JP5157174B2 - Method for producing ethylene-α-olefin-polyene random copolymer - Google Patents

Description

  The present invention relates to a method for producing an ethylene-α-olefin-polyene random copolymer.

  Since ethylene-α-olefin-polyene random copolymers have excellent properties such as heat resistance, weather resistance, ozone resistance, etc., they are used as automotive materials, building materials, industrial materials, electric wire materials, etc. Widely used. The copolymer has been conventionally produced with a vanadium-based catalyst, but this catalyst has a low catalytic efficiency (polymer production amount per unit vanadium catalyst), and the catalytic efficiency at a particularly high temperature is greatly reduced. Therefore, the catalyst cost may increase and the utility cost in the post-treatment process may increase.

  In recent years, metallocene catalysts have been studied as catalysts capable of high-temperature polymerization, but metallocene catalysts using alumoxane as a co-catalyst have drawbacks such as difficulty in increasing the molecular weight of the resulting copolymer (Patent Document 1). As another metallocene catalyst, there is a catalyst using an alkylaluminum compound and a boron compound as co-catalysts (Patent Document 2). In this catalyst, a boron compound that is solid at room temperature is used as a boron compound, and an aromatic is used as a polymerization solvent. In many cases, high catalytic efficiency can be stably obtained when using an aromatic hydrocarbon, but the post-treatment step of the polymerization is time-consuming as compared with the case of using an aliphatic hydrocarbon as a polymerization solvent. there were.

JP 58-19309 A JP-A-3-207704

  Under such circumstances, the problem to be solved by the present invention is an ethylene-α-olefin polyene random copolymer in which ethylene, α-olefin and polyene are polymerized in an aliphatic hydrocarbon solvent in the presence of a polymerization catalyst. An object of the present invention is to provide a production method having a high catalytic efficiency of a polymerization catalyst.

The present invention provides at least the following component (a) in the presence of a catalyst comprising a transition metal complex (A) having at least one cyclopentadienyl skeleton, an organoaluminum compound (B), and a boron compound (C), In the production of an ethylene-α-olefin-polyene random copolymer in which (b) and (c) are polymerized in an aliphatic hydrocarbon solvent, at least a part of component (c) and boron compound (C) is charged into the polymerization tank. The present invention relates to a method for producing an ethylene-α-olefin-polyene random copolymer that is pre-contacted beforehand.
(A): Ethylene (b): C3-C20 α-olefin (c): Polyene

  According to the present invention, in a method for producing an ethylene-α-olefin polyene random copolymer in which ethylene, α-olefin, and polyene are polymerized in an aliphatic hydrocarbon solvent in the presence of a polymerization catalyst, the catalyst efficiency of the polymerization catalyst is high. A manufacturing method can be provided.

  Component (a) used in the present invention is ethylene.

  Component (b) used in the present invention is an α-olefin having 3 to 20 carbon atoms. As the α-olefin, two or more types of monomers can be used at the same time. Specific examples of α-olefins include linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl- Examples thereof include branched olefins such as 1-butene, 3-methyl-1-pentene and 4-methyl-1-pentene, vinylcyclohexane and the like. Preferred are propylene and 1-butene, and particularly preferred is propylene.

  Component (c) used in the present invention is a polyene. Examples of polyenes include linear non-conjugated polyenes, cyclic non-conjugated polyenes, and conjugated polyenes. Specifically, 1,4-hexadiene, 1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,7-nonadiene, 1,8 -Nonadiene, 1,8-decadiene, 1,9-decadiene, 1,12-tetradecadiene, 1,13-tetradecadiene, 3-methyl-1,4-hexadiene, 3-methyl-1,5-hexadiene 3-ethyl-1,4-hexadiene, 3-ethyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,3-dimethyl-1,5-hexadiene, 5-ethylidene-2 -Norbornene, 5-propylidene-2-norbornene, 5-vinyl-2-norbornene, 2,5-norbornadiene, 7-methyl-2,5-norbornadiene, 7-eth 2,5-norbornadiene, 7-propyl-2,5-norbornadiene, 7-butyl-2,5-norbornadiene, 7-pentyl-2,5-norbornadiene, 7-hexyl-2,5-norbornadiene, 7, 7-dimethyl-2,5-norbornadiene, 7,7-methylethyl-2,5-norbornadiene, 7-chloro-2,5-norbornadiene, 7-bromo-2,5-norbornadiene, 7-fluoro-2,5 -Norbornadiene, 7,7-dichloro-2,5-norbornadiene, 1-methyl-2,5-norbornadiene, 1-ethyl-2,5-norbornadiene, 1-propyl-2,5-norbornadiene, 1-butyl-2 , 5-norbornadiene, 1-chloro-2,5-norbornadiene, 1-bromo-2,5-norbornadi Emissions, 1,3-butadiene, isoprene, 1,3-pentadiene (piperine), 2,3-dimethyl-1,3-butadiene, it may be mentioned 1,3-hexadiene and the like. Furthermore, the cyclic diene of the following structure is also mentioned.

