MXPA99009023A

MXPA99009023A - Ethylene/alpha-olefin/diene interpolymers and their preparation

Info

Publication number: MXPA99009023A
Application number: MXPA/A/1999/009023A
Authority: MX
Inventors: T Kale Lawrence; R Parikh Deepak; J Mangold Debra; D Vanderlende Daniel
Original assignee: Dupont Dow Elastomers Llc; T Kale Lawrence; J Mangold Debra; R Parikh Deepak; The Dow Chemical Company; D Vanderlende Daniel
Filing date: 1999-10-01
Publication date: 2000-07-01

Abstract

Random ethylene/alpha-olefin/diene monomer interpolymers with an alpha-olefin distribution that is more clustered than Bernoullian are prepared using Group 4 metal constrained geometry complex catalyst and an activating cocatalyst. The catalyst includes a fused ring indenyl derivative ligand.

Description

INTERPOLIMEROS DE ETILEÑO / ALFA-OLE INA / DIENO AND ITS PREPARATION This invention relates to interpolymers of ethylene (C2), at least one alpha-olefin (α-olefin), preferably propylene (C3), butene-1, hexene-1 or octene-1, and at least one monomer of diolefin, preferably a non-conjugated diene monomer, and its preparation using an olefin polymerization catalyst derived from a class of Group 4 metal complexes.

Metal complexes of restricted geometry and methods for their preparation are described in EP-A-4IL6,815 (US Patent Application Serial No. 545,403, filed on July 3, 1990); EP-A-468,651 (U.S. Patent Application Serial Number 547,718, filed July 3, 1990); EP-A-514,828 (US Patent Application Serial No. 702,475, filed May 20, 1991); EP-A-520,732 (US Patent Application Serial No. 876,268, filed May 1, 1992) and WO93 / 19104 (US Patent Application Serial Number 8,003, filed January 21, 1993), as well as as US-A-5,055,438, US-A-5, 057, 475, US-A-5, 096, 867, US-A-5, 064, 802, US-A-5,132,380, WO95 / 00526, and Provisional Application US 60-005913. Metal complexes containing variously substituted indenyl are taught in Patent Application Ref. 031141 US Serial No. 592,756, filed January 26, 1996, as well as document O95 / 14024. The relevant teachings of all the patents mentioned above or the corresponding US patent applications are therefore incorporated by reference.

One aspect of the present invention is an interpolymer of ethylene / α-olefin / diene monomer (EAODM) disordered, the interpolymer having (a) a weight ratio of ethylene to α-olefin in the range from 90:10 to 10: 90, the α-olefin is a C3-2o α-olefin; (b) a diene monomer content within the range of greater than 0 to 25 percent by weight (% by weight), based on the weight of the interpolymer; and (c) a B value from 0.94 to 1.0, the B value is determined by 13 C NMR spectroscopy (carbon 13 nuclear magnetic resonance) and the formula B = POE / (2 PE-Po) # where PE is a fraction molar of the ethylene units derived from ethylene, P0 is a mole fraction of the a-olefin units derived from the α-olefin, and P0E is a ratio of the number of α-olefin / ethylene chains to the number of all the chains diadas in the interpolymer. J.C. Randall, Macromolecules, 15, pg 353 (1982) and J. Ray, Macromolecules, 10, pg 773 (1977) also provide explanations of the B value. A Bernoulli distribution will provide a B value of 1, a Alternating polymer will perfectly provide a B value of 2 and a block polymers, such as a polymer in ethylene / propylene diblock, will give a B value approaching 0. In practical terms, a B value of less than 1 indicates that the The polymer has an α-olefin distribution that is more clustered than the Bernoulli distribution and a B value of more than 1 indicates that the polymer has an α-olefin distribution that is more isolated than the Bernoulli distribution.

The 13C NMR samples for the determination of the B value are prepared appropriately in a 50% / 50% solvent mixture (base volume) of 1, 1, 2, 2-tetrachloroethane-d2 and 1, 2,4-trichlorobenzene including enough paramagnetic relaxation agent to produce an NMR solvent having a concentration of 0.05 M in chromium (III) acetylacetonate. The samples are prepared by mixing a polymer and the NMR solvent in a volumetric ratio of 10:90 in a 10 millimeter (mm) NMR tube capped and purged with nitrogen. The contents of the tube are heated to reflux periodically until homogeneity is achieved. The spectrum is obtained at 130 degrees Celsius (° C) using an inverse uncoupled sequence with a pulse width of 90 ° C and a delay of 5-9 seconds.

A second aspect of the present invention is a process for preparing the interpolymer of the first aspect, the process comprising contacting ethylene, at least one C3_2o α-olefin monomer and a diene monomer with a catalyst and an activating cocatalyst, the catalyst is a metallic complex that corresponds to the formula ZA'M XpX'q. where M is titanium, zirconium or hafnium in the conventional oxidation state +2, +3 or +4, - A 'is a substituted indenyl group, substituted in at least position 2 with a selected group of hydrocarbyl, fluorocarbon hydrocarbyl substituted, hydrocarbyloxy-substituted hydrocarbyl, dialkylamino-substituted hydrocarbyl, silyl, germyl and mixtures thereof, the group contains up to 40 non-hydrogen atoms, and A 'is also covalently bound to M by a divalent Z group, - Z is a divalent part bound to both A1 and M via the bonds s, Z comprises boron, or a member of Group 14 of the Periodic Table of the Elements, and also includes nitrogen, phosphorus, sulfur and oxygen; X is an anionic or dianionic ligand group having up to 60 atoms regardless of the class of ligands which are delocalized, cyclic, p-link ligand groups; X 'independently each occurrence is a neutral Lewis base binder compound, having up to 20 atoms; p is 0, 1 or 2, and is 2"smaller than the conventional oxidation state of M, with the proviso that when X is a dianionic ligand group, p is 1; Y q is 0, 1 or 2.

The preferred X 'groups are carbon monoxide; phosphines, especially trimethylphosphine, triethylphosphine, triphenylphosphine and bis (1,2-dimethylphosphino) ethane; P (0R) 3, wherein R is a C1_2Q hydrocarbyl; ethers, especially tetrahydrofuran (THF); amines, especially pyridine, bipyridine, tetramethylethylenediamine (TMEDA), and triethylamine, -olefins, and conjugated dienes, preferably neutral conjugated dienes, having from 4 to 40 carbon atoms. Complexes that include the last X groups include those where the metal is in the conventional oxidation state +2.

The above metal complexes can be presented as isolated crystals, optionally in pure form or as a mixture with other complexes, in the form of a solvated adduct, optionally in a solvent, especially an organic liquid, as well as in the form of a dimer or derivative chelate thereof, wherein the chelating agent is an organic material, preferably a neutral Lewis base, especially a trihydrocarbylamine, trihydrocarbylphosphine, or halogenated derivative thereof.

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

The present process results in a highly efficient production of interpolymers or polymers of EAODM (ethylene / alpha-olefin / diene monomer) of average molecular weight by weight (Mw) high over a wide range of polymerization conditions, and especially at temperatures elevated. These are especially useful for the solution polymerization of EAODM polymers, where the diene is 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene or a similar unconjugated diene. or a conjugated diene, such as 1,3-pentadiene. The use of elevated temperatures dramatically increases the productivity of such a process due to the fact that the solubilization of the polymer increased at elevated temperatures allows the use of increased conversions (higher concentration of the polymer product) without exceeding the limitations of the solution viscosity of the polymerization, as well as the reduced energy costs necessary to devolatilize the reaction product.

All references to the Periodic Table of the Elements here refer to the Periodic Table of the Elements, published and protected by copyright by CRC Press, Inc., 1989. Also, any reference to a Group or Groups will be at Group or Groups as contemplated in this Periodic Table of the Elements using the IUPAC system to number the groups.

The EAODM interpolymers of the present invention have three distinct characteristics. One is the rheology ratio (V? .I / V10O) at a temperature of 190 ° C in the range from about 3 to about 90. The second is Mooney Viscosity or MV (ML1 + 4 @ 125 ° C, ASTM D1646-94) within a range from 1 to 150, preferably from 10 to 120, and more preferably from 15 to 100. The third is the product of the reactivity ratio (RRP) within the range from 1 to < 1.25.

When prepared at a contact temperature from 40-185 ° C, and compared to the corresponding EAODM polymers prepared from the same monomers and at the same temperature using dimethyl (tetramethylcyclopentadienyl) -dimethyl (t-butylamido) silane- titanium or 1, 3 -pentadiene from (tetramethylcyclopentadienyl) dimethyl (t-butylamido) -silane-titanium as the catalyst, the EAODM polymers of the present invention offer certain improvements. For example, they have a rheology ratio that is at least 10% greater than that of the corresponding EAODM polymers. They also have a diene content which is, on a weight basis, at least 50 percent (%) greater, an Mw (molecular weight) that is at least 1.5 times higher, a vitreous transition temperature (Tg), obtained from a curve of the differential scanning calorimeter (DCS) using the first temperature derivative, which is at least one lower C ° and one MV which is at least 2.5 times higher than that of the corresponding EAODM polymers. For comparison purposes of the Tg, the corresponding EAODM polymers have a crystallinity which is > 0, but < 5%.

The process of the present invention can be used to polymerize C2 together with at least one α-olefin monomer C3-20 (ethylenically unsaturated) and a C4-40 diene monomer. The α-olefin may be either an aliphatic or aromatic compound and may contain a vinyl unsaturation or a cyclic compound, such as cyclobutene, cyclopentene, and norbornene, including the norbornene substituted in the 5 and 6 position with the hydrocarbyl groups C? _20 . La-α-olefin is preferably a C3-20 aliphatic compound, more preferably a C3.16 aliphatic compound. Preferred ethylenically unsaturated monomers include 4-vinylcyclohexene, vinylcyclohexane, norbornadiene and C3_? 0 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. The most preferred monomers are ethylene, and mixtures of ethylene, at least one of propylene, butene-1, hexene-1, and octene-1, and a non-conjugated diene, especially ENB.

The C4-40 diolefin or diene monomer is desirably an unconjugated diolefin. The unconjugated diolefin can be a stht chain, branched chain or cyclic C6-? 5 hydrocarbon diene. Illustrative non-conjugated dienes are acyclic linear chain dienes, such as 1,4-hexadiene, 1,5-heptadiene, and 1,6-octadiene; branched chain acyclic dienes, such as 5-methyl-1,4-hexadiene, 2-methyl-1, 5-hexadiene, 6-methyl-1, 5-heptadiene, 7-methyl-l, 6-octadiene, 3, 7-dimethyl-l, 6-octadiene, 3, 7-dimethyl-l, 7-octadiene, 5,7-dimethyl-l, 7-octadiene, 1, 7-octadiene, 1, 9-decadiene and mixed isomers of dihydromircene, single-ring alicyclic dienes, such as 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene; multi-ring alicyclic fused and bridged dienes, such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo- (2,2,1) -hepta-2, 5-diene (norbornadiene), norbornadiene methyl; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylen-2-norbornene (MNB), ENB, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene and 5-cyclohexylidene-2-norbornene.

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

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

The preferred coordination complexes used according to the present invention are complexes corresponding to formula IA: Formula IA where; Ri and R2 / independently are groups selected from hydrogen, hydrocarbyl, substituted perfluoro hydrocarbyl, silyl, germyl and mixtures thereof, the group contains up to 20 non-hydrogen atoms, with the proviso that at least one of Ri and R2 is not hydrogen; R3, R4, R5, and Re independently are selected groups of hydrogen, hydrocarbyl, substituted perfluoro hydrocarbyl, silyl, germyl and mixtures thereof, the group contains up to 20 non-hydrogen atoms; M is titanium, zirconium or hafnium; Z is a divalent part comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprises nitrogen, phosphorus, sulfur or oxygen, the part has up to 60 non-hydrogen atoms, - p is 0.1 or 2, - q is zero or one; with the condition that: when p is 2, q is zero, M is in the conventional oxidation state +4, and X is an anionic ligand selected from the group consisting of halide, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amido, di (hydrocarbyl) phosphide groups , hydrocarbylsulfide, and silyl, as well as halo-, di (hydrocarbyl) amino-, hydrocarbyloxy- and di (hydrocarbyl) phosphino-substituted derivatives thereof, group X has up to 20 non-hydrogen atoms, when p is 1, q is zero, M is in the conventional oxidation state +3, and X is a stabilizing anionic ligand group selected from the group consisting of allyl, 2- (N, N-dimethylaminomethyl) phenyl, and 2- (N, N-dimethyl) -aminobenzyl, or M is in the conventional oxidation state +4, and X is a divalent derivative of a conjugated diene, M and X together form a metallocyclopentene group, and when p is 0, q is 1, M is in the conventional oxidation state +2, and X 'is a conjugated or non-conjugated diene, neutral, optionally substituted with one or more hydrocarbyl groups, X' has up to 40 carbon atoms and forms an IT complex with M.

The most preferred coordination complexes used according to the present invention are the complexes corresponding to formula IB: Formula IB where : Ri and R2 are hydrogen or C? -S alkyl, with the proviso that at least one of Rx or R2 is not hydrogen; R3, R4, R5, and Rg independently are hydrogen or C6-alkyl; M is titanium, - And it is -O-, -S-, -NR * -, -PR * -; Z * is SiR * 2, CR * 2, SiR * 2SiR * 2, CR * 2CR * 2, CR * = CR *, CR * 2SiR * 2, or GeR * 2; R * each occurrence is independently hydrogen, or a selected member of hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, R * has up to 20 non-hydrogen atoms, and optionally, two R * groups of Z (when R * is not hydrogen), or a group R * of Z and a group R * of Y form a ring system; p is 0, 1 or 2, - q is zero or one; with the condition that: when p is 2, q is zero, M is in the conventional oxidation state +4, and X independently each occurrence is methyl or benzyl, when p is 1, q is zero, M is in the conventional oxidation state +3, and X is 2- (N, N-dimethyl) aminobenzyl; or M is in the conventional oxidation state +4 and X is 1,4-butadienyl, and when p is 0, q is 1, M is in the conventional oxidation state +2, and X 'is 1,4-diphenyl-1,3-butadiene, 2,4-hexadiene, or 1,3-pentadiene. The last diene is illustrative of asymmetric diene groups that result in the production of metal complexes that are currently mixtures of the particular geometric isomers.

Still the most preferred coordination complexes used according to the present invention are the complexes corresponding to formula II: Formula II where : R 'is hydrogen, hydrocarbyl, di (hydrocarbylamino), or a hydrocarbylene amino group, R' has up to 20 carbon atoms, R "is C1-2o hydrocarbyl or hydrogen; M is titanium; And it is -O-, -S-, -NR * -, -PR * -; -NR2 *, or -PR2 *; Z * is as previously defined; R *, in each occurrence, is as previously defined; X is a monovalent anionic ligand group having up to 60 atoms regardless of the clof ligands that are cyclic, delocalised, ligand binding groups II; X 'is, independently in each occurrence, a neutral binder compound having up to 20 atoms; X "is a divalent anionic ligand group having up to 60 atoms; p is 0, 1 or 2, - q is zero or 1; Y r is zero or 1; with the condition that: when p is 2, qyr is zero, M is in the conventional oxidation state +4 (or M is in the conventional oxidation state +3 if Y is -NR * 2 or -PR * 2), and X is a ligand selected anionic of halide, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amido, di (hydrocarbyl) phosphide, hydrocarbyl sulphide, and silyl groups, as well as halo-, di (hydrocarbyl) amino-, hydrocarbyloxy-, and di (hydrocarbyl) phosphine derivatives -substituted from them, group X has up to 30 non-hydrogen atoms, when r is 1, p and q are zero, M is in the conventional oxidation state +4, and X "is a dianionic ligand selected from the group consisting of hydrocarbaryl, oxyhydrocarbyl, and hydrocarbyle dioxy groups, group X has up to 30 carbon atoms. no hydrogen, when p is 1, qyr is zero, M is in the conventional oxidation state +3, and X is a stabilizing anionic ligand group selected from the group consisting of allyl, 2- (N, N-dimethylamino) phenyl, 2- ( N, N-dimethylaminomethyl) phenyl, and 2- (N, N-dimethylamino) benzyl, and when pyr is zero, q is 1, M is in the conventional oxidation state +2, and X 'is a conjugated or non-conjugated diene, neutral, optionally substituted with one or more hydrocarbyl groups, X' has up to 40 carbon atoms and forms a complex II with M.

The most preferred metal complexes are those according to formula (II) or (III) above, wherein M, X, X ', X1 d Rd R' d Z *, Y. P and r are as previously defined, with the condition that: when p is 2, q and r are zero, M is in the conventional oxidation state +4, and X, independently of each occurrence, is methyl, benzyl, or halide; when p and q are zero, r is one, and M is in the conventional oxidation state +4, X1 'is a 1,4-butadienyl group that forms a metallocyclopentene ring with M, when p is 1, q and r are zero, M is in the conventional oxidation state +3, and X is 2- (N, N-dimethylamino) benzyl; Y when p and r are zero, q is 1, M is in the conventional oxidation state +2, and X 'is 1, 4-diphenyl-1,3-butadiene or 1,3-pentadiene.

Especially preferred coordination complexes corresponding to the previous formula (II) are originally substituted depending on the particular end use thereof. In particular, highly useful metal complexes for use in the catalyst compositions for the copolymerization of ethylene, one or more α-olefins and a diolefin comprise the above-mentioned complexes (II), wherein R 1 is as defined above, and R '' is hydrogen or methyl, especially hydrogen.

A particularly preferred coordination complex, 2, 4-hexadiene of (t-butylamido) dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (II), is structurally represented by formula III.

Formula III A second especially preferred coordination complex, dimethyl (t-butylamido) dimethyl (η 5-2-methyl-s-indacen-1-yl) silane-titanium (IV), is structurally represented by formula IV.

Formula IV A third especially preferred coordination compound, 1,4-diphenyl-1,3-butadiene of (t-butylamido) -dimethyl (γ 5-2, 3-dimethylindenyl) silane-titanium (II), is structurally represented by the formula V.

Formula V A fourth especially preferred coordination complex, dimethyl (t-butyl-amido) -dimethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (IV), is structurally represented by the formula SAW .

Formula VI A fifth especially preferred coordination complex, 1,3-pentadiene of (t-butylamido) -dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (II), has two isomers, sometimes referred to as geometric isomers, represented by formulas VII and VIII.

Formula VII Formula VIII A group of preferred metal complexes include: 1,4-diphenyl-1,3-butadiene of (t-butylamido) dimethyl (? 5-2-methylindenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) dimethyl (? 5-2-methylindenyl) silane-titanium: n) 1, 3-pentadiene (t-butyl-amido) -dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (II), 2,4-hexadiene (t-butylamido) - dimethyl (? 5-2-methylindenyl) -silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) -dimethyl (? 5-2-methylindenyl) silane-titanium (III), dimethyl (t-butylamido) -dimethyl (? 5-2-methylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) dimethyl (? 5-2-methyl-indenyl) silane-titanium (IV), 1, 4-diphenyl-1,3-butadiene of (t-butylamido) dimethoxy (? 5-2-methylindenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) -dimethoxy (? 5-2 -methylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) -dimethoxy (? 5-2-methylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) -dimethoxy (? s-2-methylindenyl) silane-titanium (III), dimethyl (t-butylamido) -dimethoxy (? 5-2 -methylindenyl) -silane-titanium (IV), dibenzyl ( t-butylamido) -dimethoxy (? 5-2-methylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene from (t-butylamido) -diisopropoxy (? 5-2-methylindenyl) silane-titanium (II), 1,3-pentadiene of (t-butylamido) -diisopropoxy (r | 5-2-methylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) -diisopropoxy (? -2-methyl-indenyl) silane-titanium (II), 2- (N, -dimethylamino) benzyl (t-butylamido) diisopropoxy (? 5-2-methylindenyl) silane-titanium (III), dimethyl (t-butylamido) -diisopropoxy (? 5-2-methylindenyl) silane-titanium (IV), dibenzyl (t-) butylamido) -diisopropoxy (? 5-2-methylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) ethoxymethyl (? 5-2-methylindenyl) silane-titanium (II) ), 1, 3 -pentadiene from (t-butylamido) -ethoxymethyl (? 5-2 -methylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) -ethoxymethyl (? 5-2-methyl-indenyl) silane-titanium (II ), 2- (N, N-dimethylamino) benzyl of (t-butylamido) -ethoxymethyl (? 5-2 -methylindenyl) silane-titanium (III), dimethyl (t-butylamido) ethoxymethyl (??-2-methylindenyl) silane-titanium (IV), dibenzyl (t-) butylamido) -ethoxy-methyl (? 5-2-methylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) dimethyl (? 5-2-ethyl-indenyl) silane -titanium (II), 1,3-pentadiene of (t-butylamido) dimethyl (? 5-2-ethylindenyl) -silane-titanium (II), 2,4-hexadiene of (t-butylamido) -dimethyl (? 5-2-ethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethyl (? 5-2-ethyl-indenyl) ) silane-titanium (III), dimethyl (t-butylamido) dimethyl (? 5-2-ethyl-indenyl) silane-titanium (IV), dibenzyl (t-butyl-amido) dimethyl (? 5-2-ethylindenyl) silane- titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butylamido) dimethoxy (? 5-2-ethylindenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) dimethoxy (? 5-2-ethylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) dimethoxy (? 5-2-ethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) ) benzyl (t-butylamido) dimethoxy (? 5-2-ethylindenyl) silane-titanium (III), dimethyl (t-butylamido) -dimethoxy (? 5-2-ethylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) dimethoxy (? 5-2-ethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) -diisopropoxy (? 5-2-ethylindenyl) silane- titanium (11) / 1, 3-(t-butylamido) -diisopropoxy (? 5-2-ethylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) -diisopropoxy (? 5- 2-Ethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butyl-amido) diisopropoxy (? 5-2-ethylindenyl) silane-titanium (III), dimethyl (t-butyl-amido) -diisopropoxy (? 5-2-ethylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) -diisopropoxy (? 5-2-ethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butylamido) ethoxymethyl (5-ethylindenyl) silane-titanium (II), 1,3-pentanediene (t-butylamido) -ethoxymethyl (? 5-2-ethylindenyl) silane-titanium (II), 2, 4-hexadiene of (t-butylamido) ethoxymethyl (? 5-2-ethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) -ethoxymethyl (? 5-2-ethylindenyl) silane-titanium (III), dimethyl (t-butylamido) -ethoxymethyl (? 5-2-ethylindenyl) silane-titanium (IV), dibenzyl (t) -butylamido) -ethoxymethyl (? 5-2-ethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butyl-amido) dimethyl (? 5-2-methyl-s- indacen-l-yl) silane-titanium (II), 1,3-pentadiene of (t-butylamido) dimethyl (? 5-2-methyl-s-indace-1-yl) -silane-titanium (II), 2 , 4-hexadiene of (t-butylamido) -dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) -benzyl of (t-butylamido) dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) dimethyl (? 5-2-methyl-s-indacen-1-yl) silane -titanium (IV), dibenzyl (t-butylamido) dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene ( t-butylamido) dimethoxy (? 5-2-methyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) dimethoxy (? 5-2-methyl-s- indacen-1-yl) silane-titanium (II), 2, 4-hex adieno of (t-butylamido) dimethoxy (? 5-2-methyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethoxy (? 5-2-methyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) -dimethoxy (? 5-2-methyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl of (t-butylamido) dimethoxy (? 5-2-methyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-) butylamido) diisopropoxy (? s-2-methyl-s-indacen-1-yl) silane- titanium (II), 1,3-pentadiene of (t-butylamido) diisopropoxy (? -2-methyl-s-indace-1-yl) -silane-titanium (II), 2,4-hexadiene of (t-butylamido) -diisopropoxy (??? 2-methyl-s-indacen-1-yl) silane-titanium (11) / 2- (N, N-dimethylamino) benzyl of (t-butylamido) diisopropoxy (? 5 -2-methyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butyl-amido) diisopropoxy (ε 5-2-methyl-s-indacen-1-yl) silane-titanium ( IV), dibenzyl (t-butylamido) diisopropoxy (? 5-2-methyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butylamido) ethoxymethyl (? 5) -2-methyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene of (t-butylamido) ethoxymethyl (? 5-2-methyl-s-indacen-1-yl) silane- titanium (II), 2, 4-hexadiene from (t-butyl-amido) ethoxymethyl (??? 2-methyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) ethoxymethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (III), dimethyl of (t-butylamido) -ethoxymethyl (5-2-methyl-s-indacen-1-yl) silane-titanium ( IV), dibenzyl (t-butylamido) ethoxy-methyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) dimethyl ( 5-2-ethyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene of (t-butylamido) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (II), 2- (N, -dimethylamino) benzyl of (t-butylamido) -dimethyl (? -2-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl of (t-butylamido) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane- titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butylamido) dimethoxy (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (II), 1,3 - pentadiene of (t-butylamido) dimethoxy (? 5-2-ethyl-s-indacen-l-yl) -silane-titanium (II), 2,4-hexadiene of (t-butylamido) -dimethoxy (??? -ethyl-s-indacen-l-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) -dimethoxy (? 5-2-ethyl-s-indacen-1-) il) silane-titanium (III), dimethyl (t-butylamido) dimethoxy (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (IV), (t-butylamido) dimethoxy (?? - 2-ethyl-s-indacen-1-yl) silane-titanium (IV) dibenzyl, 1,4-diphenyl-1,3-butadiene (t-butylamido) diisopropoxy (? 5-2-ethyl-s-indacen-l-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) diisopropoxy (? S-2-ethyl-s-indacen-1-yl) ) silane-titanium (II), 2,4-hexadiene of (t-butylamido) diisopropoxy (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-) dimethylamino) -benzyl of (t-butylamido) diisopropoxy (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl of (t-butylamido) diisopropoxy (? 5-2 -ethyl- s-indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) diisopropoxy (? 5-2-ethyl-s-indacen-l-yl) silane-titanium (IV) 1,4-diphenyl-1,3-butadiene from "" (t-butylamido) ethoxy-methyl (? -2-ethyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene from (t-butylamido) ethoxy-methyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) ethoxymethyl (? 5-2-ethyl) -s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) ethoxymethyl (? 5-2-ethyl-s-indacen-1-yl) silane -titanium (III), dimethyl of (t-butylamido) ethoxymethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl of (t-butylamido) ethoxymethyl (? 5-2) -ethyl-s-indacen-1-yl) silane-titanium (IV), dimethyl (dimethylamine) dimethyl (??-2-methylindenyl) silane-titanium (III), dibenzyl (dimethylamine) -dimethyl (? 5- 2-methylindenyl) silane-titanium (III), dimethyl (diisopropyl-amine) -dimethyl (? 5-2-methylindenyl) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl (? 5-2 -methylindenyl) - silane-titanium (III), dimethyl (di-n-butylamine) dimethyl (? 5-2-methylindenyl) silane-titanium (III), dibenzyl (di-n-butylamine) dimethyl (? 5-2 -methylindenyl) silane-titanium (III), dimethyl (di-iso-butylamine) dimethyl (? 5-2-methylindenyl) silane-titanium (III), dibenzyl (di-iso-butylamine) dimethyl (? 5-2-methylindenyl) silane-titanium (III), dimethyl (dimethylamine) dimethyl- (5-2-methyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (dimethylamine) dimethyl (5-2-methyl-s- indacen- 1-yl) silane-titanium (III), dimethyl of (diisopropylamine) dimethyl- (? 5-2 -methyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl- (? 5-2-methyl-s-indacen-1-yl) ) silane-titanium (III), dimethyl (di-n-butylamine) -dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (di-n-butylamine) dimethyl- (? 5-2-methyl-s-indacen-1-yl) silane-titanium (III), dimethyl (di-isobutyl-amine) dimethyl- ( ? 5-2-methyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (di-isobutyl-amine) dimethyl (? 5-2-methyl-s-indacen-1-yl) silane- titanium (III), dimethyl (dimethylamine) -dimethyl (? 5-2-ethylindenyl) silane-titanium (III), dibenzyl (dimethylamine) dimethyl (? 5-2-ethyl-indenyl) silane-titanium (III), dimethyl (diisopropylamine) dimethyl- (? s-2-ethylindenyl) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl (? 5-2-ethylindenyl) silane-titanium (III), dimethyl (di-n-) butylamine) -dimethyl (? 5-2-ethylindenyl) silane-titanium (III), dibenzyl (di-n-butylamine) -dimethyl (? 5-2-ethyl-indenyl) silane-titanium (III), dimethyl ( di-iso-butylamine) dimethyl (? 5-2-ethylindenyl) -silane-titanium (III), dibenzyl (di-iso-butylamine) dimethyl (? 5-2-ethylindenyl) silane-titanium (III), dimethyl (dimethylamine) -dimethyl (? 5-2-ethyl-s-indacen-l-yl) silane-titan io (III), dibenzyl (dimethylamine) -dimethyl (? 5-2-ethyl-s-indacen-l-yl) silane-titanium (III), dimethyl (diisopropyl-amine) dimethyl (? 5-2-ethyl) - s-indacen-1-yl) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (di-n) -butylamine) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (di-n-butylamine) dimethyl (? 5-2-ethyl-s-indacen-l) -yl) silane-titanium (III), dimethyl (di-iso-butylamine) dimethyl (??-2-ethyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (di-iso-) butylamine) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (III). Preferred members of this group include: (t-butylamido) -dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (IV) dimethyl and 2,4-hexadiene (t-butylamido) ) -dimethyl (? 5-2-methylindenyl) -silane-titanium (II).

A second group of preferred catalysts includes: 1,4-diphenyl-1,3-butadiene of (t-butylamido) -dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) -dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium ( II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III), dimethyl of (t-butylamido) -dimethyl (? 5- 2, 3-dimethylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) -dimethyl (rj5-2, 3-dimethylindenyl) silane-titanium (IV), 1,4-diphenyl- 1,3-butadiene of (t-butylamido) -dimethoxy (? -2,3-dimethylindenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) dimethoxy (? 5-2, 3-dimethylindenyl) silane-titanium (II), 2, 4-hexadiene of (t-butylamido) dimethoxy (? 5-2, 3-dimethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) - dimethoxy (? 5-2, 3-dimethylindenyl) silane-titanium (III), dimethyl (t-butylamido) dimethoxy (? 5-2, 3-dimethylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) dimethoxy (? 5-2, 3-dimethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) -diisopropoxy (? 5-2, 3 - dimethylindenyl) silane-titanium (II), 1,3-pentadiene of (t-butylamido) diisopropoxy- (? 5-2, 3-dimethylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) diisopropoxy (? 5-2, 3-dimethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl (t-butylamido) diisopropoxy (? 5-2, 3-dimethylindenyl) silane-titanium (III), dimethyl (t-butylamido) -diisopropoxy (? 5-2, 3-dimethylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) diisopropoxy (? 5-2, 3-dimethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) -ethoxymethyl (? 5-2, 3 - dimethylindenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) ethoxymethyl (? 5-2, 3-dimethylindenyl) silane-titanium (II), 2, 4-hexadiene of (t-butylamido) ethoxymethyl (? 5-2, 3- dimethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) ethoxymethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III), dimethyl (t-butylamido) ethoxymethyl (? 5-2, 3-dimethylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) ethoxymethyl (? 5-2, 3-dimethylindenyl) silane-titanium (IV), 1,4-diphenyl-1 , 3-butadiene of (t-butylamido) dimethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) -dimethyl ( ? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) dimethyl (? S-2,3-dimethyl-s-indacen- 1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium ( III), dimethyl (t-butylamido) -dimethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) dimethyl (? -2, 3-dimethyl-s-indacen-l-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) dimethoxy (? 5-2, 3-dimethyl-s-indacen) -l-il) silane-titanium (II), 1,3-pentadiene of (t-butylamido) -dimethoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) dimethoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t -butylamido) dimethoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) -dimethoxy (? 5-2, 3-dimethyl-s- indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) -dimethoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) diisopropoxy (?? - 2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) diisopropoxy (? 5-2, 3-dimethyl-s-indacen -l-yl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) diisopropoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 2 - (N, N-dimethylamino) benzyl of (t-butylamido) diisopropoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (III), dimethyl of (t-butylamido) diisopropoxy ( ? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) diisopropoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butylamido) ethoxymethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 1, 3 -pentadiene of (t-butylamido) ethoxymethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) ethoxymethyl ( ? 5-2, 3-dimethyl-s-indacen-li l) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) ethoxymethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (III) dimethyl (t-butylamido) ethoxymethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) ethoxymethyl (? 5-2, 3-) dimethyl-s-indacen-l-yl) silane-titanium (IV), dimethyl (dimethylamine) dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III), dibenzyl (dimethylamine) dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III), dimethyl (diisopropylamine) dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III), dimethyl (di-n-butylamine) dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III), dibenzyl (di-n-butylamine) -dimethyl (? 5-2, 3-dimethyl-indenyl) silane-titanium (III), dimethyl (di-iso-butylamine) dimethyl (? 5-2, 3-dimethylindenyl) silane- titanium (III), dibenzyl (di-iso-butylamine) dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III), dimethyl (dimethylamine) dimethyl (? 5-2, 3-dimethyl-s- indacen-1-yl) silane-titanium (III), dibenzyl (dimethylamine) dimethyl (? s-2,3-dimethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (diisopropylamine) dimethyl (? 5-2, 3dimethyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) ) silane-titanium (III), dimethyl (di-n-butylamine) dimethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (di-n-butylamine) dimethyl- (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (di-isobutylamine) dimethyl- ( ? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (di-isobutylamine) dimethyl- (? 5-2, 3-dimethyl-s-indacen-1-yl) ) silane-titanium (III), 1,4-diphenyl-1,3-butadiene (t-butylamido) dimethyl (? 5-2-methyl-3-) ethylindenyl) silane-titanium (11) / 1,3-pentadiene (t-butylamido) dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (II), 2,4-hexadiene (t-butylamido) ) dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethyl (? 5-2-methyl-3-ethyl- indenyl) -silane-titanium (III), dimethyl (t-butylamido) dimethyl (? s-2-methyl-3-ethyl-indenyl) silane-titanium (IV), dibenzyl (t-butylamido) dimethyl (? 5-2-methyl-3-ethyl-indenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) dimethoxy (? 5-2) -methyl-3-ethylindenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) dimethoxy (5-methyl-3-ethylindenyl) silane-titanium (II), 2, 4-hexadiene of (t-butylamido) dimethoxy (? 5-2-methyl-3-ethylindenyl) silane-titanium (II), 2- (N, -dimethylamino) benzyl of (t-butylamido) dimethoxy (? s-2-methyl-3-ethylindenyl) silane-titanium (III), dimethyl (t-butylamido) dimethoxy (? 5-2-methyl-3-ethylindenyl) silane-titanium (IV ), dibenzyl (t-butylamido) dimethoxy (? 5-2-methyl-3-ethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butylamido) -diisopropoxy (5-methyl-3-ethylindenyl) silane-titanium (II), 1,3-pentadiene of (t) -butylamido) diisopropoxy- (? 5-2-methyl-3-ethylindenyl) silane-titanium (II), 2,4-hexadiene from (t-butylamido) diisopropoxy (? s-2-methyl-3-ethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) diisopropoxy (? 5-2-methyl-3-ethylindenyl) silane-titanium (III), dimethyl (t-butylamido) diisopropoxy (? 5-2-methyl-3-ethylindenyl) silane-titanium (IV ), dibenzyl (t-butylamido) diisopropoxy (? 5-2-methyl-3-ethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene from (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (II), 1,3-pentadiene of (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (11). 2, 4-hexadiene from (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (III), dimethyl (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) dimethyl (? 5-2-methyl) -3-ethyl-s-indacen-l-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) dimethyl (? 5-2-methyl-3-ethyl-s-indacen-l- il) silane-titanium (II), 2,4-hexadiene from (t-butylamido) dimethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) -dimethyl (? 5-2-methyl- 3-ethyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) dimethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-l, 3-butadiene of (t-butylamido) dimethoxy (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene "'(t-butylamido) -dimethoxy (? 5-2-methyl) -3-ethyl-s-indacen-l-yl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) dimethoxy (? 5-2-methyl-3-ethyl-s-indacen-l- il) silane-titanium (II), 2- (N, N-dimethylamino) bejicyl of (t-butylamido) dimethoxy (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium ( III), dimethyl (t-butylamido) -dimethoxy (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) dimethoxy (? -2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butylamido) diisopropoxy (? 5-2-methyl- 3-ethyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) diisopropoxy (5-2-methyl-3-ethyl-s-indacen-1-yl) ) silane-titanium (II), 2,4-hexadiene from (t-butylamido) diisopropoxy (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) diisopropoxy (t ?s-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) -diisopropoxy (α 5-2-methyl-3-ethyl-s) -indazen-l-yl) silane-titanium (IV), dibenzyl (t-butylamido) diisopropoxy (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (IV), 1 , 4-diphenyl-1,3-butadiene from (t-butylamido) -ethoxymethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) ethoxymethyl (? 5-2) -methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl (t-butylamido) ethoxymethyl (??? 2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) ethoxymethyl (?? - 2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (IV), dimethyl (dimethylamine) dimethyl (? 5-2-methyl-3-ethylindenyl) ) silane-titanium (III), dibenzyl (dimethylamine) dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (III), dimethyl (diisopropylamine) dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (III), dimethyl (di-n-butylamine) dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (III ), (di-n-butylamine) -dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium dibenzyl (III), dimethyl (di-iso-butylamine) dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (III), dibenzyl (di-iso-butylamine) dimethyl (? 5-2-methyl) -3-ethylindenyl) silane-titanium (III), Dimethyl (dimethylamine) dimethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium - (III), dibenzyl (dimethylamine) dimethyl (? 5-2 - methyl-3-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (diisopropylamine) dimethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (di-n-butylamine) dimethyl (? 5) -2-methyl-3-ethyl-s-indacen-l-yl) silane-titanium (III), dibenzyl (di-n-butylamine) dimethyl- (? 5-2-methyl-3-ethyl-s-indacen) -l-il) silane-titanium (III), dimethyl (di-isobutylamine) dimethyl- (? 5-2-methyl-3-ethyl-s-indacen-l-yl) silane-titanium (III), dibenzyl (di-isobutylamine) dimethyl- (? 5-2-methyl) -3-ethyl-s-indacen-1-yl) silane-titanium (III). Preferred members of this group include: 1,4-diphenyl-1,3-butadiene of (t-butylamido) -dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (II) and dimethyl (t-butylamido) ) -dimethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (IV).

The complexes can be prepared by the use of well-known synthetic techniques. Optionally, a reducing agent can be used to produce the lower oxidation state complexes. Such a process is described in patent application USSN 8 / 241,523, filed on May 13, 1994, published as WO 95-00526, the teachings of which they incorporate aguí by reference. The syntheses are carried out in a suitable non-interfering solvent at a temperature from -100 to 300 ° C, preferably from -78 to 100 ° C, more preferably from 0 to 50 ° C. The "reducing agent", as used herein, means a metal or compound which, under reducing conditions, causes the metal M to be reduced from a higher oxidation state to a lower one. Examples of suitable metal reducing agents are alkali metals, alkaline earth metals, aluminum and zinc, alkali metal alloys or alkaline earth metals, such as sodium / mercury amalgam and sodium / potassium alloy. Examples of the appropriate reducing agent compounds are sodium naphthalenide, potassium graphite, lithium alkyls, lithium or potassium alkadienyls; Grignard reagents. Preferred reducing agents include the alkali metals or alkaline earth metals, especially the lithium magnesium metal.

The appropriate reaction medium for the formation of the catalyst complexes includes the aliphatic and aromatic hydrocarbons, ethers, and cyclic ethers, particularly the branched chain hydrocarbons, such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures. thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; aromatic substituted hydrocarbyl compounds, such as benzene, toluene, and xylene, dialkyl C 4 ethers, C 1 4 dialkyl ether derivatives of polyalkylene glycols, and tetrahydrofuran (THF). Mixtures of those mentioned above are also appropriate.

The complexes are converted to catalytically active by combining them with an activating cocatalyst or by the use of an activation technique. Activating cocatalysts suitable for use herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, modified triisobutylaluminum methylalumoxane, or isobutylalumoxane; neutral Lewis acids, such as the compounds of the C 13 -30 substituted hydrocarbyl group, especially the tri (hydrocarbyl) aluminum or tri (hydrocarbyl) boron compounds and the halogenated (including perhalogenated) derivatives thereof, which have from 1 to 10 carbon atoms in each hydrocarbyl or halogenated hydrocarbyl group, more especially the perfluorinated tri (aryl) boron compounds, and more especially the tris (pentafluorophenyl) borane (hereinafter "FAB"); non-polymeric, compatible, non-coordinating ion formation compounds (including the use of such compounds under oxidation conditions), especially the use of ammonium, phosphonium, oxonium, carbonium, silylium or sulfonium salts of compatible, non-coordinating anions, or ferronium salts of compatible anions, they do not coordinate; and combinations of the activating cocatalysts and techniques mentioned above. The activating cocatalysts and activation techniques mentioned above have been previously taught with respect to the different metal complexes in the following references: EP-A-277, 003, US-A-5, 153, 157, US-A-5, 064, 802, EP-A-468,651 (equivalent to US Patent Application Serial No. 07 / 547,718), EP-A-520,732 (equivalent to US Patent Application Serial No. 07 / 876,268), and EP-A -520,732 (equivalent to US Patent Application Serial No. 07 / 884,966, filed May 1, 1992), the teachings of which are incorporated herein by reference.

The combinations of the neutral Lewis acids, especially the combination of a trialkylaluminum compound having from 1 to 4 carbon atoms in each alkyl group and a halogenated tri (hydrocarbyl boron) compound having from 1 to 20 carbon atoms in each hydrocarbyl group, especially FAB, further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially FAB with a polymeric or oligomeric alumoxane are desirable activating cocatalysts especially. The molar proportions of the metal complex of Group 4: FAB: alumoxane are from 1: 1: 1 to 1: 5: 20, more preferably from 1: 1: 1.5 to 1: 5: 10. The use of lower levels of alumoxane in the process of the present invention will allow the production of EAODM polymers with high catalytic efficiencies using less than the expensive alumoxane cocatalyst. Additionally, polymers are obtained with lower levels of aluminum residue, and therefore greater clarity.

Suitable ion formation compounds which are useful as cocatalysts comprise a cation, which is a Brónsted acid capable of donating a proton, and a compatible, non-coordinating anion, A ". As used herein, the term" non-coordinating " "means an anion or substrate that either does not coordinate the precursor complex containing the Group 4 metal and the catalytic derivative, derived therefrom, or is only weakly coordinated to such complexes, thereby remaining sufficiently labile to move by a neutral Lewis base A non-coordinating anion specifically refers to an anion which, when functioning as a charge-balancing anion in a cationic metal complex, does not transfer a substituent or anionic fragment thereof to the cation, thereby forming neutral complexes "Compatible anions" are anions that do not degrade until neutrality, when the complex formed initially decomposes and are not interfering with the desired subsequent polymerization or other uses of the complex.

Preferred anions contain a single coordination complex comprising a metal or metalloid core that is charged and capable of balancing the charge of the active catalyst species (the metal cation) that can be formed when the two components are combined. Also, the anion must be sufficiently labile to displace the olefinic, diolefinic and unsaturated acetylene 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 containing anions comprising coordination complexes containing a single metal or metalloid atom are, of course, well known, and many, particularly such compounds containing a single boron atom in the anionic portion, are commercially available.

Preferably, such cocatalysts can be represented by the following general formula: (L * -H) d + (A) ' where : L * is a neutral Lewis base; (L * -H) + is a Brónsted acid; Ad ~ is a non-coordinating, compatible anion that has a charge of d-, and d is an integer from 1 to 3 More preferably A "corresponds to the formula: [M 'Q4] "; where .- M1 is boron or aluminum in the conventional oxidation state +3, - and Q is, independently for each occurrence, selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halo-substituted hydrocarbyl, halo-substituted hydrocarbyloxy, and silylhydrocarbyl radicals halosubstituted (including perhalogenated hydrocarbyl radicals, perhalogenated hydrocarbyloxy and perhalogenated silylhydrocarbyl), Q has up to 20 carbons with the condition that in no more than one occurrence is Q a halide. Examples of the appropriate Q-hydroxycarbyloxide groups are described in US-A-5, 296, 433, the teachings of which are incorporated herein by referensia.

In a more preferred embodiment, d is one, that is, the counterion has a single negative charge and is Ad Activating cocatalysts comprising boron, which are particularly useful in the preparation of the catalysts of this invention can be represented by the following General Formula : (L * -H) + (BQ4) where : L * is as previously defined; B is boron in a conventional oxidation state of 3; Y Q is a hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy, or fluorinated silylhydrocarbyl group of up to 20 non-hydrogen atoms, with the condition that in no more than one occasion is Q hydrocarbyl.

More preferably, Q is each occurrence a fluorinated aryl group, especially a pentafluorophenyl group.

Illustrative, but not limiting, examples of boron compounds that can be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are: trisubstituted ammonium salts, such as trimethyl ammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) borate di (tallowalkyl hydrogenated) methylammonium, tetrakis (pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) borate tripropylammonium, tetrakis (pentafluorophenyl) borate tri (n-butyl) ammonium, tetrakis (pentafluorophenyl) borate tri (sec- butyl) -ammonium, N, N-dimethylanilinium tetrakis (pentafluoro-phenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, tetrakis (4- ( N, N-dimethylanilinium, N, N-dimethylanilinium (4- (triisopropylsilyl) -2, 3, 5, 6-tetrafluorophenyl) borate, N, N-dimethylanilinium tert-butyldimethyl-silyl) -2, 3, 5, 6-tetrafluorophenyl) borate , pentafluorofenoxitr N, N-dimethylanilinium is (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl- tetrakis (pentafluorophenyl) borate 2,4,6-trimethyl-anilinium, tetrakis (2,3,4,6-tetrafluorophenyl) borate trimethylammonium, tetrakis (2, 3, 4,6-tetrafluorophenyl) borate triethylammonium tetrakis (2, 3, 4, 6-tetrafluorophenyl) tripropylammonium borate, tetrakis (2, 3, 4, 6-tetrafluorophenyl) borate of N, N-dimethylanilinium, tetrakis (2, 3, 4, 6-tetrafluorophenyl) borate of N, N-diethylanilinium, and tetrakis (2, 3, 4, 6-tetrafluorophenyl) borate of N, N-dimethyl-2,4,6-trimethylanilinium; dialkylammonium salts, such as: di (i-propyl) ammonium tetrakis (pentafluorophenyl) borate, tetra (3, 4, 4, 6-tetrafluorophenyl) borate tri (n-butyl) ammonium, tetrakis (2, 3, 4 , 6-tetrafluorophenyl) dimethyl (t-butyl) ammonium borate and dicyclohexylammonium tetrakis (pentafluorophenyl) borate; tri-substituted phosphonium salts, such as: triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (2,6-dimethylphenyl) -phosphonium tetrakis (pentafluorophenyl) borate; di-substituted oxonium salts, such as: diphenyloxonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) oxonium tetrakis (pentafluorophenyl) borate, and di (2,6-dimethylphenyl) oxonium tetrakis (pentafluorophenyl) borate; di-substituted sulfonium salts, such as diphenylsulfonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, and bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate.

The preferred (L * -H) + cations are N, N-dimethylanilinium and tributylammonium.

Other suitable ion forming, activating cocatalysts comprise a compound "which is a salt of a carbenium ion and a non-coordinating, compatible anion represented by the formula: + A " where : c + is a carbenium ion C? -20; and "is as previously defined." A preferred carbenium ion is the trityl cation, i.e., triphenylmethylium.

An additional suitable ion-forming, activating cocatalyst comprises a compound, which is a salt of a silyl ion and a non-coordinating, compatible anion represented by the formula: R3Si (X ') q + A " where: R is hydrocarbyl C? -? 0, and Xd q and A "are as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilyl tetrakispentafluorophenylborate, triethylsilyl tetrakispentafluorophenylborate and ether substituted adducts thereof. Silylium salts have previously been described generically in J.

Chem Soc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al., Organometallics, 1994, 13, 2430-2443. The use of the above silylium salts as activating cocatalysts for the addition of polymerization catalysts are claimed in the US Patent Application Serial Number 304,314, filed September 12, 1994, published in equivalent form as WO96 / 08519 on March 21, 1996, the teachings of which are incorporated here by reference.

Certain complexes of alcohols, mercaptans, silanols, and oximes with FAB are also effective catalyst activators and can be used according to the present invention. Such cocatalysts are described in US-A-5, 296, 433, the teachings of which are incorporated herein by reference.

The activating cocatalysts mentioned above can also be used in combination. A particularly preferred combination is a mixture of a tri (hydrocarbyl) aluminum or tri (hydrocarbyl) borane compound having from 1 to 4 carbons in each hydrocarbyl group with an oligomeric or polymeric alumoxane compound.

The molar ratio of the catalyst / cocatalyst employed preferably ranges from 1: 10,000 to 100: 1, more preferably from 1: 5000 to 10: 1, more preferably from 1: 1000 to 1: 1. Alumoxane, when used by itself as an activating cocatalyst, is used in large quantities, generally at least 100 times the amount of the metal complex on a molar basis (calculated in moles of aluminum (Al)). The FAB, when used as an activating cocatalyst, is employed in a molar ratio to the metal complex from 0.5: 1 to 10: 1, more preferably from 1: 1 to 6: 1, more preferably from 1: 1 up to 5: 1. The remaining activating cocatalysts are generally used in an approximately equimolar amount with the metal complex.

In general, the polymerization is carried out under conditions well known in the art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, ie, temperatures from 0-250 ° C, preferably 30 to 200 ° C and pressures from atmospheric to 10,000 atmospheres. Polymerization in suspension, solution, slurry, gas phase, solid powder or other process condition can be used if desired. A support, especially silica, alumina, or a polymer (especially poly (tetrafluoroethylene) or a polyolefin) can be employed, and is desirably employed when the catalysts are used in a gas phase polymerization process. The support is preferably employed in an amount to provide a weight ratio of catalyst (based on the metal): support from 1: 100,000 to 1:10, more preferably from 1: 50,000 to 1:20, and more preferable from 1: 10,000 to 1:30. In most polymerization reactions, the molar ratio of catalyzed: polymerizable compounds employed is from 10"12: 1 to 10" 1: 1, most preferably from 10"9: 1 to 10" 5: 1.

Inert liquids are suitable solvents for polymerization. Examples include straight and branched chain hydrocarbons, such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; perfluorinated hydrocarbons, such as C4_? or perfluorinated alkanes; and aromatic and aromatic substituted alkyl compounds, such as benzene, toluene, xylene, and ethylbenzene. Suitable solvents also include liquid olefins that can act as monomers or comonomers, including butadiene, cyclopentene, 1-hexene, 1-hexane, 4-vinylcyclohexene, vinylcyclohexane, 3-methyl-1-pentene, 4-methyl-1 pentene, 1,4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene, allylbenzene, and vinyltoluene (including all isomers alone or in a mixture). Mixtures of those mentioned above are also appropriate. If desired, gaseous olefins can usually be converted to liquid by the application of pressure and used here.

The catalysts can be used in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in separate reactors connected in series or in parallel to prepare the polymer blends having desirable properties. An example of such a process is described in WO 94/00500, equivalent to U.S. Patent Application. Serial Number 07 / 904,770, as well as U.S. Patent Application Serial Number. Serial Number 08/10958, filed January 29, 1993, the teachings of which are incorporated herein by reference.

Using these catalysts in the process of the present invention, the interpolymers having high comonomer incorporation and correspondingly low density, which have Still a high MV are easily prepared. That is, high Mw polymers are easily obtained by the use of the present catalysts, even at elevated reactor temperatures. This result is highly desirable because the Mw of the α-olefin interpolymers can be easily reduced by the use of hydrogen or a similar chain transfer agent, however the molecular weight increase of the alpha-olefin interpolymers is obtainable only usually reducing the polymerization temperature of the reactor. Disadvantageously, the operation of the polymerization reactor at reduced temperatures significantly increases the operating cost, since the heat must be removed from the reactor to maintain the reduced reaction temperature, while at the same time the heat must be added to the effluent of the reactor. reactor to vaporize the solvent. In addition, productivity increases due to improved polymer solubility, decreased solution viscosity, and higher polymer concentration. Using the present catalysts, alpha-olefin homopolymers and copolymers having densities from 0.85 g / cm 3 to 0.96 g / cm 3, and an MV from 1 to 150 are easily obtained in a high temperature process.

The catalysts used in the process of the present invention are advantageous particularly for the production of interpolymers that have high levels of long chain branching. The use of the catalysts in continuous polymerization processes, especially continuous solution polymerization processes, allows high reactor temperatures that favor the formation of finished vinyl polymer chains that can be incorporated into a growth polymer, thereby It gives a long chain branch. The unique combination of high reactor temperatures, high molecular weight (or low melt indexes) at high reactor temperatures and high comonomer reactivity, advantageously allow economical production of polymers having excellent physical properties and processability.

The process used to prepare the EAODM interpolymers of the present invention can be either a solution or slurry process, both of which are previously known in the art. Kaminsky, J. Poly. Sci .. Vol. 23, pp. 2151-64 (1985) reports the use of a soluble bis (cyclopentadienyl) zirconium-alumoxane dimethyl catalyst system for the solution polymerization of EP elastomers and EAODM. US-A-5, 229, 478 discloses a slurry polymerization process using similar bis (cyclopentadienyl) zirconium catalyst systems.

In general terms, it is desirable to produce EAODM elastomers under conditions of increased reactivity of the diene monomer component. The reason for this is explained in the '478 patent identified above as follows, which still remains true in spite of the advances obtained in such reference. A major factor that affects production costs and therefore the usefulness of an EAODM is the cost of diene monomer. Diene is a more expensive monomer material than C2 or C3. further, the reactivity of the diene monomers with previously known metallocene catalysts is lower than that of C2 and C3. Therefore, to achieve the necessary degree of diene incorporation to produce an EAODM with an acceptably fast cure rate, it has been necessary to use a diene monomer concentration which, expressed as a percentage of the total concentration of monomers present, is in substantial excess compared to the percentage of the desired diene that is incorporated into the final EAODM product. Since the substantial amounts of the unreacted diene monomer must be recovered from the effluent of the polymerization reactor to recycle them, the production cost is unnecessarily increased.

In addition to adding to the cost of production an EAODM is the fact that, generally, the exposure of a catalyst polymerization of olefin to a diene, especially the high concentrations of diene monomer required to produce the necessary level of diene incorporation in the final EAODM product, often reduces the proportion or activity at which the catalyst will cause polymerization to proceed. the ethylene and propylene monomers. Correspondingly, lower yields and longer reaction times have been required, compared to the production of an ethylene-propylene copolymer elastomer or other α-olefin copolymer elastomer.

The catalyst systems used in the process of the present invention allow increased diene reactivity, whereby the EAODM polymers are prepared in high yield and productivity. Additionally, the process of the present invention achieves economical production of EAODM polymers with diene contents from greater than zero up to 20 percent by weight (% by weight) or greater, preferably from 0.3 to 20% by weight, more preferably from 0.5 to 12% by weight. These EAODM polymers possess highly desirable rapid cure rates.

The preferred EAODM elastomers have a C2 content of 20 to 90% by weight, more preferably 30 up to 85% by weight, and more preferably 35 to 80% by weight.

The alpha-olefin, different from C2, is generally incorporated in the EAODM polymer at 10 to 80% by weight, more preferably at 20 to 65% by weight. The non-conjugated dienes are generally incorporated in the EAODM polymer at 0.5 to 25% by weight, preferably at 1 to 15% by weight, and more preferably at 3 to 12% by weight. If desired, more than one diene can be incorporated simultaneously, for example 1, 4-hexadiene and ENB, with a total diene incorporation within the limits specified above.

The catalyst system used in the process of the present invention can be prepared as a homogeneous catalyst by adding the necessary components to a solvent in which the polymerization will be carried out by solution polymerization processes. The catalyst system can also be prepared and used as a heterogeneous catalyst by adsorbing the necessary components in a catalyst support material, such as silica gel, alumina or other suitable inorganic support material. When prepared in a heterogeneous or supported form, it is preferred to use silica as the support material. The heterogeneous form of the catalyst system is used in a polymerization in grout. As a practical limitation, the slurry polymerization takes place in liquid diluents, in which the polymer product is substantially insoluble. Preferably, the diluent for the slurry polymerization is one or more C-5 hydrocarbons. If desired, saturated hydrocarbons, such as ethane, propane or butane may be used in whole or in part as a diluent. Likewise the alpha-olefin monomer or a mixture of different alpha-olefin monomers can be used in whole or in part as the diluent. More preferably, the diluent comprises in at least the major part the alpha-olefin monomer or monomers which are polymerized.

The EAODM polymers of the present invention can, as noted above, also be prepared by gas phase polymerization, another well known process, wherein the cooling of the reactor typically occurs via an evaporative cooling of a volatile material, such as a recirculated gas, an inert liquid or a monomer or diene that is used to prepare the EAODM polymer. A suitable inert liquid is a C3-8, preferably a C4-6, saturated hydrocarbon monomer. The volatile material or liquid evaporates in the hot fluidized bed to form a gas that mixes with the fluidizing gas. This type of process is described, for example, in EP 89691; US-A-4, 543, 399, - WO 94/25495; WO 94/28032; and US-A-5, 352, 749, the teachings of which are therefore incorporated by reference. Other pertinent teachings, also incorporated by reference, are found in US-A-4, 588, 790; US-A-4, 543, 399, -US-A-5,352,749; US-A-5, 436, 304; US-A-5, 405, 922; US-A-5, 462, 999; US-A-5,461,123; US-A-5, 453, 471; US-A-5, 032, 562; US-A-5, 028, 670; US-A-5,473,028; US-A-5, 106, 804; US-A-5, 541, 270; EP-A-659, 773; EP-A-692,500; and PCT Applications WO 94/29032, WO 94/25497, WO 94/25495, WO 94/28032; WO 95/13305; WO 94/26793; and WO 95/07942.

The polymerization reaction that occurs in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst. Such a catalyst can be supported in an inorganic or organic support material.

The gas phase processes suitable for the practice of this invention are continuous processes preferably providing a continuous supply of reactants to the reaction zone of the reactor and removal of the products from the reaction zone of the reactor, thereby providing a medium of fixed state on the macro scale in the reaction zone of the reactor.

In contrast, the solution polymerization conditions use a solvent for the particular components of the reaction. Preferred solvents include mineral oils and different hydrocarbons that are liquid at reaction temperatures. Illustrative examples of useful solvents include alkanes, such as pentane, iso-pentane, hexane, heptane, octane and nonane, as well as mixtures of alkanes, including kerosene and Isopar E ™, available from Exxon Chemicals Inc.; cycloalkanes, such as cyclopentane and cyclohexane, and aromatics, such as benzene, toluene, xylenes, ethylbenzene and diethylbenzene.

At all times, the individual ingredients, as well as the recovered catalyst components should be protected from oxygen and moisture. Therefore, the catalyst components and the catalysts should be, and preferably are, prepared and recovered in an atmosphere free of oxygen and moisture. Preferably, therefore, the reactions are carried out in the presence of an inert, dry gas such as, for example, nitrogen.

The ethylene is added to a reaction vessel in an amount sufficient to maintain a differential pressure in excess of the combined vapor pressure of the alpha-olefin and diene monomers. The C2 content of the polymer is determined by the ratio of the differential pressure of C2 to the total reactor pressure. Generally, the polymerization is presented with a differential pressure of C2 from 10 to 1000 pounds per square inch (psi) (70 to 7000 kPa), more preferably from 40 to 400 psi (30 to 300 kPa). The polymerization temperature is suitably from 25 to 200 ° C, preferably from 65 to 170 ° C, more preferably from greater than 75 to 140 ° C.

The polymerization can occur in either a batch or continuous polymerization process. A continuous process is preferred, in which case the catalyst, ethylene, alpha-olefin, diene and optional solvent are continuously supplied to the reaction zone and the polymer product is continuously removed therefrom.

Without limiting the scope of the invention in any way, a means for carrying out such a polymerization process is as follows: In a stirred tank reactor, the alpha-olefin monomer is continuously introduced together with the solvent, diene monomer and C2 monomer. The reactor contains a liquid phase composed substantially of C2, C3 and diene monomers together with any additional solvent or diluent. If desired, a small amount of an H-branch-inducing diene, such as norbornadiene, can also be added, 1, 7-octadiene or 1, 9-decadiene. The catalyst and cocatalyst are continuously introduced into the liquid phase of the reactor. The temperature and pressure of the reactor can be controlled by adjusting the solvent / monomer ratio, the proportion of catalyst addition, as well as cooling or heating coils, jackets or both. The polymerization ratio is controlled by the proportion of the catalyst addition. The ethylene content of the polymer product is determined by the amounts of ethylene, alpha-olefin and diene in the reactor, which is controlled by manipulating the particular feed ratios of these components to the reactor. The molecular weight of the polymer product is controlled, optionally, by controlling other polymerization variables, such as temperature, monomer concentration or by a stream of hydrogen introduced to the reactor, as is well known in the art. The effluent from the reactor is contacted with a catalyst neutralizing agent, such as water. The polymer solution is optionally heated, and the polymer product is recovered by flash evaporation of the ethylene and propylene gas, as well as the residual diene and the residual solvent or diluent at reduced pressure, and, if necessary, further carrying out the devolatilization in an equipment, such as a devolatilization extruder. In a continuous process, the average residence time of the catalyst and the polymer in the reactor is generally from 5 minutes to 8 hours, and preferably from 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 parallel. In a reactor, a relatively high molecular weight product is formed (Mw from 300,000 to 600,000, most preferably 325,000 to 500,000) while, in the second reactor, a relatively low molecular weight product is formed (Mw 50,000 up 300,000). As an alternative, the product of the same molecular weight can be produced in each of the two reactors. The final product is a mixture of the two reactor effluents that combine before devolatilization to result in a uniform mixture of the two polymer products. Such a dual reactor process allows the preparation of products that have improved properties. In a preferred embodiment, the reactors are connected in series, that is, the effluent from the first reactor is charged to the second reactor and the fresh monomer, solvent and hydrogen are added to the second reactor. The reactor conditions are adjusted such that the weight ratio of polymer produced in the first reactor to that produced in the second reactor is from 20:80 to 80:20. If desired, however, a wider range of weight proportions can be used.

In addition, the temperature of the second reactor is controlled to produce the lowest Mw product. This system beneficially allows the production of EAODM products that have a large MV range, as well as excellent resistance and processability. Preferably the MV of the resulting product is adjusted to fall within the range from 1 to 150, more preferably from 10 to 120 and more preferably from 15 to 100. Although this preferred mode of operation employs two reactors, it is also They can use three or more reactors.

Examples The following examples illustrate but not, either explicitly or by implication, limit the present invention. Unless otherwise indicated, all parts and percentages are expressed on a weight basis. The examples of the present invention are identified by Arabic numerals and the comparative examples are represented by letters of the alphabet.

For the catalyst examples, the XH and 13 C NMR spectrum are recorded on a Varian XL spectrometer (300 MHz). Chemical changes are determined in relation to TMS (tetramethylsilane) or through residual CHC13 in residual CDC13 or C6HD5 in C6D6, related to TMS. Tetrahydrofuran (THF), diethyl ether, toluene, and hexane are used following the passage through of double columns loaded with activated alumina and mixed metal oxide catalyst supported on alumina (Q-5® catalyst, available from Engelhard Corp.). The n-BuLi, KH, all Grignard reagents, and 1,4-diphenyl-1,3-butadiene compounds are all used as obtained from Aldrich Chemical Company. All catalyst syntheses are carried out under a dry nitrogen atmosphere using a combination of glove box and high vacuum techniques.

The preparation of the polymer example employs either a continuous process or a batch process. With a batch process, monomers and other specific components are added to a reactor apparatus before starting the process. For a continuous process, the monomers are added to a reactor apparatus as necessary, with a variation of the flow rate that is used to alter monomer concentrations. Each example specifies the type of process and conditions. Process production times of one to two hours are generally sufficient to allow the reaction to reach equilibrium and provide representative polymer samples for analysis.

The evaluation of the physical property of the EAODM polymers uses a number of standard tests: MV; analysis compositional via infrared analysis of the Fourier transform (FTIR) (ASTM D3900); and density (ASTM D-792). Other definitive properties include the B value, determined as previously described, the proportion of rheology, determined as described below, and the product of the reactivity ratio, also determined as described below.

The rheology ratio (V0.?/V?00) is determined by examining the samples using fusion rheology techniques on a Dynamic Mechanical Spectrometer (DMS) ARES (Advanced Rheometric Expansion System) from Rheometric Scientific, Inc. The samples are examine at 190 ° C using the dynamic frequency mode and parallel plate fittings of 25 millimeters in diameter with an opening of 2 millimeters. With a test speed of 8% and an oscillating ratio that increases progressively from 0.1 to 100 radians per second (rad / sec), 5 data points are taken for each ten frequencies analyzed. Each sample (either pellets or bullets) is compression molded into 3-inch plates (1.18 centimeters) (cm)) of 1/8 inch (0.049 centimeters) thickness at 20,000 psi (137.9 megapascal (Mpa)) of pressure for 1 minute at 180 ° C. The plates are turned off and cooled (for a period of 1 minute) at room temperature. A 25-millimeter plate is cut from the central portion of the larger plate. Then these aliquots of 25 millimeters in diameter are inserted into the ARES at 190 ° C and allowed to equilibrate for 5 minutes before the start of the test. The samples are kept in a nitrogen medium throughout the analysis to minimize degradation by oxidation. The reduction and manipulation of data is done by the package of programming elements based on the Windows 95 Orchestrator ARES2 / A5: RSI. The ratio V0.?/V?00 (rheology ratio or "RR") measures the inclination of the viscosity curve versus the cutting ratio.

The reactivity ratios, rl and r2, are calculated from the divalent and trivalent distributions in the 13C NMR spectrum based on a terminal copolymerization model, and then the product of the reactivity ratio (RRP) is obtained by multiplying these two values (rl and r2). The preparation of the 13 C NMR sample is as detailed above.

The crystallinity of the polymer is determined by differential scanning calorimetry (DSC) using a TA DSC-2920 equipped with a liquid nitrogen cooling accessory. The samples are prepared as thin films and placed in aluminum containers. These are initially heated to 180 ° C and maintained at this temperature for four minutes to ensure substantially complete fusion. Then they are cooled to 10 ° C for one minute to -100 ° C before reheating to 150 ° C at 10 ° C per minute. The Tg is obtained from the curve of the melting temperature using the first derivative of temperature. The total heat of fusion is obtained from the area under the melting curve. The percent crystallinity is determined by dividing the total heat of fusion by the value of the heat of fusion for the polyethylene (292 joules per gram (J / g)).

The efficiency of the catalyst (Cat. Eff.) Is specified in terms of millions of pounds of polymer per pound of Group IV metal in the catalyst (MM # / #). For the batch process, it is determined by weighting the polymer product and dividing by the amount of Group IV metal added to the reactor. For the continuous process, the weight of the polymer product is determined by the measured ethylene or by the output conversion.

Examples of the EAODM polymers that represent the present invention employ a catalyst prepared as described below, while the EAODM polymers of the comparative example are prepared using a constrained geometry catalyst, such as described in US-A -5,491,246; US-A-5, 486, 632; and US-A-5, 470, 993.

Preparation of the catalyst Example 1 - Synthesis of dimethyl (t-butylamido) -dimethyl (? 5- 2-methyl-s-indacen-1-yl) silane-titanium (IV) JLaJ Preparation of 5.6.7-tetrahydro-2-methyl-s -seecen-l- Indan (59.0876 grams (g), 0.5000 mol) and 2-bromoisobutyryl bromide (114.9493 g, 0.5000 mol) are stirred in CH2C12 (500 milliliters (mL)) at 0 ° C, since A1C13 (201.36 g, 1.5101 moles) is added slowly as a solid under a flow of nitrogen (N2). Then this mixture is stirred for 6 hours at 20-25 ° C. After the reaction period, the mixture is poured onto ice and allowed to incubate for 16 hours. The mixture is then decanted in a separatory funnel and the resulting salts are washed well with CH2C12. Then the organic layer is separated and the volatile compounds are removed resulting in the isolation of a dark oil. Vacuum distillation results in the isolation of the desired product as a yellow oil (82.43 g, 88.5% yield). lb) Preparation of s-Indacen-1.2, 3.5-tetrahydro-6-methyl The product of Example la) (40.00 g, 0.2148 mol) is stirred in diethylether (150 mL) at 0 ° C under nitrogen, since the NaBH 4 (8.12 g, 0.2148 mol) and EtOH (100 mL) are added slowly to provide a mixture which is then stirred and allowed to react for 16 hours at 20-25 ° C. After this period, the mixture is poured into ice and then acidified using an aqueous 1 Molar HCl (M) solution. Then the organic fraction is washed with 1M HCl (2 x 100 mL). The volatile compounds are removed from the solution and the residue is redissolved in benzene and refluxed with p-toluenesulfonic acid (0.11 g) using a Dean-Stark apparatus for 5 hours. The mixture is then extracted using 1M NaHCO 3 (2 x 100 mL). The organic layer is separated and the volatile compounds are removed resulting in the isolation of the desired product as a white crystalline solid (28.36 g, 77.6% yield).

JLcJ Preparation d = (1,5,6,7-tetrahydro-2-methyl-s-indacen-1-yl) lithium The product of Example lb) (25.0Q0 g, 0.14684 moles) is stirred in hexane (400 mL), since the nBuLi (0.17621 moles, 70.48 mL of 2.5M solution in hexane) is slowly added to provide a reaction mixture that then it is stirred and allowed to react for 16 hours during which time a solid precipitates. The mixture is then filtered to isolate the desired product as a pale yellow solid which is used without purification or additional analysis (24.3690 g, 94.2% yield). id) Preparation of N- (1,1-dimethylethyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-2-p? ethyl-s-indacen-1-yl, ailanamine The product from Example lc) (25.0 g, 0.1419 mol) in tetrahydrofuran (THF) (200 mL) is added dropwise to a solution of dimethylsilyl (t-butylamino) chloride (23.518 g, 0.1419 mol) in THF (250 mL) for a period of time of 1 hour to provide a reaction mixture which is then stirred and allowed to react for 20 hours. After this period, the volatile compounds are removed and the residue is extracted and filtered using hexane. The removal of hexane results in the isolation of the desired product as a red-yellow oil (37.55 g, 88.0% yield). le) Preparation of dithioN- (1,1-dimethylethyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-2-methyl-s-indacen-1-yl) Isylanamide The product of Example Id) (8.00 g, 0.2671 mol) is stirred in hexane (110 mL), since the nBuLi (0.05876 mol, 23.5 mL of 2.5 M solution in hexane) is added dropwise to provide a reaction mixture that then it is stirred and left to react for 16 hours. After this period, the The desired product is isolated as a light yellow solid via the filtration which is used without further purification or analysis (6.22 g, 75% yield). lf) Preparation of dichloroN- (1,1-dimethylethyl) -1, 1-dimethyl- [1,2,3,4, 5-?) -1,5,6,7-tetrahydro-2-methyl-s- indacen-l-illsilanamino (2-) -Nititanium The product of Example? Le) (4.504 g, 0.01446 mol) in THF (40 mL) is added dropwise to a slurry of TiCl3 (THF) 3 (5.359 g, 0.001446 mol) in THF (100 mL) which is stirred for 1 hour before adding PbCl2 (2.614 g, 0.000940 moles) with continuous stirring for an additional hour. After this period, the volatile compounds are removed and the residue is extracted and filtered using toluene. Removal of toluene results in the isolation of a dark residue. This residue is suspended in hexane and then the desired product is isolated via filtration as a red solid (3.94 g, 65% yield).

JLa) Synthesis of the Formula IV complex The product of Example lf) (0.450 g, 0.00108 mol) is stirred in diethyl ether (30 mL), since the MeMgBr (0.00324 mol, 1. 08 mL of 3.0 M solution in diethyl ether) is added slowly to provide a reaction mixture which is then stirred and allowed to react for 30 minutes. After this period, the volatile compounds are removed and the residue is extracted and filtered using hexane. The removal of hexane results in the isolation of the desired product as a solid (0.37 g, 90.6% yield).

Example 2 - Synthesis of the complex of Formula III In a dry compartment (glove box), (t-butylamido) dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium dichloride (Example lf)) (0.300 grams, 0.72 moles) is suspended in 50 mL of cyclohexane in a 100 mL round bottom flask. Ten equivalents of a mixture of 2,4-hexadiene isomers (0.822 mL, 7.21 mmol) are added to the contents of the flask to form a mixture. Two and a quarter equivalents of a 2.0 M Et20 solution of n-BuMgCl (0.81 mL, 1.62 mmol) are added to the mixture to form a reaction mixture. The flask is fixed with a condenser and the reaction mixture is heated at reflux for one hour. With cooling, the volatile compounds are removed under reduced pressure to leave a residue which is then extracted with hexane and filtered through the aid of a filter with diatomaceous earth in a glass frit of 10-15 millimeters. He Hexane is removed under reduced pressure to give 0.29 grams (g) of a brown oily solid as a desired product (equivalent to 94% yield). The product, as characterized by XH and 13C NMR, is 2-4-hexadiene of (t-butylamido) dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (II) • Example 3 - Synthesis of the complex of Formula VII and VIII Using the apparatus and procedure of Example 2, except for substituting 15 equivalents of a mixture of 1,3-pentadiene isomers (1.08 mL, 10.81 mmol) for the 10 equivalents of the mixture of hexadiene isomers, two equivalents of a solution of hexane 2.5 M n-BuLi (0.58 mL, 1.44 mmol) for the 2.25 equivalents of the 2.0 M Et20 solution of n-BuMgCl and increasing the reflux time up to three hours, 0.257 g of a brown oily solid (yield of 86%). The solid, as characterized by 1 H and 13 C NMR, is 1,3-pentadiene of (t-butylamido) -dimethyl (α 5-2 -methyl-s-indacen-1-yl) silane-titanium (II). The product is isolated as a mixture of two geometric isomers resulting in the orientation of 1,3-pentadiene with respect to the methyl group in the indacenyl ring as shown in Formulas VII and VIII.

Examples 4-7 and Comparative Examples A and B Five samples of ethylene / propylene / ENB terpolymer compositions / four represent this invention (Examples 4-7) and one is a comparative example (Comparative Example A), are prepared using the same basic procedure with certain modifications as indicated in Tables IA-1C in a 3.8 liter stirred reactor (L) designed for the continuous addition of reagents and the continuous removal of polymer solution, devolatilization and polymer recovery. Examples 4-7 are prepared using the catalyst of Example 1. Comparative Example A is prepared using 1,3-pentadiene (tetramethylcyclo-pentadienyl) dimethyl (t-butylamido) silane-titanium as the catalyst. The cocatalyst for all five samples is the FAB. The purification compound for the Examples 4-5 and Comparative Example A is MMAO (tributylaluminum modified methylalumoxane). The purification compounds for Examples 6 and 7 are, respectively, DIEL-N ((diisopropylamido) diethylaluminum) and DIBAL-NS ((bistrimethylsilylamido) diisobutyl-aluminum). The ratio of moles of FAB to moles of titanium (Ti) is 3.0 for the Examples 4-7 and 3.6 for Comparative Example A. The fusion index (MI) for Comparative Example A is 25.0g / 10 minutes. MI is used for Comparative Example A because it has an Mw that is too low to measure a MV. Examples 4-7 have a Mw high enough to measure an MV.

An additional comparative example (B) is produced 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 the production of a polymer with a narrower equality in molecular weight.

Referring to Figure 1, ethylene (4), propylene (5), and hydrogen (6) are combined in a stream (16) before being introduced into a diluent mixture (3) comprising a mixed alkane solvent ( Isopar-E ™, available from Exxon Chemicals Inc.) (1) and diene (2) to form a combined feed mixture (7) "which is continuously injected into the reactor (10). The catalyst (8) and a mixture of the cocatalyst and the purification compound (9) are combined in a single stream (17), they are also injected continuously into the reactor.

Table IA shows the flow ratios for the solvent, ethylene (C2) and propylene (C3) in pounds per hour (pph). Table IA also shows the conversion in percent of C2 and the proportion of polymer production (in pph). Table IB shows the concentrations of the catalyst (Cat), cocatalyst (Cocat) and the eliminator (Scav) in parts per million parts of Al (ppm). Table IB also shows a ratio of cocatalyst to metal (M), where M is titanium (Ti), and the flow rates, in pph, for the Catalyst, Cocatalyst and Eliminator. Table IC shows the temperature of the reactor (Temp) in ° C, the flow of hydrogen, in cubic centimeters per standard minute (sccm), the flow rate of ENB (pph), a ratio of eliminator: titanium (Scav / Ti) ) and polymer properties (MV, MI, and EAODM composition) (as determined by FTIR)), the value B, V0.?/V?0o and RRP- An output stream from the reactor (15) is continuously introduced into a separator (11), where the molten polymer is continuously separated from the unreacted comonomer, unreacted ethylene, unreacted hydrogen, unreacted ENB, and solvent (14). The molten polymer is then cut or pelletized into braid and then cooled in a water bath or pelletizer (12), the solid pellets are collected (13).

Table IA Table IB oo o IC table oo - means not measured The data presented in Table IC illustrate several points. First, under essentially the same reaction conditions, the Mw of the polymers of Examples 4-7 are in an order of magnitude greater than that of Comparative Example A as exemplified by the MV measurements. This increase in Mw is not dramatically affected by the type of eliminator used in the reaction. Second, at equal ENB flux rates (Example 4 and Comparative Example A) there is an increase of 66.7% in the incorporation of ENB in the polymer. To obtain an ENB concentration equal to that of Comparative Example A, the flow rate of ENB must be reduced from 0.7 pph to 0.4 pph for Examples 5-7. A comparison of Example A Comparative with Example 5 shows an efficiency of the catalyst dramatically improved in producing essentially the same polymer from the point of view of the incorporation of ENB.

The data in Table IC also suggest that the polymers of the present invention, as represented by Examples 4-7, have a desirable shear thinning behavior and a satisfactory level of long chain branching. The proportion of VO.Í / VK-O (rheology proportion) is a means of measuring the inclination of the viscosity curve versus the cutting ratio. A high V0.?/V100 ratio, equal to that of Examples 4-7, suggests greater sensitivity to cutting or shear thinning in relation to a V0.1 / V100 ratio, equal to that of Comparative Example B. Since the shear thinning is typically affected by both the MWD and the long chain branching level and since the polymers of Examples 4-7 and Comparative Examples A and B all have similar molecular weight distributions (MWD), a higher proportion of VQ.//100, also indicates greater long chain branching. The polymers of this invention have a higher rheology ratio to the same MV as the comparative polymers as proven by comparing Examples 4-7 with Comparative Example B. Comparative Example B, prepared in the absence of hydrogen, has a lower Vo.i / Vioo ratio than any of Examples 4-7. Since the lack of hydrogen generally results in a higher level of vinyl unsaturation and therefore an increased long chain branching and a higher shear thinning behavior and a higher V0.?/V?00, the data suggest that the necessary hydrogen is not excluded from the process of the present invention.

Example 8 The terpolymerization of ethylene, propylene, and ENB is carried out using a 3.8 L stainless steel reactor loaded with 1448 g of Isopar-E ™ (mixed alkanes, available from Exxon Chemicals, Inc.), 230.3 g of proprietary, 32.9 g of ENB, and 13.8 millimoles (mMoles) of hydrogen. The reactor is heated to 100 ° C and then saturated with ethylene at 460 psig (3.24 MPa). The catalyst is prepared in a dry compartment by syringing together 1.0 micromoles (0.005M solution) of the catalyst of Example 1, 1.5 micromoles (0.0075M solution) of FAB as the cocatalyst, 10.0 micromoles (0.050 M solution) of (diisopropylamido) diethylaluminum as the eliminator, and sufficient Isopar-E ™ to give a total volume of 18 mL. Then the catalyst solution is transferred via a syringe to a catalyst addition loop and injected into the reactor for about 4 minutes using a flow of high pressure solvent. The polymerization is allowed to proceed for 10 minutes, while "the ethylene is fed in demand to maintain a pressure of 460 psig (3.24 MPa). The amount of ethylene consumed during the reaction is monitored using a mass flow meter. Then the polymer solution is poured from the reactor into a glass kettle purged with nitrogen and approximately 200 parts per million parts of polymer (ppm) of stabilizer (Irgafos 186 ™ and Irganox ™ 1076) are added and mixed well with the polymer solution. The stabilized polymer solution is poured into a tray, dried with air overnight, and then dried thoroughly in a vacuum oven equipment at a temperature of 120 ° C for one day.

The yield of the terpolymer is 89.7 g, and the Catalyst Efficiency (Cat. Eff.) Is 1.9 million. The terpolymer has a C2 / C3 weight ratio of 2.1 (64.5% by weight of C2, 30.1% by weight of C3), and an ENB content of 5.5% by weight. The Mooney Viscosity (MV) is 84.4 and the molecular weight (Mw) is 185,500 with an MWD (Mw / Mn) of 2.04. The B value is 0.96 and the RRP for ethylene / propylene is 1.16. The terpolymer has a Tg of -44.9 ° C and a crystallinity of 4.2%.

Example 9 Using the apparatus, catalyst and procedure of Example 8, an ethylene / propylene / ENB terpolymer is prepared by changing the reactor with 1457 g of Isopar-E ™, 232.4 g of propylene, 33.8 g of ENB, and 13.8 mMoles of hydrogen. The yield of the terpolymer is 104.7 g, and the Efficiency of the catalyst (Cat. Eff.) Is 2.2 million. The terpolymer has a weight ratio of ethylene to propylene of 2.0 (65.4% by weight of ethylene, 32.1% by weight of propylene), and an ENB content of 2.5% by weight. The MV is 33.0 and the Mw is 134,300 with an MWD of 1.78. The B value is 0.94 and the RRP for ethylene / propylene is 1.21. The terpolymer has a Tg of -46.9 ° C and a crystallinity of 6.2%.

Comparative Example C (C05R03) Using the apparatus and method of Examples 4-7 and Comparative Examples A and B and the dimethyl of (tetramethylcyclo-pentadienyl) dimethyl (t-butylamido) silane-titanium as the catalyst, the FAB as the cocatalyst and the MMAO as the Purification compound, an ethylene / propylene / ENB terpolymer is prepared by flowing in the reactor the amounts shown in the following tables. The ratio of Al / Ti is 6: 1, the flow rate of the MMAO is 0.3 pph and the concentration of the MMAO is 24.91 ppm, based on.

As in Comparative Example B, there is no hydrogen flow. Tables IIA and IIB show the polymerization and property parameters of the resulting polymer.

Table HA 00 Table IIB The data in Table IIB, like those presented in Table IC for Comparative Example B, demonstrate that the polymers produced according to the present invention, even if they are made from the same starting materials and under the same conditions , but with a different catalyst, they clearly differ from those with the latest catalyst.

Example 10 Using the apparatus and method of Example 8 and the catalyst of Example 2, an ethylene / buteneol / ENB terpolymer is prepared by changing the reactor with 1455 g of Isopar-E ™, 303.3 g of butene-l, 42.6 g of ENB , and 9.46 mMoles of hydrogen.

The yield of the terpolymer is 83.0 g, and the Catalyst Efficiency (Cat. Eff.) Is 1.2 million. The resulting elastomer has a molecular weight (Mw) of 168,700, a MWD of 2.02, an MI of 1.7 g / 10 minutes and a crystallinity of 13%.

Example D Comparative Using the apparatus and procedure of Example 8 and a different catalyst, an ethylene / buteneyl / ENB terpolymer prepare by changing the reactor with 1443 g of Isopar-E ™, 304.7 g of butene-l, 90.9 g of ENB, and 9.5 mMoles of hydrogen. The catalyst is prepared in a dry compartment by injecting with a syringe altogether 2.0 micromoles (0.005 M solution) of the metal complex 1,3-pentadiene of (tetramethylcyclopentadienyl) dimethyl (t-butylamido) -silane-titanium (II), 6.0 micromoles (0.015 M solution) of the cocatalyst of the Example 8, 50.0 micromoles (0.125M solution) of the eliminator of the Example 8, and enough Isopar-E ™ to give a total volume of 18 mL. Then the catalyst solution is transferred into the reactor as in Example 8. The yield of the terpolymer is 157.7 g, and the Catalyst Efficiency (Cat. Eff.) Is 1.6 million. The terpolymer has an Mw of 46,700, MWD of 1.97, an MI of 201.7 and a crystallinity of 10.5%.

The difference in the Mw between the terpolymers of Example 10 and Comparative Example D significantly affects the properties of the polymer, such as Stress to Break (ASTM D1708) and Percent of Elongation to Break (ASTM D1708). Example 10 has a Stress at Rupture of 1150 psi (8.90 MPa) as opposed to 375 psi (2.64 MPa) for the 'Comparative Example C, and a Percent of Elongation to the Break of 840 as opposed to 567 for Comparative Example C These data prove the effect of changing catalysts on the resulting polymers.

Examples 11-13 and Example E Comparative Using the apparatus and method of Example 8, and the catalyst of Example 1 for Examples 11, 13 and 14, the catalyst of Example 2 for Example 12 and the catalyst of Comparative Example A for Comparative Example E, and variable cocatalysts, four ethylene / propylene / ENB terpolymers are prepared using the ingredient amounts shown in Table IIIA. The cocatalyst for Example 12 and Comparative Example E is FAB. The cocatalyst for Examples 11, 13 and 14 is the tetrakis (pentafluorophenyl) borate of di (tallow alkyl hydrogenated) methylammonium. The results of the polymerization are shown in Table IIIB. The scavenger for Examples 11, 13 and 14 is diethylaluminum (diisopropylamido). The eliminator for Example 12 is DIBAL-NS and for Comparative Example E it is MMAO.

Table IIIA Table IIIB - means not measured The data in Table IIIB demonstrates that the use of a preferred catalyst in the process of the present invention produces polymers having a higher content of ENB, a higher Mw or both in respect to the polymers produced under the same conditions, but with another catalyst.

Example 15 Using the catalyst of Example 13, FAB as the cocatalyst, MMAO as the scavenger, and the method and apparatus of Example 8, an ethylene / propylene / ENB interpolymer is prepared using the ingredient amounts shown in Table IVA. The interpolymer has properties as shown in Table IVB.

Table VAT Table IVB CO -P-. - means not measured The data in Table IVB show that similar results are obtained with a different preferred catalyst in conjunction with the process of the present invention.

Results similar to those in Examples 1-15 are expected with other catalysts, cocatalysts, scavengers and process parameters, all of which are described above.

It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims

1. An ethylene / α-olefin / disordered diene monomer interpolymer, characterized in that the interpolymer has (a) a weight ratio of ethylene to α-olefin in the range from 90:10 to 10:90, the α-olefin is a C3-20 α-olefin; (b) a diene monomer content in the range from greater than 0 to 25 percent by weight, based on the weight of the interpolymer; and (c) a B value from 0.94 to 1.0, the B value is determined by 13 C NMR spectroscopy and the formula B = P0E / (2 PE-P0), where PE is a mole fraction of the ethylene units derived from from ethylene, P0 is a mole fraction of the a-olefin units derived from the α-olefin, and P0E is a ratio of the number of α-olefin / ethylene chains to the number of all the chains diadas in the interpolymer .

2. The interpolymer according to claim 1, characterized in that the alpha-olefin is selected from propylene, butene-1, hexene-1 and octene-1 and the diene monomer is selected from 5-ethylidene-2-norbornene, 5-vinylidene -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-methyl-1, 5-heptadiene, norbornadiene, 1,7-octadiene, and 1,9-decadiene.

3. The interpolymer according to Claim 1, characterized in that the interpolymer has at least one feature selected from a rheology ratio (Vo.?/V00) within the range from 3 to 90, has a Mooney Viscosity (ML1 + 4 to 125) ° C) within the range from 1 to 150, a product of the reactivity ratio in the range from 1 to less than 1.25.

4. The interpolymer according to claim 1, characterized in that the interpolymer has, in relation to an interpolymer of ethylene / α-olefin / comparative diene monomer prepared from the same monomers, at the same temperature and with the same conversion using either dimethyl (tetramethylcyclopentadienyl) -dimethyl (t-butylamido) silane-titanium or dimethyl (tetramethylcyclopentadienyl) dimethyl (t-butylamido) -silane-titanium or 1,3-pentadiene (tetramethylcyclopentadienyl) dimethyl (t-butylamido) -silane-titanium as a catalyst, at least one superior characteristic selected from (a) a proportion of rheology is at least 10% greater than that of the interpolymer comparative, (b) a diene content that is at least 50 percent greater than that of the comparative interpolymer, (c) a molecular weight that is at least 1.5 times greater than that of the comparative interpolymer, (d) a Mooney Viscosity that is at least 2.5 times greater than that of the comparative interpolymer, and (e) a vitreous transition temperature (TG) that is at least one Celsius degree lower than that of the comparative polymer with a crystallinity of greater than 0, but less than 5. percent.

5. A process for preparing the interpolymer according to any of Claims 1-4, characterized in that the process comprises contacting ethylene, at least one C3-2o α-olefin monomer and a diene monomer with a catalyst and an activating cocatalyst, The catalyst is a metal complex corresponding to the formula: ZA'M XpX q, where M is titanium, zirconium or hafnium in the conventional oxidation state +2, +3 or +4; A 'is a substituted indenyl group, substituted in at least position 2 with a selected group of hydrocarbyl, fluoro-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, dialkylamino-substituted hydrocarbyl, silyl, germyl and mixtures thereof, the group contains up to 40 non-hydrogen atoms, and A 'is also covalently linked to M by a divalent Z group, - Z is a divalent part linked to both A 'and M via the bonds s, Z comprises boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprises nitrogen, phosphorus, sulfur or oxygen; X is an anionic or dianioniso ligand group having up to 60 atoms regardless of the class of ligands that are delocalized, cyclic, linkage II ligand groups; X ', independently of each occurrence, is a neutral Lewis base binder compound, having up to 20 atoms; p is 0, 1 or 2, and is 2"smaller than the conventional oxidation state of M, with the proviso that when X is a dianionic ligand group, p is 1; Y q is 0, 1 or 2

6. The process according to claim 5, characterized in that the catalyst is selected from group A which includes 1,4-diphenyl-1,3-butadiene from (t-butylamido) dimethyl (? 5-2-methylindenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) dimethyl (? 5-2-methylindenyl) silane-titanium (II), 2, 4-hexadiene from (t-butylamido) -dimethyl (? 5-2-methyl-indenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) -dimethyl (? 5-2-methylindenyl) silane-titanium (III), dimethyl (t-butylamido) -dimethyl (? 5-2-methylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) dimethyl (? 5-2-methyl-indemyl) silane-titanium (IV), 1, 4-diphenyl-1,3-butadiene of (t-butylamido) -dimethoxy (? 5-2-methylindenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) -dimethoxy (? 5-2-methylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) dimethoxy (? 5-2-methylindenyl) silane-titanium (II), 2 - (N, N-dimethylamino) benzyl of (t-butylamido) dimethoxy (? 5-2-methylindenyl) silane-titanium (III), dimethyl (t-butylamido) -dimethoxy (? 5-2-methylindenyl) -silane -titanium (IV), dibenzyl (t-butylamido) -dimethoxy (? 5-2-methylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) diisopropoxy (? 5-2-methylindenyl) silane-titanium (II), 1,3-pentadiene of (t-butyl-amido) diisopropoxy (? 5-2-methylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) -diisopropoxy (? 5-2-methyl-indenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) diisopropoxy (? 5-2 -methylindenyl) silane-titanium (III), dimethyl (t-butylamido) -diisopropoxy (? 5-2-methylindenyl) silane-titanium (IV), dibenzyl (t-) butylamido) diisopropoxy (? 5-2-methylindenyl) -silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butylamido) ethoxymethyl (? 5-2-methylindenyl) silane-titanium (II ), 1,3-pentadiene (t-butylamido) ethoxymethyl (5-2-methylindenyl) silane-titanium (II), 2,4-hexadiene (t-butylamido) ethoxymethyl (5-2-methyl-indenyl) ) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) -ethoxymethyl (? 5-2-methylindenyl) silane-titanium (III), dimethyl (t-butyl-amido) ethoxymethyl (r> 5-2-methylindenyl) silane-titanium (IV), (t-butylamido) -ethoxy-methyl (5-methylindenyl) silane-titanium (IV) dibenzyl, 1,4-diphenyl- 1, 3-butadiene of (t-butylamido) dimethyl (? 5-2-ethyl-indenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) dimethyl (? 5-2-ethylindenyl) - silane-titanium (II), 2,4-hexadiene from (t-butylamido) -dimethyl (? 5-2-ethylindenyl) silane-titanium (n: 2 - (N, N-dimethylamino) benzyl of (t-butylamido) dimethyl (? 5-2-ethyl-indenyl) silane-titanium (III), dimethyl T-butylamido) dimethyl (? 5-2-ethyl-indenyl) silane-titanium (IV), dibenzyl (t-butyl-amido) dimethyl (? 5-2-ethylindenyl) silane- titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butylamido) dimethoxy (η 5-2-ethylindenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) dimethoxy (? 5-2-ethylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butyl-amido) dimethoxy (? 5-2-ethylindenyl) silane-titanium (II), 2- (N, N -dimethylamino) benzyl of (t-butylamido) dimethoxy (? 5-2-ethylindenyl) silane-titanium (III), dimethyl of (t-butylamido) -dimethoxy (? 5-2-ethylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) dimethoxy (γ5-2-ethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) -diisopropoxy (η 5-2-ethylindenyl) silane-titanium (II), 1,3-pentadiene of (t-butylamido) -diisopropoxy (γ 5-2-ethylindenyl) silane-titanium (II), 2, -hexadiene (t-butylamido) -diisopropoxy (δ 5) -2-ethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butyl-amido) diisopropoxy (? 5-2-ethylindenyl) silane-titanium (III), dimethyl (t-butyl-amido) -diisopropoxy (? S-2-ethylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) -diisopropoxy (? 5-2-ethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butylamido) ethoxymethyl (5-ethylindenyl) silane-titanium (11) / 1,3-pentanediene of (t-butylamido) -ethoxymethyl (? 5-2-ethylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) ethoxymethyl (? 5-2-ethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) ) benzyl (t-butylamido) -ethoxymethyl (? s-2-ethylindenyl) silane-titanium (III), dimethyl (t-butylamido) -ethoxymethyl (? 5-2-ethylindenyl) silane-titanium (IV), dibenzyl (t) -butylamido) -ethoxymethyl (? 5-2-ethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butyl-amido) dimethyl (? 5-2-methyl-s- indacen-l-il) silane-titanium (II), 1,3-pentadiene of (t-butylamido) dimethyl (? 5-2-methyl-s-indace-1-yl) -silane-titanium (II), 2,4-hexadiene (t-butylamido) ) -dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethyl (? 5-2-methyl) -s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl ( t-butylamido) dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butylamido) dimethoxy (? 5- 2-methyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) dimethoxy (5-2-methyl-s-indacen-1-yl) silane-titanium (II), 2, 4-hexadiene of (t-butylamido) dimethoxy (? 5-2-methyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethoxy (? 5-2-methyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) -dimethoxy (? 5-2-methyl-s-indacen- l-il) silane-titanium (IV), dibenzyl (t-butylamido) dimethoxy (? 5-2-methyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-) butylamido) diisopropoxy (? 5-2-methyl-s-indacen-1-yl) silane- titanium (II), 1,3-pentadiene of (t-butylamido) diisopropoxy (? 5-2-methyl-s-indace-1-yl) -silane-titanium (II), 2,4-hexadiene of (t-butylamido) -diisopropoxy (? 5-2-methyl-s-indacen-1-yl) silane-titanium (11) / 2- (N, N-dimethylamino) benzyl of (t-butylamido) diisopropoxy (? 5 -2-methyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butyl-amido) diisopropoxy (ε 5-2-ethyl-s-indacen-1-yl) silane-titanium ( IV), dibenzyl (t-butylamido) diisopropoxy (r) 5-2-methyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) ethoxymethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) ethoxymethyl (5-2-methyl-s-indacen-1-yl) silane -Titanium (II), 2, 4-hexadiene of (t-butyl-amido) ethoxymethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (11) / 2- (N, N-dimethylamino) benzyl of (t-butylamido) ethoxymethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (III), dimethyl of (t-butylamido) -ethoxymethyl (5-2-methyl-s-indacen-1-yl) silane-titanium ( IV), dibenzyl (t-butylamido) ethoxy-methyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) dimethyl ( 5-2-ethyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene of (t-butylamido) dimethyl (? 5-2-ethyl-s-indasen-1-yl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) -dimethyl (? -2-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl of (t-butylamido) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-) butylamido) dimethoxy (? 5-2-ethyl-s-indacen-l-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) dimethoxy (? 5-2-ethyl-s-indacen- 1-yl) -silane-titanium (II), 2,4-hexadiene of (t-butylamido) -dimethoxy (η 5-2-ethyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) -dimethoxy (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) dimethoxy (? -2-ethyl-s-indacen-l-yl) silane-titanium (IV), dibenzyl (t-butylamido) dimethoxy (? 5-2-ethyl-s-indacen-l-yl) silane-titanium (IV) , 1,4-diphenyl-1,3-butadiene of (t-butylamido) diisopropoxy (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene (t) -butylamido) diisopropoxy (? 5-2-ethyl-e-indacen-1-yl) silane-titanium (II), 2,4-hexadiene from (t-butylamido) diisopropoxy (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (11) / 2- (N, N-dimethylamino) -benzyl of (t-butylamido) diisopropoxy (? 5) -2-ethyl-s-indacen-l-yl) silane-titanium (III), dimethyl (t-butylamido) diisopropoxy (η 5-2-ethyl-s-indacen-1-yl) silane-titanium (IV) , dibenzyl (t-butylamido) diisopropoxy (? 5-2-ethyl-s-indacen-l-yl) silane-titanium (IV) 1,4-diphenyl-1,3-butadiene of (t-butylamido) ethoxy-methyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) ethoxy-methyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (II), 2,4-hexadiene (t-butylamido) ethoxymethyl (? 5-2-ethyl) -s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) ethoxymethyl (? 5-2-ethyl-s-indacen-1-yl) silane -titanium (III), dimethyl (t-butylamido) ethoxymethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) ethoxymethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (IV), dimethyl (dimethylamine) dimethyl (? 5-2-methylindenyl) silane -titanium (III), dibenzyl (dimethylamine) -dimethyl (? 5-2-methylindenyl) silane-titanium (III), dimethyl (diisopropylamine) -dimethyl (? 5-2-methylindenyl) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl (? 5-2-methylindenyl) -silane-titanium (III), dimethyl (di-n-butylamine) dimethyl (? 5-2 -methylindenyl) silane-titanium (III) dibenzyl (di-n-butylamine) dimethyl (? 5-2-methylindenyl) silane-titanium (III), dimethyl (di-iso-butylamine) dimethyl (? 5-2-methylindenyl) silane-titanium (III), dibenzyl (di-iso-butylamine) dimethyl (? 5-2-methylindenyl) silane-titanium (III) dimethyl (dimethylamine) dimethyl- (? 5-2-methyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (dimethylamine) dimethyl (? 5-2-methyl-s-indacen-1-yl) silane-titanium (III), dimethyl (diisopropylamine) dimethyl- (? 5-2-methyl-s-indacen-l-yl) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl- (? 5-2-methyl-s-indacen-1-yl) ) silane-titanium (III), dimethyl (di-n-butylamine) -dimethyl (? 5-2-methyl-s-indacen-l-yl) silane-titanium (III), dibenzyl (di-n-butylamine) dimethyl- (? 5-2-methyl-s-indacen-1-yl) silane-titanium (III), dimethyl (di-isobutylamine) dimethyl- (? 5-2-methyl-s-indacen-l-il) ) silane-titanium (III), dibenzyl (di-isobutyl-amine) dimethyl (? 5-2-methyl-e-indacen-1-yl) silane-titanium (III), dimethyl (dimethylamine) -dimethyl (? s-2-ethylindenyl) silane-titanium (III), dibenzyl (dimethylamine) dimethyl (? 5-2-ethyl-indenyl) silane-titanium (III), dimethyl (diisopropylamine) dimethyl- (? 5-2-ethylindenyl) ) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl (? s-2-ethylindenyl) silane-titanium (III), dimethyl (di-n-butylamine) -dimethyl (? 5-2-ethylindenyl) silane- titanium (III), dibenzyl (di-n-butylamine) -dimethyl (? 5-2-ethyl-indenyl) silane-tit anium (III), dimethyl (di-iso-butylamine) dimethyl (? 5-2-ethylindenyl) -silane-titanium (III), dibenzyl (di-iso-butylamine) dimethyl (? 5-2-ethylindenyl) silane -titanium (III), dimethyl (dimethylamine) -dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (dimethylamine) -dimethyl (? 5-2-ethyl) -s-indacen-1-yl) silane-titanium (III), dimethyl (diisopropyl-amine) dimethyl (? 5-2-ethyl-s-indacen-1-yl) eilane-titanium (III), dibenzyl (diisopropylamine) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (di-n-butylamine) dimethyl (? 5-2-ethyl-s-indacen-1) -yl) silane-titanium (III), dibenzyl (di-n-butylamine) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (di-iso- butylamine) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (di-isobutylamine) dimethyl (? 5-2-ethyl-s-indacen-1-yl) silane-titanium (III), or group B including 1,4-diphenyl-1,3-butadiene of (t-butylamido) -dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (II), 1, 3-pentadiene of (t-butylamido) -dimethyl (? S-2,3-dimethylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) dimethyl (? 5-2, 3-dimethyl- indenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III), dimethyl (t-butylamido) -dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) -dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) -dimethoxy ( ? 5-2, 3-dimethylindenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) dimethoxy (? 5-2, 3-dimethylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) dimethoxy (? 5-2, 3-dimethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) -dimethoxy (? 5-2, 3 - dimethylindenyl) silane-titanium (III), dimethyl (t-butylamido) dimethoxy (? 5-2, 3-dimethylindenyl) silane-titanium (IV), (t-butylamido) dimethoxy (? 5-2, 3-dimethylindenyl) silane-titanium (IV) dibenzyl, 1, 4-diphenyl-1,3-butadiene of (t-butylamido) -diisopropoxy (? 5-2, 3-dimethylindenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) diisopropoxy- (? 5) -2, 3-dimethylindenyl) silane-titanium (11) / 2,4-hexadiene of (t-butylamido) diisopropoxy (? 5-2, 3-dimethylindenyl) silane-titanium (II), 2- (N, N- dimethylamino) benzyl (t-butylamido) diisopropoxy (? 5-2, 3-dimethylindenyl) silane-titanium (III), dimethyl (t-butylamido) -diisopropoxy (? 5-2, 3-dimethylindenyl) silane-titanium (IV), dibenzyl of (t-butylamido) diisopropoxy (? 5-2, 3-dimethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butylamido) -ethoxymethyl (? 5-2, 3) -dimethylindenyl) silane-titanium (II), 1,3-pentadiene (t-butylamido) ethoxymethyl (? 5-2, 3-dimethylindenyl) silane-titanium (II), 2, 4-hexadiene of (t-butylamido) ethoxymethyl (γ 5-2, 3-dimethylindenyl) ilane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) ethoxymethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III), dimethyl (t-butylamido) ethoxymethyl (? 5-2, 3-dimethylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) ethoxymethyl (? 5-2, 3-dimethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) dimethyl (? 5-2, 3-dimethyl-s-indacen-1) -il) silane-titanium (II), 1,3-pentadiene (t-butylamido) -dimethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) dimethyl (? 5-2, 3-dimethyl-e-indacen-1-yl) eilane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethyl (? 5-2, 3-dimethyl-s-indacen- 1-yl) silane-titanium (III), dimethyl (t-butylamido) -dimethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl (t-) butylamido) dimethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) eilane-titanium (IV), 1,4-diphenyl-1,3-butadiene from (t-butylamido) dimethoxy (? 5-2, 3-dimethyl-e-indacen-1-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) -dimethoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 2,4-hexadiene from (t-butylamido) dimethoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) -dimethoxy (? 5-2, 3-dimethyl- s-indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) -dimethoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) eilane-titanium (IV), 1,4-diphenyl-1,3-butadiene from (t-butylamido) diisopropoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) diisopropoxy (? 5-2, 3) -dimethyl-s-indacen-1-yl) silane-titanium (II), 2, 4-hexadiene from (t-butylamido) diisopropoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl (t-butylamido) diisopropoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) diisopropoxy (? 5-2, 3-dimethyl-e) -indazen-1-yl) eilane-titanium (IV), dibenzyl (t-butylamido) diisopropoxy (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (IV), 1,4 -diphenyl-1,3-butadiene of (t-butylamido) ethoxymethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) eilano-titanium (II), 1,3-pentadiene (t-butylamido) ) ethoxymethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (II), 2,4-hexadiene (t-butylamido) ethoxymethyl (? 5-2, 3-dimethyl-s) -indazen-l-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) ethoxymethyl (? s-2), 3-dimethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) ethoxymethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium ( IV), dibenzyl (t-butylamido) ethoxymethyl (? S-2,3-dimethyl-s-indacen-1-yl) silane-titanium (IV), dimethyl (dimethylamine) dimethyl (? 5-2, 3 - dimethylindenyl) silane-titanium (III), dibenzyl (dimethylamine) dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III), dimethyl (diisopropylamine) dimethyl (? 5-2, 3-dimethylindenyl) silane- titanium (III), dibenzyl (diisopropylamine) dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III), dimethyl (di-n-butylamine) dimethyl (? 5-2, 3-dimethylindenyl) eilane-titanium (III), dibenzyl (di-n-butylamine) -dimethyl (? 5-2, 3- dimethyl-indenyl) silane-titanium (III), dimethyl (di-iso-butylamine) dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III), dibenzyl (di-isobutylamine) dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (III ), dimethyl (dimethylamine) dimethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (dimethylamine) dimethyl (? 5-2, 3-dimethyl-s) -indazen-l-yl) silane-titanium (III), dimethyl (diisopropylamine) dimethyl (? 5-2, 3-dimethyl-s-indacen-l-yl) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (di-n-butylamine) dimethyl (? 5-2, 3-dimethyl-s-indacen- l-yl) silane-titanium (III), dibenzyl (di-n-butylamine) dimethyl- (? 5-2, 3-dimethyl-s-indacen-1-yl) eilane-titanium (III), dimethyl ( di-isobutylamine) dimethyl- (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (III), dibenzyl (di-isobutylamine) dimethyl- (? 5-2, 3-dimethyl- e-indacen-1-yl) eilano-titanium (III), 1,4-diphenyl-1,3-butadiene of (t-butylamido) dimethyl (? 5-2-methyl- 3-ethynydenyl) eilane-titanium (II), 1,3-pentadiene (t-butylamido) dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (II), 2, 4-hexadiene of (t-butylamido) dimethyl (? S-2-methyl-3-ethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethyl (? 5-2-methyl-3-ethyl-indenyl) -silane-titanium (III), dimethyl (t-butylamido) dimethyl (? 5-2-methyl-3-ethyl-indenyl) eilane-titanium (IV), dibenzyl (t-butylamido) dimethyl (? s-2-methyl-3-ethyl-indenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene (t-butylamido) dimethoxy (? 5-2) -methyl-3-ethylindenyl) eilano-titanium (II), 1,3-pentadiene of (t-butylamido) dimethoxy (? 5-2-methyl-3-ethylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) dimethoxy (? 5-2-methyl-3-ethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethoxy (? 5-2-methyl) -3-ethylindenyl) silane-titanium (III), dimethyl (t-butylamido) dimethoxy (5-methyl-3-ethylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) dimethoxy (? 5) -2-methyl-3-ethylindenyl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene of (t-butylamido) -diisopropoxy (? 5-2-methyl-3-ethylindenyl) silane-titanium (II), 1,3-pentadiene of (t) -butylamido) diisopropoxy- (? 5-2-methyl-3-ethylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) diisopropoxy (? 5-2 -methyl-3-ethylindenyl) eilano- titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) diieopropoxy (? 5-2-methyl-3-ethylindenyl) silane-titanium (III), dimethyl of (t-butylamido) diisopropoxy ( ? 5-2-methyl-3-ethylindenyl) silane-titanium (IV), dibenzyl (t-butylamido) diisopropoxy (? 5-2-methyl-3-ethylindenyl) silane-titanium (IV), 1,4-diphenyl -1, 3-butadiene of (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (II), 1,3-pentadiene of (t-butylamido) ethoxymethyl (? 5-2- methyl-3- ethylindenyl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl from (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (III), dimethyl (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethylindenyl) eilane-titanium (IV ), (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (IV) dibenzyl, 1,4-diphenyl-1,3-butadiene (t-butylamido) dimethyl (? 5) dibenzyl. -2-methyl-3-ethyl-s-indacen-l-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) dimethyl (? 5-2-methyl-3-ethyl-s- indacen-l-il) silane-titanium (II), 2,4-hexadiene from (t-butylamido) dimethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) -dimethyl (? 5-2-methyl-3-ethyl-s- indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) dimethyl (? 5-2 -methyl-3-ethyl-s-indacen-1-yl) silane-titanium (IV), 1, 4-diphenyl-1,3-butadiene of (t-butylamido) dimethoxy (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene of ( t-butylamido) -dimethoxy (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) dimethoxy (? 5-2 -methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) dimethoxy (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (t-butylamido) -dimethoxy (? 5-2-methyl- 3-ethyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) dimethoxy (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3-butadiene from (t-butylamido) diisopropoxy (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 1,3-pentadiene (t-butylamido) diisopropoxy (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 2,4-hexadiene of (t-butylamido) diisopropoxy (? 5-2) -methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl (t-butylamido) diisopropoxy (? 5-2-methyl-3-ethyl-e-indacen-1-yl) eilane-titanium (III), (t-butylamido) -diisopropoxy dimethyl (? 5-2-methyl- 3-ethyl-s-indacen-l-yl) silane-titanium I (IV), dibenzyl (t-butylamido) diisopropoxy (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (IV), 1,4-diphenyl-1,3- butadiene of (t-butylamido) -ethoxymethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) eilano-titanium (II), 1,3-pentadiene (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (II), 2, 4-hexadiene from (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethyl-s-indasen-1-yl) silane-titanium (II), 2- (N, N-dimethylamino) benzyl of (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethyl-s-indacen-l- il) silane-titanium (III), dimethyl (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (IV), dibenzyl (t-butylamido) ethoxymethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) eilane-titanium (IV), dimethyl (dimethylamine) dimethyl (? 5-2-methyl-3-ethylindenyl) ) silane-titanium (III), dibenzyl (dimethylamine) dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (III), dimethyl (diisopropylamine) dimethyl (? 5-2-methyl-3-ethylindenyl) ) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (III), dimethyl (di-n-butylamine) dimethyl (? 5-2-methyl) -3-ethylindenyl) silane-titanium (III), dibenzyl (di-n-butylamine) -dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (III), dimethyl (di-iso-butylamine) ) dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (III), dibenzyl (di-isobutylamine) dimethyl (? 5-2-methyl-3-ethylindenyl) silane-titanium (III), dimethyl (dimethylamine) dimethyl (? 5-2-methyl-3-ethyl-s-indacen-1-yl) eilane-titanium (III), dibenzyl (dimethylamine) dimethyl (? 5-2-methyl-3-ethyl-e) -indane-1-yl) silane-titanium (III), dimethyl (diisopropylamine) dimethyl (? 5-2-methyl-3-ethyl-s-indacen-l-yl) silane-titanium (III), dibenzyl (diisopropylamine) dimethyl (? 5-2-methyl-3-ethyl-s-indacen) -l-il) ilane-titanium (III), dimethyl of (di-n- butylamine) dimethyl (? 5-2-methyl-3-ethyl-s-indacen-l-yl) silane-titanium (III), dibenzyl (di-n-butylamine) dimethyl- (? 5-2-methyl-3) -ethyl-s-indacen-1-yl) silane-titanium (III), dimethyl (di-isobutylamine) dimethyl- (? 5-2-methyl-3-ethyl-s-indacen-1-yl) -lane-titanium (III), dibenzyl (di-isobutylamine) dimethyl - (? 5-2-methyl-3-ethyl-s-indacen-1-yl) silane-titanium (III).

7. The process according to claim 5, characterized in that the catalyst is a Group A catalyst selected from dimethyl (t-butyl-amido) -dimethyl (? S-2-methyl-s-indacen-1-yl) silane- titanium (IV), 1,3-pentadiene of (t-butylamido) -dimethyl- (? 5-2-methyl-s-indacen-1-yl) silane-titanium (II) and 2,4-hexadiene of (t) -butylamido) dimethyl- (? 5-2-methyl-s-indacen-1-yl) silane-titanium (II) or a Group B catalyst selected from 1,4-diphenyl-1,3-butadiene of (t-) butylamido) -dimethyl (? 5-2, 3-dimethylindenyl) silane-titanium (II) and dimethyl (t-butyl-amido) -dimethyl (? 5-2, 3-dimethyl-s-indacen-1-yl) silane-titanium (IV).

8. The process according to any of Claims 5-7, characterized in that the activating cocatalyst is selected from: tripentafluorophenyl borane, cocatalysts repreeentados by the formula (L * -H) d + (A) d " where : L * is a neutral Lewis base; (L * -H) + is a Brónsted acid; and Ad ~ either (a) is a non-coordinating, compatible anion that has a charge of d-, with d being an integer from 1 to 3, or (b) corresponds to the formula: where : M 'is boron or aluminum in the conventional oxidation state +3, - and Q is, independently for each occurrence, selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, haloalubstituted hydrocarbyl, hydrocarbyloxy haloubstituted, and halo-substituted hydrocarbyl radicals (including perhalogenated hydrocarbyl radicals, perhalogenated hydrocarbyloxy radicals, and perhalogenated silylhydrocarbyl), Q up to 20 atoms with the condition that in no more than one occurrence is Q a halide; cocatalysts represented by the formula (L * -H) + (BQ4) where L * is a neutral Lewis base; B is boron in a conventional oxidation state of 3; Y Q is a hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy, or fluorinated silylhydrocarbyl group of up to 20 non-hydrogen atoms, with the proviso that in no more than one occasion is hydrocarbyl; or a cocatalyst which is a salt of a carbenium ion and a non-coordinating, compatible anion represented by the formula ® + (BQ4) " where © + ee a carbenium ion C? _20; Y A hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy, or fluorinated silylhydrocarbyl group of up to 20 non-hydrogen atoms, with the proviso that on no more than one occasion is hydrocarbyl.

9. The process according to claim 8, characterized in that the polymerization occurs in the presence of a purification compound, the purification compound is selected from an aluminoxane and a hydrocarbylamide compound of Group 13 according to the formula R12Me (NR22) , where Rl and R2 are independently in each occurrence a hydrocarbyl C? -30, and Me is a Metal of Group 13.

10. The process according to claim 9, characterized in that the depuration component is (bistrimethylsilylamido) diisobutylaluminum.

11. The process according to claim 5, characterized in that the diene is selected from the group consisting of 5-ethylidene-2-norbornene, 5-vinylidene-2-norbornene, 5-methylene-2-norbornene, 1,4-hexadiene, 1, 3 -pentadiene, dicyclopentadiene, 7 -methyl-1,6-octanediene, 1,3-butadiene, 4-methyl-1,3-pentadiene, 5-methyl-1,4-hexadiene, 6-methyl-1, 5-heptadiene, norbornadiene, 1, 5-octanediene, and 1, 9-decadiene, and the contact occurs at a temperature from about 40 ° C to about 185 ° C.

12. The process according to claim 12, characterized in that the activating cocatalyst is selected from tris (pentafluorophenyl) borane, tetrakis- (pentafluorophenyl) borate di (tallowalkyl hydrogenated) methylammonium, tetrakis (pentafluorophenyl) borate tri (n-butyl) ammonium , and dimethylanilinium tetrakis (pentafluorophenyl) borate.