JP5739054B2 - Vinyl-terminated higher olefin copolymer and method for producing the same - Google Patents

Description

Inventors: Donna J. Crowther, Matthew W. Holtcamp, John R. Hagadorn, Charles J. Ruff, George Rodriguez and Patrick Brant
This application claims the benefit and priority of U.S. Patent Application No. 13 / 072,249 filed on March 25, 2011 and European Patent Application No. 11167059.2 filed on May 23, 2011. Is.

  The present invention relates to the copolymerization of olefins, and in particular to producing vinyl terminated copolymers.

Alpha-olefins, particularly those containing from about 6 to about 20 carbon atoms, have been used as intermediates in the manufacture of detergents or other types of commercial products. In addition, such alpha-olefins are particularly used as comonomers for linear low density polyethylene. Alpha-olefins that are produced commercially are generally produced by oligomerizing ethylene. Longer chain length alpha-olefins such as vinyl terminated polyethylene are also known and may be useful as components after functionalization or as macromonomers.
Also, low molecular weight solids and liquids of ethylene or propylene having an allyl terminus are generally produced for use as branches in the polymerization reaction. 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. 5425-5435).
In addition, US Pat. No. 4,814,540 discloses methylalumoxane in toluene or hexane, with or without hydrogen, to produce allylic vinyl-terminated propylene homooligomers having low degrees of polymerization of 2-10. The accompanying bis (pentamethylcyclopentadienyl) hafnium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride and bis (tetramethyl n-butylcyclopentadienyl) hafnium dichloride are disclosed. These oligomers are not high in Mn and do not have at least 93% allylic vinyl unsaturation. Similarly, these oligomers have no comonomer and are produced with low productivity even with a large excess of alumoxane (Al / M with a molar ratio ≧ 600; M = Zr, Hf). Furthermore, more than 60% by weight of solvent (based on solvent + propylene) is present in all of these examples.

Teubenet al. (J. Mol. Catal ., 62, 1990, pp. 277-287) _{^{is, [Cp * 2 MMe (THT}} )] + [BPh 4] (M = Zr and Hf, Cp ^* = pentamethyl cyclo The use of pentadienyl, Me = methyl, Ph = phenyl, THT = tetrahydrothiophene) to produce propylene oligomers. In M = Zr, oligomers of up to C ₂₄ (number average molecular weight (Mn) of 336) broad product distribution with was obtained at room temperature. On the other hand, at M = Hf, only the dimer 4-methyl-1-pentene and the trimer 4,6-dimethyl-1-heptene were formed. The main termination mechanism appears to be the return of beta-methyl from the growing chain to the metal center, as demonstrated by deuterium labeling studies.

X. Yang et al. (Angew. Chem. Intl. Ed. Engl., 31, 1992, pg. 1375) is an amorphous low molecular weight polypropylene produced at low temperatures with low reaction activity and ¹ H NMR discloses a product with 90% allylic vinyl for all unsaturations. Resconi et al. (J. Am. Chem. Soc., 114, 1992, pp. 1025-1032) then introduced bis (pentamethylcyclopentadienyl) zirconium and bis (pentamethylcyclopentadienyl) hafnium. It is disclosed to polymerize propylene and terminate the resulting beta-methyl to obtain oligomers and low molecular weight polymers having “mainly allyl-terminated and iso-butyl-terminated” chains. As in U.S. Pat. No. 4,814,540, the resulting oligomer does not have at least 93% of the allyl chain ends and is from about 500 to about 20,000 g / mol of Mn ( ¹ H (Measured by NMR) and the catalyst has low productivity (1-12,620 g / mmol metallocene / hour,> 3000 wppm Al in the product).
Similarly, Small and Brookhart, (Macromolecules, 32, 1999, pg. 2322) use dominant or exclusive 2,1 chain growth, beta-, using pyridylbisamido iron catalyst in low temperature polymerization. It discloses chain termination by hydride elimination and the production of low molecular weight amorphous propylene materials with apparently high amounts of vinyl end groups.

Weng et al. (Macromol Rapid Comm. 2000, 21, pp. 1103-1107) uses dimethylsilylbis (2-methyl, 4-phenyl-indenyl) zirconium dichloride and methylalumoxane at about 120 ° C. in toluene. A material having a vinyl termination of up to about 81 percent. 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, pp. 8541-8548, discloses the preparation of a branched block ethylene-butene polymer produced by reincorporating vinyl-terminated polyethylene, said branched block polymer being methylalumoxane. Produced by a combination of activated Cp ₂ ZrCL ₂ and (C ₅ Me ₄ SiMe ₂ NC ₁₂ H ₂₃ ) TiCl ₂ .
Moscardi et al. (Organometallics, 20, 2001, pg. 1918) uses rac-dimethylsilylmethylenebis (3-tert-butylindenyl) zirconium dichloride and methylalumoxane in a batch polymerization of propylene. It is disclosed that the end group produces a material that always takes precedence over any other end group in any [propene]. In these reactions, morphology control is limited and approximately 60% of the chain ends are allylic.
Coates et al. (Macromolecules, 38, 2005, pg. 6259) describes bis (phenoxyimine) titanium dichloride ((PHI) ₂ TiCl) activated with modified methylalumoxane (MMAO; Al / Ti molar ratio = 200). ₂ ) was used for 4 hours at −20 ° C. to + 20 ° C., and low molecular weight syndiotactic polypropylene ([rrrr] = 0.46 to 0.93) having about 100% allyl end groups was obtained. It is disclosed to prepare. In these polymerizations, propylene was dissolved in toluene to produce a 1.65 M toluene solution. The catalyst productivity was very low (0.95 to 1.14 g / mmol Ti / hour).

JP 2005-336092 A discloses that a vinyl-terminated propylene polymer is produced using a material such as montmorillonite, triethylaluminum, triisopropylaluminum treated with H ₂ SO ₄ , in which case a liquid is used. Propylene is fed to the catalyst slurry in toluene. This method produces low amounts of amorphous material and substantially isotactic macromonomers.

Rose et al. (Macromolecules, 41, 2008, pp. 559-567) discloses poly (ethylene-co-propylene) macromonomers with low amounts of iso-butyl chain ends. These are produced in semi-batch polymerization using modified methylalumoxane (MMAO; Al / Ti molar ratio range 150-292) activated bis (phenoxyimine) titanium dichloride ((PHI) ₂ TiCl ₂ ). (30 psi of propylene was added to toluene at 0 ° C. over 30 minutes, followed by flowing ethylene gas at an overpressure of 32 psi at about 0 ° C. for a polymerization time of 2.3 to 4 hours, Produced an EP copolymer having 23,300). In the four copolymerizations reported, the allylic chain ends decreased as ethylene incorporation increased, generally according to the following equation:
Allyl chain end (%) (all unsaturated) = -0.95 (incorporated ethylene (mol%)) +100
For example, an EP copolymer containing 29 mol% ethylene reported 65% (compared to all unsaturations) allyl. This is the best allyl population achieved. When 64 mol% ethylene is incorporated, only 42% of the unsaturation is allylic. Their polymerization productivity ranged from 0.78 × 10 ² g / mmolTi / hour to 4.62 × 10 ² g / mmolTi / hour.

Prior to this study, Zhu et al. Used a constrained geometry metallocene catalyst [C ₅ Me ₄ (SiMe ₂ N-tert-butyl) TiMe ₂ ] activated with B (C ₆ F ₅ ) ₃ and MMAO. Reported that very small amounts (about 38%) of vinyl-terminated ethylene-propylene copolymers were produced (Macromolecules, 35, 2002, pp. 10062-10070 and Macromolecules Rap. Commun., 24, 2003, pp. 311-315).
Janiak and Blank review various studies on olefin oligomerization (Macromol. Symp., 236, 2006, pp. 14-22).

  However, the polymerization of higher olefins to produce allyl-terminated higher olefin copolymers is not known. Accordingly, there is a need for new catalysts that produce allyl-terminated higher olefin copolymers with a wide range of molecular weights and high catalytic activity, especially in high yields. In addition, it is controlled over a wide range of molecular weights, has an abundance of allyl termination (over 40%), can be produced at commercial temperatures, and produces commercial rates (above 5,000 g / mmol / hour). The higher olefin copolymer macromonomer that can be produced at the same time. In addition, there is a need for higher olefin copolymer reactive materials with allyl terminations that can be functionalized and used in additive applications or as macromonomers for the synthesis of poly (macromonomers).

The present invention has a Mn (measured by ¹ H NMR) of 300 g / mol or higher, (i) about 20-99.9 mol% of at least one C ₅ -C ₄₀ higher olefin, and (ii) about 0.00. It relates to higher olefin copolymers comprising from 1 to about 80 mol% propylene and having at least 40% allyl chain ends.
The present invention has 300 g / mol or more (preferably 300-60,000 g / mol) of Mn (measured by ¹ H NMR), (i) about 80-99.9 mol% of at least one C ₄ olefin, And (ii) higher olefin copolymers comprising about 0.1-20 mol% propylene and having at least 40% allyl chain ends.
The present invention also includes (i) at least one C ₅ -C ₄₀ higher olefins 20～99.9Mol%, contacting under polymerization conditions and (ii) 0.1~80mol% propylene, A process for producing higher olefin copolymers, wherein the contacting occurs in the presence of an activator and a catalyst system comprising at least one metallocene compound represented by at least one of the following formulae.
(I)

式Ｉ
または（ｉｉ）

Formula I
Or (ii)

式ＩＩ
または（ｉｉｉ）

Formula II
Or (iii)

式ＩＩＩ
または（ｉｖ）

Formula III
Or (iv)

式ＩＶ

Formula IV

Wherein M is hafnium or zirconium, and each X is independently a hydrocarbyl radical having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halogen, a diene, an amine, Selected from the group consisting of phosphine, ether and combinations thereof (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, R ¹ may be the same or different as 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 from 1 to 8 carbon atoms, provided that at least 3 R ³ groups are not hydrogen and each R ⁴ Independently, hydrogen, or Is a substituted or unsubstituted hydrocarbyl group, a 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 a C ₁ -C ₈ alkyl group, provided that at least 7 R ⁷ groups are not hydrogen, R ₂ ^a T is a bridging group, and T is Group 14 element (preferably C, Si or Ge, preferably Si), each R ^a is independently hydrogen, halogen or C ₁ -C ₂₀ hydrocarbyl, and the two R ^a are aromatic May form a cyclic structure comprising a group, partially saturated, or saturated cyclic or fused ring system, provided that any two adjacent R groups may be fused rings or multicentric. May form an aromatic condensed ring system, and the ring is aromatic. May be partially saturated or saturated],
Or (v)

式Ｖ

Formula V

[Wherein M is hafnium or zirconium and each X is independently a hydrocarbyl radical having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine. , Phosphine, ether and combinations thereof (two Xs may form part of a fused ring or ring system) and each R ⁸ is independently C ₁ -C ₁₀ An alkyl group, each R ⁹ is independently a C ₁ -C ₁₀ alkyl group, each R ¹⁰ is hydrogen, and each R ¹¹ , R ^12, and R ¹³ is independently hydrogen or substituted Or an unsubstituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group, and T is a bridging group, provided that any of the adjacent R ¹¹ , R ^12, and R ¹³ groups are fused rings or multicentric Fused ring May form a, the ring may be aromatic or partially saturated, or may be saturated,
Or (vi)

式ＶＩ
［式中、Ｍは、ハフニウムまたはジルコニウムであり、各Ｘは、独立に、１〜２０個の炭素原子を有するヒドロカルビルラジカル、水素化物、アミド、アルコキシド、スルフィド、リン化物、ハロゲン、ジエン、アミン、ホスフィン、エーテルまたはその組合せからなる群から選択され、各Ｒ¹⁵およびＲ¹⁷は、独立に、Ｃ₁−Ｃ₈アルキル基であり、各Ｒ¹⁶、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴、Ｒ²⁵、Ｒ²⁶、Ｒ²⁷およびＲ²⁸は、独立に、水素であり、または１〜８個の炭素原子を有する置換もしくは非置換ヒドロカルビル基である］

Formula VI
Wherein M is hafnium or zirconium, and each X is independently a hydrocarbyl radical having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halogen, a diene, an amine, Selected from the group consisting of phosphine, ether or combinations thereof, 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 , 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]

The present invention also includes at least one C ₄ olefin (i) 80~99.9mol%, the (ii) and 0.1 to 20 mol% of propylene comprising contacting under polymerization conditions, higher olefin copolymer A method of producing, wherein the contacting occurs in the presence of an activator and a catalyst system comprising at least one metallocene compound represented by at least one of the following formulae:
(I)

式Ｉ
または（ｉｉ）

Formula I
Or (ii)

式ＩＩ
または（ｉｉｉ）

Formula II
Or (iii)

式ＩＩＩ
または（ｉｖ）

Formula III
Or (iv)

式ＩＶ

Formula IV

Wherein M is hafnium or zirconium, and each X is independently a hydrocarbyl radical having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halogen, a diene, an amine, Selected from the group consisting of phosphine, ether and combinations thereof (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, R ¹ may be the same or different as 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 from 1 to 8 carbon atoms, provided that at least 3 R ³ groups are not hydrogen and each R ⁴ Independently, hydrogen, or Is a substituted or unsubstituted hydrocarbyl group, a 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 a C ₁ -C ₈ alkyl group, provided that at least 7 R ⁷ groups are not hydrogen, R ₂ ^a T is a bridging group, and T is Group 14 element (preferably C, Si or Ge, preferably Si), each R ^a is independently hydrogen, halogen or C ₁ -C ₂₀ hydrocarbyl, and the two R ^a are aromatic May form a cyclic structure comprising a group, partially saturated, or saturated cyclic or fused ring system, provided that any two adjacent R groups may be fused rings or multicentric. May form an aromatic condensed ring system, and the ring is aromatic. May be partially saturated or saturated],
Or (v)

式Ｖ

Formula V

[Wherein M is hafnium or zirconium and each X is independently a hydrocarbyl radical having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine. , Phosphine, ether and combinations thereof (two Xs may form part of a fused ring or ring system) and each R ⁸ is independently C ₁ -C ₁₀ An alkyl group, each R ⁹ is independently a C ₁ -C ₁₀ alkyl group, each R ¹⁰ is hydrogen, and each R ¹¹ , R ^12, and R ¹³ is independently hydrogen or substituted Or an unsubstituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group, where T is a bridging group (such as R ₂ ^a T as defined above), but further adjacent R ¹¹ , R ¹² and R ¹³ groups Either May form a Gowa or multicentric fused ring system, the ring may be aromatic or partially saturated, or may be saturated,
Or (vi)

式ＶＩ
［式中、Ｍは、ハフニウムまたはジルコニウムであり、各Ｘは、独立に、１〜２０個の炭素原子を有するヒドロカルビルラジカル、水素化物、アミド、アルコキシド、スルフィド、リン化物、ハロゲン、ジエン、アミン、ホスフィン、エーテルまたはその組合せからなる群から選択され、各Ｒ¹⁵およびＲ¹⁷は、独立に、Ｃ₁−Ｃ₈アルキル基であり、各Ｒ¹⁶、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴、Ｒ²⁵、Ｒ²⁶、Ｒ²⁷およびＲ²⁸は、独立に、水素であり、または１〜８個の炭素原子を有する置換もしくは非置換ヒドロカルビル基である］

Formula VI
Wherein M is hafnium or zirconium, and each X is independently a hydrocarbyl radical having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halogen, a diene, an amine, Selected from the group consisting of phosphine, ether or combinations thereof, 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 , 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]

The present invention still further has Mn greater than 200 g / mol (measured by ¹ H NMR), (i) about 20-99.9 mol% of at least one C ₅ -C ₄₀ higher olefin, and (ii) about It relates to a composition comprising a higher olefin copolymer comprising 0.1 to 80 mol% propylene and having at least 40% allyl chain ends.
The present invention still further has a Mn greater than 200 g / mol (measured by ¹ H NMR), (i) from about 80 to 99.9 mol% of at least one C ₄ olefin, and (ii) from about 0.1 to about 0.1 It relates to a composition comprising a higher olefin copolymer comprising 20 mol% propylene and having at least 40% allyl chain ends.
The present invention still further relates to the use of the composition disclosed herein as a lubricant.

