JP2004217918A - Addition polymerization catalyst component, addition polymerization catalyst, and producing method of addition polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst component for addition polymerization by which a high-molecular weight addition polymer is obtained, to provide a catalyst for the addition polymerization comprising using the catalyst component for the addition polymerization, and to provide a producing method of the addition polymer using the catalysts for the addition polymerization. <P>SOLUTION: The catalyst component for the addition polymerization comprises contacting the following components (a)-(c): (a) a compound represented by formula (1): BiL<SP>1</SP><SB>r</SB>(wherein r is a valence of Bi, L<SP>1</SP>is a hydrogen atom, a halogen atom, a hydrocarbon group, or a hydrocarbonoxy group) ; (b) another compound represented by formula (2): R<SP>1</SP><SB>s-1</SB>T<SP>1</SP>H (wherein R<SP>1</SP>is an electron attracting group or a group containing the electron attracting group, T<SP>1</SP>is a group XV or XVI non-metal atom of the periodic table, and s is an atomic value of T<SP>1</SP>) ; and (c) still another compound represented by the formula (3): R<SP>2</SP><SB>t-2</SB>T<SP>2</SP>H<SB>2</SB>(wherein R<SP>2</SP>is a hydrocarbon group, T<SP>2</SP>is a group XV or XVI non-metal atom of the periodic table, and t is a valence of T<SP>2</SP>). <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a catalyst component for addition polymerization, a catalyst for addition polymerization using the catalyst component for addition polymerization, and a method for producing an addition polymer using the catalyst for addition polymerization.

  Olefin polymers such as polypropylene and polyethylene are used in many fields, including the packaging field, because of their excellent mechanical properties, chemical resistance, etc., and their excellent balance between properties and economy. . Conventional addition polymerization catalysts used in the production of these olefin polymers include solid catalyst components mainly obtained using Group 4 metal compounds such as titanium trichloride and titanium tetrachloride, and organic aluminum compounds. Conventional solid catalysts (multi-site catalysts) in combination with a Group 13 metal compound have been used. However, in recent years, as an addition polymerization catalyst which is less sticky than an addition polymer produced by a conventional solid catalyst and has excellent strength, metallocene complexes such as metallocene complexes and half metallocene complexes are used. A so-called single-site catalyst comprising a catalyst component and an activating co-catalyst component such as aluminoxane or tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate has been proposed. Studies have been made to use it (for example, Patent Document 1, Patent Document 2, etc.). Also, recently, as an activating co-catalyst component, a compound formed by contacting diethyl zinc, pentafluorophenol and water has been developed, and a catalyst formed by contacting the compound with a metallocene complex or a half metallocene complex has been developed. It has been proposed as a highly active catalyst (for example, Patent Document 3).

JP-A-58-19309 Japanese Unexamined Patent Publication No. Hei 1-502036 JP 2001-247612 A

However, when the addition polymerization of olefins is carried out using the above catalyst, the molecular weight of the obtained addition polymer is not sufficiently satisfactory.
Under the current situation, the problem to be solved by the present invention is to provide an addition polymerization catalyst component that can provide a high-molecular weight addition polymer, an addition polymerization catalyst using the addition polymerization catalyst component, and an addition polymerization catalyst. An object of the present invention is to provide a method for producing an addition polymer using a polymerization catalyst.

That is, the first aspect of the present invention relates to a catalyst component for addition polymerization obtained by contacting the following components (a) to (c).
(A): Compound represented by the following general formula [1] BiL ¹ _r [1]
(B): a compound represented by the following general formula [2] R ¹ _s-1 T ¹ H [2]
(C): a compound represented by the following general formula [3] R ² _t-2 T ² H ₂ [3]
(In the above general formulas [1] to [3], r represents a valence of Bi, L ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group or a hydrocarbon oxy group, and when a plurality of L ¹ are present, A plurality of L ¹ may be the same or different, T ¹ and T ² each independently represent a non-metallic atom of Group 15 or 16 of the periodic table of the element, and s is T ¹ the valence, t represents the valence of T ^2, R ¹ represents a group containing an electron withdrawing group or an electron withdrawing group, R ¹ there are a plurality of when R ¹ existing in plural numbers the same as each other or different even, R ² represents a hydrocarbon group, a plurality of R ² is when R ² existing in plural numbers may be different be the same as each other.)
The second aspect of the present invention relates to an addition polymerization catalyst using the above addition polymerization catalyst component.
The third aspect of the present invention relates to a method for producing an addition polymer using the above catalyst for addition polymerization.

  According to the present invention, a catalyst component for addition polymerization from which a high molecular weight addition polymer is obtained, a catalyst for addition polymerization using the catalyst component for addition polymerization, and a method for producing an addition polymer using the catalyst for addition polymerization Can be provided. Further, the addition polymerization catalyst of the present invention exhibits high polymerization activity and is suitable for producing an addition polymer.

Bi in the above general formula [1] is a bismuth atom.
In the general formula [1], r represents the valence of Bi, and is 3 or 5, and preferably 3.

