KR20010020395A - Ethylene/Alpha-Olefin/Diene Interpolymers and Their Preparation - Google Patents

Abstract

Random ethylene / alpha-olefin / diene monomer copolymers with alpha-olefin distribution more clustered than Bernoullian are prepared using Group 4 metal constrained complex catalysts and activating promoters. Catalysts include fused ring indenyl derivative ligands.

Description

Ethylene / Alpha-Olefin / Diene Interpolymers and Their Preparation}

The present invention relates to ethylene (C ₂ ), at least one alpha-olefin (α-olefin), preferably propylene (C ₃ ), butene-1, hexene-1 or octene-1, and at least one diolefin monomer, Preferably, the present invention relates to copolymers of non-conjugated diene monomers and their preparation methods using olefin copolymerization catalysts derived from the Group 4 metal complex class.

Constrained geometry metal complexes and methods of making them are described in European Patent A-416,815 (US Application No. 545,403, filed Jul. 3, 1990) and European Patent A-468,651 (July 3, 1990). US Application No. 547,718), European Patent A-514,828 (US Application No. 702,475, filed May 20, 1991), European Patent A-520,732 (US Application No. 1, 1992) 876,268) and International Publication No. 93/19104 (US Application No. 8,003, filed Jan. 21, 1993), as well as US Pat. Nos. 5,055,438, 5,057,475, 5,096,867, 5,064,802, 5,132,380, International Publication No. 95/00526, and US Provisional Application 60-005913. Various substituted indenyl containing metal complexes are taught in US Application No. 592,756 and International Publication 95/14024, filed January 26, 1996. Related teachings of all prior patents or equivalent US patent applications are incorporated herein by reference.

The first aspect of the present invention is a random ethylene / α-olefin / diene monomer (EAODM) copolymer, wherein the copolymer has a weight ratio of ethylene to α-olefin, which is (a) C _3-20 α-olefin. To 10:90, (b) the content of diene monomer is in the range of 0 to 25% by weight based on the weight of the copolymer, (c) ¹³ C NMR spectroscopy and formula B = P _OE / (2P _E · P _O ) (where P _E is the mole fraction of ethylene units derived from ethylene, P _O is the mole fraction of α-olefin units derived from α-olefins, and P _OE is the mole fraction of all divalent chains in the copolymer) Ethylene / α-olefin / diene monomer (EAODM) random copolymer, having a B value determined by α-olefin / ethylene chain number to water ratio) of 0.94 to 1.0. JC Randall (Macromolecules, 15, pg 353 (1982)) and J. Ray (Macromolecules, 10, pg 773 (1977)) describe B values in more detail. The Bernoullian distribution will give a B value of 1, a perfectly alternating polymer will give a B value of 2, and block copolymers such as ethylene / propylene diblock copolymers will give a B value close to zero. . In practical terms, a B value of less than 1 indicates that the polymer has an α-olefin distribution more clustered than the Bernoulli distribution, and a B value of 1 or more indicates that the polymer has an isolated α-olefin distribution that is more isolated than the Bernoulli distribution.

The ¹³ C NMR sample for determination of B value contains 1,1,2,2-tetrachloroethane-d containing a paramagnetic mitigating agent sufficient to prepare an NMR solvent having a concentration of 0.05 M in chromium (III) acetylacetone. Suitably prepared in a 50% / 50% (by volume) solvent blend of ₂ and 1,2,4-trichlorobenzene. Samples are prepared by mixing the polymer and NMR solvent in a volume ratio of 10:90 in a nitrogen-washed and capped 10 mm NMR tube. Uniformity is achieved by heating and recirculating the contents of the tube regularly. Spectra were obtained using a back-out decoupling scheme that delayed for 5-9 seconds with a pulse width of 130 ° C. to 90 ° C.

The second aspect of the present invention comprises the process of contacting ethylene, at least one C _3-20 α-olefin monomer and diene monomer with a catalyst and activating promoter which is a metal complex of the formula It is a method for preparing coalesce.

Wherein M is titanium, zirconium, or hafnium in a formal oxidation state of +2, +3 or +4,

A ′ is hydrocarbyl, fluoro-substituted hydrocarbyl, hydrocarbyloxy substituted hydrocarbyl, dialkylamino substituted hydrocarbyl at two or more positions containing up to 40 non-hydrogen atoms Is a substituted indenyl group substituted with a group selected from silyl, germanyl and mixtures thereof, A 'is also covalently bonded to M by a divalent Z group,

Z is a divalent moiety bonded to both A 'and M via σ-bond, Z comprises boron or a Group 14 constituent element of the periodic table of the elements and also nitrogen, phosphorus, sulfur or oxygen,

X is an anionic or divalent anionic ligand group of up to 60 atoms excluding the class of ligands that are cyclic, unlocalized, π-bonded ligands,

Each X ′ is a neutral Lewis base ligating compound and has 20 or less atoms,

p is 0, 1, or 2, 2 is less than the formal oxidation state of M, except that when X is a divalent anionic ligand, p is 1,

q is 0, 1 or 2.

Preferred X 'groups are phosphines which are carbon monoxide, in particular trimethylphosphine, triethylphosphine, triphenylphosphine and bis (1,2-dimethylphosphino) ethane, P (OR) ₃ , where R is C _1-20 hydro Carbil), in particular tetrahydrofuran (THF) ether, in particular pyridine, bipyridine, tetramethylethylenediamine (TMEDA) and triethylamine amines, olefins, and conjugated dienes, preferably neutrals having 4 to 40 carbon atoms Conjugated diene. Complexes containing the latter X 'group include metals with a formal oxidation state of +2.

The metal complex is in isolated form, optionally in pure form or in admixture with other complexes, in the form of solvated adducts, optionally in liquid form, especially in organic liquids, and dimers or chelating agents are organic substances, preferably Preferably in the form of a neutral Lewis base, in particular trihydrocarbylamine, trihydrocarbylphosphine or halogenated derivative chelated derivative.

1 is a schematic flow chart illustrating the method used in Examples 4-7 and Comparative Example A. FIG.

The process of the invention consequently makes it possible to produce high efficiency of EAODM copolymers or polymers of high weight average molecular weight (M _w ) at a wide range of polymerization conditions, in particular at elevated temperatures. These are particularly useful for solution polymerization of EAODM polymers in which the diene is a conjugated diene such as 5-ethyldiene-2-norbornene (ENB), 1,4-hexadiene or similar non-conjugated diene or 1,3-pentadiene. With elevated temperatures, the increased solubility of the polymer at elevated temperatures not only exceeds the limit of solution viscosity of the polymerization equipment, but also improves the conversion rate (higher concentration of polymer product) as well as improves the energy costs required to devolatilize the reaction product. Due to the fact that it reduces, the productivity of this method is greatly improved.

All periodic table of elements mentioned herein is referred to the Periodic Table of Elements, published in 1989 by CRC Press, Inc. Further, all references to foot or foots are as shown in the Periodic Table of Element, above, using the IUPAC foot numbering system.

The EAODM copolymer of the present invention has three distinct features. The first feature is that the rheology ratio (V _0.1 / V ₁₀₀ ) at 190 ° C. is from about 3 to about 90. The second feature is a Mooney viscosity or MV (ML _{1 + 4} at 125 ° C. _, ASTM D1646-94) in the range of 1 to 150, preferably 10 to 120, particularly preferably 15 to 100. A third feature is the Reactivity ratio product (RRP) of 1 to less than 1.25.

(Tetramethylcyclopentadienyl) -dimethyl (t-butylamido) silanitanium dimethyl or (tetramethylcyclopentadienyl) -dimethyl (t-butylamido) silanitanium prepared at a contact temperature of 40 to 185 ° C. When compared to corresponding EAODM polymers prepared from the same monomers at the same temperature using 1,3-pentadiene as a catalyst, the EAODM polymers of the present invention provide certain improvements. For example, they have a rheological ratio of at least 10% higher than the rheological ratio of the corresponding EAODM polymer. They are also at least 1 ° C. obtained from differential scanning calorimeter (DSC) curves using a first derivative of temperature of at least 50% by weight higher diene, at least 1.5 times higher M _w , compared to the corresponding EAODM polymer. Has a lower glass transition temperature (Tg) and at least 2.5 times higher MV. For the purpose of comparing Tg, the corresponding EAODM polymer has a degree of crystallization that is greater than zero and less than 5%.

The process of the invention can be used to polymerize C ₂ with at least one C _3-20 α-olefin (ethylenically unsaturated) monomer and C _4-40 diene monomer. α-olefins may be aliphatic or aromatic compounds and unsaturated vinyl or cyclic compounds such as cyclobutene, cyclopentene and norbornene, including norbornene substituted with C _1-20 hydrocarbyl groups at positions 5 and 6 It may include a compound. α-olefins are preferably C _3-20 aliphatic compounds, more preferably C _3-16 aliphatic compounds. Preferred ethylenically unsaturated monomers are 4-vinylcyclohexene, vinylcyclohexane, norbornadiene, C _3-10 aliphatic α-olefins (especially ethylene, propylene, isobutylene, butene-1, pentene-1, hexene-1 , 3-methyl-1-pentene, 4-methyl-1-pentene, octene-1, decene-1 and dodecene-1) and mixtures thereof. Most preferred monomers are ethylene and ethylene mixtures, one or more propylene, butene-1, hexene-1 and octene-1, and nonconjugated dienes, especially ENB.

The C _4-40 diolefin or diene monomer is preferably a nonconjugated diolefin. Non-conjugated diolefins can be C _6-15 straight, branched or cyclic hydrocarbon dienes. Examples of nonconjugated dienes include straight chain acyclic dienes such as 1,4-hexadiene, 1,5-heptadiene, and 1,6-octadiene, 5-methyl-1,4-hexadiene, 2-methyl-1 , 5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7 Branched chain acyclic dienes, such as mixed isomers of octadiene, 5,7-dimethyl-1,7-octadiene, 1,7-octadiene, 1,9-decadiene and dihydromircene, 1,4- Monocyclic alicyclic dienes such as cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene, tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo- (2 Multiple ring alicyclic fused and crosslinked ring dienes, alkenyl, alkylidene, cycloalkenyl and 5, such as 2,1) -hepta-2,5-diene (norbornadiene), methylnorbornadiene Methylene-2-norbornene (MNB), ENB, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-isopro Vinylidene-2-norbornene is norbornene, 5- (4-cyclopentenyl) -2-norbornene and 5-cyclohexylidene-2-norbornene and cycloalkylidene norbornene, such as.

When the diolefin is a conjugated diene, 1,3-pentadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 4-methyl-1,3-pentadiene, or 1,3-cyclopentadiene Can be.

The diene is preferably a nonconjugated diene selected from ENB, 1,4-hexadiene and norbornadiene, more preferably ENB. The content of the EAODM diene monomer is preferably greater than 0 and up to 25% by weight, more preferably 0.3 to 20% by weight, most preferably 0.5 to 15% by weight.

Preferred coordination complexes used according to the invention are complexes according to formula (IA).

Where

R ₁ and R ₂ are independently a group selected from hydrogen, hydrocarbyl, perfluoro substituted hydrocarbyl, silyl, germanyl and mixtures thereof, provided that these groups have up to 20 non-hydrogen atoms, provided that R ₁ Or one of R ₂ is not hydrogen,

R ₃ , R ₄ , R ₅ , and R ₆ are independently groups selected from hydrogen, hydrocarbyl, perfluoro-substituted hydrocarbyl, silyl, germanyl, and mixtures thereof, these groups having up to 20 non-hydrogen sources Have a ruler,

M is titanium, zirconium or hafnium,

Z is a divalent moiety containing boron or a constituent element of group 14 of the periodic table of elements and comprising nitrogen, phosphorus, sulfur or oxygen and having up to 60 non-hydrogen atoms,

p is 0,1 or 2,

q is 0 or 1,

Provided that p is 2, q is 0, and the formal oxidation state of M is +4, then X is halide, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amido, di (hydrocarbyl) Phosphido, hydrocarbyl sulfido, and silyl groups as well as halo-, di (hydrocarbylamino)-, hydrocarbyloxy-, and di (hydrocarbyl) phosphino substituted derivatives thereof. Is an anionic ligand, and such X groups have 20 or less non-hydrogen atoms,

If p is 1, q is 0 and the formal oxidation state of M is +3, then X is allyl 2- (N, N-dimethylaminomethyl) phenyl, and 2- (N, N-dimethyl) -aminobenzyl Or a stabilizing anionic ligand group selected from the group consisting of or when the formal oxidation state of M is +4, X is a divalent derivative of conjugated diene, and M and X together form a metallocyclopentene group,

If p is 0, q is 1 and the formal oxidation state of M is +2, then X 'is a neutral conjugated or nonconjugated diene optionally substituted with one or more hydrocarbyl groups, which X' is 40 or less It has a carbon atom of and forms a π-complex with M.

More preferred coordination complexes used according to the invention are complexes according to formula (IB).

Where

R ₁ and R ₂ are hydrogen or C _1-6 alkyl, provided that at least one of R ₁ or R ₂ is hydrogen,

R ₃ , R ₄ , R ₅ and R ₆ are independently hydrogen or C _1-6 alkyl,

M is titanium,

Y is -O-, -S-, -NR ^* -, -PR ^* -,

Z ^* is SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ^* ₂ or GeR ^* ₂ ,

Each R ^* is independently a member selected from hydrogen or hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, and R ^* has a non-hydrogen atom of less than 20, optionally, Two R ^* groups from Z (if R ^* is not hydrogen) or R ^* groups from Z and R ^* groups from Y form a ring system,

p is 0,1 or 2,

q is 0 or 1,

Provided that when p is 2, q is 0, and the formal oxidation state of M is +4, each X is independently methyl or benzyl,

If p is 1, q is 0 and the formal oxidation state of M is +3, then X is 2- (N, N-dimethyl) aminobenzyl, or if M formal oxidation state is +4, then X is 1, 4-butadienyl,

When p is 0, q is 1, and the formal oxidation state of M is +2, X 'is 1,4-diphenyl-1,3-butadiene, 2,4-hexadiene, or 1,3-pentadiene to be. The latter dienes result in an asymmetric diene group which produces a metal complex which is a substantial mixture of the individual geometric isomers.