FIG. 5 shows viscosity as a function of time when a representative allyl-terminated hexene-propylene copolymer is compared to an allyl-terminated propylene homopolymer.

  The inventors have surprisingly discovered a new class of vinyl-terminated polymers. Described herein are vinyl-terminated higher olefin copolymers, methods for producing such vinyl-terminated higher olefin copolymers, and compositions comprising vinyl-terminated higher olefin copolymers. These vinyl-terminated higher olefin copolymers can find utility as macromonomers for synthesizing poly (macromonomers) and block copolymers and as additives, for example as additives to lubricants. Advantageously, the vinyl groups of these vinyl terminated copolymers provide a route to functionalization. These functionalized copolymers may be useful as additives in lubricants and the like.

As used herein, “molecular weight” means number average molecular weight (Mn) unless otherwise specified.
For the purposes of the present invention and the appended claims, a new numbering scheme of the periodic table family is used, as seen in CHEMICAL AND ENGINEERING NEWS, 63 (5), pg. 27 (1985). Therefore, “Group 4 metal” is an element of Group 4 of the periodic table.

“Catalytic activity” is a measure of how much polymer (P) (grams) is produced over a T time period using a polymerization catalyst containing the catalyst (cat) Wg, and has the formula P / (T × W) and can be represented by the unit gPgcat ^-1 hr ^-1 . “Catalyst productivity” is a measure of how much polymer (P) (grams) is produced over a T time using a polymerization catalyst containing the catalyst (cat) Wg, and is given by the formula P / (T × W), and can be represented by the unit gPgcat ⁻¹ hr ⁻¹ . Conversion is the amount of monomer converted to polymer product, reported as mol%, and is calculated based on the polymer yield and the amount of monomer fed to the reactor.

“Olefin”, also referred to as “alkene”, is a straight chain, branched or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the appended claims, polymers or copolymers are considered to contain olefins including, but not limited to, ethylene, propylene and butene. The olefin present in is the polymerized form of the olefin. For example, if the copolymer is said to have an “ethylene” content of 35 wt% to 55 wt%, the mer units of the copolymer are derived from ethylene in the polymerization reaction, and the derived units are based on the weight of the copolymer. It is understood that it is present at 35% to 55% by weight. A “polymer” has two or more mer units that are the same or different. 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 the same mer units. A “copolymer” is a polymer having two or more mer units that are different from each other. A “terpolymer” is a polymer having three different mer units. “Different”, when used in reference to a mer unit, indicates that the mer units differ from each other by at least one atom or differ by isomer. Thus, as used herein, the definition of copolymer includes terpolymers and the like.
A “higher olefin” as used herein is a C ₄ -C ₄₀ olefin, preferably a C ₅ -C ₃₀ α-olefin, more preferably a C ₅ -C ₂₀ α-olefin, or even more preferably C ₅ -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 monomer unit (different means that the monomer units differ by at least one atom). .

As used herein, Mn is the number average molecular weight (measured by ¹ H NMR unless otherwise stated), Mw is the weight average molecular weight (measured by gel permeation chromatography, GPC), Mz Is the z-average molecular weight (measured by GPC), weight percent is weight percent, mol% is mole percent, volume percent is volume percent, and mol is mole. Molecular weight distribution (MWD) is defined as Mw (measured by GPC) divided by Mn (measured by GPC), ie Mw / Mn. Unless otherwise indicated, all molecular weights (eg, Mw, Mn, Mz) have units g / mol.

Vinyl-terminated copolymers In a preferred embodiment, the vinyl-terminated higher olefin (VT-HO) copolymer described herein has a Mn of greater than 200 g / mol (preferably 300-60,000 g / mol, 400-50,000 g). / Mol, 500-35,000 g / mol, 300-15,000 g / mol, 400-12,000 g / mol, or 750-10,000 g / mol) (measured by ¹ H NMR), (i) about 20～99.9Mol% of at least one C ₅ -C ₄₀ (preferably C ₆ -C ₂₀₎ higher olefins (preferably about 25 to about 90 mol%, from about 30 to about 85 mol%, from about 35 to about 80 mol% About 40 to about 75 mol%, or about 50 to about 95 mol%), and (ii) about 0.1 to 80 mol% propylene. Len (preferably about 5 mol% to 70 mol%, about 10 to about 65 mol%, about 15 to about 55 mol%, about 25 to about 50 mol%, or about 30 to about 80 mol%) for all unsaturations At least 40% of allyl chain ends (preferably at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, at least 80% allyl chain ends, at least 90% allyl chain ends) In some cases, the ratio of isobutyl chain end to allyl chain end is less than 0.70: 1, less than 0.65: 1, less than 0.60: 1, 0 Less than 50: 1, or less than 0.25: 1, and in some cases, the ratio of allyl chain end to vinylidene chain end is greater than 2: 1 (preferably Greater than 5: 1, greater than 3: 1, greater than 5: 1, or greater than 10: 1), and in some cases, the ratio of allyl chain end to vinylene is greater than 1: 1 (preferably 2: 1 Or greater than 5: 1).

In another embodiment, the higher olefin copolymer comprises 300 g / mol or more of Mn (measured by ¹ H NMR, preferably 300-60,000 g / mol, 400-50,000 g / mol, 500-35,000 g / mol, 300-15,000 g / mol, 400-12,000 g / mol, or 750-10,000 g / mol)
(I) from about 80 to about 99.9 mol%, preferably from about 85 to about 99.9 mol%, more preferably from about 90 to about 99.9 mol% of at least one C ₄ olefins,
(Ii) about 0.1 to about 20 mol%, preferably about 0.1 to about 15 mol%, more preferably about 0.1 to about 10 mol% propylene,
For all unsaturations, at least 40% of allyl chain ends (preferably at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, or at least 80% allyl chain ends) , At least 90% allyl chain ends, and at least 95% allyl chain ends), and in some embodiments, the ratio of isobutyl chain ends to allyl chain ends is less than 0.70: 1, 0.65: 1 Less than 0.60: 1, less than 0.50: 1, or less than 0.25: 1, and in further embodiments, the ratio of allyl chain end to vinylidene group is greater than 2: 1, 2.5: Greater than 1, greater than 3: 1, greater than 5: 1, or greater than 10: 1.

The VT-HO polymer may be a copolymer, a terpolymer or the like.
VT-HO copolymers generally have saturated chain ends (or ends) and / or unsaturated chain ends or ends. The unsaturated chain ends of the copolymers of the present invention include “allyl chain ends”. The allyl chain end is

（Ｍは、コポリマー鎖を表す）で示される通り、ＣＨ₂ＣＨ−ＣＨ₂−によって表される。「アリル性ビニル基」、「アリル鎖末端」、「ビニル鎖末端」、「ビニル終端」、「アリル性ビニル基」および「ビニル末端」は、以下の説明では互換的に使用される。

(M represents a copolymer chain) and is represented by CH ₂ CH—CH ₂ —. “Allyl vinyl group”, “allyl chain end”, “vinyl chain end”, “vinyl end”, “allylic vinyl group” and “vinyl end” are used interchangeably in the following description.

The number of allyl chain ends, vinylidene chain ends and vinylene chain ends is determined with an NMR spectrometer of at least 250 MHz at 120 ° C. using ¹ H NMR, using deuterated tetrachloroethane as solvent, If selected, it is confirmed by ¹³ C NMR. Resconi reports the proton and carbon assignments of vinyl-terminated propylene oligomers that are also useful herein in J. American Chemical Soc, 114, 1992, pp. 1025-1032. Hydrogenated tetrachloroethane was used and the carbon spectrum was a 50:50 mixture of normal tetrachloroethane and perdeuterated tetrachloroethane, operating a Bruker spectrometer at 500 MHz for protons and 125 MHz for carbon, All spectra were recorded at 100 ° C). Allyl chain ends are reported as mole percentages of the total number of moles of unsaturated groups (ie, the sum of allyl chain ends, vinylidene chain ends, vinylene chain ends, etc.).

In another embodiment, any of the vinyl-terminated polyolefins described or useful herein are also referred to as “3-alkyl chain ends” or “3-alkyl vinyl terminations”: 3-alkyl vinyl terminal group represented by (alkyl, C ₁ -C ₃₈ alkyl) with a.

式中、「・・・・」は、ポリオレフィン鎖を表し、Ｒ^bは、Ｃ₁−Ｃ₃₈アルキル基、好ましくはメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル（ｄｏｃｅｃｙｌ）などのＣ₁−Ｃ₂₀アルキル基である。３−アルキル鎖末端の量は、下記の通り¹³Ｃ ＮＭＲを使用して決定される。

In the formula, “...” represents a polyolefin chain, and R ^b is a C ₁ -C ₃₈ alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, C ₁ -C ₂₀ alkyl groups such as undecyl and dodecyl. The amount of 3-alkyl chain ends is determined using ¹³ C NMR as follows.

In one preferred embodiment, any of the vinyl terminated polyolefins described or useful herein is at least 5% (preferably, 3-alkyl chain terminated to all unsaturation) At least 10% 3-alkyl chain ends, at least 20% 3-alkyl chain ends, at least 30% 3-alkyl chain ends, at least 40% 3-alkyl chain ends, at least 50% 3-alkyl chain ends, At least 60% 3-alkyl chain ends, at least 70% 3-alkyl chain ends, at least 80% 3-alkyl chain ends, at least 90% 3-alkyl chain ends, at least 95% 3-alkyl chain ends) Have.
In one preferred embodiment, any of the vinyl-terminated polyolefins described or useful herein is 3-alkyl + allyl chain terminated (e.g., all 3-alkyl chain ends and all allyl chain ends) at least 5%, preferably 3-alkyl + allyl chain ends at least 10%, 3-alkyl + allyl chain ends at least 20%, 3-alkyl + allyl chains At least 30% ends, at least 40% 3-alkyl + allyl chain ends, at least 50% 3-alkyl + allyl chain ends, at least 60% 3-alkyl + allyl chain ends, 3-alkyl + allyl chain ends At least 70%, at least 80% 3-alkyl + allyl chain ends, at least 90% 3-alkyl + allyl chain ends, - has at least 95% alkyl + allyl chain ends.

In some embodiments, the VT-HO copolymer has at least 40% allyl chain ends (at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, at least 70% allyl chain ends). 80%, at least 90% allyl chain ends, or at least 95% allyl chain ends).
In another embodiment, any of the vinyl-terminated polyolefins described or useful herein are also referred to as “3-alkyl chain ends” or “3-alkyl vinyl terminations”: 3-alkyl vinyl terminal group represented by (alkyl, C ₁ -C ₃₈ alkyl) with a.

式中、「・・・・」は、ポリオレフィン鎖を表し、Ｒ^bは、Ｃ₁−Ｃ₃₈アルキル基、好ましくはメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシルなどのＣ₁−Ｃ₂₀アルキル基である。３−アルキル鎖末端の数は、下記の通り¹³Ｃ ＮＭＲを使用して決定される。

In the formula, “...” represents a polyolefin chain, and R ^b is a C ₁ -C ₃₈ alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, C ₁ -C ₂₀ alkyl groups such as undecyl and dodecyl. The number of 3-alkyl chain ends is determined using ¹³ C NMR as follows.

In one preferred embodiment, any of the vinyl terminated polyolefins described or useful herein is at least 5% (preferably, 3-alkyl chain terminated to all unsaturation) At least 10% 3-alkyl chain ends, at least 20% 3-alkyl chain ends, at least 30% 3-alkyl chain ends, at least 40% 3-alkyl chain ends, at least 50% 3-alkyl chain ends, At least 60% 3-alkyl chain ends, at least 70% 3-alkyl chain ends, at least 80% 3-alkyl chain ends, at least 90% 3-alkyl chain ends, at least 95% 3-alkyl chain ends) Have.
In one preferred embodiment, any of the vinyl-terminated polyolefins described or useful herein is 3-alkyl + allyl chain terminated (e.g., all 3-alkyl chain ends and all allyl chain ends) at least 5%, preferably 3-alkyl + allyl chain ends at least 10%, 3-alkyl + allyl chain ends at least 20%, 3-alkyl + allyl chains At least 30% ends, at least 40% 3-alkyl + allyl chain ends, at least 50% 3-alkyl + allyl chain ends, at least 60% 3-alkyl + allyl chain ends, 3-alkyl + allyl chain ends At least 70%, at least 80% 3-alkyl + allyl chain ends, at least 90% 3-alkyl + allyl chain ends, - has at least 95% alkyl + allyl chain ends.

“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, the ratio of allyl chain end to vinylidene chain end is greater than 2: 1 (preferably greater than 2.5: 1, greater than 3: 1, greater than 5: 1, or greater than 10: 1). . In some embodiments, the ratio of allyl chain end to vinylidene chain end ranges from about 10: 1 to about 2: 1 (preferably from about 5: 1 to about 2: 1 or from 10: 1 to about 2). .5: 1).
“Ratio of allyl chain ends to vinylene chain ends” is defined as the ratio of the percentage of allyl chain ends to the percentage of vinylene chain ends. In some embodiments, the ratio of allyl chain end to vinylene is greater than 1: 1 (preferably greater than 2: 1 or greater than 5: 1).