L ¹ is a hydrogen atom in the above general formula [1], a halogen atom, a hydrocarbon group or a hydrocarbon oxy group, even if L ¹ there are plural different even plurality of L ¹ are the same as each other Good. Specific examples of the halogen atom in L ^1, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom. As the hydrocarbon group for L ^1, an alkyl group, an aryl group or an aralkyl group, it is preferred. The hydrocarbon group in L ¹ alkoxy group or an aryloxy group.

Examples of the alkyl group used for L ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, and a neopentyl group. , N-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like.

Any of the alkyl groups used for L ¹ may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group substituted with a halogen atom include, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, 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, pentachloro group Ethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl , Perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl, perchlorooctyl, perchloro Dodecyl, perchloropentadecyl, perchloroeicosyl, perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopentadecyl And a perbromoeicosyl group.
In addition, any of the alkyl groups used for L ¹ may be substituted with an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group.

The alkyl group used for L ¹ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and an isobutyl group.

Examples of the aryl group used for L ¹ include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 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, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl Group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group, etc. Is mentioned.
Each of these aryl groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkyl group such as a methyl group, an ethyl group and an isopropyl group; an alkoxy group such as a methoxy group and an ethoxy group; May be substituted with an aralkyloxy group such as a benzyloxy group.

The aryl group used in L ^1, preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group, a tolyl group.

Examples of the aralkyl group used for L ¹ include a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) methyl group, a (4-methylphenyl) methyl group, and a (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, (3,5 -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-trimethylphenyl) 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-decylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group and the like.
All of these aralkyl 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; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

The aralkyl group used for L ¹ is preferably an aralkyl group having 7 to 20 carbon atoms, more preferably a benzyl group.

Examples of the alkoxy group used for L ¹ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an isobutoxy group, an n-pentyloxy group, Neopentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, n-pentadecyloxy group, n-eico And a siloxy group.
Each of these alkoxy groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group. It may be replaced by, for example.

The alkoxy group used for L ¹ is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, an isobutoxy group, a neopentyloxy group, a tert- It is a pentyloxy group.

Examples of the aryloxy group used for L ¹ include a phenoxy group, a 2-tolyloxy group, a 3-tolyloxy group, a 4-tolyloxy group, a 2,3-xylyloxy group, a 2,4-xylyloxy group, and a 2,5-xylyloxy group 2,6-xylyloxy group, 3,4-xylyloxy group, 3,5-xylyloxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-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, isopropyl Phenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, isobutylphenoxy group, n-pentylphenoxy group, neopentylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n- Examples include a decylphenoxy group, an n-dodecylphenoxy group, an n-tetradecylphenoxy group, a naphthyloxy group, an anthracenyloxy group and the like.
All of these aryl 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; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

The aryloxy group used in L ^1, preferably an aryloxy group having 6 to 20 carbon atoms, more preferably a phenoxy group.

L ¹ is preferably a halogen atom, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, more preferably a halogen atom, an aryl group, an alkoxy group, or an aryloxy group, and particularly preferably an aryl group.

T ¹ in the general formula [2] represents a non-metallic atom of Group 15 or 16 of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989). Specific examples of Group 15 non-metallic atoms include a nitrogen atom and a phosphorus atom, and specific examples of Group 16 non-metallic atoms include an oxygen atom and a sulfur atom. T ¹ is preferably a nitrogen atom or an oxygen atom, and particularly preferably an oxygen atom.

In the above general formula [2], s represents the valence of T ¹ , s is 3 when T ¹ is a Group 15 atom, and s is 2 when T ¹ is a Group 16 atom.

R ¹ in the general formula [2] represents an electron-withdrawing group or a group containing an electron-withdrawing group. When a plurality of R ¹ are present, the plurality of R ¹ may be the same or different. Good. As an index of electron withdrawing property, a Hammett's rule substituent constant σ and the like are known, and a functional group having a positive Hammett's substituent constant σ is mentioned as an electron withdrawing group.

  Specific examples of the electron-withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfonyl group, and a phenyl group. Examples of the group containing an electron-withdrawing group include halogenated hydrocarbon groups such as halogenated alkyl groups and halogenated aryl groups; cyanated hydrocarbon groups such as cyanated aryl groups; and nitrated hydrocarbon groups such as nitrated aryl groups. A hydrocarbon oxycarbonyl group such as an alkoxycarbonyl group, an aralkyloxycarbonyl group and an aryloxycarbonyl group, and an acyloxy group.

Specific examples of the halogenated alkyl group used for R ¹ include fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, dichloromethyl, dibromomethyl, diiodomethyl, trifluoromethyl, and trichloromethyl. Group, tribromomethyl group, triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2- Triiodoethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,3,3,3-pentabromopropyl group, 2,2,3,3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,2,2-trichloro-1 Trichloromethylethyl group, 2,2,2-tribromo-1-tribromomethylethyl group, 2,2,2-triiodo-1-triiodomethylethyl group, 1,1-bis (trifluoromethyl) -2, 2,2-trifluoroethyl group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group, 1,1-bis (tribromomethyl) -2,2,2-tribromoethyl group And 1,1-bis (triiodomethyl) -2,2,2-triiodoethyl groups.

Specific examples of the halogenated aryl group used for R ¹ include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, and a 2-chlorophenyl group. Bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 2,6-dichlorophenyl group, 3,5-dichlorophenyl group, 2,6-dibromophenyl group, 3,5-dibromophenyl group, 2,6-diiodophenyl group, 3,5-diiodophenyl group, 2, 4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,4,6-trichlorophenyl group, 2,4 An aryl group in which hydrogen of an aromatic ring such as a tribromophenyl group, a 2,4,6-triiodophenyl group, a pentafluorophenyl group, a pentachlorophenyl group, a pentabromophenyl group, a pentaiodophenyl group is substituted with halogen; Is mentioned.

Specific examples of the halogenated aryl group used for R ¹ include a 2- (trifluoromethyl) phenyl group, a 3- (trifluoromethyl) phenyl group, a 4- (trifluoromethyl) phenyl group, a 2,6 An aryl group substituted with a halogenated alkyl group such as -bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group; No.

Specific examples of the cyanated aryl group used for R ¹ include a 2-cyanophenyl group, a 3-cyanophenyl group, and a 4-cyanophenyl group.

Specific examples of the nitrated aryl group used for R ¹ include a 2-nitrophenyl group, a 3-nitrophenyl group, and a 4-nitrophenyl group.

Specific examples of the alkoxycarbonyl group used for R ¹ include a methoxycarbonyl group, an ethoxycarbonyl group, a normal propoxycarbonyl group, an isopropoxycarbonyl group, a trifluoromethoxycarbonyl group, and the like.

Specific examples of the aralkyloxycarbonyl group used for R ¹ include a benzyloxycarbonyl group.

Specific examples of the aryloxycarbonyl group used for R ¹ include a phenoxycarbonyl group and a pentafluorophenoxycarbonyl group.

Specific examples of the acyloxy group used for R ¹ include a methylcarbonyloxy group and an ethylcarbonyloxy group.

R ¹ is preferably a halogenated hydrocarbon group, more preferably a halogenated alkyl group or a halogenated aryl group, still more preferably a fluoroalkyl group, a fluoroaryl group, a chloroalkyl group or a chloroaryl group. More preferably a fluoroalkyl group or a fluoroaryl group, particularly preferably a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3, 3-pentafluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 4-fluorophenyl Group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6- A trifluorophenyl group, a 3,4,5-trifluorophenyl group or a pentafluorophenyl group, most preferably a trifluoromethyl group, a 2,2,2-trifluoro-1-trifluoromethylethyl group, , 1-bis (trifluoromethyl) -2,2,2-trifluoroethyl, 3,4,5-trifluorophenyl or pentafluorophenyl.

T ² in the general formula [3] represents a non-metallic atom of Group 15 or 16 of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989). Specific examples of Group 15 non-metallic atoms include a nitrogen atom and a phosphorus atom, and specific examples of Group 16 non-metallic atoms include an oxygen atom and a sulfur atom. T ² is preferably a nitrogen atom or an oxygen atom, and particularly preferably an oxygen atom.

Represents a valence of t is T ² in the general formula [3], if T ² is a Group 15 atom t is 3, if T ² is a Group 16 atom and t is 2.

R ² in the general formula [3] represents a hydrocarbon group, and when a plurality of R ² are present, the plurality of R ² may be the same or different. As the hydrocarbon group for R ² , an alkyl group, an aryl group and an aralkyl group are preferable, and the hydrocarbon group described as L ^{1 in} the above general formula [1] and the halogenation described as R ^{1 in the} above general formula [2] Hydrocarbons can be exemplified.

R ² is preferably a halogenated hydrocarbon group, and more preferably a fluorinated hydrocarbon group.

