TW200413420A - Process for homo-or copolymerization of conjugated dienes and in situ formation of polymer blends and products made thereby - Google Patents

Abstract

Metal complexes are disclosed containing at least one metal-nitrogen or metal-phosphorus bond, more particularly at least one metal-nitrogen or metal-phosphorus bond and at least one bond by the metal to an aromatic ring system. The preparation of the catalyst and the use of the prepared catalyst to produce homopolymers or copolymers of conjugated dienes or copolymers of conjugated dienes with alpha-olefins are also disclosed. In particular, the production of (1) polymer blends of (a) homo-or copolymers of conjugated dienes through polymerization of 1,3-butadiene and/or isoprene with (b) copolymers of conjugated dienes with alpha olefins through copolymerization of 1,3-butadiene or isoprene with ethylene, propene, octene or styrene and (2) polymer blends of (a) homo- or copolymers of conjugated dienes through polymerization of 1,3-butadiene and/or isoprene with (b) homopolymers or copolymers of alpha olefins through homo- or copolymerization of ethylene, propene, octene or styrene in the same reaction system using the catalyst system of the invention is described.

Description

Description of the invention: Statement with reference to reference material This application claims the benefit of US Provisional Application No. 60 / 424,670 (filed on November 7, 2002). [Technical field to which the invention belongs] TECHNICAL FIELD [0001] The present invention relates to a metal complex composition, which is manufactured with a metal complex composition and used to form a catalyst to produce a conjugated diene via a polymerization reaction or a copolymerization reaction of a conjugated diene monomer. Polymers and conjugated dienes with aromatic or non-aromatic "-olefins or copolymers with non-conjugated dienes. BACKGROUND OF THE INVENTION Metal complex catalysts for the manufacture of polymers and copolymers from conjugated diene monomers and aromatic and aliphatic α-dilute hydrocarbon monomers are known. Desirably a polymer having a conjugated diene (such as polybutadiene) and a copolymer of a conjugated diene and an olefin lacking a conjugated double bond (such as a butadiene-ethylene copolymer) And copolymers of conjugated dienes and conjugated dienes and olefins lacking conjugated double bonds (such as 'butadiene-ethylene copolymers') The olefin derivative of the bond is the same as that of the polymer blend of the polymer (such as polyethylene or polypropylene). It is also advantageous to select a catalyst that enables the conjugated diene to react with the olefin-containing monomer. The conjugated bonds produce copolymer reactions in different proportions. Further research: The ground system obtains rubber materials containing a diene concentration that is generally high to ensure typical rubber properties but that can be widely changed (for example, between 40 and 100% conjugated diene content). The molecular weight of the zizidan i with Λκ compound and copolymer or polymer blend, and its decoration and microstructure (such as 4… M · and 1,2, polybutadiene — polybutadiene, human Diene ratio, but not limited to this, and knowledge of the distribution of co-early bodies in the polymer molecule (4 in the control device > 'ϋ, ethylene in the butadiene-ethylene copolymer) The polymer system is important. Although several patents describe some of the characteristics of polydienes and their surnames M, few deliberate efforts have been made to modify the microstructure of polybutadiene or polybutadiene containing ethylene. In: Dioxins are used to obtain polymers with different properties or to obtain polymer polymers of butadiene-ethylene copolymers obtained during the polymerization reaction of polybutadiene, σ-based catalysts. Instead, it is necessary to make the polymerization method occur under reasonable processing conditions (such as 40 ° C, 日 日 山, temperature between 1U0C) to avoid moving the spear from the polymerization reactor, inherent heat or a large amount of heating to A catalyst to save production costs. In addition, 'to have a catalyst component that can be directly injected into the polymerization reactor and the catalyst or catalyst component needs to be aged, (aged, broadcasted or stored) for a long time. Especially for the solution polymerization method Or continuous polymerization, the liquid or dissolved catalyst or catalyst component is more suitable to be added to the reaction container in an appropriate dose. [Summary of the invention] Summary of the invention The present invention relates to a method containing at least -metal or metal bonds. Metal complexes, and more particularly, the present invention relates to compounds containing at least -metal 200413420

-Nitrogen or metal-phosphorus bonding and at least one metal complex compound bonded to the aromatic ring system through metal bonding, and the manufacture of catalysts and the use of the prepared catalysts to produce a total of two dilute homopolymers or Copolymers, or copolymers of diene and olefins, preferably via polymerization of 1,3-butadiene or isoprene5 or via 1,3-butadiene and isoprene Copolymerization reaction or via 1,3-butadiene or isoprene copolymerization reaction with ethylene, propylene or styrene, but is not limited thereto, or use the same reaction system and use the catalyst system 1) Manufacturing a) Iso-or co-polymers of conjugated diene via polymerization of 1,3-butadiene and / or isoprene and b) via 1,3-butadiene or isoprene 10 Polymer blends of copolymers of conjugated dilute and alpha-dilute hydrocarbons in copolymerization of m-diene with ethylene, propylene, octene or styrene, or 2) manufacture a) via 1,3-butane Iso- or co-polymer of conjugated diene polymerization of olefins and / or isoprene and b) α-diluted by iso- or co-polymerization of ethylene, propylene, octene or styrene The homopolymers or copolymers of the same polymer blend. 15 More specifically, the present invention relates to a metal-nitrogen or metal-

Bonds and at least one metal complex complex bonded to an aromatic ring system through a metal; catalysts prepared therefrom, catalyst manufacture and the use of the catalysts produced to produce 1,3-butadiene are the same The polymer is produced either through the copolymerization of 1,3-butadiene with ethylene or propylene, or it is produced using the catalyst of the present invention in the same reaction system and 20) 1) via the polymerization of a) 1,3-butadiene Reactions and b) Polymer blends of copolymerization of 1,3-butadiene with ethylene, propylene, or octene, or production 2) Polymerization via a) 1,3-butadiene and b) ethylene , Propylene or a dilute polymer blend with the same polymerization reaction. Additive polymerization 8 200413420 monomer for polymerizing conjugated ethylenically unsaturated polymers according to the present invention, which is a phase complex 3, 4, 5 or 6 group of sodium #, $ lanthyl and fluorene metal complexes , Which corresponds to the chemical formula ...

(I) Chemical formula I: Among them, '10 15 Μ is a metal of group 3, 4, 5, 6 or lanthanum group, preferably a metal compound such as group, and more preferably titanium, copper, bell, or star, and more preferably It is Qin, Wrong or Gong, and more preferably Wrong or Giving, its fine, bonding mode is bonded to cyclopentadienyl; R ,, R "and R ,, in each case are individually hydrogen or have 丨Up to 80 atoms (not counting hydrogen) is a radical, i.e., nicotinyl, nicotinyl, nicotine substituted with dentate, silk substituted with fluorenyloxy, and nicotyl substituted with fluorenyl, Or substituted by hydrocarbyl weiss, nicotinylamino or hydrocarbyloxy, and mixtures thereof, having up to 20 carbon or silicon atoms, or optionally 'adjacent R' and / or adjacent R ',' groups are bonded together to form a divalent derivative, that is, one of these substituents can be bonded together; T-based nitrogen or phosphorus 'preferred nitrogen; E-based or silicon' Jia Shi Xi; x Yu per case is halo, prostitute, aryl, and aryl oxy, up to 10 carbons; 20 m is 1 or 2; η is 1 or 2 (depending on the valence of M) Depends); 9 200413420 LB is a selective Lewis base And b is a number from 0 to 2. It should be noted that the complex can exist as a dimer or a higher agglomerate. Further according to the present invention, a conjugated ethylene unsaturated unsaturated addition-polymerizable 5 monomer is provided. The catalyst for the polymerization reaction comprises: 1) a mixture of one or more of the above metal complexes and one or more activators (co-catalysts) and optional supports (support materials), or 2) by a Or a reaction product formed by contacting one or more of the above metal complexes with one or more activators and selective supports, or 10) 3) by making one or more of the above metal complexes and selectivity The product formed by the support receiving activation technology. The present invention also provides a method for manufacturing a catalyst for the polymerization reaction of ethylene unsaturated addition polymerizable monomers, comprising dissolving one or more of the above metals Contact with one or more active agents and selective supports, or subject one or more of the above metal complexes and selective supports to activation technology. The present invention also provides a conjugated diene A method of polymerization or copolymerization, comprising Totally ethylenically unsaturated addition-polymerizable 20 monomers that are selectively present in one or more of the inert, aliphatic, cycloaliphatic, or cyclic or aromatic hydrocarbons are in contact with the catalyst under polymerization conditions This catalyst comprises: 1) a mixture of at least one metal complex according to formula I) and one or more activator compounds and selective catalyst supports, or 2) by at least one metal according to formula I) A reaction product formed by contacting a complex with one or more activator compounds and selective supports, 10 3) by bringing at least one metal complex and The building body is formed by the activation technology. Polymerization can be carried out under solution, suspension, cruise or gas phase treatment conditions, and the silk agent or its individual components can be treated as heterogeneous (i.e., 'supported') ) 'Or used in a homogeneous state. The catalyst may be combined with-or more additional catalysts of the same or different nature and in the same: Simultaneously in the reactor and / or sequentially in individual reactors. The catalyst may be formed in situ in the presence or prior to the addition of a reaction mixture containing-or more ethylene unsaturated addition polymerizable monomers. Furthermore, the present invention relates to a metal complex composition, which is manufactured and used to form 1) a) a diene polymer and b) to produce a) through polymerization of a co-light diene monomer. Copolymer diene with an aromatic or non-aromatic α _ dilute twist or with a non-copolymer lightly thin copolymer I compound exchange, or 2) produces a) via a conjugated diene monomer Catalyst for polymer blends of conjugated diene polymers and b) polymers of ethylene unsaturated olefins. Further according to the present invention, there are provided polymers and copolymers, and a method for forming the same, comprising more than one conjugated ethylene unsaturated addition-polymerizable monomer, and one or more conjugated ethylene unsaturated addition-polymerizable monomers. Monomers and ethylene monounsaturated addition polymerizable monomers (especially non-aromatic ethylene monounsaturated addition polymerizable monomers, but also includes aromatic vinyl monounsaturated addition polymerizable monomers, such as benzene Ethylene), combined hydrate. This method is used for homopolymerization or copolymerization of conjugated diene, or a polymer or copolymer or conjugated diene and ethylene and conjugated diene formed in situ in 200413420. / Or a copolymer of α-dilute hydrocarbons. Further according to the present invention, a) providing a) a homopolymer or copolymer consisting of one or more co-ethylenically unsaturated addition-polymerizable monomers and a package- or more co-ethylene Unsaturated addition polymerizable monomers and one or more 5 ethylene monounsaturated addition polymerizable monomers (especially non-aromatic ethylene ^ unsaturated unsaturated addition polymerizable monomers, or aromatic ethylenically unsaturated monomers) Polymer blends of copolymers of saturated additive monomers. In a preferred embodiment, these two methods are used for homopolymerization or copolymerization of two dilute copolymers, or homopolymers or copolymers that form ^ conjugated diene in situ and b) contain one or more copolymers. Polymer blends of conjugated diene and copolymers of 10 ethylene and / or olefins, especially where the homopolymer or copolymer is produced during a polymerization reaction in one of a reaction system. The diene / ethylene or α-olefin copolymer or the diene / ethylene or α-olefin copolymer portion of the polymer blend may be a random or block copolymer, and the random copolymer is relatively good. The copolymer or copolymer blend may preferably contain discrete or pseudo-randomly dispersed units of aromatic 15 aromatic olefins. Further according to the present invention, there is provided a) a homopolymer or copolymer composed of one or more ethylenically unsaturated addition polymerizable monomers and ^ ethylene-containing monosaturated addition polymerizable monomers (especially non- Aromatic ethylene mono- and addition polymerizable monomers, or polymer blends of homopolymers or copolymers of aromatic ethylene mono-unsaturated addition polymerizable monomers, including ethylene mono-unsaturated polymer The diene content of the homopolymer or copolymer of the addition polymerized monomer is less than 5 mole%. #Polymerb) preferably contains acetamidine and / or α • dilute ammonium, and the total diene content in the homopolymer or copolymer is preferably less than 5 mole%, especially among the homopolymers. Or the copolymer is produced in a reaction system during a polymerization reaction.

Further according to the present invention, there is provided a homopolymer or copolymer for forming a) comprising one or more conjugated ethylene unsaturated addition polymerizable monomers and b) comprising i) one or more conjugated ethylene Unsaturated addition polymerizable monomers and ii) 5 one or more ethylene monounsaturated addition polymerizable monomers (especially non-aromatic ethylene monounsaturated addition polymerizable monomers, or aromatic ethylene monounsaturated polymerizable monomers) The method for saturating polymer blends of copolymers of addition polymerizable monomers) is selective in situ. Further according to the present invention, there is provided a homopolymer or copolymer for forming a) containing one or more conjugated ethylene unsaturated addition polymerizable monomers and b) containing ethylene mono unsaturated addition polymerizable monomers Polymer blends of homopolymers or copolymers (especially non-aromatic ethylene monounsaturation addition polymerizable monomers, or aromatic vinyl monounsaturation addition polymerizable monomers), preferably In situ, the dilute content of the same 15 polymer or copolymer containing ethylene monounsaturated addition polymerizable monomer is less than 5 moles / °.

Catalysts for the polymerization of conjugated ethylene unsaturated addition polymerizable monomers are also provided according to the present invention, which have good catalytic properties and are particularly useful for the polymerization of conjugated diene. In addition, this complex is compatible with and mixed with alkyl aluminum compounds that can be used to remove monomer impurities and have no adverse effects on catalytic properties. The polymers of the invention can be used to produce many useful shaped articles, molded parts, films, foams, golf balls, tires, hoses, conveyor belts and other tapes, gaskets, seals, shoes, and used in plastics Modifications, such as high-impact polystyrene (HIPS) or polypropylene. 13 200413420 Brief description of the figure Figure 1 shows the GC / MS spectrum of the product identified after pyrolysis of the polymer. Figure 2 shows the RI chromatogram of the polymer 5 produced in Experiment 3.3.A) in THF solvent, showing the two separated polymer fractions. Figure 3 shows the RI chromatogram of a polymer made according to experiment 3.3.A) in toluene, showing the two separated polymer fractions. Figure 4 shows the RI chromatogram of the polymer produced according to Experiment 3.3.A), which was separated by SEC, resulting in a peak of the dipolymer. 10 Fig. 5 shows a 1H NMR spectrum of a high molecular weight portion of a polymer produced according to Experiment 3 · 3 · A). Figure 6 shows the 13C NMR spectrum of the high molecular weight portion of the polymer made according to Experiment 3.3.A). Figure 7 shows the 1HNMR spectrum of 15 parts of the low molecular weight portion of the polymer produced according to Experiment 3.3.A). Figure 8 shows the 13C NMR spectrum of the low molecular weight portion of the polymer made according to Experiment 3.3.A). Figure 9 shows the RI chromatogram of a polymer made according to Experiment 3.3.B) in toluene, showing essentially a polymer portion. 20 Figure 10 shows the RI chromatogram of a polymer made according to Experiment 3.3.D), showing a low molecular weight polymer peak with a polymer molecular weight of 3,500 g / mol. I: Embodiment 3 Detailed description of the present invention All those concerning the 7L prime periodic table of 14 5 shall refer to CRC Press ^ and own the copyright of the periodic table of elements. Moreover, any number of families is related to the number of families reflected in the periodic table. According to the present invention, the metal coordination complex of the above formula I is provided. The complex coordination complex of the formula I can be prepared by the following steps:

A) In an inert solvent, make the metal compound or basin complex adduct of the chemical formula MXn + 2 correspond to the chemical formula; ^ (II) (L) y (Cp *-(ER "WTR ,,)-2