The VT-HO copolymer also has saturated chain ends that can include isobutyl chain ends or higher olefin chain ends. In propylene / higher olefin copolymerization, the polymer chain can initiate propylene monomer growth, thereby producing a saturated chain end of the isobutyl chain. Alternatively, the polymer chain can initiate the growth of higher olefin monomers to produce higher olefin chain saturated ends.
“Isobutyl chain end” is defined as the end or end of the polymer, expressed as:

Ｍは、ポリマー鎖を表す。
「高級オレフィン鎖末端」は、次式で示す通りに表される、ポリマーの末端または終端と定義される。

M represents a polymer chain.
“Higher olefin chain end” is defined as the end or end of the polymer, expressed as:

Ｍは、ポリマー鎖を表し、ｎは、４〜４０から選択される整数である。
飽和鎖末端近くのコポリマーの構造は、使用されるモノマーのタイプおよび量、ならびに重合プロセス中の挿入方法に応じて変わり得る。いくつかの好ましい実施形態では、イソブチル鎖末端の４個の炭素内のポリマー構造は、次式の１つによって表される。

M represents a polymer chain, and n is an integer selected from 4 to 40.
The structure of the copolymer near the saturated chain ends can vary depending on the type and amount of monomer used and the method of insertion during the polymerization process. In some preferred embodiments, the polymer structure within the four carbons of the isobutyl chain end is represented by one of the following formulas:

Ｍは、ポリマー鎖の残りを表し、Ｃ_mは、重合高級オレフィンモノマーを表し、各Ｃ_mは、同じでも異なっていてもよく、ｍは、整数２〜３８である。

M represents the rest of the polymer chain, C _m represents a polymerized higher olefin monomer, each C _m may be the same or different, and m is an integer from 2 to 38.

The percentage of isobutyl chain ends used ¹³ C NMR (as described in the example section) and Resconi et al., J. Am. Chem. Soc. 114, 1992, pp. 1025- for 100% propylene oligomer. A chemical shift assignment of 1032 is used and for VT-HO copolymers is determined using the chemical shift assignment reported herein.

  “Ratio of isobutyl chain ends to allyl chain ends” is defined as the ratio of the percentage of isobutyl chain ends to the percentage of allyl chain ends. In some embodiments, the isobutyl chain end and the allyl chain end are less than 0.70: 1 (preferably less than 0.65: 1, less than 0.60: 1, less than 0.50: 1, or 0. Less than 25: 1). In some embodiments, the ratio of isobutyl chain end to allyl chain end ranges from about 0.01: 1 to about 0.70: 1 (preferably from about 0.05: 1 to about 0.65: 1 or 0.1: 1 to about 0.60: 1).

The VT-HO copolymer preferably has a Mn of 300 g / mol or more (preferably about 300-60,000 g / mol, 400-50,000 g / mol, preferably 500-500, as determined by ¹ H NMR. 35,000 g / mol, preferably 300 to 15,000 g / mol, preferably 400 to 12,000 g / mol, or preferably 750 to 10,000 g / mol). Furthermore, the desired molecular weight range may be any combination of any of the aforementioned molecular weight upper limits and any molecular weight lower limit. As used herein, Mn is the number average molecular weight (measured by ¹ H NMR unless otherwise stated), Mw is the weight average molecular weight (measured by gel permeation chromatography, GPC), Mz Is the z-average molecular weight (measured by GPC) and the molecular weight distribution (MWD, Mw / Mn) is defined as Mw (measured by GPC) divided by Mn (measured by GPC). Mn ( ¹ H NMR) is determined according to the NMR method of the example part below. Mn can also be determined using the GPC-DRI method described below. For the purposes of the claims, Mn is determined by ¹ H NMR.

In another embodiment, the VT-HO copolymer described herein has a Mw of 1,000 g / mol or more (preferably from about 1,000 to about 400,000 g / mol, preferably from about 2,000 to 300. 3,000 g / mol, preferably about 3,000 to 200,000 g / mol) (measured using the GPC-DRI method as described below), and / or about 1,700 to about 150,000 g / mol, or preferably Has a Mz in the range of about 800-100,000 g / mol and / or a Mw / Mn in the range of about 1.2-20 (or about 1.7-10, alternatively about 1.8-5.5). .
In certain embodiments, the VT-HO copolymer has a Mn of 300 g / mol or more (preferably about 300 to about 60,000 g / mol, about 400 to about 50,000 g / mol, about 500 to about 35,000 g / mol). About 300 to about 15,000 g / mol, about 400 to about 12,000 g / mol, or about 750 to about 10,000 g / mol), 1,000 Mw or more (preferably about 1,000 to about 400, 000 g / mol, about 2,000 to 300,000 g / mol, or about 3,000 to 200,000 g / mol), and about 1,700 to about 150,000 g / mol, or preferably about 800 to 100,000 g. Mz of / mol.

Mn, Mw, and Mz were measured by GPC-DRI method at a high temperature size exclusion chromatograph equipped with a differential refractive index detector (DRI) (one type of gel permeation chromatography from either Waters Corporation or Polymer Laboratories). , GPC)). 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 cited therein. Three 10 mm Mixed-B columns from Polymer Laboratories PLgel are used. The nominal flow rate is 0.5 cm ³ / min and the nominal injection volume is 300 μL. The various transfer lines, columns and differential refractometer (DRI detector) are placed in an oven maintained at 135 ° C. 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 and then through a 0.1 μm Teflon filter. The TBC is then degassed with an online degasser and then placed in the SEC. The polymer solution is prepared by placing the dry polymer in a glass container, adding the desired amount of TCB, and then heating the mixture at 160 ° C. with continuous stirring for about 2 hours. All quantities are measured gravimetrically. The TCB density (in units of mass / volume) used to represent the polymer concentration 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, and low concentrations are used for high molecular weight samples. Prior to running each sample, the DRI detector and injector are purged. Next, the flow rate in the apparatus is increased to 0.5 mL / min, the DRI is allowed to stand for 8-9 hours to stabilize, and then the first sample is injected. The concentration c at each point in the chromatogram is calculated from I _DRI, which is the DRI signal minus the baseline, using the following equation:
c = K _DRI I _DRI / (dn / dc)
_Where K _DRI is a constant determined by calibration of DRI and (dn / dc) is the increment of the refractive index of the system. For TCB, the refractive index n = 1.500 at 135 ° C. and λ = 690 nm. For purposes of the present invention and the appended claims, (dn / dc) = 0.104 for propylene polymers and 0.1 for others. The parameter units used throughout the description of the SEC method are as follows. The concentration is expressed in g / cm ³ , the molecular weight is expressed in g / mol, and the intrinsic viscosity is expressed in dL / g.

In embodiments herein, the VT-HO copolymer comprises from about 20 to about 99.9 mol% of at least one (preferably 2 or more, 3 or more, 4 or more, etc.) C ₅ -C ₄₀ (preferably _{C 5 -C 30, C 6 -C} 20 or C ₈ -C ₁₂₎ comprising a higher olefin monomer (preferably about 25 to about 90 mol%, from about 30 to about 85 mol%, from about 35 to about 80 mol% is about 40 to about 75 mol%, or about 50 to about 95 mol%). In other embodiments, VT-HO copolymers (preferably _{C 5 -C 30, C 6 -C} 20 or _{C 8 -C 12,) C 5} -C 40 exceeding 20 mol% containing higher olefin monomer (preferably Is greater than 30 mol%, greater than 40 mol%, greater than 45 mol%, greater than 50 mol%, greater than 65 mol%, greater than 75 mol%, or greater than 85 mol%). In still other embodiments, VT-HO copolymer comprises C ₅ -C ₄₀ higher olefin monomers of less than 99.9 mol% (preferably less than 85 mol%, less than 75 mol%, less than 65 mol%, less than 50 mol%, 35 mol% Less than or less than 25 mol%).

  In embodiments herein, the VT-HO copolymer comprises about 0.1 to about 80 mol% propylene (preferably about 5 mol% to about 70 mol%, about 10 to about 65 mol%, about 15 to about 55 mol%. , About 25 to about 50 mol%, or about 30 to about 80 mol%). In other embodiments, the VT-HO copolymer comprises more than 5 mol% propylene (preferably more than 10 mol%, more than 20 mol%, more than 35 mol%, more than 50 mol%, more than 65 mol%, or 75 mol% Over). In still other embodiments, the VT-HO copolymer comprises less than 80 mol% propylene (preferably less than 75 mol%, less than 70 mol%, less than 65 mol%, less than 50 mol%, less than 35 mol%, less than 20 mol%, or 10 mol%. Less than).

VT-HO copolymers herein comprise at least one C ₅ -C ₄₀ higher olefins and propylene. In some embodiments, the VT-HO copolymer comprises two or more different C ₅ -C ₄₀ higher olefin monomers, three or more different C ₅ -C ₄₀ higher olefin monomers, or four or more different C _5- Contains _C40 higher olefin monomer. In some embodiments, the VT-HO copolymer also includes ethylene and / or butene.

In embodiments where butene is a termonomer, the higher olefin copolymer has a Mn (determined by ¹ H NMR) of 300 g / mol or higher, preferably 300-60,000 g / mol, and (i) about 80 to about 99 at least one C ₄ olefin .9Mol% (preferably from about 85 to about 99.9 mol%, more preferably from about 90 to about 99.9 mol%), and (ii) from about 0.1 to about 20 mol% of propylene ( Preferably from about 0.1 to about 15 mol%, or from about 0.1 to about 10 mol%) and having at least 40% allyl chain ends (preferably at least 50% allyl chain ends and at least 60 allyl chain ends). %, At least 70% allyl chain ends, or at least 80% allyl chain ends), in some embodiments, isobutyl chain ends The ratio of allyl chain ends to less than 0.70: 1 (preferably less than 0.65: 1, less than 0.60: 1, less than 0.50: 1, or less than 0.25: 1); In embodiments, the ratio of allyl chain end to vinylidene group is greater than 2: 1 (preferably greater than 2.5: 1, greater than 3: 1, greater than 5: 1, or greater than 10: 1).
In a preferred embodiment, the VT-HO copolymer is less than 3% by weight relative to the weight of the copolymer (preferably less than 2%, less than 1%, less than 0.5%, less than 0.1%, or 0% by weight) 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 copolymer has at least 36 carbon atoms (preferably at least 51 carbon atoms, assuming 1 unsaturation per chain, as measured by ¹ H NMR. Or at least 50% by weight, preferably at least 75% by weight, preferably at least 90% by weight, based on the weight of the copolymer composition.

  In another embodiment, the VT-HO copolymer comprises less than 20 wt% dimer and trimer as measured by GC (preferably less than 10 wt%, preferably less than 10 wt%, based on the weight of the copolymer composition). Is less than 5% by weight, more preferably less than 2% by weight). “Dimer” (and “trimer”) is defined as a copolymer having two (or three) monomer units, where the monomer units may be the same or different from each other (here And “different” means that at least one carbon is different). The product was analyzed by GC (Agilent 6890N with automatic injector) using helium as the carrier gas at 38 cm / sec. 60 m long column (J & W Scientific DB-1, 60 m × 0.25 mm ID × 1.0 μm film thickness) equipped with a flame ionization detector (FID), injector temperature 250 ° C. and detection A vessel temperature of 250 ° C. was used. The sample was injected into the column, placed in an oven at 70 ° C. and then heated to 275 ° C. over 22 minutes (the ramp rate was maintained at 10 ° C./min up to 100 ° C. and 30 ° C./min up to 275 ° C. ). An internal standard, usually a monomer, is used to derive the amount of dimer or trimer product obtained. The yields of dimer and trimer products are calculated from the data recorded on the spectrometer. The amount of dimer or trimer product is calculated from the area under the relevant peak of the GC curve relative to the internal standard.

In another embodiment, the VT-HO copolymer is less than 25 ppm hafnium or zirconium, preferably less than 10 ppm hafnium or zirconium, preferably less than 5 ppm hafnium, relative to the yield of the polymer produced and the mass of catalyst used. Or it contains zirconium. 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. 633-644, using ICPES (Inductively Coupled Plasma Atomic Emission Spectrometry).
In still other embodiments, the VT-HO copolymer is liquid at 25 ° C.

In another embodiment, the VT-HO copolymer described herein has a melting temperature ( _Tm , DSC first melting) in the range of 60-130C, alternatively 50-100C. 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 copolymer is preferably 0 ° C. or less (determined by differential scanning calorimetry as described below), preferably −10 ° C. or less, more preferably −20 ° C. or less, more preferably −30 ° C. or less, more preferably Has a glass transition temperature (Tg) of −50 ° C. or lower. Melting temperature (T _m ) and glass transition temperature (Tg) are measured using differential scanning calorimetry (DSC) using a commercially available device such as TA Instruments 2920 DSC. Generally, 6-10 mg of sample that has been stored at room temperature for at least 48 hours is placed in an aluminum container, sealed, and mounted on 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 an endothermic melting transition is present, the onset of transition and peak temperature are analyzed. The reported melting temperature is the peak melting temperature from the first heating unless specified otherwise. For samples that exhibit multiple peaks, the melting point (or melting temperature) is defined as the peak melting temperature of the DSC melting curve (ie, associated with the maximum endothermic calorimetric response in that temperature range).

In another embodiment, the VT-HO copolymer described herein has a viscosity of greater than 1,000 cP, greater than 12,000 cP, or greater than 100,000 cP at 60 ° C. In other embodiments, the VT-HO copolymer 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, which is measured at an elevated temperature using a Brookfield viscometer.
In some embodiments, the VT-HO polymer is a propylene / hexene copolymer, a propylene / octene copolymer, a propylene / decene copolymer, a propylene / dodecene copolymer, a propylene / hexene / octene terpolymer, a propylene / hexene / decenter polymer, Propylene / hexene / dodecenter polymer, propylene / octene / decenter polymer, propylene / octene / dodecenter polymer, propylene / decene / dodecenter polymer, and the like.

Use of Vinyl-Terminated Higher Olefin Copolymers The vinyl-terminated polymers prepared herein can be functionalized by reacting heteroatom-containing groups with the allyl groups of the polymer, with or without a catalyst. . Examples include catalytic hydrosilylation, hydroformylation, hydroboration, epoxidation, hydration, dihydroxylation with or without an activator such as a free radical generator (eg, peroxide). , Hydroamination 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, J. Am. Chem. Soc., 1990, 112, pp. 7433-7434 and US patent application Ser. No. 12 / 487,739 filed Jun. 19, 2009. .
Functionalized polymers can be used in oil addition and many other applications. Preferred uses include lubricants and / or additives for fuel. 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. Certain 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 to prepare polymer products. Methods that can be used to prepare 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 the monomer, it is possible to form a homopolymer product of formulation (A) _n (where n is the degree of polymerization).
In other embodiments, the polymer product formed from a mixture of monomeric vinyl-terminated polymers can be a mixed polymer, each comprising two or more different repeating units. For example, if a vinyl terminated polymer (A) and a different vinyl terminated polymer (B) are copolymerized, the blend (A) _n (B) _m (n is the vinyl terminated polymer (A) present in the mixed polymer product. Is the number of molar equivalents, and m is the number of molar equivalents of vinyl terminated polymer (B) present in the mixed polymer product).

In still 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, compound (A) _n (B) _m (n is the number of molar equivalents of vinyl terminated polymer present in the mixed polymer product. , M is the number of molar equivalents of alkene present in the mixed polymer product).