  Specific examples of the component (a) include bismuth (III) halides such as bismuth (III) fluoride, bismuth (III) chloride, bismuth (III) bromide and bismuth (III) iodine; and trialkylbismuth such as trimethylbismuth. Triarylbismuth such as triphenylbismuth; trimethoxybismuth, triethoxybismuth, triisopropoxybismuth, tri (tert-butoxy) bismuth, triisobutoxybismuth, trineopentyloxybismuth, tri (tert-pentyloxy) bismuth Trialkoxybismuth; triphenoxybismuth, tri (2-tolyloxy) bismuth, tri (3-tolyloxy) bismuth, tri (4-tolyloxy) bismuth, tri (2,3-xylyloxy) bismuth, tri (2,4- (Silyloxy) bismuth, tri (2,5-xylyloxy) bismuth, tri (2,6-xylyloxy) bismuth, tri (3,4-xylyloxy) bismuth, tri (3,5-xylyloxy) bismuth, tri (2,3 4-trimethylphenoxy) bismuth, tri (2,3,5-trimethylphenoxy) bismuth, tri (2,3,6-trimethylphenoxy) bismuth, tri (2,4,6-trimethylphenoxy) bismuth, tri (3 4,5-trimethylphenoxy) bismuth, tri (2,3,4,5-tetramethylphenoxy) bismuth, tri (2,3,4,6-tetramethylphenoxy) bismuth, tri (2,3,5,6) -Tetramethylphenoxy) bismuth, tri (pentamethylphenoxy) bismuth, tri (ethylphenoxy) Bismuth, tri (n-propylphenoxy) bismuth, tri (isopropylphenoxy) bismuth, tri (n-butylphenoxy) bismuth, tri (sec-butylphenoxy) bismuth, tri (tert-butylphenoxy) bismuth, tri (isobutylphenoxy) Bismuth, tri (n-pentylphenoxy) bismuth, tri (neopentylphenoxy) bismuth, tri (n-hexylphenoxy) bismuth, tri (n-octylphenoxy) bismuth, tri (n-decylphenoxy) bismuth, tri (n- Triaryloxybismuth such as dodecylphenoxy) bismuth, tri (n-tetradecylphenoxy) bismuth, trinaphthyloxybismuth, and trianthracenyloxybismuth; bismuth (V) fluoride, bismuth (V ) Halogenated bismuth (V) such as chloride, bismuth (V) bromide, bismuth (V) iodine; pentaalkyl bismuth such as pentamethyl bismuth; pentaaryl bismuth such as pentaphenyl bismuth; Pentaalkoxybismuth; pentaaryloxybismuth such as pentaphenoxybismuth;

  Component (a) is preferably bismuth (III) halide, trialkylbismuth, triarylbismuth, trialkoxybismuth or triaryloxybismuth, and more preferably bismuth (III) halide, triarylbismuth, trialkoxybismuth , Triaryloxybismuth, and particularly preferably triarylbismuth such as triphenylbismuth.

  When the component (b) is exemplified as a specific example, the amines include di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, di (iodomethyl) amine, bis (difluoromethyl) amine, and bis (difluoromethyl) amine. (Dichloromethyl) amine, bis (dibromomethyl) amine, bis (diiodomethyl) amine, bis (trifluoromethyl) amine, bis (trichloromethyl) amine, bis (tribromomethyl) amine, bis (triiodomethyl) amine, Bis (2,2,2-trifluoroethyl) amine, bis (2,2,2-trichloroethyl) amine, bis (2,2,2-tribromoethyl) amine, bis (2,2,2-triethyl) amine Iodoethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine, bis (2,2,3,3) -Pentachloropropyl) amine, bis (2,2,3,3,3-pentabromopropyl) amine, bis (2,2,3,3,3-pentaiodopropyl) amine, bis (2,2,2 -Trifluoro-1-trifluoromethylethyl) amine, bis (2,2,2-trichloro-1-trichloromethylethyl) amine, bis (2,2,2-tribromo-1-tribromomethylethyl) amine, Bis (2,2,2-triiodo-1-triiodomethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine, bis (1,1- Bis (trichloromethyl) -2,2,2-trichloroethyl) amine, bis (1,1-bis (tribromomethyl) -2,2,2-tribromoethyl) amine, bis (1,1- Bis (triiodomethyl) -2,2,2-triiodoethyl) amine, bis (2-fluorophenyl) amine, bis (3-fluorophenyl) amine, bis (4-fluorophenyl) amine, bis (2- Chlorophenyl) amine, bis (3-chlorophenyl) amine, bis (4-chlorophenyl) amine, bis (2-bromophenyl) amine, bis (3-bromophenyl) amine, bis (4-bromophenyl) amine, bis (2 -Iodophenyl) amine, bis (3-iodophenyl) amine, bis (4-iodophenyl) amine, bis (2,6-difluorophenyl) amine, bis (3,5-difluorophenyl) amine, bis (2 6-dichlorophenyl) amine, bis (3,5-dichlorophenyl) amine, bis (2,6-dibromophen Nyl) amine, bis (3,5-dibromophenyl) amine, bis (2,6-diiodophenyl) amine, bis (3,5-diiodophenyl) amine, bis (2,4,6-trifluorophenyl) ) Amine, bis (2,4,6-trichlorophenyl) amine, bis (2,4,6-tribromophenyl) amine, bis (2,4,6-triiodophenyl) amine, bis (pentafluorophenyl) Amine, bis (pentachlorophenyl) amine, bis (pentabromophenyl) amine, bis (pentaiodophenyl) amine, bis (2- (trifluoromethyl) phenyl) amine, bis (3- (trifluoromethyl) phenyl) amine , Bis (4- (trifluoromethyl) phenyl) amine, bis (2,6-di (trifluoromethyl) phenyl) a , Bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-tri (trifluoromethyl) phenyl) amine, bis (2-cyanophenyl) amine, bis (3-cyano Phenyl) amine, bis (4-cyanophenyl) amine, bis (2-nitrophenyl) amine, bis (3-nitrophenyl) amine, bis (4-nitrophenyl) amine and the like.

  Examples of the phosphines as specific examples of the component (b) include the compounds of the above specific examples in which a nitrogen atom is substituted with a phosphorus atom.

