WO2004096879A1

WO2004096879A1 - Process for producing block copolymer

Info

Publication number: WO2004096879A1
Application number: PCT/JP2004/005926
Authority: WO
Inventors: Shojiro Kaita; Yasuo Wakatsuki; Yoshiharu Doi
Original assignee: Riken
Priority date: 2003-04-25
Filing date: 2004-04-23
Publication date: 2004-11-11
Also published as: JP2004323743A

Abstract

A process for producing a block copolymer of a conjugated diene and a polar monomer, which comprises: polymerizing a conjugated diene alone in the presence of a catalyst composition comprising (A) a metallocene complex comprising a rare earth metal compound and (B) an ionic compound comprising a non-coordinating anion and a cation and/or an aluminoxane; and then adding a polar monomer to produce the target block copolymer.

Description

Description Method for producing block copolymer

The present invention relates to a method for producing a block copolymer of a conjugated diene and a polar monomer, and a specific block copolymer produced by the above method. Background art

Numerous proposals have been made on catalysts for copolymerizing conjugated gens and polar monomers, and they have played an extremely important role in industry. In particular, to obtain a block copolymer of a conjugated gen and a polar monomer with improved thermal and mechanical properties, a live-on polymerization using alkyllithium as a polymerization initiator was researched and developed. Have been.

In living anion polymerization, it is possible to produce copolymers having various properties with different chemical structures by appropriately selecting various polymerization conditions such as the amount of polymerization initiator added, the amount of monomer used and the timing of addition. it can. Regarding the copolymerization of conjugated diene and polar monomer, it is known that butadiene and polar monomer (for example, acrylate) are copolymerized by living lithium polymerization with alkyllithium (HL Hsieh, RP Quirk). , Marcel Dekker Inc., New York-Basel, 1996 .; Y. S. Yu, R. Jerome, R. Fayt, Ph. Teyssie Macromolecules, 1994, 27, 5957.). Specifically, diblock copolymers in which methyl acrylate is polymerized after butadiene, and triplock copolymers in which methyl methacrylate is polymerized on both sides of butadiene, have been developed. Living anion polymerization is generally a reaction that does not involve the deactivation of the reactive end by a chain transfer reaction during the polymerization and no new generation compared to the radical polymerization, and the molecular weight distribution of the obtained polymer is based on the polymer obtained by the radical polymerization. Is known to be significantly narrower than the molecular weight distribution of Has been. However, in a polymerization system using alkyllithium, it was difficult to control the stereoregularity of the conjugated gen moiety of the copolymer to cis 1,4 bonds. For example, in the above literature, the content of cis 1,4 in the butadiene portion of the polymer is about 50 mol%.

On the other hand, polymerization catalysts have been researched and developed so that the stereoregularity of the conjugated gen moiety is controlled to a high cis 1,4 bond. For example, a composite catalyst system containing a transition metal compound such as nickel, cobalt, titanium or the like as a main component (Industrial Chemistry, 72, 2081, 1969; Plast. Kautsch., 40, 356, 1993; Makromol. Chem. Phys. , 195, 2623, 1994) and a complex hornworm medium containing a rare earth metal conjugate such as neodymium or gadolinium (Macromol. Rapid Commun. 16, 563, 1992; J. Polym. Sci., Par A; Polyra. Chem., 32, 1195, 1994; Polymer, 37, 349, 1996). However, although these catalyst systems exhibit a high degree of cis 1,4 controllability, the polymerization reaction of the gens does not proceed in a riving manner, and it is extremely difficult to introduce a polar monomer into the polymerization terminal. Was. In contrast, technology has been developed to introduce a polar monomer (for example, ratatones) at the polymerization end, exhibiting somewhat high cis 1,4 controllability in a composite catalyst system containing a rare earth metal compound as the main component. (Japanese Patent Publication No. 2000-3505657). However, the development of further polymerization catalysts exhibiting high cis 1,4 controllability was desired. There was also a need for the development of a polymerization catalyst suitable for the polymerization of conjugated gens with polar monomers such as (meth) acrylic monomers and acrylonitrile monomers. Disclosure of the invention

An object of the present invention is to provide a method for producing a block copolymer of a conjugated diene and a polar monomer. More specifically, a method for producing a block copolymer having a high content of cis-1,4-structure in the microstructure, and a method for preparing a conjugated diene and a (meth) acrylic monomer or an acrylonitrile monomer. It is an object of the present invention to provide a method for producing a block copolymer with a polar monomer containing grease. Another object of the present invention is to provide a block copolymer having the above characteristics. To provide.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a rare earth metal metallocene-type polymerization catalyst, an ionic compound composed of a non-coordinating anion and a cation, and / or an aluminoxane are contained. By using a catalyst composition in which a cocatalyst is combined, a conjugated diene and a polar monomer containing a (meth) acrylic monomer or an acrylonitrile monomer can be efficiently block-copolymerized. By using the catalyst composition for copolymerization described above, a conjugated diene and a polar monomer can be copolymerized to form a block copolymer having a high cis 1,4-structure content in the microstructure. It has been found that a polymer can be produced. The present invention has been completed based on these findings.

That is, the present invention relates to a process for producing a block copolymer of a conjugated diene and a polar monomer, comprising the following components: (A) a meta-acene complex of a rare earth metal compound; After homopolymerization of a conjugated gen in the presence of a catalyst composition containing an ionic compound comprising a cation and / or an aluminoxane, a polar monomer is added to produce a block copolymer of the conjugated gen and the polar monomer. To provide a way to:

According to a preferred embodiment of the present invention, the above-mentioned method, wherein the metallocene complex is a samarium complex; the ionic compound is trifluorocarbodimethylene trakis (pentafunolene rofeninolate) volat; Enenylcarbonate trakis (tetrafluorophenyl) borate, N, N-dimethylanilini dimethyl trakis (pentafluorophenyl) borate, 1,1'-Dimethyl fluorescein-dimethytrakis (pentaf / leophenyl) borate The above method, wherein the catalyst composition further comprises an organic metal compound of an element belonging to Group I to πιι of the periodic table; and the polar monomer is a (meth) acrylic monomer or an atalylonitrile. A method as described above which is a monomer is provided.

From another viewpoint, it is a block copolymer of a conjugated diene and a (meth) acrylic monomer, which contains a cis 1,4-structure in the microstructure. A block copolymer having an amount of 80 mol% or more; and a block copolymer of a conjugated gen and an acrylotrilyl-based monomer. These copolymers can be produced by block copolymerization of a conjugated diene with a (meth) acrylic monomer or an acrylonitrile-based monomer according to the above method. BRIEF DESCRIPTION OF THE FIGURES

Figure 1 is a diagram showing an ^X H Esupeku Torr.

A is the butadiene polymer obtained in Example 1.

B is a block copolymer of butadiene and methyl methacrylate obtained in Example 1.

C is a block copolymer of butadiene and acryl ether obtained in Example 2. BEST MODE FOR CARRYING OUT THE INVENTION

Is a meta-port Sen-type complex of a rare earth metal compound, for example, the general formula _{_{(I): R a MX b}} - L. Or a general formula (II): R _a MX _b QX _b (wherein M represents a rare earth metal; R is a cyclopentagel group, a substituted cyclopentagenenyl group, an indul group, a substituted indenyl group, a fluorenyl group) X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, or a hydrocarbon group having 1 to 20 carbon atoms; L represents a Lewis basic compound; Q represents a Group III element of the periodic table; a represents an integer of 1, 2, or 3; b represents an integer of 0, 1, or 2; c represents an integer of 0, 1, or 2 Or a divalent or trivalent rare earth metal compound represented by

In the above general formula (I), as the rare earth metal represented by M, an element having an atomic number of 57 to 71 in the periodic table can be used. Specific examples of rare earth metals include, for example, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, tenoré Examples include beam, dysprosium, holmium, enolebium, thulium, ytterbium, and lutetium, of which samarium is preferred.

When a is 2 or 3, two or three Rs may be the same or different. Similarly, when b or c is 2, two X or L may be the same or different, respectively.

The type, number, and substitution position of the substituents in the substituted cyclopentagenenyl group, the substituted indenyl group, or the substituted fluorene group are not particularly limited, but, for example, a methyl group, an ethyl group, an n-propyl group, and a Contains silicon atoms such as isopropyl group, n-butyl group, isoptinole group, sec-butylinole group, tert-butynole group, hexinole group, phenyl group, benzyl group, etc., and trimethylsilyl group And hydrocarbon groups. R may be mutually bonded to a part of X by a cross-linking group such as a dimethylsilylene group, a dimethynolemethylene group, a methynolefe-noremethylene group, a diphenylmethylene group, an ethylene group, or a substituted ethylene group. And R may be bonded to each other by a cross-linking group such as a dimethylsilyl group, a dimethylmethylene group, a methylphenylmethylene group, a diphenylmethylene group, an ethylene group, and a substituted ethylene group.

Specific examples of the substituted cyclopentagenenyl group include, for example, a methylcyclopentagenenyl group, a benzylcyclopentagenenyl group, a bulcyclopentagenenyl group, a 2-methoxysylcyclopentagel group, and a trimethylsilinolecyclopentageniyl group. Nore group, tert-butylinolectic pentageninole group, ethynolecyclopentadenyl group, pheninolecyclopentadenyl group, 1,2-dimethinolectic pentageninole group, 1,3-dimethylcyclopentadienyl group, 1,3-di (t ert-butyl) pentagenenyl group with 1,2,3-trimethylcyclopentane group, 1,2,3,4-tetramethylic / pentacyclic group, 1,2-, 3-tetramethylic / pentagonyl group , 1-Echinole-2,3,4,5-tetramethylcyclyl pentagenenyl group, 1- Sopropynoley 2,3,4,5-Tetramethylcyclopentagenenyl group, 1-benzyl-2,3,4,5-tetramethylcyclopentagenenole group, 1-Feninole-2,3,4,5 -Tetramethinoresic mouth Pentagenenyl group, 1-trimethylsilyl-2,3,4,5-tetramethylcyclyl pentagenenyl group, and 1-triphenyloleromethyl-2,3,4,5-tetramethinoresic-opening pentageninole group. Specific examples of the substituted indenyl group include, for example, 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7-hexamethylindull group. And the like. As R, a 1-isopropyl-2,3,4,5-tetramethylcyclopentapentaenyl group is preferable.

Examples of the alkoxide group represented by X include an aliphatic alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a tert-butoxy group. Phenoxy group, 2,6-di-tert-butyl phenoxy group, 2,6-diisopropyl phenoxy group, 2,6-dineopentyl phenoxy group, 2-tert-butyl-6-isopropyl phenoxy group, Any aryloxy group such as 2-tert-butyl-6-neopentylphenoxy group and 2-isopropyl-6-neopentylphenoxy group may be used, but 2,6-di-tert-butylphenoxy group may be used. Groups are preferred.

Examples of the thiolate group represented by X include aliphatic thiols such as thiomethoxy, thioethoxy, thiopropoxy, thio-n-butoxy, thioisobutoxy, thio sec-butoxy, and thiotert-butoxy. Group, thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropynolethiophenoxy group, 2,6-dineopentinolethiophenoxy group, 2-tert-butyl-6-isopropylpropylthiophenoxy group, 2-tert-butyl-6-thionopentylphenoxy group, 2-isopropyl-6-thionopentylphenoxy group, 2,4, Any of arylthiolate groups such as 6-triisopropylthiophenoxy group may be used, but 2,4,6-triisopropylthiophenoxy group is preferred.

The amide groups represented by X include aliphatic amide groups such as dimethyl amide group, getyl amide group, diisopropyl amide group, phenyl amide group, 2,6-di-tert-butyl phenyl amide. Group, 2, 6-diisopropylphenylamide group, 2, 6-dineopentylphenylamide group, 2-tert-butyl-6-isopropyl Pyrphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenyl-amide group, 2,4,6-tert-butyl-ethylamide Although it may be any arylamide group such as a benzyl group, a 2,4,6-tert-butylphenylamide group is preferred.

The hachigen atom represented by X may be any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, but is preferably a chlorine atom or an iodine atom.

Specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by X include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutynole group, sec-butyl group, straight- or branched-chain aliphatic hydrocarbon groups such as tert-butynole group, neopentyl group, hexinole group, and octyl; aromatic hydrocarbon groups such as phenyl, tolyl, and naphthyl groups; In addition to an aralkyl group, a hydrocarbon group containing a silicon atom such as a trimethylsilylmethyl group or a bistrimethylsilylmethyl group may be used. Of these, a methyl group, an ethyl group, an isobutyl group, and a trimethylsilylmethyl group are preferred.

X is preferably a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms.

The Lewis basic compound represented by L is not particularly limited as long as it is a Lewis basic compound that can coordinate to a metal with a counter electron, and may be either an inorganic compound or an organic compound. As the Lewis basic compound, for example, an ether compound, an ester compound, a ketone compound, an amine compound, a phosphine compound, a silyloxy compound, and the like can be used, but are not limited thereto.

In the general formula (II), Q represents an element of Group III of the periodic table, and specific examples of the element include boron, aluminum, and gallium, and aluminum is preferable.

Specific examples of the meta-orthocene type complex of the rare earth metal compound represented by the formula (I) include, for example, bispentamethylcyclopentadenyl bis (methyl) bisulfate, fransamarium, bis (trimethylisopropylcyclopentade) -Norete Trahidrofransamarium, Methinolebispentamethinolecyclopentane-Norete Trahidrofransamarium, Clos bispentamethinolesic mouth Methynocyclopentageninolete transhydrofuran samarium and the like. Specific examples of the metallocene complex of the rare earth metal compound represented by the formula (II) include, for example, dimethyl aluminum (μ- Dimethyl) bis (pentamethylcyclopentagenenyl) summary. The ionic compound used as the co-catalyst is not particularly limited as long as it is composed of a non-coordinating ion and a thione. For example, the ionic compound reacts with the rare earth metal compound to form a cationic transition metal compound. And the like. Examples of non-coordinating aions include tetra (phenyl) borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) porate, and tetrakis (triphenylenolol) Pheninole), Tetrakis (tri-Fnoroleolopheninole) volate, Tetrakis (pentafrenole), and Tetrax (tetrafluoromethylfuel) volate, Tetra ( Trinorate), Tetra (xylyl) borate, (Triphenyl, pentafluorophenylinole), [Tris (pentaphnoleolopheninole), Hue-nolet], Tridecahydrate-7, 8-dicarbanedecaprate and the like.

Examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatriel cation, and a feline mouth cation having a transition metal. Specific examples of the carbon cation include a tri-substituted carbon cation such as a triphenylcarbaium cation and a trisubstituted phenylcarbonium cation. Specific examples of the tri-substituted phenolic carbonyl cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation. Specific examples of ammonium cations include Triammonium cations such as luammonium cation, triethylammonium cation, tripropylammonium cation, triptylammonium cation, tri (n-butylinole) ammonium cation, etc. N, N-dialkylanilyuium cations such as mucation, N, N-Jetinorea dilinium cation, N, N-2,4,6-pentamethinorea dilinium cation, di (isopropyl) ammonium cation, dicyclohexyl Examples include dialkyl ammonium cations such as ammonium cation. Specific examples of the phosphonium cation include triphenyl phosphonium cations, tri (methylphenyl) phosphonium cations, and tri (dimethylphenyl) phosphonium cations. Phosphonium cations can be mentioned.

As the ionic compound, a combination of arbitrarily selected non-coordinating aeons and cations can be preferably used. For example, as ionic compounds, triphenylcarbodimethyl traxate (pentaf / reo mouth phenyle) porate, triphenylenolecanolepodimente trakis (tetrafluorophenyl) borate, N, N- Preference is given to dimethylanilini emuthate trakis (pentaphnolenophenyl) borates, Ι, -dimethinolef erosenidume trakis (pentafuneole sulphate). The ionic compounds may be used alone or in combination of two or more. B (C ₆ F ₅ ) ₃ , A 1 (C ₆ F ₅ ) _{3 and the} like can be used as Lewis acids capable of producing a cationic transition metal compound by reacting with the transition metal compound. It may be used in combination with an ionic compound.

As the aluminoxane used as the co-catalyst, for example, an aluminoxane obtained by contacting an organic aluminum compound with a condensing agent can be used, and more specifically, A chain aluminoxane or a cyclic aluminoxane represented by the general formula (-A1 (R ') 0-) _n can be used. In the above formula, R ′ is a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may be substituted with a halogen atom and / or an alkoxy group. n represents the degree of polymerization, and is preferably 5 or more, more preferably 10 or more. R ' Examples include a methyl group, an ethyl group, a propyl group and an isobutyl group, and a methyl group is preferable. Examples of the organic aluminum compound used as a raw material of the aluminoxane include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and a mixture thereof. Particularly preferred is trimethylaluminum. Aluminoxane using a mixture of trimethylaluminum and triptylumium as a raw material can also be suitably used. Aluminoxane may be used in combination with an ionic compound.

The catalyst composition used in the method of the present invention contains the above-mentioned components (A) and (B), and further contains, as component (C), an organic compound of Group II element of the periodic table. It may contain a metal compound. Examples of the organic metal compound include an organic aluminum compound, an organic lithium compound, an organic magnesium compound, an organic zinc compound, an organic boron compound, and the like. More specifically, methyllithium, butynolelithium, feninolelithium, benzinolelithium, neopentinolelithium, trimethylsilylmethyllithium, bistrimethylsilylmethyllithium, dibutylmagnesium, dihexylmagnesium, and methylzinc zinc , Dimethylzinc, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like can be used. In addition, organic metals such as ethyl magnesium chloride, butyl magnesium chloride, dimethyl aluminum chloride, getyl aluminum chloride, sesquiethyl aluminum chloride, ethyl aluminum dichloride, etc. A hydride organometallic compound such as a halogen compound, getyl aluminum hydride, or sesquiethyl aluminum hydride may be used. These organometallic compounds may be used in combination of two or more.

The mixing ratio of the components (A) and (B) in the composition can be appropriately selected depending on the type of the monomer to be polymerized, the type of the reaction, and the conditions. Generally, in a composition containing a rare earth metal compound and an aluminoxane, the component (A): component (B) (molar ratio) is 1: 1 to 1: 10000, preferably 1:10 to 1: 1000. More preferably, the ratio can be about 1:50 to 1: 500. In the composition containing the rare earth metal compound and the ionic compound, the component (A): component (B) (molar ratio) is 1: 0.1 to 1:10, preferably 1: 0.2 to: 1. : 5, more preferably 1: 0.5 to 1: 2. In the catalyst composition containing the component (C), the mixing ratio (molar ratio) of the rare earth metal compound and the component (C) is, for example, from 1: 0.1 to 1: 1000, preferably 1: 0.2. 11: 500, more preferably about 1: 0.5 01:50. The catalyst composition used in the method of the present invention can be produced according to a conventional method.

The dose of the catalyst composition in the polymerization method of the present invention can be appropriately selected depending on the type of the monomer to be polymerized, the type of the reaction, and the conditions. Generally, the rare earth metal compound is, for example, about 0.0002 to 0.02 mol, preferably about 0.0002 to 0.01 mol, and more preferably about 0.0004 to 0.004 mol, per 100 g of the monomer. Just use it.

The type of the conjugated diene compound monomer copolymerizable by the polymerization method of the present invention is not particularly limited, and examples thereof include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, Examples thereof include 2,3-dimethinolebutadiene, 2-methylenolepentadiene, 4-methynolepentadiene, and 2,4-hexadiene. Of these, 1,3-butadiene is preferable. These monomer components may be used alone or in combination of two or more.