In certain embodiments herein, the present invention provides 300 g / mol or more, preferably 300-60,000 g / mol (measured by ¹ H NMR), 400-50,000 g / mol, preferably 500-35, 000 g / mol, preferably 300 to 15,000 g / mol, preferably 400 to 12,000 g / mol, or preferably 750 to 10,000 g / mol, (i) about 20 to 99.9 mol% , about 25 to about 90 mol%, from about 30 to about 85 mol%, from about 35 to about 80 mol%, from about 40 to about 75 mol%, or from about 50 to about 95 mol% of at least one C ₅ -C ₄₀ higher olefin, and ( ii) about 0.1 to about 80 mol%, about 5 mol% to about 70 mol%, about 10 to about 65 mol%, about 15 to about 55 mol%, A VT-HO copolymer comprising about 25 to about 50 mol%, or about 30 to about 80 mol% propylene, wherein the allyl chain ends are at least 40%, allyl chain ends are at least 50%, allyl chain ends are at least 60%, Having at least 70% allyl chain ends, or at least 80% allyl chain ends, and in some cases the ratio of isobutyl chain ends to allyl chain ends is less than 0.70: 1, less than 0.65: 1, Less than 60: 1, less than 0.50: 1, or less than 0.25: 1, and in some cases the ratio of allyl chain end to vinylidene group is greater than 2: 1, greater than 2.5: 1, 3 Relates to a composition comprising a VT-HO copolymer that is greater than 1: 1, greater than 5: 1, or greater than 10: 1.

In another embodiment, the present invention has a Mn (measured by ¹ H NMR) of 300 g / mol or higher, preferably 300-60,000 g / mol, and (i) about 80 to about 99.9 mol%, preferably about 85 to about 99.9 mol%, more preferably from about 90 to about 99.9 mol% of at least one C ₄ olefin, and (ii) from about 0.1 to about 20 mol%, preferably from about 0.1 to about A VT-HO copolymer comprising 15 mol%, more preferably about 0.1 to about 10 mol% propylene, wherein the allyl chain ends are at least 40%, preferably allyl chain ends are at least 50%, preferably allyl chain ends. Some embodiments having at least 60%, preferably at least 70% allyl chain ends, or preferably at least 80% allyl chain ends, The ratio of isobutyl chain end to allyl chain end is less than 0.70: 1, less than 0.65: 1, less than 0.60: 1, less than 0.50: 1, or less than 0.25: 1 In a further embodiment, a VT-HO copolymer having an allyl chain end to vinylidene group ratio of greater than 2: 1, greater than 2.5: 1, greater than 3: 1, greater than 5: 1, or greater than 10: 1. It relates to using the composition comprising.
In some embodiments, the composition is a lubricant blend.
In some embodiments, the present invention relates to the use of the composition as a lubricant blend.

Process for Producing Vinyl End-Higher Olefin Copolymers The present invention also provides a method of (i) about 20 at a temperature of 0-250 ° C (preferably 35-150 ° C, preferably 40-120 ° C, preferably 45-80 ° C). to about 99.9 mol% of at least one C ₅ -C ₄₀ higher olefins and (preferably about 25 to about 90 mol%, from about 30 to about 85 mol%, from about 35 to about 80 mol%, from about 40 to about 75 mol%, or About 50 to about 95 mol%), (ii) about 0.1 to about 80 mol% propylene and (preferably about 5 mol% to about 70 mol%, about 10 to about 65 mol%, about 15 to about 55 mol%, about 25 to about 25 mol%) About 50 mol%, or about 30 to about 80 mol%), wherein the contacting comprises an activator, and And a process that takes place in the presence of a catalyst system comprising at least one metallocene compound represented by at least one of the following formulae:
(I)

式Ｉ
または（ｉｉ）

Formula I
Or (ii)

式ＩＩ
または（ｉｉｉ）

Formula II
Or (iii)

式ＩＩＩ
または（ｉｖ）

Formula III
Or (iv)

式ＩＶ

Formula IV

Wherein M is hafnium or zirconium, and each X is independently a hydrocarbyl radical having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halogen, a diene, an amine, Selected from the group consisting of phosphine, ether and combinations thereof (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, R ¹ may be the same or different as 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 from 1 to 8 carbon atoms, provided that at least 3 R ³ groups are not hydrogen and each R ⁴ Independently, hydrogen, or Is a substituted or unsubstituted hydrocarbyl group, a 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 a C ₁ -C ₈ alkyl group, provided that at least 7 R ⁷ groups are not hydrogen, R ₂ ^a T is a bridging group, and T is Group 14 element (preferably C, Si or Ge, preferably Si), each R ^a is independently hydrogen, halogen or C ₁ -C ₂₀ hydrocarbyl, and the two R ^a are aromatic May form a cyclic structure comprising a group, partially saturated, or saturated cyclic or fused ring system, provided that any two adjacent R groups may be fused rings or multicentric. May form an aromatic condensed ring system, and the ring is aromatic. May be partially saturated or saturated],
Or (v)

式Ｖ

Formula V

[Wherein M is hafnium or zirconium and each X is independently a hydrocarbyl radical having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, a diene, an amine. , Phosphine, ether and combinations thereof (two Xs may form part of a fused ring or ring system) and each R ⁸ is independently C ₁ -C ₁₀ An alkyl group, each R ⁹ is independently a C ₁ -C ₁₀ alkyl group, each R ¹⁰ is hydrogen, and each R ¹¹ , R ^12, and R ¹³ is independently hydrogen or substituted Or an unsubstituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group, and T is a bridging group (such as R ₂ ^a T described above), but any of adjacent R ¹¹ , R ^12, and R ¹³ groups Or a fused ring Others may form a multicentric fused ring system, the ring may be aromatic or partially saturated, or may be saturated,
Or (vi)

式ＶＩ

Formula VI

Wherein M is hafnium or zirconium, and each X is independently a hydrocarbyl radical having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halogen, a diene, an amine, Selected from the group consisting of phosphine, ether or combinations thereof, 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 , 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]

The present invention also provides (i) about 80 to about 99.9 mol%, preferably about 85 to about 99.9 mol%, more preferably about 90 to about 99.9 mol% of at least one C ₄ olefin, and (ii) A higher olefin copolymer comprising contacting about 0.1 to about 20 mol%, preferably about 0.1 to about 15 mol%, more preferably about 0.1 to about 10 mol% of propylene under polymerization conditions. A method of producing, wherein the contacting occurs in the presence of an activator and a catalyst system comprising at least one metallocene compound represented by at least one of the following formulae:
(I)

式Ｉ
または（ｉｉ）

Formula I
Or (ii)

式ＩＩ
または（ｉｉｉ）

Formula II
Or (iii)

式ＩＩＩ
または（ｉｖ）

Formula III
Or (iv)

式ＩＶ

Formula IV

Wherein M is hafnium or zirconium, and each X is independently a hydrocarbyl radical having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halogen, a diene, an amine, Selected from the group consisting of phosphine, ether and combinations thereof (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, R ¹ may be the same or different as 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 from 1 to 8 carbon atoms, provided that at least 3 R ³ groups are not hydrogen and each R ⁴ Independently, hydrogen, or Is a substituted or unsubstituted hydrocarbyl group, a 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 a C ₁ -C ₈ alkyl group, provided that at least 7 R ⁷ groups are not hydrogen, R ₂ ^a T is a bridging group, and T is Group 14 element (preferably C, Si or Ge, preferably Si), each R ^a is independently hydrogen, halogen or C ₁ -C ₂₀ hydrocarbyl, and the two R ^a are aromatic May form a cyclic structure comprising a group, partially saturated, or saturated cyclic or fused ring system, provided that any two adjacent R groups may be fused rings or multicentric. May form an aromatic condensed ring system, and the ring is aromatic. May be partially saturated or saturated],
Or (v)

式Ｖ

Formula V

[Wherein M is hafnium or zirconium and each X is independently a hydrocarbyl radical having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halide, a diene, an amine. , Phosphine, ether and combinations thereof (two Xs may form part of a fused ring or ring system) and each R ⁸ is independently C ₁ -C ₁₀ An alkyl group, each R ⁹ is independently a C ₁ -C ₁₀ alkyl group, each R ¹⁰ is hydrogen, and each R ¹¹ , R ^12, and R ¹³ is independently hydrogen or substituted Or an unsubstituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group, and T is a bridging group (such as R ₂ ^a T described above), but any of adjacent R ¹¹ , R ^12, and R ¹³ groups Or a fused ring Others may form a multicentric fused ring system, the ring may be aromatic or partially saturated, or may be saturated,
Or (vi)

式ＶＩ

Formula VI

Wherein M is hafnium or zirconium, and each X is independently a hydrocarbyl radical having 1 to 20 carbon atoms, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a halogen, a diene, an amine, Selected from the group consisting of phosphine, ether or combinations thereof, 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 , 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]

  In general, to produce the VT-HO copolymers described herein, propylene and a higher olefin monomer (hexene) are obtained by contacting (i) one or more higher olefin monomers with (ii) a propylene monomer. Or octene, etc.) can be copolymerized, and the contacting takes place in the presence of a catalyst system (comprising one or more metallocene compounds and one or more activators as described below). Other additives such as one or more scavengers, promoters, modifiers, reducing agents, oxidizing agents, hydrogen, aluminum alkyls or silanes can be used as desired. 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 0 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

Useful higher olefin monomers herein, C ₄ -C ₄₀ olefin, preferably a C ₅ -C ₃₀ olefins, preferably C ₆ -C ₂₀ olefins or preferably C ₈ -C ₁₂ olefins. When butene is a comonomer, the butene source may be a mixed butene stream containing various isomers of butene. 1-butene monomer is expected to be preferentially consumed by the polymerization process.

The higher olefin monomer may be linear or cyclic. The higher olefin cyclic olefins may be mono- or polycyclic with or without distortion, and may include heteroatoms and / or one or more functional groups. Exemplary higher olefin monomers include butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, cyclopentene, cycloheptene, cyclooctene, cyclododecene, 7-oxanorbornene, substituted derivatives thereof, and isomers thereof. Hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, cyclopentene, norbornene, and their respective homologues and derivatives Is included.
In some embodiments where butene is a comonomer, the butene source may be a mixed butene stream containing various isomers of butene. 1-butene monomer is expected to be preferentially consumed by the polymerization process. Such mixed butene streams are often waste streams resulting from the refining process, such as C ₄ distillate streams, and therefore may be substantially less expensive than pure 1-butene. Using a mixed butene stream is an economic benefit.

  The method of the present invention can be performed 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. Such a process can be carried out in a batch, semi-batch or continuous mode. Homogeneous polymerization methods and slurries are preferred. (A homogeneous polymerization process is defined as a process in which at least 90% by weight of the product is dissolved in the reaction medium). A homogeneous bulk method is particularly preferred. (Bulk method is defined as a method in which the monomer concentration in all feeds to the reactor is greater than 70% by volume). Alternatively, no or no solvent or diluent is present or added to the reaction medium (but a small amount of solvent or diluent used as a carrier for the catalyst system or other additive, or an amount commonly found in monomers) Solvents or diluents such as propane in propylene).

  In another embodiment, the method is a slurry method. As used herein, the term “slurry polymerization method” means a polymerization method in which a supported catalyst is used and monomers are polymerized on the supported catalyst particles. At least 95% by weight of the polymer product derived from the supported catalyst is present as solid particles in particulate form (not dissolved in the diluent).

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 , Methylcyclohexane, methylcycloheptane and mixtures thereof such as commercial products (Isopar ™); perhalogenated hydrocarbons such as perfluorinated C _4-10 alkanes, chlorobenzene, and aromatic and alkyl substituted aromatic compounds such as Benzene, toluene, mesitylene and xylene are included. Suitable solvents include ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Also included are liquid olefins that can act as monomers or comonomers. In a preferred embodiment, aliphatic hydrocarbon solvents 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 are used as solvents. In another embodiment, the solvent is not aromatic, preferably the aromatic is present in the solvent at less than 1 wt%, preferably 0.5 wt%, preferably 0 wt%, based on the weight of the solvent. To do.

In a preferred embodiment, the feed concentration of the solvent for the polymerization is 60% or less, preferably 40% or less, or preferably 20% or less, preferably 0% by volume, relative to the total volume of the feed stream. It is. Preferably the polymerization is carried out in a bulk process.
In some embodiments, the productivity is 4,500 g / mmol / hour or more, preferably 5,000 g / mmol / hour or more, preferably 10,000 g / mmol / hour or more, preferably 50,000 g / mmol / hour. It's over time. 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. Time, preferably at least 300,000 g / mmol / hour. In another embodiment, the activity of the catalyst is at least 50 g / mmol / hour, preferably 500 g / mmol / hour or more, preferably 5,000 g / mmol / hour or more, preferably 50,000 g / mmol / hour or more. . In another embodiment, the conversion of the olefin monomer is at least 10%, preferably more than 20%, preferably more than 30%, preferably more than 50%, preferably more than the polymer yield and the weight of monomers entering the reaction zone. Is 80% or more.

Preferred polymerizations can be carried out at any temperature and / or pressure suitable to obtain the desired VT-HO copolymer. Typical temperatures and / or pressures are, for example, temperatures in the range of about 0 ° C to 250 ° C (preferably 35 ° C to 150 ° C, 40 ° C to 120 ° C, 45 ° C to 80 ° C), and about 0.35 The pressure is in the range of -10 MPa (preferably 0.45-6 MPa or 0.5-4 MPa).
In a typical polymerization, the reaction run time ranges up to 300 minutes, preferably about 5 to 250 minutes, or preferably about 10 to 120 minutes.

In one preferred embodiment, hydrogen is introduced into 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. Present at -10 psig (0.7-70 kPa). In the system of the present invention, it has been found that the use of hydrogen can provide high activity without significantly impairing 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 one preferred embodiment, little or no alumoxane is used in the process for producing vinyl-terminated polymers. Preferably, the alumoxane is present at 0 mol%, or the alumoxane 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. To do.

In another embodiment, when an alumoxane is used to produce a vinyl terminated polymer, the alumoxane is pretreated to remove free alkyl aluminum compounds, particularly trimethylaluminum.
Further, in one preferred embodiment, the activator used herein to produce the vinyl terminated polymer is a bulky activator as defined herein and is separate.
In a preferred embodiment, little or no scavenger is used in the process for producing vinyl-terminated polymers. Preferably, the capture agent (such as trialkylaluminum) is present at 0 mol%, or the capture agent 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 agent metal to transition metal.

  In a preferred embodiment, the polymerization is carried out 1) at a temperature of 0-300 ° C (preferably 25-150 ° C, preferably 40-120 ° C, preferably 45-80 ° C), 2) at an atmospheric pressure of 10 MPa. Carried out (preferably 0.35 to 10 MPa, preferably 0.45 to 6 MPa, preferably 0.5 to 4 MPa), 3) carried out in an aliphatic hydrocarbon solvent (for example, isobutane, butane, pentane, isopentane, Hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic and cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof, wherein preferably the aromatics are in a solvent Less than 1% by weight, preferably less than 0.5% by weight, preferably 0% by weight, based on the weight of the solvent 4) the catalyst system used in the polymerization comprises less than 0.5 mol%, preferably 0 mol% alumoxane, or alternatively the alumoxane is less than 500: 1, preferably less than 300: 1, preferably 100: Present in a molar ratio of aluminum to transition metal of less than 1, preferably less than 1: 1, 5) polymerization occurs in one reaction zone, and 6) the productivity of the catalyst compound is at least 80,000 g / mmol / Time (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), 7 ) In some cases, there are no scavengers (such as trialkylaluminum compounds) For example, present at 0 mol%, or the scavenger is present in a molar ratio of scavenger metal to transition metal of less than 100: 1, preferably less than 50: 1, preferably less than 15: 1, preferably less than 10: 1. 8) In some cases, 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 a preferred embodiment, the catalyst system used in the polymerization contains only one type of catalyst compound. A “reaction zone” is also referred to as a “polymerization zone” and is a vessel in which polymerization is carried out, for example a batch reactor. If multiple reactors are used in a series or parallel arrangement, each reactor is considered a separate polymerization zone. For multi-stage polymerizations in both batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. In one preferred embodiment, the polymerization occurs within one reaction zone. Room temperature is 23 ° C. unless otherwise indicated.