  Specific examples of component (b) include alcohols such as fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodomethanol, trifluoromethanol, trichloromethanol, tribromomethanol, tribromomethanol, and tribromomethanol. Iodomethanol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2,2,2-tribromoethanol, 2,2,2-triiodoethanol, 2,2,3,3 3-pentafluoropropanol, 2,2,3,3,3-pentachloropropanol, 2,2,3,3,3-pentabromopropanol, 2,2,3,3,3-pentaiodopropanol, 2, 2,2-trifluoro-1-trifluoromethyl And 2,2,2-trichloro-1-trichloromethylethanol, 2,2,2-tribromo-1-tribromomethylethanol, 2,2,2-triiodo-1-triiodomethylethanol, 1,1- Bis (trifluoromethyl) -2,2,2-trifluoroethanol, 1,1-bis (trichloromethyl) -2,2,2-trichloroethanol, 1,1-bis (tribromomethyl) -2,2 , 2-tribromoethanol, 1,1-bis (triiodomethyl) -2,2,2-triiodoethanol and the like.

  As specific examples of the component (b), thiols include compounds in which the oxygen atom of the specific examples of the alcohols is replaced with a sulfur atom, for example, methanol of the specific examples of the alcohols is methanethiol, and ethanol is ethanethiol. Examples thereof include compounds represented by rewriting propanol with propanethiol, and the like.

  Phenols as specific examples of compound (b) include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol, and 3-chlorophenol. Bromophenol, 4-bromophenol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,6-dichlorophenol, 3,5-dichlorophenol , 2,6-dibromophenol, 3,5-dibromophenol, 2,6-diiodophenol, 3,5-diiodophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol 2,4,6-trichlorophenol, 2,4,6-to Bromophenol, 2,4,6-triiodophenol, pentafluorophenol, pentachlorophenol, pentabromophenol, pentaiodophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- ( (Trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol, 2-cyanophenol, 3 -Cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol and the like.

  As specific examples of the component (b), thiophenols include compounds in which the oxygen atom of the specific examples of the above-mentioned phenols is replaced with a sulfur atom. For example, phenols of the specific examples of the above-mentioned phenols are replaced with thiophenols. And the like.

  As specific examples of the component (b), carboxylic acids include 2-fluorobenzoic acid, 3-fluorobenzoic acid, 4-fluorobenzoic acid, 2,3-difluorobenzoic acid, 2,4-difluorobenzoic acid, 2,5 -Difluorobenzoic acid, 2,6-difluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2,3,5-trifluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2,4 5-trifluorobenzoic acid, 2,4,6-trifluorobenzoic acid, 2,3,4,5-tetrafluorobenzoic acid, 2,3,4,6-tetrafluorobenzoic acid, pentafluorobenzoic acid, fluoro Acetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropanoic acid, heptafluorobutanoic acid, 1,1-bis (trifluoromethyl) -2,2,2-trifluoro Etc. Etanoikku acid, and the like.

  Specific examples of the component (b) include sulfonic acids such as fluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, and 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanesulfonic acid and the like.

  As component (b), preferably, amines include bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) ) Amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine or bis Examples of (pentafluorophenyl) amine and alcohols include trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, and 2,2,2-trifluoro-1. -Trifluoromethylethanol or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, as phenols , 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, Pentafluorophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (tri Fluoromethyl) phenol or 2,4,6-tris (trifluoromethyl) phenol, carboxylic acids are pentafluorobenzoic acid or trifluoroacetic acid, and sulfonic acids are trifluoromethanesulfonic acid.

  More preferably, component (b) is bis (trifluoromethyl) amine, bis (pentafluorophenyl) amine, trifluoromethanol, 2,2,2-trifluoro-1-trifluoromethylethanol, 1,1-bis (Trifluoromethyl) -2,2,2-trifluoroethanol, 4-fluorophenol, 2,6-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, pentafluoro Phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol or 2,4,6-tris (trifluoromethyl) phenol, more preferably 3,4,5- Trifluorophenol, pentafluorophenol, or 1,1-bis (trifluoro Oromechiru) -2,2,2 it is trifluoride ethanol.

  Component (c) is preferably water, hydrogen sulfide, alkylamine, arylamine or aralkylamine, and more preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentylamine, neopentylamine, isopentylamine, n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, n -Eicosylamine, allylamine, cyclopentadienylamine, aniline, 2-tolylamine, 3-tolylamine, 4-tolylamine, 2,3-xylylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine , 2,4-xylylamine, 3,5-xylylamine, 2,3,4-trimethylaniline, 2,3,5-trimethylaniline, 2,3,6-trimethylaniline, 2,4,6-trimethylaniline, 3,4 , 5-Trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,4,6-tetramethylaniline, 2,3,5,6-tetramethylaniline, pentamethylaniline, ethylaniline, n -Propylaniline, isopropylaniline, n-butylaniline, sec-butylaniline, tert-butylaniline, n-pentylaniline, neopentylaniline, n-hexylaniline, n-octylaniline, n-decylaniline, n-dodecylaniline , N-tetradecylaniline, naphthylamine, anthracenylamine

