TW200302235A - Metal complex compositions and their use as catalysts for olefin polymerization and copolymerization - Google Patents

Abstract

This invention relates to metal complex compositions, their preparation and their use as catalysts to produce polymers of conjugated dienes through polymerization of conjugated diene monomers and copolymers of conjugated dienes with aromatic or nonaromatic alpha olefins or with nonconjugated dienes. The used metal complex compositions comprise cobalt complex compositions in combination with activator compounds type 1 and activator compounds type 2 and a catalyst modifier. Particularly the invention relates to cobalt complexes containing at least one cobalt - oxygen bond and to the preparation of the catalyst and the use of the prepared catalyst to produce homopolymers of conjugated dienes or copolymers of conjugated dienes with aromatic or nonaromatic alpha-olefins or with nonconjugated dienes, preferably polymerization of 1,3-butadiene or isoprene or copolymerization of 1,3-butadiene or isoprene with styrene or divinyl benzene. The activator compounds can be one alumoxane type activator or a noncoordinating anion-forming reagent such as, but not limited to, organoborates or organoborone compounds and one alkylaluminum halide type activator are used in combination with the cobalt complexes and with one or more aromatic compounds for the synthesis of homopolymers or copolymers. The aromatic modifier is applied in amounts similar or smaller than the amounts of the used activators.

Description

200302235 发明 Description of the invention (The description of the invention should state: the technical field, prior art, content, embodiments, and drawings of the invention are briefly explained.) [Technical field to which the invention belongs] The present invention relates to a metal complex composition. Preparation and its use as a catalyst for the production of conjugated diene polymers by polymerization of conjugated diene monomers, and conjugated diene and aromatic or non-aromatic alpha-hydrocarbons, or A total of one fine copolymer. The metal complex composition used includes a cobalt complex composition combination of a type 1 activator compound and a type 2 activator compound and a catalyst modifier. In particular, the present invention relates to a cobalt complex containing at least one cobalt-oxygen bond, as well as the preparation of the catalyst and the use of a catalyst to obtain 10 for the manufacture of conjugated diene homopolymers, or co-diene and aromatics. Family or non-aromatic alpha olefins, or copolymers with non-conjugated dienes, preferably for copolymers of 1,3-butadiene or isoprene, more preferably for copolymers of 1,3- Polymerization of butadiene or isoprene, or copolymerization of butadiene or isoprene with styrene or divinylbenzene. 15 [Prior art] Metal complex catalysts for producing polymers from a dilute monomer are known. EP 816,386 states that olefin polymerization catalysts containing transition metal compounds are preferably selected from the group consisting of IIIA, IVA, VA, VIA, VIIA or VIII transitions. 20 metals or lanthanides are preferably titanium, zirconium, or hafnium and alkanes. A compound consisting of an alkenyl ligand. The catalyst further includes an auxiliary alkylaluminoxane catalyst, which can be used for the polymerization and copolymerization of tobacco. Based on cobalt complexes and organoaluminum activators, 3_butadiene polymerization catalyst 200302235 发明, description of invention Chemical agents are described in patent cases and published references. In particular, there are two major types of catalysts based on incipient complexes that have been thoroughly studied. A) Typical cobalt catalysts' are composed of at least one Wei acid (organic slow acid starting salt) combined with one or more aluminum-based compounds, B) A cobalt compound or complex comprising a complex of cobalt compound 5 or a combination of at least one alumoxane component. Traditionally, cobalt carboxylates have been used in combination with appropriate organoaluminum activator ingredients for the polymerization of conjugated diene (such as 1,3-butadiene and isoprene). A) Typical cobalt catalyst A process for the preparation of polybutadiene is described in EP 0106596. A catalyst composed of at least one cobalt 10 compound, organic toothed aluminum (composed of at least one trialkyl aluminum compound and water reaction product), and carbon difluoride or / and phenyl isocyanate compounds, Polymerization of 3-butadiene. For example, butadiene is exposed to a benzene solvent to diethylaluminum monochloride and the reaction product of triethylaluminum and water (ratio j: 0.87). The polymerization was then started by adding cobalt octoate and carbon disulfide. As a result of the polymerization reaction, a high proportion of cis-1,3-polybutadiene was recovered (cis content was 95% to 97.1%). Patent case EP 770631 B1 describes the preparation of Gao Shun 1,4-polybutadiene. The preparation method of rhenium uses at least one cobalt compound, at least one organoaluminum compound, water, and in addition to naphthenes as the main solvent, substituted 20 benzene is used as a polymerization regulator of the formula (C6H5_n) R1 + n [wherein 11 is an integer of 3 to 5, and each R table does not contain a low-carbon alkoxy group of 1 to 4 carbon atoms]. Preferably, R is oxy. For example, cobalt ethylacetonate (11) combined with diethylaluminum chloride is used for the polymerization of 1,4-butadiene in a polymerization solvent. The polymerization solvent consists of hexane, water, butene, and various concentrations. Composition of methoxy substituted benzene. 200302235 Rhenium, description of inventions, and descriptions of the requirements of the so-called typical polymerization system lead to relatively low-profile results, and still require water to combine difluorenyl halides to activate misregistrations for butadiene Polymerization. Ming complex / two organic _ chemical Ming / water system solubility in water is low, often leading to process instability. P. Cass et al., Polymer Science Journal: Part A Polymer Chemist, 39 2001 2244-2255 "Yan Erming replaced the benzene with a regulator for the catalytic polymerization of butadiene, and the polymerization became Gao Shun-1 , 4-Polybutadiene is a typical octanoic acid / diethyl chloride / water system using 1,3,5-trimethoxybenzene or methylbenzidine, and is used as a cyclobutadiene in cyclohexane / 10 catalysts for butene solvents. U, 5-trimethoxybenzene is presumed to be used as a 4 polymerization regulator by bonding to the active catalyst through coordination. The addition of trimethoxybenzene was found to increase the percentage of active catalytic cobalt particles to approximately 200% of the original value. However, the conversion rate and cis content of the polybutadiene formed at the same time are reduced. For example, the conversion of butadiene has not been reported to be higher than 45% in the presence of 1,3,5-trimethoxybenzene. Although solvent 5 does not contain benzene with special restrictions on the mounting substrate, the use of water is unavoidable, and it is still necessary to use water to activate the cobalt octylate combination dialkyl aluminum halide. As mentioned above, the solubility of the water in the amidine complex / diorganoaluminum chloride / water system is low, resulting in unstable process. B) Ming compound or complex containing at least one cobalt compound or 20 cobalt complex combination alumoxane activator component WO 0004064 illustrates the use of a combination of organoaluminum compounds and modifiers in aromatic vinyl compounds such as Polymerization of conjugated dimerization in the presence of styrene. The cobalt compound is, for example, an organic acid salt, and the organic aluminum compound must be sintered. In addition, another organic compound is aluminum halide (A1Ud, R is alkyl, cycloalkyl, or aryl) and organic formula HYR'e (Y is Vb or VIb group element of the periodic table, R Is a product obtained by reacting a donor compound such as hydrogen, alkyl, sulfanyl or aryl). Although cobalt carboxylate is exclusively for the purpose of the present invention, cobalt bromide phosphine adduct catalyst 5 CoBr2 (PPh3) 2 is far from validating the present invention. For example, butadiene and styrene need no additional polymerization solvent, use CoBr2 (PPh3) 2, Ionol (Ionol) [(2,6_ mono-second butylmethyl)] and methyl aluminum A catalyst system consisting of oxane (MAO) was copolymerized. Patent DE 19832455 A1 is similar to the aforementioned patent WO 0004064. 10 According to US 5,879,805, a compound such as a halogenated compound, a cobalt compound of an organic acid organic salt, and the like is a combination of an organoaluminum compound and a compound [selected from the group consisting of phosphine, xanthogen, or sulfur isocyanide] for gas Reverse reactor polymerizes 1,3-butadiene. The organoaluminum compound is represented by one of the compounds selected from the group consisting of triorganic AIR3, organo-aluminum AlR'X ^ m, or alumoxane 15 A1Rn2 (0R3) 34. Cobalt dihalide phosphine adduct

CoBr2 (PPh3) 2, Cobalt acetamylpyruvate Co (acac) 3 or methyl_bupropenyl) (but-1,3-diene) triphenylphosphine cobalt is activated by methylalumoxane alone, Alternatively, it can be activated in the presence of a suitable support material and subsequently used for butadiene polymerization. Taking the catalyst based on cobalt acetopyruvate as an example, the microstructure or molecular weight of the polymer has not been mentioned. 1 ^ 6,001,478 describes an example similar to patent case 1) 8 5,879,805, but the scope of the patent application is related to inert granular materials required for gas phase polymerization. In EP 0816398 and JP 10-7717, at least one cobalt component, at least one trialkylaluminum compound, and the formula AlR2mX3-m (X is a halogen anion, 200302235 玖, description of the invention R2 represents a hydrocarbon group, and m is a number from 0 to 2) A catalyst system consisting of an alkylaluminum halide compound or / and a halogenated halogen compound of the formula RX (R represents a radical) and water is used for the polymerization of 1,3-butadiene. The optimum aluminoxane component is prepared in advance by mixing water with a trialkylaluminum compound. In this way, a catalyst system composed of at least one pentad compound, alumoxane component, aluminum alkyl compound, and / or alkyl functional compound has also been patented as a catalyst for the polymerization of 3-butadiene. By way of example, cobalt octoate, methylalumoxane, and ethyl sesquicarbonate (EASC) in combination with 1,5-cyclooctadiene are used as molecular weight modifiers. As a result, the obtained polymer contained more than 97% cis-polybutadiene in the examples, and the average molecular weight was 390,000 and 450,000 g / mole. Mooney values (ML 1 + 4) are 29 to 34. It should be noted that the conversion rate of ι, 3-dioxane in each of the examples is not more than 50%. JP 10-158333 requests a procedure for the preparation of 1,2-polybutadiene. ι, 2_ polybutadiene is prepared through the polymerization of 1,3-butadiene using a catalyst. The catalyst is a cobalt compound, a phosphine compound, methylalumoxane, or trimethylaluminum and water. Reaction products and silicon atom-containing compounds. JP 11-140118 claims a process for preparing polybutadiene using a catalyst, which is composed of a cobalt compound, an alumoxane component, and an organic halide compound. The aluminoxane and organic compounds must be aged before use. A procedure for preparing a polymer from a conjugated diene was introduced according to JP 114817. The catalyst used for the polymerization of diene contains a cobalt compound, at least one aluminizing component ', and a compound containing a halide atom. The compounds containing autogen atoms are the reaction products of metal south compounds and Lewis bases. 10 200302235 (ii) Description of the invention Patent JP 8-325331 describes the preparation procedure of polybutadiene. The L3-butadiene system is a combination of a compound consisting of a trialkyl group compound of the general formula AIR3, an alumina compound, and a compound selected from the group consisting of carbon dioxide, phenyl isocyanate, and a flavin orthoate compound. Aggregation reaction. JP 6-116316 and JP 128301 request a butadiene polymer having a high content of ethylene bonds. The polybutadiene content is at least 50 mole percent. The catalyst used to prepare the copolymer is composed of a cobalt salt, an aluminoxane-containing organoaluminum compound, and a phosphine compound. The polymerization was carried out in an inert organic solvent and using hydrogen 10. Patent JP 6-128301 additionally requests the preparation of the aforementioned polymers using continuous and discontinuous polymerization processes. The patent JP 6-1163 15 is similar to the aforementioned patent jp 6-116316, but the catalyst for the production of succinic polymers additionally contains an organic aluminum compound. JP 6-116342 is also similar to the aforementioned patent jP 6-116316 and claims a butadiene copolymer having a high content of 15 ethylene bonds. The second monomer (1 to 30 mole% copolymer) also contains a conjugated double bond. The butadiene portion of the copolymer contains 80% or more of ethylene bonds. The catalyst for the preparation of the copolymer contains, for example, a cobalt compound, methylalumoxane (MAO) and triphenylphosphine (pph3). Patent JP 7-102014 describes the procedure for preparing a poly 20 compound containing at least 50 mole% polybutadiene. The obtained polymer is prepared by using a cobalt compound in combination with an organoaluminum compound containing an alumoxane component and an alkyl benzene alumina compound of the following general formula.