Catalyst System In an embodiment herein, the present invention comprises a higher olefin comprising contacting propylene and a higher olefin monomer in the presence of an activator and a catalyst system comprising at least one metallocene compound shown below. It relates to a method of producing a copolymer.

In the description herein, a metallocene catalyst can be described as a catalyst precursor, precatalyst compound or 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 appended claims, where a catalyst system is described as including a stable neutral form of a component, the ionic form of the component is the form that reacts with the monomer to form a polymer. Those skilled in the art will fully appreciate this.

Metallocene catalysts have at least one π-bonded cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) and often have two π-bonded cyclopentadienyl or substituted moieties. Defined as a metal compound. This includes other π-bonded moieties such as indenyl or fluorenyl or derivatives thereof.
The metallocene, activator, optional coactivator, and optional support component of the catalyst system are discussed below.

(A) Metallocene component The term “substituted” means that the 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” has at least one hydrogen atom. A radical generated from carbon and hydrogen replaced by a heteroatom.
For purposes of this invention and the accompanying claims, “alkoxide” includes those where the alkyl group is a C ₁ -C ₁₀ hydrocarbyl. The alkyl group may be linear, branched or cyclic. Alkyl groups can be saturated or unsaturated. In some embodiments, the alkyl group can include 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 Formulas I, II, III, and IV.
(I)

式Ｉ
または（ｉｉ）

Formula I
Or (ii)

式ＩＩ
または（ｉｉｉ）

Formula II
Or (iii)

式ＩＩＩ
または（ｉｖ）

Formula III
Or (iv)

式ＩＶ

Formula IV

[Wherein M is hafnium or zirconium;
Each X is independently a hydrocarbyl radical having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halogen, diene, amine, phosphine, ether or combinations thereof, preferably methyl, ethyl, Selected from the group consisting of 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 3 Q are the same or different heteroatoms, or at least 4 Q are the same or different heteroatoms),
Each R ¹ is independently hydrogen or a 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 as or different from R ² ,
Each R ² is independently 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. Wherein at least one of R ¹ or R ² is not hydrogen, preferably both R ¹ and R ² are not 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 substituted or unsubstituted C ₁ -C _8. Straight chain alkyl groups, 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 groups are not hydrogen)
Each R ⁴ is independently hydrogen or has a substituted or unsubstituted hydrocarbyl group, heteroatom, or heteroatom-containing group, preferably 1-20 carbon atoms, preferably 1-8 carbon atoms a substituted or unsubstituted 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 (propylphenyl, etc.), phenyl Silyl, substituted silyl (such as CH ₂ SiR ′, where R ′ is a C ₁ -C ₁₂ hydrocarbyl such as methyl, ethyl, propyl, butyl, phenyl),
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 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; However, 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 each Cp ring of formula IV The R ⁷ groups in the 3 and 4 positions above are not hydrogen)
R ₂ ^a T is a bridging group, preferably T 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 two R ^a May form a cyclic structure comprising an aromatic, partially saturated or saturated cyclic or fused ring system;
In addition, however, any two adjacent R groups may form a fused ring or a multicentric fused ring system, which ring may be aromatic and partially saturated. Or may be saturated]

In another embodiment, at least one R ⁴ group is not hydrogen, or at least 2 R ⁴ groups are not hydrogen, or at least 3 R ⁴ groups are not hydrogen, or at least 4 R ⁴ groups in are not hydrogen or all R ⁴ groups are not hydrogen.

In some embodiments, the bridging group R ₂ ^a T includes at least one Group 13-16 atom, often referred to as a divalent moiety, such as, but not limited to, carbon, oxygen, Cross-linking groups containing at least one of nitrogen, silicon, aluminum, boron, germanium and tin atoms, or combinations thereof are included. Preferably, the bridging group T contains carbon, silicon or germanium atoms, most preferably T contains at least one silicon atom or at least one carbon atom. The bridging group T can also contain a substituent R ^* as defined below, including halogen and iron.

Non-limiting examples of substituents R ^* include hydrogen or a straight or branched alkyl radical, alkenyl radical, alkenyl radical, cycloalkyl radical, aryl radical, acyl radical, aryl radical, alkoxy radical, aryloxy radical, alkylthio 1 of a group selected from a radical, dialkylamino radical, alkoxycarbonyl radical, aryloxycarbonyl radical, carbamoyl radical, alkyl- or dialkyl-carbamoyl radical, acyloxy radical, acylamino radical, arylamino radical, or combinations thereof One or more are included. In a preferred embodiment, the substituent R ^* has a maximum of 50 non-hydrogen atoms, preferably 1-30 carbons, which may be substituted with halogens or heteroatoms and the like. 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 and the like are included. Other hydrocarbyl radicals include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and hydrocarbyl substituted organic metalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl, and the like; and tris (trifluoromethyl ) Halocarbyl-substituted organic metalloid radicals including silyl, methyl-bis (difluoromethyl) silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals including, for example, dimethylboron; and dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine Disubstituted pnictogen radicals, including methoxy, ethoxy, propoxy, phenoxy, methyl sulfide and ethyl sulfide It includes non-chalcogen radical. Non-hydrogen substituents R ^* include carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium, and other atoms, but not limited to vinyl-terminated ligands such as butane Olefins such as olefinically unsaturated substituents including -3-enyl, prop-2-enyl, hexa-5-enyl and the like are included. Also, in some embodiments, at least two R ^* groups, preferably two adjacent R groups, are taken together to form carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, or the like A ring structure having 3 to 30 atoms selected from the combination is formed. In other embodiments, R ^* may be a diradical that bonds to L at one end to form a carbon sigma bond with metal M. Particularly preferred R ^* substituents include C ₁ -C ₃₀ hydrocarbyl, heteroatoms, or heteroatom containing groups (preferably methyl, ethyl, propyl (including isopropyl, sec-propyl), butyl (t-butyl and sec-butyl). 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 of formula III or bridging groups T of 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 C-O —CR ′ ₂ , R ′ ₂ CR ′ ₂ C—O—CR ′ ₂ CR ′ ₂ , R ′ ₂ C—O—CR ′ ₂ CR ′ ₂ , R ′ ₂ C—O—CR ′ = CR ′ R ′ ₂ C—S—CR ′ ₂ , R ′ ₂ CR ′ ₂ C—S—CR ′ ₂ CR ′ ₂ , R ′ ₂ C—S—CR ′ ₂ CR ′ ₂ , R ′ ₂ C—S— 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 C-N = 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 ′ can be represented by _2, wherein, R 'is hydrogen or C ₁ -C ₂₀ containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituent, two or more adjacent and in some cases R ′ together can be substituted or unsubstituted Saturated, partially unsaturated, or aromatic, may form a cyclic or polycyclic substituent. Preferably, the bridging group comprises carbon such as dialkylsilyl or silica, and preferably the bridging group is CH ₂ , CH ₂ CH ₂ , C (CH ₃ ) ₂ , SiMe ₂ , SiPh ₂ , SiMePh, silylcyclobutyl ( 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.
(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-propyllindenyl) (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 tert-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 dicyclopropylsilyl bis (tetramethylcyclopentadienyl) hafnium dimethyl.

  In another embodiment, in the list of catalyst compounds above, “dimethyl” after the transition metal is dihalide (dichloride or difluoride) or bisphenoxide, particularly for use with an alumoxane activator. Is replaced by

式Ｖ (Ii) Formula V
In some embodiments, the metallocene can be represented by the following formula V:

Formula V

[Wherein M is hafnium or zirconium, preferably hafnium;
Each X independently comprises a substituted or unsubstituted hydrocarbyl radical having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether and combinations thereof it is selected from the group (two X may form part of a fused ring or ring system), preferably each X is independently selected from halide and 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 isomers thereof, preferably methyl, n-propyl or n-butyl, or 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 isomers thereof, preferably methyl, n-propyl or butyl, or 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 Yes,
T is a bridging group represented by the formula R ₂ ^a J, 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 two R ^a May form a cyclic structure comprising an aromatic, partially saturated or saturated cyclic or fused ring system;
In addition, however, any two adjacent R groups may form a fused ring or a multicentric fused ring system, which ring may be aromatic and partially saturated. Or may be saturated,
T may be a bridging group as defined above for R ₂ ^a T;
However, any of the adjacent R ¹¹ , R ¹² and R ¹³ groups may form a condensed ring or a polycentric condensed ring system, the ring may be aromatic, Saturated or may be saturated]

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

  In another embodiment, in the list of catalyst compounds above, “dimethyl” after the transition metal is dihalide (dichloride or difluoride) or bisphenoxide, particularly for use with an alumoxane activator. Is replaced by

  In certain embodiments, the metallocene compound is rac-dimethylsilylbis (2-methyl, 3-propylindenyl) hafnium dimethyl (VI), rac-dimethylsilylbis (2-methyl, represented by the formula: 3-propylindenyl) zirconium dimethyl (V-II).

（ｉｉｉ）式ＶＩ
いくつかの実施形態では、メタロセンは、次式ＶＩによって表すことができる。

(Iii) Formula VI
In some embodiments, the metallocene can be represented by the following formula VI:

式ＶＩ

Formula VI

[Wherein M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl radicals 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 , preferably both are methyl;

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 1 to 6 carbon atoms, preferably substituted or unsubstituted C ₁ -C ₈ linear hydrocarbyl groups, preferably methyl, ethyl, propyl, butyl, pentyl, Hexyl, heptyl or octyl, provided that at least three of the R ^{24 to} R ²⁸ groups are not hydrogen (or four of the R ^{24 to} R ²⁸ groups are not hydrogen, or alternatively, R ^{24 to} R ²⁸ groups. Are not hydrogen), 1) preferably all 5 groups of R ^{24 to} R ²⁸ are methyl, or 2) 4 of R ^{24 to} R ²⁸ groups are not hydrogen and R ²⁴ At least one of to R ²⁸ groups, C ₂ -C ₈ substituted or Substituted hydrocarbyl (preferably at least two R ²⁴ to R ²⁸ groups, 3, 4 or 5 is a C ₂ -C ₈ substituted or unsubstituted hydrocarbyl)
In one embodiment, R ¹⁵ and R ¹⁷ are methyl groups, R ¹⁶ is hydrogen, R ¹⁸ -R ²³ are all hydrogen, R ²⁴ -R ²⁸ are all methyl groups, Each X is a methyl group.

Catalyst compounds particularly useful in the present invention include (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-Buchirubenzo [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- flop (Lopyl) (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-Buchirubenzo [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- propyl-benzo [ ] Indenyl) HfMe _2, (CPME ₄ n-butyl) (1-n-propyl, 3-methylbenzo [e] indenyl) HfMe _2, (CPME ₄ n-butyl) (1-methyl -3-n-Buchirubenzo [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 analogs.

In another embodiment, in the list of catalyst compounds above, “dimethyl” (Me ₂ ) after the transition metal is a dihalide (dichloride or difluoride, especially for use with an alumoxane activator. ) Or bisphenoxide.

(B) Activator component of the catalyst system The terms "cocatalyst" and "activator" are used interchangeably herein to convert a neutral catalyst compound into a catalytically active cationic catalyst compound. Defined as any compound that can be activated to activate any one of the aforementioned catalyst compounds. Non-limiting activators include, for example, alumoxanes, aluminum alkyls, ionizing activators, which can be neutral or ionic, and conventional cocatalysts. Preferred activators generally include an alumoxane compound, a modified alumoxane compound, and an anion precursor compound to be ionized, which extract a single σ-bonded reactive metal ligand to form a metal Provide a non-coordinating or weakly coordinating anion that renders the complex cationic and balances the charge.

In one embodiment, the alumoxane activator is utilized as an activator in the catalyst composition. Alumoxane is generally, -Al (R ¹⁾ -O- subunits (R ¹ is an alkyl group) oligomeric compounds containing. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, especially when the ligand to be withdrawn is an alkyl, halide, alkoxide or amide. Mixtures of different alumoxanes and modified alumoxanes can also be used. It may be preferred to use a visually clear methylalumoxane. The cloudy or gelled alumoxane can be filtered to produce a clear solution, or the cloudy solution can be decanted to a clear alumoxane. Another alumoxane is a modified methylalumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trademark Modified Metalluxane type 3A, covered by US Pat. No. 5,041,584 ).

  When the activator is an alumoxane (modified or unmodified), in some embodiments, the maximum amount of activity that results in a 5000-fold molar excess of Al / M (per metal catalyst site) relative to the catalyst precursor. An agent is selected. The minimum molar ratio of activator to catalyst precursor is 1: 1. Other 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 another embodiment, little or no alumoxane is used in the method of producing the VT-HO copolymer. Preferably, the alumoxane is present at 0 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 another embodiment, when alumoxane is used to produce the VT-HO copolymer, the alumoxane is pretreated to remove free alkylaluminum compounds, particularly trimethylaluminum. Further, in a preferred embodiment, the activator used herein to produce the VT-HO copolymer is bulky and distinct as defined herein.

  Aluminum alkyl or organoaluminum compounds that can be used as coactivators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like.

Activating agents to be ionized The scope of the present invention includes tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, trisperfluorophenyl boron metalloid precursor or trisperfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane Neutral or ionic, ionized or stoichiometric activation, such as anions (WO 98/43983), boric acid (US Pat. No. 5,942,459), or combinations thereof The use of agents is included. The scope of the present invention also includes the use of neutral or ionic activators alone or in combination with alumoxanes or modified alumoxane activators. Preferred activators are ionic activators.
Examples of neutral stoichiometric activators include trisubstituted boron, tellurium, aluminum, gallium and indium or mixtures thereof. The three substituents are each 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, alkenyl compounds and mixtures thereof, preferably 1-20 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 (including substituted aryl) having 3 to 20 carbon atoms . More preferably, the three groups are alkyl having 1 to 4 carbon groups, phenyl, naphthyl or mixtures 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 can contain active protons, or is associated with the remaining ions of the compound to be ionized but not coordinated, or very loosely coordinated Can contain some other cations. Such compounds are disclosed in European Patent Application Nos. 0 570 982, 0 520 732, 0 495 375, 0 500 944, 0 277 003, 0 277 004. U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 No. 5,502,124, and US application Ser. No. 08 / 285,380 filed Aug. 3, 1994, all of which are fully incorporated herein by reference.
Ionic catalysts can pre-react transition metal compounds with certain neutral Lewis acids such as B (C ₆ F ₆ ) ₃ , which neutral Lewis acids are hydrolyzable of the transition metal compounds. Reaction with ligand (X) forms an anion such as ([B (C ₆ F ₅ ) ₃ (X)] ⁻ ), which stabilizes the cationic transition metal species generated from the reaction. . The catalyst can be prepared with an activator component that is an ionic compound or composition, and is preferably prepared as such.

  Compounds useful as activator components in the preparation of the ionic catalyst system used in the process of the present invention are preferably cations that are Bronsted acids capable of donating protons and active catalyst species (Group 4 cations). And a relatively large (bulky) compatible non-coordinating anion formed when the two compounds are combined, said anion being olefinic, divalent It is very easily replaced by olefinic and acetylenically unsaturated substrates or other neutral Lewis bases such as ethers, amines. The following two types of compatible non-coordinating anions are disclosed in European Patent Application Nos. 0 277 003 and 0 277 004 published in 1988. 1) An anionic coordination complex containing a plurality of lipophilic radicals that are covalently coordinated to and shield the core metal or metalloid core having a charge, and 2) carborane, metallacarborane And anions containing multiple boron atoms, such as borane.

In one preferred embodiment, the stoichiometric activator comprises cation and anion components and can be represented by the following formula:
(L−H) _d ⁺ (A ^d− ) (14)
Where L is a neutral Lewis base, H is hydrogen, (L—H) ⁺ is a Bronsted acid, A ^d− is a non-coordinating anion with charge d−, d Is 1, 2 or 3.
The cationic component (L—H) _d ⁺ may include a Bronsted acid such as a protonated Lewis base, which is an alkyl of a metallocene catalyst precursor of a bulky ligand containing a transition metal. Or a moiety such as aryl can be protonated, thereby resulting in a cationic transition metal species.

The activated cation (L—H) _d ⁺ may be a Bronsted acid that can donate a proton to the transition metal catalyzed precursor, thereby providing a transition metal cation, including ammonium, Oxonium, phosphonium, silylium and mixtures thereof, preferably methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromoN, N -Ammonium of dimethylaniline, p-nitro-N, N-dimethylaniline; phosphonium derived from triethylphosphine, triphenylphosphine and diphenylphosphine; ethers such as dimethyl ether diethyl ether, Rahidorofuran and dioxane-derived oxonium; thioethers such as diethyl thioethers and tetrahydrothiophene-derived sulfonium, and mixtures thereof.

Anionic components A ^d− include those having the formula [M ^{k +} Q _n ] ^d− , where k is 1, 2 or 3, and n is 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 a hydride, bridged or unbridged dialkylamide , Halides, alkoxides, aryloxides, hydrocarbyls, substituted hydrocarbyls, halocarbyls, substituted halocarbyls and halosubstituted hydrocarbyl radicals, wherein Q has a maximum of 20 carbon atoms, provided that Q is halogen at a rate of 1 or less It is a monster. Preferably, each Q is a fluorinated hydrocarbyl group having from 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is pentafluoryl. An aryl group. Suitable A ^d-example, diboron compounds as disclosed in U.S. Patent No. 5,447,895 also included, this document is fully incorporated herein by reference.

  Illustrative but non-limiting 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, Ν, Ν-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate N, N-dimethyl- (2,4,6-trimethylanilinium) tetraphenylborate, tropylium tetraphenylborate, triphenylcarbeniumtetraphenylborate Triphenylphosphonium tetraphenylborate, triethylsilylium tetraphenylborate, benzene (diazonium) tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (penta Fluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, Ν, Ν-dimethylanilinium tetrakis (pentafluorophenyl) borate, Ν, Ν-Diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl Ru- (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, tropylium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluoro) Phenyl) 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) L) 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, Ν, Ν-diethylanilinium tetrakis- (2,3,4,6-tetrafluorophenyl) borate N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate, tropylium tetrakis- (2,3,4,6-tetrafluoro Phenyl) borate, triphenylcarbenium tetrakis- (2,3,4,6-tetrafluorophenyl) Rate,

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, tripropylammonium tetrakis (perfluoronaphthyl) borate, tri (n-butyl) ammonium tetrakis (Perfluoronaphthyl) borate, tri (t-butyl) ammonium tetrakis (perfluoronaphthyl) borate, Ν, Ν-dimethylanilinium tetrakis (perfluoronaphthyl) ) Borate, Ν, Ν-diethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluoronaphthyl) borate, tropylium tetrakis (perfluoronaphthyl) ) Borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylphosphonium tetrakis (perfluoronaphthyl) borate, triethylsilyl tetrakis (perfluoronaphthyl) borate, benzene (diazonium) tetrakis (perfluoronaphthyl) borate, trimethyl Ammonium 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, Ν, Ν-dimethylanilinium tetrakis (perfluorobiphenyl) ) Borate, Ν, Ν-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) borate, triethylsilylium te Lakis (perfluorobiphenyl) borate, benzene (diazonium) tetrakis (perfluorobiphenyl) borate, trimethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triethylammonium tetrakis (3,5-bis (trifluoro) Methyl) 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, Ν, Ν-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, Ν, Ν-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 (trifluoromethyl) 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, and additional trisubstituted phosphonium salts such as tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate and tri (2,6-dimethylphenyl) phosphonium tetrakis (penta Fluorophenyl) borate.

Most preferably, the ionic stoichiometric activator (L—H) _d ⁺ (A ^d− ) is N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium. Tetrakis (perfluorobiphenyl) borate, Ν, Ν-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylcarbenium tetrakis (per Fluorobiphenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, or triphenylcarbenium tetrakis (perfluorophenyl) borate.
In one embodiment, an activation method is also contemplated that uses an ionizing ionic compound that does not contain an active proton, but can generate bulky ligand metallocene-catalyzed cations and their non-coordinating anions. This compound is described in European Patent Application Nos. 0 426 637, 0 573 403 and US Pat. No. 5,387,568, all of which are incorporated herein by reference. It is.

  The term “non-coordinating anion” (NCA) is an anion that does not coordinate to the cation or is very weakly coordinated with the cation, thereby being kept in a state that is highly amenable to replacement by a neutral Lewis base. Means. A “compatible” non-coordinating anion is an anion that does not degrade to neutrality when the initially formed complex degrades. In addition, the anion prevents these substituents or fragments from being transferred to the cation so that the anionic substituent or fragment forms a neutral 4-coordinate metallocene compound and an anion-derived neutral by-product. . The useful non-coordinating anion of the present invention stabilizes the metallocene cation in the sense that it keeps the ionic charge of the metallocene cation at +1 equilibrium, and is also highly displaced by ethylenic or acetylenically unsaturated monomers during polymerization. It is a compatible anion that is kept in a state of being easily deformed. In addition to these activator compounds or cocatalysts, scavengers such as tri-isobutyl aluminum or tri-octyl aluminum are used.

  The process of the present invention is also initially a neutral Lewis acid, but reacts with a compound of the present invention to form a cationic metal complex and a non-coordinating anion, or a cocatalytic compound or activity that forms a zwitterionic complex. An agent compound can be used. For example, tris (pentafluorophenyl) boron or aluminum acts to abstract hydrocarbyl or hydride ligands to produce the cationic metal complexes of the invention and stabilizing non-coordinating anions. For examples of similar Group 4 metallocene compounds, see EP 0427 697 and 0 520 732. See also the methods and compounds of European Patent Application 0 495 375. See US Pat. Nos. 5,624,878 and 5,486,632 and 5,527,929 for the formation of zwitterionic complexes using similar Group 4 compounds. .

Another suitable activated cocatalyst that forms ions comprises a salt of a cationic oxidant and a compatible non-coordinating anion and is represented by the following formula:
(OX ^{e +} ) _d (A ^d- ) _e (16)
Where OX ^{e +} is a cationic oxidant with charge e +, e is 1, 2 or 3, A ^d− is a non-coordinating anion with charge d−, d is 1, 2 or 3. Examples of cationic oxidizing agents include ferrocenium, hydrocarbyl substituted ferrocenium, Ag ⁺ or Pb ⁺² . A preferred embodiment of A ^d- is an anion already defined for activators containing Bronsted acids, in particular tetrakis (pentafluorophenyl) borate.

  A common ratio of NCA activator (or non-alumoxane activator) to catalyst is a 1: 1 molar ratio. Other 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.

［式中、
各Ｒ₁は、独立に、ハロゲン化物、好ましくはフッ化物であり、
各Ｒ₂は、独立に、ハロゲン化物、Ｃ₆−Ｃ₂₀置換芳香族ヒドロカルビル基、または式−Ｏ−Ｓｉ−Ｒ_a（式中、Ｒ_aは、Ｃ₁−Ｃ₂₀ヒドロカルビルまたはヒドロカルビルシリル基である）のシロキシ基であり（好ましくはＲ₂は、フッ化物または全フッ素置換フェニル基である）、
各Ｒ₃は、ハロゲン化物、Ｃ₆−Ｃ₂₀置換芳香族ヒドロカルビル基、または式−Ｏ−Ｓｉ−Ｒ_a（式中、Ｒ_aは、Ｃ₁−Ｃ₂₀ヒドロカルビルまたはヒドロカルビルシリル基である）のシロキシ基であり（好ましくはＲ₃は、フッ化物またはＣ₆全フッ素置換芳香族ヒドロカルビル基である）、Ｒ₂およびＲ₃は、１つまたは複数の飽和または不飽和の、置換または非置換の環を形成することができ（好ましくはＲ₂およびＲ₃は、全フッ素置換フェニル環を形成する）、
Ｌは、中性ルイス塩基であり、（Ｌ−Ｈ）⁺は、ブレンステッド酸であり、ｄは、１、２または３であり、
アニオンは、１０２０ｇ／ｍｏｌを超える分子量を有し、
Ｂ原子上の置換基の少なくとも３個は、それぞれ、２５０立方Åを超える、あるいは３００立方Åを超える、あるいは５００立方Åを超える分子体積を有する］ Bulky activator “Bulky activator” as used herein refers to an anionic activator represented by the formula:

[Where:
Each R ₁ is independently a halide, preferably a 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 hydrocarbylsilyl group. A siloxy group (preferably R ₂ is a fluoride or a perfluorinated phenyl group),
Each R ₃ is 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 hydrocarbylsilyl group. A siloxy group (preferably R ₃ is a fluoride or C ₆ perfluorinated aromatic hydrocarbyl group) and R ₂ and R ₃ are one or more saturated or unsaturated, substituted or unsubstituted A ring can be formed (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;
The anion has a molecular weight greater than 1020 g / mol;
At least three of the substituents on the B atom each have a molecular volume of more than 250 cubic cubic, or more than 300 cubic cubic, or more than 500 cubic cubic]

  “Molecular volume” is used herein to resemble the spatial steric bulk of an activator molecule in solution. When comparing substituents having different molecular volumes, substituents having a smaller molecular volume can be considered “not bulky” compared to substituents having a larger molecular volume. Conversely, a substituent with a larger molecular volume can be considered “bulky” than a substituent with a smaller molecular volume.

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 as it is. Molecular volume (MV) (unit cubic Å) the formula MV = 8.3V _S (V _S is scaled the volume) is calculated using. 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 following table of relative volumes. For fused rings, V _S decreases by 7.5% per fused ring.

本明細書に適した活性化剤の例示的な嵩高い置換基、ならびにそれらのそれぞれのスケーリングされた体積および分子体積を、以下の表に示す。点線の結合は、先の一般式と同様に、ホウ素との結合を示している。

Illustrative bulky substituents of activators suitable herein and their respective scaled and molecular volumes are shown in the table below. The dotted bond indicates a bond with boron as in the general formula.

Exemplary bulky activators useful in the catalyst systems herein include 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, Ν, Ν-dimethylanilinium tetrakis (perfluoronaphthyl) borate, Ν, Ν- Diethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluoronaphthyl) borate, tropyliumtetra Su (perfluoronaphthyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylphosphonium tetrakis (perfluoronaphthyl) borate, triethylsilylium tetrakis (perfluoronaphthyl) borate, benzene (diazonium) tetrakis (perfluoro) Naphthyl) 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, Ν, -Dimethylanilinium tetrakis (perfluorobiphenyl) borate, Ν, Ν-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) 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] and U.S. Patent No. 7, It includes the type disclosed in EP 97,653.

Combinations of Activators The scope of the present invention includes that the catalyst compound can be combined with one or more activators or activation methods as described above. For example, combinations of activators include US Pat. Nos. 5,153,157, 5,453,410, EP 0 573 120, PCT International Publication Nos. 94/07928 and 95. / 14044. All these documents discuss the use of alumoxane in combination with an ionizing activator.

(Iii) Optional coactivators and scavengers In addition to these activator compounds, scavengers or coactivators can also 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 embodiments herein, the catalyst system can include an inert support material. Preferably, the support material is a porous support material such as talc and inorganic oxides. Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support materials, etc., or mixtures thereof.

Preferably, the support material is an inorganic oxide in micronized form. Inorganic oxide materials suitable for use herein in metallocene catalyst systems 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 support materials can also be used, for example micronized functionalized polyolefins such as micronized polyethylene. Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolite, talc, clay and the like. A combination of these support materials, for example, silica-chromium, silica-alumina, silica-titania and the like can also be used. Preferred support materials include Al ₂ O ₃ , ΖrO ₂ , SiO ₂ and combinations thereof, more preferably SiO ₂ , Al ₂ O ₃ , or SiO ₂ / Al ₂ O ₃ .

Preferably the support material, most preferably the 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 about 5 to about 500 μm. Having an average particle size in the range of 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. It is. Most preferably, the surface area of the support material is in the range of about 100 to about 400 m ² / g, the pore volume is about 0.8 to about 3.0 cc / g, and the average particle size is about 5 to about 100 μm. It is. The average pore size of the support material useful in the present invention is in the range of 10 to 1000 〜, preferably 50 to about 500 Å, most preferably 75 to about 350 Å. In some embodiments, the support material is high surface area amorphous silica (surface area = 300 m ² / gm, pore volume 1.65 cm ³ / gm), examples of R. Commercially available from Davison Chemical Division of Grace and Company under the trademarks DAVISON 952 or DAVISON 955. In other embodiments, DAVIDSON 948 is used.

  The support material should be dry, i.e. unabsorbed. The support material can be dried by heating or baking 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, for about 1 minute to about 100 hours, about 12 hours to about 72 hours, or Heat for about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups in order to produce 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 Generating a Supported Catalyst System A support material having reactive surface groups, generally hydroxyl groups, is slurried in 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 about 25 ° C to about 60 ° C, preferably room temperature. . Contact times generally range from about 0.5 hours to about 24 hours, from about 0.5 hours to about 8 hours, or from about 0.5 hours to about 4 hours.
A suitable nonpolar solvent is a material that at least partially dissolves all of the reactants used herein, ie, the activator and metallocene compound, and renders it liquid at the reaction temperature. Preferred non-polar solvents are alkanes such as isopentane, hexane, n-heptane, octane, nonane and decane, but use various other materials including cycloalkanes such as cyclohexane, aromatics such as benzene, toluene and ethylbenzene. You can also.