Benzylamine, (2-methylphenyl) methylamine, (3-methylphenyl) methylamine, (4-methylphenyl) methylamine, (2,3-dimethylphenyl) methylamine, (2,4-dimethylphenyl) methyl Amine, (2,5-dimethylphenyl) methylamine, (2,6-dimethylphenyl) methylamine, (3,4-dimethylphenyl) methylamine, (3,5-dimethylphenyl) methylamine, (2,3 , 4-trimethylphenyl) methylamine, (2,3,5-trimethylphenyl) methylamine, (2,3,6-trimethylphenyl) methylamine, (3,4,5-trimethylphenyl) methylamine, (2 , 4,6-trimethylphenyl) methylamine, (2,3,4,5-tetramethylphenyl) methylamido (2,3,4,6-tetramethylphenyl) methylamine, (2,3,5,6-tetramethylphenyl) methylamine, (pentamethylphenyl) methylamine, (ethylphenyl) methylamine, (n -Propylphenyl) methylamine, (isopropylphenyl) methylamine, (n-butylphenyl) methylamine, (sec-butylphenyl) methylamine, (tert-butylphenyl) methylamine, (n-pentylphenyl) methylamine, (Neopentylphenyl) methylamine, (n-hexylphenyl) methylamine, (n-octylphenyl) methylamine, (n-decylphenyl) methylamine, (n-tetradecylphenyl) methylamine, naphthylmethylamine, anthra Cenylmethylamine, fluorome Ruamine, chloromethylamine, bromomethylamine, iodomethylamine, difluoromethylamine, dichloromethylamine, dibromomethylamine, diiodomethylamine, trifluoromethylamine, trichloromethylamine, tribromomethylamine, triiodomethylamine, 2,2,2-trifluoroethylamine, 2,2,2-trichloroethylamine, 2,2,2-tribromoethylamine, 2,2,2-triiodoethylamine, 2,2,3,3,3-pentane Fluoropropylamine, 2,2,3,3,3-pentachloropropylamine, 2,2,3,3,3-pentabromopropylamine, 2,2,3,3,3-pentaiodopropylamine, 2 , 2,2-trifluoro-1-trifluoromethylethylamine, 2,2 , 2-Trichloro-1-trichloromethylethylamine, 2,2,2-tribromo-1-tribromomethylethylamine, 2,2,2-triiodo-1-triiodomethylethylamine, 1,1-bis (trifluoromethyl ) -2,2,2-trifluoroethylamine, 1,1-bis (trichloromethyl) -2,2,2-trichloroethylamine, 1,1-bis (tribromomethyl) -2,2,2-tribromo Ethylamine, 1,1-bis (triiodomethyl) -2,2,2-triiodoethylamine,

2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2-iodoaniline, 3-iodoaniline, 4-iodoaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline, 2,6-dibromoaniline, 3,5-dibromo Aniline, 2,6-diiodoaniline, 3,5-diiodoaniline, 2,4,6-trifluoroaniline, 2,4,6-trichloroaniline, 2,4,6-tribromoaniline, 2,4 , 6-triiodoaniline, pentafluoroaniline, pentachloroaniline, pentabromoaniline, pentayo Aniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-di (trifluoromethyl) aniline, 3,5-di (trifluoromethyl ) Aniline, 2,4,6-tri (trifluoromethyl) aniline.

  More preferably, component (c) is water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-octylamine, aniline, , 6-xylylamine, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine , Perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroaniline, 3-fluoroaniline, 4- Fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (Trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, and 2,4,6-tris (trifluoromethyl) aniline, particularly preferably , Water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine, perfluoropentadecylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoro Aniline, 2,4,6-trifluoroani Pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (Trifluoromethyl) aniline and 2,4,6-tris (trifluoromethyl) aniline, most preferably water and pentafluoroaniline.

  The catalyst component for addition polymerization of the present invention is a compound (hereinafter, referred to as compound (A)) obtained by bringing the above components (a) to (c) into contact. The contact treatment of the components (a) to (c) is preferably performed in an inert gas atmosphere. The contact treatment temperature is generally -100 to 200C, preferably -80 to 150C, more preferably 10 to 150C, and further preferably 40 to 100C. The contact treatment time is generally 1 minute to 36 hours, preferably 10 minutes to 24 hours. In such a contact treatment, a solvent may be used, or the components (a) to (c) may be directly contacted without using a solvent, but it is preferable to perform the contact treatment using a solvent. Examples of the solvent used include non-polar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents; and polar solvents such as halide solvents and ether solvents. Specific examples thereof include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; dichloromethane, difluoromethane , Chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene and other halide solvents Dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl-ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, tetrahydrofuran Ether solvents such as tetrahydrofuran and tetrahydropyran. Preferred are aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents and ether solvents, more preferred are aromatic hydrocarbon solvents, and still more preferred are toluene.