(R1 is an alkyl group, R2-R6 are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, and η is 1 or 2) in an inert organic solvent. Patent RU 21255778 C1 describes a procedure for the synthesis of 5cis-1, 'polybutadiene with an aromatic solvent. The polymerization of conjugated diene (especially 1,3-butadiene) is based on soluble cobalt salts, (a) aluminum chloride or sesquigas, and polyalumoxane (R) 2Al- [OAlR] n-〇-Al (R) 2 or amine aluminoxane (r) 2A1-〇_ cH2_n (r ') (r ”) [where r is ethyl or isobutyl, R is a1 (R2), r, is hydrogen or A1 (R2) and η is 0, 1 or 2]. The cobalt compound, for example, 10 is ignite, octanoate, or ethylpyruvate. Patent Case RU 2082721 C1 Description A process for synthesizing cis-1,4-polybutadiene in a hydrocarbon solvent (such as toluene) using a catalyst system consisting of a cobalt compound, an alkyl aluminum oxide compound, water, and a polyalumoxane compound of the following formula : (R) 2Al- [0AlR] n-0-Al (R) 2, where R represents ethyl or iso 15 butyl and η is at least 2. The cobalt compound is, for example, cobalt naphthenate, cobalt octoate, stearic acid Cobalt, cobalt 2-ethylhexanoate or cobalt acetopyruvate. The alkylaluminum chloride compound is selected from the group consisting of diisobutylaluminum gaseous, diethylaluminum chloride, isobutylaluminum chloride, and ethyl A group consisting of sesquichloride. One exists in the catalyst The method for making polybutadiene is described in Ερ 20 0511015 B1. The catalyst is composed of a phosphine complex and an organoaluminum compound that roughly contains alumoxane. For example, osmium (triphenylphosphine) cobalt dibromide, formazan Aluminoxane (ΜΑΟ), toluene solvent and ι, 3-butadiene are placed on stainless steel 12 200302235 玖, invention description high pressure pin. Molecular weight is 101,000 to 384000. Butadiene conversion is low, not more than 40 after 4 hours %. The microstructure of the obtained polybutadiene (cis_u_ / trans-1,3- / 1,2-polybutadiene ratio) was not provided in the patent case. EP 0511015 B1 describes a polybutadiene Production method. According to the 5 patents of this patent, U · butadiene is polymerized in the presence of a catalyst, which is composed of a cobalt-phosphine complex and an organoaluminum compound (preferably an alumoxane component). For example, triphenyl Cobalt phosphine) Cobalt di-molybdenum is treated with methylaluminoxane in toluene to form a catalyst. The polymerization reaction results in a high proportion of polybutadiene greater than 60%. However, the polymer conversion rate reported in this patent case In all the examples 10, it is lower than 24%. 15 20 BP 0433943 A2 request for reminder The catalyst component A is a transition metal compound represented by the general formula M (R) 1 (0R,) mXn (i + m), where M represents a transition metal atom, a ruler and a ruler each represent a hydrocarbon group, And X represents a function atom. The preferred gold material of the transition metal compound represents titanium or copper. The catalyst component B is an organoaluminum compound, which may be an alumoxane, a trihydrocarbyl aluminum compound, or a hydrocarbyl aluminum halide. The catalyst component. Two hydroxy organic compounds (such as burned glycol) or aromatic compounds with two or more warp groups. The group of organic compounds is, for example, mixed dimethylbenzyl. The aforementioned catalysis is mainly used for preparing trans-polybutadiene. Typical examples include the reaction of titanium tetragas with an aromatic diol (such as 2,2, -diacryl_3,3, _di_thirdbutyl_5,5, · dimethyldiphenylsulfide) , And then react with methyl alumoxane. The obtained catalyst is used for the polymerization of U-butadiene. This patent does not cover the second aluminum-based component in the catalyst formation process, which is basically limited to the catalytic core 15 mainly composed of titanium and tungsten. The organic compound representing component C is used to form the desired 13 200302235 玖, description of the invention The catalyst precursor, but not as a modifier for the ongoing polymerization process. Cobalt octoate is used as a catalyst 'combined with Methyl Oxygen Institute and a third butyl chloride, used to prepare a high cis polybutadiene using a solvent mixture. The solution contains cyclohexyl'15% benzene, 35% τene and articles Dibutene monomers (see P. Cass et al. 'Journal of Polymer Science: Part A. Polymer Chemistry, W277-pass). At 30% u_butadiene conversion, the highest dynamic spray-M-polybutadiene content was reached. Comparing the typical octane / diethyl ㈣m㈣ octanoic acid / third butyl chloride catalysts did not show significant differences in terms of the quality of 15 20 polybutadiene, but the linearity of the polymer improved slightly. The effect is a significant reduction in aromatic benzene solvent content. In addition, a dynamic study of U-butadiene polymerization using octanoic acid / alumoxane / di __ ^^ ^ milk precipitation / second butyl gas catalyst system is described in p. Cass et al. (Journal of Polymer Science : Part A: Polymer Chemistry, 39 read 2256_2. I hope there is a catalyst system that can be activated without the use of water, which guarantees easy process. In addition, the required catalyst system must be free of benzene and / or even A solvent system containing substantially no aromatic compounds is carried out. Such a catalytic system is more active than the known silk-fired amidine-containing system which has been known so far. In addition, it is desirable to have a catalyst component, which can be directly injected into the polymerization reaction. "Fenger ..., and aging" (stirring, shaking or storage) catalysts or catalyst components undergo a long period of time. In addition, if the required catalyst system can copolymerize diene and alpha olefins, it is preferable to bind them. Smoke is more advantageous. For example, butadiene-styrene copolymers are interesting for many purposes. Preparation, roasting homopolymer, only one type of conjugated diene monomer polymerization method 14 200302235 玖, Description of the invention or a copolymer produced by a copolymerization method, and such polymerization methods are the purpose of the present invention, the copolymerization method is-a conjugated dimer monomer and another _ -type light monomer copolymerization, or with-or The second class of non-aromatic soot or non-5, pure compounds or complexes are used in combination with activators and catalyst modifiers for copolymerization. It is especially used for the synthesis of homopolymers or copolymers of dimer monomers. The compound or complex contains at least one oxygen bond. More particularly, the diene monomer is, for example, U.butadiene, and the isoprene is homopolymerization; or the monomer (for example, but not limited to U- Butadiene and isoprene) are aromatic 10 or non-aromatic 4 smoke or non-aromatic non-co-light diene (such as, but not limited to, stilbene, diethenylbenzene or divinyltoluene, 1-hexene, 1. succinyl, decadiene, 1,5-hexadiene, u-octadiene or u decadiene), use the aforementioned starting compound or complex to combine an activator, and combine one or A variety of aromatic compounds U are changed to jt agent for copolymerization reaction. In particular, sintering activators or non-coordinating anion forming agents (such as but not In organic borate or organic boron 15-ite) X and germ-based denatured activators, combined complexes and combined-or multiple aromatic compounds are used to synthesize homopolymers or copolymers. More specifically a 1 Lu Xuanxuan type activator and a kind of burn-based halogenated Shao type activator combined initial complex and combined with an aromatic compound for the synthesis of homopolymer 20 or copolymer. Special aromatic modifier is used in a similar amount of activator Or less than the amount of activator to be applied. [Summary of the invention] The object of the present invention is a complex complex, which can be used to form a catalyst composition for the polymerization of olefin monomers, especially diene monomers, and more particularly conjugated diene monomers. Another purpose is to record the wrong compound, which can be used to form olefin monomers, especially 15 玖, invention description two dilute monomers, two materials such as a total of two materials, the engineer early body 'special two dilute monomers

„The catalyst composition for tr or fragrant aromatic or non-aromatic CC women's hydrocarbon ping poly A. Eight, mouth, t: two and one, the method of preparing the catalyst composition, the product can be used for dilute hydrocarbon monomer Polymer, especially dimer monomer, more special /, polymerization of nidene early body, or the catalyst composition may: monomer and dilute hydrocarbon monomer in particular 0 0 ~, conjugated monoene, /, monoene Copolymerization of aromatic or aromatic alpha olefins or non-aromatic hydrocarbons. 10 Ben! X Mingzhi-The purpose is a catalyst composition which can be used for the polymerization of dilute monomers, more specifically, dilute monomers. Or the group I of the catalyst can be used for the copolymerization of a co-light diene monomer and an olefin monomer, particularly a diene monomer or an aromatic α㈣ or a non-aromatic α dilute hydrocarbon. 15 Another object of the present invention It is a method for polymerizing olefin monomers, particularly dilute monomers, and more particularly divinyl monomers. The method uses the catalyst composition for conjugated dilute monomers and dilute monomers, and particularly dilute diethyl monomers. Copolymerization reaction of aromatic or non-aromatic alpha olefins or non-aromatic olefins. This month-purpose is to use the The polymer made from the chemical composition is a special polymer and a more special polymer. 20 Another purpose of the present invention is a catalyst composition. The catalyst composition, ^ a, coexists with unsaturated carbon-carbon. Monomers of double bonds, especially one of the two types of dimer monomers, obtain polydiene, which comprises a) a quaternary compound or a cobalt complex, b) a metal complex activator compound, and c) at least A catalyst modifier is preferably an aromatic compound. In addition, the object of the present invention is two or more cobalt complexes / activator component type 1 / activator 16 200302235 玖, the second part of the description of the invention Type / catalyst composition containing catalyst modifier. Preferably the cobalt complex contains at least one cobalt-oxygen bond. The formula of the cobalt complex is less than 2000, more preferably less than 80. 〇 It is preferable that the cobalt complex according to the present invention contains a carboxylate ligand. 5 More preferably, the cobalt complex according to the present invention contains octanoate, neodecanoate, cyclamate, versatate, ethyl Amidinopyruvate, 2-ethylhexanoate or stearic acid ligands. The cobalt complexes of the invention include, for example, cobalt octoate, cobalt neodecanoate, cobalt naphthenate, cobalt vesartate, cobalt acetopyruvate, cobalt 2-ethylhexanoate, and 10 cobalt stearate. The metal complex can be activated using an activator compound (at least one type 1 activator combined with at least one type 2 activator). Activation can be performed during a separate reaction step, optionally including isolation of the activating compound, or can be The activation is preferably after the activation of the metal complex, if the isolation and / or purification of the activated complex is not required, the activation is performed in situ. Preferably, the metal complex of the present invention is combined with at least one first Type activator compound, at least one type 2 activator compound, and at least one catalyst modifier to become catalytically active. The metal complex according to the present invention may use an appropriate activator (type activator 20 and type 2 Type activator) and appropriate catalyst modifiers. For example, the type 1 activator may be an organometallic compound, in which at least one aromatic radical is directly bonded to the metal, and at least one (aromatic) carbon-metal bond is obtained. The hydrocarbyl group directly bonded to the organometallic compound to the metal preferably contains and more preferably 1 to 10 carbon atoms. The metal of the organometallic compound may be selected from element 17 200302235 rhenium, description of the invention Groups 11, 12, 13 or 14 of the periodic table. Suitable metals are, for example, inscriptions and deletions. Suitable type activator compounds for use herein include fluorinated aromatic boron compounds, in particular fluorinated or perfluorinated tri (aryl) boron compounds such as gins (pentafluorophenyl) boron, ginseno (o-ninefluoro) Biphenyl) boron, ginseng [3,5_wu (trifluoromethyl) benzene 5yl], fluorinated or perfluorinated tri (aryl) ming compounds such as ginsyl (pentaphenyl), ginseng ( O-Nine fluorobiphenyl), ginseng [3,5_ bottom (trifluoromethyl) phenyl], and polymers or oligomers Butylming modified methylalumoxane or isobutylalumoxane; non-polymer, compatible, non-coordinating, ion-generating compounds (including using these compounds for oxidation conditions), especially using compatibility Non-valent anion recorded salt, scale salt, oxo salt, carbon recorded salt, Shi Xiyuan recorded salt, continued iron salt or ferrocene salt; and a combination of the foregoing activating compounds. The aforementioned type 1 activating compound has previously been taught in the following references for different metal complexes: National Patent Case "M., 5,153,157. 5,064,802, 5,321,106. 5,721,185, 5,350,723, and WO-97 / 04234, which is equivalent to U.S. 08 / 818,53 (), the application date is March 14, 1997. Ion-generating compounds can be used as the activator compounds of the first type according to the present invention. The cations (which are In one embodiment of the present invention, suitable ionogenic compounds of useful compounds include a compatible non-coordinating anion (an anion or substance that does not have a protonic Bronsted acid) and one for use herein "The term" non-coordinating "means a coordination to a metal-containing precursor complex and a catalyzed derivative derived from the precursor complex, or the anion is only weakly coordinated to such 18 20 发明, invention Explain that the complex compound, therefore, maintains the stability of the drag knife placed by octabutadiene, which can be unstable by Lewis base (such as alkene monocation; 卩 complex anion refers specifically to an anion, which is equivalent to = Use as When the anion is balanced, it will not transfer. "When the compatibilities are decomposed, the anions will be decomposed, and the misformation that is well formed is neutral, and it will also interfere with the desired post-drum polymerization or other uses of the complex. Good anion Hegu g — an early coordination complex containing an electric 10 15 k metal or metalloid center, the anion balances the active catalyst species (the metal cation 'may form when the two components are combined) In addition, the anion is sufficiently unstable and can be substituted by olefins and saturates. Substances or neutral Lewis bases such as ethers or nitriles. Suitable acids include, but are not limited to, aluminum, gold, and platinum. Suitable classes Metals include, but are not limited to, boron, phosphorus, and stone. Anionic compounds that contain coordination dislocations containing a single metal or metal-like atom are, of course, well-known. A variety of complexes, particularly compounds containing a single boron atom in the anion portion, are commercially available. Available. The preferred type 1 activator compound is represented by the following formula: (L * -H) / Ad- where: 20 L * is neutral Lewis test; (L * -H) + is Bronsted acid ;