  In embodiments herein, the support material is contacted with a solution of a metallocene compound and an activator to form a supported polymerization catalyst such that reactive groups on the support material are titrated. The contact time of the metallocene compound, the activator and the support material is the time required for titration of reactive groups on the support material. “Titrate” 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%. means. The concentration of surface reactive groups can be determined depending on the firing temperature and the type of support material used. The temperature at which the support material is fired affects the number of surface reactive groups on the support material that are available for reaction with the metallocene compound and the activator, and the higher the drying temperature, the fewer the sites. For example, if the support material is silica, it is generally fluidized with nitrogen prior to use in the first catalytic system synthesis step and dehydrated by heating at about 600 ° C. for 16 hours, generally about 0.7 per gram. A surface hydroxyl group concentration of millimolar (mmol / gm) is achieved. Thus, the exact molar ratio of activator to surface reactive groups on the carrier will vary. Preferably, this molar ratio is individual in each case to ensure that only a limited amount of activator is added to the solution so that no excess activator is deposited on the support material in the solution. It is decided according to.

The amount of activator that deposits on the support material without leaving an excess in solution is detected as a solution in the solvent by any technique known in the art, such as, for example, ¹ H NMR. Until done, the activator can be determined in any conventional manner by adding the slurry to the carrier slurry in the solvent while simultaneously stirring the slurry. For example, for a silica support 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 the silica is about 0.5: 1 to about The amount is 4: 1, preferably about 0.8: 1 to about 3: 1, more preferably about 0.9: 1 to about 2: 1, and most preferably about 1: 1. The amount of B on silica was determined by JW Olesik, "Encyclopedia of Materials Characterization, CR Brundle, CA Evans, Jr. and S. Wilson, eds., Butterworth-Heinemann, Boston, Mass., 1992, pp. 633-644. It can be determined by using ICPES (Inductively Coupled Plasma Emission Spectroscopy) described in “Inductively Coupled Plasma-Optical Emission Spectroscopy”. In another embodiment, it is possible to add an amount of activator that exceeds the amount deposited on the support, and then remove any excess activator, for example by filtration and washing. It is.

In another embodiment, the invention relates to:
1. 300 g / mol or more of Mn (measured by ¹ H NMR), preferably 300 to 60,000 g / mol, preferably 400 to 50,000 g / mol, preferably 500 to 35,000 g / mol, preferably 300 to Having a Mn of 15,000 g / mol, preferably 400-12,000 g / mol, or preferably 750-10,000 g / mol;

(I) at least one C ₅ -C ₄₀ higher olefins of from about 20 to about 99.9 mol%, from about 25 to about 90 mol%, from about 30 to about 85 mol%, from about 35 to about 80 mol%, from about 40 to about 75 mol% Or about 50 to about 95 mol% of at least one C ₅ -C ₄₀ higher olefin, preferably two or more C ₅ -C ₄₀ higher olefins (preferably 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), and ( ii) about 0.1 to about 80 mol%, about 5 m l% ~ about 70 mol%, including about 10 to about 65 mol%, from about 15 to about 55 mol%, from about 25 to about 50 mol%, or about 30 to about 80 mol% of propylene,
At least 40% allyl chain end, at least 50% allyl chain end, at least 60% allyl chain end, at least 70% allyl chain end, or at least 80% allyl chain end, at least 90% allyl chain end, allyl Having at least 95% chain ends;
In some embodiments, the ratio of isobutyl chain end to allyl chain end is less than 0.70: 1, less than 0.65: 1, less than 0.60: 1, less than 0.50: 1, or 0.25. Is less than 1:
In other embodiments, the higher olefin copolymer has an allyl chain end to vinylidene group ratio of greater than 2: 1, greater than 2.5: 1, greater than 3: 1, greater than 5: 1, or greater than 10: 1.
2. Paragraph 1, comprising at least 50% by weight of olefins having at least 36 carbon atoms, based on the weight of the copolymer composition, assuming 1 unsaturation per chain, as determined by ¹ H NMR Higher olefin copolymer.
3. Paragraph 1 and comprising less than 20%, preferably less than 10%, preferably less than 5%, or more preferably less than 2% by weight of dimer and trimer relative to the weight of the copolymer composition; 2. A higher olefin copolymer.

4. A paragraph according to paragraphs 1-3 having a viscosity of greater than 1,000 cP, greater than 12,000 cP, or greater than 100,000 cP (or less than 200,000 cP: 1, less than 50,000 cP, or less than 100,000 cP) at 60 ° C. Higher olefin copolymer.
5. More than 300 g / mol Mn (measured by ¹ H NMR), preferably 300 to 60,000 g / mol Mn, (i) about 80 to about 99.9 mol%, preferably about 85 to about 99 .9Mol%, more preferably from about 90 to about 99.9 mol% of at least one C ₄ olefin, and (ii) from about 0.1 to about 20 mol%, preferably from about 0.1 to about 15 mol%, more preferably About 0.1 to about 10 mol% propylene, at least 40% allyl chain ends, preferably at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, or allyl chains Having at least 80% ends, at least 90% allyl chain ends, and at least 95% allyl chain ends;
In some embodiments, the ratio of isobutyl chain end to allyl chain end is less than 0.70: 1, less than 0.65: 1, less than 0.60: 1, less than 0.50: 1, or 0.25. In a further embodiment, the ratio of allyl chain end to vinylidene group is greater than 2: 1, greater than 2.5: 1, greater than 3: 1, greater than 5: 1, or greater than 10: 1. Higher olefin copolymer.
6). (I) about 20 to about 99.9 mol% (preferably about 25 to about 90 mol%, about 30 to about 85 mol%, about 35 to about 80 mol%, about 40 to about 75 mol%, or about 50 to about 95 mol%) At least one C ₅ -C ₄₀ higher olefin, preferably two or more C ₅ -C ₄₀ higher olefins (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)

(Ii) about 0.1 to about 80 mol% (preferably about 5 mol% to about 70 mol%, about 10 to about 65 mol%, about 15 to about 55 mol%, about 25 to about 50 mol%, or about 30 to about 80 mol% Propylene)
(Iii) A process for producing a higher olefin copolymer of paragraphs 1-4, optionally comprising contacting with ethylene,
The process wherein the contacting occurs in the presence of an activator and a catalyst system comprising at least one metallocene compound represented by at least one of the following formulae:
(I)

式Ｉ
または（ｉｉ）

Formula I
Or (ii)

式ＩＩ
または（ｉｉｉ）

Formula II
Or (iii)

式ＩＩＩ
または（ｉｖ）

Formula III
Or (iv)

式ＩＶ
［式中、
Ｍは、ハフニウムまたはジルコニウムであり、
各Ｘは、独立に、１〜２０個の炭素原子を有するヒドロカルビルラジカル、水素化物、アミド、アルコキシド、スルフィド、リン化物、ハロゲン、ジエン、アミン、ホスフィン、エーテルおよびその組合せからなる群から選択され（２個のＸは、縮合環または環系の一部を形成していてもよい）、
各Ｑは、独立に、炭素またはヘテロ原子であり、
各Ｒ¹は、独立に、Ｃ₁−Ｃ₈アルキル基であり、Ｒ¹は、Ｒ²と同じでも異なっていてもよく、

Formula IV
[Where:
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl radicals having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers and combinations thereof ( 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, 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 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),
Each R ^a is independently hydrogen, halogen or C ₁ -C ₂₀ hydrocarbyl;
The two R ^a may form a cyclic structure comprising an aromatic, partially saturated or saturated cyclic or fused ring system, but in addition any two adjacent R The group may form a fused ring or a polycentric fused ring system, which ring may be aromatic and 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 radicals having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers and combinations thereof. (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 preferably a bridging group represented by the formula R ₂ ^a J, J is a group 14 element (preferably C, Si or Ge);
Each R ^a is independently hydrogen, halogen or C ₁ -C ₂₀ hydrocarbyl;
The two R ^a may form a cyclic structure comprising an aromatic, partially saturated or saturated cyclic or fused ring system, but in addition any two adjacent R The group may form a fused ring or a polycentric fused ring system, the ring may be aromatic, partially saturated or saturated,
However, any of the adjacent R ¹¹ , R ¹² and R ¹³ groups may form a condensed ring or a polycentric condensed ring system, the ring may be aromatic, Saturated, or may be saturated],
Or (vi)

式ＶＩ

Formula VI

[Where:
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl radicals 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 of a substituted or unsubstituted hydrocarbyl group having carbon atoms, C ₅ -C ₄₀ higher olefins are 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]
7). (I) from about 80 to about 99.9 mol%, preferably from about 85 to about 99.9 mol%, and more is about 90 to about 99.9 mol% of at least one C ₄ olefin (preferably preferably comprises 1-butene Mixed butene streams are used)
(Ii) about 0.1 to about 20 mol%, preferably about 0.1 to about 15 mol%, more preferably about 0.1 to about 10 mol% of propylene;
(Iii) A process for producing a higher olefin copolymer of paragraphs 1-4, optionally comprising contacting with ethylene,
The process wherein the contacting occurs in the presence of an activator and a catalyst system comprising at least one metallocene compound represented by at least one of the following formulae:
(I)

式Ｉ
または（ｉｉ）

Formula I
Or (ii)

式ＩＩ
または（ｉｉｉ）

Formula II
Or (iii)

式ＩＩＩ
または（ｉｖ）

Formula III
Or (iv)

式ＩＶ

Formula IV

[Where:
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl radicals having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halogens, dienes, amines, phosphines, ethers and combinations thereof ( 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, 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 7 R ⁷ groups are not hydrogen,
R ₂ ^a T is a bridging group, T is a Group 14 atom, preferably C, Si or Ge;
Each R ^a is independently hydrogen, halogen or C ₁ -C ₂₀ hydrocarbyl;
The two R ^a may form a cyclic structure comprising an aromatic, partially saturated or saturated cyclic or fused ring system, but in addition any two adjacent R The group may form a fused ring or a polycentric fused ring system, which ring may be aromatic and 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 radicals having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers and combinations thereof. (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 preferably a bridging group represented by the formula R ₂ ^a J, J is a group 14 element (preferably C, Si or Ge);
Each R ^a is independently hydrogen, halogen or C ₁ -C ₂₀ hydrocarbyl;
The two R ^a may form a cyclic structure comprising an aromatic, partially saturated or saturated cyclic or fused ring system, but in addition any two adjacent R The group may form a fused ring or a polycentric fused ring system, the ring may be aromatic, partially saturated or saturated,
However, any of the adjacent R ¹¹ , R ¹² and R ¹³ groups may form a condensed ring or a polycentric condensed ring system, the ring may be aromatic, Saturated, or may be saturated],
Or (vi)

式ＶＩ

Formula VI

[Where:
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl radicals 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 the following carbon atoms]
8). 8. The method of paragraph 6 or 7, wherein the activator is a bulky activator represented by the formula

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

9. Bulky activators include 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, Ν, Ν-dimethylanilinium tetrakis (perfluoronaphthyl) borate, Ν, Ν-diethylanilinium tetrakis (perfluoronaphthyl) borate, N, N -Dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluoronaphthyl) borate, tropyliumtetrakis (perfluoronaphthyl) borate, tri Enylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylphosphonium tetrakis (perfluoronaphthyl) borate, triethylsilylium tetrakis (perfluoronaphthyl) borate, benzene (diazonium) tetrakis (perfluoronaphthyl) borate, trimethylammonium tetrakis (per Fluorobiphenyl) borate, triethylammonium tetrakis (perfluorobiphenyl) borate, tripropylammonium tetrakis (perfluorobiphenyl) borate, tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate, tri (t-butyl) ammonium tetrakis ( Perfluorobiphenyl) borate, Ν, Ν-dimethylanilinium tetrakis (perf Orobiphenyl) borate, Ν, Ν-diethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate, tropylium tetrakis (per Fluorobiphenyl) 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] ( wherein, Ph is phenyl, Me is methyl), at least in One is that, Paragraph 6 or 7 methods.
10. A composition comprising a higher olefin copolymer of paragraphs 1-5, or a higher olefin copolymer produced by the process of paragraphs 6-9, preferably a lubricant blend.
11. Use of the composition of paragraph 10 as a lubricant.

Determination of product properties Product properties were determined by ¹ H NMR, GPC and ¹³ C NMR as follows.

GPC
Mn, Mw and Mz were measured by using a high temperature size exclusion chromatograph (SEC, either from Waters Corporation or from Polymer Laboratories) equipped with a differential refractive index detector (DRI). Details of experiments described in T. Sun, P. Brant, RR Chance and WW Graessley, Macromolecules, Volume 34, Number 19, pp. 6812-6820 (2001) and references cited therein were used. Three 10 mm Mixed-B columns made by Polymer Laboratories PLgel were used. The nominal flow rate was 0.5 cm ³ / min and the nominal injection volume was 300 μL. The various transfer lines, columns and differential refractometer (DRI detector) were placed in an oven maintained at 135 ° C. The solvent for the SEC experiment was 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 was then filtered through a 0.7 μm glass prefilter and then through a 0.1 μm Teflon filter. The TCB was then degassed with an online degasser and then placed in the SEC. A polymer solution was prepared by placing the dry polymer in a glass container, adding the desired amount of TCB, and then heating the mixture at 160 ° C. for about 2 hours with continuous stirring. All quantities were measured gravimetrically. The TCB density (unit: mass / volume) used to represent the polymer concentration was 1.463 g / mL at room temperature and 1.324 g / mL at 135 ° C. The injection concentration was 1.0-2.0 mg / mL, and low concentrations were used for high molecular weight samples. Prior to running each sample, the DRI detector and injector were purged. Next, the flow rate in the apparatus was increased to 0.5 mL / min and the DRI was allowed to stand for 8-9 hours to stabilize, after which the first sample was injected. The concentration c at each point in the chromatogram was calculated from I _DRI, which is the DRI signal minus the baseline, using the following equation:

c = K _DRI I _DRI / (dn / dc)
_Where K _DRI is a constant determined by calibration of DRI and (dn / dc) is the increment of the refractive index of the system. For TCB, the refractive index n = 1.500 at 135 ° C. and λ = 690 nm. For purposes of the present invention and the appended claims, (dn / dc) = 0.104 for propylene polymers and 0.1 for others. The parameter units used throughout the description of the SEC method are as follows. The concentration was expressed in g / cm ³ , the molecular weight was expressed in g / mol, and the intrinsic viscosity was expressed in dL / g.

¹³ C NMR
¹³ C NMR data was collected at 120 ° C. with a ¹³ C frequency of 100 MHz. During all acquisition periods, acquisition time adjusted to give a 90 degree pulse, digital resolution of 0.1-0.12 Hz, with continuous broadband proton decoupling using swept square wave modulation without gating, An acquisition delay time of at least 10 seconds pulses was used. Spectra were acquired by time averaging resulting in a signal-to-noise level suitable for measuring the signal of interest. The sample was dissolved in tetrachloroethane-d ₂ at a concentration of 10% to 15% by weight and then inserted into the spectrometer magnet.
Prior to data analysis, the spectra were referenced by setting the chemical shift of the TCE solvent signal to 74.39 ppm.

The chain ends were identified using the signals shown in the table below for quantization. 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 obtained on a Varian spectrometer using a ¹ H frequency of 250 MHz, 400 MHz or 500 MHz (for the purposes of the claims, a proton frequency of 400 mHz was used) at room temperature or 120 ° C. in a 5 mm probe. (For purposes of the claims, 120 ° C. should be used). Data were recorded using signal averaging of a transient response with a maximum pulse width of 45 ° C., a pulse interval of 8 seconds, and 120 transients. Spectral signals were combined and the number of unsaturated types per 1000 carbons was calculated by multiplying 1000 for each different group and dividing the result by the total number of carbons. Mn was calculated by dividing the total number of unsaturated species by 14,000. The unit is g / mol.

The chemical shift region for each olefin type is defined to be between the following spectral regions.

Viscosity Viscosity was measured using a Brookfield digital viscometer.
Metallocenes used in the examples The following metallocenes were used in the following examples.

使用した活性化剤
以下の活性化剤を、以下の例で使用した。

Activators used The following activators were used in the following examples.

Polymerization Conditions for Examples 1-6 Polymerization grade propylene was used and further purified by passing through the following series of columns. 2250 cc Oxyclear cylinder from Labclear (Oakland, Calif.), Then a 2250 cc column packed with a dry 3 mol mole sieve purchased from Aldrich Chemical Company (St. Louis, MI), purchased from Aldrich Chemical Company 5 Two 500 cc columns packed with sieve, one 500 cc column packed with ALCOA Selexsorb CD (7 × 14 mesh) purchased from Coastal Chemical Company (Abbeville, LA), and ALCOA Sels purchased from Coastal Chemical Company (Coral Chemical Company) One 500cc column packed with 7x14 mesh) .

  Polymerization grade hexane was further purified by passing through a series of columns. 2 500cc Oxyclear cylinders from Labclear, followed by two 500cc columns packed with dry 3 mol sieves purchased from Aldrich Chemical Company, and 2 5 mol sieves purchased from Aldrich Chemical Company 500 cc columns were used.

Scavenger and Cocatalyst Triisobutylaluminum (TIBAL) was 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.

Description and preparation of the reactor The polymerization was carried out in an inert atmosphere (N ₂ ) dry box with an external heater for temperature control, a glass insert (reactor internal volume = 22.5 mL), a septum inlet, nitrogen, Performed using a 48 Cell Parallel Pressure Reactors (PPR) equipped with a regulated source of propylene and equipped with a disposable PEEK (polyetheretherketone) mechanical stirrer (800 RPM). The PPR was prepared for polymerization by purging with dry nitrogen at 150 ° C. for 5 hours and then purging at 25 ° C. for 5 hours.
Example 1 Polymerization of decene-propylene, hexene-propylene and decene-hexene-propylene using metallocene E and F A reactor was prepared as described above and then charged with 1-decene and / or 1-hexene. The reactor was heated to 25 ° C. and then propylene was charged to the reactor. The scavenger / cocatalyst solution was then added to the reactor via syringe at process temperature and pressure. The reactor was heated to the process temperature (85 ° C.) and stirred at 800 RPM.
The metallocene catalyst was mixed with the activator and stirred in toluene at ambient temperature and pressure and added as a solution via syringe to the reactor (at process temperature and pressure) to initiate the polymerization. . Since the solution is added via a syringe, the hexane solution is also injected via the same syringe according to their addition so that a minimal amount of solution remains in the syringe. This procedure is applied after adding the scavenger / cocatalyst solution as well as the catalyst solution.
Propylene was placed in a reactor brought to the desired pressure by use of a regulator and dropped during the polymerization. No pressure control was used during the run. The temperature of the reactor was monitored and generally maintained within a temperature range of +/- 1 ° C. The polymerization was quenched by adding approximately 50 psi (345 kPa) delta of industrial air for about 60 seconds. The polymerization was quenched after the desired polymerization time had elapsed. The reactor was cooled and vented. After the remaining reaction components were removed under reduced pressure, the polymer was isolated. The reported yield includes the total weight of polymer and remaining catalyst. Yields are listed in Table 1A below.

セル生成物のいくつかの分析データを、以下の表２Ｂに示す。

Some analytical data of the cell product is shown in Table 2B below.

  Runs A1, A2 and A5 are copolymerizations of propylene and hexene using metallocene E and activator III. Runs E1 and E4 are copolymerizations of propylene and hexene using metallocene F and activator II. The inventors have observed that vinyl (%) increased with increasing propylene content. It was also observed that when the propylene feed rate decreased, Mn increased, possibly due to the incorporation of higher molecular weight hexene.

  Runs B1, B3 and B6 are terpolymer polymerizations of propylene, hexene and decene using metallocene E and activator III. Runs F1 and F3 are terpolymer polymerizations of propylene, hexene and decene using metallocene F and activator II. Again, it was observed that vinyl (%) increased with increasing propylene content. It was also observed that when the propylene feed rate decreased, Mn increased, possibly due to the incorporation of higher molecular weight hexene and decene.

(Example 2) Copolymerization of octene-propylene with metallocenes E and G The solution was run as follows. First, propylene was added to the reaction cell, then octene and isohexane were added to bring the total volume of the solution to 5.0 mL. TNOAL was used as a scavenger at a concentration of 1M. First, a toluene solution of activator III was added, and then a solution of metallocene E or F was added to make the ratio of activator to metallocene 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 reduced pressure. Some analyzes of cell products are listed in Table 2B.

セル生成物のいくつかの分析データを、以下の表２Ｂに示す。

Some analytical data of the cell product is shown in Table 2B below.

（例３）デセン−プロピレンの重合（メタロセンＥ対メタロセンＤの比較）
実施時間は６０分であり、活性化剤対メタロセンの比＝１：１、反応温度は８５℃であり、ＴＮＯＡＬ＝１．２×１０−４ｍｏｌ／Ｌであった。

Example 3 Polymerization of decene-propylene (comparison of metallocene E vs. metallocene D)
The run time was 60 minutes, the ratio of activator to metallocene = 1: 1, the reaction temperature was 85 ° C. and TNOAL = 1.2 × 10 −4 mol / L.

セル生成物のいくつかの分析データを、以下の表３Ｂに示す。

Some analytical data of the cell product is shown in Table 3B below.

（例４）デセン−プロピレンの重合（メタロセンＥと比較用メタロセンＡ、ＢおよびＣの比較）
本発明のものではないメタロセンＡ、ＢおよびＣを、本発明のメタロセンＥと比較した。実施時間は６０分であり、活性化剤対メタロセンの比＝１：１、反応温度は８５℃であり、ＴＮＯＡＬ＝１．２×１０−４ｍｏｌ／Ｌであった。

(Example 4) Polymerization of decene-propylene (Comparison of metallocene E and comparative metallocenes A, B and C)
Metallocenes A, B and C that are not of the present invention were compared to the metallocene E of the present invention. The run time was 60 minutes, the ratio of activator to metallocene = 1: 1, the reaction temperature was 85 ° C. and TNOAL = 1.2 × 10 −4 mol / L.

セル生成物のいくつかの分析データを、以下の表４Ｂに示す。

Some analytical data of the cell product is shown in Table 4B below.

Example 5 Comparison of Activators I-III The implementation time was changed as shown in Table 6. The ratio of activator to metallocene = 1: 1, the reaction temperature was 85 ° C., MCN = 5 × 10 ⁻⁵ mol / L, TNOAL = 1.2 × 10 ⁻⁴ mol / L. The total volume of the solution was 5 mL.

セル生成物のいくつかの分析データを、以下の表５Ｂに示す。

Some analytical data of the cell product is shown in Table 5B below.

（例６および７）重合条件
無水トルエンをＳｉｇｍａ Ａｌｄｒｉｃｈ（Ｃｈｉｃａｇｏ、ＩＬ）から購入し、不活性雰囲気において４Åの分子ふるい上でさらに乾燥させた。

Examples 6 and 7 Polymerization Conditions Anhydrous toluene was purchased from Sigma Aldrich (Chicago, IL) and further dried on a 4Å molecular sieve in an inert atmosphere.

In the dry box, 10 mL of toluene was used to dissolve the 1 / 1.1 equivalent ratio metallocene / activator. The solution was stirred for 30 minutes. Next, 5 mL of the solution was transferred to a catalyst charger.
Higher olefin comonomer (5 g) was dissolved in 5 mL of toluene and filled into a syringe. A syringe was filled with TIBAL (0.5 mL of 1M solution).

Reactor Preparation A 2 L Zipper autoclave reactor was baked at 120 ° C. for 1 hour with a nitrogen purge. The reactor was then cooled to room temperature with a continuous nitrogen purge. The isohexane and propylene feed lines were connected to the reactor line and the feed stream was passed through a molecular sieve dryer (4M molecular sieve) before being filled into the sight glass.

Reactor Operating Procedure A catalyst charger containing a metallocene / activator solution was coupled to the inlet port of the reactor. A high pressure nitrogen line was connected to the charger and the catalyst was released into the reactor at the appropriate time.
The vent line to the reactor was closed. Less than one pound of pressure was removed from the reactor and the higher olefin comonomer was placed by syringe into the bottom of the reactor using the second port. The same port was then used to fill the reactor with scavenger and the port was closed. The nitrogen line to the reactor was closed. After isohexane was added to the reactor, propylene was added. The agitator was started at 800 rpm and the reactor was heated to the required process temperature.
When the reactor pressure was stable at the required process temperature, the catalyst was forced into the reactor using a nitrogen pressure 40 lb above the reactor pressure. The charger port was disconnected from the reactor and the reactor software was run to monitor pressure loss and temperature changes in the reactor. The reactor was operated for the desired run time. Once the software was stopped, the reactor was cooled to RT and the pressure was vented. The product and solvent solution was poured from the reactor into a glass beaker and the solvent was removed by a nitrogen purge.

Example 6 Copolymerization of hexene and propylene for viscosity studies Higher olefin (hexene / propylene) copolymers were produced under the conditions shown in Table 7A. In a dry box, 10 mL of toluene was used to dissolve a 1 / 1.1 equivalent ratio of metallocene E / activator III (10.7 mg / 24.1 mg). A syringe was filled with TIBAL (0.5 mL of 1M solution). The volume of isohexane was 600 mL. Implementation conditions are shown in Table 6A below.

実施１および２のＶＴ−ＨＯＣ₆／Ｃ₃コポリマーの粘度を、ＶＴ−ＨＯアタクティックＣ₃ホモポリマーと比較したものを、以下の表６Ｂに報告し、図１に示す。

The viscosities of the VT-HOC ₆ / C ₃ copolymers of Examples 1 and 2 compared to the VT-HO atactic C ₃ homopolymer are reported in Table 6B below and are shown in FIG.

Example 7 Preparation of norbornene and propylene copolymerization catalyst, norbornene and scavenger In a dry box, 10 mL of toluene was used, each with a 1 / 1.1 equivalent ratio of metallocene G / activator III (13.7 mg). /30.9 mg) was dissolved. The solution was stirred for 30 minutes. Next, 5 mL of the solution (3 mg) was transferred to the catalyst charger. Norbornene (5 g) was dissolved in 5 mL of toluene and filled into a syringe. A syringe was filled with TIBAL (0.5 mL of 1M solution). The volume of isohexane was 300 mL.

  Any document described herein, including any priority documents, related applications and / or test procedures, is hereby incorporated by reference for the purpose of any jurisdiction enabling such implementation, unless otherwise inconsistent with the text. Embedded in the book. However, any priority document that is not named in the earlier application or application documents is not incorporated herein by reference. While embodiments of the present invention have been illustrated and described above, various changes can be made without departing from the spirit and scope of the present invention, as will be apparent from the foregoing summary and specific embodiments. Accordingly, the present invention is not intended to be limited by these outlines and embodiments. Similarly, the term “comprising” is considered synonymous with the term “including” for purposes of Australian law. Similarly, whenever a composition, element, or group of elements is preceded by a transitional phrase “comprising”, the transitional phrase “consisting essentially of” preceding the enumeration of that composition, element or elements, It should be understood that the same composition or group of elements with “consisting of”, “selected from the group consisting of” or “is” is also contemplated, and vice versa.

Claims (8)

Having 300 g / mol or more of Mn (measured by ¹ H NMR),
(I) 2 0 ~9 9.9mol% of at least one C ₅ -C ₄₀ higher olefin; and (ii) 0. 1 to 80 mol% propylene ;
And higher olefin copolymers having at least 40% allyl chain ends.   The higher olefin copolymer of claim 1 wherein the ratio of isobutyl chain end to allyl chain end is less than 0.7: 1.   The higher olefin copolymer of claim 1 or 2, wherein the ratio of allyl chain end to vinylidene chain end is greater than 2: 1.   The higher olefin copolymer according to any one of claims 1 to 3, which has a viscosity of more than 1000 cP at 60 ° C. ^The olefin having at least 36 carbon atoms, as measured by ¹ H NMR, assuming one unsaturation per chain, comprises at least 50% by weight relative to the weight of the copolymer composition. To a higher olefin copolymer according to any one of 4 to 4.   A composition comprising the higher olefin copolymer according to any of claims 1-5. (I ) 2 0 to 9 9.9 mol% of at least one C ₅ -C ₄₀ higher olefin,
(Ii ) 0 . 1 to 80 mol% propylene ;
Comprising contacting a a method of producing a higher olefin copolymer,
An activator wherein the contact is selected from the group consisting of dimethylanilinium tetrakis (perfluorophenyl) borate, dimethylanilinium tetrakis (perfluorobiphenyl) borate and dimethylanilinium tetrakis (perfluoronaphthyl) borate , and A process that occurs in the presence of a catalyst system comprising at least one metallocene compound represented by at least one.
(I)

[ Where:
M is hafnium or zirconium;
Each X is methyl;
R ¹ is methyl ;
R ² is methyl ;
Each R ³ is methyl ;
Each R ⁴ is hydrogen ;
R ⁵ is, Ru Oh in hydrogen],
Or (v)

[Where:
M is hafnium or zirconium;
Each X is methyl ;
Each R ⁸ is methyl ;
Each R ⁹ is propyl ;
Each R ¹⁰ is hydrogen;
Each R ¹¹ , R ¹² and R ¹³ is hydrogen ;
T is a bridging group represented by the formula R ^a ₂ J, J is Si ,
Each R ^a, Ru methyl der],
Or (vi)

[Where:
M is hafnium or zirconium;
Each X is methyl ;
Each R ¹⁵ and R ¹⁷ is methyl ;
Each R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ is hydrogen ;
Each R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ is methyl ] C ₅ -C ₄₀ higher olefins is, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxa-norbornene The method of claim 7, selected from: 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof.

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