The method for bringing the above components (a) to (c) into contact is not particularly limited, and for example, the following methods can be employed.
(A): A method in which the component (a) is brought into contact with the component (b), and then the component (c) is brought into contact.
(B): A method in which the component (a) is brought into contact with the component (c) and then the component (b) is brought into contact.
(C): A method in which the component (b) is brought into contact with the component (c) and then the component (a) is brought into contact.
Preferably, the method (a) or (b), that is, as the addition polymerization catalyst component of the present invention, a contact product obtained by contacting the component (a) with the component (b) and the component (c) Or a compound obtained by contacting component (b) with a contact product obtained by contacting component (a) with component (c), and more preferably (a) ), That is, the catalyst component for addition polymerization of the present invention is more preferably obtained by contacting a contact product obtained by contacting component (a) with component (b) and component (c). Compound. In the method (a), a contact product obtained by bringing the component (a) into contact with the component (b) is dissolved in a solvent to form a solution, and then the solution is brought into contact with the component (c). Is preferred. In the method of bringing the components (a) to (c) into contact with each other, after contacting any two components selected from the components (a) to (c), the contact product is purified, and the purified product is selected. A method of contacting the remaining components that have not been performed may be performed. After contacting any two components selected from components (a) to (c), the contact material is contacted without purification. A method of contacting the remaining unselected components may be performed.

  From the viewpoint of enhancing the catalytic activity, the contact treatment amount ratio of the components (a) to (c) is represented by the molar ratio of the contact treatment amount of each component: component (a): component (b): component (c) = 1: y : Z, y is preferably 0.7 × r to 1.3 × r, more preferably 0.8 × r to 1.2 × r, and still more preferably 0.9 × r to 1.1 × r. Here, r represents the valence of Bi. z is preferably 0.1 to 2, more preferably 0.4 to 1.8, still more preferably 0.6 to 1.6, and particularly preferably 0.8 to 1.4. And most preferably from 0.9 to 1.3.

  As a result of the contact treatment of the components (a) to (c), the compound (A) of the present invention is obtained by converting the raw materials of the component (a) and / or the component (b) and / or the component (c) as unreacted products. It may remain.

  Specific examples of the method for producing the compound (A) of the present invention will be described in more detail in the case where the component (a) is triphenylbismuth, the component (b) is pentafluorophenol, and the component (c) is water. It is shown below. To a toluene solution of triphenylbismuth, pentafluorophenol in a molar amount 3 times the amount of triphenylbismuth was added dropwise as a toluene solution of pentafluorophenol, and the mixture was stirred under reflux for 10 minutes to 24 hours, and then cooled to room temperature. I do. The precipitated crystals are separated by filtration and dried, and the crystals are dissolved in toluene. To the bismuth component in the toluene solution, water having a molar amount equal to the molar amount of the bismuth component is dropped, and the mixture is stirred at 80 ° C. for 1 hour. .

  Specific examples of the addition polymerization catalyst of the present invention include a compound (A) and an addition polymerization catalyst obtained by contacting a compound of Group 3 to 11 or a lanthanoid series metal compound (hereinafter, referred to as compound (B)). And an addition polymerization catalyst obtained by contacting the compound (A), the compound (B), and an organoaluminum compound (hereinafter, referred to as a compound (C)).

The compound (B) is not particularly limited as long as the compound obtained by bringing the compound (A) or the compound (C) into contact with the compound (B) becomes a compound exhibiting addition polymerizability. Examples of the compound (B) include a metal compound represented by the following general formula [7] and a μ-oxo type metal compound thereof.
L ² _a M ⁶ X ⁸ _b [7]
(In the formula, a represents a number satisfying 0 <a ≦ 8, b represents a number satisfying 0 <b ≦ 8. M ⁶ represents a metal belonging to Groups 3 to 11 of the periodic table of elements or a lanthanoid series metal. .L ² representing the atom is a group containing a group or a hetero atom having a cyclopentadiene type anion skeleton, if L ² there is a plurality, they may be different from one another the same, a plurality of L ² May be linked directly or via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. X ⁸ represents a halogen atom, a hydrocarbon group Excluding a group having a pentadiene-type anion skeleton) or a hydrocarbonoxy group, and when there are a plurality of X ⁸ , they may be the same or different from each other.)

In the general formula [7], M ⁶ is a metal atom belonging to Groups 3 to 11 of the Periodic Table of the Elements (IUPAC 1989) or a lanthanoid series. Specific examples thereof include scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, iron, ruthenium, cobalt, rhodium, nickel, and palladium atoms. , Samarium atom, ytterbium atom and the like. M ⁶ is preferably a metal atom of Groups 3 to 11 of the periodic table, and particularly preferably a titanium atom, a zirconium atom or a hafnium atom.

