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Title:
METAL COMPLEX COMPOSITIONS BASED ON COBALT AND THEIR USE AS POLYMERIZATION CATALYST FOR OLEFINS AND DIENES
Document Type and Number:
WIPO Patent Application WO/2003/064484
Kind Code:
A1
Abstract:
This invention relates to metal complex compositions, their preparation and their use as catalysts to produce polymers of conjugated dienes through polymerization of conjugated diene monomers and copolymers of conjugated dienes with aromatic or nonaromatic alpha olefins or with nonconjugated dienes. The used metal complex compositions comprise cobalt complex compositions in combination with activator compounds type 1 and activator compounds type 2 and a catalyst modifier. Particularly the invention relates to cobalt complexes containing at least one cobalt - oxygen bond and to the preparation of the catalyst and the use of the prepared catalyst to produce homopolymers of conjugated dienes or copolymers of conjugated dienes with aromatic or nonaromatic alpha-olefins or with nonconjugated dienes, preferably polymerization of 1,3-butadiene or isoprene or copolymerization of 1,3-butadiene or isoprene with styrene or divinyl benzene. The activator compounds can be one alumoxane type activator or a noncoordinating anion-forming reagent such as, but not limited to, organoborates or organoborone compounds and one alkylaluminum halide type activator are used in combination with the cobalt complexes and with one or more aromatic compounds for the synthesis of homopolymers or copolymers. The aromatic modifier is applied in amounts similar or smaller than the amounts of the used activators.

Inventors:
Thiele, Sven K. -. H. (Roepzigerstr. 19, Halle, 06110, DE)
Edel, Hans A. R. (Angerweg 15, Erdeborn, 06317, DE)
Application Number:
PCT/US2003/000673
Publication Date:
August 07, 2003
Filing Date:
January 09, 2003
Export Citation:
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Assignee:
DOW GLOBAL TECHNOLOGIES INC. (Washington Street, 1790 Building Midland, MI, 48674, US)
Thiele, Sven K. -. H. (Roepzigerstr. 19, Halle, 06110, DE)
Edel, Hans A. R. (Angerweg 15, Erdeborn, 06317, DE)
International Classes:
C08F36/06; (IPC1-7): C08F36/06
Foreign References:
US4503202A
EP0511015A1
EP1092735A1
US3778424A
GB1372399A
US4255543A
Other References:
P.CASS ET AL: "REPLACEMENT OF BENZENE WITH REGULATORS FOR THE CATALYZED POLYMERIZATION OF 1,3-BUTADIENE TO HIGH CIS-1,4-POLYBUTADIENE" JOURNAL OF POLYMER SCIENCE: PART A, 2001, pages 2244-2255, XP002240204 cited in the application
Attorney, Agent or Firm:
Willis, Reid S. (The Dow Chemical Company, Intellectual Property P.O. Box 196, Midland MI, 48641-1967, US)
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Claims:
Claims :
1. A metal complex catalyst compositions comprising a) at least one cobalt compound or complex containing at least one cobalt oxygen bond and b) an activator compound type 1 and c) an activator compound type 2 and d) a catalyst modifier.
2. The metal catalyst compositions according to one of claim 1, characterized in that the cobalt complex contains carboxylate ligands.
3. The cobalt catalyst compositions according to one of claims 12, characterized in that the cobalt complex contains octoate, neodecanate, naphthenate, versatate, acetylacetonate, 2ethylhexalate or stearate ligands.
4. The metal catalyst compositions according to Claim 1 characterized in that the activator compound of type 1 is a halogenated aromatic boron or aluminum compound chosen from tris (pentafluorophenyl) boron, tris (pentafluorophenyl) aluminum, tris (ononafluorobiphenyl) boron, tris (o nonafluorobiphenyl) aluminum, tris [3,5bis (trifluoromethyl) phenyl] boron, tris [3,5 bis (trifluoromethyl) phenyl] aluminum ; or is a polymeric or oligomeric alumoxane chosen from methylalumoxane (MAO), triisobutyl aluminummodified methylalumoxane, or isobutylalumoxane.
5. The metal catalyst compositions according to Claim 1 characterized in that the activator compound of type 1 is a nonpolymeric, compatible, noncoordinating, ionforming compound chosen from ammonium, phosphonium, oxonium, carbonium, silylium, sulfonium, or ferroceniumsalts of compatible, noncoordinating anions; and combinations of the foregoing activating compounds.
6. The metal catalyst compositions according to Claim 1 characterized in that the activator compound of type 1 is represented by the following general formula : (L*H) d+Ad wherein: L* is a neutral Lewis base; (L*H) + is a Bronsted acid; Adis a noncoordinating, compatible anion having a charge of d, and d is an integer from I to 3 and preferably Adcorresponds to the formula : [M*Q4] ; wherein: M* is boron or aluminum in the +3 formal oxidation state; and Q is a hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy, or fluorinated silylhydrocarbylgroup of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl and most preferably, Q is each occurrence a fluorinated aryl group, especially, a pentafluorophenyl or nonafluorobiphenyl group.
7. The metal catalyst compositions according to Claim 1 characterized in that the activator compound of type 1 is represented by a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula : axe+) d (Ad) e, wherein oxe+ is a cationic oxidizing agent having a charge of e+; d is an integer from 1 to 3; e is an integer from 1 to 3; and Adis a noncoordinating, compatible anion having a charge of d, whereby a preferred embodiment of Adis tetrakis (pentafluorophenyl) borate.
8. The metal catalyst compositions according to Claim 1 characterized in that the activator compound of type 1 is represented by a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula: R3Si+A wherein: R is C1 10 hydrocarbyl ; and Ais a noncoordinating, compatible anion having a charge of d, whereby. preferred silylium salt activator compounds are trimethylsilylium tetrakis (pentafluorophenyl) borate, trimethylsilylium tetrakis (nonafluorobiphenyl) borate, triethylsilylium tetrakis (pentafluorophenyl) borate and other substituted adducts thereof.
9. The metal catalyst compositions according to Claim 18 characterized in that the molar ratio of the catalyst activator of type 1 relative to the cobalt center of the cobalt complex in the catalyst according to Claim 1 usually is in a range of from 1: 10 to 10,000 : 1, more preferably from 1: 10 to 5000: 1 and most preferably in a range of from 1: 1 to 2,500 : 1 or if a compound containing or yielding a non coordinating or poorly coordinating anion is selected as activator compound, the molar ratio usually is in a range of from 1: 100 to 1,000 : 1, and preferably is in a range of from 1: 2 to 250: 1.
10. The metal catalyst compositions according to Claim 1 are characterized in that the activator of type 2 can be a neutral organometallic compound, wherein at least one or more than one halogen atom or hydrocarbyl radical is bound directly to the metal to provide a metalhalogen or carbonmetal bond and the hydrocarbyl radicals are non aromatic and are bound directly to the metal in the organometallic compounds and preferably contain 130, more preferably 110 carbon atoms, whereby the metal of the organometallic compound is selected from group 1,2, 3,4 , 5, 6, 7,12, 13 or 14 of the Periodic Table of the Elements, whereby suitable catalyst activators of type 2 for use do not include polymeric or oligomeric alumoxanes.
11. The metal catalyst compositions according to Claim 10 are characterized in that the activator compound of type 2 is a hydrocarbyl sodium, sodium halide, hydrocarbyl lithium, lithium halide, hydrocarbyl zinc, zinc dihalide, magnesium dihalide, hydrocarbyl magnesium halide, dihydrocarbyl magnesium, especially alkyl sodium, alkyl lithium, alkyl zinc, alkyl magnesium halide, dialkyl magnesium, such as noctyl sodium, butyl lithium, neopentyl lithium, methyl lithium, ethyl lithium, diethyl zinc, dibutyl zinc, butyl magnesium chloride, ethyl magnesium chloride, octyl magnesium chloride, dibutyl magnesium, dioctyl magnesium, butyl octyl magnesium, whereby suitable catalyst activators of type 2 for use herein also include neutral nonaromatic Lewis acids, such as nonaromatic Cl30 hydrocarbyl substituted Group 13 compounds substituents, especially (hydrocarbyl) aluminum or (hydrocarbyl) boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 20 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially trialkyl aluminum compounds, such as triethyl aluminum and triisobutyl aluminum, alkyl aluminum hydrides, such as diisobutyl aluminum hydride alkylalkoxy aluminum compounds, such as dibutyl ethoxy aluminum, halogenated aluminum compounds, such as diethyl aluminum chloride, ethylaluminum chloride, diisobutyl aluminum chloride, isobutylaluminum chloride, ethyl octyl aluminum chloride, ethyl aluminum sesquichloride, ethyl cyclohexyl aluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride.
12. The metal catalyst compositions according to Claim 10 are characterized in that the activator compounds of type 2 are aluminum and boron trihalides such as for example aluminum trichloride, aluminum trifluoride, boron trifluoride and adducts of aluminum and boron trihalides with Lewis bases, whereby suitable optional catalyst activators of type 2 for use herein also include neutral Lewis acids, such as Cl30 hydrocarbyl substituted Group 3 to Group 7 compounds, especially (hydrocarbyl) scandium, (hydrocarbyl) titanium, (hydrocarbyl) zirconium, (hydrocarbyl) vanadium or (hydrocarbyl) molybdenum compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 20 carbons in each hydrocarbyl or halogenated hydrocarbyl group and they also include halides of Group 3 to Group 7 metals, especially scandium, titanium, zirconium, vanadiumor molybdenum halides such as titanium dichloride, titanium trichloride, titanium tetrachloride, zirconium dichloride, zirconium trichloride, zirconium tetrachloride, vanadium dichloride, vanadium trichloride, molybdenum pentachloride.
13. The metal catalyst compositions according to Claims 1011 are characterized in that the activator compound of type 2 preferably are aluminum halide compounds, such as diethyl aluminum chloride, ethylaluminum chloride, diisobutyl aluminum chloride, ethyl octyl aluminum chloride, ethyl aluminum sesquichloride, methylaluminum sesquichloride, ethyl cyclohexyl aluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride.
14. The metal catalyst compositions according to Claims 1 and 1013 are characterized in that the molar ratio of the catalyst activator of type 2 relative to the cobalt center of the cobalt complex in the catalyst according to Claim 1 is characterized in that the catalyst activator of type 2 to the cobalt complex usually is in a range of from 1: 10 to 1,000 : 1, more preferably from 1: 10 to 500: 1 and most preferably in a range of from 1: 1 to 250: 1.
15. The metal catalyst compositions according to Claims 114 are characterized in that activator compound mixtures for use herein are combinations ofactivator compounds of type 2 such as for example neutral optional Lewis acids, especially the combination of a dialkyl aluminum halide compound having from 1 to 4 carbons in each alkyl group such as for example ethylaluminum sesquichloride, ethyloctylaluminum chloride and diethylaluminum chloride withactivator compounds of type 1 such as for example C1 _ 30 hydrocarbylsubstituted Group 13 Lewis acid compounds, especially halogenated tri (hydrocarbyl) boron oraluminum compounds having from 1 to 20 carbons in each hydrocarbyl group, especially tris (pentafluorophenyl) borane or tris (pentafluorophenyl) alumane, further combinations of type 2 activators such as neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane (type 1 activator), and combinations of a single neutral Lewis acid (type 2 activator), with especially tris (pentafluorophenyl) borane or tris (pentafluorophenyl) alumane and a polymeric or oligomeric alumoxane (type 1 activator).
16. The metal catalyst compositions according to Claim 1 are characterized in that the catalyst modifier is an aromatic compound.
17. The metal catalyst compositions according to Claim 16 are characterized in that the catalyst modifier preferably is an aromatic compound, wherein at least two or more than twoOH groups are bound to the aromatic compound.
18. The metal catalyst compositions according to Claims 1 and 1617 are characterized in that the aromatic modifier compound having at least two hydroxyl groups is represented by one of the following formulas : wherein R'and R"independently a hydrocarbon group of 120 carbon atoms; R', R2, R3 R4, R5, R6, R7, R, R9, R10 R", R may be the same or different and respectively denote a hydrocarbon group of 120 carbon atoms, hydroxyl groups, nitro groups, hydrocarbyloxy groups or halogen atoms; Z denotes a hydrocarbon group of 120 carbon atoms, an oxygen atom, a sulfur' atom, a (C=O) group, a(NR13) group or a(SiR142)group, wherein R13 and R14 may be the same or different and respectively denote a hydrocarbon group of 120 carbon atoms; d is 0, 1, or 2; m, n, q., r, s, t are 0, 1,2, 3, or 4;. o, p are 0,1, 2,3 or 4 ; m + n < 4 ; o + p < 4 ; r + q < 4 ; s + t < 4.
19. The metal catalyst compositions according to Claim 18 are characterized in that the aromatic modifier compound having at least two hydroxyl groups is represented by the following formula : wherein R'and R2 may be the same or different and respectively denote a hydrocarbon group of 120 carbon atoms, hydroxyl groups, nitro groups, hydrocarbyloxy groups or halogen atoms; m, n are 0,1, 2,3, or 4;. m + n < 4 ; 20 The metal catalyst compositions according to Claim 19 are characterized in that the aromatic modifier compound having at least two hydroxyl groups is represented by one of the following compounds: 21. The metal catalyst compositions according to Claims 1 and 1620 are characterized in that the molar ratio of the catalyst modifier relative to the metal center in the cobalt complex in the case an organometallic compound is selected as the catalyst modifier usually is in a range of from 1: 10 to 1,000 : 1, more preferably from 1: 10 to 500: 1 and most preferably in a range of from 1: 1 to 250: 1.
20. 22 A process to produce polyolefines characterized in that metal catalyst compositions according to the claims 1 to 21 are used.
21. 23 The process to produce copolymers produced by using of metal complex catalysts according to claims 1 to 22 characterized in that the monomers which are copolymerized are monomers containing conjugated unsaturated carboncarbon bonds or monomers containing conjugated unsaturated carboncarbon binds in combination with aromatic alphaolefins or in combination with aliphatic alpha olefins.
22. 24 The process to produce copolymers produced by using of metal complex catalysts according to claim 23 characterized in that the monomers which are copolymerized are monomers containing conjugated unsaturated carboncarbon bonds or monomers containing conjugated unsaturated carboncarbon binds in combination with aromatic alphaolefins.
23. 25 The process to produce polymers or copolymers of olefines according to claims 124 characterized in that the molar ratio of activator of type 1 relative to the cobalt center in the metal complex in a range of from 1: 10 to 10,000 : 1, more preferably from 1: 10 to 5000: 1 and most preferably in a range of from 1: 1 to 2,500 : 1 or if a compound containing or yielding a noncoordinating or poorly coordinating anion is selected asactivator compound, the molar ratio usually is in a range of from 1: 100 to 1,000 : 1, and preferably is in a range of from 1: 2 to 250: 1.
24. 26 The process to produce polymers or copolymers of olefines according to any of claims 125 characterized in that the molar ratio of activator of type 2 relative to the cobalt center in the metal complex is in a range of from 1: 10 to 1,000 : 1, more preferably from 1: 10 to 500: 1 and most preferably in a range of from 1: 1 to 250: 1.
25. 27 The process to produce polymers or copolymers of olefines according to Claims 2126 characterized in that the diolefin monomer (s) are chosen from the group comprising 1,3butadiene, isoprene (2methyl1, 3butadiene), 2, 3dimethyl 1,3butadiene, 1,3pentadiene, 2,4hexadiene, 1,3hexadiene, 1,3heptadiene, 1,3 octadiene, 2methyl2, 4pentadiene, cyclopentadiene, 2,4hexadiene, 1,3 cyclooctadiene, norbornadiene.
26. 28 The process to produce copolymers according to Claim 26 characterized in that the conjugated diolefin monomer (s) are chosen from the group comprising 1,3 butadiene, isoprene (2methyl1, 3butadiene), 2, 3dimethyl1, 3butadiene, 1,3 pentadiene, 2,4hexadiene, 1,3hexadiene, 1,3heptadiene, 1,3octadiene, 2 methyl2, 4pentadiene, cyclopentadiene, 2,4hexadiene, 1, 3cyclooctadiene, norbornadiene and the aromatic alpha olefin monomer (s) are chosen from the group comprising styrene, paramethylstyrene, 1, 3divinylbenzene, 1, 4 divinylbenzene, 2, 6divinyltoluene, 2, 4divinyltoluene and aliphatic olefin monomer (s) are chosen from the group comprising propene, 1butene, 1hexene, 1octene, 1decene.
27. The process to produce polydienes according to Claim 28 characterized in that the diolefin monomer (s) are chosen from the group comprising butadiene, isoprene and cyclopentadiene.
28. The process to produce polydienes according to Claim 29 characterized in that the diolefin monomer (s) are chosen from the group comprising butadiene and isoprene.
29. The process to produce polydienes according to Claim 30 characterized in that the diolefin monomer is butadiene.
Description:
METAL COMPLEX COMPOSITIONS AND THEIR USE AS CATALYSTS FOR OLEFIN POLYMERIZATION AND COPOLYMERIZATION This invention relates to metal complex compositions, their preparation and their use as catalysts to produce polymers of conjugated dienes through polymerization of conjugated diene monomers and copolymers of conjugated dienes with aromatic or nonaromatic alpha olefins or with nonconjugated dienes. The used metal complex compositions comprise cobalt complex compositions in combination with activator compounds type 1 and activator compounds type 2 and a catalyst modifier. More particularly, the invention relates to cobalt complexes containing at least one cobalt-oxygen bond and to the preparation of the catalyst and the use of the prepared catalyst to produce homopolymers of conjugated dienes or copolymers of conjugated dienes with aromatic or nonaromatic alpha-olefins or with nonconjugated dienes, preferably through, but not limited to, polymerization of 1,3- butadiene or isoprene or copolymerization of 1, 3-butadiene or isoprene with styrene or divinyl benzene.