Even more preferred coordination complexes used according to the invention are complexes according to formula (II).

Where

R 'is hydrogen, hydrocarbyl, di (hydrocarbylamino), or hydrocarbyleneamino group, wherein R' has 20 or less carbon atoms,

R ″ is C _1-20 hydrocarbyl or hydrogen,

M is titanium,

Y is -O-, -S-, NR ^* -, -PR ^* -, -NR ₂ ^* -or -PR ₂ ^* -,

Z ^* is as defined above,

R ^* are each as defined above,

X is a monovalent anionic ligand of up to 60 atoms, excluding the class of ligands that are cyclic, unbiased, π-bonded ligands,

Each X 'is independently a neutral ligation compound having 20 or less atoms,

X "is a divalent anionic ligand group having up to 60 atoms,

p is 0, 1 or 2,

q is 0 or 1,

r is 0 or 1,

Provided that when p is 2, q and r are 0 and the formal oxidation state of M is +4 (or if the formal oxidation state of M is +3 when Y is -NR ^* ₂ or -PR ^* ₂ ), then X is a halide. , Hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amido, di (hydrocarbyl) phosphido, hydrocarbyl sulfido, and silyl groups as well as halo-, di (hydrocarbyl) amido An anionic ligand selected from hydrocarbyloxy-, and di (hydrocarbyl) phosphino substituted derivatives thereof, and such X groups have up to 30 non-hydrogen atoms,

When r is 1, p and q are 0 and the formal oxidation state of M is +4, X "is a divalent anionic ligand selected from the group consisting of hydrocarbodiyl, oxyhydrocarbyl and hydrocarbylenedioxy groups X group has a non-hydrogen atom number of 30 or less,

If p is 1, q and r are 0 and the formal oxidation state of M is +3, then X is allyl, 2- (N, N-dimethylamino) phenyl, 2- (N, N-dimethylaminomethyl) phenyl , And a stabilized anion ligand group selected from the group consisting of 2- (N, N-dimethylamino) benzyl,

If p and r are 0, q is 1 and the formal oxidation state of M is +2, then X 'is a neutral conjugated or nonconjugated diene optionally substituted with one or more hydrocarbyl groups, such X' It has a carbon number of 40 or less and forms a π-complex with M.

Most preferred metal complexes are according to formula (II) or (III), wherein M, X, X ', X ", R', R", Z ^* , Y, p, q and r are as defined above. Equal,

Provided that when p is 2, q and r are 0, and the formal oxidation state of M is +4, each X is independently methyl, benzyl, or halide,

when p and q are 0, r is 1 and the formal oxidation state of M is +4, X "is a 1,4-butadienyl group forming a metallocyclopentene ring with M,

if p is 1, q and r are 0 and the formal oxidation state of M is +3, then X is 2- (N, N-dimethylamino) benzyl,

If p and r are 0, q is 1 and the formal oxidation state of M is +2, X 'is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene.

Particularly preferred coordination complexes according to formula (II) above are inherently substituted according to their particular end use. In particular, metal complexes which are very useful for use in catalyst compositions for the copolymerization of ethylene, at least one α-olefin and diolefin are those complexes (II), wherein R ′ is as defined above and R ″ is hydrogen or methyl , Especially hydrogen).

Particularly preferred coordination complex (t-butylamido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (II) 2,4-hexadiene is structurally represented by the formula (III) do.

Second particularly preferred coordination complex (t-butylamido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (IV) dimethyl is structurally represented by the following general formula (IV).

Third particularly preferred coordination complex (t-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene is structurally represented by Is indicated by).

Fourth particularly preferred coordination complex (t-butylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl is structurally represented by the formula (VI) .

Fifth particularly preferred coordination complex (t-butylamido) dimethyl (η ⁵ -2-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene is often referred to as the geometric isomer It has two isomers and is represented by following general formula (VII) and (VIII), respectively.

The first group of preferred metal coordination complexes (t- butylamido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido Fig.) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene, (t- butylamido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethyl (η ⁵ -2- inde-methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethyl (η ⁵ -2- inde-methyl-indenyl) silane titanium (IV) dimethyl, (t- butylamido) dimethyl (η ⁵ -2-methyl-inde indenyl) silane titanium (IV) dibenzyl, (t- butylamido) dimethoxy (η ⁵ inde-2-methyl-indenyl) silane titanium ( II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) dimethoxy (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butyl Amido) dimethoxy (η ⁵ -2-methylindenyl) silanetitanium (II) 2,4-hexadiene, (t- butylamido) dimethoxy (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethoxy (η ⁵ -2- methyl-indenyl) silane titanium (IV) dimethyl, (t- butylamido) dimethoxy (η ⁵ -2- methyl-indenyl) silane titanium (IV) dibenzyl, (t- butyl amido) di isopropoxy (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) di isopropoxy (η ⁵ - 2-methyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido) di isopropoxy (η ⁵ -2- methyl-indenyl) silane titanium (II) 2,4- hexadiene , (t- butylamido) di isopropoxy (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) di isopropoxy (η ⁵ -2-methyl-inde indenyl) silane titanium (IV) dimethyl, (t- butylamido) di isopropoxy (inde η ⁵ -2-methyl-indenyl) silane titanium (IV) dibenzyl, (t- butyl the amino degrees) ethoxymethyl (η ⁵ -2- methyl Carbonyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) to inde ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (II) penta-1,3- diene, (t- butylamido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (IV) dimethyl, (t in -Butylamido) ethoxymethyl (η ⁵ -2-methylindenyl) silanetitanium (IV) dibenzyl, (t-butylamido) dimethyl (η ⁵ -2-ethylindenyl) silanetitanium (II) 1 , 4-diphenyl-1,3-butadiene, (t- butylamido) dimethyl (η ⁵ -2- ethyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido) dimethyl (η ⁵ -2- ethyl inde indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethyl (η ⁵ -2- inde ethyl indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethyl (η ⁵ -2- ethyl inde Indenyl) silane titanium (IV) dimethyl, (t- butylamido) dimethyl (η ⁵ -2- ethyl-indenyl) silane titanium (IV) dibenzyl, (t- butylamido) dimethoxy (η ⁵ -2- ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) dimethoxy (η ⁵ -2- ethyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido) dimethoxy (η ⁵ -2- ethyl-indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethoxy (η ⁵ -2- ethyl indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethoxy (η ⁵ -2- ethyl-indenyl) silane titanium (IV) dimethyl, (t- butyl Amido) dimethoxy (η ⁵ -2-ethylindenyl) silanetitanium (IV) dibenzyl, (t-butylamido) diisopropoxy (η ⁵ -2-ethylindenyl) silane titanium (II) 1 , 4-diphenyl-1,3-butadiene, (t- butylamido) di isopropoxy (η ⁵ -2- ethyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido FIG inde) di isopropoxy (η ⁵ -2- ethyl carbonyl) room Titanium (II) 2,4- hexadiene, (t- butylamido) di isopropoxy (η ⁵ -2- ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, ( t- butylamido) di isopropoxy (η ⁵ -2-ethyl-inde indenyl) silane titanium (IV) dimethyl, (t- butylamido) di isopropoxy (η ⁵ inde-2-ethyl-indenyl) silane titanium (IV) dibenzyl, (t- butylamido) ethoxymethyl (η ⁵ -2- ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido ) ethoxymethyl (η ⁵ -2- ethyl inde indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido inde degrees) ethoxymethyl (η ⁵ -2- ethyl indenyl) silane titanium (II ) 2,4-hexadiene, (t- butylamido) ethoxymethyl (η ⁵ inde-2-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido Ethoxymethyl (η ⁵ -2-ethylindenyl) silanetitanium (IV) dimethyl, (t-butylamido) ethoxymethyl (η ⁵ -2-ethylindenyl) silanetitanium (IV) dibenzyl, (t- butylamido) dimethyl (η ⁵ -2- methyl -s- Line indazol-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) Silanetitanium (II) 1,3-pentadiene, (t-butylamido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (II) 2,4-hexadiene, ( t-butylamido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) dimethyl ( η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl, (t- butylamido) dimethoxy (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) dimethoxy (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene, (t- butylamido) (η ⁵ 2-methyl-s-indacene-1-yl) silanetitanium (II) 2,4-hexadiene, (t-butylamido) dimethoxy (η ⁵ -2-methyl-s-indacene-1- (I) silanetitanium (III) 2- (N, N-di Methylamino) benzyl, (t-butylamido) dimethoxy (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) dimethoxy (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl, (t-butylamido) diisopropoxy (η ⁵ -2-methyl-s-indasen-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) di isopropoxy (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II ) 1,3-pentadiene, (t- butylamido) di isopropoxy (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 2,4- hexadiene, (t -butylamido) di isopropoxy (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) Diisopropoxy (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) diisopropoxy (η ⁵ -2-methyl-s-inda Sen-1-yl) silanetitanium (IV) dibenzyl, (t-butylamido) ethoxymethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (II ) 1,4-diphenyl-1,3-butadiene, (t- butylamido) ethoxymethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- To pentadiene, (t-butylamido) ethoxymethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (II) 2,4-hexadiene, (t-butylamido) Toxymethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) ethoxymethyl (η ^5- 2-methyl-indazol -s- metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) ethoxymethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium ( IV) Dibenzyl, (t-butylamido) dimethyl (η ⁵ -2-ethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t -Butylamido) dimethyl (η ⁵ -2-ethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene, (t-butyl amido) dimethyl (η ⁵ -2-ethyl -s- indazol metallocene-1-yl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium ( III) 2- (N, N-dimethylamino) Quality, (t- butylamido) dimethyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) dimethyl (η ⁵ -2- ethyl- s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl, (t- butylamido) dimethoxy (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (II) 1, 4-diphenyl-1,3-butadiene, (t- butylamido) dimethoxy (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene, ( t- butylamido) dimethoxy (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethoxy (η ⁵ - 2-ethyl-indazol -s- metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethoxy (η ⁵ -2- ethyl-indazol -s- Sen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) dimethoxy (η ⁵ -2-ethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl, (t- Butyl amido) diisopropoxy (η ⁵ -2-ethyl-s-indasen-1-yl) silane titanium (II) 1,4-diphenyl-1,3-butadiene, (t-butyl amido) Diisopropoxy When (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene, (t- butylamido) di isopropoxy (η ⁵ -2- ethyl -s - indazol metallocene-1-yl) silane titanium (II) 2,4- hexadiene, (t- butylamido) di isopropoxy (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) di isopropoxy (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) di isopropoxy (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl, in (t- butylamido) ethoxymethyl (η ⁵ - 2-ethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) ethoxymethyl (η ⁵ -2-ethyl-s - indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene, (t- butylamido) ethoxymethyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium ( II) 2,4- hexadiene, (t- butylamido) ethoxymethyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino ) Benzyl, (t-butyl Shown) ethoxymethyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) ethoxymethyl (η ⁵ -2- ethyl-indazol -s- Sen-1-yl) silanetitanium (IV) dibenzyl, (dimethylamine) dimethyl (η ⁵ -2-methylindenyl) silane titanium (III) dimethyl, (dimethylamine) dimethyl (η ⁵ -2-methylindenyl ) silane titanium (III) dibenzyl, (diisopropylamine) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (III) dimethyl, (diisopropylamine) dimethyl (η ⁵ -2-methyl-inde carbonyl) silane titanium (III) dibenzyl, (di -n- butylamine) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (III) dimethyl, (di -n- butylamine) dimethyl (η ⁵ -2- methyl indenyl) silane titanium (III) dibenzyl, (di-iso-butylamine) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (III) dimethyl, (di-iso-butylamine) dimethyl (η ⁵ - 2-methyl-indenyl) silane titanium (III) dibenzyl, (dimethylamino) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (III) dimethyl, (di Butyl amine) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (III) dibenzyl, (diisopropylamine) dimethyl (η ⁵ -2- methyl -s- indazol metallocene -1 -yl) silane titanium (III) dimethyl, (diisopropylamine) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (III) dibenzyl, (di -n- butylamine) Dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanitanium (III) Dimethyl, (di-n-butylamine) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl ) silane titanium (III) dibenzyl, (di-iso-butylamine) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (III) dimethyl, (di-iso-butylamine) dimethyl ( η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, (dimethylamine) dimethyl (η ⁵ -2-ethylindenyl) silanetitanium (III) dimethyl, (dimethylamine) dimethyl (η ⁵ -2- ethyl-indenyl) silane titanium (III) dibenzyl, (diisopropylamine) dimethyl (η ⁵ -2- ethyl-indenyl) silane titanium (III) dimethyl, (diisopropylamine) dimethyl (η ⁵ -2- ethyl inde ) Silane titanium (III) dibenzyl, (di -n- butylamine) dimethyl (η ⁵ -2- ethyl-indenyl) silane titanium (III) dimethyl, (di -n- butylamine) dimethyl (η ⁵ -2- Ethylindenyl) silanetitanium (III) dibenzyl, (di-iso-butylamine) dimethyl (η ⁵ -2-ethylindenyl) silanetitanium (III) dimethyl, (di-iso-butylamine) dimethyl (η ⁵ 2-ethylindenyl) silanetitanium (III) dibenzyl, (dimethylamine) dimethyl (η ⁵ -2-ethyl-s-indasen-1-yl) silanetitanium (III) dimethyl, (dimethylamine) dimethyl ( η ⁵ -2-ethyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, (diisopropylamine) dimethyl (η ⁵ -2-ethyl-s-indasen-1-yl) silanitanium (III) Dimethyl, (diisopropylamine) dimethyl (η ⁵ -2-ethyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, (di-n-butylamine) dimethyl (η ^5- 2-ethyl-indazol -s- metallocene-1-yl) silane titanium (III) dimethyl, (di -n- butylamine) dimethyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (III ) Dibenzyl, (di-isobutylamine) Methyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (III) dimethyl, (di-iso-butylamine) dimethyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) Silantitanium (III) dibenzyl. Preferred members of this group are (t-butylamido) -dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silantitanium (IV) dimethyl and (t-butylamido) -dimethyl (η ^{5-methyl-2-inde} include indenyl) silane titanium (II) 2,4- hexadiene.