In the general formula [7], L ² is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ² may be the same or different. A plurality of L ² may be connected directly or via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Group having a cyclopentadiene type anion skeleton in L ² is, for example, eta ⁵ - (substituted) cyclopentadienyl group, eta ⁵ - (substituted) indenyl group, eta ⁵ - and the like (substituted) fluorenyl group. Specific examples include η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ -tert-butylcyclopentadienyl group, η ⁵ -1,2-dimethylcyclopentadienyl group, eta ^{5-1,3-dimethyl} cyclopentadienyl group, η ⁵ -1-tert- butyl-2-methylcyclopentadienyl group, η ⁵ -1-tert- butyl-3-methylcyclopentadienyl group, eta ^{5-1-methyl-2-isopropyl-cyclopentadienyl} group, eta ^{5-1-methyl-3-isopropyl-cyclopentadienyl} group, eta ^{5-1,2,3-trimethyl} cyclopentadienyl group, eta ^{5-1,2,4-trimethyl} cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - indenyl group, eta ⁵ Tetrahydroindenyl group, eta ^{5-2-methylindenyl} group, eta ^{5-3-methylindenyl} group, eta ^{5-4-methylindenyl} group, eta ^{5-5-Mechiruinde} alkenyl group, eta ^{5-6-methylindenyl} group, eta ^{5-7-methylindenyl} group, η ⁵ -2-tert- butyl indenyl group, η ⁵ -3-tert- butyl indenyl group, eta ⁵ - 4-tert-butyl indenyl group, η ⁵ -5-tert- butyl-indenyl group, η ⁵ -6-tert- butyl indenyl group, η ⁵ -7-tert- butyl indenyl group, η ⁵ -2, 3-dimethyl-indenyl group, eta ^{5-4,7-dimethyl-indenyl} group, eta ^{5-2,4,7-trimethyl} indenyl group, eta ^{5-2-methyl-4-isopropylindenyl} group, eta ⁵ - 4,5 benzindenyl group, eta ^5-2-methyl - , 5-benzindenyl group, eta ^5-4-phenyl indenyl group, eta ^{5-2-methyl-5-phenyl} indenyl group, eta ^{5-2-methyl-4-phenyl} indenyl group, eta ^5-2-methyl 4-naphthyl indenyl group, eta ⁵ - fluorenyl group, eta ^{5-2,7-dimethyl} fluorenyl group, eta ^5-2,7-di -tert- butyl fluorenyl groups, and their substitution products Is mentioned.

Examples of the hetero atom in the group containing a hetero atom used for L ² include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Examples of such a group include an alkoxy group; an aryloxy group; a thioalkoxy group; Thioaryloxy group; alkylamino group; arylamino group; alkylphosphino group; arylphosphino group; aromatic or aliphatic having at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom in the ring Group heterocyclic groups; chelating ligands and the like.

  Specific examples of the group containing a hetero atom include methoxy, ethoxy, propoxy, butoxy, phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, and 2,4,6-trimethylphenoxy. Group, 2-ethylphenoxy group, 4-n-propylphenoxy group, 2-isopropylphenoxy group, 2,6-diisopropylphenoxy group, 4-sec-butylphenoxy group, 4-tert-butylphenoxy group, 2,6- Di-sec-butylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2,6-di-tert-butylphenoxy group, 4-methoxyphenoxy group, 2,6-dimethoxyphenoxy group, 3,5- Dimethoxyphenoxy group, 2-chlorophenoxy group, 4-nitrosophenoxy group, 4-nitropheno Group, 2-aminophenoxy group, 3-aminophenoxy group, 4-aminothiophenoxy group, 2,3,6-trichlorophenoxy group, 2,4,6-trifluorophenoxy group, thiomethoxy group, dimethylamino group, Diethylamino group, dipropylamino group, diphenylamino group, isopropylamino group, tert-butylamino group, pyrrolyl group, dimethylphosphino group, 2- (2-oxy-1-propyl) phenoxy group, catecholate group, 2-hydroxy Phenyl group, resorcinolate group, 3-hydroxyphenyl group, 4-isopropylcatecholate group, 4-isopropyl-2-hydroxyphenyl group, 3-methoxycatecholate group, 3-methoxy-2-hydroxyphenyl group, 1,8- Dihydroxynaphthyl group, 1,2-dihydroxynaph 1,2′-hyphenyldiol group, 1,1′-bi-2-naphthol group, 2,2′-dihydroxy-6,6′-dimethylbiphenyl group, 4,4 ′, 6,6 ′ -Tetra-tert-butyl-2,2'methylenediphenoxy group, 4,4 ', 6,6'-tetramethyl-2,2'-isobutylidenediphenoxy group and the like.

Examples of the group containing a hetero atom include a group represented by the following general formula [8].
_{^{R 3 3 P = N- [8}} ]
(In the formula, R ³ represents a hydrogen atom, a halogen atom, or a hydrocarbon group in each case, and a plurality of R ³ may be the same or different from each other. May form a ring.)

Specific examples of R ³ in the general formula [8] include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Examples include a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cycloheptyl group, a cyclohexyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a benzyl group.

（式中、Ｒ⁶¹〜Ｒ⁶⁶はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、炭化水素オキシ基、シリル基、アミノ基を表し、それら２つ以上が互いに結合していてもよく、環を形成していてもよい。） Examples of the group containing a hetero atom also include a group represented by the following general formula [9].

(Wherein, R ^{61 to} R ