg, R ₂ ^a T as described above); and any adjacent R ¹¹ , R ¹² , and R ¹³ groups are also fused or multi-centered fused ring systems (including The ring may be aromatic, partially saturated or saturated) As a condition);
Or (vi)

式VI；

Formula VI;

Wherein M is hafnium or zirconium; each X is independently a hydrocarbyl group having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halogen, diene, amine, phosphine, ether. Each R ¹⁵ and R ¹⁷ is independently a C ₁ -C ₈ alkyl group; and each R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² is selected from the group consisting of: , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ are independently hydrogen or a substituted or unsubstituted hydrocarbyl group having 1 to 8 carbon atoms)
And a process that takes place in the presence of a catalyst system comprising at least one metallocene compound represented by:

Figure 2 shows the NMR spectrum of poly (1-decene) (the starting material of 1-decene is isotopically enriched).

DETAILED DESCRIPTION The inventors have surprisingly discovered a new class of vinyl-terminated polymers. Described herein are vinyl-terminated higher olefin polymers that are substantially free of propylene-derived units, methods for making the vinyl-terminated higher olefin polymers, and compositions that include vinyl-terminated higher olefin polymers. These vinyl terminated higher olefin polymers may find utility as poly (macromonomers), macromonomers for the synthesis of block copolymers, and as additives, for example as additives to lubricants. Advantageously, the vinyl groups of these vinyl-terminated polymers provide a route to functionalization. These functionalized polymers can also serve as additives, for example as lubricant additives.
In the present specification, “molecular weight” means number average molecular weight (Mn) unless otherwise specified.
For the purposes of the present invention and the accompanying claims, a new numbering scheme for the periodic table family is used as in CHEMICAL AND ENGINEERING NEWS, 63 (5), pg. 27 (1985). Thus, “Group 4 metals” are Group 4 elements of the Periodic Table.
“Catalytic activity” is a measure of how many grams of polymer (P) are produced using a polymerization catalyst containing Wg of catalyst (cat) over a T time; P / (T × W ) And gPgcat ⁻¹ hour− ¹ .

“Olefin”, sometimes referred to as “alkene”, is a linear, branched or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended hereto, when a polymer or copolymer is said to include, but is not limited to, olefins such as ethylene, propylene, and butene, the olefin present in the polymer or copolymer. Is a polymerized form of olefin. For example, when the copolymer is said to have an “ethylene” content of 35 wt% to 55 wt%, the mer units in the copolymer are derived from ethylene in a polymerization reaction, and the derived units are based on the weight of the copolymer. And 35 wt% to 55 wt%. A “polymer” has two or more identical or different mer units. As used herein, the term “polymer” includes oligomers (up to 100 mer units), and larger polymers (greater than 100 mer units). A “homopolymer” is a polymer having identical mer units. A “copolymer” is a polymer having two or more different mer units. A “terpolymer” is a polymer having three different mer units. “Different” as used to represent a mer unit indicates that the mer units differ from one another or are isomerically different by at least one atom. Therefore, in the present specification, the definition of copolymer includes terpolymer and the like.
As used herein, “higher olefin” refers to a C _{4 to} C ₄₀ olefin; preferably a C _{4 to} C ₃₀ α olefin; more preferably a C _{4 to} C ₂₀ α olefin; even more preferably a C _{4 to} C ₁₂ α olefin. Means. A “higher olefin copolymer” is a polymer comprising two or more different monomer units, at least one of which is a higher olefin. In a preferred embodiment, all monomer units in the polymer are derived from higher olefins.
In the present specification, Mn is a number average molecular weight (measured by ¹ H NMR unless otherwise specified), Mw is a weight average molecular weight (gel permeation chromatography, measured by GPC), and Mz is a z average molecular weight (measured by GPC). Wt% is weight percent, mol% is mole percent, vol% is volume percent, and mol is mole. Molecular weight distribution (MWD) is defined as Mw / Mn divided by Mw (measured by GPC) divided by Mn (measured by GPC). Unless otherwise specified, all molecular weights (eg, Mw, Mn, Mz) have units of g / mol.
JW Olesik, “Inductively Coupled Plasma-Optical Emission Spectroscopy,” in the Encyclopedia of Materials Characterization, CR Brundle, CA Evans, Jr. and S. Wilson, eds., Butterworth-Heinemann, Boston, Mass., 1992, pp. 633 ICPES (Inductively Coupled Plasma Atomic Emission Analysis) described in -644 is used to determine the amount of elements in the material.

Vinyl-terminated polymers Preferred vinyl-terminated higher olefin polymers (VT-HO) of the present invention are at least 200 g / mol, (preferably 200-100,000 g / mol, preferably 200-75,000 g / mol, preferably 200-60,000 g / mol). mol, preferably 300-60,000 g / mol, preferably 750-30,000 g / mol) of Mn (measured by ¹ H NMR), 1 or more (preferably 2 or more, 3 or more, 4 or more) C ₄ -C ₄₀ (preferably _{C 4 ~C 30, C 4 ~C} 20 etc.), or C ₄ -C _12, preferably butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, Norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof) Wherein the vinyl terminated higher olefin polymer is substantially free of propylene derived units (preferably 0.1 wt% propylene, preferably 0 wt%); and the higher olefin polymer is at least 5% (at least 10%, at least 15%). %, At least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%; at least 80%, at least 90%, or at least 95%) allylic chain ends (relative to total unsaturation) Optionally; allyl chain end pairs of 1: 1 or more (preferably greater than 2: 1, greater than 2.5: 1, greater than 3: 1, greater than 5: 1 or greater than 10: 1) Still more optionally, preferably substantially free of isobutyl chain ends (preferably less than 0.1 wt% isobutyl chain ends). In some embodiments, these higher olefin vinyl terminated polymers are ethylene derived units, preferably at least 5 mol% ethylene (preferably at least 15 mol% ethylene, preferably at least 25 mol% ethylene, preferably at least 35 mol% ethylene. , Preferably at least 45 mol% ethylene, preferably at least 60 mol% ethylene, preferably at least 75 mol% ethylene, preferably at least 90 mol% ethylene). In other embodiments, the higher olefin vinyl-terminated polymers of the present invention contain less than 90 mol% ethylene derived units (preferably less than 5 mol% ethylene, preferably less than 15 mol% ethylene, preferably less than 25 mol% ethylene, preferably 35 mol%). % Ethylene, preferably less than 45 mol% ethylene, preferably less than 60 mol% ethylene, preferably less than 75 mol% ethylene). In some embodiments of the present invention, the higher olefin vinyl terminated polymer is substantially free of ethylene derived units (preferably less than 0.1 wt% propylene, preferably 0 wt%).

Preferred vinyl-terminated higher olefin polymers (VT-HO) of the present invention are at least 200 g / mol (preferably 200 to 100,000 g / mol, preferably 200 to 75,000 g / mol, preferably 200 to 60,000 g / mol, preferably Mn (measured by ¹ H NMR) of 300-60,000 g / mol, preferably 750-30,000 g / mol) and at least 5 mol% (preferably at least 10 mol%, at least 15 mol%, at least 20 mol%, at least 30 mol%) At least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70 mol%; at least 80 mol%, at least 90 mol%, or at least 95 mol%) (preferably 2 or more, 3 or more, 4 or more, etc.) of C ₄ -C ₄₀ (preferably _{C 4 ~C 30, C 4 ~C} 20, or C ₄ -C _12, preferably butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, Norbornadiene, dicyclopentadiene, Clopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof) containing higher olefin-derived units, wherein the vinyl-terminated higher olefin polymer is substantially Contains no propylene-derived units (preferably 0.1 wt% propylene, preferably 0 wt%); and higher olefin polymers are at least 5% (at least 10%, at least 15%, at least 20%, at least 30%, at least 40% At least 50%, at least 60%, at least 70%; at least 80%, at least 90%, or at least 95%) of allyl chain ends (relative to total unsaturation); optionally 1: 1 or more ( (Preferably greater than 2: 1, greater than 2.5: 1, greater than 3: 1, greater than 5: 1 or greater than 10: 1) Has a down chain end ratio; Note further optionally and preferably, substantially free of isobutyl chain ends (preferably less than 0.1 wt% isobutyl chain ends). In some embodiments, these higher olefin vinyl terminated polymers are ethylene derived units, preferably at least 5 mol% ethylene (preferably at least 15 mol% ethylene, preferably at least 25 mol% ethylene, preferably at least 35 mol% ethylene. , Preferably at least 45 mol% ethylene, preferably at least 60 mol% ethylene, preferably at least 75 mol% ethylene, preferably at least 90 mol% ethylene). In other embodiments, the higher olefin vinyl-terminated polymers of the present invention contain less than 90 mol% ethylene derived units (preferably less than 5 mol% ethylene, preferably less than 15 mol% ethylene, preferably less than 25 mol% ethylene, preferably 35 mol%). % Ethylene, preferably less than 45 mol% ethylene, preferably less than 60 mol% ethylene, preferably less than 75 mol% ethylene). In some embodiments of the present invention, the higher olefin vinyl terminated polymer is substantially free of ethylene derived units (preferably less than 0.1 wt% propylene, preferably 0 wt%).

Preferred vinyl-terminated higher olefin polymers (VT-HO) of the present invention are at least 200 g / mol (preferably 200 to 100,000 g / mol, preferably 200 to 75,000 g / mol, preferably 200 to 60,000 g / mol, preferably Mn (measured by ¹ H NMR) of 300-60,000 g / mol, preferably 750-30,000 g / mol) and at least 5 mol% (preferably at least 10 mol%, at least 15 mol%, at least 20 mol%, at least 30 mol) %, At least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70 mol%; at least 80 mol%, at least 90 mol%, or at least 95 mol% or 100 mol%) (preferably 2 or more, 3 or more, 4 C _{4 to} C ₄₀ (preferably C _{4 to} C ₃₀ , C _{4 to} C ₂₀ , or C _{4 to} C ₁₂ , preferably butene, pentene, hexene, heptene, octene, nonene, decene, undecene, Dodecene, norbornene, norbornadiene, dicyclope Teradiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof) containing higher olefin-derived units, where the vinyl-terminated higher olefin polymer is Substantially free of propylene-derived units (preferably less than 0.1 wt% propylene, preferably 0 wt%); and at least 5% (at least 10%, at least 15%, at least 20%, at least 30%, higher olefin polymers, At least 40%, at least 50%, at least 60%, at least 70%; at least 80%, at least 90%, or at least 95%) of allyl chain ends (relative to total unsaturation); and optionally 1 : 1 or more (preferably greater than 2: 1, greater than 2.5: 1, greater than 3: 1, greater than 5: 1 or greater than 10: 1) An allyl chain end to vinylidene chain end ratio; still more optionally, preferably substantially free of isobutyl chain ends (preferably less than 0.1 wt% isobutyl chain ends). In some embodiments of the invention, these higher olefin vinyl terminated polymers are ethylene derived units, preferably at least 5 mol% ethylene (preferably at least 15 mol% ethylene, preferably at least 25 mol% ethylene, preferably at least 35 mol% ethylene, preferably at least 45 mol% ethylene, preferably at least 60 mol% ethylene, preferably at least 75 mol% ethylene, preferably at least 90 mol% ethylene). In another embodiment of the invention, the higher olefin vinyl-terminated polymers of the invention have less than 90 mol% ethylene derived units (preferably less than 5 mol% ethylene, preferably less than 15 mol% ethylene, preferably less than 25 mol% ethylene, Preferably less than 35 mol% ethylene, preferably less than 45 mol% ethylene, preferably less than 60 mol% ethylene, preferably less than 75 mol% ethylene). In some embodiments of the present invention, the higher olefin vinyl terminated polymer is substantially free of ethylene derived units (preferably less than 0.1 wt% propylene, preferably 0 wt%). In a particularly preferred embodiment, C ₄ -C ₄₀ higher olefin derived units of the present invention, C ₅ -C ₃₀ olefins, preferably C ₆ -C ₃₀ olefins, preferably C ₆ -C ₂₀ olefins, preferably C ₈ ~ C ₁₆ olefins, preferably C ₈ -C ₁₂ olefins, preferably three, four, five, six or more butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, Dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof) or selected from the group consisting of these Is done. In a particularly preferred embodiment, VT-HO is a homopolymer (e.g. Homoporipenten homo polyhexene, Homoporiokuten, Homoporidesen, Homoporidodesen etc.) or essentially copolymers of C ₅ -C ₄₀ olefins present invention, for example hexene And octene copolymers, octene and decene copolymers, or octene, decene and dodecene copolymers. In a preferred embodiment of the invention, VT-HO is at least 5 mol% (preferably at least 10 mol%, at least 15 mol%, at least 20 mol%, at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70 mol%; At least 80 mol%, at least 90 mol%, or at least 95 mol%) of a C _{5 to} C ₄₀ olefin (such as pentene, hexene, octene or decene), with the remainder being composed of different C _{5 to} C ₄₀ olefins.

The VT-HO polymer may be a homopolymer, a copolymer, a terpolymer, and the like.
VT-HO polymers generally have saturated chain ends (or ends) and / or unsaturated chain ends, or ends. The unsaturated chain ends of the inventive VT-HO polymer include “allyl chain ends”. The allyl chain terminal is represented by CH ₂ CH—CH ₂ — as shown in the following formula.

In the formula, M represents a polymer chain. In the following description, “allyl vinyl group”, “allyl chain terminal”, “vinyl chain terminal”, “vinyl termination”, “allyl vinyl group” and “vinyl terminal” are used interchangeably.
In some embodiments, the VT-HO polymer has at least 5% allyl chain ends (preferably at least 10% allyl chain ends, at least 15% allyl chain ends, at least 20% allyls based on total unsaturation. Chain end, at least 30% allyl chain end, at least 40% allyl chain end, at least 50% allyl chain end, at least 60% allyl chain end, at least 70% allyl chain end; at least 80% allyl chain end At least 90% allyl chain ends, or at least 95% allyl chain ends). The number of allyl chain ends, vinylidene chain ends, vinylene chain ends, and other unsaturated chain ends is determined using ¹ H NMR at 120 ° C. with deuterated tetrachloroethane as solvent on at least 250 MHz NMR spectrometer. In selected cases, it is confirmed by ¹³ C NMR. Resconi uses the proton-carbon assignment of vinyl-terminated oligomers (pure perdeuterated tetrachloroethane for the proton spectrum, while ordinary tetrachloroethane and perdeuterated tetrachloroethane are used for the carbon spectrum. A 50:50 mixture was used; all spectra were recorded on a Bruker spectrometer operating at 100 ° C. operating at 500 MHz for protons and 125 MHz for carbon) J. American Chemical Soc., 114, 1992, pp Reported at 1025-1032. These are useful herein. Allyl chain ends are reported as a mole percentage of the total number of moles of unsaturated groups (ie, the sum of allyl chain ends, vinylidene chain ends, vinylene chain ends, etc.).
“Allyl chain end to vinylidene chain end ratio” is defined as the ratio of the percentage of allyl chain ends to the percentage of vinylidene chain ends. In some embodiments, 1: 1 or more (preferably greater than 2: 1, greater than 2.5: 1, greater than 3: 1, greater than 4: 1, greater than 5: 1, greater than 7: 1, Allyl chain end to vinylidene chain end ratio (greater than 9: 1, greater than 10: 1). In some embodiments, the allyl chain end to vinylidene chain end ratio is in the range of about 10: 1 to about 1: 1 (preferably about 5: 1 to about 2: 1, preferably about 10: 1 to about 2.5. : 1, or preferably 10: 1 to about 3.5: 1).
“Allyl chain end to vinylene chain end ratio” is defined as the ratio of the percentage of allyl chain ends to the percentage of vinylene chain ends. In some embodiments, the allyl chain end to vinylene chain end ratio is greater than 1: 1 (preferably greater than 2: 1 or greater than 5: 1).
VT-HO polymers typically also have saturated chain ends. In polymerization without ethylene, the saturated chain end is a higher olefin chain end, as shown in the formula below.

In the formula, M represents a polymer chain, and n is an integer selected from 4 to 40. In ethylene / higher olefin copolymerization, the polymer chain can initiate the growth of ethylene monomer, thereby creating a saturated chain end that is an ethylene chain end. Here, the VT-HO polymer is substantially free of propylene (preferably less than 0.1 wt%, preferably 0 wt%) and thus substantially free of isobutyl chain ends (preferably less than 0.1 wt%, preferably 0 wt%). ). The isobutyl chain end is determined according to the procedure shown in WO 2009/155471.
The VT-HO polymer may further comprise ethylene derived units. In some embodiments, these VT-HO polymers are at least 5 mol% ethylene (preferably at least 15 mol% ethylene, preferably at least 25 mol% ethylene, preferably at least 35 mol% ethylene, preferably at least 45 mol%). Ethylene, preferably at least 60 mol% ethylene, preferably at least 75 mol% ethylene, preferably at least 90 mol% ethylene). In other embodiments, the VT-HO polymer is about 1.0 to about 99 mol% (about 10 to about 90 mol%, about 15 to about 95 mol%, about 20 to about 85 mol%, about 25 to about 75 mol%, or about 30 to about About 70 mol%) of ethylene.
In certain embodiments, the VT-HO copolymer is greater than 300 g / mol (preferably about 300 to about 60,000 g / mol, 400 to 50,000 g / mol, preferably 500 to 35,000 g / mol, preferably 300 to 15,000 g / mol. mol, preferably 400 to 12,000 g / mol, preferably in the range of 750 to 10,000 g / mol), 1000 or more (preferably about 1,000 to about 60400,000 g / mol, preferably about 2000 to 50300,000 g / mol) mol, preferably from about 3,000 to 35200,000 g / mol), and from about 1700 to about 150,000 g / mol, preferably from about 800 to 100,000 g / mol. Furthermore, the desirable molecular weight range can be any combination of any of the above molecular weight upper limits and any molecular weight lower limits. Mn ( ¹ H NMR) is determined according to the NMR method described below in the Examples section. As will be described later, Mn may be determined by the GPC-DRI method. For the purposes of the claims, Mn is determined by ¹ H NMR.

Mn, Mw, and Mz are measured by gel permeation chromatography (GPC) using a high temperature size exclusion chromatograph (SEC, Waters Corporation or Polymer Laboratories) equipped with a differential refractive index detector (DRI). Is possible. Details of the experiment are described in T. Sun, P. Brant, RR Chance, and WW Graessley, Macromolecules, Volume 34, Number 19, pp. 6812-6820, (2001) and references therein. Three Polymer Laboratories PLgel 10mm Mixed-B columns are used. The nominal flow rate is 0.5 cm ³ / min and the nominal injection volume is 300 μL. The oven maintained at 135 ° C contains various transfer lines, columns and differential refractometers (DRI detectors). The solvent for the SEC experiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 μm glass prefilter followed by a 0.1 μm Teflon filter. The TCB is then degassed with an online degasser before entering the SEC. A polymer solution is prepared by placing the dry polymer in a glass container and heating the mixture at 160 ° C. with constant stirring for about 2 hours after adding the desired amount of TCB. All quantities are measured gravimetrically. The density of TCB used to express polymer concentration in units of mass / volume is 1.463 g / mL at room temperature and 1.324 g / mL at 135 ° C. The injection concentration is 1.0-2.0 mg / mL, with lower concentrations being used for higher molecular weight samples. Purge the DRI detector and injector before running each sample. The flow rate in the apparatus is then increased to 0.5 mL / min and the first sample is injected after the DRI has stabilized for 8-9 hours. The concentration c at each point of the chromatogram is calculated from the baseline subtraction DRI signal I _DRI using the following formula.
c = K _DRI I _DRI / (dn / dc)
_Where K _DRI is a constant determined by calibrating the DRI and (dn / dc) is the refractive index increment of the system. TCB has a refractive index n = 1.500 at 135 ° C. and λ = 690 nm. For the purposes of the present invention and the appended claims, (dn / dc) = 0.104 for propylene polymers and 0.1 for others. The unit of parameters used throughout the description of the SEC method is as follows: concentration is expressed in g / cm ³ , molecular weight is expressed in g / mol, and intrinsic viscosity is expressed in dL / g.

In a preferred embodiment, the VT-HO polymer is less than 3 wt%, preferably less than 2 wt%, more preferably less than 1 wt%, more preferably less than 0.5 wt%, more preferably less than 0.1 wt%, based on the weight of the copolymer. And more preferably 0 wt% of functional groups selected from hydroxide, aryl and substituted aryl, halogen, alkoxy, carboxylate, ester, acrylate, oxygen, nitrogen, and carboxyl.
In another embodiment, the VT-HO polymer is at least 50 wt% (preferably at least 75 wt% based on the weight of the copolymer composition) as measured by ¹ H NMR assuming one unsaturation per chain. , Preferably at least 90 wt%) of olefins having at least 36 carbon atoms (preferably at least 51 carbon atoms, preferably at least 102 carbon atoms).
In another embodiment, the VT-HO polymer is less than 20 wt% (preferably less than 10 wt%, preferably less than 5 wt%, more preferably, based on the weight of the copolymer composition) as measured by gel chromatography (GC). Is less than 2 wt%) dimers and trimers. The product was analyzed on a GC (Agilent 6890N with automatic injector) using helium as the carrier gas at 38 cm / sec. 60m long column (J & W Scientific DB-1, 60m x 0.25mm ID x 1.0μm film thickness) loaded with flame ionization detector (FID), 250 ° C injector temperature, and 250 ° C Detector temperature was used. The sample was injected into a column in a 70 ° C. oven and heated to 275 ° C. over 22 minutes (ramp rate 10 ° C./min to 100 ° C., 30 ° C./min to 275 ° C. hold). The amount of dimer or trimer obtained is derived using an internal standard, usually a monomer. The yield of dimer and trimer products is calculated from the data recorded on the spectrometer. For internal standards, calculate the amount of dimer or trimer product from the area under the relevant peak for the GC trace.
In another embodiment, the VT-HO polymer is less than 25 ppm hafnium or zirconium, preferably less than 10 ppm hafnium or zirconium, preferably less than 5 ppm hafnium, based on the yield of the polymer product and the weight of catalyst used. Or zirconium. ICPES (Inductively Coupled Plasma Emission Spectroscopy) (JW Olesik “Inductively Coupled Plasma-Optical Emission Spectroscopy,” in the Encyclopedia of Materials Characterization, Brundle et al., Editors, Butterworth-Heinemann, Boston, Mass., 1992, pp. 633- To determine the amount of atoms in the material.
In yet other embodiments, the VT-HO polymer is liquid at 25 ° C. In another embodiment, the VT-HO polymers described herein have a 60 ° C. viscosity greater than 1000 cP, greater than 12,000 cP, or greater than 100,000 cP. In other embodiments, the vinyl terminated polymer has a viscosity of less than 200,000 cP, less than 150,000 cP, or less than 100,000 cP. Viscosity is measured using a Brookfield digital viscometer.

In another embodiment, the VT-HO polymers described herein preferably have a melting temperature (T _m , DSC first melting) in the range of 60-150 ° C., alternatively 50-100 ° C. In another embodiment, the copolymers described herein do not have a melting temperature detectable by DSC after storage for at least 48 hours at ambient temperature (23 ° C.). The VT-HO polymer preferably has a glass transition temperature (Tg) of 0 ° C or lower, preferably -10 ° C or lower, more preferably -20 ° C or lower, more preferably -30 ° C or lower, and more preferably -50 ° C or lower. As determined later by differential scanning calorimetry). Melting temperature (T _m ) and glass transition temperature (Tg) are measured using differential scanning calorimetry (DSC) using commercially available equipment such as TA Instruments 2920 DSC. Typically, 6-10 mg of sample stored at room temperature for at least 48 hours is sealed in an aluminum pan and loaded into the instrument at room temperature. The sample is equilibrated at 25 ° C and then cooled to -80 ° C at a cooling rate of 10 ° C / min. The sample is held at −80 ° C. for 5 minutes and then heated to 25 ° C. at a heating rate of 10 ° C./min. The glass transition temperature is measured from the heating cycle. Alternatively, the sample is equilibrated at 25 ° C. and then heated to 150 ° C. at a heating rate of 10 ° C./min. If present, the endothermic melting transition is analyzed for onset of transition and peak temperature. The reported melting temperature is the peak melting temperature obtained from the first heating unless otherwise specified. For samples showing multiple peaks, the melting point (or melting temperature) is defined as the peak melting temperature obtained from the DSC melting trace (ie, related to the maximum endothermic calorimetric response at that range of temperatures).
In another embodiment, the VT-HO polymers described herein have a 60 ° C. viscosity greater than 1000 cP, greater than 12,000 cP, or greater than 100,000 cP. In other embodiments, the VT-HO polymer has a viscosity of less than 200,000 cP, less than 150,000 cP, or less than 100,000 cP. Viscosity is defined as flow resistance and the melt viscosity of a pure copolymer is measured at an elevated temperature using a Brookfield digital viscometer.

In some embodiments, the VT-HO polymer is a hexene / octene copolymer, hexene / decene copolymer, hexene / dodecene copolymer, octene / decene copolymer, octene / dodecene copolymer, decene / dodecene copolymer, hexene / decene / Dodecenter polymer, hexene / octene / decenter polymer, octene / decene / dodecenter polymer, etc.
In another embodiment, here described or where any useful vinyl terminated polyolefins also, 3-alkyl vinyl end group represented by the following formula (alkyl is C ₁ -C ₃₈ alkyl) ( "3-alkyl Also referred to as “chain end” or “3-alkyl vinyl end”.

Wherein "..." represents a polyolefin chain, R ^b is C ₁ -C ₃₈ alkyl group, preferably a C ₁ -C ₂₀ alkyl group, e.g. methyl, ethyl, a propyl, butyl, pentyl, hexyl, heptyl Octyl, nonyl, decyl, undecyl, dodecyl and the like. The amount of 3-alkyl chain ends is determined using ¹³ C NMR as shown below.
In preferred embodiments, any vinyl-terminated polyolefin described or useful herein has at least 5% 3-alkyl chain ends (preferably at least 10% 3-alkyl chain ends, at least 20%, based on total unsaturation. 3-alkyl chain end, at least 30% 3-alkyl chain end; at least 40% 3-alkyl chain end, at least 50% 3-alkyl chain end, at least 60% 3-alkyl chain end, at least 70% At least 80% of 3-alkyl chain ends, at least 90% of 3-alkyl chain ends; at least 95% of 3-alkyl chain ends).
In a preferred embodiment, any vinyl-terminated polyolefin described or useful herein is at least 5% 3-alkyl + allyl chain ends (e.g., all 3-alkyl chain ends plus all of the total unsaturations). Allyl chain end), preferably at least 10% 3-alkyl + allyl chain end, at least 20% 3-alkyl + allyl chain end, at least 30% 3-alkyl + allyl chain end; at least 40% 3-alkyl + Allyl chain end, at least 50% 3-alkyl + allyl chain end, at least 60% 3-alkyl + allyl chain end, at least 70% 3-alkyl + allyl chain end; at least 80% 3-alkyl + allyl Has chain ends, at least 90% 3-alkyl + allyl chain ends; at least 95% 3-alkyl + allyl chain ends.

Use of Vinyl-Terminated Higher Olefin Polymers The vinyl-terminated polymers prepared here can be functionalized by reacting a heteroatom-containing group with an allyl group of the polymer, with or without a catalyst. Examples include catalytic hydrosilylation, hydroformylation, hydroboration, epoxidation, hydration, dihydroxylation, hydroamination, with or without an activator such as a free radical generator (e.g., peroxide), Or maleation.
In some embodiments, the vinyl-terminated polymers produced herein are US Pat. No. 6,022,929; A. Toyota, T. Tsutsui, and N. Kashiwa, Polymer Bulletin 48, pp. 213-219, 2002; Am. Chem. Soc., 1990, 112, pp. 7433-7434; and USSN 12 / 487,739, filed Jun. 19, 2009, and functionalized.
The functionalized polymer can be used in oil additivation and many other applications. Preferred uses include lubricants and / or fuel additives. Preferred heteroatom-containing groups include amines, aldehydes, alcohols, acids, succinic acid, maleic acid, and maleic anhydride.
In certain embodiments herein, the vinyl-terminated polymers disclosed herein, or functionalized analogs thereof, are useful as additives. In some embodiments, the vinyl-terminated polymers disclosed herein, or functionalized analogs thereof, are useful as additives to lubricants. Particular embodiments relate to lubricants comprising the vinyl terminated polymers disclosed herein, or functionalized analogs thereof.

In other embodiments, the vinyl-terminated polymers disclosed herein can be used as monomers for the preparation of polymer products. Methods that can be utilized for the preparation of these polymer products include coordination polymerization and acid catalyzed polymerization. In some embodiments, the polymer product may be a homopolymer. For example, when vinyl terminated polymer (A) is used as a monomer, a homopolymer product of formula (A) _n (where n is the degree of polymerization) can be formed.
In other embodiments, the polymer product formed from a mixture of monomeric vinyl terminated polymers can be a mixed polymer comprising two or more repeating units that are different from each other. For example, when a vinyl-terminated polymer (B) different from the vinyl-terminated polymer (A) is copolymerized, a mixed polymer of formula (A) _n (B) _m , where n is the vinyl present in the mixed polymer product The number of molar equivalents of the terminal polymer (A), and m is the number of molar equivalents of the vinyl-terminated polymer (B) present in the mixed polymer product.
In yet other embodiments, the polymer product can be formed from a mixture of a vinyl terminated polymer and another alkene. For example, when vinyl terminated polymer (A) and alkene (B) are copolymerized, a mixed polymer of formula (A) _n (B) _m (where n is the vinyl terminated polymer present in the mixed polymer product). M is the number of molar equivalents, and m is the number of molar equivalents of alkene present in the mixed polymer product.

In certain embodiments herein, the present invention is at least 200 g / mol (preferably 200-100,000 g / mol, preferably 200-75,000 g / mol, preferably 200-60,000 g / mol, preferably 300-60,000 g. / Mn, preferably 750 to 30,000 g / mol) of Mn (measured by ¹ H NMR), and one or more (preferably two or more, three or more, four or more, etc.) C _{4 to} C ₄₀ (preferably _{C 4 ~C 30, C 4 ~C} 20, or C ₄ -C _12, preferably butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, Cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof) containing higher olefin-derived units, where The mer is substantially free of propylene derived units (preferably less than 0.1 wt% propylene, preferably 0 wt% propylene); and the higher olefin polymer is at least 5% (at least 10%, at least 15%, at least 20%, At least 30%, at least 40%, at least 50%, at least 60%, at least 70%; at least 80%, at least 90%, or at least 95%) having allylic chain ends; optionally 1: 1 or more (preferably Has an allyl chain end to vinylidene chain end ratio of greater than 2: 1, greater than 2.5: 1, greater than 3: 1, greater than 5: 1, or greater than 10: 1; Preferably, it relates to a composition comprising a VT-HO polymer substantially free of isobutyl chain ends (preferably 0.1 wt% isobutyl chain ends). In some embodiments, these higher olefin vinyl terminated polymers are ethylene derived units, preferably at least 5 mol% ethylene (preferably at least 15 mol% ethylene, at least 25 mol% ethylene, at least 35 mol% ethylene, at least 45 mol). % Ethylene, at least 60 mol% ethylene, at least 75 mol% ethylene, or at least 90 mol% ethylene).
In some embodiments, the composition is a lubricant blend. In another embodiment, the present invention relates to the use of the above composition as a lubricant blend.