Metal complex catalysts for producing polymers from conjugated diene monomer (s) are known.

EP 816,386 describes olefin polymerization catalysts comprising transition metal compounds, preferably transition metals from groups IIIA, IVA, VA, VIA, VIIA or VIII or a lanthanide element, preferably titanium, zirconium or hafnium, with an alkadienyl ligand.

The catalyst further comprises an auxiliary alkylaluminoxane catalyst and can be used for polymerization and copolymerization of olefins.

Catalysts for the polymerization of 1,3-butadiene based on cobalt complexes and organoaluminum activators are described in the patent and open literature. More in particular, there are two main groups of catalysts based on cobalt complexes which were investigated more intensively : A) Classical cobalt catalysts consisting of at least one cobalt carboxylate (cobalt salt of organic carboxylic acids) in combination with one or more alkylaluminum compounds, B) cobalt compounds or complexes

'which comprise cobalt compounds or complexes in combination witn at east one alumoxane component.

Traditionally, cobalt carboxylates were used in combination with suitable organoaluminum activator components for polymerization reactions of conjugated dienes such as 1,3-butadiene and isoprene.

A) Classical cobalt catalysts A method for producing polybutadiene was described in EP 0106596. A catalyst consisting of at least one cobalt compound, an organoaluminum halide component, a component consisting of at least one reaction product of a trialkylaluminum compound with water and a carbon disulfide or/and phenylisocyanate compound was used for polymerization of 1,3-butadiene. For example, butadiene in benzene solvent was exposed to diethylaluminum monochloride and the reaction product of triethylaluminum and water (ratio 1: 0,87). Subsequently the polymerization reaction was started by addition of cobalt octoate and carbon disulfide. High cis- 1, 3-polybutadienes (cis content ranged between 95 and 97.1 percent) were recovered as the result of the polymerization reaction.

Patent EP 770631 B1 describes the preparation of high cis 1, 4-polybutadiene using at least one cobalt compound, at least one organoaluminum compound, water and, in addition to cycloalkane as the primary solvent, a substituted benzene as polymerization regulator of the formula (C6H5 n) R1+n wherein n is an integer in the range of from 3 to 5 and wherein each R represents a lower alkoxy group containing from 1 to 4 carbon atoms. Preferably the R group represented an alkoxy group. For example, cobalt (ll) acetylacetonate was used in combination with diethylaluminum chloride for 1,4-butadiene polymerization in a polymerization solvent consisting of cyclohexane, water, butene and various concentrations of methoxy-substituted benzenes.

It has to be pointed out, that the so-called classical polymerization systems mentioned above led to relatively low molecular weight polymers and still required

water in combination with dialkylaluminum halides to activate the cobalt complex for butadiene polymerization. The low solubility of water in cobalt complex/ diorganoaluminum chloride/water systems often led to process instability.

Reference"P. Cass et al., Journal Polymer Science: Part A: Polymer Chemistry, 39 2001 2244-2255"described the replacement of benzene with regulators for the catalyzed polymerization of 1,3-butadiene to high cis-1, 4-polybutadiene. The classical cobalt octoate/diethylaluminum chloride/water system was stabilized with 1,3, 5-trimethoxybenzene or mesitylene and used as a catalyst for 1,3- butadiene in a cyclohexane/butene solvent. 1,3, 5-trimethoxybenzene was assumed to act as polymerization regulator by coordinating itself via -bonding to the active catalyst center. It was found out that the addition of trimethoxybenzene increased the percentage of active catalytic cobalt particles to approximately 200 percent-of the original value. However, at the same time the conversion rate and the cis content of the formed polybutadiene was reduced. For example, no butadiene conversions higher than 45 percent were reported in the presence of 1,3, 5- trimethoxybenzene. Though the solvent was free of the environmentally critical benzene, no way was found to avoid water which still was needed to activate cobalt octoate in combination with dialkylaluminum halides. As previously mentioned, the low solubility of water in cobalt complex/diorganoaluminum chloride/water systems can lead to process instability.

B) Cobalt compounds or complexes which comprise at least one cobalt compound or complex in combination with an alumoxane activator component WO 0004064 described polymerization reactions of conjugated dienes in the presence of aromatic vinyl compounds such as styrene using cobalt compounds in combination with organoaluminum compounds and modifiers. The cobalt compound is for example a salt of an organic acid and one of the organoaluminum compounds has to be an alumoxane. In addition, one further organoaluminum compound is the product from the reaction of an organoaluminum halide (AlR3 dXd, R is alkyl, cycloalkyl or aryl) with a donor compound of the formula HYR'e (Y is an

element of group Vb or Vlb of the periodic table of the elements, R'is hydrogen, alkyl, cycloalkyl or aryl). Though cobalt carboxylates are the object of this invention exclusively, the cobalt bromide phosphine adduct catalyst CoBr2 (PPh3) 2 was chosen to demonstrate the invention. For example, butadiene and styrene are copolymerized without additional polymerization solvent using a catalyst system consisting of CoBr2 (PPh3) 2"lonol ((2, 6-di-tert.-butyl) (4-methyl) phenol) and methylalumoxane (MAO). Patent DE 19832455 A1 resembles the aforementioned patent WO 0004064.

According to US 5,879, 805 cobalt compounds such as cobalt halides, cobalt compounds of organic salts of organic acids and others were used in combination with organoaluminum compounds and a compound selected from the group consisting of a phosphine, a xanthogen or a thioisocyanide to polymerize 1,3- butadiene in a gas phase reactor. The organoaluminum compound is represented by one of the compounds selected from triorganoaluminum AIR3, organoaluminum halide AIR', X3-m, or alumoxane AIR"2 (OR3) 3-n. For example, cobalt dihalide phosphine adduct CoBr2 (PPh3) 2, cobalt acetylacetonate Co (acac) 3 or (1-methyl- allyl) (buta-1,3 diene) triphenylphosphine cobalt were activated with the help of methylalumoxane alone or in the presence of a suitable support material and subsequently used for butadiene polymerization. In the case of cobalt acetylacetonate based catalyst, nothing was mentioned the microstructure or molecular weight of the polymer.

US 6,001, 478 describes similar examples to patent US 5,879, 805, however the claims concern the inert particulate material necessary for gas phase polymerization.

In EP 0816398 A1 and in JP 10-7717 a catalyst system consisting of at least one cobalt component, at least one trialkylaluminum compound and an alkylaluminum halide compound of the formula AlR2mX3 m (X is a halide atom, R2 represents a hydrocarbon group, m is a number of 0 to 2) or/and an alkyl halide compound of the formula R3X (R3 represents a hydrocarbon group) and water was used for the polymerization of 1,3-butadiene. As a matter of choice an alumoxane component

was pre-prepared by mixing the trialkylaluminum compound with water.

Accordingly, the catalyst system consisting of at least one cobalt compound, an alumoxane component, an alkylaluminum halide compound and/or an alkyl halide compound were claimed as catalyst for the polymerization of 1,3-butadiene as well.

As an example, cobalt octoate, methylalumoxane, ethylaluminum sesquichloride (EASC) are combined with 1, 5-cyclooctadiene which served as a molecular weight modifier. The resulting polymer consisted of more than 97 percent cis polybutadiene in the mentioned examples and the average molecular weight varied between 390,000 and 450,000 g/mol. The Mooney values (ML1+4) were between 29 and 34. It should be pointed out that the 1,3-butadiene conversion in all examples did not exceed 50 percent.

JP 10-158333 claimed a procedure for the preparation of 1, 2-polybutadiene. 1,2- polybutadiene was prepared through polymerization of 1,3-butadiene using a catalyst made from cobalt compounds, phosphine compounds, methylalumoxane or the product of the reaction of trimethylaluminum with water and compounds containing silicon atoms.

JP 11-140118 claimed a procedure for the preparation of polybutadiene using catalysts consisting of cobalt compounds, and alumoxane component and organic halogen compounds. The alumoxane component and the organic halogen compound had to be aged before use.

According to JP 114817 a procedure for the preparation of polymers from conjugated dienes was introduced. The catalyst applied to the diene polymerization contained cobalt compounds, at least one alumoxane component and compounds containing halogen atoms. The halogen atom-containing compounds were the product of the reaction of metal halogen compounds and Lewis bases.

Patent JP 8-325331 describes a procedure for the preparation of polybutadiene.

1,3-Butadiene was polymerized using a cobalt compound in combination with a trialkyl aluminum compound of the general formula AIR3, an aluminum oxide compound and a compound chosen from the group of compounds consisting of

carbon dioxide, phenylisocyanate and xanthogenate compounds.

JP 6-116316 and JP 6-128301 claim butadiene polymers containing a high content of vinyl bonds. The polybutadiene content amounted to at least 50 mol percent. The catalyst used for the preparation of the copolymer consisted of cobalt salts, organoaluminum compounds containing alumoxane and phosphine compounds. The polymerization was carried out in an inactive organic solvent and under use of hydrogen gas. Patent JP 6-128301 additionally claims the preparation of the above mentioned polymer using the continuous and discontinuous polymerization process.

Patent JP 6-116315 resembles aforementioned patent JP 6-116316 however, the catalyst for the preparation of butadiene polymers contained additionally a halogenated organic aluminum compound.

JP 6-116342 also resembles aforementioned patent JP 6-116316 and claims a butadiene copolymer containing a high content of vinyl bonds. The second monomer (1 to 30 mol percent of the copolymer) comprised conjugated double bonds as well. The butadiene part of the copolymer contained 80 percent or more vinyl bonds. The catalyst used for the preparation of the copolymer contained for example a cobalt compound, methylalumoxane (MAO) and triphenylphosphine. (PPh3).

Patent JP 7-102014 describes a procedure for the preparation of polymers containing at least 50 mol percent polybutadiene. The resulting polymer was prepared using a cobalt compound in combination with a organic aluminum compound containing an alumoxane component and an alkylaluminum phenoxide compound of the general formula (Rl is an alkyl group, R2-R6 are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups or aryl groups, n is 1 or 2) in an inactive organic solvent.

Patent RU 21255778 C1 describes a procedure for the synthesis of cis-1,4- polybutadiene in aromatic solvents. The polymerization reaction of conjugated dienes, especially of 1,3-butadiene, was carried out in the presence of dissolvable cobalt salts, aluminum (mono) chlorides or aluminum sesquichlorides and polyalumoxanes (R) 2AI- [OAIR] n-O-AI (R) 2 or aminoalumoxanes (R) 2AI-O-CH2- N (R') (R") wherein R represents an ethyl or isobutyl radical, R'is AI (R) 2, R"is hydrogen or AI (R) 2 and n is 0,1 or 2. The cobalt compounds were for example cobalt naphthenate, cobalt octoate or cobalt acetylacetonate.

Patent RU 2082721 C1 describes a procedure for the synthesis of cis-1, 4- polybutadiene in hydrocarbon solvents such as for example toluene using a catalytic system consisting of a cobalt compound, an alkylaluminum chloride compound, water and a polyalumoxane compound of the following formula : (R) 2AI- [OAIR] n-O-AI (R) 2 wherein R represents an ethyl or isobutyl radical and n is at least 2. The cobalt compounds were for example cobalt naphthenate, cobalt octoate, cobalt stearate, cobalt 2-ethylhexanoate or cobalt acetylacetonate. The alkyl aluminum chloride compound was chosen from the group consisting of <BR> <BR> <BR> diisobutylaluminum chloride, diethylaluminum chloride, isobutylaluminum chloride and ethylaluminum sesquichloride.

A process for producing a polybutadiene in the presence of a catalyst consisting of a cobalt-phosphine complex and an organoaluminum compound consisting essentially of an aluminoxane is described in EP 0511015 B1. For example, cobalt bis (triphenylphosphine) dibromide, methylalumoxane (MAO), toluene solvent and 1,3-butadiene were placed in a stainless steel autoclave. The molecular weight ranged between 101000 and 384000. The butadiene conversion was low and did not exceed 40 percent after 4 hours. The microstructure of the resulting polybutadiene (cis-1, 3-/trans-1, 3-/1, 2-polybutadiene ratio) was not given in the patent.

EP 0511015 B1 describes a process for producing polybutadiene. According to this patent 1,3-butadiene was polymerized in the presence of a catalyst consisting of a cobalt-phosphine complex and an organoaluminum compound, which preferably represents an alumoxane component. For example bis (triphenylphosphine) cobalt dibromide was treated with methylalumoxane in toluene to form the catalyst. The polymerization reaction led to a high proportion of 1, 2-polybutadiene of more than 60 percent. However, the polymer conversion reported in the patent was lower than 24 percent in all examples presented.

EP 0433943 A2 claims a catalyst component A consisting of a transition metal compound represented by the general formula M (R)' (OR') mXn (i+m), wherein M denotes a transition metal atom, R and R'independently denote hydrocarbon groups and X denotes halogen atoms. Preferably the metal M of the transition metal compound represents titanium or zirconium. Catalyst component B was an organoaluminum compound, which may be an alumoxane, a trihydrocarbylaluminum compound or an hydrocarbylaluminum halide. The catalyst component C is an organic compound having at least two hydroxyl groups such as for example alkanediols or aromatic compounds carrying two or more hydroxyl groups. Examples of the group of organic compounds are xylols. The above mentioned catalyst was used for the preparation of mainly trans-polybutadiene. The typical examples include reactions of titanium tetrachloride with aromatic diols such as 2,2'-dihydroxy-3, 3'-di-t-butyl-5, 5'-dimethyidiphenyl sulfide, followed by reactions with methylalumoxane. The resulting catalyst was used for polymerization of 1,3- butadiene. This patent did not include a second aluminum based component into the catalyst formation process and was basically limited to titanium and zirconium based catalyst precursors. The organic compound representing component C was used to form the desired catalyst precursor but did not function as modifier for the ongoing polymerization process.

Cobalt octoate was used as catalyst in combination with methylalumoxane and tert.-butyl chloride for the preparation of high cis polybutadiene using a solvent mixture containing 30 percent cyclohexane, 15 percent benzene, 35 percent butene and 20 percent 1,3-butadiene monomer (see P. Cass et al., Journal Polymer Science: Part A: Polymer Chemistry, 37 1999 3277-3284). The maximum cis-1,4- polybutadiene content of 96 percent was reached at 30 percent 1,3-butadiene conversion. In comparison with the classical cobalt octoate/diethylaluminum chloride/water system the proposed cobalt octoate/alumoxane/tert.-butyl chloride catalyst showed no significant differences with regard to the polybutadiene quality except a slight enhancement in polymer linearity. The benefit was a considerably reduced amount of aromatic benzene solvent.

Further kinetic investigations of the polymerization of 1, 3.-butadiene using the cobalt octoate/alumoxane/tert.-butyl chloride catalyst system were described by P. Cass et al. (Journal Polymer Science: Part A: Polymer Chemistry, 39 2001 2256- 2261).

It would be desirable to have a cobalt catalyst system which is activated without having water involved to guarantee easy process control. Additionally, the desired catalyst system ought to work in a solvent system free of benzene and or even substantially free of aromatic compounds. This catalyst system should be more active than alumoxane containing-cobalt catalyst systems known up to date.

In addition, it would be desirable to have catalyst components that could be directly injected into the polymerization reactor without the need to"age" (stir, shake or store) the catalyst or catalyst components for a longer period of time.

Furthermore, it would be beneficial if the desired cobalt catalyst system could

copolymerize conjugated dienes with alpha olefins, preferably aromatic alpha olefins. For example, butadiene-styrene copolymers would be interesting for many applications.

Polydiene homopolymers produced in a process for the polymerization of only one type of conjugated diene monomer or copolymers produced in a process for the copolymerization of one type of conjugated diene monomer with another type of conjugated diene monomer or with one or two types of aromatic or nonaromatic alpha olefins or nonconjugated dienes under use of cobalt compounds or complexes in combination with activators and catalyst modifiers, as well as said process of polymerization are objects of the invention. More particularly, the cobalt compounds or complexes used for the synthesis of homo-or copolymers of conjugated diene monomers contain at least one cobalt-oxygen bond. Even more particularly, diene monomers such as, but not limited to, 1, 3-butadiene and isoprene are homopolymerized or diene monomers such as, but not limited to, 1,3- butadiene and isoprene are copolymerized with aromatic or nonaromatic alpha olefins or nonaromatic nonconjugated dienes such as, but not limited to, styrene, divinylbenzene or divinyltoluene, 1-hexene, 1-octene, 1-decene, 1,5-hexadiene, 1,7-octadiene or 1,9-decadiene using the aforementioned cobalt compounds or complexes in combination with activators and with one or more aromatic compounds as modifier. Even more particularly, one alumoxane type activator or a noncoordinating anion-forming reagent such as, but not limited to, organoborates or organoborone compounds and one alkylaluminum halide type activator are used in combination with the cobalt complexes and with one or more aromatic compounds for the synthesis of homopolymers or copolymers. Even more particularly, one alumoxane type activator and one alkylaluminum halide type activator are used in combination with the cobalt complexes and with one aromatic compound for the synthesis of homopolymers or copolymers. Even more particularly, the aromatic modifier is applied in amounts similar or smaller than the amounts of the used activators.

An object of the invention are cobalt complexes which are useful in forming catalyst compositions for the polymerization of olefinic monomers, especially diene monomers, more especially conjugated diene monomers. Another object of the

invention are cobalt complexes which are useful in forming catalyst compositions for the copolymerization of olefinic monomers, especially diene monomers, more especially conjugated diene monomers with olefinic monomers, especially diene monomers such as conjugated diene monomers or with aromatic or nonaromatic alpha olefins.

Yet a further object of the invention is a process for the preparation of catalyst compositions which are useful in the polymerization of olefinic monomers, especially diene monomers, more especially conjugated diene monomers or which are useful in the copolymerization of conjugated diene monomers with olefinic monomers, especially conjugated diene monomers or aromatic alpha olefins or nonaromatic alpha olefins.