A second group of preferred catalysts are (t-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido Fig.) Dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium ( II) 2,4-hexadiene, (t-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butyl Amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dimethyl, (t-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl , (t-butylamido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) dimethoxy ( η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 2 , 4-hexadiene, (t- butylamido) dimethoxy (η ⁵ -2,3- dimethyl Denil) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethoxy (η ⁵ -2,3- dimethyl-indenyl) silane titanium (IV) dimethyl, (t- Butyl amido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silane Titanium (IV) dibenzyl, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silane Titanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-penta Diene, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 2,4-hexadiene, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) Silanetitanium (IV) dimethyl, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silane titanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 2,4-hexadiene, (t-butylamido) ethoxymethyl (η ⁵ -2, 3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) Dimethyl, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl, (t-butylamido) dimethyl (η ⁵ -2,3-dimethyl- s-indacene-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indacene- 1-yl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 2, 4-hexadiene, (t- butylamido) dimethyl (η ⁵ -2,3- dimethyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethyl amino ) Benzyl, (t- butylamido) dimethyl (η ⁵ -2,3- dimethyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) dimethyl (η ⁵ -2 , 3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl, (t-butylamido) dimethoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) Silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) dimethoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II ) 1,3-pentadiene, (t-butylamido) dimethoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 2,4-hexadiene, (t -Butyl amido) dimethoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) Dimethoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) dimethoxy (η ⁵ -2,3-dimethyl-s-inda Sen-1-yl) silanetitanium (IV) dibenzyl, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1 , 4-diphenyl-1,3- Other diene, (t- butylamido) di isopropoxy (η ⁵ -2,3- dimethyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene, (t- butylamido Fig. 2) Diisopropoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 2,4-hexadiene, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) diisopropoxy (η ⁵ -2 , 3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl ) Silanetitanium (IV) dibenzyl, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl- 1,3-butadiene, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene, (t- Butyl amido) ethoxymethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 2,4-hexadiene, (t-butylamido) ethoxymethyl (η ⁵ -2,3- Dimethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethyl-s- Indansen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl , (Dimethylamine) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) dimethyl, (dimethylamine) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) dibenzyl, (Diisopropylamine) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) dimethyl, (diisopropylamine) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) Dibenzyl, (di-n-butylamine) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) dimethyl, (di-n-butylamine) dimethyl (η ⁵ -2,3-dimethyl Nil) silanetitanium (III) dibenzyl, (di-iso-butylamine) dimethyl (η ⁵ -2,3-dimethylindenyl) silanitanium (III) dimethyl, (di-iso-butylamine) dimethyl (η ⁵ -2,3-dime Tildeinyl) silanetitanium (III) dibenzyl, (dimethylamine) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) dimethyl, (dimethylamine) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, (diisopropylamine) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl ) Silanetitanium (III) dimethyl, (diisopropylamine) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, (di-n-butylamine) Dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanitanium (III) Dimethyl, (di-n-butylamine) dimethyl (η ⁵ -2,3-dimethyl-s-indacene -1-yl) silanetitanium (III) dibenzyl, (di-isobutylamine) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) dimethyl, (di- Isobutylamine) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, (t-butylamido) dimethyl (η ⁵ -2-methyl-3- Ethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) Methyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t-butylamido) dimethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (IV) dimethyl, (t-butylamido) dimethyl (η ⁵ -2-methyl-3-ethylindenyl ) silane titanium (IV) dibenzyl, (t- butylamido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido) dimethoxy (η ⁵ -2- -methyl-3-ethyl-indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethoxy (η ⁵ -2--methyl-3-ethyl-carbonyl) Silane titanium (IV) dimethyl, (t- butylamido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dibenzyl, (t- butylamido) di isopropoxy ( η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) diisopropoxy (η ⁵ -2-methyl- 3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 2, 4-hexadiene, (t- butylamido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- Butyl amido) diisopropoxy (η ⁵ -2-methyl-3-ethylindenyl) silane titanium (IV) dimethyl, (t-butyl amido) diisopropoxy (η ⁵ -2-methyl-3- ethyl-indenyl) silane titanium (IV) dibenzyl, (t- butylamido) ethoxymethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,4- diphenyl -1, 3-butadiene, ethoxymethyl (η ⁵ -2- methyl-3-on (t- butylamido) Butylindenyl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) ethoxymethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (II) 2,4-hexa diene, (t- butylamido) ethoxymethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) in Ethoxymethyl (η ⁵ -2-methyl-3-ethylindenyl) silane titanium (IV) dimethyl, (t-butyl amido) ethoxymethyl (η ⁵ -2-methyl-3-ethyl indenyl) silane titanium (IV) Dibenzyl, (t-butylamido) dimethyl (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3 -Butadiene, (t-butylamido) dimethyl (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene, (t-butylamido ) dimethyl (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethyl (η ⁵ -2- methyl indazol-3-ethyl -s- metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethyl (η ⁵ -2- methyl-3 Ethyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) dimethyl (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium ( IV) Dibenzyl, (t-butylamido) dimethoxy (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3 -Butadiene, (t-butylamido) dimethoxy (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene, (t-butylamido Fig.) dimethoxy (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethoxy (η ⁵ - 2-methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethoxy (η ⁵ -2- methyl indazol-3-ethyl -s- metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) dimethoxy (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-yl ) Silanetitanium (IV) dibenzyl, (t-butylamido) diisopropoxy (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (II) 1,4- Diphenyl-1,3-butadiene, (t-butyl Amido) di isopropoxy (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene, (t- butylamido) di isopropoxy Foxy (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (II) 2,4-hexadiene, (t-butylamido) diisopropoxy (η ⁵ -2 -indazol-3-ethyl -s- metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) di isopropoxy (η ⁵ -2- indazol-3-ethyl -s- metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) di isopropoxy (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene- 1-yl) silanetitanium (IV) dibenzyl, (t-butylamido) ethoxymethyl (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (II) 1, 4-diphenyl-1,3-butadiene, (t- butylamido) ethoxymethyl (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3 in -Pentadiene, (t-butylamido) ethoxymethyl (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (II) 2,4-hexadiene, (t- Butyl amido) ethoxymethyl (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) ethoxymethyl (η in ^{5-ethyl-2-methyl-3--s-} indazol metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) ethoxymethyl (η ⁵ -2-methyl-3-ethyl -s- in Indasen-1-yl) silanetitanium (IV) dibenzyl, (dimethylamine) dimethyl (η ⁵ -2-methyl-3-ethylindenyl) silane titanium (III) dimethyl, (dimethylamine) dimethyl (η ^5- 2-methyl-3-ethyl-indenyl) silane titanium (III) dibenzyl, (diisopropylamine) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) dimethyl, (diisopropyl Amine) dimethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (III) dibenzyl, (di-n-butylamine) dimethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (III) Dimethyl, (di-n-butylamine) dimethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (III) dibenzyl, (di-iso-butylamine) dimethyl (η ⁵ -2 -Methyl-3-ethylindenyl) silanetitanium (III) dimethyl, (Di-iso-butylamine) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) dibenzyl, (dimethylamino) dimethyl (η ⁵ -2- methyl-3-ethyl -s- Line indazol-1-yl) silane titanium (III) dimethyl, (dimethylamine) dimethyl (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (III) dibenzyl, (di Isopropylamine) dimethyl (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanitanium (III) dimethyl, (diisopropylamine) dimethyl (η ⁵ -2-methyl-3- Ethyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, (di-n-butylamine) dimethyl (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silane Titanium (III) Dimethyl, (di-n-butylamine) Dimethyl (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (III) Dibenzyl, (di-iso-butyl Amine) dimethyl (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanitanium (III) dimethyl, (di-iso-butylamine) dimethyl (η ⁵ -2-methyl-3- Ethyl-s-indasen-1-yl) silantitanium (III) dibenzyl. Preferred members of this group are (t-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silantitanium (II) 1,4-diphenyl-1,3-butadiene and (t-butylamido ) Dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silantitanium (IV) dimethyl.

Complexes can be prepared by using well known synthetic techniques. In some cases, reducing agents may be used to produce complexes in lower oxidation states. This method is published internationally as US Patent Application No. 8 / 241,523, filed May 13, 1994, entitled 95-00526, the teachings of which are incorporated herein by reference. Synthesis is carried out in a suitable non-intrusive solvent of temperature -100 to 300 ° C, preferably -78 to 100 ° C, most preferably 0 to 50 ° C. As used herein, "reducing agent" means a metal or compound that causes a reduction of the metal M from a higher oxidation state to a lower oxidation state under reducing conditions. Examples of suitable metal reducing agents are alkali metal or alkaline earth metals, such as alkali metals, alkaline earth metals, aluminum and zinc, sodium / mercury amalgam and sodium / potassium alloys. Examples of suitable reducing agent compounds are sodium naphthalenide, potassium graphite, lithium alkyl, lithium or potassium alkadienyl and Grignard reagents. Preferred reducing agents include alkali or alkaline earth metals, in particular lithium or magnesium metals.

Suitable reaction media for the formation of catalyst complexes are aliphatic and aromatic hydrocarbons, ethers, and cyclic ethers, especially branched chain hydrocarbons such as isobutane, butane, pentane, hexane, octane, and mixtures thereof, cyclohexane, cycloheptane, methyl cyclohexane and methyl cycloheptane, and mixtures thereof, such as cyclic hydrocarbons or alicyclic hydrocarbons, benzene, toluene, and xylene, C _1-4 dialkyl ethers, (poly) alkylene glycol of C _1-4 dialkyl Ether derivatives, and aromatic or hydrocarbyl substituted aromatic compounds such as tetrahydrofuran (THF). Mixtures thereof are also suitable.

The complex is catalytically activated by combining the complex with an activation promoter or by using an activation technique. Suitable activating promoters for use in the present invention are polymerization or oligomeric alumoxanes, C _1-30 hydrocarbyl substituted Group 13 compounds, in particular methylalumoxane, triisobutyl aluminum modified methylalumoxane, or isobutylalumoxane Tri (hydrocarbyl) aluminum or tri (hydrocarbyl) boron compounds and their halogenated derivatives (perhalogenated derivatives) having, in particular, each hydrocarbyl or halogenated hydrocarbyl group having from 1 to 10 carbon atoms ), More particularly perfluorinated tri (aryl) boron compounds, and neutral Lewis acids, most specifically tris (pentafluorophenyl) borane (hereinafter referred to as "FAB"), non-polymerized, compatible, non- Coordination ion-forming compounds (the use of such compounds under oxidative conditions, in particular ammonium salts of phosphate noncoordinating anions, phosphonium salts, oxonium salts, carbonium salts, It includes a reel salts or sulfonium salts, or comprises a ferro used senyum salt of a non-coordinating anion in the chemical conversion), and blends and techniques of the activation cocatalyst. The activation promoters and activation techniques are described in the following references, European Patent A-277,003, US Patent 5,153,157, US Patent 5,064,802, and European Patent A-468,651 for each different metal complex (US Application No. 07). / 547,718), European Patent A-520,732 (equivalent to US Application No. 07 / 876,268), and European Patent A-520,732 (filed May 1, 1992) / 884,966), the teachings of which are incorporated herein by reference.

Blends of neutral Lewis acids, in particular combinations of trialkyl aluminum compounds having from 1 to 4 carbon atoms in each alkyl group and halogenated tri (hydrocarbyl) borons having from 1 to 20 carbon atoms in each hydrocarbyl group, Particularly preferred activating promoters are in particular FABs, also combinations of such neutral Lewis acids with polymerized or oligomeric alumoxanes and single neutral Lewis acids, especially combinations of FAB with polymerized or oligomeric alumoxanes. The preferred molar ratio of Group 4 metal complex: FAB: alumoxane is 1: 1: 1 to 1: 5: 20, more preferably 1: 1: 1.5 to 1: 5: 10. The use of lower levels of alumoxane in the process of the present invention enables the production of EAODM polymers with high catalytic efficacy with little use of expensive alumoxane promoters. In addition, polymers with a low level of aluminum residue and thereby higher transparency are obtained.

Suitable ion forming compounds useful as cocatalysts contain cations, Bronsted acid, capable of providing protons, and compatible, uncoordinated anions A ⁻ . As used herein, the term "non-coordinating" is unstable or unstable enough to be substituted with a neutral Lewis base because it is not coordinatively bound to the Group 4 metal-containing precursor complexes and the catalytic derivatives derived therefrom or only weakly coordinating to such complexes. Means an anion or substance to be maintained. By non-coordinating anion is specifically meant an anion which, when acting as a charge balanced anion in a cationic metal complex, does not transfer anion substituents or fractions thereof to the cation thereby forming a neutral complex. "Compatible anions" means anions that do not decompose neutrally when the complexes formed initially collapse and do not interfere with the next polymerization or other complex required.

Preferred anions include a single coordination complex containing a charged metal or metalloid core and can balance the charge of active catalytic species (metal cations) that can be formed when the two components are combined. In addition, the anion must be sufficiently unstable to be replaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds comprising anions containing coordinating complexes containing single metal or metalloid atoms are well known and many, especially such compounds containing a single boron atom in part of a cation, are commercially available.

Preferably such promoter is represented by the following formula.

(L ^* -H) _d ⁺ (A) ^d-

Wherein L ^* is a neutral Lewis base,

(L ^* -H) ⁺ is Bronsted acid,

A non-coordinating anion having the charge of the chemical conversion ^- A ^d- d is an integer of 1 to 3 d. More preferably A ^d- is of the formula [M'Q ₄ ] ^- (wherein M 'is boron or aluminum in the formal oxidation state +3, and Q is each independently hydride, dialkylamido, halide, hydrocarby). Bill, hydrocarbyloxide, halogen substituted hydrocarbyl, halogen substituted hydrocarbyloxy, and halogen substituted silylhydrocarbyradical (perhalogenated hydrocarbyl-, perhalogenated hydrocarbyloxy- and perhalogenated silyl Hydrocarbyl radicals), and Q has up to 20 carbon atoms, with Q being halide if less than one. Examples of suitable hydrocarbyloxide Q groups are disclosed in US Pat. No. 5,296,433, the teachings of which are incorporated herein by reference.

In a more preferred embodiment, d is 1, ie the counter ion has a single negative charge and is A ⁻ . Boron-containing activating promoters which are particularly useful for preparing the catalyst of the present invention are

(L ^* -H) ⁺ (BQ ₄ ) ^-

Wherein L ^* is as defined above, B is boron in formal oxidation state 3, Q is hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy having up to 20 carbon atoms Or a fluorinated silylhydrocarbyl group, where Q is hydrocarbyl when there is no more than one.

Most preferably, Q is each a fluorinated aryl group, in particular a pentafluorophenyl group.

Specific examples of the boron compounds that can be used as activating promoters in the improved catalyst preparation of the present invention include trimethylammonium tetrakis (pentafluorophenyl) borate, di (hydrogen-taloalkyl) methylammonium tetrakis (pentafluorophenyl) Borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl ) Ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (t-butyldimethyl-silyl) -2,3,5,6-tetrafluorophenyl) borate , N, N- Methylanilinium tetrakis (4- (triisopropylsilyl) 2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium pentafluorophenoxycitries (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium 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-tetrafluoro Rophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6-tetra Tri-substituted ammo, such as fluorophenyl) borate, and N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate Salts, di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl Dialkylammonium salts such as ammonium tetrakis (2,3,4,6-tetrafluorophenyl and dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate Tri-substituted phosphonium salts such as tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, Diphenyloxonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) oxonium tetrakis (pentafluorophenyl) borate, and di (2,6-dimethylphenyl) oxonium tetrakis (pentafluoro Di-substituted oxonium salts such as phenyl) borate, diphenylsulfonium tetraki Such as s (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, and bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate Di-substituted sulfonium salts include, but are not limited to.

Preferred (L ^* -H) ⁺ cations are N, N-dimethylanilinium and tributylammonium.

Other suitable ion forming, activating promoters are

Ⓒ ⁺ A ^-

(Wherein ⓒ ⁺ is C _1-20 carbenium ions and A ⁻ is as defined above) and a compound which is a salt of a carbenium ion and a non-coordinating, compatible anion. Preferred carbenium ions are trityl cations, ie triphenylmethyllium.

More suitable ion formation, activation promoters are represented by the formula

_{R 3 Si (X ') q} + A -

_Wherein R is a hydrocarbyl of C _1-10 and X ', q and A ^- are as defined above.

Preferred silyllium salt activation cocatalysts are trimethylsilyllium tetrakispentafluorophenyl borate, triethylsilyllium tetrakispentafluorophenyl borate and ether substituted their adducts. Silylium salts are described in J. Chem. Chem Soc. Chem. Comm., 1993, 383-384, as well as already described in Lambert et al. (Organometallics, 1994, 13, 2430-2443) by Lambert et al. The use of such silyllium salts as activating co-catalysts for addition polymerization catalysts is in equivalent form US Application No. 304,314, filed September 12, 1994, filed internationally on September 21, 1996, filed 96/08519. And its teachings are incorporated herein by reference.

Certain complexes of alcohols, mercaptans, silanols and oximes with FAB are also useful catalytic activators and may be used according to the invention. Such promoters are disclosed in US Pat. No. 5,296,433, the teachings of which are incorporated herein by reference.

The above activation promoters may be used in combination. Particularly preferred combinations are mixtures of tri (hydrocarbyl) aluminum or tri (hydrocarbyl) borane compounds with oligomeric or polymeric alumoxane compounds having from 1 to 4 carbon atoms in each hydrocarbyl group.

The molar ratio of catalyst / cocatalyst used is in the range from 1: 10,000 to 100: 1, more preferably from 1: 5000 to 1:10 and most preferably from 1: 1000 to 1: 1. When used as an activation promoter, alumoxane is used in large quantities, generally in molar amounts (calculated based on molar amounts of aluminum (Al)) and at least 100 times the amount of metal complex. . FAB is used in a molar ratio of 0.5: 1 to 10: 1, more preferably 1: 1 to 6: 1 and most preferably 1: 1 to 5: 1 relative to the metal complex when used as an activating promoter. The remaining activating promoter is generally used in an approximately molar amount with respect to the metal complex.

In general, the polymerization can be carried out at Ziegler-Natta or Kaminsky-thin form polymerization reaction conditions well known in the art, that is, at a temperature of 0 to 250 ° C., preferably 30 to 200 ° C. and at atmospheric pressure to 10,000 atm. have. Suspensions, solutions, slurries, gas phase, solid state powder polymerization or other process conditions may be used if desired. Supports, in particular silica, alumina or polymers (particularly poly (tetrafluoroethylene) or polyolefins) can be used, preferably when the catalyst is used in a gas phase polymerization process. The support is preferably an amount such that the weight ratio of catalyst (based on metal): support is from 1: 100,000 to 1:10, more preferably from 1: 50,000 to 1:20, most preferably from 1: 10,000 to 1:30. Used as Used in the majority of the polymerization catalyst, the molar ratio of polymerizable compound is 10 ^-12: 1 to 10 ^-1: 1: 1, more preferably from 10 ^-9: 1 to 10 ^-5.

Inert liquids are suitable solvents for polymerization. Cyclic or alicyclic hydrocarbons such as, for example, straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof , Perfluorinated hydrocarbons such as perfluorinated C _4-10 alkanes, and aromatic or alkyl substituted aromatic compounds such as benzene, toluene, xylene, and ethylbenzene. Suitable solvents also include butadiene, cyclopentene, 1-hexene, 1-hexane, 4-vinylcyclohexene, vinylcyclohexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene Liquid olefins that can act as monomers or comonomers, including 1-octene, 1-decene, styrene, divinylbenzene, allylbenzene, and vinyltoluene (including all single isomers or mixed isomers). Mixtures of these are also suitable. If desired, gaseous olefins can generally be converted to liquid by pressurization and used in the present invention.

The catalyst can be used to prepare polymer blends with desirable properties in individual reactors connected in series or in parallel as a combination with additional one or more homogeneous or heterogeneous polymerization catalysts. Examples of such methods are disclosed in US application Ser. No. 07 / 904,770 and US Ser. No. 08/10958, filed Jan. 29, 1993, which is equivalent to International Publication No. 94/00500, the teachings of which are incorporated herein by reference. Cited for reference.

By using such catalysts in the process of the invention, copolymers having high comonomer incorporation and corresponding low density, but high MV, are readily prepared. That is, high M _w polymers are readily obtained by using the catalyst of the invention even at elevated temperatures of the reactor. These results indicate that the M _w of the α-olefin copolymer can be readily reduced by the use of hydrogen or similar chain transfer agents, but the increased molecular weight of the α-olefin copolymer is generally obtained only by reducing the polymerization temperature of the reactor. It is very desirable as it can. Operation of the polymerization reactor at reduced temperatures is disadvantageous due to a significant increase in operating costs since heat from the reactor must be removed to maintain the reduced reaction temperature while simultaneously applying heat to the reactor discharge to evaporate the solvent. . In addition, productivity is improved because of improved polymer solubility, reduced solution viscosity, and higher polymer concentration. By using the catalyst of the present invention, α-olefin homogeneous polymers and copolymers having a density of 0.85 g / cm ³ to 0.96 g / cm ³ and MV of 1 to 150 can be easily produced in a high temperature process.

The catalyst used in the process of the invention is particularly advantageous for the production of copolymers with high long chain branching levels. The use of a catalyst in a continuous polymerization process, in particular in a continuous solution polymerization process, can be incorporated into a growing polymer, thereby allowing the temperature of the reactor to promote the formation of vinyl terminated polymer chains that provide long chain branching. The inherent blend at elevated temperatures of the reactor, high molecular weight (or low melt index) and high comonomer reactivity at high temperatures in the reactor are advantageous to enable economic production of polymers with good physical properties and processability.

The method used to prepare the EAODM copolymer of the present invention may be a solution or slurry process already known in the art. Kaminsky is described in J. Poly. Sci., Vol. 23, pp. 2151-64 (1985) suggests the use of soluble bis (cyclopentadienyl) zirconium dimethyl-alumoxane catalyst systems for the solution polymerization of EP and EAODM elastomers. U.S. Patent 5,229,478 discloses a slurry polymerization process using a catalyst system based on a similar bis (cyclopentadienyl) zirconium.

In general terms, it is desirable to produce EAODM elastomers under conditions of improved reactivity of the diene monomer component. The reason is explained in the above '478 patent as follows and is still true despite advances made in this reference. The main factor influencing the cost of production and hence the use of EADOM is the cost of the diene monomer. Dienes are more expensive monomer materials than C ₂ or C ₃ . In addition, the reactivity of the diene monomer with the metallocene catalyst already known is lower than that of C ₂ or C ₃ . The result is a substantial excess of the percentage of diene required to be incorporated into the final EAODM product, expressed as a percentage of the total concentration of monomer present, to achieve the appropriate level of diene incorporation to produce EAODM at an acceptable fast cure rate. It is necessary to use the concentration of the diene monomer. Substantial amounts of unreacted diene monomer must be recovered from the discharge of the polymerization reactor to recover unnecessarily increased production costs.

In addition, increasing the cost of producing EAODM generally results in the exposure of olefin polymerization catalysts to dienes, particularly the high concentrations of diene monomers required to produce the appropriate level of diene incorporation in the final EAODM product. It is a fact that reduces the rate or reactivity of advancing the polymerization of monomers. Thus, lower raw material throughput and longer reaction times are required as compared to the production of ethylene-propylene copolymer elastomers or other α-olefin copolymer elastomers.

The catalyst system used in the process of the present invention advantageously makes it possible to produce EAODM polymers with improved diene reactivity and thereby high yields and high productivity. The process also achieves the production of economical EAODM of diene content of greater than 0 to 20% by weight, or even higher, preferably 0.3 to 20% by weight, more preferably 0.5 to 12% by weight. Such EAODM polymers have very desirable fast cure rates.

The EAODM elastomer preferably has a C ₂ content of 20 to 90% by weight or less, more preferably 30 to 85% by weight, most preferably 35 to 80% by weight.

Α-olefins other than C ₂ are generally incorporated in EAODM polymers at 10-80% by weight, more preferably 20-65% by weight. Non-conjugated dienes are generally incorporated into the EAODM polymer at 0.5 to 25% by weight, preferably 1 to 15% by weight, more preferably 3 to 12% by weight. If desired, one or more dienes may be incorporated simultaneously, for example 1,4-hexadiene and ENB, with the overall diene mixing rate being within the above specified limits.

The catalyst system used in the process of the present invention can be prepared as a homogeneous catalyst by adding appropriate components to the solvent in which the polymerization is carried out by a solution polymerization process. The catalyst system can also be prepared and used as a heterogeneous catalyst by adsorbing the appropriate components on a catalyst support material such as silica gel, alumina or other suitable inorganic support material. When produced in non-uniform or supported form, preference is given to using silica as a support material. The heterogeneous catalyst system is used for slurry polymerization. As a practical limitation, slurry polymerization is carried out in liquid diluents in which the polymer product is substantially insoluble. Preferably, the diluent for slurry polymerization is at least one C _1-5 hydrocarbon. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or in part as diluents. Similarly, α-olefin monomers or mixtures of different α-olefin monomers may be used in whole or in part as diluents. Most preferably the diluent contains, as a major part, at least the α-olefin monomer or monomers to be polymerized.

As described above, the EAODM polymers of the present invention are another well known, in which the cooling of the reactor is typically caused by the evaporative cooling of volatiles such as recycle gases, inert liquids or monomers or dienes used in the preparation of the EAODM polymers. It may also be prepared by gas phase polymerization, which is a conventional method. Suitable inert liquids are C _3-8 , preferably C _4-6 , saturated hydrocarbon monomers. The volatiles or liquid evaporate in the hot fluidized bed to form a gas that is mixed with the fluidizing gas. Such process forms are described, for example, in European Patent No. 89691, US Patent No. 4,543,339, International Publication No. 94/25495 and US Patent No. 5,352,749, the teachings of which are incorporated herein by reference. have. U.S. Patents 4,588,790, 4,543,399, 5,352,749, 5,436,304, 5,405,922, 5,462,999, 5,461,123, 5,453,471, 5,032,562, 5,028,670 5,473,028, 5,106,804, 5,541,270, European Patent A-659,773, A-692,500, PCT International Publication Nos. 94/29032, 94/25497, 94 Other related teachings found in / 25495, 94/28032, 95/13305, 94/26793, and 95/07942 are also incorporated by reference.

The polymerization reaction taking place in the gas fluidized bed is catalyzed by continuous or semicontinuous addition of the catalyst. Such catalysts may be supported on inorganic or organic support materials.

Gas phase processes suitable for the practice of the present invention preferably provide a continuous supply of reactants to the reaction zone of the reactor and remove product from the reaction zone of the reactor, thereby providing a steady state environment on a large scale in the reactor reaction zone. It is a continuous process.

In contrast, solution polymerization conditions use a solvent for each reaction component. Preferred solvents include mineral oils and various hydrocarbons that are liquid at reaction temperatures. Specific examples of useful solvents include pentane, iso-pentane, hexane, heptane, octane and nonane, as well as alkanes such as kerosene and isopar-E (registered trademark), available from Exxon Chemical Inc. And cycloalkanes such as cyclopentane and cyclohexane, and aromatics such as benzene, toluene, xylene, ethylbenzene and diethylbenzene.

At all times, the recovered components as well as the individual components must be protected from oxygen and moisture. Therefore, the catalyst component and the catalyst are preferably produced and recovered in an atmosphere free of oxygen and moisture, and should be so. The reaction is therefore preferably carried out in the presence of a dry and inert gas such as for example nitrogen.

Ethylene is added to the reaction vessel in an amount sufficient to maintain a differential pressure above the combined vapor pressure of the α-olefin and diene monomers. The C ₂ content of the polymer is determined by the ratio of C ₂ differential pressure to the total reactor pressure. Generally, the polymerization takes place with a C ₂ differential pressure of 10 to 1000 psi (70 to 7000 kPa), most preferably 40 to 400 psi (30 to 300 kPa). The polymerization temperature is suitably 25 to 200 ° C., preferably 65 to 170 ° C., most preferably higher than 75 and up to 140 ° C.

The polymerization can be carried out in a batch or continuous polymerization process. A continuous process is preferred, in which the event catalyst, ethylene, α-olefin, diene and optionally a solvent are continuously fed to the reaction zone and the polymer product is continuously removed therefrom.

Without limiting the scope of the present invention in any way, the method for carrying out this polymerization process is as follows. The α-olefin monomer is continuously introduced into the stirred tank reactor together with the solvent, diene monomer and C ₂ monomer. The reactor comprises substantially a liquid phase composed of C ₂ , C ₃ and diene monomers and any solvent or additional diluent. If necessary, small amounts of “H” branched derivative dienes such as norbornadiene, 1,7-octadiene or 1,9-decadiene may be added. The catalyst and cocatalyst are introduced continuously into the liquid phase in the reactor. The reaction temperature and pressure can be controlled by adjusting the solvent / monomer ratio, catalyst addition rate as well as cooling or heating coils, jackets or both. The rate of polymerization is controlled by the rate of catalyst addition. The ethylene content in the polymer product is determined by the amount of ethylene, α-olefin and diene in the reactor, which is controlled by the respective rates of feeding these components to the reactor. The polymer product molecular weight is optionally controlled by control of other polymerization parameters such as temperature, monomer concentration, or stream of hydrogen introduced into the reactor, as is known in the art. The reactor discharge is contacted with a catalyst deactivator such as water. The polymer solution is optionally heated by flashing gas ethylene and propylene as well as residual diene and residual solvents or diluents at reduced pressure and, if necessary, further devolatilization in an apparatus such as a devolatilizing extruder. It is recovered. In a continuous process, the average residence time of the catalyst and polymer in the reactor is generally 5 minutes to 8 hours, preferably 10 minutes to 6 hours.

In a preferred manner of operation, the polymerization is carried out in a continuous solution polymerization system comprising two reactors connected in series or in parallel. In a first reactor, a product of relatively high molecular weight (300,000 to 600,000, more preferably 325,000 to 500,000 Mw) is formed, and in a second reactor, a product of relatively low molecular weight (50,000 to 300,000 Mw) is formed. . Alternatively, products of the same molecular weight can each be formed in two reactors. The final product is a blend of two reactor effluents that are combined into a uniform blend of two polymer products before devolatilization. This two reactor process allows for the production of products with improved properties. In a preferred embodiment, the reactors are connected in series. That is, the discharge from the first reactor is charged to the second reactor and fresh monomer, solvent and hydrogen are added to the second reactor. The reactor conditions are adjusted so that the weight ratio of the polymer produced in the first reactor and the polymer produced in the second reactor is 20:80 to 80:20. However, if necessary, a wider range of weight ratios can be used. In addition, the temperature of the second reactor is controlled to produce a lower M _w product. This system allows for the production of EAODM products with a wide MV range as well as good strength and processability. The MV of the resulting product is adjusted to be low, preferably from 1 to 150, more preferably from 10 to 120, most preferably from 15 to 100. Although this mode of operation using two reactors is preferred, three or more reactors may be used.

The following examples illustrate the invention without limiting it, either directly or by suggestion. Unless stated otherwise, all parts and percentages are by weight. Examples of the present invention are indicated by Arabic numerals, and comparative examples are indicated by the alphabet.

For catalyst examples, ¹ H and ¹³ C NMR spectra were recorded on a Varian XL (300 MHz) spectrometer. Chemical shifts are determined with respect to TMS (tetramethylsilane) or via residual C ₆ HD ₅ in CHCl ₃ or residual C ₆ D ₆ in CDCl _{3 relative to} TMS. Tetrahydrofuran (THF), diethylether, toluene, and hexane are activated alumina or alumina supported mixed metal oxide catalysts (Q-5 (registered trademark) catalysts available from Engelhard Corp.). It is used in the following path through a packed double column. Compound n-BuLi, KH, all Grignard reagents, and 1,4-diphenyl-1,3-butadiene were purchased from Aldrich Chemical Company and used. All catalyst synthesis was performed under a dry nitrogen atmosphere using a combination of glove box and high vacuum technology.

Polymer Example Preparation used a continuous process or a batch process. In a batch process, monomers and other specific components are added to the reactor equipment prior to initiation of the process. In a continuous process, monomers are added to the reactor apparatus when needed, and a change in flow rate is used to change the monomer concentration. Each example specifies process form and conditions. The process run time of 1-2 hours is generally enough time to reach equilibrium and provide a representative polymer sample for analysis.

A number of standard tests were used to determine the physical properties of EAODM polymers such as MV, compositional analysis via Fourier Transform infrared analysis (FTIR), and density (ASTM D-792). Other critical properties including the B value are determined as above, the rheological ratio is determined as follows, and the reactive ratio product is also determined as follows.

The rheology ratio (V _1.0 / V ₁₀₀ ) uses melt rheology technology for Advanced Rheometric Expansion System (ARES) dynamic mechanical spectrometers (RRES) from Rheometric Scientific, Inc. Is determined by testing the sample. This sample was tested at 190 ° C. using an automatic frequency system and parallel plate holders of 25 mm diameter with 2 mm spacing. The rate of strain is 8% and the rate of oscillation rapidly increases from 0.1 to 100 radians per second at five measurement points taken every tenth of the analyzed frequency. Each sample (pellet or bail) is compression molded for 1 minute at 138.9 MPa (20,000 psi), 180 ° C., to a thickness of 0.049 cm (1/8 inch) of 1.18 cm (3 inch) plaque. The plaques are quenched and cooled (over 1 minute) to room temperature. Cut 25 mm plaques from the central portion of the large plaques. This 25 mm diameter aliquot is inserted into the ARES at 190 ° C. and allowed to equilibrate for 5 minutes before starting the test. Samples are maintained in a nitrogen environment during analysis to minimize oxidative degradation. Data organization and manipulation was performed by a software package based on the ARES2 / A5: RSI Orchestrator Windows 95 standard. The V _0.1 / V ₁₀₀ ratio (the rheological ratio, or “RR”) is determined by measuring the slope of the viscosity against the shear rate curve.

Reactivity ratios, r1 and r2, are calculated from divalent and trivalent atom distributions in ¹³ C NMR spectra based on the final copolymerization model, and the reactivity ratio product (RRP) is obtained by multiplying these two values (r1 and r2). . ¹³ C NMR sample preparation was as described above.

Polymer crystallinity is determined by differential scanning calorimetry (DSC) using a TA DSC-2920 equipped with a liquid nitrogen cooling accessory. Samples are made into thin films and placed in aluminum baths. They are initially heated to 180 ° C. and held at this temperature for 4 minutes to ensure substantially complete melting. They are then cooled to −100 ° C. at 10 ° C. per minute and then reheated to 150 ° C. at 10 ° C. per minute. Tg is obtained from the melting point curve using the first derivative of the temperature. The total heat of fusion is obtained from the lower area of the melting point curve. Percentage crystallinity is determined by dividing the entire row of fusion by the polyethylene fusion row value (292 J / g).

Catalytic efficacy (Cat. Eff) is characterized as one million pounds of polymer (MM # / #) per pound of Group IV metal in the catalyst. For the batch process, this is determined by weighing the polymer product and dividing by the amount of Group IV metal added to the reactor. For continuous processes, the weight of the polymer product is determined by measuring ethylene or vent conversion.

Examples of EAODM polymers representing the present invention use catalysts prepared as follows, while comparative example EAODM polymers are the same as those described in US Pat. Nos. 5,491,246, 5,486,632 and 5,470,993. It is made using a confinement catalyst.

Catalyst manufacturing

Example 1 Synthesis of (t-butylamido) -dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (IV) dimethyl

1a) Preparation of 5,6,7-tetrahydro-2-methyl-s-indasen-1-one

Indan (59.0876 grams (g), 0.5000 moles) and 2-bromoisobutyryl bromide (114.9493 g, 0.5000 moles) at 0 ° C. with AlCl ₃ (201.36 g, 1.5101 moles) as a solid under a nitrogen (N ₂ ) flow. Stir in CH ₂ Cl ₂ (500 milliliters (mL)) with slow addition. The mixture was stirred at 20-25 ° C. for 6 hours. After the reaction period the mixture was poured into ice and left for 16 hours. The mixture was then poured into a separatory funnel and the remaining salts washed well with CH ₂ Cl ₂ . The organic layer was then separated and the dark oil was isolated by removing volatiles. Vacuum distillation isolated the desired product as a yellow oil (82.43 g, 88.5% yield).

1b) Preparation of s-indacene-1,2,3,5-tetrahydro-6-methyl

The product of Example 1a) (40.00 g, 0.2148 mol) was added to diethyl ether (150 mL) at 0 ° C. at 0 ° C. with stirring slowly under nitrogen with slow addition of NaBH ₄ (8.12 g, 0.2148 mol) and EtOH (100 mL). The mixture was then stirred and reacted at 20-25 ° C. for 16 hours. After this period, the mixture was poured onto ice and acidified with aqueous 1 mol (M) HCl solution. The organic portion was washed with 1 M HCl (2 × 100 mL). The volatiles were removed from the solution and the residue was redissolved in benzene and refluxed with p-toluenesulfonic acid (0.11 g) for 5 hours using Dean Stark apparatus. The mixture was extracted using 1M NaOH ₃ (2 × 100 mL). The organic layer was then separated and the volatiles removed to isolate the desired product as a white crystalline solid.

1c) Preparation of (1,5,6,7-tetrahydro-2-methyl-s-indasen-1-yl)

The product of Example 1b) (25.000 g, 0.14684 mol) was added to hexane (400 mL) with slow addition of nBuLi (0.17621 mol, 70.48 mL of a 2.5 M solution in hexane) to give a reaction mixture which was then stirred and The reaction was carried out for 16 hours, during which solid precipitated. The mixture was filtered to isolate the desired product as a pale yellow solid (24.3690 g, 94.2% yield), which was used without further purification or analysis.

1d) Preparation of N- (1,1-dimethylethyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-2-methyl-s-indasen-1-yl) silaneamine

The product of Example 1a) in tetrahydrofuran (THF) (200 mL) (25.0 g, 0.1419 mol) was converted to dimethylsilyl (t-butylamino) chloride (23.518 g, 0.1419) in tetrahydrofuran (THF) (250 mL). Molar) over 1 hour to give the reaction mixture which was then stirred and reacted for 20 hours. After this period, the volatiles were removed and the residue was extracted using hexanes and filtered. Hexane was removed to isolate the desired product as red yellow oil (37.55 g, 88.0% yield).

1e) Preparation of N- (1,1-dimethylethyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-2-methyl-s-indasen-1-yl) silaneamide

The product of Example 1d) (8.00 g, 0.2671 mol) was stirred dropwise with hexane (110 mL) nBuLi (0.05876 mol, 23.5 mL of a 2.5 M solution in hexane) to give a reaction mixture and the reaction mixture was stirred and then 16 The reaction was carried out for a time. After this period, a pale yellow solid (6.22 g, 75% yield) used without further purification or analysis was produced by filtration as the desired product.

1f) dichloro [N- (1,1-dimethylethyl) -1,1-dimethyl- [1,2,3,4,5-η] -1,5,6,7-tetrahydro-2-methyl- Preparation of s-indasen-1-yl] silaneamineto (2-)-N] titanium

The product of Example 1e) in THF (40 mL) (4.504 g, 0.01446 mol) was added dropwise to a slurry of TiCl ₃ (THF) ₃ (5.359 g, 0.001446 mol) in THF (100 mL) and stirred for 1 hour. , PbCl ₂ (2.614 g, 0.000940 mol) was added and stirring continued for an additional hour. After this period the volatiles were removed and the residue was extracted and filtered using toluene. Toluene was removed to isolate the dark colored residue. The residue was slurried in hexane and the desired product was isolated via filtration as a red solid (3.94 g, 65.0% yield).

1g) Synthesis of Complexes of Formula IV

The product of Example 1f) (0.450 g, 0.00108 mol) was stirred with slowly adding MeMgBr (0.00324 mol, 1.08 mL of 3.0 tmol solution in diethyl ether) to diethyl ether (30 mL) to give a reaction mixture, The reaction mixture was then stirred and reacted for 30 minutes. After this period, the volatiles were removed and the residue was extracted and filtered using hexanes. Hexane was removed to isolate the desired product as a solid (0.37 g, 90.6% yield).

Example 2-Synthesis of Complexes of Formula III

Dry box (glove box) in, (t- butylamido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium dichloride (Example 1f)) (0.300 g, 0.72 mmol ) Was suspended in 50 mL of cyclohexane in a 100 mL round bottom flask. An equal amount of 2,4-hexadiene (0.822 mL, 7.21 mmol) isomer of the mixture was added to the contents of the flask to form a mixture. A 2.0 M Et ₂ O solution of 2 and 1/4 equivalents of n-BuMgCl (0.81 mL, 1.62 mmol) was added to the mixture to form a reaction mixture. The flask was placed in a condenser and the reaction mixture was heated to reflux for 1 hour. While cooling, the volatiles were removed under reduced pressure to leave a residue and the residue was extracted with hexane and hexane was removed under reduced pressure through a diatomaceous earth filling aid to give 0.29 g of brown oily solid as the desired product (94% yield and equivalent). Got it. The product specified by ¹ H and ¹³ C NMR was (t-butylamido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanitanium (II) 2,4-hexadiene.

Example 3-Synthesis of Complexes of Formulas VII and VIII

Using the apparatus and method of Example 2, 15 equivalents of 1,3-pentadiene (1.08 mL, 10.81 mmol) isomeric mixture for 10 equivalents of hexadiene isomer, 2 for 2.25 equivalents of n-BuMgCl solution 2.0 M Et2O Replace the same amount of 2.5 M hexane solution n-BuLi (0.58 mL, 1.44 mmol) and store 0.257 g of brown oily solid (86% yield) to extend the reflux time to 3 hours. ^The solid specified by ¹ H and ¹³ C NMR was (t-butylamido) -dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene . The product was isolated as a mixture of two geometric isomers obtained in the orientation of 1,3-pentadiene relative to the methyl group on the indasenyl ring as shown in formulas (VII) and (VIII).

Examples 4-7 and Comparative Examples A and B

Five sample ethylene / propylene / ENB ternary copolymer compositions, namely four (Examples 4-7) and one comparative example (Comparative Example A) representing the present invention, were continuously added with the reactants and the polymer solution It was prepared using the same basic process with the specific differences indicated in Table IA-1C in a 3.8 liter (L) stirred reactor designed for the continuous removal, devolatilization and polymer recovery. Examples 4-7 were prepared using the catalyst of Example 1. Comparative Example A was prepared using (tetramethylcyclo-pentadienyl) dimethyl (t-butylamido) silanetitanium 1,3-pentadiene as a catalyst. The promoter for all five samples was FAB. The scavenger for Examples 4-5 and Comparative Example A was MMAO (triisobutyl aluminum modified methylalumoxane). The scavengers for Examples 6 and 7 were DIEL-N ((diisopropylamido) diethylaluminum) and DIBAL-NS ((bistrimethylsilamido) diisobutylaluminum), respectively. The molar ratio of FAB to mole of titanium (Ti) was 3.0 for Examples 4-7 and 3.6 for Comparative Example A. Melt index (MI) for Comparative Example A was 25.0 g / 10 min. Comparative Example A had M _w too low to measure MV, so MI was used for Comparative Example A. Examples 4-7 had M _w high enough to measure MV.

Further comparative example (B) was prepared in a similar manner but without hydrogen. The composition of this polymer is similar to that of Examples 4-7, and the removal of hydrogen allows for a polymer production that is more closely matched to the molecular weight.

Referring to FIG. 1, isopar commercially available from alkane solvents (Exxon Chemical Inc.) mixed after combining ethylene (4), propylene (5), and hydrogen (6) into a single stream (16). (Isopar) -E; Trademark] (1) and diene (2) are introduced into the diluent mixture to form a combined feed mixture (7) which is continuously injected into the reactor (10). The catalyst (8) and the blend (9) of the cocatalyst and the scavenger are combined in a single stream (17) and also continuously injected into the reactor.

Table IA lists the flow rates of solvent, ethylene (C ₂ ) and propylene (C ₃ ) in pounds per hour (pph). Table IA also indicates the percent conversion of C ₂ and the rate of polymer production in pph. Table IB indicates the concentrations of catalyst (Cat), cocatalyst (Cocat) and scavenger (Scav) in parts per million (ppm) corresponding to Al parts. Table IB also shows the ratio of promoter to metal (M) where M is titanium (Ti) and the flow rate in pph for catalyst, promoter and scavenger. Table IC shows reactor temperature (Temp) in ° C, hydrogen flow in standard cubic centimeters per minute (sccm), ENB flow rate (pph), ratio of scavenger: titanium (Scav / Ti) and polymer properties [MV, MI, and EAODM composition (determined by FTIR)], B value, V _0.1 / V ₁₀₀ and RRP.

Reactor outlet stream 15 is continuously introduced into separator 11 where the molten polymer is continuously separated from unreacted comonomer, unreacted ethylene, unreacted hydrogen, unreacted ENB and solvent 14. The molten polymer is subsequently broken down or pelletized strand, which is then cooled in a water bath or pelletizer, after which the solid pellets are collected (13).

The data presented in Table IC illustrate several points. First, under essentially the same reaction conditions, the M _w of the polymers of Examples 4-7 is much greater than the M _w of Comparative Example A, as exemplified in the MV measurements. This increase in M _w is not so much influenced by the type of scavenger used in the reaction. Second, at the same ENB flow rate (Example 4 and Comparative Example A), the incorporation rate of ENB into the polymer increased by 66.7%. In order to obtain an ENB concentration equal to the ENB concentration of Comparative Example A, the flow rate of ENB should be reduced from 0.7 pph to 0.4 pph in Examples 5-7. Comparison of Comparative Example A with Example 5 shows a significantly increased efficacy of the catalyst in producing essentially the same polymer in terms of ENB incorporation.

The data in Table IC also suggest that the polymers of the invention represented by Examples 4-7 have desirable shear viscosity behavior and satisfactory levels of long chain branching. The ratio of V _1.0 / V ₁₀₀ is a measure of the slope of the viscosity with respect to the shear rate curve. High V _1.0 / V ₁₀₀ ratios as in Examples 4-7 suggest higher shear sensitivity or shear viscosity for low V _1.0 / V ₁₀₀ ratios as in Comparative Example B. Shear viscosity is typically affected by both MWD and long chain branching, and the polymers of Examples 4-7 and Comparative Examples A and B all have similar molecular weight distributions (MWD), so higher ratios of V _1.0 / V ₁₀₀ Also represents longer chain branches. The polymers of the present invention have a higher rheological ratio at the same MV as the polymers being compared, as evidenced by comparing Examples 4-7 with Comparative Example B. Comparative Example B, prepared in the absence of hydrogen, has a lower V _1.0 / V ₁₀₀ ratio than any of Examples 4-7. Hydrogen deficiency usually results in higher levels of vinyl unsaturation resulting in long chain branching, higher shear viscosity behaviors, and higher V _1.0 / V ₁₀₀ ratios, so that the data do not need to be excluded from the invention. Suggests.

Example 8

Ternary copolymerization of ethylene, propylene, and ENB was charged with 1448 g of Isopar-E [commercially available from Alkanes, Exxon Chemical Inc.], 230.3 g of propylene, 32.9 g of ENB, and 13.8 mmol of hydrogen. Was carried out using a 3.8 L stainless steel reactor. The reactor was heated to 100 ° C. and saturated with ethylene to 460 psig (3.24 MPa). 1.0 micromole of catalyst of Example 1 (0.005 M solution), 1.5 micromoles of FAB as cocatalyst (0.0075 M solution), 10.0 micromoles (0.050 M solution) of diethylaluminum (diisopropylamido) as scavenger and total The catalyst was prepared by injecting enough isopar-E together to bring the volume to 18 mL into a dry box. The catalyst solution was then transferred through a syringe into the catalyst addition loop and injected into the reactor using high pressure solvent flow over about 4 minutes. The polymerization was allowed to proceed for 10 minutes while feeding ethylene in a state where it was desired to be maintained at a pressure of 460 psig (3.24 MPa). The amount of ethylene consumed during the reaction was monitored using a mass flow meter. The polymer solution is then poured from the reactor into a nitrogen washed glass kettle and 2000 parts of stabilizer (Irgafos 186® and Irganox 1076) are added per million parts of polymer and the polymer solution Mixed well with The stabilized polymer solution was poured into a tray, air dried overnight and then completely dried in a vacuum oven at 120 ° C. for one day.

The yield of the terpolymer was 89.7 g and the efficacy of the catalyst was 1900000. The ternary copolymer had a ratio of C ₂ / C ₃ of 2.1 (C ₂ 64.5 wt%, C ₃ 30.1 wt%) and an ENB content of 5.5 wt%. The MV was 84.4 and the molecular weight (M _w ) was 185,500 with a MWD (M _w / M _n ) of 2.04. The B value was 0.96 and the RRP for ethylene / propylene was 1.16. Terpolymers had a Tg of -44.9 ° C and a crystallinity of 4.2%.

Example 9

Using the apparatus, catalyst and method of Example 8, an ethylene / propylene / ENB terpolymer was charged using a reactor packed with 1457 g of isopar-E, 232.4 g of propylene, 33.8 g of ENB, and 13.8 mmol of hydrogen. Prepared. The yield of ternary copolymer was 104.7 g and the efficacy of the catalyst was 2200000. The terpolymers had a ratio of ethylene to propylene of 2.0 (C ₂ 65.4 wt%, C ₃ 32.1 wt%) and the content of ENB was 2.5 wt%. The MV was 33.0 and the molecular weight (M _w ) was 134,300 with a MWD of 1.78. The B value was 0.94 and the RRP for ethylene / propylene was 1.21. The terpolymer had a T _g of -46.9 ° C. and a crystallinity of 6.2%.

Comparative Example C (C05R03)

The apparatus and method of Examples 4-7, and Comparative Examples A and B, and (tetramethylcyclo-pentadienyl) dimethyl (t-butylamido) silanetitanium dimethyl as catalyst, FAB as cocatalyst and as scavenger MMAO was used to flow the reactor in the amounts shown in the table below to make ethylene / propylene / ENB terpolymers. The Al / Ti ratio was 6: 1, the MMAO flow rate was 0.3 pph based on _______ and the MMAO concentration was 24.91 ppm. As in Comparative Example B, there is no flow of hydrogen. Tables IIA and IIB show the polymerization parameters and the properties of the resulting polymer.

The data in Table IIB shows that, as shown in Table IC for Comparative Example B, the polymers produced according to the invention are clearly different from the latter catalysts if made with different catalysts, even if made from the same starting material under the same conditions. Explain.

Example 10

Using the apparatus and method of Examples 8 and 2, terpolymers of ethylene / butene-1 / ENB were prepared with 1455 g of isopar-E, 303.3 g of butene-1, 42.6 g of ENB, and 9.46 mMol of hydrogen. Was prepared by charging into the reactor.

The yield of ternary copolymer was 83.0 g and the efficacy of the catalyst was 1200000. The resulting elastomer had a MW of 168,700, a MWD of 2.02 and a MI of 1.7 g / 10 min and a crystallinity of 13%.

Comparative Example D

Using the apparatus and method of Example 8 and a different catalyst, 1443 g of isopar-E, 304.7 g of butene-1, 90.9 g of ENB, and 9.5 mMol of hydrogen were reacted using a different catalyst of ethylene / butene-1 / ENB. It was prepared by filling in. 2.0 micromoles (0.005 M solution) of metal complex (tetramethylcyclopentadienyl) dimethyl (t-butylamido) -silanetitanium (II) 1,3-pentadiene, promoter 6.0 micromoles of Example 8 ( 0.015 M solution), Example 8 Scavenger 50.0 micromole (0.125 M solution) and enough Isopar-E to make the total volume 18 mL were prepared by injection into a dry box together. The catalyst solution was then transferred to the reactor as in Example 8. The yield of ternary copolymer was 157.7 g and the efficacy of the catalyst was 1600000. The ternary copolymer had a MW of 46,700, a MWD of 1.97 and a MI of 201.7 and a crystallinity of 10.5%.

The difference in MW between the terpolymer of Example 10 and the terpolymer of Comparative Example D was found in Tensile at Break (ASTM D1708) and Percent Elongation at Break (ASTM). D1708) has a significant effect on the properties of polymers. Example 10 has a tensile strength of 1150 psi (8.90 MPa) at break corresponding to 375 psi (2.64 MPa) of Comparative Example C and a percentage elongation at break 840 corresponding to 567 of Comparative Example C. This data demonstrates the effect of catalytic changes on the resulting polymer.

Examples 11-13 and Comparative Example E

The apparatus and method of Example 8 for Examples 11, 13 and 14, and the catalyst of Example 1, the catalyst of Example 2 for Example 12 and the catalyst of Comparative Example A for Comparative Example E Four ethylene / propylene / ENB terpolymers were prepared using various catalysts and the amounts of the components shown in Table IIIA. The promoter for Example 12 and Comparative Example E was FAB. The cocatalyst for Examples 11, 13 and 14 was di (hydrogen-taloalkyl) methylammonium tetrakis (pentafluorophenyl) borate. The polymerization results are shown in Table IIB. The scavengers for Examples 11, 13 and 14 were (diisopropylamido) diethylaluminum. The scavenger for Example 12 was DIBAL-NS and MMAO for Comparative Example E.

The data in Table IIIB demonstrate that the use of preferred catalysts in the process of the present invention results in polymers having higher ENB content, higher M _w , or both with respect to polymers prepared under the same conditions and different catalysts. .

Example 15

A copolymer of ethylene / propylene / ENB was prepared using Example 3, FAB as cocatalyst, MMAO as scavenger and the apparatus and method of Example 8, and using the components shown in Table IVA. The properties of the copolymers are shown in Table IVB.

The data in Table IVB show similar results obtained with different preferred catalysts in combination with the process of the present invention.

Similar results to those presented in Examples 1-15 are expected for all of the other catalysts, promoters, scavengers and process parameters disclosed above.

Claims (12)

(a) the weight ratio of ethylene to α-olefin, which is a C _3-20 α-olefin, is within the range of 90:10 to 10:90, and (b) the content of diene monomer is 0 to based on the weight of the copolymer. Within 25% by weight, (c) ¹³ C NMR spectroscopy and formula B = P _OE / (2P _E .P _O ), where P _E is the mole fraction of ethylene units derived from ethylene and P _O is an α-olefin Mole fraction of α-olefin units derived from P _OE is an ethylene / α having a B value of 0.94 to 1.0, determined by the ratio of α-olefin / ethylene chain number to the number of all divalent chains in the copolymer). -Olefin / diene monomer random copolymer. The method of claim 1 wherein the α-olefin is selected from propylene, butene-1, hexene-1 and octene-1 and the diene monomers are 5-ethyldiene-2-norbornene, 5-vinyldiene-2-norborne , 5-methylene-2-norbornene, 1,4-hexadiene, 1,3-pentadiene, dicyclopentadiene, 7-methyl-1,6-octadiene, 1,3-butadiene, 4- From methyl-1,3-pentadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,5-heptadiene, norbornadiene, 1,7-octadiene and 1,9-decadiene Copolymer selected. The method of claim 1, wherein the one selected from a rheology ratio of 3 to 90 (V _0.1 / V ₁₀₀ ), a Mooney viscosity of 1 to 150 (ML _{1 + 4} at 125 ° C.), and a reactive ratio product of less than 1 to 1.25. Copolymer having the above characteristics. The (tetramethylcyclopentadienyl) -dimethyl (t-butylamido) silanetitanium dimethyl or (tetramethylcyclopentadienyl) dimethyl (t-butylamido) silanetitanium 1,3-penta (A) a rheology that is at least 10% greater than the rheological ratio of the comparative copolymer, compared to a comparative ethylene / a-olefin / diene monomer copolymer prepared from the same monomer at the same temperature using the diene as catalyst Ratio, (b) a diene content at least 50% higher than the diene content of the comparative copolymer, (c) a molecular weight at least 1.5 times greater than the molecular weight of the comparative copolymer, (d) at least 2.5 times more than the Mooney viscosity of the comparative copolymer One or more good features selected from glass transition temperatures at least 1 ° C. below the glass transition temperature (T _g ) of the comparative copolymer having a large Mooney viscosity and (e) a crystallinity of greater than 0% and less than 5%. polymer. The copolymer of any one of claims 1 to 4, comprising contacting ethylene, at least one C _3-20 α-olefin monomer and diene monomer with a catalyst and an activating promoter which are metal complexes of the formula How to. Wherein M is titanium, zirconium, or hafnium in a formal oxidation state of +2, +3 or +4, A ′ is hydrocarbyl, fluoro-substituted hydrocarbyl, hydrocarbyloxy substituted hydrocarbyl, dialkylamino substituted hydrocarbyl at two or more positions containing up to 40 non-hydrogen atoms Is a substituted indenyl group substituted with a group selected from silyl, germanyl and mixtures thereof, A 'is also covalently bonded to M by a divalent Z group, Z is a divalent moiety bonded to both A 'and M via σ-bond, Z comprises boron or a Group 14 constituent element of the periodic table of the elements and also nitrogen, phosphorus, sulfur or oxygen, X is an anionic or divalent anionic ligand group of up to 60 atoms excluding the class of ligands that are cyclic, unlocalized, π-bonded ligands, Each X 'is independently a neutral Lewis base ligation compound and has 20 or less atoms, p is 0, 1, or 2, 2 is less than the formal oxidation state of M, except that when X is a divalent anionic ligand, p is 1, q is 0, 1 or 2. The catalyst of claim 5 wherein the catalyst is (t-butylamido) dimethyl (η ⁵ -2-methylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido ) Dimethyl (η ⁵ -2-methylindenyl) silane titanium (II) 1,3-pentadiene, (t-butylamido) dimethyl (η ⁵ -2-methylindenyl) silane titanium (II) 2,4 -hexadiene, (t- butylamido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (Fig t- butylamido) dimethyl (η ⁵ 2-methylindenyl) silanetitanium (IV) dimethyl, (t-butylamido) dimethyl (η ⁵ -2-methylindenyl) silanetitanium (IV) dibenzyl, (t-butylamido) dimethoxy ( η ⁵ -2- methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) dimethoxy (η ⁵ -2- methyl-indenyl) silane titanium (II ) 1,3-pentadiene, (t- butylamido) dimethoxy (η ⁵ -2- methyl-indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethoxy (η ⁵ inde-2-methyl-indenyl) silane titanium (III) 2- (N, N- dimethyl amino No) benzyl, (t- butylamido) dimethoxy (η ⁵ -2- methyl-indenyl) silane titanium (IV) dimethyl, (t- butylamido) dimethoxy (η ⁵ -2- methyl-indenyl) silane titanium (IV) dibenzyl, (t- butylamido) di isopropoxy (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butyl amido) di isopropoxy (η ⁵ inde-2-methyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido) di isopropoxy (η ⁵ -2-methyl-inde carbonyl) silane titanium (II) 2,4- hexadiene, (t- butylamido) di isopropoxy (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) di isopropoxy (η ⁵ -2- methyl-indenyl) silane titanium (IV) dimethyl, (t- butylamido) di isopropoxy (η ⁵ -2- methyl-indenyl) silane titanium (IV) dibenzyl, (t- butylamido) ethoxymethyl (η ⁵ -2- inde-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido Fig.) ethoxymethyl (η ⁵ -2--methyl carbonyl to) Silane titanium (II) 1,3- pentadiene, (t- butylamido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido ) Ethoxymethyl (η ⁵ -2-methylindenyl) silane titanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) ethoxymethyl (η ⁵ -2-methylindenyl ) silane titanium (IV) dimethyl, (t- butylamido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (IV) dibenzyl, (t- butylamido) dimethyl (η ⁵ -2- ethyl inde indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) inde-dimethyl (η ⁵ -2- ethyl-indenyl) silane titanium (II) penta-1,3- diene, (t- butylamido) dimethyl (η ⁵ -2- ethyl inde indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethyl (η ⁵ -2- inde ethyl carbonyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethyl (η ⁵ inde-2-ethyl-indenyl) silane titanium (IV) dimethyl, (t- butylamido) dimethyl (η ⁵ inde-2-ethyl-indenyl) silane titanium (IV) diben , (T- butylamido) dimethoxy dimethoxy (η ⁵ -2- ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) (η ⁵ inde-2-ethyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido) dimethoxy (η ⁵ inde-2-ethyl-indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethoxy (η ⁵ -2- ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethoxy (η ⁵ -2 -ethyl-indenyl) silane titanium (IV) dimethyl, (t- butylamido) dimethoxy (η ⁵ -2- ethyl-indenyl) silane titanium (IV) dibenzyl, (t- butylamido) di isopropoxy (η ⁵ -2-ethyl-inde indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) di isopropoxy (η ⁵ inde-2-ethyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido) di isopropoxy (η ⁵ -2- ethyl-indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido ) di isopropoxy (η ⁵ -2- ethyl-indenyl) silane titanium (II I) 2- (N, N- dimethylamino) benzyl, (t- butylamido) di isopropoxy (inde η ⁵ -2- ethyl-indenyl) silane titanium (IV) dimethyl, (t- butylamido) di isopropoxy (η ⁵ -2- ethyl-indenyl) silane titanium (IV) dibenzyl, (t- butylamido) ethoxymethyl (η ⁵ -2- ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) ethoxy ethoxymethyl (η ⁵ -2- ethyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido) methyl (η ⁵ -2- ethyl inde indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido) ethoxymethyl (η ⁵ -2- inde ethyl indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) ethoxymethyl (η ⁵ ethoxymethyl (η ⁵ -2- ethyl-indenyl) silane titanium (IV) dimethyl, (t- butylamido) -2-ethylindenyl) silanetitanium (IV) dibenzyl, (t-butylamido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (II) 1,4-di Phenyl-1,3-butadiene, (t-butylamido) dimethyl (η ⁵ -2-methyl-s-phosphorus Dacene-1-yl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanitanium (II) 2, 4-hexadiene, (t-butylamido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t- Butyl amido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanitanium (IV) dimethyl, (t-butyl amido) dimethyl (η ⁵ -2-methyl-s-indacene- 1-yl) silanetitanium (IV) dibenzyl, (t-butylamido) dimethoxy (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl- 1, 3-butadiene, (t- butylamido) dimethoxy (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3-pentadiene, (t- butylamido ) dimethoxy (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethoxy (η ⁵ -2- methyl -s - indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethoxy (η ⁵ -2- methyl -s- indazol metallocene-yl Silane Titanium (IV) Dimeth , (T- butylamido) dimethoxy (η ⁵ -2- methyl -s- indazol-1-yl Sen) a silane titanium (IV) dibenzyl, (t- butylamido) di isopropoxy (η ⁵ - 2-methyl-indazol -s- metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) di isopropoxy (η ⁵ -2- methyl- s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene, (t- butylamido) di isopropoxy (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane Titanium (II) 2,4-hexadiene, (t-butylamido) diisopropoxy (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N -dimethylamino) benzyl, (t- butylamido) di isopropoxy (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) di-isopropyl Propoxy (η ⁵ -2-methyl-s-indacene-1-yl) silanetitanium (IV) dibenzyl, (t-butylamido) ethoxymethyl (η ⁵ -2-methyl-s-indacene- 1- yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) ethoxymethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene, (t- butylamido) ethoxymethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 2,4- hexadiene, ( t-butylamido) ethoxymethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) ethoxymethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) ethoxymethyl (η ⁵ -2- methyl -s- indazol metallocene- 1-yl) silanetitanium (IV) dibenzyl, (t-butylamido) dimethyl (η ⁵ -2-ethyl-s-indasen-1-yl) silanitanium (II) 1,4-diphenyl-1 , 3-butadiene, (t-butylamido) dimethyl (η ⁵ -2-ethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) dimethyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethyl (η ⁵ -2- ethyl -s- indazol metallocene- 1- yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (IV ) Dimethyl, (t-butylamime ) Dimethyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl, (t- butylamido) dimethoxy (η ⁵ -2- ethyl -s- indazol metallocene -1 -yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) dimethoxy (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium ( II) 1,3- pentadiene, (t- butylamido) dimethoxy (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethoxy (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethoxy ( η ⁵ -2-ethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) dimethoxy (η ⁵ -2-ethyl-s-indasen-1-yl) silane titanium (IV) dibenzyl, (t- butylamido) di isopropoxy (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (II) 1,4- diphenyl-l, 3 -butadiene, (t- butylamido) di isopropoxy (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene, (t- butylamido) Diisopropoxy ( ^{5-ethyl-2--s-} indazol metallocene-1-yl) silane titanium (II) 2,4- hexadiene, (t- butylamido) di isopropoxy (η ⁵ -2-ethyl-indazol metallocene -s- 1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) di isopropoxy (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) di isopropoxy (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl, (t- butylamido) Ethoxymethyl (η ⁵ -2-ethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) ethoxymethyl (η ^{5-ethyl-2--s-} indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene, (t- butylamido) ethoxymethyl (η ⁵ -2-ethyl-indazol -s- metallocene- 1-yl) silanetitanium (II) 2,4-hexadiene, (t-butylamido) ethoxymethyl (η ⁵ -2-ethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) ethoxymethyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido Ethoxy Methyl (η ⁵ -2-ethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl, (dimethylamine) dimethyl (η ⁵ -2-methylindenyl) silane titanium (III) dimethyl, (dimethyl Amine) dimethyl (η ⁵ -2-methylindenyl) silane titanium (III) dibenzyl, (diisopropylamine) dimethyl (η ⁵ -2-methylindenyl) silane titanium (III) dimethyl, (diisopropylamine ) dimethyl (η ⁵ -2-methyl-inde indenyl) silane titanium (III) dibenzyl, (di -n- butylamine) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (III) dimethyl, (di -n -Butylamine) dimethyl (η ⁵ -2-methylindenyl) silanetitanium (III) dibenzyl, (di-iso-butylamine) dimethyl (η ⁵ -2-methylindenyl) silane titanium (III) dimethyl, ( di-iso-butylamine) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (III) dibenzyl, (dimethylamino) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (III) dimethyl, (dimethylamine) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (III) dibenzyl, (diisopropylamine) di Butyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (III) dimethyl, (diisopropylamine) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane Titanium (III) dibenzyl, (di-n-butylamine) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanitanium (III) dimethyl, (di-n-butylamine) dimethyl ( η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, (di-isobutylamine) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silane Titanium (III) dimethyl, (di-isobutylamine) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, (dimethylamine) dimethyl (η ⁵ -2- ethyl inde indenyl) silane titanium (III) dimethyl, (dimethylamine) dimethyl (η ⁵ inde-2-ethyl-indenyl) silane titanium (III) dibenzyl, (diisopropylamine) inde-dimethyl (η ⁵ -2-ethyl-carbonyl ) silane titanium (III) dimethyl, (diisopropylamine) inde-dimethyl (η ⁵ -2- ethyl-indenyl) silane titanium (III) dibenzyl, (di -n- butylamine) inde-dimethyl (η ⁵ -2- ethyl Nil) silanetitanium (III) Dimeth , (Di -n- butylamine) dimethyl (η ⁵ -2-ethyl-inde indenyl) silane titanium (III) dibenzyl, (di-iso-butylamine) dimethyl (η ⁵ inde-2-ethyl-indenyl) silane titanium ( III) dimethyl, (di-iso-butylamine) dimethyl (η ⁵ -2- ethyl-indenyl) silane titanium (III) dibenzyl, (dimethylamino) dimethyl (η ⁵ -2- ethyl -s- indazol metallocene -1 -Yl) silanetitanium (III) dimethyl, (dimethylamine) dimethyl (η ⁵ -2-ethyl-s-indasen-1-yl) silane titanium (III) dibenzyl, (diisopropylamine) dimethyl (η ⁵ -2-ethyl-s-indasen-1-yl) silanetitanium (III) dimethyl, (diisopropylamine) dimethyl (η ⁵ -2-ethyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, (di -n- butylamine) dimethyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (III) dimethyl, (di -n- butylamine) dimethyl (η ⁵ -2 -ethyl -s- indazol metallocene-1-yl) silane titanium (III) dibenzyl, (di-iso-butylamine) dimethyl (η ⁵ -2- ethyl -s- indazol metallocene-1-yl) silane titanium (III) dimethyl, (di-iso-butylamine) dimethyl (η ⁵ -2- Group A comprising butyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, or (t-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene, (t-butylamido Fig.) Dimethyl (η ⁵ -2,3-dimethylindenyl) silane titanium (II) 2,4-hexadiene, (t-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silane titanium ( III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dimethyl, (t-butylamido) dimethyl ( η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl, (t-butylamido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-di Phenyl-1,3-butadiene, (t-butylamido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 2,4-hexadiene, (t- Butylamido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) dimethoxy (η ⁵ -2, 3-dimethylindenyl) silanetitanium (IV) dimethyl, (t-butylamido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl, (t-butylamido) di Isopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) diisopropoxy (η ⁵ -2, 3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 2,4- Hexadiene, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) Diisopropoxy (η ⁵ -2,3-dimethylindenyl) silane titanium (IV) Dimethyl, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silane titanium (IV ) Dibenzyl, (t-butylamido) ethoxy Butyl (η ⁵ -2,3- dimethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) ethoxymethyl (η ⁵ -2,3- dimethyl Indenyl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 2,4-hexadiene, ( t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dimethyl, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl, (t- Butyl amido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) dimethyl (η ⁵ -2,3-dimethyl-s -Indasen-1-yl) silanetitanium (II) 2,4-hexadiene, (t-butylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indacene-1 -Yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium ( IV) Dimethyl, (t-butylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl, (t-butylamido) dimethoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) dimethoxy (η ⁵ -2, 3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) dimethoxy (η ⁵ -2,3-dimethyl-s-indacene-1 -Yl) silanetitanium (II) 2,4-hexadiene, (t-butylamido) dimethoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamido) dimethoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido Fig. 2) Dimethoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl, (t-butylamido) diisopropoxy (η ⁵ -2,3- Dimethyl-s-inda 1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) di isopropoxy (η ⁵ -2,3- dimethyl -s- indazol metallocene -1 -Yl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 2,4-hexadiene, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethyl Amino) benzyl, (t-butylamido) diisopropoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) diiso Propoxy (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethyl-s -Indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethyl-s-indacene -1-yl) silanetitanium (II) 1,3-pentadiene, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II ) 2,4-hexadi N, (t-butylamido) ethoxymethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t -Butylamido) ethoxymethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) ethoxymethyl (η ⁵ -2, 3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl, (dimethylamine) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) dimethyl, (dimethylamine) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) dibenzyl, (diisopropylamine) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) dimethyl, (diisopropyl Amine) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) dibenzyl, (di-n-butylamine) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) dimethyl , (Di-n-butylamine) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) dibenzyl, (di-iso-butylamine) dimethyl (η ⁵ -2,3-dimethylindenyl Silanetitanium (III) dimethyl, ( Di-iso-butylamine) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) dibenzyl, (dimethylamine) dimethyl (η ⁵ -2,3-dimethyl-s-indacene-1- (I) silanetitanium (III) dimethyl, (dimethylamine) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, (diisopropylamine) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) dimethyl, (diisopropylamine) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) Silanetitanium (III) dibenzyl, (di-n-butylamine) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanitanium (III) dimethyl, (di-n-butylamine ) Dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, (di-isobutylamine) dimethyl (η ⁵ -2,3-dimethyl-s-inda Sen-1-yl) silanetitanium (III) dimethyl, (di-isobutylamine) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) dibenzyl, (t -Butylamido) dimethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (II) 1, 4-diphenyl-1,3-butadiene, (t- butylamido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido Fig.) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido) dimethyl (η ⁵ -2--methyl-3-ethyl-carbonyl ) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl, (t- Butyl amido) dimethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (IV) dibenzyl, (t-butylamido) dimethoxy (η ⁵ -2-methyl-3-ethylindenyl) Silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t-butylamido) dimethoxy (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (II) 1,3- Pentadiene, (t-butylamido) dimethoxy (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (II) 2,4-hexadiene, (t-butylamido) dimethoxy (η ⁵ 2-methyl-3-ethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl, (t-butylamimi Fig. 2) Dimethoxy (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (IV) Dimethyl, (t-butylamido) dimethoxy (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (IV) dibenzyl, (t- butylamido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, ( t- butylamido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido) di isopropoxy (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (II) 2,4-hexadiene, (t-butylamido) diisopropoxy (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl, (t- Butyl amido) diisopropoxy (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (IV) dibenzyl, (t-butyl amido) ethoxymethyl (η ⁵ -2-methyl-3- Ethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene, (t- Butyl amido) ethoxymethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene, (t- butylamido) ethoxymethyl (η ⁵ -2- methyl inde-3-ethyl-indenyl) silane titanium (II) 2,4- hexadiene, (t- butylamido inde degrees) ethoxymethyl (η ⁵ -2- methyl-3-ethyl indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl, (t- butylamido) ethoxy ethoxymethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl, (t- butylamido) Methyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (IV) dibenzyl, (t-butylamido) dimethyl (η ⁵ -2-methyl-3-ethyl-s-indacene-1- yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) dimethyl (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene, (t- butylamido) dimethyl (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (II) 2,4- hexamethylene diene, (t- butylamido) dimethyl (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) Ben , (T- butylamido) dimethyl (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) dimethyl (η ⁵ -2 -indazol-3-ethyl -s- metallocene-1-yl) silane titanium (IV) dibenzyl, (t- butylamido) dimethoxy (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene- 1- yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) dimethoxy (η ⁵ -2- methyl-3-ethyl-1-sen indazol -s- yl) silane titanium (II) 1,3- pentadiene, (t- butylamido) dimethoxy (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (II) 2 , 4-hexadiene, (t-butylamido) dimethoxy (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino ) Benzyl, (t-butylamido) dimethoxy (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) dimethoxy ( η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl, (t- butylamido) di isopropoxy (η ⁵ -2- methyl-3-ethyl -s-indasen-1-yl) silanita Titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butylamido) di isopropoxy (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane Titanium (II) 1,3-pentadiene, (t-butylamido) diisopropoxy (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (II) 2, 4-hexadiene, (t- butylamido) di isopropoxy (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethyl amino) benzyl, (t- butylamido) di isopropoxy (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl, (t- butylamido) Diisopropoxy (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl, (t-butylamido) ethoxymethyl (η ⁵ -2-methyl indazol-3-ethyl -s- metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, (t- butyl amido) ethoxymethyl (η ⁵ -2- methyl- 3-ethyl-indazol -s- metallocene-1-yl) silane titanium (II) 1,3- pentadiene, (t- butylamido) ethoxymethyl (η ⁵ -2- methyl-3-ethyl-indazol -s- Sen-1-yl) silanetitanium (II) 2, 4-hexadiene, (t-butylamido) ethoxymethyl (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino ) Benzyl, (t-butylamido) ethoxymethyl (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) ethoxy Methyl (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl, (dimethylamine) dimethyl (η ⁵ -2-methyl-3-ethylindenyl) silane Titanium (III) Dimethyl, (dimethylamine) dimethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (III) Dibenzyl, (diisopropylamine) dimethyl (η ⁵ -2-methyl-3- ethyl-indenyl) silane titanium (III) dimethyl, (diisopropylamine) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) dibenzyl, (di -n- butylamine) dimethyl ( η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (III) dimethyl, (di-n-butylamine) dimethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (III) dibenzyl , (Di-iso-butylamine) dimethyl (η ⁵ -2-methyl-3 -Ethyl-indenyl) silane titanium (III) dimethyl, (di-iso-butylamine) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) dibenzyl, (dimethylamino) dimethyl (η ^{5-ethyl-2-methyl-3--s-} indazol metallocene-1-yl) silane titanium (III) dimethyl, (dimethylamine) dimethyl (η ⁵ -2-methyl-3-ethyl-1-sen indazol -s- yl) silane titanium (III) dibenzyl, (diisopropylamine) dimethyl (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (III) dimethyl, (diisopropylamine ) dimethyl (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (III) dibenzyl, (di -n- butylamine) dimethyl (η ⁵ -2- methyl-3 Ethyl-s-indasen-1-yl) silanetitanium (III) dimethyl, (di-n-butylamine) dimethyl (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanitanium (III) Dibenzyl, (di-iso-butylamine) dimethyl (η ⁵ -2-methyl-3-ethyl-s-indasen-1-yl) silanetitanium (III) dimethyl, (di-iso-butylamine ) dimethyl (η ⁵ -2- methyl-3-ethyl -s- indazol metallocene-1-yl) silane titanium (III) di B is selected from the group comprising quality. The catalyst of claim 5 wherein the catalyst is (t-butylamido) -dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) -dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene and (t-butylamido) -dimethyl (η ⁵ -2-methyl-s-indacene -1-yl) silanetitanium (II) is a group A catalyst selected from 2,4-hexadiene or (t-butylamido) -dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene and (t-butylamido) -dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl A group B catalyst. The method according to any one of claims 5 to 7, wherein the activating promoter is trispentafluorophenyl borane, L ^* -H) _d ⁺ (A) ^d- [Wherein L ^* is a neutral Lewis base, (L ^* -H) ⁺ is Bronsted acid, and A ^d- is (a) a non-coordinated compatible with a charge of d ^- where d is an integer from 1 to 3 An anion, or (b) the formula [M'Q ₄ ] ^- (wherein M 'is boron or aluminum in the formal oxidation state +3, and Q is each independently hydride, dialkylamido, halide, hydrocarbyl , Hydrocarbyloxides, halogen substituted hydrocarbyl, halogen substituted hydrocarbyloxy, and halogen substituted silylhydrocarbyl radicals (perhalogenated hydrocarbyl-perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbs) Including a radical of Q), and Q has 20 or less carbons, provided that Q is a halide if 1 or less). Formula (L ^* -H) ⁺ (BQ ₄ ) ^- Wherein L ^* is a neutral Lewis base, B is boron in formal oxidation state 3, and Q is hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydro Carbyloxy-, or a fluorinated silylhydrocarbyl group, provided that Q is hydrocarbyl if one or less, Or the following formula Ⓒ ⁺ (BQ ₄ ) ^- (Wherein, ⓒ ⁺ is C _1-20 carbenium ion, Q is hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or less than 20 non-hydrogen atoms), or Fluorinated silylhydrocarbyl groups, provided that Q is hydrocarbyl if one or less) or a cocatalyst that is a salt of a non-coordinating compatible anion. The process of claim 8, wherein the polymerization is Group 13 according to aluminoxane and the formula R ¹ ₂ Me (NR ² ₂ ), wherein R 1 and R 2 are each independently C _1-30 hydrocarbyl, Me is a Group 13 metal. The process is carried out in the presence of a scavenger selected from hydrocarbylamide compounds. The method of claim 9, wherein the scavenger is (bistrimethylsilylamido) diisobutylaluminum. The diene of claim 5, wherein the diene is 5-ethyldiene-2-norbornene, 5-vinyldiene-2-norbornene, 5-methylene-2-norbornene, 1,4-hexadiene, 1,3 -Pentadiene, dicyclopentadiene, 7-methyl-1,6-octadiene, 1,3-butadiene, 4-methyl-1,3-pentadiene, 5-methyl-1,4-hexadiene, 6- The method is selected from the group consisting of methyl-1,5-heptadiene, norbornadiene, 1,5-octadiene and 1,9-decadiene, and the contacting is carried out at a temperature of about 40 ℃ to about 185 ℃. 13. The method of claim 12, wherein the activating promoter is tris (pentafluorophenyl) borane, di (hydrogenated tallowalkyl) methylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluoro Rophenyl) borate, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.