10 or an anion salt compound of formula III (III) ((LXn) + x) y (Cp * gas ER, "m"), wherein,

L is a metal of group 1 or 2 of the periodic table, 15 Cp is a cyclopentadienyl or substituted ring C5H, 4 of the chemical formula ϊ—Noryl XH is a fluorine, gas, desert, or e, χ and y 1 or 2 'and the product of x & y is equal to 2, and R, R, R,' ', T, n, E, M, m, R. and X are as defined above; 2B) optionally borrow Oxidation of the metal to a higher oxidation state by contacting the reaction product of step A) with a non-drying oxidant; Lice 15 200413420 C) Selectively isolate this product. The metal coordination complex of the present invention is used as a catalyst for addition polymerization with an activated cocatalyst. The use of a catalyst can provide a polymer or copolymer of a conjugated diene, or a copolymer of ethylene and / or α-olefin, or i) a) a homopolymer or copolymer of a diene. With b) a polymer blend comprising one or more conjugated diene and a copolymer of ethylene and / or alpha-olefin, or 2) a) a homopolymer or blend of conjugated diene with b ) A polymer blend comprising a homopolymer or copolymer of ethylene and / or an α-olefin, wherein the content of the conjugated diene in the same 10 polymer or copolymer including ethylene and / or an α-olefin is Less than 5 mol%, especially where the polymer is produced during a polymerization reaction in a reaction system. "Polymers are manufactured during a polymerization reaction in a reaction system. The term refers to the homopolymers or copolymers of components 1) a) and 2) a) of conjugated dienes that make up a polymer blend. And 1) b) copolymers and 2) b) homopolymers or copolymers comprising ethylene are used in the same reaction system (which comprises one or more individual reactors in series or parallel) using the catalyst of the present invention Manufacturing. Further use of catalysts can provide conjugated diene olefins or one or more conjugated diene monomers and "-olefins (especially ethylene) and vinylidene aromatic monomers, hindered aliphatic vinylidene Pseudorandom 20 copolymers based on monomers or mixtures thereof. As described by uranium, the complexes according to the present invention preferably comprise a catalytic activity that has a change or promotion at the metal position when the complex is combined with a cocatalyst. In this regard, the R substituent of the electron donor has been selectively found to improve the catalytic properties of the wrong cough. 16 200413420 Bad pentadienyl c #, 4 contains cyclopentadienyl, indenyl, and fluorenyl , Benzoyl, s-benzodiindenyl, fluorenyl-dimethylfluorenyl, and cyclopentafluorene Groups, and one or more individually selected R, substituted substituents and their substituted derivatives. Examples of the above-mentioned preferred metal coordination complexes include R on amino groups 5 or R, , Is fluorenyl, ethyl, propyl, butyl, fluorenyl, hexyl, (including isomers), norbornyl, benzyl, phenyl, or tolyl; R ,,, Chlorine, methyl, ethyl, propyl, butyl, fluorenyl, hexyl, (including isomers), norbornyl, benzyl, phenyl, methoxy, ethoxyisopropoxy, and Tributoxy, dimethylamino, oxo, or mono R, groups are bonded together to form a divalent tri-, tetra-, 5-, or penta-methyl; cyclopentadienyl R on the alkenyl group is hydrogen, methyl, ethyl, propyl, butyl, fluorenyl, and hexyl, (including ^ 冓 compounds) p-bornyl, benzyl, phenyl, Methoxy, ethoxy, isopropoxy, tertiary butoxy, dimethylamino, pyrrolidinyl, piperidine, 15 morpholinyl, Liwenkou 2, Saccharine. Manganese; and X-based gas, bromine, iodine, , Ethyl, propylbutyl, pentyl, hexyl, (including isomers), norbornyl, phenylbenzyl, dimethylsilylmethyl or bis (trimethylsilyl) fluorenyl compounds 20 The metal complex of the present invention represented by the aforementioned chemical formula may optionally exist as a coordination complex of a Lewis base adduct, and is preferably a neutral Lewis base adduct, and therefore, selectively Contains a Lewis base ligand, LB. The term "Lewis base ligand" refers to a group having sufficient nucleophilicity that can form a coordinate bond with a Mon atom of the metal complex of the present invention. In order not to miss this temple base, rabbit, that is, the neutral Lewis base ligand, or /, er Ho. With electricity 17 200413420 Dutch Lewis base ligand is an anionic group, which has enough The nucleophilicity can form a coordination bond with the metal atom of the metal complex of the present invention, thereby imparting a negative charge to the complex. Preferred charged Lewis base ligands include chloride, bromide, iodide, fluorenyloxy, ethoxyl, fluorenyl, ethyl, 5trimethylsilylmethyl, and acetamylpyruvate , Especially the chloride. Of course, a mega charge can also be present, which can be implemented, for example, by bell, nano, magnesium, calcium, aluminum, ammonium, or scale cations, preferably lithium, magnesium, aluminum, or ammonium. Alternatively, a positively-charged counter-ion can be bound to a charged Lewis base ligand. The term "neutral Lewis base ligand" means an uncharged group having sufficient nucleophilicity to form a coordination bond with a metal atom of the metal complex of the present invention. Preferred neutral Lewis ligands, LB, are carbon monoxide, ether, thioether, polyether, amine, polyamine, phosphine, phosphite, polyphosphine, alcohol, amidine, imine, ketone, aldehyde, Nitriles, esters, olefins and co-diene. Examples of preferred Lewis ligands include, but are not limited to, THF, DME, tris 15 fluorenylamine, TMEDA, or Et20. Exemplary, but non-limiting, metal complexes according to the present invention include the following zirconium and hafnium dichloride complexes: (third butyl fluorenylamino) dimethyl (tetramethyl 15-cyclopentanedifluorene) (Silyl) sulfanilium dichloride; 20 (benzylfluorenylamino) dimethyl- (tetrafluorenyl-7? 5-cyclopentafluorenyl) silylfluorene digas; (2-methoxyphenyl Fluorenyl) difluorenyl- (tetrafluorenyl-7? 5-cyclopentafluorenyl) silyl sulfonium dichloride; ((2,6-bis (1-fluorenylethyl) phenyl) fluorenyl ) Difluorenyl- (tetramethyl-η5-ring 18 200413420 pentanefluorenyl) silane dichloride; (4-methoxyphenylamidino) dimethyl · (tetramethyl-5-cyclo (Pentafluorenyl) silane zirconium dichloride; (4-methylphenylfluorenylamino) dimethyl- (tetramethyl-77 5-cyclopentafluorenyl) silane 5 zirconium dichloride; (cyclohexyl Fluorenylamino) difluorenyl- (tetrafluorenyl 1 5-cyclopentafluorenyl) silyl sulfonium dichloride; (fluorenyldi-butylamino) dimethyl- (5-badfluorinyl) Calcined and burned compound; 10 (fluorenilidine) dimethyl- (tetramethyl-7? 5-cyclopentanefluorenyl) -silane sulfonium dichloride; (methylsulfonylamino) Dimethyl- (tetramethyl-77 5-cyclopentafluorenyl) silyl dichloride; (third-butylamidino) dimethyl (1-indenyl) silanyl dichloride; 15 (Third-butylamidinoamino) dimethyl (pyridyl) silyl zirconium digas; (third-butylamidino) dimethyl (2-dimethylamino-1-benzyl) Silane zirconium digas; (tertiary-butylphosphoniumamino) dimethyl (3-difluorenylamino-1-indenyl) silane zirconium dichloride; 20 (tertiary-butylphosphoniumamine) Dimethyl (2-pyrrolidin-1-benzyl) silane zirconium digas; (third-butylamidinyl) dimethyl (3-.pyrrolidine-1-indenyl) silane Digas 19 200413420 compounds; (Third-butylamidino) dimethyl (2-piperidinyl-1-indenyl) silane sulfonium dichloride; (Third-butylamidino) dimethyl (3-piperidinyl-1-indenyl) silylphosphonium dichloride; (third-butylphosphoniumamino) dimethyl (2-isoindolinyl-1-benzyl) silyl zirconium dichloride Chloride; (Third-butylphosphoniumamino) dimethyl (3-isoindolinyl-1-indenyl) silylphosphonium dichloride; 10 (Third-butylphosphoniumamino) dimethyl (2-Methoxy-l-zyl) Broken misfired digas; (tertiary-butyl acid amine) dimethyl (3-methoxy-l-Sp group) Methyl (tetramethyl-T / 5-cyclopentadienyl) silane 15 to dichloride; (benzylamidinyl) dimethyl_ (tetrafluorenyl-77 cyclopentadienyl) silane Digassing; (2-Methoxyphenylfluorenylamino) dimethyl- (tetrafluorenyl-7? 5-cyclopentafluorenyl) silylsulfonium dichloride; 20 ((2,6-bis ( 1-fluorenylethyl) phenyl) fluorenylamino) difluorenyl- (tetrafluorenyl-7? 5-cyclopentadidonyl) -crumb burned fluorene dichloride; (4-fluorenylphenylfluorene) Amine) dimethyl- (tetramethyl-7? 5-cyclopentanefluorenyl) silicon 20 200413420 Burned to dichloride; (4-methylphenylphosphonium amine) dimethyl- (tetramethyl -7? 5-Cyclopentylfluorenyl) silazine dichloride; (cyclohexylfluorenylamino) difluorenyl- (tetramethyl-7? 5-cyclopentylfluorenyl) silanyldi-5 chloride; (Third-butylamidino) dimethyl- (7 ?, cyclopentafluorenyl) silane-fluorenyl dichloride; (fluorenilidine) difluorenyl- (tetrafluorenyl 5-cyclopentanedi) Fluorenyl) -silane sulfonium dichloride; 10 (methyl fluorenyl ) Difluorenyl- (tetramethyl-7? 5-cyclopentafluorenyl) silyl sulfonium dichloride; (third-butylfluorenylamino) dimethyl (1-indenyl) silyl fluorenyl dichloride Compounds; (Third-butylamidinoamino) dimethyl (pyridyl) silanesulfonyl dichloride; (Third-butylamidinoamino) dimethyl (32-diamidinoamino-1-indenyl) ) Silane 15 dichloride; (Second-butyl donkey amine) Difluorenyl (3-dimethylamino-l-Sp group) cleavage to dichloride; Amino group) dimethyl (2- ° slightly alkynyl-l-πρ) group to the dichloride; 20 (third-butylamido) dimethyl (3-pyrrolidinyl-1- Indenyl) silyl sulfonium dichloride; (third-butylfluorenylamino) dimethyl (2-piperidinyl-1-indenyl) silanyl fluorinated 21 200413420; and (third-butyl Fluorenylamino) bisfluorenyl (3-piperidinyl-1-indenyl) silane hydrazone; and (third-butylfluorinylamino) dimethyl (2-isoindolinyl-1- Indenyl) silazine di-5 chloride; (third-butylphosphoniumamino) dimethyl (3-isoindolinyl-1-indenyl) silylphosphonium dichloride; (third-butylphosphonium dichloride) Amine group) Base) silane sulfonium dichloride; 10 (third-butyl fluorenylamino) difluorenyl (3- methoxy-1-indenyl) silane sulfonium dichloride; those skilled in the art understand the previous list The additional members will include their corresponding Louis test additions. The catalyst composition is obtained by 1) contacting one or more of the above metal complexes 15 with one or more activators and selective supports, or 2) bringing one or more of the above metal complexes Accept activation technology (selective presence in etiquette) to make the metal complexes catalytically active in the process. The method of activating the metal complex with an activator or co-catalyst or by activation techniques can be carried out during individual reaction steps, optionally including isolating compounds with an activity of 20, or preferably in situ in a polymerization reactor Or, for example, before it is carried out in the aging reactor. If isolation and / or purification of the activated complex after activation of the metal complex is not necessary, the activation is preferably performed in situ. 22 200413420 The method for activating metal complexes is in a suitable non-interfering solvent or reaction medium and at -78 ° C to 250 ° C (preferably -5 ° C to 160 ° C, more preferably 10 ° C to 110 ° C). Suitable reaction media for forming the catalyst composition are aliphatic and aromatic hydrocarbons and il hydrocarbons. Examples include straight-chain and branched 5-chain hydrocarbons, such as isobutane, butene (including isomers), pentane, hexane, heptane, octane, and mixtures thereof, cyclic and alicyclic Hydrocarbons, such as cyclohexane, cycloheptane, fluorenylcyclohexane, fluorenylcycloheptane, and mixtures thereof; chlorinated, fluorinated, or chlorofluorinated hydrocarbons, such as chloroform, dichloromethane, chlorobenzene , Dichlorobenzene and perfluorinated C4_1G alkanes; aromatic and aromatic compounds substituted with hydrocarbon groups, such as benzene, toluene, xylene and styrene. In addition, the reaction medium used for activation is the same reaction medium used for subsequent polymerization reactions, excluding the need to use a second solvent system. In addition to the above reaction medium, suitable solvents include heptane or mineral oil fractions, such as light and general gasoline, naphtha, kerosene or gas oil, and other 15 low-priced hydrocarbons or mixtures thereof, sold by the petrochemical industry as solvents . The advantage of the present invention is that the metal complex catalyst precursor according to the present invention can be stored in solid state for an extended period of time at room temperature or even at an elevated temperature (such as 50 ° C, but not limited to this). In addition, the catalyst solution in a suitable solvent can also be stored at room temperature for at least several hours. This extreme increase in production variability within industrial equipment. A further advantage of the present invention is that the catalyst of the present invention generally does not require a separate aging step, and if a selective aging step is to be used, it advantageously does not require a long aging time. Therefore, it is only necessary to start the polymerization reaction by adding the catalyst in the desired order or the components used to form the catalyst into the polymerization reactor. 23 200413420 The polymerization reaction can be initiated, for example, by adding a metal complex as the final component or by adding a monomer (such as a conjugated diene, but not limited thereto, as the final component). If a selective aging step is incorporated into the catalyst polymerization process, the aging time is short, such as less than 2 hours, and 5 is preferably less than 1 hour, more preferably less than 30 minutes or even wider. Ranges (such as 0 ° C to 150 ° C and shorter for those with high catalytic activity. The temperature range for catalyst manufacturing, catalyst aging, and polymerization are individually selected and range from -5 (TC and + 250 °). Between C, preferably between -5 and + 160 ° C, more preferably between 10 ° C and 110 ° C. A further advantage of the present invention is that the aging of the catalyst does not require extreme temperatures. Advantageous The polymerization reaction can be induced with or without a large waiting period (delay) when the final catalyst component is added to the polymerization reactor. Suitable activated cocatalysts used here include: 〇 Neutral Lewis acid, especially a) Organic group 13 compounds, especially 15 1) CrC3G organic or organoaluminum compounds, more particularly (hydrocarbyl) aluminum- or (hydrocarbyl) boron compounds, more particularly triaryl or trialkyl aluminum compounds,. Examples are monoethylsaurus, diisobutylaluminum, trioctylaluminum; alkylaluminum hydride such as, such as, diisobutylaluminum hydride; alkylalkoxyaluminum compounds, such as, dibutylethoxy Aluminum halide; aluminum halide compounds such as diethyl 20 chloride, ethyl sodium dichloride, diisobutylammonium chloride, ethyl (octyl chloride, ethyl 1 lubesemichloride, ethyl (ring Hexyl)! Lu chloride, hexyl, dioctyl halide, and H) dentine organic (including fully bleached) derivatives of organic sulfonium compounds, especially bleached Cl30 organic stone or organic compounds, Better dentification (hydrocarbon fine- or functional (hydrocarbyl)) 24 200413420 People's chemistry 044 'Better fluorinated or perfluorinated tris (aryl) stone palates or famous compounds such as, two (Pentafluorophenyl) boron, tris (pentafluorobenzyl) aluminum, tris (o-nine-air-auricular benzyl) boron, bis (o-ninefluorobiphenyl) aluminum, tris [3, 孓 bis (tris) Fluoromethyl) phenyl] phenyl, stilbene, tris [3,5_bis (trifluorofluorenyl) phenyl] aluminum; or b) K-alkaline or agglomerated aluminum smoldering, especially methyl aluminum smoldering ( MA〇), triisobutyl aluminum modified Fluorenyl aluminoxane (MMA〇), or isobutylaluminum oxalate *, or 2) non-polymeric, compatible, non-coordinating, ion-forming compounds (including 10 using these compounds under oxidizing conditions) ), In particular, salts which are compatible with non-coordinating anion at position 10-, scale-, oxo -... carbon-, Wei-, thio-, or ferrocene-; and the aforementioned activating compound mixture. The aforementioned activated cocatalyst has been taught in advance in the following references for different metal complexes. US Patent Nos. 5,132538G, 5,153,157,5, () 64,8G2,5,321,106, 5'721,185, No. 5,350,723, and WO-97 / 〇4234, which are equivalent to the US No. 08 / 818,530 case number 15 (application on March 14, 1997). Suitable activators used here include sodium hydrocarbyl sodium, hydrocarbyl lithium, hydrocarbyl zinc, hydrocarbyl magnesium halides, dihydrocarbyl magnesium, especially alkyl sodium, alkyl lithium, alkyl zinc, alkyl magnesium halides, dialkyl magnesium, Such as n-octyl sodium, butyl lithium, neopentyl lithium, methyl lithium, ethyl lithium, phenyl lithium, phenylfluorenyl lithium, diethyl 20 zinc, dibutyl zinc, butyl magnesium chloride, Ethylmagnesium chloride, octylmagnesium vapor, monobutylphosphonium, monooctylmagnesium, butyl (octyl) phosphonium. The desired activated cocatalyst used in the method of the present invention is a mixture of the aforementioned activated compounds. The special desired co-catalyst used here is a 25 mixture of neutral Lewis acid, 200413420, 15 especially for trialkylaluminum compounds with 8 to 8 carbons per alkyl group (especially triethylaluminum, Isobutylaluminum, or trioctylaluminum) and one or more nicotinyl-substituted Group 13 Lewis acid compounds (particularly halogenated tris (hydrocarbyl) groups with 1 to 20 carbons per hydrocarbon group) Compounds, especially mixtures of tris (pentafluorophenyl) borane, tris (nonafluorobiphenyl) borane or tris (pentafluorophenyl) alane), or at least one neutral Lewis acid and at least one Ionic compounds (especially compounds containing 1 to 20 carbon halides of tetra (hydrocarbyl) borate or aluminate in each hydrocarbyl group forming ions, especially containing tetrakis (pentafluorobenzyl) borate ions, tetra (nine Fluorobibenzyl) borate ion, methyltris (pentamyl) borate ion, fluorenyltris (nonafluorobiphenyl) borate ion, tetrakis (pentaphenyl) aluminate ion, or formazan Tris (pentafluorophenyl) aluminate ion-forming compounds), among which A further mixture of a mixture of volatile Lewis acid and polymerized or agglomerated alumoxane, a single Louis Xia Jiu (particularly tris (pentafluorophenyl) borane, tris (nonafluorobiphenyl) borane or tris ( A mixture of pentafluorobenzyl) alane) and polymerized or agglomerated alumoxane, and mono-ionized compounds (especially those containing tetrakis (pentafluorophenyl) borate ion, tetrakis (9-biphenyl)) Salt ion, methyl tris (pentafluorophenyl) acid salt ion, 20 methyl bis (nine I biphenyl) acid ion, tetra (pentafluorophenyl) acid salt ion 'or methyl tris (pentafluorophenyl) Phenyl) sulfonium ion (preferably borate ion 戋 甲 其 -α # 使, # both the base group) to form ionic group of methine bis (pentadyl group borate ion)) and polymerization Or a mixture of oligomeric alumoxane. B = The system of the present invention found that the use of tris (pentafluorobenzyl) is very disgusting. The most effective catalyst activation of the mixture is Jiangxian. Evil Fan Li inch X students. Metal complex: Tris (pentafluorophenyl sintered 26 200413420 The preferred molar ratio is 1: 1: 1 to 1: 5: 5, more preferably 1: 1: 1.5 to 1: 5: 3. Surprisingly effective use of lower levels of alumoxane enables the use of less expensive alumoxane activators to produce diene polymers with high catalytic efficiency. In addition, aluminum residues with lower levels (and therefore larger Polymers) are obtained. 5 Suitable ion-forming compounds used as activators in one embodiment of the present invention include cations (which are protonated Bronsted acids) and compatible non-coordinating or poorly coordinating compounds. Anion. As used herein, the term "non-coordinating" means not coordinating to a metal-containing precursor complex and a catalytic derivative derived therefrom or only weakly coordinating to this complex to thereby maintain An anion or substance that is sufficiently unstable to be replaced by 10 Lewis bases (such as olefin monomers) in a manner that enables polymerization to proceed. Non-coordinating anions refer specifically to the charge balance in cationic metal complexes Does not transfer anionic substituents or fragments thereof to anions The cation thereby forms the anion of the non-activated neutral complex. "Compatible anion" means that when the initially formed complex is decomposed, it will not degrade to neutral and will not be subject to subsequent polymerization reactions or errors. Other anions that interfere with the use of compounds. Preferred anions contain a single compound containing a metal or metalloid core that carries a charge whose anion balances the charge of the active catalyst species (metal cations) formed when the two components are combined. Dislocations. Furthermore, the anion 20 ion should be sufficiently unstable to be replaced by olefins, diolefins, and acetylene unsaturated compounds or other neutral Lewis bases such as ether or nitrile. Suitable metals Includes aluminum, gold, and platinum without limitation. Suitable metals include boron, phosphorus, and silicon without limitation. Compounds containing anions (which includes coordination complexes containing a single metal or metal-like atom) are of course already And many (especially those compounds containing a single boron atom in the anion part of 27 200413420) are commercially available. Preferably, these activators can be represented by the following formula: (L * -H) + dAd. 5 where: L * is neutral Lewis base; (] >, + is Bronsted acid;