Even further objects of the invention are catalyst compositions for the polymerization of olefinic monomers, especially diene monomers, more especially conjugated diene monomers or for the copolymerization of conjugated diene monomers with olefinic monomers, especially conjugated diene monomers or aromatic alpha olefins or nonaromatic alpha olefins.

A further object of the invention is a process for the polymerization of olefinic monomers, especially diene monomers, more especially conjugated diene monomers which uses said catalyst compositions for the copolymerization of conjugated diene monomers with olefinic monomers, especially conjugated diene monomers or aromatic alpha olefins or nonaromatic alpha olefins.

Further objects of the invention are polymers, especially polydienes, more especially polymers of conjugated dienes produced using said catalyst compositions.

Further objects of the invention are catalyst compositions used to polymerize monomers containing conjugated unsaturated carbon-carbon bonds, especially one type of conjugated diene monomer, giving polydienes which comprise a) a cobalt compound or a cobalt complex, b) activator compounds for the metal complex and

c) at least one catalyst modifier, preferably an aromatic compound. Further objects of the invention are combinations of two or more cobalt complex/activator component type 1/activator component type 2/catalyst modifier-containing catalyst compositions.

Preferably, the cobalt complex contains at least one cobalt-oxygen bond.

The formula weight of the cobalt complex preferably is lower than 2000, more preferably lower than 800.

Preferably, the cobalt complex according to the invention contains carboxylate ligands.

More preferably the cobalt complex according to the invention contains octoate, neodecanate, naphthenate, versatate, acetylacetonate, 2-ethylhexanoate or stearate ligands.

Examples of the cobalt complex according to the invention include cobalt octoate, cobalt neodecanate, cobalt naphthenate, cobalt versatate, cobalt acetylacetonate, cobalt 2-ethylhexanoate and cobalt stearate.

The metal complexes of the invention can be activated using activator compounds (at least one activator of type 1 in combination with at least one activator of type 2).

The activation can be performed during a separate reaction step optionally including an isolation of the activated compound or can be performed in situ. The activation is preferably performed in situ if, after the activation of the metal complex, separation and/or purification of the activated complex is not necessary.

Preferably, the metal complexes of the invention are rendered catalytically active by combining with at least one activator compound of type 1, at least one activator compound of type 2 and at least one catalyst modifier.

The metal complexes according to the invention can be activated using suitable activators (activator of type 1 and activator of type 2) and suitable catalyst modifiers. For example, the activator of type 1 can be an organometallic compound, wherein at least one aromatic hydrocarbyl radical is bound directly to the metal to provide at least one (aromatic) carbon-metal bond. The hydrocarbyl radicals bound directly to the metal in the organometallic compounds preferably contain 1-30, more preferably 1-10 carbon atoms. The metal of the organometallic compound can be selected from group 11,12, 13 or 14 of the Periodic Table of the Elements. Suitable metals are, for example aluminum and boron.

Suitable activator compounds of type 1 for use herein include halogenated aromatic boron compounds, especially fluorinated or perfluorinated tri (aryl) boron compounds, such as tris (pentafluorophenyl) boron, tris (o-nonafluorobiphenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, fluorinated or perfluorinated tri (aryl) aluminum compounds, such as tris (pentafluorophenyl) aluminum, tris (o- nonafluorobiphenyl) aluminum, tris [3,5-bis (trifluoromethyl) phenyl] aluminum ; polymeric or oligomeric alumoxanes, especially methylalumoxane (MAO), triisobutyl aluminum-modified methylalumoxane, or isobutylalumoxane ; nonpolymeric, compatible, noncoordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium-, sulfonium-, or ferrocenium-salts of compatible, noncoordinating anions; and combinations of the foregoing activating compounds. The foregoing activator compounds of type 1 have been previously taught with respect to different metal complexes in the following references: U. S. Pat. Nos. 5,132, 380,5, 153,157, 5,064, 802,5, 321,106, 5,721, 185, 5,350, 723, and WO-97/04234, equivalent to U. S. Ser. No. 08/818,530, filed Mar.

14,1997.

lon-forming compounds are useful as activator compounds of type 1 according to the invention.

Suitable ion-forming compounds useful as activator compounds of type 1 in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion. As used herein, the term"noncoordinating"means an anion or substance which either does not coordinate to the metal-containing precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a Lewis base such as olefin monomer. A noncoordinating anion specifically refers to an anion which when functioning as a charge-balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation thereby forming neutral complexes."Compatible anions"are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerization or other uses of the complex.

Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined. Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenic unsaturated compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions which comprise 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 anion portion, are available commercially.

Preferably such activator compounds of type 1 may be represented by the following general formula :

(L*-H) d+Ad- wherein: L* is a neutral Lewis base; (L*-H) + is a Bronsted acid; Ad-is a noncoordinating, compatible anion having a charge of d-, and d is an integer from I to 3.

More preferably Ad-corresponds to the formula : [M*Q4] ; wherein: M* is boron or aluminum in the +3 formal oxidation state; and Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, halohydrocarbyl, halocarbyl, hydrocarbyloxide, hydrocarbyloxy substituted-hydrocarbyl, organometal substituted-hydrocarbyl, organometalloid substituted-hydrocarbyl, halohydrocarbyloxy, halohydrocarbyloxy substituted hydrocarbyl, halocarbyl-substituted hydrocarbyl, and halo-substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl-perhalogenated hydrocarbyloxy-and perhalogenated silythydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide.

Examples of suitable hydrocarbyloxide Q groups are disclosed in U. S. Pat. No.

5,296, 433.

In a more preferred embodiment, d is one, that is, the counter ion has a single negative charge and is A-. Activator compounds comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula : (L*-H) + (BQ4)- ; wherein: L* is as previously defined; B is boron in a formal oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl-group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.

Most preferably, Q is each occurrence a fluorinated aryl group, especially, a pentafluorophenyl or nonafluorobiphenyl group.

Illustrative, but not limiting, examples of boron compounds which may be used as an activator compound in the preparation of the improved catalysts of this invention are tri-substituted ammonium salts such as: trimethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, methyidioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammoniurn tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, methyltetradecyloctadecylammonium tetraphenylborate, N, N- dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N- dimethyl (2,4, 6-trimethylanilinium) tetraphenylborate, N, N-dimethyl anilinium bis (7,8- dicarbundecaborate) cobaltate (III), trimethylammonium tetrakis (pentafluorophenyl) borate, methyldi (tetradecyl) ammonium tetrakis (pentafluorophenyl) borate, methyldi (octadecyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl (2,4, 6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3, 4,6- tetrafluorophenyl) borate, triethylammonium tetrakis (2,3, 4,6- tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3, 4,6- tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (2,3, 4, 6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3, 4, 6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3, 4, 6-tetrafluorophenyl) borate, N, N- diethylanilinium tetrakis (2,3, 4, 6-tetrafluorophenyl) borate, and N, N-dimethyl- (2, 4,6- trimethylanilinium) tetrakis- (2, 3,4, 6- tetrafluorophenyl) borate; dialkyl ammonium salts such as: di (octadecyl) ammonium tetrakis (pentafluorophenyl) borate,

di (tetradecyl) ammonium tetrakis (pentafluorophenyl) borate, and dicyclohexylammonium tetrakis (pentafluorophenyl) borate ; tri-substituted phosphonium salts such as: triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyidi (octadecyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (2, 6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate.

Preferred are tetrakis (pentafluorophenyl) borate salts of long chain alkyl mono-and disubstituted ammonium complexes, especially C14-C20 alkyl ammonium complexes, especially methyldi (octadecyl) ammonium tetrakis (pentafluorophenyl) borate and methyidi (tetradecyl) ammonium tetrakis (pentafluorophenyl) borate, or mixtures including the same. Such mixtures include protonated ammonium cations derived from amines comprising two C14, Ci6 or C 18 alkyl groups and one methyl group. Such amines are available from Witco Corp. , under the trade name KemamineT" T9701, and from Akzo-Nobel under the trade name Armeen M2HT.

Examples of the most highly preferred catalyst activators of type 1 herein include the foregoing trihydrocarbylammonium-, especially, methylbis (tetradecyl) ammonium-or methylbis (octadecyl) ammonium-salts of: bis (tris (pentafluorophenyl) borane) imidazolide, bis (tris (pentafluorophenyl) borane)-2-undecylimidazolide, bis (tris (pentafluorophenyl) borane)-2-heptadecylimidazolide, bis (tris (pentafluorophenyl) borane)-4, 5-bis (undecyl) imidazolide, bis (tris (pentafluorophenyl) borane) -4,5-bis (heptadecyl) imidazolide, bis (tris (pentafluorophenyl) borane) imidazolinide, bis (tris (pentafluorophenyl) borane)-2-undecylimidazolinide, bis (tris (pentafluorophenyl) borane)-2-heptadecylimidazolinide, bis (tris (pentafluorophenyl) borane) -4, 5-bis (undecyl) imidazolinide, bis (tris (pentafluorophenyl) borane) -4,5-bis (heptadecyl) imidazolinide, bis (tris (pentafluorophenyl) borane) -5, 6-dimethylbenzimidazolide, bis (tris (pentafluorophenyl) borane) -5,6-bis (undecyl) benzimidazolide, bis (tris (pentafluorophenyl) alumane) imidazolide, bis (tris (pentafluorophenyl) alumane)-2-undecylimidazolide, bis (tris (pentafluorophenyl) alumane)-2-heptadecylimidazolide,

bis (tris (pentafluorophenyl) alumane)-4, 5-bis (undecyl) imidazolide, bis (tris (pentafluorophenyl) alumane)-4, 5-bis (heptadecyl) imidazolide, bis (tris (pentafluorophenyl) alumane) imidazolinide, bis (tris (pentafluorophenyl) alumane)-2-undecylimidazolinide, bis (tris (pentafluorophenyl) alumane)-2-heptadecylimidazolinide, bis (tris (pentafluorophenyl) alumane)-4, 5-bis (undecyl) imidazolinide, bis (tris (pentafluorophenyl) alumane)-4, 5-bis (heptadecyl) imidazolinide, bis (tris (pentafluorophenyl) alumane)-5, 6-dimethylbenzimidazolide, and bis (tris (pentafluorophenyl) alumane)-5, 6-bis (undecyl) benzimidazolide. The foregoing activator compounds have been previously taught with respect to different metal complexes in the following reference: EP 1 560 752 A1.

Another suitable ammonium salt, especially for use in heterogeneous catalyst systems is formed upon reaction of an organometallic compound, especially a tri (Cl-6 alkyl) aluminum compound with an ammonium salt of a hydroxyaryltris (fluoroaryl) borate compound. The resulting compound is an organometaloxyaryltris (fluoroaryl) borate compound which is generally insoluble in aliphatic liquids. Examples of suitable compounds include the reaction product of a tri (C1 6 alkyl) aluminum compound with the ammonium salt of hydroxyaryltris (aryl) borate. Suitable hydroxyaryltris (aryl) borates include the ammonium salts, especially the foregoing long chain alkyl ammonium salts of: (4-dimethylaluminumoxy-1-phenyl) tris (pentafluorophenyl) borate, (4-dimethylaluminumoxy-3, 5-di (trimethylsilyl)-1-phenyl) tris (pentafluorophenyl) borate, (4-dimethylaluminumoxy-3, 5-di (t-butyl)-1-phenyl) tris (pentafluorophenyl) borate, (4-dimethylaluminumoxy-1-benzyl) tris (pentafluorophenyl) borate, (4-dimethylaluminumoxy-3-methyl-1-phenyl) tris (pentafluorophenyl) borate, (4-dimethylaluminumoxy-tetrafluoro-1-phenyl) tris (pentafluorophenyl) borate, (5-dimethylaluminumoxy-2-naphthyl) tris (pentafluorophenyl) borate, 4- (4-dimethylaluminumoxy-1-phenyl) phenyltris (pentafluorophenyl) borate, 4- (2- (4- (dimethylaluminumoxyphenyl) propane-2-yl) phenoxy) tris (pentafluorophenyl) borate, (4-diethylaluminumoxy-1-phenyl) tris (pentafluorophenyl) borate,

(4-diethylaluminumoxy-3, 5-di (trimethylsilyl)-1-phenyl) tris (pentafluorophenyl) borate, (4-diethylaluminumoxy-3, 5-di (t-butyl)-1-phenyl) tris (pentafluorophenyl) borate, (4-diethylaluminumoxy-1-benzyl) tris (pentafluorophenyl) borate, (4-diethylaluminumoxy-3-methyl-1-phenyl) tris (pentafluorophenyl) borate, (4-diethylaluminumoxy-tetrafluoro-1-phenyl) tris (pentafluorophenyl) borate, (5-diethylaluminumoxy-2-naphthyl) tris (pentafluorophenyl) borate, 4-(4-diethylaluminumoxy-1-phenyl)phenyl tris (pentafluorophenyl) borate, 4- (2- (4- (diethylaluminumoxyphenyl) propane-2-yl) phenoxy) tris (pentafluorophenyl) borate, (4-diisopropylaluminumoxy-1-phenyl) tris (pentafluorophenyl) borate, (4-diisopropylaluminumoxy-3, 5-di (trimethylsilyl)-1-phenyl) tris (pentafluorophenyl) borate, (4-diisopropylaluminumoxy-3, 5-di (t-butyl)-1-phenyl) tris (pentafluorophenyl) borate, (4-diisopropylaluminumoxy-1-benzyl) tris (pentafluorophenyl) borate, (4-diisopropylaluminumoxy-3-methyl-1-phenyl) tris (pentafluorophenyl) borate, (4-diisopropylaluminumoxy-tetrafluoro-1-phenyl) tris (pentafluorophenyl) borate, (5-diisopropylaluminumoxy-2-naphthyl) tris (pentafluorophenyl) borate, 4- (4-diisopropylaluminumoxy-1-phenyl) phenyl tris (pentafluorophenyl) borate, and 4- (2- (4- (diisopropylaluminumoxyphenyl) propane-2-yl) phenoxy) tris (pentafluorophenyl) borate.

Especially preferred ammonium compounds are methyidi (tetradecyl) ammonium (4-diethylaluminumoxy-1-phenyl) tris (pentafluorophenyl)borate, methyldi(hexadecyl) ammonium (4- diethylaluminumoxy-1-phenyl) tris (pentafluorophenyl) borate, methyldi (octadecyl) ammonium (4-diethylaluminumoxy-1-phenyl) tris (pentafluorophenyl) borate, and mixtures thereof. The foregoing complexes are disclosed in U. S. Pat. Nos. 5,834, 393 and 5,783, 512.

Another suitable ion-forming, activator compound of type 1 comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula :

axe+) d (Ad-) e, wherein Oxe+ is a cationic oxidizing agent having a charge of e+ ; d is an integer from 1 to 3; e is an integer from 1 to 3; and Ad-is as previously defined.

Examples of cationic oxidizing agents include : ferrocenium, hydrocarbyl- substituted ferrocenium, Pb+2 or Ag+. Preferred embodiments of Ad-are those anions previously defined with respect to the Bronsted acid containing activator compounds, especially tetrakis (pentafluorophenyl) borate.

Another suitable ion-forming, activator compound of type 1 comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula : @+A- wherein: @+ is a Cul-20 carbenium ion; and A-is a noncoordinating, compatible anion having a charge of-1. A preferred carbenium ion is the trityl cation, especially triphenylmethylium.

Preferred carbenium salt activator compounds of type 1 are triphenylmethylium tetrakis (pentafluorophenyl) borate, triphenylmethylium tetrakis (nonafluorobiphenyl) borate, tritolylmethylium tetrakis (pentafluorophenyl) borate and ether substituted adducts thereof.

A further suitable ion-forming, activator compound of type 1 comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula :

R3Si+A- wherein: R is C1 10 hydrocarbyl ; and A-is as previously defined.

Preferred silylium salt activator compounds of type 1 are trimethylsilylium tetrakis (pentafluorophenyl) borate, trimethylsilylium tetrakis (nonafluorobiphenyl) borate, triethylsilylium tetrakis (pentafluorophenyl) borate and other substituted adducts thereof.

Silylium salts have been previously generically disclosed 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 activator compounds for addition polymerization catalysts is claimed in U. S. Pat. No. 5,625, 087.

Certain complexes of alcohols, mercaptans, silanol, and oximes with tris (pentafluorophenyl) borane are also effective catalyst activators of type 1 and may be used according to the present invention. Such activator compounds are disclosed in U. S. Pat. No. 5,296, 433.

The activator compounds of type 1 may also be used in combination. An especially 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 catalyst/cocatalyst employed preferably ranges from 1: 10,000 to 10 : 1, more preferably from 1: 5000 to 10: 1, most preferably from 1: 2500 to 1: 1. Alumoxane, when used by itself as an activator compound of type 1, is preferably employed in large molar ratio, generally at least 50 times the quantity of metal complex on a molar basis. Tris (pentafluorophenyl) borane, where used as an activator compound of type 1 is preferably employed in a molar ratio to the metal complex of from 0.5 : 1 to 10: 1, more preferably from 1: 1 to 6: 1 most preferably from 1: 1 to 5: 1. The remaining activator compounds are generally preferably employed in approximately equimolar quantity with the metal complex.

If the above-mentioned non-coordinating or poorly coordinating anion is used as theactivator compound of type 1, it is preferable for the metal complex according to the invention to be alkylated (that is, one of the R'groups of the metal complex is an alkyl or aryl group). activator compounds comprising boron are preferred. Most preferred are activator compounds comprising tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borane, tris (o-nonafluorobiphenyl) borane, tetrakis (3,5- bis (trifluoromethyl) phenyl) borate, tris (pentafluorophenyl) alumane, tris (o- nonafluorobiphenyl) alumane.

The molar ratio of the activator compound of type 1 relative to the metal center in the cobalt complex in the case an organometallic compound is selected as the activator compound, usually is in a range of from 1: 10 to 10,000 : 1, more preferably from 1: 10 to 5000: 1 and most preferably in a range of from 1: 1 to 2,500 : 1. If a compound containing or yielding a non-coordinating or poorly coordinating anion is selected as activator compound, the molar ratio usually is in a range of from 1: 100 to 1,000 : 1, and preferably is in a range of from 1: 2 to 250: 1.

The formation of the catalyst according to the invention is completed by combination of the cobalt complex with at least one activator of type 1, at least one activator of type 2 and at least one catalyst modifier.

For example, the activator of type 2 can be an organometallic compound, wherein at least one or more than one halogen atom or hydrocarbyl radical is bound directly to the metal to provide a metal-halogen or carbon-metal bond. The hydrocarbyl radicals are non aromatic and are bound directly to the metal in the organometallic compounds and preferably contain 1-30, more preferably 1-10 carbon atoms. The metal of the organometallic compound can be selected from group 1,2, 3, 4, 5, 6 , 7,12, 13 or 14 of the Periodic Table of the Elements.

Suitable activators of type 2 for use herein include hydrocarbyl sodium, sodium halide, hydrocarbyl lithium, lithium halide, hydrocarbyl zinc, zinc dihalide, magnesium dihalide, hydrocarbyl magnesium halide, dihydrocarbyl magnesium, especially alkyl sodium, alkyl lithium, alkyl zinc, alkyl magnesium halide, dialkyl magnesium, such as n-octyl sodium, butyl lithium, neopentyl lithium, methyl lithium,

ethyl lithium, diethyl zinc, dibutyl zinc, butyl magnesium chloride, ethyl magnesium chloride, octyl magnesium chloride, dibutyl magnesium, dioctyl magnesium, butyl octyl magnesium. Suitable catalyst activators of type 2 for use herein also include neutral Lewis acids, such as nonaromatic Cl-30 hydrocarbyl substituted Group 13 compounds substituents, especially (hydrocarbyl) aluminum- or (hydrocarbyl) boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 20 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially trialkyl aluminum compounds, such as triethyl aluminum and triisobutyl aluminum : dialkyl aluminum hydrides, such as diisobutyl aluminum hydride; alkylalkoxy aluminum compounds, such as dibutyl ethoxy aluminum; halogenated aluminum compounds, such as diethyl aluminum chloride, ethylaluminum chloride, diisobutyl aluminum chloride, isobutylaluminum chloride, ethyl octyl aluminum chloride, ethyl aluminum sesquichloride, ethyl cyclohexyl aluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride.

Suitable catalyst activators of type 2 for use herein also include aluminum and boron trihalides such as for example aluminum trichloride, aluminum trifluoride, boron trifluoride and adducts of aluminum and boron trihalides with Lewis bases.

Suitable optional catalyst activators of type 2 for use herein also include neutral Lewis acids, such as C1 _ 30 hydrocarbyl substituted Group 3 to Group 7 compounds, especially (hydrocarbyl) scandium-, (hydrocarbyl) titanium-, (hydrocarbyl) zirconium-, (hydrocarbyl) vanadium-or (hydrocarbyl) molybdenum compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 20 carbons in each hydrocarbyl or halogenated hydrocarbyl group.

Suitable catalyst activators of type 2 for use herein also include halides of Group 3 to Group 7 metals, especially scandium-, titanium-, zirconium-, vanadium-or molybdenum halides such as titanium dichloride, titanium trichloride, titanium tetrachloride, zirconium dichloride, zirconium trichloride, zirconium tetrachloride, vanadium dichloride, vanadium trichloride, molybdenum pentachloride.

Preferably, halogenated aluminum compounds, such as diethyl aluminum chloride, ethylaluminum chloride, diisobutyl aluminum chloride, ethyl octyl aluminum chloride, ethyl aluminum sesquichloride, methyl aluminum sesquichloride, ethyl

cyclohexyl aluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride, are activators of type 2.

The molar ratio of the catalyst activator of type 2 relative to the metal center of the cobalt complex is characterized in that it usually is in a range of from 1: 10 to 1,000 : 1, more preferably from 1: 10 to 500: 1 and most preferably in a range of from 1: 1 to 250: 1.

Especially desirable activator compound mixtures for use herein are combinations of activator compounds of type 2, such as, for example, neutral optional Lewis acids, especially the combination of a dialkyl aluminum halide compound having from 1 to 4 carbons in each alkyl group, such as, for example, ethylaluminum sesquichloride, ethyloctylaluminum chloride and diethylaluminum chloride, with activator compounds of type 1, such as, for example, C1 _ 30 hydrocarbyl- substituted Group 13 Lewis acid compounds, especially halogenated tri (hydrocarbyl) boron or-aluminum compounds having from 1 to 20 carbons in each hydrocarbyl group, especially tris (pentafluorophenyl) borane or tris (pentafluorophenyl) alumane, further combinations of type 2 activators, such as neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane (type 1 activator), and combinations of a single neutral Lewis acid (type 2 activator), especially with tris (pentafluorophenyl) borane or tris (pentafluorophenyl) alumane and a polymeric or oligomeric alumoxane (type 1 activator).

As mentioned above, the formation of the catalyst according to the invention is completed by combination of the cobalt complex with at least one activator of type 1, at least one activator of type 2 and at least one catalyst modifier.

For example, the catalyst modifier is an aromatic compound. Preferably, the catalyst modifier is an aromatic compound having at least two or more than two- OH groups are bound to the aromatic compound.

Preferably the aromatic compound having at least two hydroxyl groups is represented by one of the following formulas : wherein R'and R"independently denote a hydrocarbon group of 1-20 carbon atoms;

R', R, R3, R4, R5, R6, R7, R8, R9, R10 R", R may be the same or different and respectively denote a hydrocarbon group of 1-20 carbon atoms, hydroxyl groups, nitro groups, hydrocarbyloxy groups or halogen atoms; Z denotes a hydrocarbon group of 1-20 carbon atoms, an oxygen atom, a sulfur atom, a-(C=O)-group, a-(NR13)-group or a -(SiR214)- group, wherein R, and R14 may be the same or different and respectively denote a hydrocarbon group of 1-20 carbon atoms; d is 0,1, or 2; m, n, q, r, s, t are 0,1, 2,3, or 4;. o, p are 0, 1,2, 3 or 4 ; m + n < 4 ; o + p < 4 ; <BR> r + q < 4 ;<BR> s + t # 4.

Preferably, the catalyst modifier is an aromatic compound, wherein each of at least two-OH groups is bound directly to one of the aromatic rings of the aromatic compound.

More preferably, the catalyst modifier is selected from formula 1.

Even more preferably one of the following catalyst modifiers is used in combination with the cobalt complex, activator compound type 1 andactivator compound type 2: Even more preferably the catalyst modifier contains three hydroxyl groups.

The molar ratio of the catalyst modifier relative to the metal center in the cobalt complex in the case an organometallic compound is selected as the catalyst

modifier usually is in a range of from 1: 10 to 1,000 : 1, more preferably from 1: 10 to 500: 1 and most preferably in a range of from 1: 1 to 250: 1.

The surprising efficient use of the catalyst modifier in combination with the cobalt complex, activator compound type 1 andactivator compound type 2 according to the present invention allows for the production of diene polymers with considerably increased catalytic efficiencies. Alternatively, comparable catalyst efficiencies using less of the expensive alumoxaneactivator compound are achieved when small amounts of catalyst modifier are applied to the polymerization reaction. Additionally, polymers with lower levels of aluminum residue, and hence greater clarity, are obtained.

In addition to the metal complex and theactivator compound according to the invention, the catalyst composition can also contain a small amount of another organometallic compound that is used as a so-called scavenger agent. The scavenger agent is added to react with impurities in the reaction mixture. It may be added at any time, but normally is added to the reaction mixture before addition of the metal complex and theactivator compound. Usually organoaluminum compounds are used as scavenger agents. Examples of scavengers are trioctylaluminum, triethylaluminum and tri-isobutylaluminum. As a person skilled in the art would be aware, the metal complex, theactivator compound of type one, theactivator compound of type 2 as well as the catalyst modifier can be present in the catalyst composition as a single component or as a mixture of several components. For instance, a mixture may be desired where there is a need to influence the molecular properties of the polymer, such as molecular weight distribution.

The metal complex according to the invention can be used for the homo- and copolymerization of olefin monomers. One type of olefins envisaged in particular are dienes, preferably conjugated dienes. The comonomer envisaged in particular are aromatic or nonaromatic alpha olefins. The metal complex according to the invention is particularly suitable for a process for the polymerization of one or more conjugated diene (s). Preferably the diene monomer (s) are chosen from the group comprising 1,3-butadiene, isoprene (2-methyl-1, 3-butadiene), 2, 3-dimethyl-

1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,3- heptadiene, 1,3-octadiene, 2-methyl-2, 4-pentadiene, cyclopentadiene, 2,4- hexadiene, 1, 3-cyclooctadiene, norbornadiene, ethylidenenorbornene. More preferably, butadiene, isoprene or cyclopentadiene are used as the conjugated diene. Preferably the aromatic alpha olefins are styrene, para-methylstyrene, divinylbenzene, such as 1, 2-divinylbenzene, 1, 3-divinylbenzene, 1,4- divinylbenzene and divinyltoluene, such as 2, 3-divinyltoluene, 2, 4-divinyltoluene, 2, 5-divinyltoluene, 2, 6-divinyltoluene, 3, 4-divinyltoluene, 3, 5-divinyltoluene monomers. More preferably styrene is used as aromatic alpha olefin. Preferably the nonaromatic alpha olefins are ethylene and aliphatic 1-alkenes containing 1-35 carbon atoms in the alkyl chain such as propene, 1-butene, 1-hexene, 1-octen, 1- decene. The monomers needed for such products and the processes to be used are known to the person skilled in the art.

With the metal complex according to the invention, amorphous or rubber- like or rubber polymers can be prepared depending on the monomer or monomers used.

Polymerization of the diene monomer (s) can be effected in a known manner, in the gas phase as well as in a liquid reaction medium. In the latter case, both solution and suspension polymerization are suitable. The quantity of metal to be used generally is such that its concentration in the dispersion agent amounts to 1 o-8-10-3 mol/l, preferably 10-7 _l 0-4 mol/l. The polymerization process can be conducted as a gas phase polymerization (for example in a fluidized bed reactor), as a suspension/slurry polymerization, as a solid phase powder polymerization or as a so-called bulk polymerization process, in which an excess of olefinic monomer is used as the reaction medium. Dispersion agents may suitably be used for the polymerization, which be chosen from the group comprising, but not limited to, cycloalkanes such as cyclohexane ; saturated, straight or branched aliphatic hydrocarbons, such as butanes, pentanes, hexanes, heptanes, octanes, pentamethylheptane or mineral oil fractions such as light or regular petrol, naphtha, kerosene or gas oil. Fluorinated hydrocarbon fluids or similar liquids are also suitable for that purpose. Likewise, aromatic solvents such as toluene are suitable for that purpose. Some aromatic hydrocarbons, especially benzene, can be used, but because of safety considerations, it is preferred to eliminate these solvents used for production on a technical scale. In polymerization processes on a technical scale, it is preferred therefore to use low-priced aliphatic hydrocarbons or mixtures thereof, as marketed by the petrochemical industry as solvents or to use low-priced aliphatic hydrocarbons in combination with aromatic solvents or to use aromatic solvents. If an aliphatic hydrocarbon is used as solvent, the solvent may optionally contain minor quantities of aromatic hydrocarbon, for instance toluene.

Thus, if for instance methyl aluminoxane (MAO) is used asactivator compound, toluene can be used as solvent for the MAO in order to supply the MAO in dissolved form to the polymerization reactor. Drying or purification of the solvents is desirable if such solvents are used; this can be done without problems by one skilled in the art.

In the polymerization process the metal complex, theactivator compounds (type 1 and 2) as well as the catalyst modifier are used in a catalytically effective amount, that is, any amount that successfully results in the formation of polymer.

Such amounts may be readily determined by routine experimentation by the worker skilled in the art.

Those skilled in the art will easily understand that the catalyst compositions used in accordance with this invention may also be prepared in situ.

If a solution or bulk polymerization is to be used, it is preferably carried out typically at, but not limited to, temperatures between 0 °C and 200 °C, preferably between 0 °C and 100 °C.

The polymerization process can also be carried out under suspension or gas phase polymerization conditions which typically are at, but not limited to, temperatures below 150 °C.

The polymer resulting from the polymerization can be worked up by a method known per se. In general the catalyst is deactivated at some point during the processing of the polymer. The deactivation is also effected in a manner known per se, for example by means of water or an alcohol. Removal of the catalyst residues can mostly be omitted because the quantity of catalyst in the homo-or copolymer, in particular the content of halogen and metal, is very low now owing to the use of the catalyst system according to the invention. If desired, however, the level of catalyst residues in the polymer can be reduced in a known manner, for

example, by washing. The deactivation step can be followed by a stripping step (removal of organic solvent (s) from the (homo) polymer).

Polymerization can be effected at atmospheric pressure, at sub- atmospheric pressure, or at elevated pressures of up to 500 MPa, continuously or discontinuously. Preferably, the polymerization is performed at pressures between 0.01 and 500 MPa, most preferably between 0.01 and 10 MPa, in particular between 0.1-2 MPa. Higher pressures can be applied. In such a high-pressure process the metal complex according to the present invention can also be used with good results. Slurry and solution polymerization normally take place at lower pressures, preferably below 10 MPa.

The polymerization can also be performed in several steps, in series as well as in parallel. If required, the catalyst composition, monomer composition, temperature, hydrogen concentration, pressure, residence time, etc. , may be varied from step to step. In this way it is also possible to obtain products with a wide property distribution, for example, molecular weight distribution. By using the metal complexes according to the present invention for the polymerization of olefins, polymers are obtained with a polydispersity (Mw/Mn) of 1.0-50.

Examples It is understood that the present invention is operable in the absence of any component which has not been specifically disclosed. The following examples are provided in order to further illustrate the invention and are not to be constructed as limiting. Unless stated to the contrary, all parts and percentages are expressed on a weight basis. The term"overnight", if used, refers to a time of approximately 16- 18 hours, "room temperature", if used, refers to a temperature of 20-25 °C.

All tests in which organometallic compounds were involved were carried out in an inert nitrogen atmosphere, using standard Schlenk equipment and techniques or in a glovebox. In the following,'THF'stands for tetrahydrofuran, Et3Al2Cl3 stands for ethylaluminumsesquichloride, (CH3) 3SiCl stands for trimethylchlorosilane,'DME' stands for 1,2-dimethoxyethane,'Me'stands for'methyl','Et'stands for'ethyl','Bu' stands for'butyl','Ph'stands for'phenyl','MMAO'or'MMAO-3a'stands for'modified methyl alumoxane'and'PMAO-lP'stands for'polymeric methyl alumoxane with

improved performance', both purchased from AKZO Nobel.'IBAO'stands for 'isobutylalumoxane'and'MAO'stands for'methylalumoxane', both purchased from Albemarle. Pressures mentioned are absolute pressures. The polymerizations were performed under exclusion of moisture and oxygen in a nitrogen atmosphere. The products were characterized by means of SEC (size exclusion chromatography), Elemental Analysis, NMR (Avance 400 device ('H = 400 MHz; 13C = 100 MHz) of Bruker Analytic GmbH) and IR (IFS 66 FT-IR spectrometer of Bruker Optics GmbH). The IR samples were prepared using CS2 as swelling agent and using a two or fourfold dissolution. DSC (Differential Scanning Calorimetry) was measured using a DSC 2920 of TA Instruments.

Mn and Mw are molecular weights and were determined by universal calibration of SEC. Mw/Mn is the molecular weight distribution and is called the polydispersity herein.

The ratio between the 1,4-cis-, 1, 4-trans- and 1, 2-polydiene content of the butadiene or isoprene polymers was determined by IR and 13C-NMR-spectroscopy.

The glass transition temperatures (TG) of the polymers were determined by DSC determination.

Example l 1. Cobalt complexes 1. 1 Cobalt octoate 1 Cobalt octotate (Co 10 HEX-CEM) was obtained from OMG as a solution of the cobalt complex (10percent cobalt) in mineral spirit D 60.

2. Polymerization 2. 1 Description of the polymerization procedure 2. 1. 1 Description of the polymerization procedure-Method 1 The polymerizations were performed in a double wall 2 L steel reactor, which was purged with nitrogen before the addition of organic solvent, metal complex,

activator (s), monomer (s), electron acceptor or electron donor component (s), alkylaluminum halide component (s) or other compounds such as aromatic modifiers. The polymerization reactor was tempered to 25 °C if not stated otherwise. The following components were then added into the polymerization reactor in the following order: organic solvent (s), a portion of the activator 1, a portion of the conjugated diene monomer (s), optionally a second olefin and a portion of an alkylaluminum halide component. The mixture was allowed to stir for 30 minutes.

In a separate 200 mL double wall steel reactor, which was tempered to the same temperature as the polymerization reactor, the following components were added in the following order: organic solvent (s), a portion of the activator 1, a portion of an alkylaluminum halide component, optionally an aromatic compound and a portion of the conjugated diene monomer. The mixture was stirred for the time listed below.

Then the cobalt compound was added and the resulting mixture was allowed to stir for an additional period listed below.

The polymerization was started by addition of the contents of the 200 mL steel reactor into the 2 L polymerization vessel. The polymerization was performed at 25°C unless stated otherwise. The polymerization time varied depending on the experiment.

For the termination of the polymerization process, the polymer solution was transferred into a third double wall steel reactor containing 50 mL of methanol containing lonol as stabilizer for the polymer (1 L of methanol contains 2 g of lonol).

This mixture was stirred for 15 minutes. The recovered polymer was then stripped with steam for 1 hour to remove solvent and other volatiles and dried in an oven at 45°C for 24 hours.

2. 1. 2 Description of the polymerization procedure-Method 2 The polymerizations were performed in a double wall 2 L steel reactor, which was purged with nitrogen before the addition of organic solvent, metal complex, activator (s), monomer (s), electron acceptor or electron donor component (s), alkylaluminum halide component (s) or other compounds. The polymerization reactor was tempered to 25 °C unless stated otherwise. The following components were then added in the following order: organic solvent (s), the activator (s), the conjugated diene monomer (s), optionally a second olefin, the alkylaluminum halide component and optionally an aromatic compound. The mixture was allowed to stir for the time listed below, then the cobalt compound was added to start the polymerization.

The polymerization was performed at 25 °C unless stated otherwise. The polymerization time varied depending on the experiment.

For the termination of the polymerization process, the polymer solution was transferred into a third double wall steel reactor containing 50 mL of methanol containing lonol as stabilizer for the polymer (1 L of methanol contains 2 g of lonol).

This mixture was stirred for 15 minutes. The recovered polymer was then stripped with steam for 1 hour to remove solvent and other volatiles and dried in an oven at 45 °C for 24 hours.

3 Polymerization Examples : 3.1 Polymerization of 1,3-butadiene 3.1. 1 Polymerization of 1,3-butadiene using 1,2, 4-trimethoxybenzene A) Polymerization of 1,3-butadiene using metal complex 1, MMAO-3a, ethylaluminum sesquichloride and 1,2, 4-trimethoxybenzene (Run 1) The experiment was carried out according to the general polymerization procedure described above (2.1. 1). The polymerization was carried out in a polymerization solvent containing 373 g of cyclohexane and 125 g of toluene. Thus 338 g of cyclohexane, 22.2 g of toluene, 49.8 g (0.92 mol) of 1,3-butadiene monomer, MMAO-3a (1.6 g of a heptane solution containing 4.1 mmol of MMAO), 0,248 g (1,47 mmol) of 1,2, 4-trimethoxybenzene and 0.5 g (0. 2 mmol) of ethylaluminum sesquichloride were added into the polymerization reactor. 35 g of cyclohexane, 64.8 g of toluene, 3.5 g (0.06 mol) of 1,3-butadiene monomer, 6.2 g of a heptane solution containing 16.1 mmol of MMAO and 2.0 g (0.8 mmol) of ethylaluminum sesquichloride were stirred for one hour and subsequently mixed with 156 mg

(0.264 mmol) of the metal complex 1 in a separate reaction vessel and stirred for 10 minutes.

Afterwards the resulting mixture was transferred into the polymerization reactor to start the polymerization reaction.

After one hour and four minutes the polymerization reaction was terminated as described above (see 2.1. 1). At this point, the conversion level of the monomers into polybutadiene was 99.9 percent. 53.2 g of polybutadiene were recovered as result of the stripping process.

The polymer contained 90.0 percent cis-1, 4- ; 6.0 percent trans-1,4-, 4.0 percent 1, 2-polybutadiene according to 13C-NMR determination.

The molecular weight of the polymer amounted to 368,000 g/mol and the polydispersity amounted to 5.94. (Mn = 62,000 ; Mz = 1,228, 000). The Mooney value amounts to 27. 1.

B) Polymerization of 1,3-butadiene using metal complex 1, MMAO-3a, ethylaluminum sesquichloride and 1,2, 4-trimethoxybenzene (Run 2) The experiment was carried out according to the general polymerization procedure described above (2.1. 1). The polymerization was carried out in a polymerization solvent containing 505.9 g of cyclohexane. Thus 402.7 g of cyclohexane, 50.1 g (0.9 mol) of 1,3-butadiene monomer, MMAO-3a (1.7 g of a heptane solution containing 4.3 mmol of MMAO), 0.248 g (1.47 mmol) of 1,2, 4-trimethoxybenzene and 0.5 g (0.2 mmol) of ethylaluminum sesquichloride were added into the polymerization reactor. 103.2 g of cyclohexane, 3.5 g (0.06 mol) of 1,3-butadiene monomer, 6.3 g of a heptane solution containing 16.3 mmol of MMAO and 2.0 g (0.8 mmol) of ethylaluminum sesquichloride were stirred for one hour and three minutes and subsequently mixed with 156 mg (0.264 mmol) of the metal complex 1 in a separate reaction vessel and stirred for 10 minutes.

Afterwards the resulting mixture was transferred into the polymerization reactor to start the polymerization reaction.

After one hour and fourteen minutes the polymerization reaction was terminated as described above (see 2.1. 1). At this point, the conversion level of the monomers into polybutadiene was 67.2 percent. 36.0 g of polybutadiene were recovered as result of the stripping process.

The polymer contained 82.0 percent cis-1, 4- ; 10.0 percent trans-1,4-, 8.0 percent 1, 2-polybutadiene according to 13C-NMR determination.

The molecular weight of the polymer amounted to 63,000 g/mol and the polydispersity amounted to 2.1. (Mn = 30,000 ; Mz = 113,000).

C) Polymerization of 1,3-butadiene using metal complex 1, MMAO-3a, ethylaluminum sesquichloride and 1,2, 4-trimethoxybenzene (Run 10) The experiment was carried out according to the general polymerization procedure described above (2.1. 1). The polymerization was carried out in a polymerization solvent containing 3814 g of cyclohexane and 1000 g of toluene. Thus 3814 g of cyclohexane, 1000 g of toluene, 537.4 g (9. 9 mol) of 1,3-butadiene monomer, MMAO-3a (8. 0 g of a heptane solution containing 20.5 mmol of MMAO), 1.24 g (7.35 mmol) of 1,2, 4-trimethoxybenzene and 2.5 g (17.2 mmol) of ethylaluminum sesquichloride were added into the polymerization reactor. 180 g of toluene, 4.0 g (0.07 mol) of 1,3-butadiene monomer, 31.0 g of a heptane solution containing 79.5 mmol of MMAO and 10.0 g (87.8 mmol) of ethylaluminum sesquichloride were stirred for one hour and subsequently mixed with 780 mg (1.320 mmol) of the metal complex 1 in a separate reaction vessel and stirred for 5 minutes.

Afterwards the resulting mixture was transferred into the polymerization reactor to start the polymerization reaction.

After one hour and two minutes the polymerization reaction was terminated as described above (see 2.1. 1). At this point, the conversion level of the monomers into polybutadiene was 87.5 percent. 473.9 g of polybutadiene were recovered as result of the stripping process.

3.1. 2 Polymerization of 1,3-butadiene according to polymerization method 2 Polymerization of 1,3-butadiene using metal complex 1, MMAO-3a, ethylaluminum sesquichloride and 1,2, 4-trimethoxybenzene (Run 3) The experiment was carried out according to the general polymerization procedure described above (2.1. 2). The polymerization was carried out in a polymerization solvent containing 5002 g of toluene. Thus 5002 g of toluene, 542 g (10.0 mot) of

1,3-butadiene monomer, MMAO-3a (78.7 g of a heptane solution containing 200.1 mmol of MMAO), 2.48 g (14.7 mmol) of 1,2, 4-trimethoxybenzene and 24.56 g (9.94 mmol) of ethylaluminum sesquichloride were added into the polymerization reactor.

The mixture was stirred for one hour. Subsequently 115 mg (2.26 mmol) of the cobalt complex 1 were added into the polymerization reactor to start the polymerization reaction.

After one hour the conversion level of the monomers into polybutadiene was 73.8 percent (400.1 g). After two hours and 10 minutes the polymerization reaction was terminated as described above (see 2.1. 1). 356.6 g of polybutadiene were recovered as result of the stripping process.

The polymer contained 91.0 percent cis-1, 4- ; 6.0 percent trans-1, 4-, 3.0 percent 1, 2-polybutadiene according to 13C-NMR determination. The molecular weight of the polymer amounted to 302,000 g/mol and the polydispersity amounted to 2.77.

(Mn = 109,000 ; Mz= 649,000).

The Mooney value amounted to 35.0.

3.1. 3 Copolymerization of 1,4-butadiene and styrene 3.1. 3.1 Copolymerization of 1, 4-butadiene and styrene using metal complex 1, MMAO-3a, and 1,2, 4-trimethoxybenzene and ethylaluminum sesquichloride (Run 4) The experiment was carried out according to the general polymerization procedure described above (2.1. 1). The polymerization was carried out in a polymerization solvent containing 510.9 g of cyclohexane. Thus 403.7 g of cyclohexane, 27.0 g (0. 5 mol) of 1,3-butadiene monomer, MMAO-3a (11.8 g of a heptane solution containing 30.0 mmol of MMAO), 26.0 g (0.25 mol) of styrene monomer, 0. 248 g (1.47 mmol) of 1,2, 4-trimethoxybenzene and 1.56 g (6.3 mmol) of ethylaluminum sesquichloride were added into the polymerization reactor. 107.2 g of cyclohexane, 4.0 g (0.07 mol) of 1,3-butadiene monomer, and 0.57 g (2.3 mmol) of ethylaluminum sesquichloride were stirred for one hour and subsequently mixed with 470 mg (0.798 mmol) of the cobalt complex 1 in a separate reaction vessel and stirred for 15 minutes.

Afterwards the resulting mixture was transiened into the @@@. start the copolymerization reaction.

After one hour and 15 minutes the copolymerization reaction was terminated as described above (see 2.1. 1). At this point, the conversion level of the monomers into polymer was 34.0 percent. 19.4 g of polymer were recovered as result of the stripping process.

The polymer contained 1.5 percent styrene (50 percent of the styrene content were detected to be polystyrene blocks). The polybutadiene part of the copolymer contained 88.5 percent cis-1, 4- ; 6.5 percent trans-1,4-, 3.5 percent 1,2- polybutadiene according to 13C-NMR determination.

The molecular weight of the polymer amounted to 76,000 g/mol and the polydispersity amounted to 13.0. (Mn = 6,000 ; Mz = 357,000).

3.1. 4 Comparative Examples A) Polymerization of 1,3-butadiene using complex 1 and MMAO-3a (Run 5; Comparative Example) The experiment was carried out according to the general polymerization procedure described above (2.1. 1). The polymerization was carried out in 500 g of cyclohexane solvent. Thus 409 g of cyclohexane, 50.0 g (0.92 mol) of 1,3- butadiene monomer and MMAO-3a (9.0 g of a heptane solution containing 23.1 mmol of MMAO) were added into the polymerization reactor. 91 g of cyclohexane, 4.0 g (0.07 mol) of 1,3-butadiene monomer and 2.7 g of a heptane solution containing 6.9 mmol of MMAO were mixed with 470 mg (0.80 mmol) of the metal complex 1 in a separate reaction vessel and stirred for 10 minutes.

Afterwards the resulting mixture was transferred into the polymerization reactor to start the polymerization reaction.

After one hour the polymerization reaction was terminated as described above (see 2.1. 1). At this point, the conversion level of the monomers into polybutadiene was 41.8 percent. 21.2 g of polybutadiene were recovered as result of the stripping process.

The polymer contained 97.0 percent cis-1, 4- ; 1. 5 percent trans-1,4-, 1.5 percent 1, 2-polybutadiene according to 13C-NMR determination The molecular weight of the polymer amounted to 123,000 g/mol and the polydispersity amounted to 6.25. (Mn = 20,000 ; Mz = 210,000).

B) Polymerization using metal complex 1, MMAO-3a and ethylaluminum sesquichloride (Run 6, Comparative Example) The experiment was carried out according to the general polymerization procedure described above (2.1. 1). The polymerization was carried out in a polymerization solvent containing 381 g of cyclohexane and 118 g of toluene. Thus 331 g of cyclohexane, 87 g of toluene, 50.2 g (0.93 mol) of 1,3-butadiene monomer, MMAO- 3a (1.6 g of a heptane solution containing 4.1 mmol of MMAO) and 0.5 g (0.2 mmol) of ethylaluminum sesquichloride were added into the polymerization reactor.

50 g of cyclohexane, 31 g of toluene, 3.5 g (0.06 mol) of 1,3-butadiene monomer, 6.2 g of a heptane solution containing 16.1 mmol of MMAO and 2.0 g (0.8 mmol) of ethylaluminum sesquichloride were stirred for 65 minutes and subsequently mixed with 156 mg (0.264 mmol) of the metal complex 1 in a separate reaction vessel and stirred for 10 minutes.

Afterwards the resulting mixture was transferred into the polymerization reactor to start the polymerization reaction.

After one hour and five minutes the polymerization reaction was terminated as described above (see 2.1. 1). At this point, the conversion level of the monomers into polybutadiene was 87.3 percent. 46.9 g of polybutadiene were recovered as result of the stripping process.

The polymer contained 93.5 percent cis-1, 4- ; 3.5 percent trans-1,4-, 3.0 percent 1, 2-polybutadiene according to 13C-NMR determination The molecular weight of the polymer amounted to 378,000 g/mol and the polydispersity amounted to 4.85. (Mn = 78,000 ; Mz = 1,114, 000). The Mooney value amounts to 32.7.

C) Polymerization using metal complex 1, MMAO-3a and ethylaluminum sesquichloride (Run 7; Comparative Example)

The experiment was carried out according to the general polymerization procedure described above (2.1. 1). The polymerization was carried out in a polymerization solvent containing 571.9 g of cyclohexane. Thus 462.1 g of cyclohexane, 51.2 g (0.95 mol) of 1,3-butadiene monomer, MMAO-3a (46.8 g of a heptane solution containing 120 mmol of MMAO) and 3. 12 g (12.6 mmol) ethylaluminum sesquichloride were added into the polymerization reactor. Using ethylene gas the pressure inside of the polymerization reactor was adjusted to seven bar. 109.8 g of cyclohexane, 3.0 g (0.06 mol) of 1,3-butadiene monomer and 2.0 g (0.8 mmol) of ethylaluminum sesquichloride were stirred for one hour and subsequently mixed with 470 mg (0.798 mmol) of the metal complex 1 in a separate reaction vessel and stirred for 10 minutes.

Afterwards the resulting mixture was transferred into the polymerization reactor to start the polymerization reaction. Subsequently the pressure in the polymerization reactor was adjusted to 9.3 bar using ethylene gas.

After one hour and 30 minutes the polymerization reaction was terminated as described above (see 2.1. 1). At this point, the conversion level of the monomers into polybutadiene was 95.0 percent. 51.5 g of polybutadiene were recovered as result of the stripping process.

The polymer contained 91.5 percent cis-1, 4- ; 5.5 percent trans-1,4-, 3.0 percent 1, 2-polybutadiene according to 13C-NMR determination.

The molecular weight of the polymer amounted to 18,000 g/mol and the polydispersity amounted to 2.25. (Mn = 8,000 ; Mz = 31,000).

D) Polymerization using metal complex 1, MMAO-3a and trimethyl (chloro) silane (Run 8; Comparative Example) The experiment was carried out according to the general polymerization procedure described above (2.1. 1). The polymerization was carried out in a polymerization solvent containing 372.9 g of toluene. Thus 298.9 g of toluene, 51.1 g (0.94 mol) of 1,3-butadiene monomer were added into the polymerization reactor. 74.0 g of toluene, 4.3 g (0.07 mol) of 1,3-butadiene monomer, MMAO-3a (13.9 g of a heptane solution containing 35.3 mmol of MMAO) and 2.08 g (0.019 mmol) of

trimethyl (chloro) silane were stirred for 10 minutes and subsequently mixed with 119 mg (0.201 mmol) of the metal complex 1 in a separate reaction vessel and stirred for 4 minutes.

Afterwards the resulting mixture was transferred into the polymerization reactor to start the polymerization reaction.

After two hours and 18 minutes the polymerization reaction was terminated as described above (see 2.1. 1). At this point, the conversion level of the monomers into polybutadiene was 23.5 percent. 13.0 g of polybutadiene were recovered as result of the stripping process.

The polymer contained 93.0 percent cis-1, 4- ; 4.0 percent trans-1,4-, 3.0 percent 1, 2-polybutadiene according to 13C-NMR determination.

The molecular weight of the polymer amounted to 86,000 g/mol and the polydispersity amounted to 4.41. (Mn = 19,500 ; Mz = 645,000).

E) Polymerization using cobalt complex 1, MMAO-3a and tert.-butylchloride (Run 9; Comparative Example) The experiment was carried out according to the general polymerization procedure described above (2. 1. 2). The polymerization was carried out in a polymerization solvent containing 504 g of cyclohexane. Thus 504 g of toluene, 54.6 g (1.01 mol) of 1,3-butadiene monomer, MMAO-3a (11.9 g of a heptane solution containing 30.3 mmol of MMAO) and 2.2 g (24 mmol) of tert.-butylchloride were added into the polymerization reactor. The mixture was stirred for 13 minutes. Subsequently 115 mg (0.20 mmol) of the metal complex 1 were added into the polymerization reactor to start the polymerization reaction.

After two hours and 19 minutes the polymerization reaction was terminated as described above (see 2.1. 1). At this point, the conversion level of the monomers into polybutadiene was 29.5 percent. 16.1 g of polybutadiene were recovered as result of the stripping process.

The polymer contained 25.0 percent cis-1, 4- ; 66.0 percent trans-1,4-, 9.0 percent 1, 2-polybutadiene according to 13C-NMR determination

3.2 Polymerization activity-Comparison Run Activity Run Activity [kg {polymer}/mmol {Co} [hr] ] [kg {polymer}/mmol {Co} [hr] ] 1 0. 64** 6 0. 35** 2 0. 51 ** (0. 82*) 7 0. 18** 3 0.42*** 8 0.11** 4 0. 08** 9 0. 14** 5 0. 12** 10 1. 18** (1.72*) C.... comparative example ; measured after 6 rrnnutes ; measured after 15 minutes; ***..... measured after 20 minutes 3.3 Molecular weight-Comparison Run Mw Mn Mz Run Mw Mn Mz 1 368, 000 62,000 1,228, 000 6 378,000 78,000 1,114, 000 2 63, 000 30,000 113,000 7 18,000 8,000 31, 000 3 302, 000 109,000 649, 000 8 86, 000 19,500 645,000 4 76, 000 6,000 357, 000 9 not not not determ. determ. determ. 5 123, 000 20,000 210,000 3.4 Molecular weight distribution (MWG) & Mooney viscosity-Comparison Run Mw/Mn Mooney Tg in °C Run Mw/Mn Mooney Tg in °C 1 5.94 27.1 not det. 6 4.85 32.7 not det. 2 2. 1 not det. not det, 7 2. 25 not det. not det. 3 2. 77 35. 0 not det. 8 4. 41 not det. not det. 4 13.0 not det. not det. 9 not det. not det. not det. 5 6.25 not det. not det.

3.5 Microstructure-Comparison Run Cis-1, 4- Trans-1, 2- Run Cis-1, 4- Trans-1, 2- PB 1, 4-PB Polymer PB 1, 4-PB Polymer 1 90.0 6.0 4.0 6 93.5 3. 5 3.0 2 82. 0 10. 0 8. 0 7 91. 5 5. 5 3. 0 3 91. 0 6. 0 3. 0 8 93. 0 4. 0 3. 0 4 88.5 6.5 3.5 9 25.0 66.0 9.0 5 97. 0 1. 5 1. 5

PB = Polybutadiene Tg = Glass Transition Temperature An advantage of the invention is a considerably increased catalytic activity of the polymerization reaction. The cobalt based catalysts of the invention demonstrated by the examples give activities two to three times higher than other cobalt carboxylate-based catalysts. The polymerization activity of catalyst modifier containing catalyst systems as defined according to this invention (see Run 1 and Run 2) were compared with catalyst systems lacking the catalyst modifier according to this invention (see Comparative Examples above, especially Run 5-9, paragraph 3.2). For example the combination of cobalt octoate, modified alumoxane (MMAO-3a), ethylaluminum sesquichloride and 1,2, 4- trimethoxybenzene polymerizes 1,3-butadiene in cyclohexane solvent with a polymerization activity as high as 0.64 kg [polybutadiene]/mmol [Co] hr (see Run 1) or with a polymerization activity as high as 1.18 kg [polybutadiene]/mmol [Co] hr (see Run 19). Without 1,2, 4-trimethoxybenzene as catalyst modifier the polymerization activity amounted to 0.18 kg [polybutadiene]/mmol [Co] hr (see comparative example Run 7). The combination of cobalt octoate and modified alumoxane as catalyst led to a polymerization activity of 0.12 kg [polybutadiene]/ mmol [Co] hr (see comparative example Run 5). The same trend is observed when cyclohexane/toluene mixtures were used as polymerization solvent (compare Run 2 and 6).

Also other possible catalyst mixtures such as the combination of cobalt octoate, modified alumoxane (MMAO-3a) and trimethylchlorosilane (Run 8) or t-

butylchloride (Run 9) as chloride ion containing compounds gave lower polymerization activities (0,11 or 0,14 0,12 kg [polybutadiene]/mmol [Co] hr).

A further advantage of the invention is that the catalysts of the invention often do not require a separate aging step (see Run 3) and if it is desirable to employ an optional aging step, it advantageously does not require long aging times.

Therefore, it is possible to start the polymerization reaction just by adding the catalyst components in the desired order into the polymerization reactor. The polymerization can be started for example by addition of the catalyst precursor as the last component (see Runs 10,11 and 12). If an optional aging step is incorporated into the catalyst preparation/polymerization procedure, the aging time is short, such as, but not limited to 10 (see Run 1 and 2) minutes and can be performed under mild conditions such as at 25°C, for example, but not limited to it this, with high catalyst activity. The temperature ranges of the catalyst aging and polymerization are independently selected and are between-50°C and +250°C, preferably between-10 and +120°C, more preferably between 0 °C and 80 °C. For example the catalyst activity of polymerization Run 1 (polymerization temperature 25 °C, aging temperature 25 °C) amounts to 0.64 kg polybutadiene per mmol cobalt per hour. A further advantage of the invention is that aging the catalyst does not require extreme temperatures. It is beneficial that the polymerization reaction can be induced either without any waiting period or delay or without substantial waiting period or delay upon addition of the last catalyst component into the polymerization reactor.

A further advantage of the invention is the possibility to copolymerize conjugated dienes with alpha olefins, preferably aromatic alpha olefins. For example (see Run 4) the copolymerization of 1,3-butadiene and styrene gives a butadiene-styrene copolymer (styrene content 1.5 percent).

A further advantage of the metal catalysts of the invention, which are the result of a defined combination of the metal complex with activator compounds of type 1 and type 2 and with catalyst modifiers is the production of tailor-made polymers. In

particular, the choice of the activators, of the metal complex and of the aromatic catalyst modifier, which is used in stoichiometric or lower amounts compared to the activator of type 1, and also the manner of preparation of catalyst, as well as the solvent used for the polymerization reaction (nonaromatic or aromatic) and the ratio of the solvents (aromatic and nonaromatic) used, the concentration of the diene and the polymerization temperature enable an adjustment of the polymer microstructure (ratio of cis-, trans-and vinyl content) and of the molecular weight of the resulting polydiene using a given cobalt complex.

Another advantage of the invention for diene polymerization reactions is that the manner of preparation of the catalyst (for example order of addition of the catalyst components and catalyst aging) can favorably influence the polymer properties such as the molecular weight.

The catalysts according to the invention can be used for solution polymerization processes and also for gas phase polymerization using the appropriate techniques such as, but not limited to, spray techniques.