The present invention is a method for producing a higher olefin polymer, which is one or more (preferably two or more, three or more, four or more, etc.) C _{4 to} C ₄₀ (preferably _{C 4 ~C 30, C 4 ~C} 20, or C ₄ -C _12, preferably butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene , Cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof) monomer (substantially no propylene monomer (preferably 0.1 wt% propylene, preferably 0 wt% propylene)); and optionally, at least 5 mol% ethylene (preferably at least 15 mol% ethylene, preferably at least 25 mol% ethylene, preferably at least 35 mol% ethylene, preferably at least 45 mol% ethylene, preferably at least 60 mol% ethylene, preferably at least 75 mol% ethylene, preferably at least 90 mol% (Wherein the contacting step occurs in the presence of a catalyst system comprising an activator and at least one metallocene compound represented by one of the following formulas):
(i)

式I；

Formula I;

式II； Or (ii)

Formula II;

式III； Or (iii)

Formula III;

式IV； Or (iv)

Formula IV;

Wherein M is hafnium or zirconium; each X is independently a hydrocarbyl group having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halogen, diene, amine, phosphine, ether , And combinations thereof (two Xs may form part of a fused ring or ring system) and each Q is independently a carbon or heteroatom; each R ¹ is independently a C ₁ -C ₈ alkyl group, R ¹ is may be identical or different and R ^2; each R ² is independently a C ₁ -C ₈ alkyl group; each R ³ is independently , Hydrogen, or substituted or unsubstituted hydrocarbyl groups having 1 to 8 carbon atoms, provided that at least three R ³ groups are not hydrogen; each R ⁴ is independently hydrogen or substituted or unsubstituted hydrocarbyl Group, heteroatom or heteroatom-containing group ; R ⁵ is hydrogen or C ₁ -C ₈ alkyl group; R ⁶ is hydrogen or C ₁ -C ₈ alkyl group; each R ⁷ is independently hydrogen, or C ₁ -C ₈ alkyl group Yes (but at least 7 R ⁷ groups are not hydrogen); R ₂ ^a T is a bridging group, T is a group 14 element (preferably C, Si, or Ge, preferably Si), and each R ^a Are independently hydrogen, halogen or C ₁ -C ₂₀ hydrocarbyl and the two R ^{a form a} cyclic structure (including aromatic, partially saturated or saturated cyclic or fused ring systems) In addition, any two adjacent R groups may form a fused ring or a multi-centered fused ring system, provided that the ring may be aromatic, partially saturated or saturated);
Or (v)

式V；

Formula V;

Wherein M is hafnium or zirconium; each X is independently a hydrocarbyl group having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether. Selected from the group consisting of, and combinations thereof, wherein two Xs may form part of a fused ring or ring system; each R ⁸ is independently a C ₁ -C ₁₀ alkyl group; R ⁹ is independently a C ₁ -C ₁₀ alkyl group; each R ¹⁰ is hydrogen; each R ¹¹ , R ¹² , and R ¹³ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, hetero An atom or a heteroatom-containing group; T is a bridging group (eg, R ₂ ^a T as described above); and any adjacent R ¹¹ , R ¹² , and R ¹³ groups are also fused or multi-centered fused ring systems (including The ring may be aromatic, partially saturated or saturated) As a condition);
Or (vi)

式VI;

Formula VI;

Wherein M is hafnium or zirconium; each X is independently a hydrocarbyl group having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halogen, diene, amine, phosphine, ether. Each R ¹⁵ and R ¹⁷ is independently a C ₁ -C ₈ alkyl group; and each R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² is selected from the group consisting of: , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ are independently hydrogen or a substituted or unsubstituted hydrocarbyl group having 1 to 8 carbon atoms)
It also relates to a method comprising:

In general, to produce the vinyl terminated VT-HO polymers described herein, one or more (preferably 2 or more, 3 or more, 4 or more, etc.) C ₄ -C ₄₀ (preferably _{C 4 ~C 30, C 4 ~C} 20, or C ₄ -C _12, preferably butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, A higher olefin monomer (for example, hexene or octene) is polymerized by contacting cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof (for example, hexene or octene). Here, the contact is performed in the presence of a catalyst system (including one or more metallocene compounds described later and one or more activators). Stiff). If desired, other additives such as one or more scavengers, promoters, modifiers, reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes may be used. In a preferred embodiment, little or no scavenger is used in the process for producing the VT-HO copolymer. Preferably, the scavenger is present at zero mol%, or the scavenger is less than 100: 1, preferably less than 50: 1, preferably less than 15: 1, preferably less than 10: 1. Present in a molar ratio of transition metal.
The higher olefin monomer may be linear, branched or cyclic. The higher olefin cyclic olefin may be distorted or undistorted monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups. Typical higher olefin monomers include butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7- Oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof (preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologues and derivatives, preferably as shown below Bornene, norbornadiene, and dicyclopentadiene) may be mentioned.

In some embodiments where butene is a comonomer, the butene source may be a mixed butene stream comprising various isomers of butene. In the polymerization process, 1-butene monomer is expected to be preferentially consumed. Because these mixed streams are often purification process waste streams, such as C ₄ raffinate streams, and therefore are less expensive than substantially pure 1-butene, the use of such mixed butene streams would provide economic benefits. .
The method of the present invention can be carried out in any manner known in the art. Any suspension, homogeneous bulk, solution, slurry, or gas phase polymerization process known in the art can be used. The method can be performed in batch, semi-batch, or continuous mode. Such methods and modes are well known in the art. Homogeneous polymerization and slurry polymerization are preferred (homogeneous polymerization is defined as a method in which at least 90 wt% of the product is soluble in the reaction medium). A bulk homogeneous process is particularly preferred (a bulk process is defined as a process in which the monomer concentration in all feeds to the reactor is 70 vol% or higher). Alternatively, no solvent or diluent is present or no solvent or diluent is added to the reaction medium (a small amount used as a support for a catalyst system or other additive, or an amount typically found with monomers; for example, propylene Except propane etc.)
Suitable diluents / solvents for polymerization include non-coordinating inert liquids. Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methyl Cyclohexane, methylcycloheptane, and mixtures thereof as commercially available (Isopar ^™ ); perhalogenated hydrocarbons such as perfluorinated C _4-10 alkanes, chlorobenzene, and aromatic and alkyl-substituted aromatic compounds such as Examples include benzene, toluene, mesitylene, and xylene. As a monomer or comonomer, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof Liquid olefins that can act are also mentioned as suitable solvents. In a preferred embodiment, the solvent is an aliphatic hydrocarbon solvent 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 another embodiment, the solvent is not aromatic, preferably the aromatic compound is present in the solvent at less than 1 wt%, preferably 0.5 wt%, preferably 0 wt%, based on the weight of the solvent.
In a preferred embodiment, the concentration of the polymerization feed is 60 vol% or less, preferably 40 vol% or less, preferably 20 vol% or less, based on the total volume of the feed stream. The polymerization is preferably carried out by a bulk method.

“Catalyst productivity” is a measure of how many grams of polymer (P) are produced using a polymerization catalyst containing Wg catalyst (cat) over a T time period; P / (T × W) and can be expressed in units of gPgcat ⁻¹ hour ⁻¹ . Conversion is the amount of monomer converted to polymer, reported as mol%, and is calculated based on the polymer yield and the amount of monomer fed to the reactor. Catalytic activity is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP / molcat).
In an alternative embodiment, the activity of the catalyst is at least 50 g / mmol / hour, preferably 500 g / mmol / hour or more, preferably 5000 g / mmol / hour or more, preferably 50,000 g / mmol / hour or more. In an alternative embodiment, the conversion of the olefin monomer is at least 10%, preferably 20% or more, preferably 30% or more, preferably 50% or more, preferably based on the polymer yield and the weight of monomer entering the reaction zone. Is over 80%.
In some embodiments, the productivity is 4500 g / mmol / hour or more, preferably 5000 g / mmol / hour or more, preferably 10,000 g / mmol / hour or more, preferably 50,000 g / mmol / hour or more. In other embodiments, the productivity is at least 80,000 g / mmol / hour, preferably at least 150,000 g / mmol / hour, preferably at least 200,000 g / mmol / hour, preferably at least 250,000 g / mmol / hour, preferably At least 300,000 g / mmol / hour.
Preferred polymerizations can be conducted at any temperature and / or pressure suitable to obtain the desired VT-HO polymer. The polymerization can be carried out at any suitable temperature, for example a temperature in the range of about 0-250 ° C, preferably 15-200 ° C, preferably 23-120 ° C; and any suitable pressure, It may be in the range of about 0.35-10 MPa, preferably 0.45-6 MPa, preferably 0.5-4 MPa.
In a typical polymerization, the reaction run time is in the range of up to 300 minutes, preferably about 5 to 250 minutes, preferably about 10 to 120 minutes.
In a preferred embodiment, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), preferably 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa). In this system, we have found that hydrogen can be used to enhance the activity without significantly harming the ability of the catalyst to produce allylic chain ends. Preferably the catalytic activity (calculated as g / mmol catalyst / hour) is at least 20% higher, preferably at least 50% higher, preferably at least 100% higher than the same reaction without hydrogen.

  In a preferred embodiment, the polymerization is carried out at a temperature of: 1) 0-300 ° C. (preferably 25-150 ° C., preferably 40-120 ° C., preferably 45-80 ° C.); 2) Atmospheric pressure to 10 MPa (preferably Is carried out at a pressure of 0.35 to 10 MPa, preferably 0.45 to 6 MPa, preferably 0.5 to 4 MPa; 3) an aliphatic hydrocarbon solvent (for example 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; wherein preferably the aromatic compound is 1 wt% in the solvent based on the weight of the solvent Less than, preferably less than 0.5 wt%, preferably present at 0 wt%); 4) the catalyst system used in the polymerization contains less than 0.5 mol%, preferably 0 mol% alumoxane, or The lumoxane is present in a molar ratio of aluminum to transition metal of less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1: 1; 5) the polymerization takes place in one reaction zone 6) The productivity of the catalyst compound is at least 80,000 g / mmol / hour (preferably at least 150,000 g / mmol / hour, preferably at least 200,000 g / mmol / hour, preferably at least 250,000 g / mmol / hour, preferably At least 300,000 g / mmol / hr); 7) Optionally, no scavenger (eg trialkylaluminum compound) is present (eg present at zero mole% or scavenger is less than 100: 1, preferably Is present in a molar ratio of scavenger metal to transition metal of less than 50: 1, preferably less than 15: 1, preferably less than 10: 1); and 8) optionally, hydrogen is 0.001 to 50 psig in the polymerization reactor. (0.007 to 345 kPa) (preferably 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 Exists at a partial pressure of psig (0.7-70 kPa). In a preferred embodiment, the catalyst system used in the polymerization contains only one catalyst compound. A “reaction zone”, also referred to as a “polymerization zone”, is a vessel in which polymerization occurs, such as a batch reactor. When multiple reactors are used in a series or parallel arrangement, each reactor is considered a separate polymerization zone. In a multistage polymerization, whether batch or continuous, each polymerization stage is considered a separate polymerization zone. In a preferred embodiment, the polymerization occurs in one reaction zone. Room temperature is 23 ° C unless otherwise specified.

In an embodiment herein, the present invention is a process for producing a higher olefin polymer, as described below, in the presence of a catalyst system comprising an activator and at least one metallocene compound. The present invention relates to a method comprising a step of contacting a monomer.
In the description herein, a metallocene catalyst can be described as a catalyst precursor, a pre-catalyst compound, or a transition metal compound, and these terms are used interchangeably. A polymerization catalyst system is a catalyst system that can polymerize monomers into a polymer. A “catalytic system” is a combination of at least one catalyst compound, at least one activator, an optional coactivator, and an optional support material. An “anionic ligand” is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A “neutral donor ligand” is a neutrally charged ligand that donates one or more pairs of electrons to a metal ion.
For purposes of this invention and the accompanying claims, if the catalyst system is described as containing a neutral stable form of a component, those skilled in the art will recognize that the ionic form of the component reacts with the monomer to react with the polymer. As you can see, it is a form to generate.
A metallocene catalyst is defined as an organometallic compound having at least one π-bonded cyclopentadienyl moiety (or substituted cyclopentadienyl moiety), more frequently two π-bonded cyclopentadienyl moieties or substituted moieties. This includes other π-bonded moieties such as indenyl or fluorenyl or derivatives thereof.
The catalyst system metallocene, activator, optional co-activator, and optional support components are described below.

(a) Metallocene component The term “substituted” means that a hydrogen group is replaced with a hydrocarbyl group, a heteroatom, or a heteroatom-containing group. For example, methylcyclopentadiene (Cp) is a Cp group substituted with a methyl group, ethyl alcohol is an ethyl group substituted with an —OH group, and “substituted hydrocarbyl” is composed of carbon and oxygen, A group in which at least one hydrogen is replaced by a heteroatom.
For purposes of this invention and the claims appended hereto, “alkoxides” include those where the alkyl group is a C ₁ -C ₁₀ hydrocarbyl. The alkyl group may be linear, branched or cyclic. The alkyl group may be saturated or unsaturated. In some embodiments, the alkyl group includes at least one aromatic group.
The metallocene component of the catalyst system is represented by at least one of formulas I, II, III, IV, V, or VI.
(i) Formulas I, II, III, and IV
In some embodiments, the metallocene compound is represented by at least one of the following formulas I, II, III, and IV.

式I；

Formula I;

式II； Or (ii)

Formula II;

式III； Or (iii)

Formula III;

式IV； Or (iv)

Formula IV;

Where M is hafnium or zirconium;
Each X is independently a group consisting of a hydrocarbyl group having from 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halogen, diene, amine, phosphine, ether, or combinations thereof; preferably methyl, Selected from ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, iodide (or two Xs may form part of a fused ring or ring system);
Each Q is independently a carbon or heteroatom, preferably C, N, P, S (preferably at least one Q is a heteroatom, or at least two Q are the same or different heteroatoms; Or at least three Q are the same or different heteroatoms, or at least four Q are the same or different heteroatoms);
Each R ¹ is independently hydrogen or C ₁ -C ₈ alkyl group, preferably a C ₁ -C ₈ straight chain alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, R ¹ may be the same or different from R ² ;
Each R ² is independently hydrogen or C ₁ -C ₈ alkyl group, preferably a C ₁ -C ₈ straight chain alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, Provided that at least one of R ¹ or R ² is not hydrogen, preferably R ¹ and R ² are not both hydrogen, preferably R ¹ and / or R ² are not branched;
Each R ³ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, preferably a substituted or unsubstituted C _{1 to} C ₈ straight chain An alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, provided that at least three R ³ groups are not hydrogen (or four R ³ groups are not hydrogen, or five R ³ group is not hydrogen);
Each R ⁴ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, heteroatom or heteroatom-containing group, preferably 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. hydrocarbyl group, preferably a substituted or unsubstituted C ₁ -C ₈ straight chain alkyl groups, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, substituted phenyl (such as propyl phenyl etc.), phenyl, silyl, Substituted silyl (eg, CH ₂ SiR ′, where R ′ is C ₁ -C ₁₂ hydrocarbyl, eg, methyl, ethyl, propyl, butyl, phenyl, etc.);
R ⁵ is hydrogen or a C ₁ -C ₈ alkyl group, preferably a C ₁ -C ₈ linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl;
R ⁶ is hydrogen or a C ₁ -C ₈ alkyl group, preferably a C ₁ -C ₈ linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl;
Each R ⁷ is, independently, hydrogen, or C ₁ -C ₈ alkyl group, there preferably C ₁ -C ₈ straight chain alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl Provided that at least 7 R ⁷ groups are not hydrogen, or at least 8 R ⁷ groups are not hydrogen, or all R ⁷ groups are not hydrogen (preferably at positions 3 and 4 of each Cp ring of formula IV. The R ⁷ group at the position is not hydrogen);
R ₂ ^a T is a bridging group, preferably T comprises C, Si, or Ge, preferably Si;
Each R ^a is independently hydrogen, halogen or C ₁ -C ₂₀ hydrocarbyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, benzyl, substituted phenyl, and the two R ^a Cyclic structures (including aromatic, partially saturated, or saturated cyclic or fused ring systems) can be formed;
Further, provided that any two adjacent R groups may form a condensed ring or a multi-centered condensed ring system (the ring may be aromatic, partially saturated or saturated). )

In alternative embodiments, at least one R ⁴ group is not hydrogen, or at least two R ⁴ groups are not hydrogen, or at least three R ⁴ groups are not hydrogen, or at least four R ⁴ groups are hydrogen. Or not all R ⁴ groups are hydrogen.
In some embodiments, the bridging group T is at least one group 13-16 atom (often referred to as a divalent moiety), such as, but not limited to, at least one carbon, oxygen, Includes bridging groups containing nitrogen, silicon, aluminum, boron, germanium and tin atoms, or combinations thereof. Preferably, the bridging group T comprises a carbon, silicon or germanium atom, most preferably T comprises at least one silicon atom or at least one carbon atom. As described later, the bridging group T may contain a substituent R ^* such as halogen and iron.
Non-limiting examples of the substituent R ^* are hydrogen or a linear or branched alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, acyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, A dialkylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or dialkylcarbamoyl group, an acyloxy group, an acylamino group, an arylamino group, or a combination thereof can be given. In preferred embodiments, the substituent R ^* has up to 50 non-hydrogen atoms, preferably 1 to 30 carbons (which may be substituted with halogens or heteroatoms, etc.). Non-limiting examples of alkyl substituents R ^* include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups, and all their isomers, such as tertiary butyl, isopropyl, etc. Is included. Other hydrocarbyl groups include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and hydrocarbyl substituted organic metalloid groups such as trimethylsilyl, trimethylgermyl, methyldiethylsilyl, and the like; Metal groups such as tris (trifluoromethyl) silyl, methyl-bis (difluoromethyl) silyl, bromomethyldimethylgermyl and the like; and disubstituted boron groups such as dimethylboron; and disubstituted pnictogen groups such as dimethylamine, dimethyl Examples include phosphine, diphenylamine, methylphenylphosphine and the like, chalcogen groups such as methoxy, ethoxy, propoxy, phenoxy, methyl sulfide, and ethyl sulfide. Non-hydrogen substituents R ^* include atomic carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium, etc., for example, but not limited to, vinyl-terminated ligands such as Olefins such as olefinically unsaturated substituents are included, including but-3-enyl, prop-2-enyl, hexa-5-enyl and the like. Also, in some embodiments, at least two R ^* groups, preferably two adjacent R groups, are combined and selected from carbon, nitrogen, hydrogen, phosphorus, silicon, germanium, aluminum, boron, or combinations thereof. To form a ring structure having 3 to 30 atoms. In other embodiments, R ^* may be a diradical bonded to L at one end to form a carbon σ bond to metal M. Particularly preferred R ^* substituents, C ₁ -C ₃₀ hydrocarbyl, heteroatom or heteroatom containing group (preferably including methyl, ethyl, propyl (isopropyl, sec- propyl), butyl (t-butyl and sec- butyl ), Neopentyl, cyclopentyl, hexyl, octyl, nonyl, decyl, phenyl, substituted phenyl, benzyl (including substituted benzyl), cyclohexyl, cyclododecyl, norbornyl, and all isomers thereof.

Examples of bridging groups R ₂ ^a T in formula III or bridging groups T in formula V useful herein are R ′ ₂ C, R ′ ₂ Si, R ′ ₂ Ge, R ′ ₂ CCR ′ ₂ , R ′ ₂ CCR ' ₂ CR' ₂ , R ' ₂ CCR' ₂ CR ' ₂ CR' ₂ , R'C = CR ', R'C = CR'CR' ₂ , R ' ₂ CCR' = CR'CR ' ₂ , R'C = CR'CR '= CR', R'C = CR'CR ' ₂ CR' ₂ , R ' ₂ CSiR' ₂ , R ' ₂ SiSiR' ₂ , R ₂ CSiR ' ₂ CR' ₂ , R ' ₂ SiCR ' ₂ SiR' ₂ , R'C = CR'SiR ' ₂ , R' ₂ CGeR ' ₂ , R' ₂ GeGeR ' ₂ , R' ₂ CGeR ' ₂ CR' ₂ , R ' ₂ GeCR' ₂ GeR ' _{2, R '2 SiGeR' 2} , R'C = CR'GeR '2, R'B, R' 2 C-BR ', R' 2 C-BR'-CR '2, R' 2 CO-CR ' ₂ , R ' ₂ CR' ₂ CO-CR ' ₂ CR' ₂ , R ' ₂ CO-CR' ₂ CR ' ₂ , R' ₂ CO-CR '= CR', R ' ₂ CS-CR' ₂ , R ' ₂ CR' ₂ CS-CR ' ₂ CR' ₂ , R ' ₂ CS-CR' ₂ CR ' ₂ , R' ₂ CS-CR '= CR', R ' ₂ C-Se-CR' ₂ , R ' ₂ CR ' ₂ C-Se-CR' ₂ CR ' ₂ , R' ₂ C-Se-CR ₂ CR ' ₂ , R' ₂ C-Se-CR '= CR', R ' ₂ CN = CR', R ' ₂ C-NR'-CR' ₂ , R ' ₂ C-NR'-CR' ₂ CR ' ₂ , R' ₂ C-NR'-CR '= CR', R ' ₂ CR' ₂ C-NR ' -CR ' ₂ CR' ₂ , R ' ₂ CP = CR', and R ' ₂ C-PR'-CR' ₂ (where R 'is hydrogen or hydrocarbyl containing C ₁ -C ₂₀ , A substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituent, optionally substituted by two or more adjacent R ′, substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or A polycyclic substituent may be formed). Preferably, the bridging group is a carbon or silica, e.g., comprise a dialkyl silyl or the like, preferably bridging _{group, CH 2, CH 2 CH 2} , C (CH 3) 2, SiMe 2, SiPh 2, SiMePh, silyl cyclobutyl Selected from (Si (CH ₂ ) ₃ , (Ph) ₂ C, (p- (Et) ₃ SiPh) ₂ C and silylcyclopentyl (Si (CH ₂ ) ₄ ).

Particularly useful catalyst compounds in the present invention include one or more of the following compounds:
(1,3-dimethylindenyl) (pentamethylcyclopentadienyl) hafnium dimethyl,
(1,3,4,7-tetramethylindenyl) (pentamethylcyclopentadienyl) hafnium dimethyl,
(1,3-dimethylindenyl) (tetramethylcyclopentadienyl) hafnium dimethyl,
(1,3-diethylindenyl) (pentamethylcyclopentadienyl) hafnium dimethyl,
(1,3-dipropylindenyl) (pentamethylcyclopentadienyl) hafnium dimethyl,
(1-methyl, 3-propyl-1-indenyl) (pentamethylcyclopentadienyl) hafnium dimethyl,
(1,3-dimethylindenyl) (tetramethylpropylcyclopentadienyl) hafnium dimethyl,
(1,2,3-trimethylindenyl) (pentamethylcyclopentadienyl) hafnium dimethyl,
(1,3-dimethylbenzoindenyl) (pentamethylcyclopentadienyl) hafnium dimethyl,
(2,7-bis t-butylfluorenyl) (pentamethylcyclopentadienyl) hafnium dimethyl,
(9-methylfluorenyl) (pentamethylcyclopentadienyl) hafnium dimethyl,
(2,7,9-trimethylfluorenyl) (pentamethylcyclopentadienyl) hafnium dimethyl,
Dihydrosilylbis (tetramethylcyclopentadienyl) hafnium dimethyl,
Dihydrosilylbis (tetramethylcyclopentadienyl) hafnium dimethyl,
Dimethylsilyl (tetramethylcyclopentadienyl) (3-propyltrimethylcyclopentadienyl) hafnium dimethyl and dicyclopropylsilylbis (tetramethylcyclopentadienyl) hafnium dimethyl.

式V； In an alternative embodiment, specifically for use with an alumoxane activator, “dimethyl” after the transition metal in the catalyst compound list is replaced with a dihalide (eg, dichloride or difluoride) or bisphenoxide.
(ii) Formula V
In some embodiments, the metallocene is represented by Formula V below.

Formula V;

Where M is hafnium or zirconium, preferably hafnium;
Each X is independently a substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, and combinations thereof (two X Are preferably selected from the group consisting of a halide and a C ₁ -C ₆ hydrocarbyl group, preferably each X is methyl, Ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide, or iodide;
Each R ⁸ is independently a substituted or unsubstituted C ₁ -C ₁₀ alkyl group; preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or an isomer thereof; preferably Is methyl, n-propyl or n-butyl, preferably methyl;
Each R ⁹ is independently a substituted or unsubstituted C ₁ -C ₁₀ alkyl group; preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or an isomer thereof; preferably methyl N-propyl or butyl, preferably n-propyl;
Each R ¹⁰ is hydrogen;
Each R ¹¹ , R ¹² , and R ¹³ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, heteroatom or heteroatom-containing group; preferably each R ¹¹ , R ¹² , and R ¹³ is hydrogen ;
T is a bridging group represented by the formula R ₂ ^a J, wherein J is C, Si, or Ge, preferably Si;
Each R ^a is independently hydrogen, halogen or C ₁ -C ₂₀ hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, benzyl, substituted phenyl and the like, the two R ^a May form a ring structure (including aromatic, partially saturated, or saturated cyclic, or fused ring systems);
In addition, any two adjacent R groups may form a fused ring or multi-centered fused ring system (wherein the ring may be aromatic, partially saturated or saturated); T is a bridging group as defined above. And any adjacent R ¹¹ , R ¹² , and R ¹³ groups may be fused or multi-centered fused ring systems (rings may be aromatic, partially saturated or saturated). It is a condition that it may be formed.

Particularly useful metallocene compounds in the present invention include one or more of the following compounds:
rac-dimethylsilyl bis (2-methyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylsilyl bis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilyl bis (2-ethyl, 3-propylindenyl) hafnium dimethyl;
rac-dimethylsilyl bis (2-ethyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilyl bis (2-methyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylsilyl bis (2-methyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylsilyl bis (2-methyl, 3-isopropylindenyl) hafnium dimethyl,
rac-dimethylsilyl bis (2-methyl, 3-isopropylindenyl) zirconium dimethyl,
rac-dimethylsilyl bis (2-methyl, 3-butyl-indenyl) hafnium dimethyl,
rac-dimethylsilyl bis (2-methyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylgermanyl bis (2-methyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylgermanyl bis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylgermanyl bis (2-ethyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylgermanyl bis (2-ethyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylgermanyl bis (2-methyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylgermanyl bis (2-methyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylgermanyl bis (2-methyl, 3-isopropylindenyl) hafnium dimethyl,
rac-dimethylgermanyl bis (2-methyl, 3-isopropylindenyl) zirconium dimethyl,
rac-dimethylgermanyl bis (2-methyl, 3-butyl-indenyl) hafnium dimethyl,
rac-dimethylgermanyl bis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilyl bis (2-propyl, 3-methylindenyl) hafnium dimethyl,
rac-dimethylsilyl bis (2-propyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylsilyl bis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylgermanyl bis (2,3-dimethylindenyl) hafnium dimethyl,
rac-dimethylsilyl bis (2,3-dimethylindenyl) hafnium dimethyl, and
rac-dimethylsilyl bis (2,3-diethylindenyl) hafnium dimethyl.

In an alternative embodiment, specifically for use with an alumoxane activator, “dimethyl” after the transition metal in the catalyst compound list is replaced with a dihalide (eg, dichloride or difluoride) or bisphenoxide.
In a specific embodiment, the metallocene compound is rac-dimethylsilylbis (2-methyl, 3-propylindenyl) hafnium dimethyl (VI), rac-dimethylsilylbis (2-methyl, 3-propyl) represented by the following formula: Indenyl) zirconium dimethyl (V-II).

式VI； (iii) Formula VI
In some embodiments, the metallocene is represented by Formula VI below.

Formula VI;

Where M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or combinations thereof;
Each R ¹⁵ and R ¹⁷ is independently a C ₁ -C ₈ alkyl group; preferably a C ₁ -C ₈ linear alkyl group, preferably methyl ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl; R ¹⁵ may be the same as or different from R ¹⁷ and is preferably both methyl; and each R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are independently hydrogen or a substituted or unsubstituted hydrocarbyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms; preferably substituted or unsubstituted C ₁ -C ₈ straight chain alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, but not at least three hydrogen R ²⁴ to R ²⁸ group (or R ²⁴ to R ²⁸ group at least 5 of the at least four are not hydrogen, or is the R ²⁴ to R ²⁸ group With the proviso it is not hydrogen) can. Preferably methyl five all groups R ²⁴ to R ^28, and / or R ²⁴ not four are hydrogen to R ²⁸ radicals, at least one C ₂ -C ₈ substituted R ²⁴ to R ²⁸ group Or unsubstituted hydrocarbyl (preferably at least 2, 3, 4 or 5 of the R ^{24 to} R ²⁸ groups are C _{2 to} C ₈ substituted or unsubstituted hydrocarbyl).

In one embodiment, R ¹⁵ and R ¹⁷ are methyl groups, R ¹⁶ is hydrogen, R ^{18 to} R ²³ are all hydrogen, R ^{24 to} R ²⁸ are all methyl groups, and each X is methyl It is a group. The following compounds are particularly useful catalyst compounds in the present invention.
(CpMe ₅ ) (1,3-Me ₂ benzo [e] indenyl) HfMe ₂ ,
(CpMe ₅ ) (1-methyl-3-n-propylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₅ ) (1-n-propyl, 3-methylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₅ ) (1-methyl-3-n-butylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₅ ) (1-n-butyl, 3-methylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₅ ) (1-ethyl, 3-methylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₅ ) (1-methyl, 3-ethylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ n-propyl) (1,3-Me ₂ benzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ -n-propyl) (1-methyl-3-n-propylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ -n-propyl) (1-n-propyl, 3-methylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ -n-propyl) (1-methyl-3-n-butylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ -n-propyl) (1-n-butyl, 3-methylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ -n-propyl) (1-ethyl, 3-methylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ -n-propyl) (1-methyl, 3-ethylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ n-butyl) (1,3-Me ₂ benzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ n-butyl) (1-methyl-3-n-propylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ n-butyl) (1-n-propyl, 3-methylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ n-butyl) (1-methyl-3-n-butylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ n-butyl) (1-n-butyl, 3-methylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ n-butyl) (1-ethyl, 3-methylbenzo [e] indenyl) HfMe ₂ ,
(CpMe ₄ n-butyl) (1-methyl, 3-ethylbenzo [e] indenyl) HfMe ₂ ,
And its zirconium analogues.
In an alternative embodiment, “dimethyl (Me ₂ )” after the transition metal in the catalyst compound list is replaced with a dihalide (eg, dichloride or difluoride) or bisphenoxide, particularly for use with an alumoxane activator.

(b) Catalyst system activator component The terms "cocatalyst" and "activator" are used interchangeably herein to convert a neutral catalyst compound to a catalytically active catalyst compound cation. Is defined as any compound capable of activating any one of the above catalyst compounds. Non-limiting activators include, for example, alumoxanes, aluminum alkyls, ionization activators that can be neutral or ionic, and conventional cocatalysts. As preferred activators, typically alumoxane compounds, modified alumoxane compounds, and ionized anion precursor compounds (withdrawing one reactive σ-bonded metal ligand to make the metal complex cationic and charge balanced Give non-coordinating or weakly coordinating anions).
In one embodiment, an alumoxane activator is utilized as the activator in the catalyst composition. Alumoxanes are generally oligomeric compounds containing -Al (R ¹ ) -O-subunit (R ¹ is an alkyl group). Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Particularly when the abstractable ligand is an alkyl, halide, alkoxide, or amide, alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators. Mixtures of different alumoxanes and modified alumoxanes can also be used. It may be preferred to use visually clear methylalumoxane. The cloudy or gelled alumoxane can be filtered to produce a clear solution or the clear alumoxane can be decanted from the cloudy solution. Another alumoxane is modified methylalumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, protected by US Pat. No. 5,041,584).

When the activator is alumoxane (modified or unmodified), some embodiments select the maximum amount of activator with a 5000-fold molar excess of Al / M over the catalyst precursor (per metal catalyst site). . The minimum activator to catalyst precursor is in a 1: 1 molar ratio. Alternative preferred ranges include up to 500: 1, alternatively up to 200: 1, alternatively up to 100: 1, alternatively from 1: 1 to 50: 1. In a preferred embodiment, little or no alumoxane is used in the process of making the VT-HO polymer. Preferably, the alumoxane is present at zero mol%, or the alumoxane is in a molar ratio of aluminum to transition metal of less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1: 1. Exists. In an alternative embodiment, when producing a VTM using alumoxane, the alumoxane was treated to remove free alkylaluminum compounds, particularly trimethylaluminum. Furthermore, in a preferred embodiment, the activator used here to produce the VT-HO polymer is separate.
Examples of aluminum alkyl or organoaluminum compounds that can be used as a coactivator (or scavenger) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.
In a preferred embodiment, little or no scavenger is used in the process for producing the VT-HO polymer. Preferably, the scavenger is present at zero mol%, or the scavenger is less than 100: 1, preferably less than 50: 1, preferably less than 15: 1, preferably less than 10: 1. Present in a molar ratio of

Ionization activators Ionization or stoichiometric activators (neutral or ionic) such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, trisperfluorophenylboron metalloid precursors, or trisperfluoronaphthyl It is within the scope of the present invention to use boron metalloid precursors, polyhalogenated heteroborane anions (WO 98/43983), boric acid (US Pat. No. 5,942,459), or combinations thereof. It is also within the scope of the present invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators. A highly preferred activator is an ionic activator rather than neutral borane.
Examples of neutral stoichiometric activators include trisubstituted boron, tellurium, aluminum, gallium and indium or combinations thereof. Each of the three substituents is independently selected from alkyl, alkenyl, halogen, substituted alkyl, aryl, aryl halide, alkoxy, and halide. Preferably, the three groups are independently selected from halogen, monocyclic or polycyclic (including halo-substituted) aryl, alkyl, and alkenyl compounds, and mixtures thereof, and have 1 to 20 carbons. An alkenyl group having an atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 3 to 20 carbon atoms (including substituted aryl) preferable. More preferably, the three groups are alkyl having 1 to 4 carbon atoms, phenyl, naphthyl, or a mixture thereof. Even more preferably, the three groups are halogenated, preferably fluorinated aryl groups. Most preferably, the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoronaphthyl boron.
An ionic stoichiometric activator compound is associated with an active proton or the rest of the ions of the ionized compound but is not coordinated or is only loosely coordinated. Can contain cations. Such compounds are described in European publications EP 0 570 982 A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B1; EP 0 277 003 A; EP 0 277 004 A; US Pat. No. 5,153,157; No. 5,198,401; No. 5,066,741; No. 5,206,197; No. 5,241,025; No. 5,384,299; No. 5,502,124; and US patent application Ser. All of these documents are hereby fully incorporated by reference.

An ionic catalyst can react a transition metal compound with some neutral Lewis acid such as B (C ₆ F ₆ ) _{3 in the} ready state, which is a hydrolyzable ligand of the transition metal compound ( Reaction with X) forms an anion such as ([B (C ₆ F ₅ ) ₃ (X)] ⁻ ), which stabilizes the cationic transition metal species produced by this reaction. The catalyst can be prepared using an activator component that is an ionic compound or composition, and is preferably prepared in this way.
Compounds useful as activator components in the preparation of the ionic catalyst system used in the process of the present invention preferably include a cation, which is a Bronsted acid capable of donating protons, and an active catalyst species (Group 4) that results when the two compounds are combined. A relatively large (bulky) compatible non-coordinating anion that can stabilize the cation), said anion being an olefinic, diolefinic and acetylenically unsaturated substrate or other neutral Lewis base, such as an ether , Sufficiently unstable to be replaced by amines or the like. EP 0 277,003 A and EP 0 277,004 A published in 1988 disclose two classes of compatible non-coordinating anions: 1) covalently coordinated to a central charged metal or metalloid core An anionic coordination complex comprising a plurality of lipophilic groups shielding the core, and 2) anions comprising a plurality of boron atoms, such as carborane, metallacarborane and borane.

In a preferred embodiment, the stoichiometric activator comprises a cation component and an anion component and can be represented by the following formula:
(LH) _d ⁺ (A ^d- ) (14)
Where L is a neutral Lewis base; H is hydrogen; (LH) ⁺ is a Bronsted acid; A ^d− is a non-coordinating anion having a charge d−; 2 or 3.
The cationic component (LH) _d ⁺ includes protonated Lewis bases that can protonate alkyl or aryl moieties derived from bulky ligand metallocene-containing transition metal catalyst precursors to yield cationic transition metal species, etc. Examples include Bronsted acid.
The activated cation (LH) _d ⁺ may be a Bronsted acid that can donate a proton to the transition metal catalyst precursor to give a transition metal cation, and is preferably ammonium, oxonium, phosphonium, silylium, and mixtures thereof. Is methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N , N-dimethylaniline ammonium; phosphonium derived from triethylphosphine, triphenylphosphine, and diphenylphosphine; oxonium derived from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane; diethylthio And sulfoniums derived from thioethers such as ether and tetrahydrothiophene; and mixtures thereof.
The anion component A ^d- is a compound of the formula [M ^{k +} Q _n ] ^d- (wherein k is 1, 2, or 3; n is an integer of 2, 3, 4, 5, or 6; nk = d; M is an element selected from group 13 of the periodic table of elements, preferably boron or aluminum, and Q is independently hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, Halocarbyl, substituted halocarbyl, and halo-substituted hydrocarbyl groups, wherein said Q has up to 20 carbon atoms (provided that in the maximum of one occurrence, Q is a halide), preferably each Q is 1 to a fluorinated hydrocarbyl group having 20 carbon atoms, more preferably from each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group. preferred a example of ^d-, US Patent No. 5,447, There are also diboron compounds, as disclosed in No. 895, which is hereby fully incorporated by reference.

Non-limiting and illustrative examples of boron compounds that can be used as activated cocatalysts in the preparation of the catalyst system of the process of the present invention include trisubstituted ammonium salts such as:
Trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri (t-butyl) ammonium tetraphenylborate, N, N- Dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetraphenylborate, tropylium tetraphenylborate, tri Phenylcarbenium tetraphenylborate, triphenylphosphonium tetraphenylborate, triethylsilylium tetraphenylborate, benzene (diazonium) tetraphenylborate, trimethylammonium tetrakis (pentafluorophen ) Borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (penta Fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl- (2,4,6-trimethylanily (Nium) tetrakis (pentafluorophenyl) borate, tropylium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluoro Rophenyl) borate, triethylsilylium tetrakis (pentafluorophenyl) borate, benzene (diazonium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis- (2,3,4 , 6-tetrafluoro-phenyl) borate, dimethyl (t-butyl) ammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis- (2,3,4, 6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, N, N-di Til- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate, tropylium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, tri Phenylcarbenium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, triphenylphosphonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, triethylsilylium tetrakis- (2,3, 4,6-tetrafluorophenyl) borate, benzene (diazonium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate, trimethylammonium tetrakis (perfluoronaphthyl) borate, triethylammonium tetrakis (perfluoronaphthyl) borate, tri Propyl ammonium tetrakis (perfluoronaphthyl) borate, tri (n-butyl) ammonium tetrakis (perfluoro (Ronaphthyl) borate, tri (t-butyl) ammonium tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate, N, N- Dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluoronaphthyl) borate, tropyliumtetrakis (perfluoronaphthyl) borate, triphenylcarbeniumtetrakis (perfluoronaphthyl) borate, triphenylphosphoniumtetrakis (perfluoronaphthyl) borate, Triethylsilyl tetrakis (perfluoronaphthyl) borate, benzene (diazonium) tetrakis (perfluoronaphthyl) borate, trimethylammonium tetrakis (perfluorobiphenyl) borate , Triethylammonium tetrakis (perfluorobiphenyl) borate, tripropylammonium tetrakis (perfluorobiphenyl) borate, tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate, tri (t-butyl) ammonium tetrakis (perfluorobiphenyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate, Tropylium tetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylphosphonium tetrakis (perfluorobiphenyl) , Triethylsilylium tetrakis (perfluorobiphenyl) borate, benzene (diazonium) tetrakis (perfluorobiphenyl) borate, trimethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triethylammonium tetrakis (3,5-bis (Trifluoromethyl) phenyl) borate, tripropylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate , Tri (t-butyl) ammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, N, N -Diethylanilinium tetrakis (3,5-bis (trifluoromethyl) ) Phenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, tropylium tetrakis (3,5-bis (trifluoro) Methyl) phenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylphosphonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triethylsilylium tetrakis ( 3,5-bis (trifluoromethyl) phenyl) borate, benzene (diazonium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, and dialkylammonium salts such as: di- (i-propyl) ammonium tetrakis (Pentafluorophenyl) borate and dicyclohexylammonium tetrakis (pentafluorophenyl) borate Over preparative; and further trisubstituted phosphonium salts, such as tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like.

Most preferably, the ionic stoichiometric activator (LH) _d ⁺ (A ^d- ) is N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl). ) Borate, N, N-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenyl Carbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate or triphenylcarbenium tetrakis (perfluorophenyl) borate.
In one embodiment, an activation method is also contemplated that utilizes ionization of ionic compounds that are free of active protons, but that can give rise to bulky ligand metallocene-catalyzed cations and their non-coordinating anions. Are described in EP 0 426 637 A, EP 0 573 403 A, and US Pat. No. 5,387,568, all incorporated herein by reference.
The term “non-coordinating anion” (NCA) is an anion that does not coordinate to the cation or only weakly to the cation, thereby remaining sufficiently unstable to be replaced by a neutral Lewis base. Means. A “compatible” non-coordinating anion is an anion that does not degrade and become neutral when the originally formed complex degrades. In addition, the anion will not transfer an anionic substituent or fragment to the cation so that the cation forms a neutral tetracoordinate metallocene compound and a neutral by-product from the anion. Non-coordinating anions useful according to the present invention are said to remain sufficiently unstable to equilibrate their ionic charge at +1 and still allow substitution with ethylenically or acetylenically unsaturated monomers during polymerization. The compatible anion which stabilizes the metallocene cation in the sense. In addition to these activator compounds or cocatalysts, scavengers such as tri-isobutyl aluminum or tri-octyl aluminum are used.

The inventive method utilizes a cocatalyst compound or activator compound that is initially a neutral Lewis acid but forms a cationic metal complex and a non-coordinating anion, or zwitterionic complex when reacted with the inventive compound. You can also. For example, tris (pentafluorophenyl) boron or aluminum acts to abstract the hydrocarbyl or hydride ligand to form the inventive cationic metal complex, stabilizing the non-coordinating anion. See EP 0 427 697 A and EP 0 520 732 A for a description of similar Group 4 metallocene compounds. See also the methods and compounds of EP 0 495 375 A. See US Pat. Nos. 5,624,878; 5,486,632; and 5,527,929 for the formation of zwitterionic complexes using similar Group 4 compounds.
Another suitable ion forming, activating cocatalyst comprises a cationic oxidant represented by the following formula and a compatible non-coordinating anion.
(OX ^{e +} ) _d (A ^d- ) _e (16)
Where OX ^{e +} is a cationic oxidant with a charge of e +; e is 1, 2, or 3; A ^d− is a non-coordinating anion with a charge d−; , 2 or 3.
Examples of cationic oxidants include: ferrocenium, hydrocarbyl substituted ferrocenium, Ag ⁺ , or Pb ²⁺ . A preferred embodiment of A ^d- is the anion described above for Bronsted acids including activators, particularly tetrakis (pentafluorophenyl) borate.
A typical NCA (or any non-alumoxane activator) activator to catalyst ratio is a 1: 1 molar ratio. Alternative preferred ranges include 0.1: 1 to 100: 1, alternatively 0.5: 1 to 200: 1, alternatively 1: 1 to 500: 1, alternatively 1: 1 to 1000: 1. A particularly useful range is 0.5: 1 to 10: 1, preferably 1: 1 to 5: 1.

Bulky activator In the present specification, “bulk activator” means an anionic activator represented by the following formula.

Where
Each R ₁ is independently a halide, preferably fluoride;
Each R ₂ is independently a halide, a C ₆ -C ₂₀ substituted aromatic hydrocarbyl group or a formula —O—Si—R _{a where} R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl group. A siloxy group (preferably R ₂ is a fluoride or perfluorinated phenyl group);
Each R ³ is a halide, a C ₆ -C ₂₀ substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—R _{a where} R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl group (Preferably R ₃ is a fluoride or a C ₆ perfluorinated aromatic hydrocarbyl group);
Where R ² and R ³ can form one or more saturated or unsaturated substituted or unsubstituted rings (preferably R ² and R ³ form a perfluorinated phenyl ring);
L is a neutral Lewis base; (LH) ⁺ is a Bronsted acid; d is 1, 2, or 3;
Wherein the anion has a molecular weight greater than 1020 g / mol; and
At least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic cubic, or greater than 300 cubic cubic, or greater than 500 cubic cubic.
The term “molecular volume” is used herein as an approximation of the spatial steric bulk of the activator molecule in solution. Comparing substituents of different molecular volumes, smaller molecular volume substituents can be considered “not bulky” compared to larger molecular volume substituents. Conversely, larger molecular volume substituents can be considered “bulky” than smaller molecular volume substituents.
Molecular volume is reported in “A Simple“ Back of the Envelope ”Method for Estimating the Densities and Molecular Volumes of Liquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11, November 1994, pp. 962-964. It can be calculated. The molecular volume (MV) in cubic cubic units is calculated using the formula: MV = 8.3 V _s . V _s is a 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 in the table below. For fused rings, V _s decreases by 7.5% for each fused ring.

  The typical bulky substituents of suitable activators here and their respective scaled and molecular volumes are shown in the table below. The broken-line bond indicates a bond to boron as in the above general formula.

Typical bulky activators useful in the catalyst systems herein include the following:
Trimethylammonium tetrakis (perfluoronaphthyl) borate, triethylammonium tetrakis (perfluoronaphthyl) borate, tripropylammonium tetrakis (perfluoronaphthyl) borate, tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate, tri (t-butyl) ammonium tetrakis (Perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium ) Tetrakis (perfluoronaphthyl) borate, tropylium tetrakis (perfluoronaphthyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylphos Honium tetrakis (perfluoronaphthyl) borate, triethylsilyl tetrakis (perfluoronaphthyl) borate, benzene (diazonium) tetrakis (perfluoronaphthyl) borate, trimethylammonium tetrakis (perfluorobiphenyl) borate, triethylammonium tetrakis (perfluorobiphenyl) borate, tripropyl Ammonium tetrakis (perfluorobiphenyl) borate, tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate, tri (t-butyl) ammonium tetrakis (perfluorobiphenyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl- (2,4,6-trimethyl Nilinium) tetrakis (perfluorobiphenyl) borate, tropylium tetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylphosphonium tetrakis (perfluorobiphenyl) borate, triethylsilylium tetrakis (perfluorobiphenyl) borate, benzene (Diazonium) tetrakis (perfluorobiphenyl) borate, [4-t-butyl-PhNMe ₂ H] [(C ₆ F ₃ (C ₆ F ₅ ) ₂ ) ₄ B] (Ph is phenyl, Me is methyl ), And the type disclosed in US Pat. No. 7,297,653.

Combinations of activators It is within the scope of the present invention to combine the catalyst compound with one or more activators or activation methods described above. For example, combinations of activators are described in US Pat. Nos. 5,153,157; 5,453,410; European publication EP 0 573 120 B1; PCT publication WO 94/07928; and WO 95/14044. These documents all discuss the use of alumoxanes in combination with ionization activators.
(iii) Optional coactivators and scavengers In addition to these activator compounds, scavengers or coactivators may be used. Aluminum alkyl or organoaluminum compounds that can be used as coactivators (or scavengers) include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum. .
(iv) Optional Support Material In the embodiments herein, the catalyst system may include an inert support material. Preferably the support material is a porous support material such as talc and inorganic oxides. Other carrier materials include zeolites, clays, organoclays, or any other organic or inorganic carrier material, or mixtures thereof.
Preferably, the support material is a finely divided inorganic oxide. Inorganic oxide materials suitable for use in the metallocene catalyst systems herein include Group 2, 4, 13 and 14 metal oxides such as silica, alumina and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina are magnesia, titania, zirconia and the like. However, other suitable carrier materials can be utilized, such as micronized functionalized polyolefins such as micronized polyethylene. Particularly useful carriers include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolite, talc, clay and the like. Also, combinations of these carrier materials, such as silica-chromium, silica-alumina, silica-titania, etc. can be used. Preferred support materials include Al ₂ O ₃ , ZrO ₂ , SiO ₂ , and combinations thereof, more preferably SiO ₂ , Al ₂ O ₃ , or SiO ₂ / Al ₂ O ₃ .
The support material, most preferably an inorganic oxide, has a surface area in the range of about 10 to about 700 m ² / g, a pore volume in the range of about 0.1 to about 4.0 cc / g, and an average particle size in the range of about 5 to about 500 μm. It is preferable to have. More preferably, the support material has a surface area in the range of about 50 to about 500 m ² / g, a pore volume of about 0.5 to about 3.5 cc / g and an average particle size of about 10 to about 200 μm. Most preferably, the support material has a surface area in the range of about 100 to about 400 m ² / g, a pore volume of about 0.8 to about 3.0 cc / g, and an average particle size of about 5 to about 100 μm. The average pore size of the support materials useful in the present invention is in the range of 10 to 1000 mm, preferably 50 to about 500 mm, most preferably 75 to about 350 mm. In some embodiments, the support material is high surface area amorphous silica (surface area = 300 m ² / gm; 1.65 cm ³ / gm pore volume), for example by Davison Chemical Division of WR Grace and Company Examples include materials marketed under the trade name 952 or Davison 955. In other embodiments, DAVIDSON 948 is used.
The carrier material must be dry, i.e. free of absorbed water. Drying of the support material can be accomplished by heating or calcining at about 100 ° C to about 1000 ° C, preferably at least about 600 ° C. When the support material is silica, it is at least 200 ° C., preferably about 200 ° C. to about 850 ° C., most preferably about 600 ° C .; about 1 minute to about 100 hours, about 12 hours to about 72 hours, or about 24 Heat for about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups to create the catalyst system of the present invention. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one metallocene compound and an activator.

Method for Making a Supported Catalyst System A support material having reactive surface groups, typically hydroxyl groups, is slurried with a nonpolar solvent and the resulting slurry is contacted with a solution of a metallocene compound and an activator. A slurry of the support material in the solvent is prepared by introducing the support material into the solvent and heating the mixture to about 0 ° C to about 70 ° C, preferably to about 25 ° C to about 60 ° C, preferably at room temperature. Is done. Contact times typically range from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.
Suitable non-polar solvents are materials in which all reactants used herein, i.e. activators, and metallocene compounds are at least partially soluble and liquid at the reaction temperature. Preferred nonpolar solvents are alkanes such as isopentane, hexane, n-heptane, octane, nonane, and decane, but various other materials such as cycloalkanes such as cyclohexane, aromatic compounds such as benzene, toluene, and ethylbenzene May be used.
In embodiments herein, the support material is contacted with a solution of the metallocene compound and the activator so that reactive groups on the support material are titrated to form a supported polymerization catalyst. The contact time of the metallocene compound, the activator, and the support material is the time required to titrate the reactive groups on the support material. “Titration” means to react with available reactive groups on the surface of the support material, thereby reducing surface hydroxyl groups by at least 80%, at least 90%, at least 95%, or at least 98%. The concentration of reactive groups on the surface can be determined based on the calcination temperature and the type of support material used. The calcination temperature of the support material affects the number of surface reactive groups on the support material that are available for reaction with the metallocene compound and the activator; the higher the drying temperature, the fewer the number of sites. For example, if the support material is silica, before it is used in the initial catalyst system synthesis step, it is dehydrated by fluidizing it with nitrogen and heating at about 600 ° C. for about 16 hours, typically 1 A surface hydroxyl group concentration (mmols / gm) of about 0.7 mmol per gram is achieved. Thus, the exact molar ratio of activator to surface reactive groups on the support will vary. It is preferable to determine this on a case-by-case basis and ensure that a limited amount of activator is added to the solution so that it is deposited on the support material without leaving an excess of activator in the solution. .
The amount of active agent to be deposited on a support material without excessively left in solution is determinable by any of the conventional methods, for example, stirring a slurry of the carrier in the solvent, activator ¹ H It can be determined by adding activator to the slurry until it is detected as a solution in a solvent by any method known in the art such as NMR. For example, in a silica support material heated at about 600 ° C., the amount of activator added to the slurry is such that the molar ratio of B to hydroxyl groups (OH) on silica is about 0.5: 1 to about 4: 1, preferably Is about 0.8: 1 to about 3: 1, more preferably about 0.9: 1 to about 2: 1, most preferably about 1: 1. The amount of B on silica was determined by JW Olesik, “Inductively Coupled Plasma-Optical Emission Spectroscopy,” in the Encyclopedia of Materials Characterization, CR Brundle, CA Evans, Jr. and S. Wilson, eds., Butterworth-Heinemann, Boston, It can be determined using ICPES (Inductively Coupled Plasma Atomic Emission Analysis) described in Mass., 1992, pp. 633-644. In another embodiment, an excess of activator in an amount of activator that will be deposited on the carrier is added and then any excess activator is removed, for example, by filtration and washing. You can also

In another embodiment, the present invention relates to:
1. at least 200 g / mol (preferably 200-100,000 g / mol, preferably 200-75,000 g / mol, preferably 200-60,000 g / mol, preferably 300-60,000 g / mol, preferably 750-30,000 g / mol mol) Mn (measured by ¹ H NMR), a higher olefin polymer having the following:
(i) 1 or more (preferably two or more, three or more, four or more, etc.) C ₄ -C ₄₀ (preferably _{C 4 ~C 30, C 4 ~C} 20 , or C ₄ -C _12, Preferably butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene , Substituted derivatives thereof, and isomers thereof) containing higher olefin derived units;
Wherein the vinyl terminated higher olefin polymer is substantially free of propylene derived units (preferably 0.1 wt% propylene, preferably 0 wt%);
The higher olefin polymer is at least 5% (at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%; at least 80%, at least 90%, or at least 95% or 100 mol%) of allyl chain ends (relative to total unsaturation);
Optionally, 1: 1 or more (preferably greater than 2: 1, greater than 2.5: 1, greater than 3: 1, greater than 5: 1 or greater than 10: 1) allyl chain end to vinylidene chain end ratio. May include;
Still further optionally, preferably substantially free of isobutyl chain ends (preferably less than 0.1 wt% isobutyl chain ends); and still more optionally, these higher olefin vinyl terminated polymers are at least 5 mol% (preferably Higher olefin polymer, which may comprise at least 15 mol%, at least 25 mol%, at least 35 mol%, at least 45 mol%, at least 60 mol%, at least 75 mol% ethylene, at least 90 mol%) ethylene-derived units.
2. Higher olefin vinyl-terminated polymer measured by ¹ H NMR assuming one unsaturation per chain, based on the weight of the polymer composition, at least 50 wt%, at least 36 carbon atoms. A higher olefin vinyl-terminated polymer of paragraph 1 comprising an olefin having.

3. Higher olefin vinyl-terminated polymers, as measured by GC, are less than 20 wt%, preferably less than 10 wt%, preferably less than 5 wt%, more preferably less than 2 wt% of dimers and trimers based on the weight of the copolymer composition A higher olefin vinyl-terminated polymer according to paragraphs 1 and 2, comprising
4. The higher olefin of paragraphs 1-3, wherein the higher olefin copolymer has a viscosity at 60 ° C. of greater than 1000 cP, greater than 12,000 cP, or greater than 100,000 cP (or less than 200,000 cP, less than 150,000 cP, or less than 100,000 cP). Vinyl terminated polymer.
5. A vinyl-terminated higher olefin polymer having at least 200 g / mol of Mn (measured by ¹ H NMR) and containing at least 50 mol% of one or more C ₅ -C ₄₀ higher olefin-derived units, A vinyl terminated higher olefin polymer, wherein the higher olefin polymer is substantially free of ethylene, propylene or butene derived units; and the higher olefin polymer has at least 5% (based on total unsaturation) allyl chain ends.
6. The vinyl terminated higher olefin polymer of paragraph 5, further having an allyl chain end to vinylidene chain end ratio of 1: 1 or greater and / or substantially free of isobutyl chain ends.
7. The vinyl-terminated higher olefin polymer of paragraph 5 or 6, wherein the polymer is a homopolymer (eg, homopolypentene, homopolyhexene, homopolyoctene, homopolydecene, homopolydodecene, etc.).
8. The vinyl terminated higher of paragraph 5 or 6, wherein the polymer is a copolymer consisting essentially of C _{5 to} C ₄₀ olefins (eg, hexene and octene copolymers, octene and decene copolymers, octene, decene and dodecene copolymers, etc.) Olefin polymer.
9. The polymer is at least 5 mol% (preferably at least 10 mol%, at least 15 mol%, at least 20 mol%, at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70 mol%; at least 80 mol%, at least 90 mol%, or comprising at least C ₅ -C ₄₀ olefins (e.g. pentene 95 mol%), hexene, octene or decene), the remainder consists of different C ₅ -C ₄₀ olefins, vinyl terminated paragraphs 5, 6, or 8 Higher olefin polymer.

10. A process for producing a higher olefin vinyl-terminated polymer according to paragraphs 1-9, comprising:
(i) 1 or more (preferably two or more, three or more, four or more, etc.) C ₄ -C ₄₀ (preferably _{C 4 ~C 30, C 4 ~C} 20 , or C ₄ -C _12, Preferably butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene , Substituted derivatives thereof, and isomers thereof) monomers;
(ii) substantially non-propylene (preferably less than 0.1 wt% propylene) monomer;
(iii) optionally contacting at least 5 mol% (preferably at least 15 mol%, at least 25 mol%, at least 35 mol%, at least 45 mol%, at least 60 mol%, at least 75 mol%, or at least 90 mol%) ethylene monomer. A method;
The contacting step comprises an activator and the following formula:
(i)

式I；

Formula I;

式II； Or (ii)

Formula II;

式III； Or (iii)

Formula III;

式IV； Or (iv)

Formula IV;

(Where
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, and combinations thereof (2 Two Xs may form part of a fused ring or ring system);
Each Q is independently a carbon or heteroatom;
Each R ¹ is independently a C ₁ -C ₈ alkyl group, and R ¹ may be the same as or different from R ² ;
Each R ² is independently a C ₁ -C ₈ alkyl group;
Each R ³ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group having 1 to 8 carbon atoms, provided that at least three R ³ groups are not hydrogen;
Each R ⁴ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, heteroatom or heteroatom-containing group;
R ⁵ is hydrogen or a C ₁ -C ₈ alkyl group;
R ⁶ is hydrogen or a C ₁ -C ₈ alkyl group;
Each R ⁷ is independently hydrogen, or a C ₁ -C ₈ alkyl group, provided that at least seven R ⁷ groups are not hydrogen;
T is a bridging group;
Each R ^a is independently hydrogen, halogen, or C ₁ -C ₂₀ hydrocarbyl;
Two R ^a can form ^a cyclic structure (including aromatic, partially saturated, or saturated cyclic or fused ring systems); and any two adjacent R groups can also be fused or multi-centered fused A ring system, provided that the ring may form an aromatic, which may be partially saturated or saturated);
Or (v)

式V

Formula V

(Where
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof (2 Two Xs may form part of a fused ring or ring system);
Each R ⁸ is independently a C ₁ -C ₁₀ alkyl group;
Each R ⁹ is independently a C ₁ -C ₁₀ alkyl group;
Each R ¹⁰ is hydrogen;
Each R ¹¹ , R ¹² and R ¹³ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, heteroatom or heteroatom-containing group;
T is a bridging group;
Further, provided that any adjacent R ¹¹ , R ¹² , and R ¹³ groups may form a condensed ring or a multi-centered condensed ring system (the ring may be aromatic, partially saturated or saturated). Do);
Or (vi)

式VI

Formula VI

(Where
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or combinations thereof;
Each R ¹⁵ and R ¹⁷ is independently a C ₁ -C ₈ alkyl group;
Each R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ are independently hydrogen or 1-8 A substituted or unsubstituted hydrocarbyl group having carbon atoms)
Occurring in the presence of a catalyst system comprising at least one metallocene compound represented by one of:
C ₄ -C ₄₀ higher olefins, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7- Selected from oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof,
Method.
11. The activator has the following formula:

(Where
Each R ₁ is independently a halide, preferably fluoride;
Each R ₂ is independently a halide, a C ₆ -C ₂₀ substituted aromatic hydrocarbyl group or a formula —O—Si—R _{a where} R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl group. A siloxy group, preferably a fluoride or a C ₆ perfluorinated aromatic hydrocarbyl group;
Each R ³ is a halide, a C ₆ -C ₂₀ substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—R _{a where} R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbylsilyl group, preferably Is a fluoride or C ₆ perfluorinated aromatic hydrocarbyl group;
Where L is a neutral Lewis base;
H is hydrogen;
(LH) ⁺ is a Bronsted acid;
d is 1;
Wherein the anion has a molecular weight greater than 1020 g / mol; and
(At least three of the substituents on the B atom each have a molecular volume greater than 250 cubic cubic, or larger than 300 cubic cubic, or larger than 500 cubic cubic)
The method of paragraph 10, which is a bulky activator represented by:

12. Bulky activators are:
Trimethylammonium tetrakis (perfluoronaphthyl) borate, triethylammonium tetrakis (perfluoronaphthyl) borate, tripropylammonium tetrakis (perfluoronaphthyl) borate, tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate, tri (t-butyl) ammonium tetrakis (Perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium ) Tetrakis (perfluoronaphthyl) borate, tropylium tetrakis (perfluoronaphthyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylphos Honium tetrakis (perfluoronaphthyl) borate, triethylsilyl tetrakis (perfluoronaphthyl) borate, benzene (diazonium) tetrakis (perfluoronaphthyl) borate, trimethylammonium tetrakis (perfluorobiphenyl) borate, triethylammonium tetrakis (perfluorobiphenyl) borate, tripropyl Ammonium tetrakis (perfluorobiphenyl) borate, tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate, tri (t-butyl) ammonium tetrakis (perfluorobiphenyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl- (2,4,6-trimethyl Nilinium) tetrakis (perfluorobiphenyl) borate, tropylium tetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylphosphonium tetrakis (perfluorobiphenyl) borate, triethylsilylium tetrakis (perfluorobiphenyl) borate, benzene (Diazonium) tetrakis (perfluorobiphenyl) borate, [4-t-butyl-PhNMe ₂ H] [(C ₆ F ₃ (C ₆ F ₅ ) ₂ ) ₄ B] (Ph is phenyl, Me is methyl )
The method of paragraphs 10-11, wherein the method is at least one of:
13. A composition comprising a higher olefin copolymer of paragraphs 1-9 or a higher olefin copolymer prepared by the process of paragraphs 10-12, preferably a lubricant blend.
14. Use of the composition of paragraph 13 as a lubricant.

Product characterization
^The product was characterized by ¹ H NMR and ¹³ C NMR as follows.
¹³ C NMR
¹³ C NMR data was collected at a frequency of at least 100 MHz at 120 ° C. using a Bruker 400 MHz NMR spectrometer. Acquisition time adjusted to give digital resolution of 0.1-0.12Hz, 90 degree pulse utilized throughout pulse acquisition delay time of at least 10 seconds with continuous broadband proton decoupling using swept square wave modulation without gating did. Spectra were acquired by time averaging to provide sufficient signal-to-noise levels to measure the signal of interest. The sample was dissolved in tetrachloroethane-d ₂ at a concentration of 10-15 wt% and then inserted into the spectrometer magnet.
Prior to data analysis, the spectrum was normalized by setting the chemical shift of the TCE solvent signal to 74.39 ppm.
The chain ends were identified for quantization using the signals shown in the table below. N-butyl and n-propyl were not reported due to their low abundance (less than 5%) relative to the chain ends shown in the table below.

¹ H NMR
¹ H NMR data was collected using a Varian spectrometer at room temperature or 120 ° C. (120 ° C. shall be used for the purposes of the claims) with a 5 mm probe at ¹ H frequency of at least 250 MHz. Data was recorded using a maximum pulse width of 45 ° C., 8 seconds between pulses, and a signal summation average of 120 transients. The number of unsaturated types per 1000 carbons was calculated by integrating the spectral signal, multiplying the different groups by 1000, and dividing the result by the total number of carbons. Mn was calculated by dividing the total number of unsaturated species into 14,000. It has units of g / mol.
The olefin type chemical shift region is defined to be between the following spectral regions.

viscosity
Viscosity was measured using a Brookfield digital viscometer.
EXAMPLES All experiments were conducted under air and moisture free conditions using a nitrogen filled glove box and a Schlenk line. Toluene, 1-decene, and 1-hexene were purchased from Sigma Aldrich (Milwaukee, Wis.) And dried over alumina beads previously calcined at 300 ° C. Dimethylanilinium tetrakis (perfluoronaphthyl) borate was purchased from Albemarle (Baton Rouge, LA) and used as received. 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydro-2-ylidene [2- (i-propoxy) -5- (N, N-dimethyl-aminosulfonyl) phenyl] methylene ruthenium (II) Dichloride was purchased from Strem Chemicals (Newburyport, MA) and used as received.
The scavenger and cocatalyst triisobutylaluminum (TIBAL) were obtained from Akzo Chemicals, Inc. (Chicago, IL) and used without further purification. Tri-n-octylaluminum (TNOAL) was obtained from Akzo Chemicals, Inc. and used without further purification.
Metallocene used in Examples The following metallocenes A to C were synthesized. In the synthesis of air sensitive compounds, including the use of dried glassware (90 ° C., 4 hours) and anhydrous solvents purchased from Sigma Aldrich (St. Louis, MO) (further dried on 3A sieves) The typical dry box procedure was followed.
Synthesis of metallocene E and metallocene F:
Metallocenes E and F were synthesized as shown below.

Synthesis of Compound 1a + 1b: Compound A (2-methylindene, 10 g, 76.9 mmol) was dissolved in diethyl ether (150 mLs) and deprotonated with nBuLi (10 M, hexane, 77 mmol). After 4 hours, propyl bromide (CH ₃ CH ₂ CH ₂ Br, 18 g, 146 mmol) was added to the reaction mixture, tetrahydrofuran (THF, 50 mLs) was added, and the reaction was further stirred at room temperature for 12 hours. The reaction was quenched with water and the organic layer was dried over anhydrous magnesium sulfate (MgSO ₄ ). Volatiles were removed to give an isomeric mixture of 1a and 1b as a yellow oil (10.5 g, 83% yield). ¹ H NMR (C ₆ D ₆ , 500 MHz) δ ppm; Compound 1a: 6.22 (s), 3.05 (m), 1.79 (s) 0.75 (t). Compound 1b: 2.91 (s), 2.36 (t, 1.79 (s), 0.85 (t).
Synthesis of Compound 2: A mixture of 1a and 1b was dissolved in hexane (200 mL) and deprotonated with n-butyllithium (nBuLi, 6.1 mL of a 10M solution in hexane, 61 mmol). After 12 hours at room temperature, the solid was collected on a glass frit, washed with additional hexane (2 × 50 mLs) and dried in vacuo to give compound 2 as a white solid (10.8 g, quantitative yield). ¹ H NMR (THF-d8, 500 MHz) δ ppm; Compound 2: 7.09 (m, C ₆ H ₄ ring), 6.30 (m, C ₆ H ₄ ring), 5.47 (s, C ₅ H ring), 2.70 (t , C ₅ -CH _2- ), 2.17 (s, C ₅ -Me), 1.50 (m, C ₅ -CH ₂ -CH _2- ), 0.89 (t, -C ₂ H ₄ -Me).
Synthesis of Compound 4 + 1b: All lithiated ligand compound 2 was dissolved in THF (100 mL) and reacted with dichlorodimethylsilane (Me ₂ SiCl ₂ , 3.8 g, 29 mmol) at room temperature for 10 hours. ¹ H NMR showed formation of 4 and 1b. Compound 4 was purified by column chromatography (75% hexane / 25% ethyl acetate v / v) on silica gel (200-400 mesh).
Synthesis of Compound 5: A hexane extract containing Compound 4 was reacted with nBuLi (5 g, 10M in hexane) to obtain a solid. The white solid product 5 was filtered on a glass frit, washed with hexane (2 × 30 mLs) and dried in vacuo (9.1 g; 84% based on 1a, 1b). Compound 5: ¹ H NMR (THF-d8, 250 MHz) δppm; 7.57 (m), 7.12 (m), 6.30 (m), 3.55 (t), 2.70 (t), 2.34 (s), 1.46 (m) , 0.85 (t), 0.59 (s).
Synthesis of metallocene E The synthesis of metallocene E is shown below.

Synthesis of Compound 6: Compound 5 (6.6 g, 16.0 mmol) was slurried with diethyl ether (100 mLs) and reacted with hafnium tetrachloride (HfCl ₄ , 4.2 g, 13.1 mmol). After 1 hour, about 50 mLs of diethyl ether was removed and compound 6 (dimethylsilylbis (2-methyl, 3-propylindenyl) hafnium dichloride) was collected on a glass frit as a bright yellow solid (4.2 g, 49.5 %).
Synthesis of metallocene E: Compound 6 was slurried with diethyl ether (50 mL) and toluene (80 mL) and reacted with methylmagnesium iodide (MeMgI, 5.6 g, 3M in diethyl ether) at room temperature for 16 hours. Dimethoxyethane (DME, 6 g) was added to the crude reaction mixture, the mixture was filtered through a medium glass frit and the filtrate was collected. The filtrate volume was reduced, pentane was added (30 mL) and the filtrate was cooled to -35 ° C. Compound 7 (rac-dimethylsilyl bis (2-methyl, 3-propylindenyl) hafnium dimethyl) is converted into crystalline first crop (pure rac-7, 0.6 g, 16%) and second crop (5% meso -7 and 95% rac-7, 0.7 g, 19%). Compound 7: ¹ H NMR (CD ₂ Cl ₂ , 500 MHz) δppm; 7.4 (d), 7.3 (d), 7.08 (t), 6.75 (t), 2.68 to 2.22 (complex m), 1.87 (s), 1.41 (m), 0.97 (s), 0.81 (t), -1.95 (s).

In the formula, Me is methyl.
Synthesis of Compound 9: Compound 5 (8.2 g, 19.9 mmol) was slurried with diethyl ether (150 mLs) and reacted with ZrCl ₄ (4.2 g, 17.9 mmol) at room temperature. After 4 hours, the orange solid was collected on a medium frit and washed with more diethyl ether (2 × 30 mLs). The product was dried in vacuo to give pure rac-9 (3.8 g, 38%). ¹ H NMR (CD ₂ Cl ₂ , 500 MHz) δppm; 7.63 (d), 7.41 (d), 7.3 (m), 6.96 (m), 2.57 (m d), 2.04 (s), 1.42 (m) , 1.31 (s), 0.88 (t).
Synthesis of metallocene F: Compound 9 (1.12 g, 2.0 mmol) was slurried with diethyl ether (80 mL) and reacted with MeMgI (1.7 g, 4.5 mmol, 3.0 M) at room temperature. The reaction mixture was stirred at room temperature for 48 hours. Volatiles were removed in vacuo and the crude reaction mixture was extracted with hexane (3 × 20 mLs). The hexane solution was reduced to 20 mL and cooled to -35 ° C. to give F as a yellow crystalline solid (0.8 g, 77%). ¹ H NMR (CD ₂ Cl ₂ , 500MHz) δppm; 7.38 (m), 7.15 (t), 6.78 (t), 2.52 (m d), 1.85 (s), 1.57 (m), 1.06 (s), 0.86 (t), -1.71 (s).
Synthesis of metallocene C
3H-benzo [e] indene (benzo (4,5) indene) was purchased from Boulder Scientific (Boulder, Colorado). Pentamethylcyclopentadiene was purchased from Norquay. All other reagents were purchased from Sigma-Aldrich.

Synthesis of [Li] [1,3-dimethylbenzo [e] indene]
[Li] [Benzo [e] indene] is 3H-benzo [e] indene (12.0 g, 0.072 mol) in ether and 1.1 equivalents of n-BuLi (7.90 mLs 10M / hexane, 0.079 mol) added slowly. ). After 2 hours, the ether was removed under vacuum to isolate [Li] [benzo [e] indene]. The residue was triturated with hexanes to give an off-white solid. The solid was collected by vacuum filtration on a medium glass frit, washed with excess hexane and dried in vacuo to give pure [Li] [benzo [e] indene] as an off-white solid (12.0 g, 97% ). The product was characterized by ¹ H NMR: (THF-d ₈ , 250 MHz) δppm: 8.02 (d, J = 10 Hz, C ₁₀ H ₆ , 1H), 7.47 (t, J = 6.3 Hz, C ₁₀ H ₆ , 2H), 7.09 (t, J = 6.2 Hz, C ₁₀ H ₆ , 1H), 6.91 (t, J = 1 Hz, C ₁₀ H ₆ , 1H), 6.74 (d, J = 10 Hz, C ₁₀ H ₆ , 1H), 6.59 (s, indenyl proton, 1H), 6.46 (s, indenyl proton, 1H), 6.46 (s, indenyl proton, 1H), 6.09 (s, indenyl proton, 1H) .
[Li] [Benzo [e] indene] (12.0 g, 0.070 mol) was dissolved in ether, cooled to −35 ° C., and reacted with 6.0 equivalents of MeI (59.34 g, 0.418 mmol). The reaction was returned to ambient temperature. After 12 hours, the reaction was quenched with water and extracted with ether. The organics were concentrated to give a crude oil, and a clear oil was obtained using a Kugelrohr apparatus. This was a clean mixture of 3-methyl-3H-benzo [e] indene and 1-methyl-1H-benzo [e] indene isomers (7.58 g, 58%). The product was characterized by ¹ H NMR: (CD ₂ Cl ₂ , 250 MHz) δppm: 8.25-7.42 (m, C ₁₀ H ₆ , 10H), 7.15 (d, J = 6.3 Hz, C ₁₀ H ₆ , 2H), 7.09 (t, J = 6.2 Hz, C ₁₀ H ₆ , 1H), 6.91 (t, J = 1 Hz, C ₁₀ H ₆ , 1H), 6.74 (d, J = 10 Hz, C ₁₀ H ₆ , 1H), 6.59 (s, indenyl proton, 1H), 6.46 (s, indenyl proton, 1H), 6.46 (s, indenyl proton, 1H), 6.09 (s, indenyl proton, 1H).
Similarly, [Li] [methylbenzo [e] indene] is a mixture of isomers of 3-methyl-3H-benzo [e] indene and 1-methyl-1H-benzo [e] indene (7.58 g, 0.041 g) in ether. mol) and 1.1 equivalents of n-BuLi (4.45 mLs of 10 M / hexane, 0.045 mol) added slowly. After 2 hours, the ether was removed under vacuum to isolate [Li] [methylbenzo [e] indene]. The residue was triturated with hexanes to give an off-white solid. The solid was collected by vacuum filtration on a medium glass frit, washed with excess hexane and dried in vacuo to give pure [Li] [methylbenzo [e] indene] as an off-white solid (6.97 g, 85 %).
[Li] [methylbenzo [e] indene] (6.97 g, 0.037 mol) was dissolved in ether, cooled to −35 ° C., and reacted with 3.7 equivalents of MeI (19.52 g, 0.138 mmol). The reaction was returned to ambient temperature. After 12 hours, the reaction was quenched with water and extracted with ether. The organics were concentrated to give a yellow oil. This includes 1,3-dimethyl-3H-benzo [e] indene, 1,3-dimethyl-1H-benzo [e] indene, 3,3-dimethyl-3H-benzo [e] indene, and 1,1-dimethyl It was a mixture of -1H-benzo [e] indene isomers (6.63 g, 91%).

Similarly, [Li] [1,3-dimethylbenzo [e] indene] is a mixture of the above dimethylbenzoindene isomer mixture (6.63 g, 0.034 mol) in ether and 1.1 equivalents of n-BuLi (3.74 produced by reaction with mLs of 10M / hexane, 0.037 mol). After 2 hours, ether was removed under vacuum to isolate [Li] [1,3-dimethylbenzo [e] indene]. The residue was triturated with hexanes to give an off-white solid. The solid was collected by vacuum filtration on a medium glass frit, washed with excess hexane and dried in vacuo to give pure [Li] [1,3-dimethylbenzo [e] indene] as an off-white solid (5.43g, 79%). The product was characterized by ¹ H NMR: (THF-d ₈ , 250 MHz) δ ppm: 8.19 (d, J = 7.5 Hz, 1H), 7.48 (d, J = 7.5 Hz, 1H), 7.33 (d , J = 7.5 Hz, 2H), 7.09 (t, J = 1.4 Hz, 1H), 6.91 (t, J = 1.2 Hz, 1H), 6.67 (d, J = 8.5 Hz, 1H), 5.98 (s, 1H ), 2.65 (s, 3H), 2.34 (s, 3H).
Synthesis of _{(CpMe 5) (1,3-Me} 2 -benzo [e] indenyl) HfMe ₂ (metallocene C)

メタロセンC

Metallocene C

CpMe ₅ HfCl ₃ (3.8g) and _{Et 2 O (80ml) [Li} ] in [1,3-Me _2-benzo [e] indenyl] (2.5g, 4.3mmol) was reacted with 48 hours (Crowther, D Baenziger, N .; Jordan, R .; J. Journal of the American Chemical Society (1991), 113 (4), pp. 1455-1457). The pale yellow product was collected on a glass frit by filtration and dried crude _{(CpMe 5) (1,3-Me} 2 -benzo [e] indenyl) HfCl ₂ (3.2g) was obtained as a mixture with LiCl. ¹ H NMR (CD ₂ Cl ₂ , 250 MHz) δ ppm; 8.13, 7.80 (d, Ha, Ha ', 1H), 7.59-7.36 (multiplet, Hb, Hb', Hc, Hc ', 4 H) 6.10 (s, Hd, 1H), 2.62, 2.45 (s, 1,3Me ₂ C ₉ H ₅ , 3 H), 2.10 (s, CpMe ₅ ).
(CpMe ₅ ) (1,3-Me ₂ benzo [e] indenyl) HfCl ₂ (2.5 g) was slurried with toluene (100 ml) and reacted with MeMgI (4.2 g, 2.1 eq, 3.0 M in EtO). The reaction mixture was heated to 80 ° C. for 3 hours. After cooling, volatiles were removed in vacuo to give a solid that was extracted with hexane (4 × 40 ml). Hexane was removed from the combined extracts to give a yellow solid (CpMe ₅ ) (1,3-Me ₂ C ₉ H ₅ ) HfMe ₂ (1.6 g). ¹ H NMR (C ₆ D ₆ , 300 MHz) δppm; 7.55-7.48 (m, C ₆ H ₄ , 2H), 7.20-7.16 (m, C ₉ H ₅ , 3H), 2.00 (s, 1,3Me ₂ C ₉ H ₅ , 6H), 1.76 (s, CpMe ₅ , 15H), -0.95 (s, Hf-Me, 6H).
Metallocenes A, B, and C were used in the examples below.

Synthesis of ¹³ C-labeled 1-decene.
Magnetic stir bar and 5.0 milligram amount of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydro-2-ylidene [2- (i-propoxy) -5- (N, N-dimethyl) A 125 gram pressurized reaction vessel equipped with (aminosulfonyl) phenyl] methylene ruthenium (II) dichloride was charged with a 2.0 gram quantity of 1-decene. This solution was placed in a liquid nitrogen bath and placed under vacuum. ¹³ C-labeled ethylene (500 mls, 1 atm) was condensed into a pressurized reaction vessel. The liquid nitrogen bath was removed. After the solution thawed, the bottle was heated to 50 ° C. with stirring for 2 hours. The bottle was evacuated and the solution was filtered through 1 gram of silica to remove catalyst residues. 1-decene was distilled by short path distillation. No separation of the homometathesis product, 9-octadecene, was obtained (approximately 30 mol% by NMR). ¹ H NMR of the sample revealed about 60% incorporation of ¹³ C label. ¹ H NMR (500 MHz, CD ₂ ClCD ₂ Cl), δppm: 5.78 (m, 1H), 5.4 (m, vinylene derived from octadecene in sample), 5.2.-4.8 (m, 2H; ¹³ C-labeled vinyl J _HC = 154 Hz) 1.99 (m, 2H), 1.3 (m, 12H), 0.88 (t, 3H).
Polymerization of ¹³ C-labeled 1-decene.
1.0 gram of ¹³ C-labeled 1-decene was placed in a 20 ml scintillation vial with a stir bar. Two drops of TIBAL were added to 1-decene. Another solution of activated catalyst was prepared by combining 16 mg metallocene A and 27 mg dimethylanilinium tetrakis (perfluoronaphthyl) borate in 11.0 grams of toluene. Metallocene E solution (100 mgs) was mixed with 1-decene at 50 ° C. for 2 hours. The resulting oligomer was characterized by NMR spectroscopy. ¹³ C NMR (500 MHz, CD ₂ ClCD ₂ Cl), δ ppm: 115 (labeled vinyl carbon, FIG. 1).

Polymerization of 1-decene.
Example 1
A solution of activated catalyst was prepared by combining 15 mg metallocene E and 32 mg dimethylanilinium tetrakis (perfluoronaphthyl) borate in 7.0 grams toluene. The activated metallocene solution (100 mg) was added to 10.0 grams of 1-decene in a 20 ml scintillation vial preheated to 85 ° C. and containing 2 drops of TIBAL. After 2 hours, unreacted 1-decene was removed under a stream of nitrogen. The yield of poly (1-decene) was 8.3 grams. The polymer was analyzed by ¹ H NMR spectroscopy: Mn = 5,644 g / mol (by ¹ H NMR); end group analysis: vinyl = 42 mol%, vinylidene = 43 mol%, vinylene = 15 mol%.
Example 2
An oven-dried 100 mL round bottom flask was charged with a dry box with stir bar, 1-decene (40 g, 285 mmol), and TIBAL (about 60 mg, 0.23 mmol) and heated to 50 ° C. With the solution stirred, metallocene C (422 μg, 0.78 μmol) and dimethylanilinium tetrakis (perfluoronaphthyl) borate (650 μg, 0.57 μmol) were added in one portion as a solution in toluene (400 μL). After 6 hours, the reaction was quenched with 1 mL of a 10% (v / v) isopropanol mixture in pentane. The solution was heated to 160 ° C. under a vacuum of 1500 mTorr to remove more volatile components of the mixture. After distillation, 32.5 g (80%) of heavy oil remained in the distillation pot. The polymer was analyzed by ¹ H NMR spectroscopy: Mn = 12,700 g / mol; end group analysis: vinyl = 36 mol%.

External heater for description and preparation temperature control of the reactor, embedded glass (reactor internal volume = 22.5 mL), septum inlet, controlled supply of nitrogen, and disposable PEEK (polyether ether ketone) mechanical stirrer ( Polymerization was carried out in a dry box in an inert atmosphere (N ₂ ) using a 48 cell Parallel Pressure Reactors (PPR) equipped with 800 RPM. PPR was prepared for polymerization by purging with dry nitrogen for 5 hours at 150 ° C. and then for 5 hours at 25 ° C.
Polymerization of 1-hexene / 1-octene.
As shown in the table below, 1-octene and 1-hexene were added, and then isohexane was added so that the total volume of the solution was 5.0 ml. TNOAL was used as a scavenger at a concentration of 1M. First, a solution of dimethylanilinium tetrakis (perfluoronaphthyl) borate in toluene was added, and then a solution of metallocene was added so that the activator to metallocene ratio was 1: 1. The cell was heated to 85 ° C. and the reaction was allowed to proceed for 1 hour. The reaction was quenched with air and unreacted monomer was removed under vacuum. A partial analysis of the cell product is listed in Table 1.

Table 1. Decene / hexene polymers

The inventors have surprisingly produced vinyl terminated octene / hexene copolymers in the absence of propylene.
All documents mentioned herein, including any priority documents, related applications and / or test procedures, are hereby incorporated by reference to the extent they do not conflict with this text. However, any priority document not listed in the originally filed application or filing shall not be incorporated herein by reference. While the form of the invention has been demonstrated and described, as is apparent from the foregoing general description and specific embodiments, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, the present invention is not limited by the above general description and specific embodiments. Similarly, the term “comprising” is considered synonymous with the term “including” for the purposes of Australian law. Similarly, “comprising” includes the terms “consisting essentially of”, “is” and “consisting of”, and “comprising” is used. Wherever “consisting essentially of”, “being” or “consisting of” may be substituted.

Claims (25)

A higher olefin vinyl-terminated polymer having at least 200 g / mol of Mn (measured by ¹ H NMR) and comprising one or more C _{4 to} C ₄₀ higher olefin derived units, wherein the higher olefin polymer is substantially propylene A higher olefin polymer that does not contain derived units; and wherein the higher olefin polymer has at least 5% allyl chain ends.   2. The higher olefin polymer of claim 1, wherein the higher olefin polymer has a Mn in the range of 200 to 100,000 g / mol. The C ₄ -C ₄₀ higher olefins, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7 The higher olefin polymer of claim 1 or 2, selected from -oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof.   4. The higher olefin polymer of claim 1, 2 or 3, further comprising at least 5 mol% ethylene derived units.   5. The higher olefin polymer of claim 1, 2, 3, or 4, wherein the higher olefin polymer has an allyl chain end to vinylidene chain end ratio of 1: 1 or greater. The higher olefin copolymer, as measured by ¹ H NMR assuming one unsaturation per chain, is at least 50 wt% of an olefin having at least 36 carbon atoms, based on the weight of the copolymer composition The higher olefin polymer of claim 1, 2, 3, 4, or 5.   The higher olefin polymer of claim 1, 2, 3, 4, 5, or 6, wherein the higher olefin copolymer comprises less than 20 wt% dimers and trimers, based on the weight of the copolymer composition.   The higher olefin copolymer of claim 1, 2, 3, 4, 5, 6, or 7, wherein the higher olefin copolymer has a viscosity at 60 ° C greater than 1000 cP. A method for producing a higher olefin polymer comprising:
Substantially 1 or more C ₄ -C ₄₀ monomer having no propylene,
Contacting the catalyst system comprising an activator and at least one metallocene compound represented by at least one of the following formulae:
(i)

Formula I;
Or (ii)

Formula II;
Or (iii)

Formula III;
Or (iv)

Formula IV;
(Where
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, and combinations thereof (2 Two Xs may form part of a fused ring or ring system);
Each Q is independently a carbon or heteroatom;
Each R ¹ is independently a C ₁ -C ₈ alkyl group, and R ¹ may be the same as or different from R ² ;
Each R ² is independently a C ₁ -C ₈ alkyl group;
Each R ³ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group having 1 to 8 carbon atoms, provided that at least three R ³ groups are not hydrogen;
Each R ⁴ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, heteroatom or heteroatom-containing group;
R ⁵ is hydrogen or a C ₁ -C ₈ alkyl group;
R ⁶ is hydrogen or a C ₁ -C ₈ alkyl group;
Each R ⁷ is independently hydrogen, or a C ₁ -C ₈ alkyl group, provided that at least seven R ⁷ groups are not hydrogen;
T is a bridging group;
Each R ^a is independently hydrogen, halogen or C ₁ -C ₂₀ hydrocarbyl;
Two R ^a can form ^a cyclic structure (including aromatic, partially saturated, or saturated cyclic or fused ring systems); and any two adjacent R groups can also be fused or multi-centered fused A ring system, provided that the ring may form an aromatic, which may be partially saturated or saturated);
Or (v)

Formula V
(Where
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof (2 Two Xs may form part of a fused ring or ring system);
Each R ⁸ is independently a C ₁ -C ₁₀ alkyl group;
Each R ⁹ is independently a C ₁ -C ₁₀ alkyl group;
Each R ¹⁰ is hydrogen;
Each R ¹¹ , R ¹² and R ¹³ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, heteroatom or heteroatom-containing group;
T is a bridging group;
Further, provided that any adjacent R ¹¹ , R ¹² , and R ¹³ groups may form a condensed ring or a multi-centered condensed ring system (the ring may be aromatic, partially saturated or saturated). Do);
Or (vi)

Formula VI
(Where
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers, or combinations thereof;
Each R ¹⁵ and R ¹⁷ is independently a C ₁ -C ₈ alkyl group;
Each R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ are independently hydrogen or 1-8 Substituted or unsubstituted hydrocarbyl groups having carbon atoms).   10. The method of claim 9, further comprising contacting at least 5 mol% ethylene monomer with the catalyst system. The C ₄ -C ₄₀ higher olefins, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7 11. A process according to claim 9 or 10 selected from -oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof. The activator is represented by the following formula:

(Where
Each R ₁ is independently a halide, preferably fluoride;
Each R ₂ is independently a halide, a C ₆ -C ₂₀ substituted aromatic hydrocarbyl group or a formula —O—Si—R _{a where} R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl group. A siloxy group, preferably a fluoride or a C ₆ perfluorinated aromatic hydrocarbyl group;
Each R ³ is a halide, a C ₆ -C ₂₀ substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—R _{a where} R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbylsilyl group, preferably Is a fluoride or C ₆ perfluorinated aromatic hydrocarbyl group;
Where L is a neutral Lewis base;
H is hydrogen;
(LH) ⁺ is a Bronsted acid;
d is 1;
Wherein the anion has a molecular weight greater than 1020 g / mol; and
(At least three of the substituents on the B atom each have a molecular volume greater than 250 cubic liters)
12. The method according to claim 9, 10 or 11, which is a bulky activator represented by: The activator is:
Trimethylammonium tetrakis (perfluoronaphthyl) borate, triethylammonium tetrakis (perfluoronaphthyl) borate, tripropylammonium tetrakis (perfluoronaphthyl) borate, tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate, tri (t-butyl) ammonium tetrakis (Perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium ) Tetrakis (perfluoronaphthyl) borate, tropylium tetrakis (perfluoronaphthyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylphos Honium tetrakis (perfluoronaphthyl) borate, triethylsilyl tetrakis (perfluoronaphthyl) borate, benzene (diazonium) tetrakis (perfluoronaphthyl) borate, trimethylammonium tetrakis (perfluorobiphenyl) borate, triethylammonium tetrakis (perfluorobiphenyl) borate, tripropyl Ammonium tetrakis (perfluorobiphenyl) borate, tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate, tri (t-butyl) ammonium tetrakis (perfluorobiphenyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl- (2,4,6-trimethyl Nilinium) tetrakis (perfluorobiphenyl) borate, tropylium tetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylphosphonium tetrakis (perfluorobiphenyl) borate, triethylsilylium tetrakis (perfluorobiphenyl) borate, benzene (Diazonium) tetrakis (perfluorobiphenyl) borate, [4-t-butyl-PhNMe ₂ H] [(C ₆ F ₃ (C ₆ F ₅ ) ₂ ) ₄ B] (Ph is phenyl, Me is methyl )
12. The method of claim 9, 10, or 11 which is at least one of the following. At least one higher olefin vinyl terminated polymer having at least 200 g / mol Mn (measured by ¹ H NMR) and comprising one or more C _{4 to} C ₄₀ higher olefin derived units, wherein said higher olefin vinyl terminated The polymer is substantially free of propylene-derived units; and the higher olefin polymer has at least 5% allyl chain ends)
A composition comprising   15. The composition of claim 14, wherein the composition is a lubricant blend.   16. A composition according to claim 14 or 15, wherein the higher olefin polymer has a Mn in the range of 200 to 100,000 g / mol. The C ₄ -C ₄₀ higher olefins, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7 17. The composition of claim 14, 15, or 16, selected from -oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof.   18. The composition of claim 14, 15, 16, or 17, further comprising at least 5 mol% ethylene derived units.   19. The composition of claim 14, 15, 16, 17, or 18, wherein the higher olefin polymer has an allyl chain end to vinylidene chain end ratio of 1: 1 or greater.   Use of a composition according to claim 14, 15, 16, 17, 18, or 19 as a lubricant. A vinyl-terminated higher olefin polymer having at least 200 g / mol Mn (measured by ¹ H NMR) and comprising at least 5 mol% of one or more C ₅ -C ₄₀ higher olefin derived units,
A vinyl wherein the vinyl terminated higher olefin polymer is substantially free of ethylene derived units, propylene derived units or butene derived units; and the higher olefin polymer has at least 5% (based on total unsaturation) of allyl chain ends Terminal higher olefin polymer.   22. The vinyl terminated higher olefin polymer of claim 21, further having an allyl chain end to vinylidene chain end ratio of 1: 1 or greater and / or substantially free of isobutyl chain ends.   The vinyl-terminated higher olefin polymer of claim 21, wherein the polymer is a homopolymer (eg, homopolypentene, homopolyhexene, homopolyoctene, homopolydecene, homopolydodecene, etc.). Wherein the polymer is a copolymer consisting essentially of C ₅ -C ₄₀ olefins (e.g. hexene and octene copolymer, octene and decene copolymer, octene, copolymers of decene and dodecene, etc.), vinyl-terminated according to claim 21 higher olefins polymer. The polymer is at least 5 mol% (preferably at least 10 mol%, at least 15 mol%, at least 20 mol%, at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70 mol%; at least 80 mol%, at least 90 mol%, C ₅ -C ₄₀ olefins (e.g. pentene, or at least 95 mol%), hexene, comprises octene or decene), the residual is composed of different C ₅ -C ₄₀ olefins, vinyl-terminated higher olefin polymer of claim 21 .

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