Ad is a non-coordinating compatible anion with a charge d ·, and d is an integer from 1 to 3. Better Ad_ Correspondence: 19 200302235 发明, description of the invention [M * Q4]; where: M * is +3 grams of boron or aluminum in the oxidation state; and each Q is selected from the group consisting of hydrogen anion and dioxane. Hydrazone, 5 anion, hydrocarbyl, hydrocarbyl, halocarbon, hydrocarbyloxy anion, hydrocarbyloxy substituted hydrocarbyl, organometal substituted hydrocarbyl, organic metal substituted hydrocarbyl, hydrocarbyl, etc. I hydrocarbyl-substituted hydrocarbyl, alkano-substituted hydrocarbyl, and halogen-substituted silane-based hydrocarbyls (including fully halogenated hydrocarbyls, fully-halogenated via oxygen radicals, and fully-halogenated silyl hydrocarbon radicals), the Q contains up to 20 Carbon, but no more than 10 is a Q halide anion. Suitable hydrocarbyloxyanion Q groups are disclosed, for example, in U.S. Patent No. 5,296,433. In a more specific embodiment, d is 1, that is, the counter ion contains a single negative charge and is A ·. The activator compounds that are particularly useful in preparing the catalysts of the present invention are represented by the following formula: 15 (L * -H) + (BQ4)-; where: L * is as defined above; B is the deletion of grams of titanium oxide 3. ; And alkoxy, fluorinated hydrocarbyl, but Q is a hydrocarbyl group of not more than one, especially pentafluorophenyl or nine 20 Q is a hydrocarbyl group containing up to 20 non-hydrogen atoms, fluorinated alkoxy, or fluorinated silyl Hydrocarbyl, times. The best Q at each occurrence is a fluorinated aryl fluorobiphenyl. The modified ammonium salt of the improved catalyst can be used, for example, as an activator compound for the preparation of the present invention. An illustrative but non-limiting example of the compound is 20 200302235. 发明, Description of the invention: Triphenylammonium tetraphenylborate, tetraphenylborate Tris (n-butyl) ammonium, methyl di-octadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tris (n-butyl) tetraphenylborate Ammonium, tetrabenzyl borate methyl-tetradecyl-octadecyl ammonium, tetraphenyl borate N, N-dimethylaniline 5, tetrabenthoate N, N-diethylaniline, Tetraphenylheptanoic acid n, n_dimethyl (2,4,6-dimethylaniline), osmium (7,8 · dimethylformadecylboronic acid) cobalt acid (III) N, N-dimethyl Methylbenzyl ammonium, trimethylammonium (pentafluorophenyl) borate, methyldi (tetradecyl) ammonium (pentafluorophenyl) borate, methyldi (18-pentafluorophenyl) borate Alkyl) ammonium, triethylammonium (pentafluorophenyl) borate, tripropylammonium (pentafluorophenyl 10yl) borate, tri (n-butyl) ammonium (pentafluorophenyl) borate, Pentafluorophenyl) borate Methyl) ammonium, methyl (pentafluorophenyl) borate N, N_dimethylaniline, methyl (pentafluorophenyl) borate N, N_diethylbenzyl ammonium, methyl (pentafluorophenyl) butter , N_dimethyl (2,4,6-trimethylaniline), tris (2,3,4, tetrakiphenyl) trifluoroammonium borate, (2,3,4,6- Tetrafluorophenyl) triethylammonium borate, 15 (2,3,4,6-tetrafluorophenyl) tripropylammonium borate, (2,3,4,6_tetrafluorophenyl) borate di (N-butyl) ammonium, methane (2,3,4,6-tetrafluorophenyl) borate dimethyl (third butyl) ammonium, methane (2,3,4,6-tetrafluorophenyl) borate N, N-dimethylaniline, N- (2,3,4,6-tetrafluorophenyl) borate N, N_diethylaniline, and (2,3,4,6_tetrafluorophenyl) ) Boric acid N, NH (2, Mg f based); Dialkyl ammonium 20 salts such as: (pentafluorophenyl) boric acid di (octadecyl), di (pentaoxyphenyl) terephthalic acid ( Tetradecyl) ammonium, and dicyclohexylammonium (pentafluorophenyl) borate; tri-substituted phosphonium salts such as ·· (pentafluorophenyl) borate triphenyl scale, and (pentafluorobenzyl) borate Methyl bis (octadecyl) scale and tris (pentafluorophenyl) naphthalene tris (2, 6-dimethylbenzyl) scale. 21 200302235 发明, description of the invention is preferably a long-chain alkyl mono- and di-substituted ammonium complex (pentafluorobenzyl) phosphonate, especially Ci4_C20 alkyl radical complex, especially This group) methyl bis (octadecyl) ammonium rotten acid and ammonium (pentadecyl) ammonium (pentafluorophenyl) pentanoate, or mixtures thereof. Such mixtures include protonated ammonium cations derived from amines containing two Cm, 8 alkyl groups, and one methyl group. These amines are available from the company Witco under the trade name Kemamine Ding 9701 and from Akzo-Nobel under the trade name Armeen M2HT. The preferred type 1 catalyst activators used herein include, for example, the aforementioned tri-10 alkylammonium salts, in particular the following methylphosphonium (tetradecyl) ammonium salts or methylphosphonium (octadecyl) ammonium salts ·· 贰(Shen (pentafluorophenyl) borane) imidazolium, (Shen (pentafluorophenyl) side burning) -2-undecyl Imidosal, Λ (shen (pentafluorophenyl) butterfly house)- 2-Heptadecanyl imide salivate, osmium (reference (pentafluorophenyl) borane) -4,5-fluorene (undecyl) imidazolium, 15 hydrazone (reference (pentafluorophenyl) borane) -4,5-fluorene (heptadecyl) imidazolium, hydrazone (gins (pentafluorophenyl) borane) imidazolium, hydrazone (gins (pentafluorophenyl) borane) -2-undecyl Imidazolium sulfonate, Ambient (referred to (pentafluorophenyl) greenhouse) 2-Seventhyl-based salivary salivary compounds, fluorene (referred to (pentafluorophenyl) borane) -4,5-fluorene (undecane Group) imidazolium phosphonium compound, 20% (reference (pentafluorophenyl) borane) -4,5-fluorene (heptadecyl) imidazole. Cinnamate, Home (Ginseng (pentafluorophenyl) borane) -5,6-difluorenylbenzimidazole, Dai (Ginseng (pentaphenyl) township) -5,6-wu Benzyl miso compound, hydrazone (ginseng (pentafluorophenyl) alumino) imidazolium, home (ginseng (pentafluorophenyl) | g roast) -2-undecyl imidazolate, 22 200302235 pyrene 2. Description of the invention Thallium (Ginseng (pentafluorophenyl) Shaoyao) -2-heptadecanyl imidyl salivate, Thallium (Ginseng (pentafluorophenyl) alumane) -4,5-fluorene (undecyl) Imidazolium, osmium (reference (pentafluorophenyl) alane) -4,5-hydrazone (heptadecyl) imidazide, osmium (reference (pentafluorophenyl) alane) imidazolium, 5 osmium (reference (Pentafluorophenyl) alkane) -2-undecylimidazolium halide, osmium (referred to (pentaphenyl) Shaoyao)-2-heptadecyl miso throat, osmium (referenced to (pentafluoro) Phenyl) alane) -4,5 · fluorene (undecyl) imidazolium phosphonium, hydrazone (gins (pentafluorophenyl) alkane) -4,5 · fluorene (heptadecyl) imidazolium hydrazone, Wu (Shen (pentafluorophenyl) alane) -5,6-dimethylbenzimidazolium, with 10 and osmium (Shen (pentafluorobenzene) ) Ming Institute) -5,6-II (xi burn-yl) imidazole and σ Zuohua was stupid. The aforementioned activator compounds have previously been taught in the following references for different metal complexes: EP 1 560 752 A1. Another suitable ammonium salt is particularly used in non-homogeneous catalyst systems. It is formed by the reaction of 15 organic metal compounds (especially tri (Cw alkyl) aluminum compounds) with hydroxyl ammonium (fluoroaryl) borate compounds. The resulting compound is an organometallic oxyaryl ginseng (fluoroaryl) borate compound which is generally insoluble in aliphatic liquids. Suitable compounds include the reaction product of a tri (Cw alkyl) aluminum compound and a hydroxyaryl para (aryl) borate ammonium salt. Suitable hydroxyaryl ginseng (aryl) boronic acid 20 salts include ammonium salts, in particular the aforementioned long-chain alkylammonium salts ... (4-methylaluminumoxy-1-phenyl) ginseng (pentafluorophenyl) Borate, Phenyl (4-dimethyl! Lvoxy_3,5-bis (trimethylcarboxanyl) small phenyl⑷pentafluorophenyl) phosphonate, Pyridoxyl_3 , 5-Di (third butyl) small phenyl) ginseng (pentabenzene 23 200302235 玖, description of the invention) borate, (4-dimethylaluminumoxy-1-fluorenyl) ginseng (pentafluorobenzene) ) Borate, (4-dimethylammoxy-3-fluorenyl-1-phenyl) ginseng (pentaphenyl) mono ('pentafluorophenyl) monotetramide -Phenyl) Shen (pentanylphenyl) delete salt 5 5 (5-dimethylaluminumoxy-2-feltyl) shen (pentafluorophenyl) borate, 4- (4-difluorenyl aluminum) Oxy-1-phenyl) phenyl phenyl (pentafluorophenyl) borate, 4- (2- (4- (dimethylaluminumoxyphenyl) propane-2-yl) phenoxy) Pentafluorophenyl) borate, (4-diethylaluminumoxy-1 · phenyl) ginseng (pentafluorophenyl) borate, 10 (4-diethylaluminumoxy-3,5-bis ( Trimethylsilyl) -1-phenyl) ginseng ( Pentafluorophenyl) borate, (4-diethylaluminumoxy-3,5-bis (thirdbutyl) -1-phenyl) ginseng (pentafluorophenyl) borate, (4-diethyl Aluminooxy-1-fluorenyl) gins (pentafluorophenyl) borate, 15 (4-diethylaluminumoxy-3-methyl-1-phenyl) span (pentafluorophenyl) borate , (4-diethylaluminumoxy-tetrafluoro-1-phenyl) ginseng (pentafluorophenyl) borate, (5-diethylaluminumoxy-2-fetyl) ginseng (pentafluorophenyl) ) Borate, 4- (4-diethylaluminumoxy-1-phenyl) phenyl phenyl (pentafluorophenyl) borate, 4- (2- (4- (diethylamyloxyphenyl) ) Propane-2-yl) phenoxy) ginseng (penta-20 fluorophenyl) borate, (4-diisopropylaluminumoxy-1-benzyl) ginseng (pentafluorophenyl) borate, ( 4-diisopropylstiloxy-3,5-di (difluorenyl crushed alkyl) -1-benzyl) shen (pentafluorophenyl) borate, (4-diisopropylstiloxy)- 3,5-bis (second butyl) -1-phenyl) ginseng (pentafluoro 24 200302235 玖, description of the invention phenyl) borate, (4-diisopropylaluminumoxy-1-fluorenyl) ginseng (Pentafluorophenyl) borate, (4-diisopropylaluminumoxyτyl — 丨 benzene ) Ginseng (pentafluorophenyl) borate, 5 (4-diisopropylaluminumoxy-tetrafluoro-1-phenyl) ginseng (pentafluorophenyl) borate, (5-diisopropylaluminumoxy) 2-Pentyl) ginseng (pentafluorophenyl) borate, 4- (4-diisopropylaluminumoxy_ 丨 _phenyl) phenyl (pentafluorophenyl) borate, and 4- (2- (4- (diisopropylaluminumoxyphenyl) propalkyl) phenoxy) ginseng (10 pentafluorophenyl) borate. Particularly preferred ammonium compounds are (4-diethylaluminumoxy_ 丨 _phenyl) ginseng (pentafluorophenyl) borate methyldi (tetradecyl) ammonium, (4-diethylaluminumoxy-1 -Phenyl) Phenyl (pentafluorophenyl) borate methyldi (hexadecyl) ammonium, ('diethylsulphoxyphenyl) Phen (pentafluorophenyl) borate methyldi (octadecyl) ) Ammonium and its mixtures. The first 15 complexes are disclosed in U.S. Patent Nos. 5,834,393 and 5,783,512. Another suitable ion-generating type activator compound includes a salt formed by a cationic oxidant and a non-coordinating compatible anion represented by the formula: (〇xe +) d (AdJe, where 〇xe + is a cation with a charge e + D is an integer from 1 to 3; e is an integer from 1 to 3; and Ad is as defined above. Cationic oxidants include, for example, ferrocene diamonds, diamonds, Pb + 2+ Λ + η 丞 substituted ferrocene Or Ag. Preferably, the specific examples are the anions previously defined for the activator compounds containing Bronsted 25 200302235 soft, invention-explaining acids, especially pentacene benzoate. Another: a suitable ion generating property The type 1 activator compound includes a salt formed by a carbene diamond ion and a non-coordinating compatible anion of the following formula π: 5 @ + Α · Wherein: @ 为 匸】 ^ Carbene sulfonium ion; and A- Non-coordinating compatible anions of number -1. The preferred carbenesulfonium ion is a trityl cation, especially a trityl diamond. 10 The preferred type 1 carbenesulfonium salt activator compound is pentamidine (pentafluoro Phenyl) trityl hydrazone borate, Nine (nonafluorobiphenyl) boron Tritylpyrene, pentyl (pentafluorophenyl) acetate and other substituted adducts. Another suitable ion-generating type activator compound includes a compound which is represented by the formula The salt of silanium ions and non-coordination-compatible anions 15 R3Si + A_ where: R is a C 1.1 〇 hydrocarbyl group; and A has the same definition as above. 2 The preferred type 1 silane sulfonium salt activator compound Trimethylsilyl (pentafluorophenyl) borate, trimethylsilyl (pentafluorobiphenyl) borate, triethylsilyl (pentafluorophenyl) borate, and other substituted additions Silane sulfonium salts were previously outlined in the Journal of Chemical Communications of the Chemical Society, 1993, 383-384, and Lambert, J. B. et al., Organometals, 1994, 13 26 200302235 玖, Description of Inventions, 2430-2443. Silane phosphonium salts as activator compounds for addition polymerization catalysts are patented in US Patent No. 5,625,087. Certain alcohols, thiols, silanols, oximes and ginseng (pentafluorobenzene) Radical) Borane complex is also effective for Type 1 catalyst activation And can be used in the present invention 5. These catalyst compounds are disclosed in US Patent No. 5,296,433. Type 1 activator compounds can also be used in combination. A particularly preferred combination is a tri (hydrocarbyl) aluminum or tri (hydrocarbyl) borane compound ( Each hydrocarbon group contains from 1 to 4 carbons) and a mixture of an oligomer or a polymer aluminocarbon compound. The molar ratio of the catalyst / co-catalyst is preferably i: 10,000 to 10: 1, 10 It is 1: 5000 to 10: 1, and most preferably !: 2500 to i: i. When alumoxane itself is used as the type 1 activator compound, it is preferably used in a large mole ratio, usually in a molar ratio. Ear-based, at least 50 times the amount of metal complex. If ginseng (pentafluorophenyl) borane is used as the first type activator compound, it is preferable to use the molar ratio of ginseng (pentafluorophenyl) borane to metal complexes: 05: to ...:! 15 is even better! ··: [to 6 ··! And best for! : J to 5 ·· i. The remaining activator compounds are usually preferably used with metal complexes in approximately equimolar amounts. If the aforesaid non-coordinating or poorly coordinating anion is used as the type Ⅰ activator compound, the metal complex to be alkylated according to the present invention (in other words, one of R of the metal complex is an alkyl group Or aryl). Boron-activated 20-agent compounds were used as the [best activator compounds including pentamidine, pentafluorophenyl) borane, ginseng (o-ninefluorobiphenyl) borane, and (3,5_ hydrazone (trifluoromethyl) phenyl) phytate, ginseng (pentafluorophenyl) non-burned ginseng (o-nonafluorobibenzyl) alane Compound rhenium, then the metal is 27 200302235 玖, the molar ratio of the type 1 activator compound to the metal center in the invention description compound is generally between 1: 10 to 10,000: 1, more preferably i: 10 to 5000 : i and optimally in the range of 1 · 1 to 2,500 · · 1. If a compound containing or obtaining a non-coordinating or poorly coordinating anion is selected as the activator compound, Mormolitone 5 is usually 1: 10 To M00: 1, and preferably 1: 2 to 250: 1. The formation of the catalyst according to the present invention is a combination of at least one type 1 activator, at least one type 2 activator, and at least one via a cobalt complex. The combination of catalyst modifiers is completed. For example, the type 2 activator may be an organometallic compound, of which at least one or ten A metal atom or a hydrocarbon group is directly bonded to the metal to provide a metalloid bond or a carbon-metal bond. The hydrocarbon group is non-aromatic, and the hydrocarbon group is directly bonded to the metal of the organometallic compound, and preferably contains ... and more preferably Carbon atom. The metal of the organometallic compound is selected from Groups 2, 3, 4, 5, 6, 7, 12, 13, or 14 of the Periodic Table of Elements. 15 Suitable type 2 activators for use herein include sodium hydrocarbyl, _ Sodium hydride, lithium hydrocarbyl, lithium dentate, hydrocarbyl zinc, zinc dioxide, magnesium dihydrate, hydrocarbyl magnesium, dihydrocarbyl magnesium, especially sodium alkyl, lithium alkyl, alkyl zinc, alkyl magnesium halide , Dialkyl magnesium, such as n-octyl sodium, butyl lithium, neopentyl lithium, methyl chloride, ethyl bell, diethyl zinc, dibutyl chloride, butyl chloride, ethyl 20 chloride Chemical towns, octyl gas towns, dibutyl towns, dioctyl towns, butyl octyl towns. Suitable type 2 catalyst activators for use herein also include neutral Lewis acids, such as non-aromatic Cu Hydrocarbyl-substituted Group 13 compound substituents, especially | J (hydrocarbyl) aluminum compounds or (hydrocarbyl) boron compounds, Derivatives, containing up to 20 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more particularly 28 200302235 玖, description of the invention alkyl aluminum compounds, such as triethyl aluminum and triisobutyl aluminum; dialkyl aluminum hydrides such as Diisobutyl hydrogenated compounds; Alkyl compounds such as dibutylethoxyaluminum; Aluminium compounds such as diethylaluminum chloride, ethyl gasified aluminum, diisobutylchloride, isopropyl Butyl chloride, ethyloctyl chloride | Lu, ethyl 5 times aluminum chloride, ethylcyclohexyl aluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride. Used here Suitable type 2 catalyst activators also include trihalides and boron trioxides such as aluminum trichloride, aluminum trifluoride, boron trifluoride, and Erhanium and bidentate sides and Louis Vuitton. Adduct. 0 Type 2 catalyst activators suitable for use here as needed also include neutral Lewis acids such as hydrocarbyl-substituted Group 3 or 7 compounds, especially (hydrocarbyl) aeronautics, (hydrocarbyl) titanium, (hydrocarbyl) In the case of (hydrocarbyl), or (hydrocarbyl) indium compounds and their (including fully halogenated) derivatives, each hydrocarbon or alkoxylated group contains 1 to 20 carbons. 5 Suitable type 2 catalyst activators for use herein also include Group 3 to Group 7 metal halides, particularly hafnium-, titanium-, meta-, starvation- or | mesh halides, such as titanium dioxide, trichloride Titanium, titanium tetrachloride, osmium dichloride, trichloride, four gasification, vanadium dichloride, vanadium trichloride, molybdenum pentachloride. Preferred aluminum compounds are e.g. diethylaluminum chloride, ethyl chloride, chlorodiisobutylaluminum chloride, ethyloctyl aluminum chloride, ethyl sesquichloro aluminum, and fluorenyl sesquichloride. Aluminum sulfide, ethylcyclohexylaluminum chloride, dicyclohexylaluminum chloride, and dioctyl aluminum hydride are the second type activators. The molar ratio of the type 2 catalyst activator relative to the metal complex of the cobalt complex is characterized in that the molar ratio is usually in the range of 1: 1 to 〇, 〇〇〇 ·· 1, better i ·· 29 200302235 玖The invention description ranges from 10 to 500: 1 and optimally 1: 1 to 250: 1. It is particularly desirable that the activator compound used herein is a combination of type 2 activator compounds, such as neutral Lewis acid used as needed, especially dialkyl aluminum halide compounds having 1 to 4 carbon atoms in each alkyl group (Such as ethyl 5 times aluminum semichloride, ethyloctyl aluminum chloride, and diethyl aluminum chloride) and type 1 activator compounds (such as Cu hydrocarbyl-substituted Group 13 Lewis acid compounds, especially each hydrocarbyl group contains 1 to 20 carbon functional tris (hydrocarbyl) boron or aluminum compounds, especially a combination of (pentafluorophenyl) borane or (pentafluorophenyl) alane); type 2 activator (as in The combination of natural Louise g "mixture" and polymer or oligomer oxoalkane (type 1 activator); and a single neutral Lewis acid (type 2 activator) is especially used with ginseng (pentabenzene Base) butterfly or ginseng (pentaphenyl) minus and polymer or oligomer alumoxane (type activator) combination. As just mentioned, the catalyst according to the present invention can be completed by combining at least one thorium activator, at least one type 2 activator, and at least one 15 catalyst modifiers via a cobalt complex. Timo's catalytic other modifiers are aromatic compounds. A preferred catalyst modification is an aromatic compound containing at least two or more qh groups bonded to an aromatic compound. Che Jiaojia's aromatic compounds containing at least two groups are represented by one of the following formulas:

OH

30 200302235 发明, description of invention

III

(R9) s (RU) r

Where R 'and R "respectively represent a hydrocarbon group containing 1-20 carbon atoms; R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, rU, R12 may be the same or different, and Represents a hydrocarbyl, meridian, nitro, hydrocarbyloxy or ii atom of 1-20 carbon atoms, respectively; Z represents a hydrocarbyl, oxygen atom, Rau atom, _ (C = 0) -group containing 1-20 carbon atoms ,-(NR13) group- or-(SiR142)-group, in which R13 and R14 may be the same or different and each represents a hydrocarbon group of 1-20 carbon atoms; 31 200302235 玖, invention description d is 0, 1 or 2; ο, p is 0, 1, 2, 3, or 4; m + n <4; 5 o + p <4; r + q <4; s + t < 4 > A preferred catalyst modifier is an aromatic port In the beginning, at least two 0H groups are each directly bonded to one of the aromatic rings of the aromatic compound. 10 More particularly, the catalyst modifier is selected from Formula I. Still more preferably, the following catalyst modifiers are combinations of complex compounds, Use of type 2 activator compounds and type 2 activator compounds ...

Still more preferred catalyst modifiers contain three hydroxyl groups. When an organic metal compound is selected as the catalyst modifier. The molar ratio of the catalyst modifier to the metal center of the cobalt complex is usually 1:10 to 1,000: 1, more preferably 1:10 to 500: 1 and most preferably 1 ·· 1 to 250: 1 range. Unexpectedly, the effective use of the catalyst modifier combination of the cobalt 20 complex, the type 1 activator compound, and the type 2 activator compound according to the present invention allows the production of diene polymers with relatively high catalytic efficiency. In addition, when a small amount of catalyst 32 200302235 发明, description of the invention when the modifier is used in the polymerization reaction, the use of a relatively small amount of expensive alumoxane activator compound 'can achieve comparable catalyst efficiency. In addition, polymers with lower aluminum residues and thus higher clarity can be obtained. 5 10 In addition to the metal complex and the activator compound according to the present invention, the catalyst composition also contains a small amount of other organometallic compounds, which can be used as a so-called scavenger. A scavenger is added to react the impurities in the reaction mixture. It can be added at any time, but it is usually based on the metal complex and activator compound, and the scavenger is added to the reaction mixture. Timing compounds are often used as scavengers. Scavengers are, for example, trioctylamine, triethylsaw, and triisobutylaluminum. Those skilled in the art understand that metal complexes, type i activators, type 2 activator compounds, and catalyst modifiers can exist in the catalyst composition in a single form :: as a mixture of several ingredients. For example, if you need 2 polymer molecular materials (such as molecular weight distribution), you need to use 20 mixed prostitutes. ^ According to the present invention, the metal complex can be used for the homopolymerization of rare monomers and special ... special encapsulation-type diene For the second wife, a total of two wives are preferred. Invention 2 = the monomer is an aromatic or non-aromatic hydrocarbon. According to this :: genus: substances are particularly suitable for-or a variety of co-polymerization ", isoprene-J :: into: group 'contains: 1,3-butadiene, 1,3H, butadiene), 2 , 3-Dimethyl-1,3 · butane-1 丄 heptane-2, 2, heart hexadiene, π hexamethylene dichloride, hexadiene, di =: dilute, ~ pentane, cyclopentane, 4 fields, % Octadiene, orthobornadiene, ethylene ~, or cyclopentadiene 33 200302235 玖, invention description 嫦. Preferred aromatic alpha olefins are styrene, p-methylstyrene, divinylbenzene such as 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, and divinyltoluene such as 2 1,3-divinyltoluene, 2,4-divinyltoluene, 2,5-divinyltoluene, 2,6-divinylmethylbenzyl, 3,4-divinyltoluene 5, 3,5- Divinyl toluene monomer. More preferably, styrene is used as the aromatic alpha olefin. Preferred non-aromatic alpha olefins are ethylene and alkylenes having an alkyl chain having 1 to 35 carbon atoms (e.g., propylene, butene, 1-hexene, 1-octene, 1-decene). Monomers intended for such products and methods are known to those skilled in the art. Using the metal complex according to the present invention, an amorphous or rubbery or rubber polymer can be prepared depending on the monomers used. -The polymerization of the ene precursor can be carried out in a known manner in the gas phase and in the liquid phase. In the case described later, it is suitable to dissolve the silk and liquid-liquid polymerization. The amount of metal used is usually a concentration of metal in the dispersant of 0.8 to 3.0 Mo 15 20 ears / liter, and fortunately X Jia 1GMG, ears / liter. The polymerization method can be carried out in a gas phase polymerization (for example, in a fluidized bed reactor), as a suspension / liquid phase polymerization, as a solid phase powder polymerization, or as a bulk polymerization method, in which an excessive amount of dilute smoke monomer is used as a reaction medium. The dispersant is suitable for the polymerization reaction. The dispersant may be selected from the group consisting of the following groups, but is not limited to cyclic burners such as cyclohexanone; saturated, straight-chain or branched aliphatic hydrocarbons such as butan, Puyuan, hexane, Residual, scorched, pentamethylheptane or mineral oil fractions such as light or conventional petroleum, naphtha, tar, or soot fluids or similar liquids are also suitable for this ... Suitable for this purpose. Some fragrances $ ㈣❹, purely considered by Lu'an, Wei removes solvent during manufacture. In the μ method of technology «= 34 200302235 玖, description of invention 5 10 Use transcripts of aliphatic hydrocarbons or mixtures thereof, such as petrochemical caps, for sale as solvents, or use low-cost aliphatic hydrocarbons in combination with aromatic solvents, or use Aromatic solvents. If aliphatic smoke is used as the solvent, the solvent may optionally contain a small amount of aromatic smoke such as "." If, for example, "Jiming Oxygen (MAO)" is used as the activator compound, toluene may be used as the MAO solvent.俾 Supply MA0 to the polymerization reactor in dissolved form. When using these solvents, dehydration or purification of the solvent is required; this can be achieved by skilled artisans without any problems. In the polymerization method, the metal complex, activator compounds (types 1 and 2), and catalyst modifiers are used in a catalytically effective amount. In other words, any amount of polymer that can be successfully produced is used. This amount is conveniently determined by a skilled artisan through routine experimentation. Gu Yi, a skilled person, understands that the catalyst composition used according to the present invention can also be prepared in situ. If solution polymerization or bulk polymerization is to be used, it is preferably typically in the range of 0 to 24 μm and more preferably to ⑽. The reaction is carried out at a temperature of c, but is not limited. The polymerization method can also be carried out under the conditions of suspension or gas phase polymerization, and the type is carried out at a temperature below 150 ° C, but it is not limited. ^ Polymers obtained by polymerization can be subsequently processed by known methods. The catalyst is usually deactivated at some point during the polymer treatment. Deactivation can also be carried out in Example 4 using 7] C or alcohol. Since the catalyst content in the catalyst system of the present invention is used, the content of the catalyst, especially the element and metal content is extremely low, so the removal of the catalyst residue can be deleted. However, if desired, the content of the catalytic back J residue in the polymer can be reduced in known ways, such as by washing. The dehydration step may be followed by a stripping step [removal of organic from (homo) polymer 35 200302235 玖, description of invention solvent]. Polymerization can be carried out continuously or discontinuously at atmospheric pressure, below atmospheric pressure, or at elevated pressures up to 500 MPa. The preferred polymerization reaction is in the range of 0.01 to 500 MPa, most preferably 0.01 to 10 MPa, and a pressure of 0.1 to 2 Mpa in 5 rows. Higher pressures can be applied. In such a high pressure treatment, the metal complex according to the present invention can also be used with good results. Slurry polymerization and solution polymerization are usually carried out at a lower pressure, preferably below 10 MPa. Polymerization can also be performed in series and / or in parallel in several steps. If desired, the catalyst composition, monomer composition, temperature, hydrogen concentration, pressure, 10 dwell time, etc. may vary from step to step. In this way, products with a broad distribution of properties, such as a broad molecular weight distribution, can also be obtained. By using the metal complex according to the present invention for the polymerization of olefins, polymers having polydispersity (Mw / Mn) = 1.0-50 can be obtained. tEmbodiment 3 15 Example 20 It should be understood that the present invention can be operated without any components not specifically disclosed. The following examples are provided to further illustrate the invention, but are not to be considered as limiting. Unless stated to the contrary, all parts and percentages are expressed on a weight basis. The term "overnight" means about 16-18 hours when used, and "room temperature" means 20-25t when used: temperature. Wang Busha and organometallics ----- π < 珥 鳅 are all carried out using standard 胥 lenk) equipment and technology in an inert nitrogen atmosphere or in a glove box. In the following, "THF" means tetragas, palpitate means ethyl # semichloride, (CH3) 3sia means trimethylchlorite, and "face" means 36 200302235 玖, description of the invention 1, 2-2 Methoxyethane, "Me" means "methyl", "Et" means "ethyl", "Bu" means "butyl", "Ph" means "phenyl", "MMAO" or "MMAO-3a "" Modified methylaluminoxane "and" PMAO-IP "means" polymer fluorenyl aluminoxane with improved properties ", both of which were purchased from Extron Nobel Corporation. "IBAO" means "isobutylalumoxane" and "MAO" means "methylalumoxane", both of which were purchased from Albemarle. The pressure is an absolute pressure. The polymerization is carried out under a nitrogen atmosphere while excluding water and oxygen. The products are SEC (size exclusion chromatography), elemental analysis, NMR [Avance 400 device of Bmker 10 Analytical Company (4 = 400 MHz; 13C = 100 MHz)] and IR (Brook Optics The company's IFS 66 FT-IR spectrometer). IR samples were prepared using carbon sulfide as the bulking agent and using two or four times the solvent. DSC (Differential Scanning Card Meter) was measured using DSC 2920 from TA Instruments. 15 Mη and Mw are molecular weights, which are determined by SEC universal calibration. Mw / Mn is the molecular weight distribution and is referred to herein as polydispersity. The ratio between 1,4-cis-, 1,4-trans-, and 1,2-polydiene of butadiene or isoprene polymer is determined by IR and 13C-NMR-spectroscopy. The glass transition temperature (TG) of the polymer is measured by DSC. 20 Example 1 1. Initial complex 1. Cobalt octanoate (Co 10 HEX-CEM) was obtained from OMG as a solution of cobalt complex (10% cobalt) in mineral spirit D 60. 