  In the present invention, these polyenes can be used alone or in combination. Among these, norbornene derivatives are preferable, and 5-ethylidene-2-norbornene is more preferable.

  In addition to the above components (a) to (c), it is also possible to produce a copolymer using another olefin compound.

  Examples of olefinic compounds other than components (a) to (c) include vinyl aromatic compounds and cycloolefins having one unsaturated bond.

  Typical examples of the vinyl aromatic compound include nucleus or (and) side chain substituted styrene (substituents typically being a lower alkyl group, a lower alkoxy group, a halogen atom, etc.). Specific examples include styrene, α-methylstyrene, p-methylstyrene, o-chlorostyrene, p-chlorostyrene, 2,4-dimethylstyrene, t-butylstyrene, and the like.

  Examples of the cycloolefin having one unsaturated bond include a monocyclic cycloolefin and a polycyclic cycloolefin, and a polycyclic cycloolefin is preferable from the viewpoint of reactivity. Specific examples include norbornene and substituted norbornene.

  Other olefinic compounds that may be used as necessary in the present invention, and examples of olefinic compounds other than the above-mentioned vinyl aromatic compounds and cycloolefins include acrylic acids such as acrylic acid, methyl acrylate, and ethyl acrylate. Alkyl ester (the alkyl group is preferably a chain of about C1 to C6); methacrylic acid alkyl esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate (the alkyl group is a chain of about C1 to C6) Or a cyclic one is preferable); α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; N-substituted maleimides such as N-phenylmaleimide and N-methylmaleimide and the like.

  The production method of the present invention comprises the above essential components in the presence of a catalyst comprising a transition metal complex (A) having at least one cyclopentadienyl skeleton, an organoaluminum compound (B), and a boron compound (C). (A) to (c) are polymerized in an aliphatic hydrocarbon solvent. Examples of the transition metal complex (A) include various publications including JP-A-9-169878, JP-A-9-87313, JP-A-9-12635, and JP-A-8-301934. In particular, at least one transition metal complex selected from the group of transition metal complexes represented by the following general formulas [I] to [III] can be preferably used.

（上記一般式［Ｉ］〜［III］においてそれぞれ、Ｍ¹は元素の周期律表の第４族の遷移金属原子を表し、Ａは元素の周期律表の第１６族の原子を表し、Ｊは元素の周期律表の第１４族の原子を表す。Ｃｐ¹はシクロペンタジエン形アニオン骨格を有する基を表す。Ｘ¹、Ｘ²、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、置換シリル基、アルコキシ基、アラルキルオキシ基、アリールオキシ基又は２置換アミノ基を表す。Ｘ³は元素の周期律表の第１６族の原子を表す。Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は任意に結合して環を形成してもよい。複数あるＭ¹、Ａ、Ｊ、Ｃｐ¹、Ｘ¹、Ｘ²、Ｘ³、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶はそれぞれ同じであっても異なっていてもよい。）

(In the general formulas [I] to [III], M ¹ represents a group 4 transition metal atom in the periodic table of elements, A represents a group 16 atom in the periodic table of elements, and J Represents an atom belonging to group 14 of the periodic table of elements, Cp ¹ represents a group having a cyclopentadiene-type anion skeleton, X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, or a disubstituted amino group, and X ³ represents an element period. .R ^1, R ² representing an atom of the group XVI of the periodic ^{table, R 3, R 4, R} 5 and R ⁶ may form a ring optionally. plurality of M ^1, a, J ^{, Cp 1, X 1, X} 2, X 3, R 1, R 2, R 3, R 4, R 5 and R ⁶ der respectively the same And it may be different as well.)

In the general formula [I], [II] or [III], the transition metal atom represented by M ¹ is a group 4 transition metal element in the periodic table of elements (IUPAC inorganic chemical nomenclature revised edition 1989). Examples thereof include a titanium atom, a zirconium atom, and a hafnium atom. Preferred is a titanium atom or a zirconium atom. Examples of the group 16 atom in the periodic table of the element represented by A in the general formula [I], [II] or [III] include an oxygen atom, a sulfur atom, and a selenium atom, preferably an oxygen atom. It is. Examples of the group 14 atom in the periodic table of the element represented by J in the general formula [I], [II] or [III] include a carbon atom, a silicon atom, a germanium atom, and the like, and preferably a carbon atom. Or it is a silicon atom.

Examples of the group having a cyclopentadiene-type anion skeleton shown as the substituent Cp ¹ include η5- (substituted) cyclopentadienyl group, η5- (substituted) indenyl group, η5- (substituted) fluorenyl group, and the like. Specifically, for example, η5-cyclopentadienyl group, η5-methylcyclopentadienyl group, η5-dimethylcyclopentadienyl group, η5-trimethylcyclopentadienyl group, η5-tetramethylcyclopentadienyl group Group, η5-ethylcyclopentadienyl group, η5-n-propylcyclopentadienyl group, η5-isopropylcyclopentadienyl group, η5-n-butylcyclopentadienyl group, η5-sec-butylcyclopentadienyl group Η5-tert-butylcyclopentadienyl group, η5-n-pentylcyclopentadienyl group, η5-neopentylcyclopentadienyl group, η5-n-hexylcyclopentadienyl group, η5-n-octylcyclopentadienyl group, η5 -Phenylcyclopentadienyl group, η5-na Butylcyclopentadienyl group, η5-trimethylsilylcyclopentadienyl group, η5-triethylsilylcyclopentadienyl group, η5-tert-butyldimethylsilylcyclopentadienyl group, η5-indenyl group, η5-methylindenyl group, η5-dimethylindenyl group Nyl group, η5-ethylindenyl group, η5-n-propylindenyl group, η5-isopropylindenyl group, η5-n-butylindenyl group, η5-sec-butylindenyl group, η5-tert-butylindene Nyl group, η5-n-pentylindenyl group, η5-neopentylindenyl group, η5-n-hexylindenyl group, η5-n-octylindenyl group, η5-n-decylindenyl group, η5-phenylindenyl group Group, η5-methylphenylindenyl group, η5-naphthyl Indenyl group, η5-trimethylsilylindenyl group, η5-triethylsilylindenyl group, η5-tert-butyldimethylsilylindenyl group, η5-tetrahydroindenyl group, η5-fluorenyl group, η5-methylfluorenyl group, η5 -Dimethylfluorenyl group, η5-ethylfluorenyl group, η5-diethylfluorenyl group, η5-n-propylfluorenyl group, η5-di-n-propylfluorenyl group, η5-isopropylfluorene Nyl group, η5-diisopropylfluorenyl group, η5-n-butylfluorenyl group, η5-sec-butylfluorenyl group, η5-tert-butylfluorenyl group, η5-di-n-butylfluorene Nyl group, η5-di-sec-butylfluorenyl group, η5-di-tert-butylfluorenyl group, η5-n -Pentylfluorenyl group, η5-neopentylfluorenyl group, η5-n-hexylfluorenyl group, η5-n-octylfluorenyl group, η5-n-decylfluorenyl group, η5-n- Dodecylfluorenyl group, η5-phenylfluorenyl group, η5-di-phenylfluorenyl group, η5-methylphenylfluorenyl group, η5-naphthylfluorenyl group, η5-trimethylsilylfluorenyl group, η5 -Bis-trimethylsilylfluorenyl group, η5-triethylsilylfluorenyl group, η5-tert-butyldimethylsilylfluorenyl group, and the like, preferably η5-cyclopentadienyl group, η5-methylcyclopentadiyl An enyl group, η5-tert-butylcyclopentadienyl group, η5-tetramethylcyclopentadienyl group, η5 Indenyl group, or η5- fluorenyl group.

Examples of the halogen atom in the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably chlorine An atom or a bromine atom, more preferably a chlorine atom.

As the alkyl group in the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^6, an alkyl group having 1 to 20 carbon atoms is preferable, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n -Dodecyl group, n-pentadecyl group, n-eicosyl group, etc. are mentioned, More preferably, they are a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or an amyl group. Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl group. , Tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group , Tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group Perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl Group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromododecyl group Examples include a bromopentadecyl group and a perbromoeicosyl group. Any of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

As the aralkyl group in the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^6, an aralkyl group having 7 to 20 carbon atoms is preferable, for example, a benzyl group, (2- Methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5 -Dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) Methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethyl) Tilphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) Methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl Group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decyl) Phenyl) methyl group, (n-dodecylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group Such as anthracenylmethyl group and the like, more preferably a benzyl group. These aralkyl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

As the aryl group in the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ^5, and R ^6, an aryl group having 6 to 20 carbon atoms is preferable. Group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5 -Xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5- Trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl Group, n-propylphenyl group, isop Propylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, Examples thereof include an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, an anthracenyl group, and the like, more preferably a phenyl group. These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyloxy groups such as benzyloxy group Etc. may be partially substituted.

The substituted silyl group in the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a silyl group substituted with a hydrocarbon group, where Is, for example, carbon such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, etc. Examples thereof include an alkyl group having 1 to 10 atoms and an aryl group such as a phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include 1-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group, and phenylsilyl group, dimethylsilyl group, diethylsilyl group, and diphenylsilyl group. A disubstituted silyl group having 2 to 20 carbon atoms, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert 3 -carbon atoms such as -butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl group 20 trisubstituted silyl groups and the like, preferably trimethyl Lil group, tert- butyldimethylsilyl group, or a triphenylsilyl group. All of these substituted silyl groups have hydrocarbon groups such as halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or benzyloxy group. A part thereof may be substituted with an aralkyloxy group such as a group.

As the alkoxy group in the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^6, an alkoxy group having 1 to 20 carbon atoms is preferable, for example, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group Group, n-icosoxy group, and the like, more preferably methoxy group, ethoxy group, or tert-butoxy group. These alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

As the aralkyloxy group in the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^6, an aralkyloxy group having 7 to 20 carbon atoms is preferable. (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, ( 2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-) Trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethyl) Ruphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2, 3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) Methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octyl) Phenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group Naphthylmethoxy group, anthracenylmethoxy methoxy group and the like, more preferably a benzyloxy group. These aralkyloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

The aryloxy group in the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is preferably an aryloxy group having 6 to 20 carbon atoms, such as a phenoxy group, 2 -Methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3 , 4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5 -Trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group , Sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like. These aryloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

The disubstituted amino group in the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is an amino group substituted with two hydrocarbon groups, Examples of the hydrogen group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, and cyclohexyl group. And an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms such as a phenyl group, and an aralkyl group having 7 to 10 carbon atoms. Examples of the disubstituted amino group substituted with a hydrocarbon group having 1 to 10 carbon atoms include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, Di-sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino Group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group, and the like, preferably dimethylamino group or diethylamino group. All of these disubstituted amino groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyl such as benzyloxy group. A part thereof may be substituted with an oxy group or the like.

The substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be optionally combined to form a ring. Preferred examples of R ¹ include an alkyl group, an aralkyl group, an aryl group, and a substituted silyl group. Preferred examples of X ¹ and X ² include a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group and a disubstituted amino group, and more preferred examples include a halogen atom and an alkoxy group. I can give you.

Examples of the group 16 atom in the periodic table of the element represented by X ³ in the general formula [II] or [III] include an oxygen atom, a sulfur atom, and a selenium atom, and an oxygen atom is preferable.

  Examples of the transition metal complex represented by the general formula [I] include methylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl). -2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, methylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium Dichloride, Tylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, Methylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) ( -tert- butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride,

Methylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, Methylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, Methylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) Nium dichloride, methylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (tetramethylcyclo Ntadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert -Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene ( Tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium Dichloride, methylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclo Pentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium Chloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) ) Titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2) -Phenoxy) titanium dichloride, methylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-2-phen Xyl) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3- tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride,

Methylene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadi) Enyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert -Butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-t rt-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) ( 3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadi) Enyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene ( Tilcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclohexane) Pentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropyl Riden (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-chloro -2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl -2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3 -Phenyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride Isopropylidene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2) -Phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3,5- Dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclope) Tadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadi) Enyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride,

Isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2) -Phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium Dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclo) Ntadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadi) Enyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclo) Pentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3,5-dimethyl 2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropyl Riden (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-trimethylsilyl) -5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichlora Id, isopropylidene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene ( Cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopenta Dienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride Diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride Diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, Diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2) Phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-) 2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethyl Len (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenyl Methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride Diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclope). Tadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene ( tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, Diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl) -5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl Dimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride,

Diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride Diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride , Diphenylmethylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopenta Enyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene ( Trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride Diphenylmethylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-2-pheno) Si) Titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert -Butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titani Um dichloride, etc., and compounds in which titanium is changed to zirconium or hafnium, dichloride is changed to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide, or diisopropoxide (Cyclopentadienyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), or ( Compound changed to indenyl), (3,5-dimethyl-2-phenoxy) to (2-phenoxy), (3-methyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy) , (3-phenyl-5-methyl-2-phenoxy), (3-t a transition metal complex in which J in the general formula [I] is a carbon atom such as rt-butyldimethylsilyl-2-phenoxy) or a compound changed to (3-trimethylsilyl-2-phenoxy), and dimethylsilyl (cyclopentadi) Enyl) (2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium Dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, Methylsilyl (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethyl Silyl (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride , Dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) Chita Nium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) ) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, Dimethylsilyl (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium Dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl) -2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl) -5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (2-phenoxy) ) Titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) Titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-methyl) -2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (5 -Methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n- Butylcyclope Ntadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl ( n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride , Dimethylsilyl (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl ( tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2- Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert- Tyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopenta) Dienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Dimethylsilyl (tert-butylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopenta) Dienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) ( 3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethyl Silyl (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) Titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3- Trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopene) Dienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopenta) Dienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2- Phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylsilane) Clopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) ) Titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadiene) ) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl ( Trimethylsilylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-methyl-2-phenoxy) titanium dichloride, Dimethylsilyl (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethyl Silyl (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (5-methyl) -3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl) Til-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilyl (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-di-tert-butyl-2-phenoxy) ) Titanium dichloride, dimethylsilyl (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, Dimethylsilyl (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) ( 3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-diamil-2-phenoxy) titanium dichloride, Ru (tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride and the like (cyclopentadienyl) of these compounds (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (Ethylcyclopentadienyl), (n-propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclopentadienyl), (isobutylcyclopentadienyl), (tert-butyldimethylsilyl) Cyclopentadienyl), (phenylcyclopentadienyl), (methylindenyl), or a compound changed to (phenylindenyl), (2-phenoxy) to (3-phenyl2-phenoxy), (3-trimethylsilyl) -2-phenoxy) or (3-tert-butyldi) Compound changed to methylsilyl-2-phenoxy), compound changed from dimethylsilyl to diethylsilyl, diphenylsilyl, or dimethoxysilyl, compound changed from titanium to zirconium or hafnium, dichloride as dibromide, diiodide, bis (dimethylamide) , Bis (diethylamide), di-n-butoxide, or a compound changed to diisopropoxide, wherein J in general formula [I] is a group 14 atom of the periodic table of elements other than carbon atoms Can be given.

  Examples of the transition metal complex represented by the general formula [II] include μ-oxobis {isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (cyclopentadienyl) ( 2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (cyclopentadiene) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (Methylcyclopentadi Nyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) chita Um chloride}, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (cyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (Methylcyclope Ntadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (3- tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ -Oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis Dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium methoxide}, and the like.

  Examples of the transition metal complex represented by the general formula [III] include di-μ-oxobis {isopropylidene (cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (cyclopentadiene). Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {isopropyl Riden (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium}, Di-μ-oxobis {isopropylidene (tetramethylcyclopentadie ) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium}, di-μ -Oxobis {dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) ) Titanium}, di-μ-oxobis {dimethylsilylene (tetramethyl) Le cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, and the like.

  The transition metal complex represented by the above general formula [I] can be produced, for example, by the method described in the published specification of WO 97/03992. The transition metal complex represented by the general formula [II] or [III] can be produced by reacting the transition metal complex represented by the general formula [I] with 1 equivalent or 2 equivalents of water.

The aluminum compound (B) will be described. As the aluminum compound (B), a general formula E ¹ _a AlZ _3-a (where E ¹ represents a hydrocarbon group, and a plurality of E ¹ may be the same or different. Z is a hydrogen atom or And a plurality of Zs may be the same or different, and a represents a number satisfying 0 <a ≦ 3).
As the hydrocarbon group in E ^1, preferably a hydrocarbon group having 1 to 8 carbon atoms, the alkyl group is more preferable.

Specific examples of the compound represented by the general formula E ¹ _a AlZ _3-a include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum; dimethylaluminum chloride, diethylaluminum chloride Dialkylaluminum chloride such as dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichloride such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum Um hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, there can be mentioned dialkyl aluminum hydride such as dihexyl aluminum hydride. Trialkylaluminum is preferable, and triethylaluminum or triisobutylaluminum is more preferable.

The boron compound (C) will be described. As the boron compound (C), any one of the following compounds (C1) to (C3) can be preferably used.
(C1) Boron compound represented by general formula BQ ¹ Q ² Q ³ (C2) Boron compound represented by general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (C3) General formula (LH ) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (wherein B represents a boron atom in a trivalent valence state, Q ^{1 to} Q ⁴ represent a halogen atom, a hydrocarbon group, a halogen atom, Represents a hydrocarbyl group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different, G ⁺ is an inorganic or organic cation, and L is a neutral Lewis base. (LH) ⁺ represents a Bronsted acid.)

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are halogen atoms, hydrocarbon groups, halogenated hydrocarbons. Represents a group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, a halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substitution containing 1 to 20 carbon atoms A silyl group, an alkoxy group containing 1 to 20 carbon atoms, or an amino group containing 2 to 20 carbon atoms, more preferably Q ^{1 to} Q ³ are halogen atoms, carbonization containing 1 to 20 carbon atoms A hydrogen group or a halogenated hydrocarbon group containing 1 to 20 carbon atoms. More preferably, Q ^{1 to} Q ³ are each a fluorinated hydrocarbon group having 1 to 20 carbon atoms each containing at least one fluorine atom, and particularly preferably Q ^{1 to} Q ³ are each at least one fluorine atom. It is a fluorinated aryl group having 6 to 20 carbon atoms including atoms.

Specific examples of the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2 , 3,4,5-tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, etc. Most preferred is tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , G ⁺ represents an inorganic or organic cation, and B represents a trivalent valence state boron atom. , Q ^{1 to} Q ⁴ are the same as Q ^{1 to} Q ³ in (C1) above.

Specific examples of G ⁺ which is an inorganic cation in the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include ferrocenium cation, alkyl-substituted ferrocenium cation, Examples of G ^{+ in} which a silver cation or the like is an organic cation include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation. (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro). Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistri) Fluoromethylphenyl) borate and the like.

  Specific combinations of these include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylmethyl tetrakis Examples thereof include (pentafluorophenyl) borate and triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate. Most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

In the boron compound (C3) represented by the general formula (L-H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , L represents a neutral Lewis base, and (L-H) ⁺ represents represents Stead acid, B represents a boron atom in the trivalent valence state, Q1 to Q4 are the same as Q ¹ to Q ³ in the above Lewis acid (C1).

Specific examples of (LH) ⁺ which is a Bronsted acid in the boron compound (C3) represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include trialkyl-substituted ammonium , N, N-dialkylanilinium, dialkylammonium, triarylphosphonium and the like, and (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ includes the same as described above.

  Specific combinations of these include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ) Ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2 , 4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate , Diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) ) Phosphonium tetrakis (pentafluorophenyl) borate and the like, most preferably tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl). ) Borate.

  Among (C1), (C2), and (C3), the compound (C3) is preferable, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate is particularly preferable.

  In the method of the present invention, high activity is expressed by bringing the boron compound (C) and the polyene (c) into contact with each other prior to charging the polymerization tank. The time for which the boron compound (C) and the polyene (c) are pre-contacted is appropriately selected, but is preferably within 60 minutes, particularly preferably within 3 minutes, from the viewpoint of further increasing the activity. On the other hand, the lower limit of the contact time is usually 10 seconds, preferably 30 seconds.

  In addition, the temperature at which the boron compound (C) and the polyene (c) are contacted in advance is also important. The temperature at the time of prior contact between the boron compound (C) and the polyene (c) can be in the range of −50 to 250 ° C., which is the same as the polymerization temperature, but is preferably in the range of 0 to 80 ° C. from the viewpoint of further increasing the activity. Especially preferably, it is the range of 20-40 degreeC.

  The concentration in the case of using each component in a solution state or in a suspended state in a solvent is appropriately selected depending on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. Generally, the transition metal complex (A) is Usually, 0.01 to 500 μmol / g, more preferably 0.05 to 100 μmol / g, still more preferably 0.05 to 50 μmol / g, and the organoaluminum compound (B) is usually 0 in terms of Al atom. 0.01-10000 μmol / g, more preferably 0.1-5000 μmol / g, still more preferably 0.1-2000 μmol / g, and the boron compound (C) is usually 0.01-500 μmol / g, more Preferably, each component is used in a range of 0.05 to 200 μmol / g, more preferably 0.05 to 100 μmol / g.

In the production method of the present invention, for example, solvent polymerization using an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, and octane as a solvent, or slurry polymerization can be performed, and either continuous polymerization or batch polymerization is possible. But it is possible. The polymerization temperature is usually −50 ° C. or higher, preferably −20 ° C. or higher, more preferably 65 ° C. or higher, particularly preferably 80 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 85 ° C. or lower. It is. The polymerization pressure is preferably from normal pressure to 100 kg / cm ² G. In general, the polymerization time is appropriately determined depending on the type of catalyst to be used and the reaction apparatus, but can be in the range of 1 minute to 20 hours. A chain transfer agent such as hydrogen can also be added to adjust the molecular weight of the polymer.

As a preferable polymerization method for carrying out the present invention, for example, solvent polymerization using an aliphatic hydrocarbon such as hexane, heptane, and octane as a solvent can be mentioned. The polymerization may be either continuous or batch. The essential part of the present invention can be achieved only by performing the polymerization in a single tank polymerization, but it may be performed by connecting two or more reactors in parallel or in series. Specifically, it is preferable that the following conditions (I) to (IV) are satisfied.
(I) It is solution polymerization (II) The polymerization temperature is 0 to 200 ° C. (III) The residence time is 5 to 120 minutes (IV) The polymerization tank pressure is normal pressure to 100 kg / cm ² G Within range

More preferably, the polymerization is carried out under conditions of 30 ° C. or higher and 160 ° C. or lower where the polymer is dissolved using a solvent such as hexane, and a polymerization pressure of 0 kg / cm ² G or higher and 50 kg / cm ² G or lower. In the coalescence production reaction apparatus, it can produce efficiently.

  The molar ratio of ethylene-derived unit / α-olefin-derived unit in the copolymer of the present invention is 95/5 to 20/80, preferably 90/10 to 40/60, and particularly preferably 85/15 to 50/50. If the molar ratio is too high, it tends to be resinous, and if it is too low, the strength tends to be insufficient.

  The iodine value in the copolymer of the present invention is 0 to 50 (g / 100 g polymer), preferably 1 to 40, and more preferably 3 to 35. If the iodine value is too low, vulcanization may be difficult, and if it is too high, the weather resistance may be inferior.

  Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these.

[I] Measuring method The properties of the polymers in the examples were measured by the following methods.
(1) Propylene content Polypropylene, polyethylene, and ethylene / propylene copolymer (50:50) are obtained by infrared absorption spectrum (IR spectrum) using an infrared spectrophotometer (IR-810 manufactured by JASCO Corporation). Measurement was performed using a standard product. The measurement sample was measured as a film of about 0.1 mm using a hot press machine. The measured values are in order of literature values (characterized by polyethylene by infrared absorption spectrum, Takayama, Usami et al. Or Die Makromolekulare Chemie, 177, 461 (1976) Mc Rae, MA, Madam S, WF, etc.). The average of the values measured three times using the absorption peak (methyl branch) at 1155 cm ^-1 as a marker was used.
(2) Iodine value The copolymer was hot-pressed to form a film having a thickness of 0.5 mm, and then a peak (wave number derived from dicyclopentadiene and 5-ethylidene-2-norbornene was obtained using an infrared spectrometer. 1611 cm ⁻¹ , 1688 cm ⁻¹ ) permeability was determined, the molar content of double bonds in the copolymer was calculated, and converted to iodine value.
(3) Molecular weight and molecular weight distribution It is performed by gel permeation chromatograph (150C / GPC apparatus manufactured by Water). The elution temperature was 140 ° C., the column used was Showa Denko, Shodex Packed Column A-80M, and the molecular weight standard material was polystyrene (for example, Tosoh Corporation, molecular weight 500-8,400,000). The obtained polystyrene conversion weight average molecular weight (Mw), number average molecular weight (Mn), and this ratio (Mw / Mn) are defined as molecular weight distribution (Q value). As a measurement sample, about 5 mg of a polymer is dissolved in 5 ml of o-dichlorobenzene to a concentration of about 1 mg / ml. 400 μl of the obtained sample solution was injected, the elution solvent flow rate was 1.0 ml / min, and detection was performed with a refractive index detector.

[II] Catalyst Preparation Method The catalyst component was prepared according to the method described in JP-A-9-87313.

Comparative Example 1
Ethylene, propylene, and 5-ethylidene-2-norbornene were copolymerized using a 1.5 L SUS polymerizer equipped with a stirring blade. That is, hexane is introduced as a polymerization solvent into a 0.8 L polymerization vessel. On the other hand, 22 g of ethylene and 27.3 g of propylene were introduced as monomers from the upper part of the polymerization vessel, and the internal temperature of the polymerization vessel was adjusted to 80 ° C. with a water bath. Subsequently, 40 mmol of 5-ethylidene-2-norbornene (ENB) was added. Thereafter, 0.5 mmol of triisobutylaluminum (TIBA) was added, 0.001 mmol of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride was added, and finally To this, 0.004 mmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added to start the polymerization, and after the polymerization temperature converged to the polymerization start temperature, 10 ml of methanol containing 0.1 g of BHT was added. The polymerization was stopped. The polymer solution after the polymerization was concentrated, and the copolymer was recovered by a methanol precipitation method, followed by vacuum drying at 80 ° C. for 12 hours. 63.1 g of copolymer was obtained (63.1 kg in terms of 1 mmol of Ti catalyst). In addition, it adjusts so that ethylene may be supplied for the part in which the monomer in a polymerization tank is consumed during superposition | polymerization. Detailed results are summarized in Table 1.

Example 1
The same operation as in Comparative Example 1 was performed except that ENB and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate were pre-contacted at room temperature (25 ° C.) for 1 minute before being charged into the polymerization tank. 127.9 g of a copolymer was obtained (128 kg in terms of 1 mmol of Ti catalyst). Detailed results are summarized in Table 1.

Example 2
The same operation as in Comparative Example 1 was performed except that ENB and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate were pre-contacted at room temperature (25 ° C.) for 60 minutes before being charged into the polymerization tank. 92.8 g of copolymer was obtained (93 kg in terms of 1 mmol of Ti catalyst). Detailed results are summarized in Table 1.

注１ ＥＮＢ：５−エチリデン−２−ノルボルネン
注２ Ｔｉ化合物：２ジメチルシリル（テトラメチルシクロペンタジエニル）（３−ｔｅｒｔ−ブチル−５−メチル−２−フェノキシ）チタニウムジクロライド
注３ ボレート化合物：Ｎ，Ｎジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート
注４ ＴＩＢＡ： トリイソブチルアルミニウム

Note 1 ENB: 5-ethylidene-2-norbornene Note 2 Ti compound: 2 dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride Note 3 borate compound: N , N-dimethylanilinium tetrakis (pentafluorophenyl) borate Note 4 TIBA: Triisobutylaluminum

Claims (9)

In the presence of a catalyst comprising a transition metal complex (A) having at least one cyclopentadienyl skeleton, an organoaluminum compound (B), and a boron compound (C), at least the following components (a), (b) and In the method for producing an ethylene-α-olefin-polyene random copolymer in which (c) is polymerized in an aliphatic hydrocarbon solvent, only at least a part of the component (c) and the boron compound (C) is added to the polymerization tank. The manufacturing method of the ethylene-alpha-olefin-polyene random copolymer including the process made to contact previously.
(A): Ethylene (b): C3-C20 α-olefin (c): Polyene The ethylene-α-olefin-polyene random according to claim 1, wherein the transition metal complex (A) is at least one transition metal complex selected from the group of transition metal complexes represented by the following general formulas [I] to [III]. A method for producing a copolymer.

(In the general formulas [I] to [III], M ¹ represents a group 4 transition metal atom in the periodic table of elements, A represents a group 16 atom in the periodic table of elements, and J Represents an atom belonging to group 14 of the periodic table of elements, Cp ¹ represents a group having a cyclopentadiene-type anion skeleton, X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, or a disubstituted amino group, and X ³ represents an element period. .R ^1, R ² representing an atom of the group XVI of the periodic ^{table, R 3, R 4, R} 5 and R ⁶ may form a ring optionally. plurality of M ^1, a, J ^{, Cp 1, X 1, X} 2, X 3, R 1, R 2, R 3, R 4, R 5 and R ⁶ der respectively the same And it may be different as well.) The organoaluminum compound (B) has the general formula E ¹ _a AlZ _3-a (where E ¹ represents a hydrocarbon group, and a plurality of E ¹ may be the same or different. Z represents a hydrogen atom or A plurality of Z may be the same or different. A represents a number satisfying 0 <a ≦ 3), and the boron compound (C) is The method for producing an ethylene-α-olefin-polyene random copolymer according to claim 1 or 2, wherein the compound is any one of the following compounds (C1) to (C3).
(C1) Boron compound represented by general formula BQ ¹ Q ² Q ³ (C2) Boron compound represented by general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (C3) General formula (LH ) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (wherein B represents a boron atom in a trivalent valence state, Q ^{1 to} Q ⁴ represent a halogen atom, a hydrocarbon group, a halogen atom, Represents a hydrocarbyl group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different, G ⁺ is an inorganic or organic cation, and L is a neutral Lewis base. (LH) ⁺ represents a Bronsted acid.)   The method for producing an ethylene-α-olefin-polyene random copolymer according to any one of claims 1 to 3, wherein the component (c) is 5-ethylidene-2-norbornene.   The method for producing an ethylene-α-olefin-polyene random copolymer according to any one of claims 1 to 4, wherein the boron compound (C) is N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.   6. The ethylene-α-olefin-polyene random copolymer according to claim 1, wherein the boron compound (C) and the polyene (c) are in contact with each other within 60 minutes before being charged into the polymerization tank. Production method.   The time for which the boron compound (C) and the polyene (c) are in contact with each other before being charged into the polymerization tank is 3 minutes or less. The ethylene-α-olefin-polyene random copolymer according to any one of claims 1 to 5 Production method.   The method for producing an ethylene-α-olefin-polyene random copolymer according to any one of claims 1 to 7, wherein the polymerization temperature is -50 to 250 ° C.   The method for producing an ethylene-α-olefin-polyene random copolymer according to any one of claims 1 to 8, wherein the boron compound (C) and the polyene (c) are all contacted in advance.