The type of the polar monomer copolymerizable by the polymerization method of the present invention is not particularly limited. For example, (meth) acrylic acid, (meth) methyl acrylate, (meth) acrylic acid ethyl, (meth) acrylic acid-n-propyl, (meta) isopropyl acrylate, (meta) ) -N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl (meth) acrylate (Meth) acrylic monomers such as -pentyl, -n-hexyl (meth) acrylate, and cyclohexyl (meth) acrylate; Acrylonitrile monomers such as tallonitrile and methacrylonitrile are used. Of these, methyl methacrylate and attarylonitrile are preferred. These monomer components may be used alone or in combination of two or more.

The polymerization method of the present invention may be performed in the presence or absence of a solvent. When a solvent is used, the type of the solvent is not particularly limited as long as the solvent is substantially inactive in the polymerization reaction and has sufficient solubility in the monomer and the catalyst composition. For example, saturated aliphatic hydrocarbons such as butane, pentane, hexane and heptane; saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane; monoolefins such as 1-butene and 2-butene; benzene, toluene Aromatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchlorethylene, 1,2-dichloroethane, chloronobenzene, bromobenzene, chloronorenorene, etc. Hydrocarbons may be mentioned, of which toluene is preferred. Further, two or more solvents may be used in combination.

The polymerization temperature in the polymerization method of the present invention is, for example, in the range of −100 to 100 ° C., preferably in the range of −50 to 80 ° C. The polymerization time is, for example, about 1 minute to 50 hours, preferably about 5 minutes to 5 hours. However, these reaction conditions can be appropriately selected according to the type of the monomer and the type of the catalyst composition, and are not limited to the ranges exemplified above. After the homopolymerization of the conjugated diene is performed and the polymerization reaction reaches a predetermined polymerization rate, a polar monomer is added, and the polymerization can be further performed until the polymerization reaction reaches the predetermined polymerization rate. After the polymerization reaction reaches a predetermined polymerization rate, a known polymerization terminator is added to the polymerization system to stop the polymerization, and then the produced copolymer can be separated from the reaction system according to a usual method.

The content of the cis structure in the microstructure of the block copolymer of the present invention is usually 80 mol ° /. Above, preferably 85 mol ° /. Or more, more preferably 90 mol% or more, particularly preferably 92 mol% or more, and the molecular weight Mn is 5,000 or more, preferably 10,000 or more, more preferably 20,000 or more, and particularly preferably 50,000 or more. The molecular weight distribution Mw / Mn is 2.20 or less, preferably 2.00 or less, more preferably 1.80 or less, and particularly preferably 1.50 or less. Further, the copolymer of the present invention is a block copolymer having a monomer composition substantially showing a blockiness. The copolymer of the present invention is expected to have high thermal properties (such as thermal stability) and mechanical properties (such as tensile modulus, flexural modulus, and impact resistance). It can be used for various purposes. Example

Hereinafter, the present invention will be described more specifically with reference to Examples, but the scope of the present invention is not limited to these Examples. Incidentally, the microstructure of the obtained polybutadiene in the examples is the peak obtained by NMR and ¹³ C NMR [iH NMR: δ 4.8-5.0 (1,2 bullet unit = CH ₂ ), 5.2-5.8 (1,4 units — CH = and 1,2 units = CH ₂ ), ¹³ C NMR: δ 27.4 (1,4-cis unit), 32.7 (1,4-trans unit), 127.7-131.8 (1, 4 units), 113.8—114.8 and 143.3—144.7 (1, 2 units)] to calculate the mouth structure. The methyl methacrylate content was obtained by NMR. Peaks [δ: 4.8-5.0 (1,2_Bu units of butadiene = CH ₂ )] and δ 5.2-5.8 (butadiene 1,4-units and 1,2-vinyl unit -CH =) From the integral ratio of δ: 3.5-3.7 (0CH _{3 of} methyl methacrylate), the content of atalononitrile was determined by the peak [δ: 2.0-2.1 (butadiene) obtained by NMR. 1 of diene, 4-Yuni' bets and 1, 2 - Byuruyu - Tsu City of -CH ₂ -) and δ: 1, 4-1.5 (Ata Li Ronito Riruyuni' bets - CH ₂ -)] was determined from the area ratio of the . Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were determined by GPC using polystyrene as a standard substance.

In a glove box under a nitrogen atmosphere, add a sufficiently dried 30 ml pressure-resistant glass bottle to bis-tetramethylisoprovir cyclopentagel-lutet La inhibit mud Furansama Li um _{_{[(C 5 Me 4 iPr)}} 2 Sm (THF)]:;: and the (iPr Lee Sopuro propyl group THF Te Torahi Dorofuran ligand) was dissolved in 0.02mmol charged Toruen 8 ml. Next, 0.30 mmol of triisobutylaluminum and 0.02 mmol of triphenyl / recanolebo temtrakis (pentaphenylphenol) (Ph ₃ CB (C ₆ F _s ) ₄ ) 0.02 mraol were added. Was plugged. Then, the bottle was taken out of the glove box, 1.35 g of 1,3-butadiene was charged, and polymerization was performed at 25 ° C for 10 minutes. Sampling here showed that the conversion of 1,3-butadiene was 96%, and the cis content of the microstructure was 94.8 ° /. The weight average molecular weight was 107,000, the number average molecular weight was 85,200, and Mw / Mn was 1.26. The ¹ H NMR chart of this polymer is shown in FIG. 1A.

Thereafter, 2.6 ml of methyl methacrylate was added to the bottle, and polymerization was further performed at 25 ° C for 1 hour. After the polymerization, a large amount of methanol was added to terminate the reaction, and then the polymer was separated and dried at 60C under vacuum. The yield of the obtained polymer was 1.42 g. The methyl methacrylate content in the polymer was 12.2 wt ° / ₀ (7.0 mol%), the weight average molecular weight was 123,100, the number average molecular weight was 92,200, and Mw / Mn was 1.34. Was. The NMR chart of this polymer is shown in FIG. 1B. Example 2>

The experiment was performed in the same manner as in Example 1, except that 1.7 ml of acrylonitrile was added instead of methyl methacrylate. The yield of the obtained polymer was 1.45 g. The acrylo-tolyl content in the polymer was 15.lwt (15.3mol%), the weight average molecular weight was 152,500, the number average molecular weight was 92,700, and the Mw / Mn was 1.65. Was. The NMR chart of this polymer is shown in Figure 1C. Industrial potential

According to the method of the present invention, a block copolymer can be produced from a conjugated gen and a polar monomer.

Claims

The scope of the claims

1. A method for producing a block copolymer of a conjugated diene and a polar monomer, comprising the following components: (A) a metallocene complex of a rare earth metal compound, and (B) a non-coordinating anion and a cation. Homopolymerization in the presence of a catalyst composition containing a zwitterionic compound and Z or aluminoxane, and then adding a polar monomer to form a block copolymer of the conjugated gen and the polar monomer How to make.

2. The method according to claim 1, wherein the metallocene complex is a summary complex.

3. When the ionic compound is triphenylcarbodimethyl trakis (pentafluorophenyl) por- tate, triphenylcarbodimetal tetrakis (tetrafluorophenyl) bolate, N, N-dimethylanilini 3. The method according to claim 1 or 2, wherein the method is a dimethytrax (pentafunolene rofeninole) porate, a 1, -dimethinoleferrocenenimud tetrakis (pentafluorophenyl) porate.

4. The method according to any one of claims 1 to 3, wherein the catalyst composition further comprises an organometallic compound of an element in Groups I to III of the periodic table.

5. The method according to any one of claims 1 to 4, wherein the polar monomer is a (meth) acrylic monomer or an acrylonitrile monomer.

6. A block copolymer of a conjugated gen and a (meth) acrylic monomer. The content of the cis-1,4-structure in the microstructure is 80 mol. /. The block copolymer described above.

7. Block copolymers of conjugated gens and acrylonitrile monomers.