Ad_ is a non-coordinating compatible anion with a d-charge, and D is an integer from 1 to 3. 10 More preferably, the Ad- series corresponds to the chemical formula: [M * Q4]-where: is the boron or aluminum in the +3 oxidation state; and

Q is in each case individually selected from the group consisting of hydride, dialkylamido, halide, haloyl, halocarbon, hydrocarbyl oxide, hydrocarbyl substituted hydrocarbyl, organometal substituted hydrocarbyl, Organometal-substituted hydrocarbyl, halooxyl, ii-hydrocarbyl-substituted hydrocarbyl, halocarbon-substituted hydrocarbyl, and halo-substituted silyl hydrocarbyls (including fully halogenated hydrocarbyl groups, fully halogenated hydrocarbyl groups, and all (I silyl hydrocarbon group), the Q has up to 30 carbon atoms, but with 20 band conditions, Q is no more than one case. An example of a suitable hydrocarbyl oxide Q group is disclosed in U.S. Patent No. 5,296,433. In a more preferred embodiment, d is 1, i.e., has a single negative charge for megaions and is A ·. Boron-containing activated cocatalyst 28 200413420, which is particularly used in the manufacture of the catalyst of the present invention, can be represented by the following general formula: (L * -H) + (BQ4)-; where: (L * -H) + is as defined above; 5 B Boron with oxidation state 3;

Q is a hydrocarbyl group, up to 20 non-hydrogen atoms, alkoxy-, fluorinated hydrocarbyl-, fluorinated alkoxy-, or fluorinated silane alkyl group, with the exception that Q is no more than one . Optimally, Q is in each case a fluorinated aryl, in particular a pentafluorophenyl or nonafluorobiphenyl. Preferred BQ4 • anionic 10 methyltris (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, methyltris (nonafluorobiphenyl) borate or tetrakis (nonafluorobiphenyl) Borate.

Non-limiting illustrative examples of boron compounds that can be used to make the activated cocatalyst of the improved catalyst of the present invention are trisubstituted ammonium salts, such as: trimethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenyl Borates, methyldi (ten-octadecyl) ammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenyl Borate, methyltetradecyl stearyl ammonium tetraphenylborate, N, N-dimethylaniline tetraphenylborate, N, N-diethylaniline tetraphenylborate, zeal -2,4,6-pentafluorenylaniline) tetraphenylborate, N, N-difluorenylaniline bis (7,8-dicarbonunde-20 alkanoate) cobaltate (III), trimethyl Ammonium tetrakis (pentafluorophenyl) borate, fluorenyl di (tetradecyl) ammonium tetra (pentafluorophenyl) borate, methylbis (octadecyl) ammonium tetrakis (pentafluorophenyl) borate Salt, triethylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, tris Dibutyl) ammonium Phenyl) borate, N, N-29 200413420 Dimethylaniline tetrakis (pentafluorophenyl) borate, N, N-diethylaniline tetrakis (pentafluorophenyl) borate, N, N, 2, 4,6-pentafluorenylaniline) tetrakis (pentafluorophenyl) borate, trimethylammonium tetra (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetra (2,3 , 4,6-tetrafluorobenzyl) borate, tripropylammonium tetra (2,3,4,6-tetrafluorophenyl) borate, 5 tri (n-butyl) ammonium tetra (2,3,4 , 6-tetrafluorophenyl) borate, difluorenyl (third butyl) ammonium tetra (2,3,4,6-tetrafluorophenyl) borate, team dimethylaniline tetra (2,3 , 4,6-tetrafluorophenyl) petrate, N, N-diethylaniline tetra (2,3,4,6-tetrafluorophenyl) borate, and N, N, 2,4, 6-pentamethylaniline) tetra- (2,3,4,6-tetrafluorobenzyl) borate; dialkylammonium salts such as bis (octadecyl) ammonium tetrakis (penta-10fluorophenyl) ) Borates, di (tetradecyl) ammonium tetra (pentafluorophenyl) borate, and dicyclohexylammonium tetra (pentafluorophenyl) borate; tri-substituted phosphonium salts, such as triphenyl scale Tetrakis (pentafluorophenyl) borate, methylbis (octadecyl) Tetrakis (pentafluorophenyl) borate, and tri (2,6-dimethylphenyl) scales tetrakis (pentafluorophenyl) borate. 15 Preferred are tetrakis (pentafluorophenyl) borate salts of long-chain alkyl mono-, di-, and tri-substituted ammonium complexes, especially C14-C2Q alkylammonium complexes, and especially fluorenyl di (ten Octaalkyl) ammonium tetrakis (pentafluorophenyl) borate and methyldi (tetradecyl) ammonium tetra (pentafluorophenyl) borate, or mixtures containing these. These mixtures include protonated ammonium cations derived from an amine containing two c14, c16 or c18 alkyl groups and one fluorenyl group. These amines are available from Witco Corp. under the tradename Kemamine ™ T9701, and Akzo-Nobel under the tradename ArmeenTM M2HT. Examples of the best catalyst activators used here include the aforementioned trialkylammonium salts, particularly methylbis (tetradecyl) ammonium- or methylbis (eighteen 30 200413420 alkyl) ammonium-salts: bis ( Tris (pentafluorophenyl) borane) imidazolidine, bis (tris (pentafluorophenyl) borane) -2-undecylimidazolidine, bis (tris (pentafluorophenyl) borane) -2- Heptadecylimidazolidine, 5 bis (tris (pentafluorophenyl) borane) -4,5-bis (undecyl) imidazolidine, bis (tris (pentafluorophenyl) borane) -4, 5-bis (heptadecyl) imidazolidine, bis (tris (pentafluorophenyl) borane) imidazolidine,

Bis (tris (pentafluorophenyl) borane) -2-undecylimidazolidine, bis (tris (pentafluorophenyl) borane) -2-heptadecylimidazolinol, 10 bis (tris (Pentafluorophenyl) borane) -4,5-bis (undecyl) imidazolinolin, bis (tris (pentafluorophenyl) borane) -4,5-bis (heptadecyl) imidazole Porphyrin, bis (tris (pentafluorophenyl) borane) -5,6-dimethylbenzimidazolidine, bis (tris (pentafluorophenyl) borane) -5,6-bis (undecane) Yl) benzimidazolidine, bis (tris (pentafluorophenyl) alumino) imidazolidine, 15 bis (tris (pentafluorophenyl) aluminum) -2-undecylimidazolidine,

Bis (tris (pentafluorophenyl) alkane) -2-heptadecylimidazolidine, bis (tris (pentafluorophenyl) alkane) -4,5-bis (undecyl) imidazolidine, bis (Tris (pentafluorophenyl) alane) -4,5-bis (heptadecyl) imidazolidine, bis (tris (pentafluorophenyl) alane) imidazolinol, 20 bis (tris (pentafluorobenzene) Base) alumane) -2-undecylimidazolinol, bis (tris (pentafluorophenyl) alane) -2_heptadecyl imidazolinol, bis (tris (pentafluorophenyl) alane ) -4,5-bis (undecyl) imidazolidine, bis (tris (pentafluorophenyl) alane) -4,5-bis (heptadecyl) imidazolinol, bis (tri (penta Fluorophenyl) alumane) -5,6-dimethylbenzimidazolidine, and 31 200413420 bis (tris (pentafluorophenyl) alane) -5,6-bis (undecyl) benzimidazole alkyl. The aforementioned activated cocatalysts have been taught for different metal complexes in the following references: EP 1 560 752 A1. Another suitable ammonium salt (especially for heterogeneous catalyst systems) is the reaction of 5 organic metals (especially tri (CV6 alkyl) aluminum compounds) with ammonium salts of hydroxyaryl tri (fluoroaryl) borate compounds.时 formed. The compounds formed are organic metal oxyaryl tri (fluoroaryl) borate compounds, which are generally insoluble in aliphatic liquids. Examples of suitable compounds include the reaction product of a tri (cv6 alkyl) aluminum compound and an ammonium salt of a hydroxyaryl tri (aryl) borate. Suitable hydroxy 10 aryltri (aryl) borate salts include the following ammonium salts, particularly the aforementioned long-chain alkylammonium salts: (4-difluorenylalumoxyphenyl) tris (pentafluorophenyl) borate, (4-dimethylaluminumoxy-3,5-bis (trimethylsilyl) phenyl) tris (pentafluorophenyl) borate, (4-difluorenylaluminumoxy-3,5-di (No. Tributyl) phenyl) tris (pentafluorophenyl) borate, (4-di 15 fluorenylaluminobenzyl) tris (pentafluorophenyl) borate, (4-dimethylalumino-3 · Fluorenylphenyl) tris (pentafluorophenyl) borate, (4-dimethylalumino-tetrafluorophenyl) tris (pentafluorobenzyl) borate, (5-difluorenylaluminumoxy-2 -Naphthyl) tris (pentafluorophenyl) borate, 4- (4-diamidinoaluminophenyl) phenyltris (pentafluorophenyl) borate, 4- (2- (4- (difluorene) Phenyloxyphenyl) propane-2-yl) phenyloxy) tris (pentafluorophenyl) 20 borate, (4-diethylaluminumoxyphenyl) tris (pentafluorophenyl) borate, (4 -Diethylaluminumoxy-3,5 · bis (trimethylsilyl) phenyl) tris (pentafluorophenyl) borate, (4-diethylaluminumoxy-3,5-bis (third butyl) ) Phenyl) tri ( Pentafluorophenyl) borate, (4-diethylaluminumoxyphenylfluorenyl) tris (pentafluorophenyl) borate, (4-diethylaluminumoxy-3-fluorenylphenyl) tris (pentafluoro Phenyl) borate, (4-diethylaluminum 32 200413420 oxy-tetrafluorophenyl) tris (pentafluorophenyl) borate, (5-diethylaluminumoxy-2-naphthyl) tris (pentafluoro Phenyl) borate, 4- (4-diethylaluminumoxyphenyl) phenyltris (pentafluorophenyl) pentanoate, 4- (2- (4- (diethylaluminumoxyphenyl) propane) 2-yl) phenoxy) tris (pentafluorophenyl) borate, (4-diisopropylaluminumoxyphenyl) tris (pentafluorophenyl) 5 borate, (4-diisopropylaluminum Oxy-3,5-bis (trimethylsilyl) phenyl) tris (pentafluorophenyl) borate, (4-diisopropylaluminumoxy-3,5-bis (thirdbutyl) phenyl ) Tris (pentafluorophenyl) borate, (4-diisopropylaluminumoxybenzyl) tris (pentafluorophenyl) petrolate, (4-diisopropyl: i-luoxy-3- Methylphenyl) bis (pentafluorobenzyl) lithium salt, (4-diisopropylalumino-tetrafluorophenyl) tris (pentafluorophenyl) borate, 10 (5-isopropylaluminum) Oxy-2-naphthyl) tris (pentafluorophenyl) boronic acid , 4- (4-diisopropylaluminumoxyphenyl) phenyltris (pentafluorophenyl) borate, and 4- (2- (4- (diisopropylaluminumoxyphenyl) propane-2-yl ) Phenoxy) tris (pentafluorophenyl) pendant. Particularly preferred ammonium compounds are methyldi (tetradecyl) ammonium (4-diethylaluminumoxyphenyl) tris (pentafluorophenyl) borate, methyldi (hexadecyl) ammonium (4-di Ethyl 15-aluminumoxyphenyl) tris (pentafluorophenyl) borate, fluorenylbis (octadecyl) ammonium (4-diethylaluminumoxyphenyl) tris (pentafluorophenyl) borate, and mixture. The aforementioned complexes are disclosed in U.S. Patent Nos. 5,834,393 and 5,783,512. Another suitable ion-activating cocatalyst includes a cationic oxidant and a salt of a non-coordinating compatible anion, which is represented by the following chemical formula: 20 (〇xe +) d (Ad_) e, where

Oxe + is a cationic oxidant with an e + charge; d is an integer from 1 to 3; e is an integer from 1 to 3; and Ad- is as defined above. 33 200413420 Examples of cationic oxidants include: ferrocene cations, hydrocarbyl-substituted ferrocene cations, Pb + 2 or Ag +. A preferred embodiment of Ad_ is the anions previously defined with respect to the activated co-catalysts containing bristic acid, especially tetrakis (pentafluorophenyl) borate. 5 Another suitable ion-forming activated cocatalyst includes carbenesulfonium and a salt of a non-coordinating compatible anion, which is represented by the following chemical formula: where: @ + 系 CV2 () carbenesulfonium; and 10 Α · 系Non-coordinating compatible anions with a -1 charge. The carbenefluorene-based trityl cation is preferred, and triphenylfluorenyl cation is particularly preferred. Preferred carbene sulfonium salt activation cocatalysts are triphenylfluorenyl cation tetrakis (pentafluorophenyl) borate, triphenylmethyl cation tetrakis (nonafluorobiphenyl) borate, and trifluorenylmethyl cation. Tetrakis (pentafluorophenyl) borate and its ether are substituted by 15 adducts. Further suitable ion-forming activated cocatalysts include silanes and salts of non-coordinating compatible anions, which are represented by the following chemical formula: R3Si + A · where = 20 R is a CV1 () hydrocarbon group, and the __ is as above Define. Preferred co-catalysts for activation of silane and radium salts are tris (silyl) phosphonium tetrakis (pentafluorophenyl) borate, trimethylsilyl (tetrafluoro (phenylfluoro) phenyl) borate, triethylsilyl tetrakis (pentafluorobenzene) Group) borates and their substituted adducts. Silicon 34 200413420 The iron salt has been previously disclosed in J Chem Soc · Chem. Comm., 1993, 383 384 'and Lambert, J. et al. 〇ganganmetaiics, Dp' 13, 2430-2443 ° The yakiba salt as an activated cocatalyst for addition polymerization catalysts is claimed in US Patent No. 5,625,087. 5 Some complexes of alcohols, mercaptans, petrols, oximes and tris (pentafluorophenyl) borane are also effective catalyst activators and can be used in accordance with the present invention. These activators are disclosed in U.S. Patent No. 5,2%, No. 433. Activated cocatalysts can also be used in combination. A particularly preferred combination is a mixture of a tri (hydrocarbyl) aluminum or tri (hydrocarbyl) borane compound 10 having 1 to 4 carbons per hydrocarbon group and an alumoxane compound which is agglomerated or polymerized. The molar ratio of the metal complex / activator used is preferably in the range of 1: 1 to 10: 1, more preferably 1: 5000 to 10: 1, and most preferably 1: 2500 to 1: 1. When alumoxane alone is used as the activating co-catalyst, it is preferably used in a large mole ratio. 'Based on the molar content of the general metal complex is at least 50 ^ ^ (pentagasyl). When used as an activated cocatalyst, it is used at a molar ratio to metal complexes of 0.5: 1 to ι0: 1 (more preferably 1: 1 to 'optimal 1: 1 to 5: 1) compared to the bell system. . The remaining activated co-catalyst is generally used in a molar amount approximately equal to that of the metal complex. Each of the above-mentioned 20 ion-forming compounds each containing a compatible non-coordinating or poorly coordinating anion is used as an activator, which is preferably alkylated (i.e., metal One of the compounds is X-based alkyl or aryl). An activator containing boron is preferred. The best system contains tetrakis (pentafluorophenyl) peptate, tris (pentafluorophenyl) heptane, tris (o-nonafluorobiphenyl) rotane, tetras (3 5 bis (trifluorofluorenyl)) Activator of phenyl) borate, tris (pentafluorophenyl) alane, tris (ortho, nine-35-fluorobiphenyl) alane. In the case where a neutral Lewis acid is selected as the activator, the molar ratio of the activator phase to the metal complex is generally in the range of about 1:10 to about 1 ⑽: 1, and more preferably 1:10. To 5000: 1, and most preferably in the range of about u to about 2,000 to 1. If a compound containing or generating a non-coordinating or poorly coordinating anion (an ion-forming compound) is selected as the activator, the molar ratio of the metal complex to the activator is generally about 100: 1 to about 1 : 1000, and preferably in the range of about 1: 0.5 to about 1: 250. In the preferred mixtures of metal complexes, ion-forming compounds, and hydrated or agglomerated ° moxa, the molar ratio of 10 metal complexes to ions-forming compounds to alumoxane is generally about 1: A range of 0.1: 2 to about 1: 50: 1000, more preferably 1:05:10 to 1: 5: 500, more preferably a range of about 1: 0.8: 15 to about 1: 5: 250, and The optimum range is from about 1: 1: 20 to about 1: 2: 150. Particularly preferred activated cocatalysts are compounds containing tetra (pentafluorophenyl) borate ion or methyltris (pentafluorophenyl) borate ion forming ion 15 and MA0, MMAO or isobutylalumoxane (compared with Preferably exists), wherein the metal complex compound is a compound containing tetra (pentafluorophenyl) borate ion or fluorinated tris (pentafluorophenyl) heptate ion to alumoxane. The ear ratio is in a range of about 1: 0.8: 15 to about 1: 5: 250, and more preferably in a range of about 1: 1: 20 to about 1: 2: 150. 20 In addition to the metal complex and activator according to the present invention, the catalyst composition may additionally contain a small amount of another organometallic compound, which acts as a so-called scavenger. Scavengers are added to react or inertize the reduced activity impurities of the reaction mixture. It can be added at any time, but is generally added to the reaction mixture before adding the metal complex and activator (cocatalyst). 36 200413420 In general, organic compounds are used as scavengers. Examples of suitable scavengers are trioctyl aluminum, triethyl aluminum, diethyl aluminum vapor, triisobutyl aluminum, fluorenyl alumoxane or MMAO. Advantageously, the scavenger can also act as an activator. The metal complex and the activator may be present in the catalyst composition as a single component or as a mixture of components. For example, a mixture is desirable when it is necessary to affect the molecular properties of the polymer, such as molecular weight distribution. The reaction system optionally contains a solid material, which is a carrier or support material as an activator component and / or a metal complex. The carrier material may be selected from one of the following materials: clay, silica, charcoal (activated carbon), graphite, expanded 10 clay, expanded graphite, carbon black, layered silicate, and alumina. Clay and layered silicates include, without limitation, sodalite, montmorillonite, hectorite, sepiolite, attapulgite, smectite, and magnesium aluminosilicate. The supported catalyst system of the present invention can be made by several methods. Metal complexes and selective activators can be combined before the support material is added. The mixture can be prepared in a conventional liquid alkane or a conventional solution in an aromatic solvent. The solvent is also preferably suitable as a polymerization diluent for liquid-phase polymerization of olefin monomers. Alternatively, the activator may be placed on the support material, followed by the addition of a metal complex, or vice versa, the metal complex may be applied to the support material, followed by the addition of the activator. Catalysts that pass through branches can be polymerized. In addition, the third component can be added during any stage of the catalyst preparation process. The third component may be defined as a functional compound containing a Lewis acid or a base. Non-limiting examples are N, N-dimethylaniline, tetraethoxysilane, phenyltriethoxysilane , Bis-third butyl hydroxymethylbenzyl (BHT) and the like. The role of the third component is to facilitate the polymerization or the beneficial properties of the polymer. The catalyst can be used such as solid phase immobilization technology (HCL · Abbenhuis in Angew. Chem · Int · Ed · 37 (1998) 356-58 and M · Buisio et al. Micmporous mater ·), 5 ( 1995) 211 and JS · Beck et al., Described in J. Am · Chem · Soc ·, 114 (1992) 10834), and the technology of pore volume immersion 5 (PVI) (see wo 97/24344) is supported by On the carrier material. Isolation of the impregnated carrier can be by filtration or by removal of volatile materials present under reduced pressure or by heating (i.e. in the case where solvents or unreacted monomers and / or prepolymerization reactions are performed Low molecular weight polymers). If the support is used, it is preferably a metal complex (based on metal) that provides a catalyst or support: the weight ratio of the support material is 1:10 to 1: 200,000 (more preferably 1:20 to 1: 50,000, and optimally: 30 to 1: 20,000). Appropriate gas phase reactions can utilize monomers used in the concentration reaction, or inert diluents to remove heat from the reactor. 15 In the polymerization method, the catalyst is used in a catalytically effective amount, that is, any amount that is formed by a force of 5 or 5 species. This amount can be easily determined through routine experimentation by those skilled in the art, but the Molar ratio of the catalyst: polymerizable compound typically used is 1: 1: 1 to 10 ": 1, more preferably to 10.3: The catalyst can be used to polymerize ethylene and / or acetylene unsaturated monomers having 2 to 100,000 carbon atoms individually or in combination. Preferred monomers include Dilute hydrocarbons from the group consisting of α-olefins, internal olefins, cycloalkanes, and non-common diene. The preferred residual diene (diene) is i, 3-butane-dilute, isoprene (2_ Methyl-butadiene), 2,3-difluorenyl 38 200413420 butadiene, 1,3-pentanediene; 2,4-hexadiene; 1,3-hexadiene; I,) · heptane Di_ '1,3-octyl bis, 2-fluorenyl-2,4-pentadiene; cyclopentadiene, ι, 3_cyclohexadiene; 2,4 · hexadiene; 1, 3 -Cyclooctadiene; and diborneol. The preferred olefins are C ^ ea-olefins, more particularly ethylene, propylene, isobutylene, butane-5, butene, pentene, fluorenyl-1-. Pentene, 4-fluorenylpentene, dihexyl, 3,4-monofluorenylbutadiene, 1-heptane, 1-octyl Ι_decene, long chain macromolecular α-olefin, styrene, Cm alkyl substituted styrene, such as 2-fluorenylstyrene, 3-fluorenylstyrene, 4-fluorenylbenzyl ethylene, 2 , Winter difluorenyl styrene, 2,4,6-trimethyl styrene, α • methyl styrene and 1,2,10 stilbene, tetrafluoroethylene, vinylchlorohexane, vinylbenzo Cyclohexane; Non-conjugated diene (diene), especially system of norbornadiene, ethylenic norbornane, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene Olefin, 4-vinyl% hexene, divinylbenzene. Long chain macromolecular olefins are polymer residues with vinyl end groups formed in situ during continuous solution polymerization. 15 Under appropriate processing conditions These long-chain macromolecular units can be easily polymerized into polymer products together with ethylene, propylene, stupid ethylene, butadiene, isoprene and other short-chain olefin monomers, and a small amount is produced in the formed polymer. Long chain branch. More preferably, butadiene, isoprene and / or cyclopentadiene are used as conjugated diene, ethylene, propylene, 1-butene, 1-hexene and / or 1- The olefinic 20 is an aliphatic α-olefin, and the styrene and / or methyl styrene is an aromatic α-dilute hydrocarbon. In particular, the catalyst used in the present polymerization method is a co-diene. (Especially butadiene or isoprene diene) homopolymers, co-general-ene copolymers (especially random or block butadiene · isoprene 39 200413420 copolymers) and At least one conjugated diene (especially butadiene or isoprene) and at least one alpha-olefin (especially aliphatic alpha-olefin, especially ethylene, propylene, 1-butene, 1-pentene, 1 -Hexene, 4-methyl-1-pentene, 1-octene or 1-decene), aliphatic dilute hydrocarbons, aliphatic cyclic dilute hydrocarbons or aliphatic (non-common) dilute or aromatic 5 Random or block copolymers of aromatic α-olefins (especially styrene and 4-fluorenylstyrene or aromatic diolefins, especially divinylbenzene). Particularly preferred are at least one conjugated diene and at least one aliphatic α-olefin and optionally at least one aromatic diolefin or α-olefin (especially butadiene or isoprene with ethylene, propylene, 1-butane Random polymerization or copolymerization of alkene, 1-hexene, 4-fluorenyl-1-pentene or 1-octene and / or 10 or styrene, 4-fluorenylstyrene and / or divinylbenzene) Reaction, selective terpolymerization. Highly preferred polymers include a conjugated diene selected from butadiene or isoprene and an alpha-olefin selected from ethylene, propylene, octene, and styrene. Also highly preferred polymers include butadiene and isoprene. The most highly preferred polymers include 15 butadiene and ethylene and / or octene. Particularly preferred are random or pseudorandom polymers comprising a conjugated diene selected from butadiene or isoprene and an aliphatic or aromatic alpha-olefin selected from ethylene, propylene, octene, and styrene . The particularly desirable ones formed by using this catalyst in the polymerization method of the present invention are the same 20 polymers or copolymers of a) a) conjugated diene (particularly butadiene and / or isoprene), and b) i) at least one conjugated diene (particularly butadiene or isoprene) and ii) at least one olefin, especially with aliphatic α-olefins, especially ethylene, propylene, 1-butene, 1 -Hexene, 4-fluorenyl-1-pentene or 1-octene, aliphatic internal olefin, aliphatic cyclic olefin or aliphatic (non-co-) diene or aromatic α-olefin, especially styrene And 4-methylstyrene or aromatic diene, 40 special olefins) homopolymers: or copolymers, random or block identical to the fluorene hydrocarbons: i or i, especially aliphatic α- Olefins, especially ethylene, propylene, fluorinated, " small pentylene, octene, aliphatic internal olefins, ^ = or aliphatic (non-conjugated) diolefins or aromatic aliphatic olefins, two ::- Olefins and 4-methylstyrene or aromatic diolefins, especially diethylene glycol: polymer blends of homopolymers', in which the conjugated diene content of the α-olefin is less than 5%; especially Land, where ... 1) and 2) are manufactured in the same reaction system. ° As in the factory, the same-or copolymerization reaction of diene monomers, or the copolymerization of diene monomers and diene monomers, or the co-polymerization of diene monomers and a) Copolymers of olefins with α • dilute hydrocarbons or b) olefins or copolymer blends of a-olefins can be formed in Ziegler-Natta or Cummings known in the art The conditions for the radical-octane polymerization are complete = such as, -50 to 250. (: Temperature. The polymerization reaction can be continuous or discontinuous at atmospheric pressure, sub-atmospheric pressure, or up to 500 MPa or even higher pressure. Preferably, the polymerization reaction is at 001 And pressure between 500 MPa (preferably between 0.01 and 10 MPa, especially between 〇2 Μι ^). Higher pressure can be applied. In this high pressure method, according to the invention Metal complexes can also be used with good results. Slurry and solution polymerization reactions generally occur at lower pressures, preferably below ⑺ MPa. Polymerization reactions can be performed in the gas and liquid reaction media. Polymerization Generally, it is carried out under batch, continuous or semi-continuous polymerization conditions. The poly 200413420 synthesis method can be used in gas phase polymerization (for example, in a fluidized bed or agitated bed), and solution polymerization (where the formed polymerization is The system is substantially soluble in the reaction mixture), suspension / slurry polymerization (wherein the polymer formed is essentially insoluble in the reaction medium), solid-phase powder polymerization or the so-called bulk polymerization method (In which an excess of a single system to be polymerized is used as the reaction medium). The catalyst can also be used in combination with at least one other homogeneous or heterogeneous polymerization catalyst in the same or individual reactors connected in series or in parallel. To produce polymer blends with desired properties. An example of this method is shown in WO 94/00500, which is equivalent to US Serial No. 07 / 9,04,770, and US Patent Case No. 5,844,045. The amount of catalyst to be used is generally such that the concentration in the solution or dispersant is about mol / litre, preferably ΐ0.7 · ΐ0.4 · mol / litre. 15 Suitable solvents, dispersants or diluents for polymerization processes via solution or slurry processes are typically non-coordinating inert liquids and can be selected from straight and branched chain hydrocarbons (such as propane, butane) , Isobutyl, pentyl, hexane, heptane, octane), cyclic and aliphatic smoke (such as cyclohexane, cycloheptane, methylcyclohexane, fluorenylcycloheptane), aromatic And alkyl-substituted 20 aromatic compounds (such as benzene, toluene, and difluorene) ), And the aforementioned isomers and their kb compounds and pentamethyl heptane or mineral oil sales (such as light oil or general gasoline, naphtha, kerosene or gas oil), but not Limited to this. Fluorinated hydrocarbon fluids (such as perfluorinated daggerane) are also suitable. Further suitable solvents include liquid olefins, which can be used as polymerization monomers in 2004 200413420 monomers or comonomers, including propylene, 1-butane Ene, pentene, cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, butadiene, isoprene, 1,4-hexane Diene, 1,7-octadiene, 1-decene, styrene, divinylbenzene, ethylidene norbornene, alkylbenzene, 2-fluorenylstyrene, 3-fluorenylbenzene, 5 ethylene, 4-fluorenylstyrene, 4-vinylcyclohexene and vinylcyclohexane. The aforementioned mixtures are also suitable. Aromatic hydrocarbons (e.g., benzene, toluene, and xylene) can also be used. Due to cost considerations, it is preferred to use technical grade low-priced aliphatic hydrocarbons or mixtures thereof sold in the petrochemical industry as solvents in the polymerization reaction method. If an aliphatic hydrocarbon is used as the solvent, the solvent may optionally contain 10 traces of an aromatic hydrocarbon such as toluene. Therefore, if, for example, fluorenyl 1 sulphur oxalate (MAO) is used as an activator, toluene can be used as a solvent for MAO so that MAO is provided to the polymerization reactor in a dissolved form. The drying or purification of the solvent is desired when these solvents are used; this can be done without problems by those skilled in the art in known methods. 15 Preferably, the polymerization reaction is carried out in a batch, continuous or semi-continuous solution or bulk polymerization conditions, under hydrocarbon (such as propylene, propylene, butane, 1-butane, 2-butane, Ethyl, hexane, heptane, cyclohexane, fluorenylcyclohexane, benzene, toluene, including the aforementioned isomers and mixtures thereof, and at -10 ° C to 200 ° c (preferably 0 °) C to 130 ° c). The polymerization reaction 20 can be performed in one or more continuous stirred reactors or fluidized bed, gas reactors (connected in series or in parallel). Monomers and / or solvents can be added to the reactor as is known in the art. The catalyst may also be supported and / or pre-polymerized before use. A continuous method is preferred, in which, more advantageously, a mixture of the reaction components of the catalyst, solvent, diene and selective olefin is continuously supplied to the reactor system in large quantities or at frequent intervals and continuously monitored To ensure an efficient reaction, and the desired product is continuously removed from it. For example, many supported coordination catalysts and catalyst systems for polymerization processes are known to have varying degrees of high sensitivity to chelating agents such as water, oxygen, carbon dioxide, acetylene compounds, and sulfur compounds. The introduction of these compounds can cause reactor disruption and produce sub-grade products. Typically, computer control systems can be used to keep process variables within accessible limits, typically by measuring polymer variables such as viscosity, molecular weight, or catalyst productivity. If the polymerization method is carried out under suspension or gas phase polymerization conditions, the temperature is typically below 150 ° C. With the catalyst of the invention, high molecular weight polymers can be easily achieved by using the catalyst of the invention, even at elevated reaction temperatures. This result is highly desirable because the molecular weight of the diene copolymer can be easily reduced to the desired value by using hydrogen, butene, 1,5-cyclooctadiene, or a similar chain transfer agent. In addition, productivity is increased due to improved polymer solubility, reduced solution viscosity, and higher polymer concentration. Using the catalyst of the present invention, homopolymers or copolymers or polymer blends having a high comonomer incorporation can be easily prepared. Preferably, if a copolymer of a conjugated diene and an α-olefin or a) a conjugated diene 20 and i) comprises a copolymer of a dilute and an α-dilute hydrocarbon or ii) a homopolymerization of an α-broken hydrocarbon Polymer blends of polymers or copolymers are formed with each of the aromatic poly-α-olefin content and the aliphatic poly-α-olefin content being 70% or less. Preferably, the copolymer of a conjugated diene (particularly butadiene) and an α-olefin (such as ethylene or propylene) is a random copolymer. 44 200413420 With the catalyst and polymerization method of the present invention, the homopolymers and copolymers that are non-crystalline or rubber-like or rubber can be used according to the monomers used and the proportion of monomers used (particularly a thin. Ratio) and learn. The polymer formed by the polymerization can be obtained by a method known per se. Generally, the catalyst is passivated at a certain point during the polymer treatment in a manner known per se, for example, by water or alcohol. Removal of catalyst residues can be ignored 'because the catalyst content in the homopolymer or copolymer (especially the content of element and metal) is very low due to the use of the catalyst system according to the present invention. However, if desired, the catalyst residue 10 in the polymer can be reduced in a known manner, for example, by cleaning. The purification step may be followed by a stripping step (removal of organic solvents from homopolymers or copolymers). The polymerization reaction can also be carried out in several steps in series and in parallel. If necessary, the catalyst composition, temperature, hydrogen concentration, pressure, residence time, etc. can be changed according to the steps. In this way, products with a wide distribution of properties (e.g., molecular weight distribution) can also be obtained. By polymerizing olefins using the catalyst of the present invention, polymers having a molecular weight of more than 50,000 and a polydispersity (Mw / Mn) of ι · 0-50 can be obtained.

It is formed by the addition of two dilute polymerization reactions of the addition polymerization reaction machinery to the residual diethylene 'E (opposite) and Z (together) double bonds. In the case of butadiene 20, it is marked as vinyl (or 1,2-, or 1,2-polybutadiene), trans (or trans-1,4-, or trans-1,4-polybutadiene Diene) and cis (or cis-14 • or cis "polybutadiene) double bonds. An advantage of the present invention is that it is possible to make high cis, moderate cis or low cis or high trans content polybutadiene (homo) polymers or copolymers, which are dependent on the selected reaction conditions such as activator The type of components added and the order of 45 5 and the selected catalyst precursors are determined, but not limited to this). Preferably, the fraction of the residual olefinic double bond (which is a z or cis unit) in the homopolymer or copolymer formed from the polymerization reaction of the conjugated diene ranges from 5 to 100%, and £ or The fractional range of the trans-oriented units is from 0 to 95% of the total amount of 15 residual olefinic double bonds formed from the Wei 2 dilute polymerization reaction. Illustrative but non-limiting example ^ 90 · 5% (operation 1), 66% (operation 3), 32% (operation 2) cis content, or 83 · 9 / 〇 (operation 6) polymer blend The poly-butadiene fraction of the product contains trans-products containing 1 × 彳 land, a 2-product formed by a conjugated diene monomer and a mono-olefin monomer, or a copolymer containing a diene polymer / diene. Polyolefins: Do not blend the diene copolymer part is a diene_: poly random copolymer containing butyl and ethylene, monoene-α-olefin copolymer or polymer blend. More preferably, the diene-butadiene and ethylene / diene-^-olefin copolymers are part of the inclusions: 'dilute' where 'diqin'-olefin copolymers or polymers are blended And the content of butadiene in the B :: hydrocarbon copolymer part is greater than 30 moles and the amount is less than% moles. More preferably, the content of butadiene is fine. Is less than 60 mole%, more preferably, 20, preferably, but mol%, and the ethylene content is less than 50%, or the content of butadiene; the amount is more than 60%, and The ethylene content is less than 40%, and the ΓΓΓ ethylene content according to the present invention is less than 30%. The polymer blend _ ^ composition is in the dilute _α · thin smoke copolymer or olefin (preferably butyl) The content of the co-rolled diene (preferably, 3, 2 ..., 3G mole% and 4 () mole%, and a-Ί) in the copolymer part is 60 mole% and 70%. Moore%; Dilai 46 200413420, good butadiene) content is between 40 Moore% and 50 Molar%, and the content of α · olefin (preferably ethylene) is 50 Moore% and 60 Moore %; The content of diene (preferably butadiene) is 50 mol And 60 mol%, and the α-olefin (preferably ethylene) content is between 40 mol% and 50 mol%; the diene (preferably but 5-diene) content is about 60 mol% And 70 mole%, and the content of α-olefin (preferably ethylene) is between 30 mole% and 40 mole%; the content of diene (preferably butadiene) is 70 mole% and 80 Molar%, and the content of the α-olefin (preferably ethylene) is between 20 Molar% and 30 Molar%. Other preferred polymer-based copolymers include butadiene or isoprene 10 and are selected from ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-fluorenyl-1-pentene Alkenes, 1-octene, styrene, α-fluorenylstyrene, and α-olefins of divinylbenzene. More preferred are polymers comprising butadiene and ethylene or propylene (more preferably butadiene and ethylene). Other preferred polymers are composed of conjugated diene polymers (preferably containing butadiene or isoprene) and containing butadiene or isoprene and selected from ethylene, propylene, 1-butadiene Copolymer of olefin, 1-pentene, 1-hexene, 4-fluorenyl-1-pentene, 1-octene, styrene, α-fluorenylstyrene, and divinylbenzene α-olefin copolymer Polymer blend. Other preferred polymers are composed of conjugated diene polymers (preferably those containing but 20 diene or isoprene) and those selected from the group consisting of ethylene, propylene, 1-butene, 1.pentene, and 1-hexene. A polymer blend consisting of olefin, 4-methyl-1-pentene, 1-octene, styrene, α-methylstyrene and α-dilute hydrocarbon of diethylbenzene. In particular, preferred polymer blends include polybutadiene and polyethylene or 47 200413420 polybutadiene and butadiene-ethylene copolymers, especially polyethylene linear low density polyethylene, ie, Polyethylene containing 20 mol% or less of another alpha-olefin, such as polypropylene, 1-butene, 1-hexene, or 1-octene. More preferred are polymer blends containing polybutadiene and a butadiene-ethylene copolymer, and polymer blends containing polybutadiene and a butadiene-ethylene / α-olefin copolymer.

Advantageous are different products (non-limiting examples of which are homopolymers of conjugated dienes (such as polybutadiene), copolymers of fluorene and alpha-olefins (such as butadiene-ethylene copolymerization) Polymer) and butadiene · ethylene / α-olefin copolymers, 10 polymer blends of conjugated dipolymers and co-diene-α-dilute hydrocarbon copolymers (such as polybutadiene and ethylene- Butadiene copolymer) or blends of butadiene-ethylene / α-dilute hydrocarbon copolymers, and polymer blends of co-diene polymers and α-dilute hydrocarbon polymers can be used on the same catalyst system Under similar polymerization conditions (such as the same metal complex, activator, polymerization temperature15, and solvent), it is made only by changing the type and concentration of the monomer used in the polymerization method. Non-limiting examples are Polybutadiene from operation 1, polymer blend of polybutadiene and butadiene-ethylene copolymer from operation 6, and butadiene-ethylene copolymer from operation 7 and operation 9. Another preferred The polymer contains butadiene and aromatic α-olefin (preferably 20 styrene). Conjugated diene / aromatic α · olefin The aromatic alpha-olefin (preferably styrene) content of the polymer may vary from 0 to 20% by weight of the aromatic α-olefin, preferably from 0 to 10% by weight, more preferably from 0 to 5%, Among them, the aromatic α-olefin is preferably styrene, and the conjugated diene is preferably butadiene. The 1,3-butadiene-ethylene copolymer obtained by the method of the present invention is a new 48 200413420 compound. Compositions with new and unique properties. In non-limiting examples, the ethylene content can be changed by changing the reaction conditions (such as the butadiene-ethylene monomer ratio in the feed, for example, producing 61.0 mole% Ethylene-containing polybutadiene (example, operation 7) or 53.2% ethylene-containing polybutadiene (operation spoon or 5 42 · 0% ethylene-containing polybutadiene (operation 8), but not limited to This) is adjusted in a wide range. 另一 Another advantage of the polymerization reaction method of the present invention is that the glass temperature Tg of the polymer can be adjusted in a wide range of, for example, _30 and] 15t, and the melting temperature Tm of the polymer can be adjusted. By adding ethylene and changing the ethylene content of 10 (between 0 and 70%), Adjustments such as "10 and 15.0." In a non-limiting example, the low glass temperature of the acupoint and the melting temperature of the main high-cis-4-polybutadiene are recovered, and have -70.0 High glass temperature of ° C and ι3 · η: the secret temperature of the diene-ethylene copolymer is recovered (see operation 6). 15 This month's poly-a reaction method can produce special polymers. In particular, the activity Selection of agents and metal complexes and catalyst manufacturing methods, solvents (non-aromatic or aromatic) used in the polymerization reaction, diene concentration and polymerization reaction pulse. This hydrate structure (in butadiene i _ thin smoke The cis-trans and ethylene content of the copolymer case! (Proportion to the α-olefin content), and in the case of the polymer 20 blend, it has a reaction with the molecular weight of the polymer formed and the poly-a reactivity of the specific catalyst. And beneficial effects. In non-limiting examples, the cis content of the polybutadiene homopolymer can be varied over a wide range by changing / # 化 "ααa" or by using a suitable activator mixture or by changing the metal complex The composition can be adjusted by changing the order in which the catalyst components are added. 49 200413420 The following three non-limiting cases illustrate how this can be done: 1) When the metal complex 1 and [(R) 2NMeH] [B (C6F5) 4] (R = n-C18H37) and MMAO-3a activator mixture when added to a butadiene monomer-containing polymerization reactor, has a weight average molecular weight (Mw) of 530,000 g / mole 90.5% of 5 cis-1,4-polybutadiene is recovered (operation 1); 2) When the mixture of metal complex 1 and activator MMAO_3a is added to the polymerization reactor containing the butadiene monomer And when the co-activator [(R) 2NMeH] [B (C6F5) 4] (R = n-C18H37) is added after 45 minutes, it has a weight-average molecular weight of 290,000 g / mol and a molecular weight of -1.4%. -Polybutadiene is obtained (operation 2); 3) When the mixture of metal complex 3 10 and MMAO-3a is added to the polymerization reactor containing butadiene monomer, it has 495,000 g / mole Weight 1 Polybutadiene containing 66 ()% cis-1,4- with an average molecular weight is obtained (operation 3). Another advantage of the present invention is that the molecular weight distribution of the polymer can be changed in a wide range by changing the metal mismatch The component and / or activator compound and / or the temperature is adjusted by changing the reaction temperature. In two non-limiting examples, polybutadiene having a narrow molecular weight distribution of 2.6 is recovered (operation 3), and 6 Polybutadiene with a broader molecular weight distribution of 2 is recovered (operation 1). The addition of an alpha olefin monomer (such as ethylene) results in a broader molecular weight distribution. The polymers and copolymers of the present invention can be used to make many Useful shaped objects, molded parts, films, foams, golf balls, tires, hoses, conveyor belts and other tapes, cymbals, seals, shoes and improvements for plastics, such as high impact Production of polystyrene (Hips). Examples need to understand that the present invention can be operated in the absence of any group that has not been explicitly disclosed 50 200413420. The following examples are provided to further illustrate the present invention and are not to be construed as limiting. ... unless the contrary Indications, all parts and percentages are expressed on a weight basis. If used, overnight, the term refers to a time of about 16 to 18 hours 'room temperature' if used refers to about 20 to A temperature of 25 ° c. 5 All tests involving organometallic compounds are performed under inert nitrogen atmosphere using standard Schlenk equipment and technology or in a box. In the following, 'THF' means tetrahydrofuran, , Me, represents, fluorenyl ,, m, represents, ethyl, 'Bu' represents, butyl, ,, ph, represents phenyl,, MMA〇, or 'MMAO-3a' represents' modified Methyl in Lu. Smoldering 'is described from akzO 10 Nobel, and TMB stands for trisoxybenzene. The pressure is absolute pressure. The polymerization reaction is carried out in a nitrogen atmosphere excluding moisture and oxygen. The product was analyzed by SEC (size exclusion chromatography), elemental analysis, NMR (Bruker Biospin

GmbH's Avance 400 device (^ = 400 MHz; 13C = 100MHz)) and IR (IFS 66 FT-IR spectrometer from Bruker Optics GmbH. IR sample series 15 uses CS2 as the expansion agent and uses two or four-fold resolution Made)) describe its characteristics. The polymer composition determined by NMR and IR measurements is expressed in mole%. Therefore, "'%" means that it means Mol%. DSC (Differential Scanning Calorimetry) is measured using DSC 2920 from TA Instruments.

The molecular weights of Mn, Mw and Mz coefficient average, weight average and z-average, 20 are determined by SEC viscosity measurement (general calibration) in THF at room temperature. The ratio between the 1,4-cis ... 1,4, anti-2 polydiene content of polymers of butadiene or isoprene is determined by IR and NMR-spectroscopy. The glass transition temperature of the y compound is determined by the DSC determination method. Fragment 51 200413420 Pyrolysis experiment and subsequent GC / Ms analysis are used with Curie Point

Pyrolyzer 0316M (Fischer) combined with HP HC / MS-System GC 6890 / MSD 5973 was implemented. The following columns were applied: Hp5 Ms, 30m x 0.25mm x 0.25, HPPart No. 19091S-433, average rate 32, flow 0.8 ml / min. 1. Synthesis of transition metal complexes 1.1 Production of (third butyl fluorenylamino) dimethyl (tetramethyl 1 5-cyclopentadienyl) -silane 1 (A) (chlorine) ( Difluorenyl) (tetramethylcyclopentane-2,4-alkenyl) _silane 10 21.5 g (167 mmol) of dimethyl dichlorosilane in 150 ml of THF in the cold part to -40 ° C The solution was slowly added to a solution of 800 g (55.6 mmol) of 1,2,3,4-tetramethylcyclopentadiene in rib methylene chloride. The reaction mixture was warmed to room temperature and stirred overnight. The solvent was removed and the residue was taken up with pentane and filtered. Pentane was removed under reduced pressure to produce a pale yellow oil. Yield: ΐ0.50 g 〇 ％) lH NMR (C6d6) 2.89 (s, 1H), 1.91 (s5 6H), 1.71 (s, 6H), 0.14 (s, 6H); 13c NMR (C6D6) 137.8 , 131.5, 56.6, 14.6, 11.4, 0.81. (B) 11.07 g (151 mmol) of (tertiary butylamino) (difluorenyl) (tetramethylcyclopentadiene-2 pipetenyl) silane in 20 ml of THF The 20 solution was added over a period of 5 minutes to a solution of 13.00 (60.4 mmol) (chloro) (dimethyl) (tetramethylcyclopentadienyl) silane in 300 ml of THF. A precipitate formed immediately. The slurry was stirred for 3 days, then, the solvent was removed, and the residue was extracted with sintering and filtered. The pentane was removed under reduced pressure to give the product as a pale yellow oil. Yield is 14.8 g (97.2%) MS. 251 lH NMR (C6D6) 52 200413420 2.76 (s5 1 Η), 2.01 (s, 6H), 1.84 (s, 6H), 1.09 (s, 9H), 〇 1〇 (s 6H); 13c NMR (C6D6) 135.4, 133.2, 57.0, 49.3 3λ 〇 ′ ', ΐ 5. ·· 11.2, 1.3. (C) Dilithium (third butyl fluorenylamino) (difluorenyl)-(tetrafluorenylcyclopentane dilute meaning) Shixi 5 alkanedibutyl based on 3.000 g (11.98 mmol) in 100 ml of ether The solution of the (monthly female group) (dimethyl) (tetramethylene-cyclopentadienyl) crushing compound was suspended for 2.21M (23.95 ml) of 9.21 ml in a mixed C6 alkane solvent亳 Mo Er) Ding Yizhong. A white precipitate formed and the reaction mixture was stirred overnight. The solid can be washed several times with ether and then dried under reduced pressure to give the product as a white powder. The yield was 3.134 grams (99.8%). (D) (Third butylamidoamine) diamido (tetramethylί 5-cyclopentadienyl) silane dichloride 1 0.4421 g (1.90 mmol) of ZrCl4 in a flask, slowly Add 15 0 · 25 ml. The excess of THF was removed under vacuum, resulting in a solid, which was broken into a powder. 0.499 g (1.90 mmol) of bis (N-third butylamidino) (dimethyl) (2,3,4,5-tetrafluorenylcyclopentadienyl) silane and 50% Add ml of toluene. The formed slurry was stirred for several days, after which the yellow solution formed was filtered, the solvent was removed in vacuo, and the product was isolated by washing with pentane. The yield was 0.410 grams (52.6%). lH NMR (C6D6) 2.01 (s5 6H), 1.95 (s, 6H), 1.32 (s, 9H), 0.42 (s, 6H); 13c NMR (C6D6) 134.2, 131.6, 127.9, 56.6, 33.1, 14.7, 11.85 6.0. 1.2 manufacturing (second butyl fluorenylamino) difluorenyl (tetrafluorenyl 5_cyclopentadienyl) _ 53 2004l342 ° titanium silane 2 (third butyl fluorenylamino) difluorene (Tetrafluorenyl 5-cyclopentadienyl) silicon sintered titanium dichloride 2

1.000 g (3.80 mmol) of dilithium (N-third butyl fluorenylamino) (difluorenyl 5 phenylene ^ -tetramethylcyclopentadienyl ^ silane and ^ chuan ke ^ rib TiCVCTHF) 2 was mixed in a flask with 75 ml toluene. The yellow color formed turned green within 1 hour. The reaction mixture was stirred overnight, after which the dark anti-mixture was filtered, the solvent was removed in vacuo, and the formed reddish-pigmented oily residue was stirred with pentane to dissolve the dark red-brown impurities. After cooling the solution in the oven 10, the yellow-green product was collected on the glass frit, washed with pentamidine and dried under vacuum. The yield was 0.6267 grams (44.8%). 1h NMR 1.992 (s5 6H), 1.987 (s, 6H), 1.415 (s, 9H), 0.415 (s, 6H) · 13C NMR (C ^ D ^) 140.6, 137.9, 104.0, 62.1, 32.7, 16.1 13.0, 5.4. l5 I · 3 · Production of digas (N- (l, 10 difluorenylethyl) -1 dimethyl dimethyl +

((l, 2,3,3a, 7a- 77) _3- (1-. each sulfonyl group) _1H-section-1-yl) sulfanylamine (2 _) _ n) bowl 3 (A) manufacturing -(1H-indenyl) yl

According to the improvement of Noland Temple people (Noland, W.E .; Kaneswaran, V. J 20 ⑺Ctol. 1981, paper 19.1944.) Program ,! -Indanone (250 grams, 0.189 moles) and 50 ml of pyrrolidine (dried on a 3A screen) were added to a 500 ml equipped overhead stirrer, Dean Stark (Dea ~ Stark) apparatus and a 3-necked flask of a concentrator, which was maintained in an atmosphere. Ben (200 gross liters, square; 4A division online drying) was added, and the solution refluxed 30 54 200413420

hour. At the end of this period, 1H NMR analysis of the reaction aliquot indicated a 93: 7 mole% ratio of the desired product to the starting material. The solvent body was removed in vacuum 'and the crude dark product was steamed (6 ”Vigreaux column) to produce pure enamine (24.3 g, 0.132 moles) as a pale yellow oil, 70 ° /. Yield. This chemical 5 The compound is sensitive to air and water, and is transferred to a dark box during distillation. Color analysis by GC indicates that the hexane solution of the distillate is 99 area% purity: bp = 125-127 ° C @ 2.0 mm9 bp. Lit -118-120 ° C @ 1mm; lH (C6〇6) 7.61 (d, 1H, J = 7.4 Hz), 7 39 (d, ih, J = 7.4 Hz), 7.24 (t, 1H, J = 7.4 Hz ), 7.17 (t, 1H, J = 7.4 Hz), 5 〇7 (s 1H) 10 3.41 (m, 4H), 3.31 (s, 2H), 1.94, sentence; 13C {lH} (C6D6) 149.9, 145.1 , 141.6, 125 5, 124 2, 123 8, 120 · 3, 100.6, 50.2, 35.5, 25 · 2 ·

(B) Manufacture of (1- (1-Cyrrolidin) -1Η-indenyl) bell in a dry heald box '3.5 g (18.9¾ mol) of 1- (1 仏 Langyl). Pyrrolidine was mixed with 100 ml of hexane. To this solution, 9.5 ml (18.9 mmol) of n-BuLi (1.6M) was dropped. When n-BuLi was completely added, the solution was stirred overnight. The formed precipitate was collected by filtration, washed with hexane and dried under reduced pressure to give a product of 3.61. Yield: 99%. 55 200413420

(C) Production of N- (l, l-difluorenylethyl) -1, l-difluorenyl-1- (3- (1-pyrrolidinyl) -1H-benz-1-yl) silylamine

A solution of (1- (1-pyrrolidinyl) -1H-indenyl) lithium (3.30 5 g, 17.25 mmol) in 40 ml of THF was added to N- (third butyl) -N over 30 minutes -(1-chloro-1,1-difluorenylsilyl) amine (2.86 g, 17.25 mmol) in 100 ml of THF. After the addition was complete, the reaction mixture was stirred overnight. Then, the solvent was removed under reduced pressure. The residue was extracted with hexane and the solution was filtered. The solvent was then removed under reduced pressure, leaving 5.13 grams of product. Yield: 95%. 10 lH (C6D6) -0.07 (s, 3H), 0.05 (s, 3H), 1.27 (s, 9H), 2.03

(m, 4H), 3.43 (m, 4H), 5.41 (s, 1H), 7.24 (m, 2H), 7.53 (d5 1H, 3jH_H = 7.7 Hz), 7.70 (d5 1H, 3jH H = 7.7 Hz). 13C {1H} (C6D6) 2.71, 4.28, 26.19, 34 · 93, 49.06, 50.68, 54.30, 58.00, 84.15, 104.16, 123.91, 124.50, 125.05, 133.58, 15 143.95.

LiN —ί-Bu 56 200413420 (D) Manufacturing (1-(((1,1-Difluorenylethyl) amino) dimethylsilyl) -3- (1-Methylpyrrolyl) -1Η -Indenyl) lithium, lithium salt in a dry box, 5.13 g (16 · 3 mmol) of N- (l5 ^ dimethylethyl) -l, l-difluorenyl-l- (3- (l -Pyrrolidinyl) -l-^-l-yl) silylamine was mixed with 80 ml of 5 hexane. To this solution, 16.3 ml (32.6 mmol) of n-BuLi (1.6M) was dropped. When n-BuLi was added completely, the solution was stirred overnight. The formed precipitate was collected by filtration, washed with 50 ml of hexane, and dried under reduced pressure to give 5.33 g of product. Yield 100%.

10 (E) Production of dichloro (N- (l, l-difluorenylethyl) -1,1-dimethyl small ((l, 2,3,3a, 7a-T7) -3- (1- .Pyrrolidinyl) -1H-inden-1-yl) silylamine (2-)-N) Titanium 3 (1-(((1,1-dimethylethyl) amino) dimethyllithium Lithium) -3- (1-0-pyrrolidinyl) -1H-indenyl) lithium, lithium salt (5.33 g, 16.32 mmol) was dissolved in 30 15 ml of THF. To this solution, TiCl3 (THF) 3 (6.05 g, 16.32 mmol) was added as a solid. After 1 hour, PbCl2 (2.27 g, 8.16 mmol) was added as a solid. The reaction mixture was then stirred for an additional hour. The solvent was removed under reduced pressure. The residue was extracted with 70 ml of toluene and filtered. The toluene was removed under reduced pressure, and the residue was crushed with hexane. The solid was collected by filtration, washed with hexane, and then dried under reduced pressure. 5.08 g of product was obtained. The yield was 72%. 57 200413420 lH (C6D6) 0.67 (s? 3H)? 0.84 (s? 3H)? 1.316 (s? 9H)? 2.05 (br s? 4H)? 3.71 (br s? 2H) 5 4.01 (br s? 2H) 7.25 (m5 2H)? 7.63 (d, 1H), 7.91 (d, 1H). 13c {lH} (C6D6) 1.58, 25.75, 32.97, 50.49, 61.05, 93.11, 5 106.51, 126.32, 126.89, 127.14, 129.00, 135.82, 149.54. HRMS (EI, M +): Calculate 430.0881, find 430.0881.

(F) Production of (N- (l, l-difluorenylethyl) -1, l-dimethyl-1-((l, 2,3,3a, 7a-W) _3- (1-. Ratio Pyrrolidinyl) -1H-inden-1-yl) silylamine (2-)-N) dimethyl titanium ((1,2,3,3a, 7a-π) -3- (1-.pyrrolidine (1M) -1H-M-1-yl) silylamine (2-)-N) Titanium (1.15 mmol) was suspended in 40 ml of Et20. To this suspension, 0.77 ml of MeMgI (3.0M) was dropped and stirred for 20 minutes. When MeMgl was added, the solution was stirred for 20 minutes. Thereafter, Et20 was removed under reduced pressure, and the residue was extracted with hexane. The solution was filtered, and the filtrate was evaporated to dryness under reduced pressure, yielding 0.39 g of product. The yield was 86%. lH (C6D6) 0 · 10 (s5 3Η), 0.50 (s5 3Η), 0 · 65 (s, 3Η), 0.75 (s, 3H), 1.53 (s, 9H), 3.23 (m, 4H), 3.23 ( m, 4H), 5.43 (s, 1H), 6.95 (t, 1H, 3jH H = 7.9 Hz), 7.06 (t, 1H, 3jH H = 7.9 Hz), 7.54 20 (d, 1H, 3jh H = 8.5 Hz ) 5 7.63 (d, 1H, 3jh H = 8_5 Hz). 58 200413420 13c {lH} (C6D6) 2.62, 2.71, 4.82, 4.90, 26.19, 34.90, 49.06, 50.58, 54.31, 58.00, 84.15, 104.15, 123.91, 124.49, 125.05, 125.63, 133.58, 143.95. 1.4 Production of medifluorenylsilane bis (2-methyl-4-phenylinden-1-yl) zirconium (II) (1,4-5 diphenyl-1,3-butadiene) 4

This compound was synthesized according to the procedure shown in U.S. Patent No. 6,084,115. 2. Polymerization reaction 10 2.1 Description of polymerization reaction procedure The polymerization reaction is carried out in a double-walled 2 liter steel reactor. It is nitrogen-filled before adding organic solvents, metal complexes, activators, Lewis acid or other components. Clear. Unless otherwise indicated, the polymerization reactor was adjusted to 80 ° C. Then, the following components are added in the following order: organic solvent, one portion of activator 15 1. optional second activator component, and / or Lewis acid, conjugated diene monomer, selective aliphatic α -Olefin monomer and this mixture is stirred for 1 hour. In an individual 200 ml double-walled steel reactor, if no other indication is set to the same temperature as the polymerization reactor, the following components are added in the following order 20: organic solvent and an activator and the mixture is stirred 0.5 hour. 59 200413420 Then, optionally, the second activator component and / or the Lewis acid and subsequent metal complexes are added, and the resulting mixture is stirred for an additional 30 minutes. The polymerization was initiated by adding the contents of a 200 ¾ steel reactor to a 2 liter polymerization vessel. Unless otherwise indicated, the polymerization was carried out at 800 ° C. The polymerization reaction time varies depending on the experiment. To terminate the polymerization process, the polymer solution was transferred to a third double-walled steel reactor (containing 50 ml of methanol containing Irganox 1520 as a polymer stabilizer, and 1 liter of methanol containing 2 g of Irganox). This mixture was stirred for 15 minutes. Then, the recovered polymer was stripped with water vapor for 1 hour to remove the solvent and other volatile substances, and dried in an oven at 45 ° C for 24 hours. 3. Polymerization Example: 3.1 Polymerization of 1,3-butadiene A) Polymerization of 1,3-butane using complex 1, [(R) 2NMeH] [B (C6F5) 4] and MMAO-3a The ene (operation 1) 15 experiment was performed according to the general polymerization procedure described in (2.1) above. The polymerization was carried out in 589 g of cyclohexane solvent. Therefore, 499 grams of cyclohexane, 59.4 grams (1.1 mole) of 1,3-butadiene monomer and MMAO (5.8 grams of heptane solution containing 15.0 millimoles 2MMA0) were added to the polymerization reactor. 90 grams of cyclohexane, 5.8 grams of heptane solution (which contains 20 mM ΑΟΟ 15 mM) and 4.2 grams of methylcyclohexane solution (containing [3 (R) 2NMeH] [ B (C6F5) 4] (R == η-. 18% 7)) and 107.2 mg (0.27 moles) of metal complex 1 are mixed in individual reaction cereals and mixed with tax 1 〇minutes. Thereafter, the resulting mixture was transferred to a polymerization reactor to initiate a polymerization reaction of 60 200413420. After 2 hours and 42 minutes, the polymerization was terminated as described above (see 2.1). At this time, the conversion ratio of the monomer to polybutadiene was 24.6%. 14.6 grams of polybutadiene was recovered as a result of the A extraction process. The Mw of the polymer was equal to 530,000 g / 5 mol 'and the polydispersity (molecular weight distribution) was equal to 6.2. (Mn = 85,000; Mz = 1, 310,000). The polymer contains 90% of cis], 4; 60% of anti-center, ^, 3.5% of 1,2-polybutadiene, which is determined according to ^] ^ 11. The glass transition temperature is equal to -105.5 ° C ′ and the dazzling point is 8.3 ° c. B) Polymerization of 1,3-butadiene using complex, [(R) 2NMeii] [B (C6F5) 4], and MMA0-3a (operation 2) The experiment was based on the general polymerization reaction described in (H) above. The procedure is implemented. The polymerization was carried out in 608 g of a cyclohexane solvent. Therefore, 509 g of cyclohexane, 58.3 g (1.08 mol) of ι, 3-butadiene monomer, and μμα (5.7 g of a heptane solution containing 15.0 mmol of MMAO) were added. To polymerization reactor 15. 99 grams of cyclohexane, 5.7 grams of heptane solution (containing 15 mmol of MMAO) and 107.2 mg (0.27 mmol) of metal complex 1 were mixed in a separate reaction vessel and stirred for 10 minutes . Thereafter, the resulting mixture was transferred to a polymerization reactor to initiate a polymerization reaction. After 45 minutes, 4.2 grams of fluorenylcyclohexane solution (containing 0.3 mmol and 20 mol of [(R) 2NMeH] [B (C6F5) 4] (R = n-C18H37)) was added to the polymerization reactor as a further Component. After 3 hours and 30 minutes, the polymerization was terminated as described above (see 2.1). At this time, the conversion of the monomer to polybutadiene was 31.6%. 18.5 grams of polybutadiene were recovered as a result of the stripping process. The Mw of the polymer is equal to 290,000 g / 61 200413420 moles, and the polydispersity (molecular weight distribution) is equal to 3.05. (Mn = 97, 〇〇〇;

Mz = 700,000). The polymer contains 32.0% of cis-154; 49.0% of anti-1,4-, 19.0% of 1,2-polybutadiene, which is determined by nmr. C) Polymerization of butadiene using complex 3 and MMAO-3a (operation 3) 5 The experiment was performed according to the general polymerization procedure described in (2.1) above. The polymerization was carried out in 581.2 g of a cyclohexane solution. Therefore, 5 g · 1 g of bad hexane, 59.2 g (1.09 mol) of 1,3-butadiene monomer & MMA〇 (57 g of heptane solution containing 15.0 mmol of iMMA〇) were added to the polymerization Reaction | §. 81.1 g of cyclohexane, 5.7 g of heptane solution (containing 15 mmol of 10 MMAO) and 112.5 mg (0.27 mmol) of metal complex 3 were mixed in a separate reaction vessel and stirred for 10 minutes . Thereafter, the resulting mixture was transferred to a polymerization reactor to initiate a polymerization reaction. After 1 hour and 30 minutes, the polymerization was terminated as described above (see 21). At this time, the conversion of the monomer to polybutadiene was 12.9%. 7.6 grams of polybutadiene were recovered as a result of the stripping process. The Mw of the polymer was equal to 495,000 g / mol, and the polydispersity (molecular weight distribution) was equal to Mz = 905,000). The polymer contains 66.0% of cis_M; 15% of cis., 4_, 19.0A, 1 丁 ^ 1 ', which is determined by NMR. 20 D) Polymerization of 1,3-butanediene using complex 2 and MMAO-3a (The operation sentence experiment is performed according to the general polymerization procedure described in (2.1) above. The hydration reaction is performed in 574.2 g of cyclohexane solvent. Therefore, a% 1 g of ring hexane, 56.5 g (ΐ · 04mol) of 1, butadiene dimer monomer and MMAO (5.75 g of hept :): finished solution, containing ΐ 5. · (MmaO) was added to the polymerization reactor by 62 200413420. 751 grams of cyclohexane, 5.75 grams of heptane solution (which contains 15 millimoles of jv [] \ 4AO) and 96.0¾ grams (0.27 house moles) of metal complex 2 are mixed in individual reaction vessels And stirred for 10 minutes. Thereafter, the resulting mixture was transferred into a polymerization reactor 'to initiate a 5 I synthesis reaction.

After 3 hours and 30 minutes, the polymerization was terminated as described above (see 2.1). At this time, the conversion ratio of the monomer to polybutadiene was 4.9%. 2.8 grams of polybutadiene was recovered as a result of the stripping method. 3 · 2 Copolymerization of 1,3-butadiene and styrene. 10 A) Copolymerization of 1,3-butadiene and styrene with complex 1 &] vlMAO-3a (operation 5) Experimental system According to the general polymerization procedure described in (2 · 1) above. The polymerization was carried out in 5820 g of a cyclohexane solvent. Therefore, 500.1 grams of cyclohexane, 29.7 grams (0.55 moles) of ι, 3-butadiene monomer, 26.1 grams (0.25 15 moles) of styrene monomer, and MMAO (5.8 grams of heptane solution, MMAO (15.0 μmol) was added to the polymerization reactor. 81.9 g of cyclohexane, 5.8 g of heptane solution (which contains 15 millimoles of iMMA) and 0.3 millimoles of [He paper chat ((: rape 5) 4] (R = η · 〇 ΐ8Η37) of 4.2 grams of methylcyclohexane solution was mixed with 107.2 grams (0.27 zemol) of metal complex ice in a separate reaction container, and stirred for 10 minutes.

Thereafter, the resulting mixture was transferred to a polymerization reaction temperature to initiate polymerization. Into the polymerization reactor so that after 110 3 hours and 80 minutes, the polymerization reaction was reversed. 2004 200413420 3 · 3 1,3-butadiene and ethylene copolymerization reaction (C6F5) 4; ^ MMAO-3a copolymerizes 1,3-butadiene and ethylene (operation 6) The experiment was performed according to the general polymerization procedure described in (2.1) above.

5 Polymerization was carried out in 597.8 grams of solvent. Therefore, 479.8 g of cyclohexane, 53.9 g (1.0 mol) of ι, 3-butanefluorene monomer, 12.04 NL (NL = normalized volume in liters) of ethylene (14.0 g, 0.5 mol ) And MMAO (5.8 g of a heptane solution containing 15.0 millimoles of MMAO) were added to the polymerization reactor. 118.0 grams of toluene, 5.8 grams of heptane solution (which contains 10 mM MoM0) and 0.39 millimoles [(R) 2NMeH] [B (C6F5) 4] (R = nq 8H37), 5.2 grams of methyl The cyclohexane solution was mixed with 107.2 mg (0.27 mmol) of metal complex 1 in a separate reaction vessel and stirred for 30 minutes. Thereafter, the resulting mixture was transferred into a polymerization reactor to initiate a polymerization reaction.

After 3 hours, the polymerization was terminated as described above (see 2.1). At this time, the conversion ratio of the monomer to the polymer was 50.8%. 34.5 grams of polymer was recovered as a result of the k method. The polymer samples were pyrolyzed at 770 ° C (pyrolysis time: 5 seconds) and the subsequent GC / MS measurements confirmed that the product 20 was typical for polybutadiene-based fragments and polyethylene-based such as octene and The presence of fragments of octane (see Figure 1). Microstructure The polymer according to 13C NMR and 1H NMR contains 38.6% of 1,4-polybutadiene (cis and trans), 8.2% of U2-polybutadiene and 53.2% of polyethylene. 64 200413420 The 8.6 (cis) /91.4 (trans) cis / trans ratio of the polybutadiene portion is determined by iR. GPC-Research for Polymers SEC-Research for Polymers 5 SEC measurements indicate higher and lower molecular weight polymer peaks (see phantom chromatograms [Figures 2 and 3]. Table shows that 31% of the sample was detected The souther molecular weight polymer peak ^ results in a Mw of 530,000,000 g / mol (Mn = 80,000; Mz = 2,5000,000) if the sample is dissolved in THF *, and when dissolved in toluene The time is 10 49,000,000 g / mol Mw (Mn = 100,000; Mz = 1,800,000). It means that 69% of the lower molecular weight polymer peak of the sample was detected, if Samples are> 3,300 g / mol Mw when THF *, and Mw 4,000 g / mol when dissolved in toluene *. For THF and transcripts, cereals are π% polymers. Detected and included in 15 SEC analysis. The remaining 22% were not investigated by SEC. The polymer sample was dissolved and separated in SEC by SEC. The chromatogram was again composed of the two polymer peaks (see RI- in Figure 4). Chromatogram). From the middle of the two peaks, a part is collected and then researched by] H NMR and 13C NMR techniques. Umiia 20 mil gold part (see attached spectrum) a) High molecular weight part is between $ Parts based exclusively containing polybutadiene. Therefore, 9.5% of cis 1,4 79.5 / 0], Xin and Uu, 2-polybutadiene were found (see 1H NMR and 3c NMR spectra in Figures 5 and 6). 65 b) Low molecular weight part The low molecular weight part contains butadiene and ethylene, and represents a copolymer. Therefore, 30.0% of 1,4-polybutadiene, 11.5% of 1,2-polybutadiene, and 58.5 / 0 polyethylene were found in the low molecular weight fraction. For random butadiene-ethene copolymers, the signal in the 13C NMR spectrum is expected to be in the region between 22 and 40 ppm. The 13C NMR spectrum obtained indicates the signal in this pre-defined area (see the 13C NMR spectrum in Figure 8). A large number of 13C NMR resonances in the region between 22 and 40 ppm indicates that the polymer part being studied consists of an additional (saturated) poly 10 olefin part in addition to the polybutadiene part. Butadiene and the second type of olefin compound form a randomly distributed copolymer. In particular, a dense resonance (see Figure 7) at about 1.2 ppm of the 1H NMR spectrum can be designated as a fraction derived from ethylene. The Mooney value is equal to 1.4, the glass temperature of the copolymer is equal to -70.0 ° C, and the flash point is 113.9 ° C. 15 Copolymerization of 1,3-butadiene and ethylene using complex compound [(R) 2NMeH] [B (C6F5) 4] and MMAO-3a (operation 7) The experiment is based on the general as described in (2.1) above The polymerization procedure is carried out. The polymerization was carried out in 3123.3 g of solvent. Therefore, 2523 · 1 g of cyclohexane, 270.3 g (5.0 mol) of 1,3-butadiene monomer, 55.57 NL of ethylene 20 ene (64.7 g, 2.31 mol), and MMA0 (29.5 g of A heptane solution, MMA0) containing 75.7 mmoles was added to the polymerization reactor. 600.2 grams of toluene, 29.5 grams of heptane solution (which contains 75.7 millimoles of MMAO) and 1.86 millimoles [(R) 2NMeH] [B (C6F5) 4] ㊉di n_c] 8H37) of 26.0 grams of methylcyclohexane The alkane solution was mixed with 482 mg (1.35 mmol) of the metal complex 1 at the individual level 66 200413420 should be mixed within the vinegar and dried for 4 8 minutes. Thereafter, the formed mixture was transferred into a polymerization reactor to initiate a polymerization reaction. After 5 hours, the polymerization was terminated as described above (see 2.1). At this time, the conversion ratio of the monomer to the polymer was 20.3%. 68.0 grams of polymer was recovered as a result of the 5 stripping process. The polymers according to 13C NMR and 1H NMR contained 24.5% of 1,4-polybutadiene (cis and trans), 14.5% of 1,2-polybutadiene and 61.0% of polyethylene. 0.0683 (cis) /0.317 (trans) cis / trans ratio of the polybutadiene portion (Ene) is determined by IR. QPC-Polymer Studies SEC measurements indicate lower molecular weight polymer peaks and traces of higher molecular weight polymer peaks (see RI chromatogram in Figure 9). It indicates that 98.0% of the lower molecular weight polymer of the test sample has a peak of 15 and it is about 1,000 g / mole weight average molecular weight (Mw) when dissolved in THF *, and Weight average molecular weight (Mw) of about 700 g / mole (Mn about 100,000; Mz about 1,800,000). * 63% of the polymer was dissolved in THF, and 71% of the polymer was dissolved in toluene, and investigated by SEC. The remaining 37% or 29% did not use SEC studies. The glass transition temperature of the 20 copolymer is equal to -70.6 ° C, and the melting point is 113.8 t. C) Copolymerization of 1,3-butadiene and ethylene using complex 1, [(R) 2NMeH] [B (C6F5) 4] and MMAO-3a (operation 8) The experimental basis is as described in (2.1) above The general polymerization procedure is carried out. The 67 polymerization was carried out in 658.6 grams of solvent. Therefore, 521.6 grams of cyclohexamidine, 54.6 grams (1.0 mole) of 1,3-butadiene monomer, H05 NL in ethylene (12.9 grams, 0.46 mole), and MMAO (5.9 grams of heptane solution, containing 15.2 MMAO) was added to the polymerization reactor. 13.7 grams of toluene, 5.95 grams of heptane solution (which contains 15.2 millimoles of MMAO) and 107.2 mg (〇.27 millimoles) of metal complex 1 were mixed in a separate reaction vessel and stirred 10 minutes. Thereafter, the resulting mixture was transferred to a polymerization reactor to initiate a polymerization reaction. After 101 hours, 0.39 millimolar [(R) 2NMeH] [B (C6F5) 4] (R =

Cis ^ 37) of 5.2 grams of methylcyclohexane solution was added to the polymerization reactor. After 4 hours' the polymerization was terminated as described above (see 2.1). At this time, the conversion ratio of the monomer to the polymer was 44.5%. 30.0 grams of polymer was recovered as a result of the stripping process. 15 The polymer according to 13 dlH NMR contains 44.5% polybutadiene (cis and trans), 13.5% polybutadiene and 42% polyethylene. The polybutadiene part of the polymer contains 42.0% of cis-1,4-; 40.0% of trans-1,4- and 18.0% of 1,2-polybutadiene, which is determined according to nmr. D) Copolymerization of 1,3-20 butadiene and ethylene using complex compound [(R) 2NMeH] [B (C6F5) 4] and MMAO-3a (operation 9) The inspection system is based on the above (2.1) The general polymerization procedure described is carried out. The polymerization was carried out in 2557.2 grams of solvent. Therefore, 1959.6 grams of cyclohexane, 270.9 grams (5.0 mole) of 3-butadiene monomer, 18.5 NL of ethylene (21.5 grams, 0.77 mole), and ΜΑΟ (29.2 grams of heptane solution) MMAO) containing 75.068 200413420 millimoles was added to the polymerization reactor. 597.62 grams of toluene, 29.2 grams of heptane solution (which contains 75.0 millimoles of mmAO) and 2.3 millimoles of 26.0 grams of [(R) 2NMeH] [B (C6F5) 4] (R = n-C18H37) Methylcyclohexane was melted and mixed with 482 mg (1.35 mmol) of metal complex 1 in a separate reaction 5 container and stirred for 81 minutes. Thereafter, the formed mixture was transferred into a polymerization reactor to initiate a polymerization reaction.

After 5 hours and 5 minutes, the polymerization was terminated as described above (see 2.1). At this time, the conversion ratio of 'monomer to polymer was 18.3%. 53.5 grams of polymer was recovered as a result of the stripping process. The polymers according to i3C- and 1H NMR contained 10 30.5% of 1,4- (cis and trans) and polybutadiene and 59.5% of polyethylene units. It has a low molecular weight polymer peak with a polymer Mw equal to 3,500 g / mole (see chromatogram in Figure 10). The glass transition temperature is -40.8 ° C, and the melting point is 113.TC.

15 E) Copolymerization of 1,3-butadiene and ethylene using complex 4, [(R) 2NMeH] [B (C6F5) 4] and MMAO-3a (operation 10)% The experiment is based on the above (2.1 ) The general polymerization procedure described is carried out. The polymerization was carried out in 602.7 g of a cyclohexane solvent. Therefore, 500.4 grams of cyclohexane, 54.3 grams (1.0 mole); 3, butadiene monomer, ι2 · 13 NL 20 ethylene (14.1 grams, 0.5 mole), and ΜΑΟ (5 · 8 A gram of heptane solution containing 15 mmol of MMAO) was added to the polymerization reactor. 101.3 grams of toluene, 5.8 grams of heptane solution (which contains 15 millimoles of mmAO) and 4.2 milligrams of [(R) 2NMeH] [B (C6F5) 4] (R = n_C18H37) The cyclamidine was melted and mixed with 149.6 mg (0.20 mmol) of the metal complex 3 in a separate reaction 69 200413420 container and stirred for 10 minutes. Thereafter, the resulting mixture was transferred to a polymerization reactor to initiate a polymerization reaction. After 3 hours, the polymerization was terminated as described above (see 2.1). At this time, the conversion ratio of 5 monomers to polymers was 17.1%. 15.5 grams of polymer was recovered as a result of the stripping process. The Mw of the polymer was equal to 105,000 g / mole, and the polydispersity (molecular weight distribution) was equal to 5.2. (Mn = 20,000; Mz = 450,000). According to NMR, the copolymer contains 16.5% of 1,4- (cis and trans), 16.0% of 1,2-polybutadiene and 67.5% of polyethylene. 10 [Schematic description] Figure 1 shows the GC / MS spectrum of the product identified after pyrolysis of the polymer. Figure 2 shows the RI chromatogram of a polymer made according to Experiment 3.3.A) in a THF solvent, showing the two separated polymer fractions. 15 Figure 3 shows the RI chromatogram of a polymer made according to experiment 3.3.A) in toluene, showing the two separated polymer parts. Figure 4 shows the RI chromatogram of the polymer produced according to Experiment 3.3.A), which was separated by SEC, resulting in a peak of the dipolymer. Figure 5 shows the 1HNMR spectrum of 20 parts of the high molecular weight portion of the polymer produced according to Experiment 3.3.A). Figure 6 shows the 13C NMR spectrum of the high molecular weight portion of the polymer made according to Experiment 3.3.A). Figure 7 shows the 1 H NMR spectrum of the low molecular weight portion of the polymer made according to Experiment 3.3.A). 70 200413420 Figure 8 shows the 13C NMR spectrum of the low molecular weight portion of the polymer made according to Experiment 3.3.A). Figure 9 shows the RI chromatogram of a polymer made according to Experiment 3.3.B) in toluene, showing essentially a polymer portion. 5 Figure 10 shows the RI chromatogram of a polymer made according to Experiment 3.3.D), showing a low molecular weight polymer peak with a polymer molecular weight of 3,500 g / mol. [Representative Symbols for Main Components of the Schematic] (None) 71

Claims (1)

200413420 Patent application scope: 1. A method for iso- or copolymerization of conjugated diene or forming polymer blend in situ, characterized in that at least one metal complex catalyst composition is used Containing 5 a) at least one metal complex according to formula I) (I) Metals R ', R "and R'" in which M is one of group 3, 4, 5, 6 or steel group metals are in each case individually hydrogen or have 1 to 80 atoms (not counting hydrogen) ), Which are halides, hydrocarbyls, hydrocarbyllithium, hydrocarbyl substituted with halo, hydrocarbyl substituted with hydrocarbyloxy, hydrocarbyl substituted with hydrocarbylamine, or hydrocarbyl substituted with hydrocarbylsilyl, Hydrocarbylamino or hydrocarbyloxy, and mixtures thereof, having up to 20 carbon or silicon atoms, or optionally, adjacent R 'and / or adjacent R "' groups are bonded together, by 15 This forms a divalent derivative, that is, two of these substituents can be bonded together; T is nitrogen or phosphorus; E is carbon or carbon; X is halo, alkyl, aryl, or alkoxy in each case 20 m is 1 or 2; η is 1 or 2; 72 200413420 LB is a selective Lewis base; and b is a number from 0 to 2, b)-or more activated Catalyst compounds, and c) selective catalyst supports. 5 2. Iso- or copolymerization for conjugated diene as described in item 1 of the scope of patent application A method for forming a polymer blend, wherein the M complex catalyst in the metal complex catalyst composition is titanium, copper, copper, or titanium. 3. It is used for copolymerization as described in item 1 or 2 of the scope of patent application. Method for iso- or copolymerization of conjugated diene or forming polymer blend in situ, wherein the reactive compound is neutral Lewis acid, which is a compound selected from CVm organoboron or organoaluminum Contains (hydrocarbyl) aluminum compounds; (hydrocarbyl) aluminum compounds; (hydrocarbyl) boron compounds; halogenated (hydrocarbyl) boron compounds; polymeric or oligomeric alumoxane; and non-polymeric compatible non-coordinating Ion-forming compounds that include the use of these compounds under oxidizing conditions; or a mixture of 15 thereof. 4. Iso- or copolymerization for conjugated diene as described in item 1 or 2 of the scope of patent application A method for reacting or forming a polymer blend in situ, wherein the activator is sodium hydrocarbyl, hydrocarbyl lithium, hydrocarbyl zinc, hydrocarbyl magnesium compound, or dihydrocarbyl hafnium. 20 5 · As described in any of the foregoing patents It is described as the same as used for the common car- Copolymerization reaction or method for forming polymer blend in situ, wherein the selective support material is selected from clay, silica, charcoal (activated carbon), graphite, expanded clay, expanded graphite, carbon black, layer Silicate, and alumina. 6. The method for conjugated diene as described in any of the scope of the aforementioned patent application-73 200413420 or a copolymerization reaction or forming a polymer blend in situ , Characterized in that the molar ratio of the metal complex / activator used is in the range of 1: 10,000 to 10 :; 1. ▲ 7. The conjugated diene as described in any one of the aforementioned patent applications The method is the same as -5 or a copolymerization reaction or a polymer blend formed in situ, characterized in that the weight ratio of the supported metal complex to the support material ranges from 1:10 to 1: 200,000. 8. The method according to any one of the foregoing patent claims, wherein the conjugated diene is iso- or copolymerized or is formed in situ a) the conjugated diene is iso-10 or the copolymer and b ) A polymer blend comprising one or more copolymers of dilute and ethylene and / or alpha-dilute hydrocarbons. 9. The method as described in item 8 of the scope of patent application, wherein the content of the conjugated diene in the homo- or copolymer comprising ethylene and / or alpha-olefin is less than 5 mole%. 151 10. The method as described in claim 8 or 9, wherein the same-or Copolymers are manufactured during a polymerization reaction in one of the reaction systems. 11. The method for iso- or copolymerization of a co-diene or forming a polymer blend in situ as described in any one of the foregoing patent claims, wherein the conjugated diene is selected from Contains 1,3-butadiene, isoprene, 2,3-difluorenyl-20, 1,3-butane-1,1,3- 戍 ^ -1,2,4-hexan — "« Fine, 1,3-hexadiene; fep, 1,3-% heptadiene; 1,3-octadiene; 2-methyl-2,4-pentadiene; cyclopentadiene; 1,3-cyclohexan Diene; 2,4-hexadiene; 1,3-cyclooctadiene; a group of norbornadiene. 12. A method for iso- or copolymerization of co-diene or forming a polymer blend in situ as described in any one of the foregoing patent application scopes, wherein in 74 200413420, the ethylenically unsaturated monomer The system is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptyl, 4-fluorenyl-1-pentene, 1-octene, 1-decene . 13. The method as claimed in claims 8 to 12, wherein the diene / ethylene 5 or α-olefin copolymer or the polymer blend of the diene / ethylene or α-olefin copolymer Some are random copolymers. 14. The method as claimed in claims 8 to 12, wherein the diene / ethylene or α-dilute copolymer or the polymer blend of the diene / ethylene or α-olefin copolymer Part of the block copolymer. 10 15. The method of claim 13 or 14, wherein the butadiene in the diene-α-olefin copolymer or the diene-α-olefin copolymer portion of the polymer blend The ene content is less than 70 mole%. 16. The method according to any one of the foregoing patent claims, wherein the copolymer or copolymer #compound contains random or pseudo-random distribution units of aromatic alpha-dilute hydrocarbons. 17. A homopolymer, copolymer or polymer blend, which is manufactured according to any one of the scope of the aforementioned patent application. 18. A copolymer of conjugated diene and ethylene and / or alpha-olefin, wherein the butadiene content is between 30 mol% and 40 mol%, and the ethylene content is 60 20 mol% And 70 mol%. 19. A copolymer of a conjugated diene and ethylene and / or an α-olefin, wherein the butadiene content is between 40 mol% and 50 mol%, and the ethylene content is between 50 mol% and 60 Moore%. 20. —A copolymer of a conjugated diene and ethylene and / or an α-olefin, wherein the content of the 75 butadiene is between 50 mol% and 60 mol% / ❶ and 50 mol%. . ear. And the ethylene content _ 2 but I copolymer of a total of diene and ethylene-olefin, wherein, the butan-off content between mol% and 70 mol%, 乂 " mol % And 40%. The amount is 30 22 · —a copolymer of co-light dioxin and ethylene and / or diene, and the content of butadiene is 70 mol% and 80 mol μ mol% and 30 mol %between. * 10 and the diene content is 10, which is ㈣: ene or copolymer. ) 3—Copolymerization of dioxin and ethylene and smoke 15 24. Polymer homopolymers of diene as described in item 23 of the scope of patent application, and b) containing butadiene And ethylene copolymers. …, A butyl 25 ·-polymer blend, which is a) the same or the same as the total consumption b) the same or copolymers containing ethylene and / or α • dilute hydrocarbons, including: Baoren B The total of the hydrazone and / or alpha-olefin homo- or copolymer is about 5 mole%. Liyou 20 26. The polymer conjugate according to item 25 of the scope of patent application, the homopolymer of butadiene, and b) the same or copolymer containing ethylene. ..., " Ding 27. The polymer blend as described in item 24 of the scope of the patent application, wherein the content of the butadiene in the copolymer portion is between 30 mol% and 40 mol%. And the ethylene content is between 60 mol% and 70 mol%. 〇28. The polymer blend as described in item 24 of the scope of the patent application, wherein, in the copolymer portion, the butadiene content is between 40 mol% and 50 mol% 76 200413420, And the ethylene content is between 50 mol% and 60 mol%. 29. The polymer blend according to item 24 of the scope of the patent application, wherein in the copolymer portion, the butadiene content is between 50 mol% and 60 mol%, and the ethylene content is Between 40 mol% and 50 mol%. 5 30. The polymer blend according to item 24 of the scope of the patent application, wherein in the copolymer portion, the butadiene content is between 60 mol% and 70 mol%, and the ethylene content Lines are between 30% and 40%. 31. The polymer blend as described in item 24 of the scope of the patent application, wherein, in the copolymer portion, the butadiene content is between 10 mol% and 80 mol%, and the ethylene content Lines are between 20 mol% and 30 mol%. 32. Identical or copolymers or polymer blends formed in situ as described in any of claims 16 to 30, which are molded parts, films, foams, golf balls, In the form of tires, hoses, conveyor belts, gaskets, seals, shoes or modified plastics. 15 77