37 200302235 Description of the invention 2 · Polymerization 2 · 〖Description of the polymerization procedure 2 · M description of the polymerization procedure-Method 1 The polymerization is performed in a double-walled 2 liter steel reactor. The reactor is charged with 5 organic solvents and metal complex Before purging substances, activators, monomers, electron acceptors or electron donor components, alkyl aluminum halide components or other components (such as aromatic modifiers), use nitrogen to sweep away. Unless otherwise stated, the polymerization reactor was tempered to 25 ° C. The following ingredients were then added to the polymerization reactor in the following order: organic solvent, part of the activator 1, part of the conjugated diene monomer, a second olefin using 10 as needed, and part of the aluminum alkylating ingredient. Let mix for 30 minutes. In another 200-litre double-walled steel reactor (tempered to the same temperature of the polymerization reactor), add the following ingredients in the following order: organic / cereal, part of the activator, and part of the alkylation Aluminum components, aromatic compounds used as needed, and partially conjugated diene monomers. Let the mixture stir for% J%. The cobalt compound was then added and the resulting mixture was stirred for the following time. The polymerization was started by adding 200 ml of the steel reactor contents to a 2 liter polymerization vessel. Unless stated otherwise, the polymerization is at 25. 〇 Performed. The polymerization time varies from experiment to experiment. ) Q s,-The polymerization process was ended, and the polymerization solution was transferred to a third double-walled steel reactor. The anti-ml methanol contained Ionol as a polymer stabilizer (0 liter of methanol contained 2 g of Ionol). This mixture was stirred for 15 minutes. The recovered compound was then stripped with water vapor to remove the solvent and other volatiles and dehydrated in a 45 C supply box for 24 hours. 38 200302235 发明, Description of Invention 2 · 1.2 Description of Polymerization Procedure-Method 2 The polymerization reaction is carried out in a double-walled 2 liter steel reactor. In the reactor, organic / cereal, metal complex, activator, Prior to the monomer, electron acceptor or electron donor component, aluminum alkylate component or other compounds, sweep with 5 nitrogen. Unless otherwise stated, the polymerization reactor was tempered to 25 ° C. The following components are added in the following order: organic solvents, activators, conjugated diene monomers, second olefins as needed, alkyl-aluminum components, and fragrance-free compounds to be used in the products. The mixture was allowed to stir for the following time, and then the starting compound was added to start polymerization. 10 Unless stated otherwise, polymerization is performed at 25X: conducted. The polymerization time varies from experiment to experiment. To end the polymerization process, the polymerization solution was transferred to a third double-walled steel reactor. The reactor contained 50 ml of methanol containing Ionol as a polymer stabilizer (1 liter of methanol contains 2 g of Ionol). This mixture was stirred for 5 minutes. Then the polymer recovered at 15 was stripped with hydrotherapy gas for 1 hour to remove solvents and other volatiles, and dehydrated in an oven at 45 ° C for 24 hours. 3. Polymerization Example 3.1 Polymerization of 1,3 · butadiene 3.1.1 Polymerization of 1,3-butadiene using 1,2,4-trimethoxybenzene 2A) Use of metal complex 1, Polymerization of 1,3-butadiene with MMA0-3a, ethyl sesquigas, and 1,2,4-trimethoxyoxybenzene (round ^ The experiment was based on the above-mentioned rough polymerization procedure (2 · 1 · 1) The polymerization was carried out in a polymerization solvent containing 373 g of cyclohexane and 125 g of toluene. Thus, 338 g of cyclohexane, 22.2 g of benzene, 49.8 g (.92 mole) of U-butadiene monomer, 39 200302235 发明 Description of the invention MMAO-3a (1.6 g heptane solution contains 4.1 millimoles MMAO), 0.248 g (1.47 millimoles) 1,2,4-trioxobenzyl and 0.5 g (0.2 millimoles ) Ethyl sesquichloride was added to the polymerization reactor. 35 grams of cyclohexane, 64.8 grams of toluene, 3.5 grams (0.06 mole) of 1,3-butadiene monomer, 6.2 grams of heptane solution containing Mole 5 MMAO and 2.0 g (0.8 mol) of ethyl sesquihydrate aluminum were stirred for 1 hour, and then 156 亳 (0.264 mmol) of metal complex 1 was mixed in another reaction vessel and stirred for 10 minutes. The resulting mixture is then transferred to a polymerization reactor and opened. Polymerization. After 1 hour and 4 minutes, the polymerization reaction is ended as described above (Ref. 211) 10. At this time, the conversion rate of the monomer to polybutadiene is 99.9%. As a result of the stripping treatment, 53.2 grams of polybutadiene were recovered According to the C-NMR measurement, the polymer contains go ′% cis, 4-; 6.0% trans-1, 4-, 4.0% 1,2-polybutadiene. The molecular weight of the polymer is 368,000 g / mo Ear, polydispersity up to 594 15 (Μη = 62,000; Μζ = 1,228,000). Mooney value is 27 ″. B) The metal complex i, MMA〇_3a, ethyl sesquigas aluminum and 1 The polymerization of 2,4-dimethoxybenzene in 1,3-butadiene (round 2) was performed according to the aforementioned general polymerization procedure (211). The polymerization was performed in a polymerization solvent containing 505.9 cyclohexane. Thus, 4.02 g of cyclohexane, 20 5 (M g (0.9 mol) of 1,3-butadiene monomer, MMAO-3a (1.7 g of a heptane solution containing 4.3 millimoles of MMAO), 0.248 g (1.47 mol), 2,4 · trimethoxybenzene and 0.5 g (0.2 mol) of ethyl sesquichloride were added to the polymerization reactor. 103.2 g of cyclohexane, 3 5 g (〇06mol)] (3, butadiene monomer, 6.3 g heptane solution containing 16.3 millimoles MMA0 and 20 g (0.8 mole) B 40 200302235发明, description of the invention: Stirring aluminum sesquichloride for 1 hour and 3 minutes, followed by mixing 156¾ g (0.264 mmol) of metal complex i in a separate reaction vessel and stirring for 10 minutes. The resulting mixture was then transferred to a polymerization reactor and Start the polymerization reaction. After 1 minute and 14 minutes, end the polymerization reaction as described above (refer to 2.1.1). 5 At this time, the conversion rate of the monomer to polybutadiene is 67.2%, and the stripping result is recovered 36.0 G polybutadiene. According to nC-NMR measurement, the polymer contains 82.0% cis], '; 10.0% trans-1, 4-, 8.0% 1,2 polybutadiene. The molecular weight of the polymer is 63,000 grams / Mole, polydispersity up to 21 10 ( η = 30,000; Mζ = 113,00). C) The metal complex i, MMA0_3a, ethyl sesquichloride and 1,2,4-trimethoxybenzene were used for The polymerization (round 10) experiment was performed according to the above-mentioned rough polymerization procedure (2. ^). The polymerization reaction was carried out in a polymerization solvent containing 3 814 g of cyclohexane and 1000 g of toluene. Thus 15 3814 g of cyclohexane 1000 grams of toluene, 537.4 grams (99 moles) of u · butadiene monomer 'MMAO-3a (8.0 grams of heptane solution containing 20.5 millimoles of MMAO), 1.24 grams (7.35 millimoles) of 1, 2 , 4-trimethoxybenzene and 2.5 g (17.2 mmol) of ethyl sesquihydrate were added to the polymerization reactor. 80 g of toluene, 40 g (0.07 mol) of 1,3-butadiene mono Body, 31.0 g containing 79.5 mmol * MMA 0 heptane solution and 10.0 g (87.8 mol) of ethyl sesquichloride were stirred for 1 hour, and then 780 mg ( 1.320 millimolar) metal complex 1 and stirred for 5 minutes. The resulting mixture was then transferred to a polymerization reactor to start the polymerization reaction. After 1 hour and 2 minutes, the polymerization reaction was terminated as described above (refer to 2.1.1). 41 2 00302235 发明, description of the invention at this time '9 monomer polybutadiene recovered from conversion of monomers into polybutadiene. B rate cut. 5%, stripping result 3 ·] · 2 1,3-butadiene according to polymerization Method 2 Polymerization uses metal complexes, MAO-3a, ethyl sesquichloride, and 1,2,4-dimethoxybenzene—polymerization of 3-but-ene (round 3) The experiment system gathers people according to the above outline. Private sequence (2 丄 2). The polymerization was performed in a polymerization solvent of 3,5002 g of toluene. So simple gram of toluene, 542 grams of ο 15 mol monomer, M Choi 3a (78 7 g of heptane solution containing gang ·! Mol read, 2.48 g (147 mol) 124_trimethoxybenzyl and 24.56 g (9.94 ¾ mole) of ethyl sesquichloride was added to the polymerization reactor. The mixture was stirred for 1 hour. Then milligrams (2.26 mmol) of diamond complex 1 was added to the polymerization reactor to start the polymerization reaction. After 1 hour, the conversion of the monomer to polybutadiene was 73.8% (400.1 g). After 2 hours and 10 minutes, the reaction was terminated as previously described (refer to no. Stripping results recovered 356.6 g of polybutadiene According to nC-NMR measurement, the polymer contains 91% cis-154_; 6.0% trans-1, 4-, 3.0% 1,2-polybutadiene. The molecular weight of the polymer is 302,000 g / mole, and more Dispersibility up to 2.77 (Μη = 109,000; Mz = 649,000) ° Mooney value reaches 35.0. 3.1.3 Copolymerization of 1,4-butadiene and stupid ethylene 3.1.3.1 1,4-butadiene and stupid Copolymerization reaction of ethylene using metal complex 1, MMAO-3a and 1,2,4-trimethoxyoxybenzene and ethyl sesquichloride (round 4) 42 20 200302235 before The outlined polymerization procedure is carried out (211). The polymerization is carried out in a polymerization solvent containing 510.9 g of cyclohexane. Thus, 40.7 g of cyclohexane, 27.0 g (0.5 mole) of 1,3-butadiene monomer , Heptane solution contains 30.0 mol MMA0), 26.0 g (0.25 mol) styrene monomer, 5 0.248 g (1.47 mmol): 1 2 4_trimethoxybenzene and 156 g ( 6.3 millimoles) Ethyl sesquichloride was added to the polymerization reactor. 107.2 grams of cyclohexane, 40 grams (0.07 moles) of 1,3-butadiene monomer and 057 grams ( 23 millimoles) ethyl sesqui-emulsified aluminum was stirred for 1 hour, and then mixed with 470 mg (0.798 millimoles) of cobalt complex 1 in a separate reaction vessel and stirred for 15 minutes. 10 The reaction mixture was then transferred into a polymerization reactor and The copolymerization reaction was started. After 1 hour and 15 minutes, the copolymerization reaction was ended as described above (refer to 2.1.1.1). At this time, the conversion rate of the monomer to polymer was 34.0%. 19.4 g was recovered as a result of the stripping treatment. Polymer. The polymer contains 1.5% styrene (50% styrene content is detected as polystyrene 15 ethylene segments). According to the 3c-nmr measurement, the copolymer polybutadiene Contains 88.5% cis], '; 6.5% trans-1, 4-, 3.5% 1,2-polybutadiene. The molecular weight of the polymer is 76,000 g / mole, and the polydispersity is 13 ° (Mn = 6? 〇〇〇; Mz = 357,000) 〇3.1.4 Comparative Example 2A) 1,3 · butadiene polymerization using complex 1 & MMA0-3a (Round 5; Comparative Example) The experiment is based on the above outline The aggregation procedure (2.1.1) is performed. The polymerization was carried out against 500 g of cyclohexane solvent. So 409 g of cyclohexane, 500 g (0.92 mol) of U_butadiene monomer and MMA 0_3a (90 g of heptane solution contains 43 200302235 玖, description of invention 23.1 millimolar MMAO ) Is added to the polymerization reactor. 91 grams of cyclohexane, 4.0 grams (0.07 moles) of 1,3-butadiene monomer and 2.7 grams of heptane solution containing 6.9 mol mole MMAO, mixed in a separate reaction vessel with 470 mg (0 · 80 Millimoles) of metal complex 1 and stirred for 10 minutes. 5 The resulting mixture is then transferred to a polymerization reactor to begin the polymerization reaction. After 1 hour, the copolymerization reaction was terminated as described above (refer to 2.1.1). At this time, the conversion of the monomer to polybutadiene was 41.8%. As a result of the stripping treatment, 21.2 g of polybutadiene was recovered. According to 13C-NMR measurement, the polymer contains 97.0% cis-1,4-; 10 1.5% trans-1,4-, 1.5% 1,2-polybutadiene. The polymer has a molecular weight of 123,000 g / mole and a polydispersity of 6.25 (Mη = 20,000,000; Mζ = 21.0,000,000). Β) Polymerization using metal complex}, MMA0-3a and ethyl sesquichloride (Round 6, Comparative Example) 15 The experiment was performed according to the aforementioned rough polymerization procedure (2.1.1). The polymerization was performed in a polymerization solvent containing 381 g of cyclohexane and 118 g of toluene. So 33 丨 grams of cyclohexane, 87 grams of toluene, 50.2 grams (0.93 moles) of u-butadiene monomer, MMAO-3a (1.6 grams of a solution containing 4.1 millimoles of MMAO heptane) and 0.5 g (0.2 mmol) of ethyl sesquichloride was added to the polymerization reactor. 50 grams of cyclohexane, 20 '31 grams of toluene, 3.5 grams (0.06 moles) of 1,3-butadiene monomer, 6.2 grams of a solution containing 16.1 moles of MMAO heptane and 20 grams ( 〇8mmol) ethyl sesquichloride was stirred for 65 minutes, and then 156 mg (0.264 pen moles) of metal complex 1 was mixed in a separate reaction vessel, and stirred for 10 minutes. The resulting mixture was then transferred to a polymerization reactor to begin the polymerization reaction. 44 200302235 发明, description of the invention After 1 hour and 5 minutes, the copolymerization reaction is ended as described above (refer to 2.1.1). At this time, the conversion rate of monomer to polybutadiene was 87.3%. As a result of the stripping treatment, 46.9 g of polybutadiene was recovered. According to UC-NMR measurement, the polymer contains 93.5% cis-1,4-; 5 3.5% trans-1,4-, 3.0% 1,2-polybutadiene. The polymer has a molecular weight of 378,000 g / mole and a polydispersity of 4.85 (Mn = 78,000; Mz = 1,114,000). Mooney is worth 32.7. C) Polymerization using metal complex 1, MMAO-3a and ethyl sesquichloride (round 7, comparative example) 10 The experiment was performed according to the aforementioned general polymerization procedure (2 · 1 · 1). The polymerization was performed in a polymerization solvent containing 571.9 g of cyclohexane. In this way, 462.1 grams of cyclohexane, 51.2 grams (0.95 moles) of 1,3-butadiene monomer,] y [MAO-3a (46.8 grams of a solution containing 120 millimoles of MMAO heptane) and 3.12 grams (12.6亳 Mol) ethyl sesquichloride was added to the polymerization reactor. The pressure in 15 parts of the polymerization reactor was adjusted to 7 bar using ethylene gas. 109.8 grams of cyclohexane, 3.0 grams (0.06 moles, butadiene monomer and 2.0 grams (0.8 millimoles) of ethyl sesquigas) were stirred for 丨 hours, and then mixed in a separate reaction vessel for 470 hours. Milligrams (0.798 millimoles) of metal complex 1 and stirred for 10 minutes. The resulting mixture was then transferred to a polymerization reactor to begin the polymerization reaction. Subsequently, the pressure of the 20 polymerization reactor was adjusted to 9.3 bar using ethane gas. After 1 hour and 30 minutes Then, the copolymerization reaction was terminated as described above (refer to 2.1.1). At this time, the conversion rate of the monomer to polybutadiene was 95.0%. As a result of the stripping treatment, 5 1.5 g of polybutadiene was recovered. According to 13c-nmr It was determined that the polymer contained 91 · 5 ^ ι | Μ_Μ_; 45 200302235 玖, description of the invention 5.5% trans-1,4-, 3.0% 1,2-polybutadiene. The polymer molecular weight reached 18,000 g / mol, Polydispersity is 2.25 (Mn = 8,000; Mz = 31,000). D) 5 polymerizations using metal complex 1, MMAO-3a and trimethyl (chloro) silane (round 8, comparative example). The aggregation procedure (2.1.1) is performed. Thus 298.9 g of toluene and 51.1 g (0.94 mol) of 1,3-butadiene monomer were added to the polymerization reactor. 74.0 grams of toluene, 4.3 grams (0.07 moles) of 1,3-butadiene monomer, MMAO-3a (13.9 grams of a solution containing 35.3 millimoles of MMAO heptane) and 2.08 grams of 10 (0.19 moles) Trimethyl (chloro) silane was stirred for 10 minutes, and then 119 mg (0.201 mmol) of the metal complex was mixed in a separate reaction vessel and stirred for 4 minutes. The resulting mixture was then transferred to a polymerization reactor to begin the polymerization reaction. After 2 hours and 18 minutes, the copolymerization reaction was terminated as described above (Ref. 15 2, 1 · 丨). At this time, the conversion of the monomer to polybutadiene was 23.5%. 13.0 grams of polybutadiene were recovered as a result of the stripping treatment. According to the 13C-NMR measurement, the polymer contains cis; 4.0% trans-1,4-, 3.0% 1,2-polybutadiene. The polymer has a molecular weight of 86,000 g / mole and a polydispersity of 441 20 (Mn = 19,500; Mz = 645,000). E) Use Cobalt Complex! Polymerization of MMA0_3a and third butyl chloride (round 9; comparative example) The experiment was performed according to the aforementioned general polymerization procedure (2 丄 2). The polymerization was performed in a polymerization solvent containing 504 g of cyclohexane. Such 504 grams of toluene, 54.6 grams of 46 200302235 玖, invention description (1.01 mole) 1,3-butadiene monomer, MMAO-3a (11.9 grams of MMAO heptane solution containing 30.3 millimoles) and 2.2 Grams (24 mmol) of third butyl chloride were added to the polymerization reactor. The mixture was stirred for 13 minutes. Then 115 mg (0.20 mol) of metal complex 1 was added to the polymerization reactor to start the polymerization reaction. 5 After 2 hours and 19 minutes, the copolymerization reaction is terminated as described above (refer to 2.1.1). At this time, the conversion of the monomer into polybutadiene was 29.5%. As a result of the stripping treatment, 16.1 g of polybutadiene was recovered. According to nC-NMR measurement, the polymer contains 25.0% cis-1,4-; 66.0% trans, 9.0% 1,2-polybutadiene. 10 3 · 2 Polymerization activity-Comparison of round activity [kg {polymer} / millimol [start] [hour] Round activity [kg {polymer} / millimol {ming} [hour] 1 0.64 ** 6 0.35 ** 2 0.51 ** (0.82 *) 7 0.18 ** 3 0.42 ** 8 0.11 ** 4 0.08 ** 9 0.14 ** 5 0.12 ** 10 1.18 ** (1.72 *) C ···· Comparative Example; * Measured after 6 minutes; ** Measured after 15 minutes; *** ... · Measured after 20 minutes 3 · 3 Molecular Weight-Comparative Round Mw Μη Μζ Round Mw Μη Μζ 1 368,000 62,000 1,228,000 6 378,000 78,000 1,114,000 2 63,000 30,000 113,000 7 18,000 8,000 31,000 3 302,000 109,000 649,000 8 86,000 19,500 645,000 4 76,000 6,000 357,000 9 Not determined Not determined Not determined 5 123,000 20,000 210,000 47 200302235 玖, Description of the invention 3.4 Molecular weight distribution (MWG) and Mooney viscosity-comparison --------- Round Mw / Mn Mooney Tg, ° C Round Mw / Mn Mooney Tg, ° c 5.94 27.1 Not determined 6 4.85 32.7 Not determined 2 2.1 Not determined Not determined 7 2.25 Not determined Not determined 3 — 2.77 35.0 Not determined ^ 8 4.41 Not determined Not determined 4 —----— 13.0 Not determined Not determined 9 Not determined Not determined Not determined 5 -------. 6.25 Not determined Not determined 3 · 5 Microstructure-Comparison Round Cis-1,4-PB Trans-1,4-PB 1,2- Polymer Round Cis-1,4-PB Trans-1,4-PB 1,2-polymer 1 90.0 6.0 4.0 6 93.5 3.5 3.0 2 82.0 10.0 8.0 7 91.5 5.5 3.0 3 91.0 6.0 3.0 8 93.0 4.0 3.0 4 88.5 6.5 3.5 9 25.0 66.0 9.0 5 97.0 1.5 1.5 PB = Polybutadiene Tg = glass breaking transition temperature The advantage of the present invention is that the catalytic activity of the polymerization reaction is significantly increased. Examples It is confirmed that the activity obtained by the cobalt-based catalyst of the present invention is 2 to 3 times higher than that of the catalyst based on cobalt carboxylate. Polymerization activity of the 10 catalyst system containing the catalyst modifier according to the present invention (refer to Round 1 and Round 2) and the catalyst system lacking the catalyst modifier of the present invention (refer to the aforementioned Comparative Example Special Round 5_9 '3.2) compare with. For example, cobalt octoate, modified aluminoxane (MMA0_3a), combined polymerization of ethyl sesquihydrate aluminum and 1,2,4-trimethoxybenzene. 3, butadiene in hexane burned solvent, Polymerization activity up to 0.64 kg [polybutadiene] / 亳 Mor [15 cobalt] hours (refer to Round 1), or polymerization activity up to 0.18 kg [Polybutadiene 48 200302235 玖, description of the invention] / house mol [Co ] Hours (refer to Round 19). Without 丨, 2,4_trimethoxybenzyl as a catalyst modifier, the polymerization activity reached 018 kg [polybutadiene] / mole [n] hours (refer to Comparative Example Round 7). Cobalt octoate combined with modified sintered oxygen was used as a catalyst, and as a result, a polymerization activity of 012 kg [polybutadiene] / amole [5 cobalt] was obtained (refer to Comparative Example Round 5). The same tendency was observed when a cyclohexane / toluene mixture was used as a polymerization solvent (compare rounds 2 and 6). Other possible catalyst mixtures such as cobalt octoate, a combination of modified aluminoxane (MMAO-3a) and trimethyl aerosilane (round 8), or third butyl chloride (round 9) as a chlorine-containing anion compound, obtain Lower polymerization activity 10 (0.11 or 0.10 kg, 0.12 kg [polybutadiene roasted] / millimolar [gu] hours). Another advantage of the present invention is that the catalyst of the present invention does not require a separate aging step (refer to Round 3). If an aging step is used as required, its advantage is that it does not require long-term aging. Therefore, the polymerization reaction can be started in a polymerization reactor in which the catalyst components are added in the desired order. The polymerization system begins, for example, with the addition of a catalyst 15 precursor as the final component (refer to Round 10, u & 12). If the required aging step is combined with the catalyst preparation / polymerization procedure, the aging time is short, for example, 10 minutes (reference round 丨 and magical but non-limiting, can be performed under mild conditions (such as 25t: but non-limiting), catalytic activity High. The temperature ranges of catalyst aging and polymerization are selected from _50〇c S + 25〇c &c; and preferably] 0 to 20 + 120 C, and more preferably 0 ° C and 80 ° c. For example, polymerization round i (polymerization temperature 25 C, aging temperature 25 t) has a catalytic activity of 0.64 kg of polybutadiene / ammonia Z cobalt / hour. Another advantage of the present invention is that no extreme temperature is required when the catalyst is aging. Its advantage is that it can induce No need to wait or delay time for the polymerization reaction, or no substantial waiting time when adding the last catalyst component to the polymerization reactor. 49 200302235 玖, the description of the invention may be delayed or delayed. And hydrocarbons, preferably aromatic fluorenes. For example (refer to Round 4), copolymers of styrene butadiene and styrene are used to obtain T-bis-styrene-styrene copolymers (styrene content i 5%). Another advantage of the metal catalyst of the invention (metal complex and type! And type 2 activator compounds, and polymers tailored to specific groups of catalyst modifiers. In particular, activators, metal complexes, and aromatic catalyst modifiers (compare type 丨 activation The agent is selected in stoichiometric amount or lower amount) and the preparation method of the catalyst, and the 10 solvents (non-aromatic or aromatic) for the polymerization reaction, the proportion of the solvents (aromatic and non-aromatic) used, and the diene concentration Selections such as polymerization temperature and polymerization temperature allow the use of specific cobalt complexes to adjust the polymer microstructure (cis-, trans-, and vinyl content ratios) and adjust the molecular weight of the resulting polydiene. The advantage is that catalyst preparation method 15 (such as the order of catalyst component addition and catalyst aging) can favorably affect polymer properties such as molecular weight. The catalyst according to the present invention can be used in solution polymerization methods using appropriate techniques (such as spraying techniques but not limiting). Can be used for gas phase polymerization. [Schematic description of the diagram] 20 benefits [representative symbols of the main elements of the diagram] benefit 50

Claims (1)

200302235 Patent application scope 1. A metal complex catalyst composition comprising a) at least one cobalt compound or complex containing at least one cobalt-oxygen bond and b) a type 1 activator compound and c) A type 2 activator compound and d) a catalyst modifier. • The metal catalyst composition according to claim 1 of the patent scope, characterized in that the cobalt complex contains a carboxylate ligand. 3. The cobalt catalyst composition according to any one of the claims No. 丨 -2, characterized in that the cobalt complex contains octanoate, neodecanoate, naphthenate 'versatate, acetamidine Methylpyruvate, ethyl ethylhexanoate or stearate ligands. 15 20 4-The metal catalyst composition according to item 1 of the scope of patent application, characterized in that the type 1 activator compound is selected from the group consisting of ginseng (pentafluorophenyl) boron, ginseng (pentafluorophenyl), ginseng ( O-Nine fluorobiphenyl) butterfly, ginseng (o-nine-air biphenyl ginseng [3,5-home (difluoromethyl) phenyl] rotten, ginseng [3,5_wu (trifluoromethyl) ) Phenyl] aluminum halogenated aromatic boron or aluminum compound; or a polymerization selected from methylaluminoxane (MAO), triisobutylaluminum-modified methylalumoxane or isobutylsulfonium Or an oligomeric aluminoxane. 5. If the metal catalyst composition of the scope of application for item i, the type 1 activator compound is a salt or scale salt selected from compatible non-coordinating negative materials. Non-polymeric, compatible, non-coordinating ion-generating compounds of iron oxide, ferric iron salt, carbon iron salt, Shi Ximeng wrong salt, raw material or ferrocene salt. 51 200302235 Pick up and apply for patent scope 6. The metal catalyst composition of item 1 of the patent is characterized in that the type 1 activator compound is represented by the following general formula: (L * -H) / Ad- where: 5 L * is neutral Louis (L * -H) + is a Bronsted acid; A is a non-coordinating compatible anion with a charge d-, and d is an integer of 1 to 3 and preferably 8 3 corresponds to the formula: [M * Q4]; ίο where: is +3 g of boron or aluminum in the oxidation state; and Q is a hydrocarbyl group, hydrocarbyloxy group, fluorinated hydrocarbyl group, hydrogenated hydrocarbyl group: or fluorinated group containing up to 2. non-hydrogen atoms Material-based hydrocarbon group, but q is the occurrence of hydrocarbon group not more than-times and the best Q at each occurrence is a fluorinated aryl group, especially a pentagas 15 phenyl or nonafluorobiphenyl. The metal catalyst composition of the first item is characterized in that the type 1 activator compound is a cationic oxidant and a non-coordination-compatible anion salt represented by the following formula: (〇xe +) d (AdJe, where 0 〇 χ6 is a cationic oxidant with a valence number e +; d is an integer from 1 to 3; e is an integer from 1 to 3; and Ad_ is a non-coordinating compatible anion with a valence number d •, so / is more specific The example is (pentafluorophenyl) borate. 52. Application for patent scope 8. If the oldest metal catalyst composition for patent scope It is characterized in that the 5L activator compound is a compound of silicon sintered diamond ions and non-coordination-compatible anion salts represented by the following formula: R3Si + A- where: & is a hydrocarbon group; and A is a valence d -Non-coordinating compatible anions, so the preferred Shixiyan sulfonium salt activator compound is pentamethylene (pentafluorophenyl) trimethyl sulfoxane Su 7 (nine fluorobiphenyl) borate trimethylsilane diamond , Triethylsilane (pentafluorophenyl) borate, and other substituted adducts. 9. If the metal catalyst composition of any of the _ items in the scope of the application for a patent, it is characterized by type 1 catalyst activation Molar ratio of the agent relative to the cobalt complex of the catalyst as described in the scope of patent application No. 1 is usually w ·· 10 to 10, _ ·· b is better 1 ·· 10 to 5000: 1 and the best Ϊ ··! To 2'500 · 1, or if a compound containing or available with non-coordinating or poorly coordinating anions is selected as the activator compound, the molar ratio is usually 1: 100 to 1,000. I and preferably 丨: in a range of 2 to 25 〇}. 10. Such as the scope of patent application! The metal catalyst composition according to item 2, characterized in that the type 2 activator is a neutral organometallic compound in which at least one or more than one functional atom or hydrocarbon group is directly bonded to the metal to provide a metal-halogen bond or a carbon-metal key. The hydrocarbyl group is non-aromatic, the hydrocarbyl group is directly bonded to the metal of the organometallic compound, and preferably contains carbon atoms and more preferably m0 carbon atoms. Thus, the metal system of the organometallic compound is selected from the Periodic Table 1, 2, 3 Group 4, 4, 5, 6, 7, 12, 13, or 14 is suitable for 53 200302235. The type 2 catalyst activator used in the scope of patent application does not contain polymer or oligomer alumoxane. 11. The metal catalyst composition according to item 10 of the application, characterized in that the type 2 activator compound is sodium hydrocarbyl, sodium halide, hydrocarbyl lithium, lithium halide, hydrocarbyl zinc, zinc dihalide, magnesium dihalide, Hydrocarbon-based dental magnesium 5, dihydrocarbyl magnesium, especially alkyl sodium, alkyl lithium, alkyl zinc, alkyl halide, dialkyl magnesium, such as n-octyl sodium, butyl lithium, neopentyl lithium, methyl Lithium, ethyllithium, diethylzinc, dibutylzinc, butylmagnesium vapor, ethylmagnesium vapor, octylmagnesium chloride, dibutylmagnesium, dioctylmagnesium, butyloctylmagnesium, and so on Suitable type 2 catalyst activation agents here also include neutral Lewis acids, such as non-aromatic Cu hydrocarbyl substituted Group 13 compound substituents, especially (hydrocarbyl) aluminum compounds or (hydrocarbyl) boron compounds and their compounds. (Including perhalogenated) derivatives containing 1 to 20 carbons in each hydrocarbyl or halogenated hydrocarbyl group; more particularly trialkylaluminum compounds such as triethylaluminum and triisobutylaluminum; dialkylaluminum hydrides such as diiso Butyl 15 hydride; alkyl alkoxy aluminum compounds such as dibutyl ethoxy aluminum Compounds such as diethyl aluminum chloride, ethyl aluminum chloride, diisobutyl aluminum chloride, isobutyl aluminum chloride, ethyl octyl aluminum vapor, ethyl sesquichloride, ethyl Cyclohexyl vaporized aluminum, dicyclohexyl vaporized aluminum, dioctyl aluminum vaporized. 20 12. The metal catalyst composition according to the scope of the patent application, characterized in that the type 2 activator compound is aluminum and boron trioxide, such as trichloride, aluminum trifluoride, boron trifluoride, and The adduct of tridentate aluminum and boron tri-boride and Lewis base, so the type 2 catalyst activator that is suitable for use here as needed also includes neutral Lewis acids such as c 13054 54022235, The scope of the patent application is for a hydrocarbon-substituted Group 3 or Group 7 compound, especially (hydrocarbyl) fluorene, (hydrocarbyl) titanium-, (nicotyl) co-, (hydrocarbyl) hungry- or (hydrocarbyl W-mesh compounds and their halogenation (including all (Halogenated) derivatives, each hydrocarbon group or halogenated hydrocarbon group containing 1 to 20 carbons and also including Group 3 to Group 7 metal halides, especially hafnium, titanium, hafnium, hafnium- or molybdenum halide, such as titanium dichloride , Titanium trichloride, titanium tetragas, hafnium dichloride, zirconium trigas, hafnium tetrachloride, vanadium digas, vanadium trigas, and molybdenum pentagas. 13 · If the scope of patent application is the number The metal catalyst composition of item 丨 丨, characterized in that the type 2 activator compound is preferably halogenated Compounds such as diethyl sodium chloride, ethyl aluminum vapor, aluminum diisobutyl aluminum vapor, ethyl octyl aluminum vapor, ethyl sesquichloro aluminum, methyl sesqui aluminum, ethyl ring Hexylaluminum chloride, dicyclohexylaluminum chloride, dioctylaluminum chloride. 14. The metal catalyst composition according to the scope of application patent No. 10-13, characterized in that the second type catalyst activator is relatively The molar ratio of the cobalt center of the cobalt complex of the catalyst in the scope of the patent application is characterized by the ratio of the type 2 catalyst activator to the cobalt complex usually ranging from 1 ·· 丨 0 to 1,000: 1 More preferably, the range is from 10 to 500: i and the best i is from 1 to 25, 0. 15. If the metal catalyst composition according to item 4 of the patent application scope, the special purpose is to be used for The activator compound mixture here is a combination of type 2 activator compounds, such as neutral Lewis acid used as needed, especially a dialkylaluminum compound having 1 to 4 carbon atoms in each alkyl group (for example, ethyl Sesquichloro aluminum, ethyl octyl aluminum chloride, and diethyl aluminum vapor) and type 1 activator compounds (such as C i3G Hydrocarbyl Substitutions 丨 Group 3 Road 55 200302235 Pick up and apply for patents for easy acid compounds, especially halogenated tri (hydrocarbyl) boron or -aluminum compounds with 1 to 20 carbons in each hydrocarbon group, especially (pentafluorophenyl) Borane or ginseng (pentafluorophenyl) alumane), · Type 2 activator (such as neutral Lewis acid mixture) and polymer or oligomer alumoxane (type activator) , 5 and a single neutral Lewis acid (type 2 activator) especially with ginseng (pentafluorophenyl) borane or ginseng (pentafluorophenyl) alumane and polymer or oligomer aluminoxine (section Type 1 activator). 16. The metal catalyst composition according to item 丨 of the application, characterized in that the catalyst modifier is an aromatic compound. 10. The metal catalyst composition according to item 16 of the application, wherein the catalyst modifier is preferably an aromatic compound, and at least two or more OH groups are bonded to the aromatic compound. 18. The metal catalyst composition according to claims i & 16-17, wherein the aromatic modifier compound 15 having at least two hydroxyl groups is represented by one of the following formulas: Where R 'and R "respectively represent a hydrocarbon group containing U0 carbon atoms; 56 Liao 302235 ίδ, patent application patent R, R2, r3, R4, R5, R6, R7, R8, r9, R] 〇, R] ], R may be the same or different, and respectively represent a hydrocarbon group, a hydroxyl group, a nitro group, a alkoxy group, or an i atom of 1-20 carbon atoms; z represents a hydrocarbon group, an oxygen atom, which does not contain 1-20 carbon atoms, Sulfur atom (c) -group, · (NRAncsiRi,)-group, wherein r13 and r14 may be the same or different and each represents a nicotinyl group of j-20 carbon atoms, and · d is 0, 1 or 2; m , N, q, r, s, t are 0,!, 2, 3, or 4; 0, P is 0, 1, 2, 3, or 4; 10 m + n <4; 0 + p <4; r + q <4; s + t < 4 > 〇19. The metal catalyst composition according to item (1) of the patent application scope, characterized in that the aromatic modifier compound with at least two radicals is represented by the following formula: 〇Η Wherein R1 and R2 are the same or different, and respectively represent a hydrocarbon group, a hydroxyl group, a nitro group, a alkoxy group or a functional atom containing 1-20 carbon atoms 20; 111, 11 are 0, 1, 2, 3 or 4; m + n < 4 〇57 200302235, patent application scope 20, such as the metal catalyst composition of the patent application item 19, characterized in that the aromatic modifier compound with at least two hydroxyl groups are the following compounds One means: OH 5 21 · If the metal catalyst composition of the scope of application for items 1 and wo, it is characterized in that when an organometallic compound is used as the catalyst modifier, the catalyst modifier relative to the metal center of the cobalt complex is The molar ratio is usually in the range of 1:10 to 1,000: i, more preferably i: 10 to 5000: 1 and most preferably 1: 1 to 250: 1. 1022 > A method for producing a polyolefin, which is characterized by using a metal catalyst composition according to any one of claims 1 to 21 of the scope of patent application. 23. · A method for manufacturing a copolymer, which uses a metal complex catalyst such as those in claims 1 to 22, and is characterized in that the comonomer is a conjugated unsaturated carbon-carbon bond monomer, Or a combined aromatic alpha olefin or a combined aliphatic alpha olefin containing a conjugated unsaturated 15 carbon-carbon bond monomer. 24 · —A method for manufacturing a copolymer, which uses a metal complex catalyst as described in item 23 of the patent application, characterized in that the comonomer is a conjugated unsaturated carbon-carbon bond monomer, or Conjugated unsaturated carbon-carbon bond monomers combine aromatic alpha olefins. 20 25 · If the method of manufacturing an olefin polymer or copolymer according to any one of the scope of the application for a patent, characterized in that the type activator is relative to the metal 58 200302235 The molar ratio of the center is in the range of 1: 1 to 10,000: 1, more preferably i: 10 to 5000: 1 and most preferably 1: 1 to 2, 500:}; or if it contains Or compounds that can be obtained from non-coordinating or poorly coordinating anions are used as activator compounds, then the molar ratio is usually between 2: 100 to 丨, 0.0000 · ^ and preferably 1: 2 to 250. : 1 range. 26. The method for producing an olefin polymer or copolymer according to any one of claims 1 to 25 of the patent scope, characterized in that the molar ratio of the type 2 activator to the metal complex center is in 1: 1 to 10,000: 1, more preferably i: 10 to 500: 1 and most preferably 1: 1 to 250: 1. 10 15 20 27. The method for producing an olefin polymer or copolymer according to any one of claims 21 to 26, characterized in that the diene mono system is selected from the group consisting of M-dioxane (2-methylbutadiene), 2,3-dimethyl-1,3-butadiene, pentadiene, 2,4-hexadiene, ^ hexadiene, 1,3 -Heptadiene;!, 3_octadiene, fluorenyl · 2,4_pentadiene, cyclopentadiene, 2,4-hexadiene, I3 · cyclooctadiene, orthobornadiene group. 28. The method for manufacturing a copolymer according to item 26 of the patent application, characterized in that the conjugated diene monosystem is selected from the group consisting of 1,3-butadiene, isoprene (2-methylbutadiene Ene), 2,3 · dimethylpyridine butadiene, ^, pentadiene, 2,4-hexadiene, 丨, 3-hexadiene, 1,3-heptadiene,] ;, Hong octadiene, 2-methyl-2,4. Pentadiene, cyclopentadiene, hexadiene, H-cyclooctadiene, original borneol difluorene group; and the aromatic ^ dilute tobacco single system selection Self-contained group consisting of phenethylhydrazone, p-methylstyrene, u • divinylbenzene, 1,4-divinylbenzene, 2,3 · divinyltoluene, and 2,4 · divinylformin; And the aliphatic olefin single system is selected from the group consisting of propylene, 59 200302235, and patent applications ranging from 1-butene, 1-hexene, 1-octene, and 1-decene. 29. The method for manufacturing a polydiene according to item 28 of the scope of patent application, wherein the diene monosystem is selected from the group consisting of butadiene, isoprene, and cyclopentadiene. 5 30. The method for manufacturing a polydiene according to item 29 of the scope of patent application, characterized in that the diene monosystem is selected from the group consisting of butadiene and isoprene. 31. The method for producing a polydiene as claimed in claim 30, wherein the diene monomer is butadiene. 60 200302235 Lu, (1), the designated representative of the case is: Figure _ (2), the component representative symbols of the representative diagram are simply explained: None 柒, if there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: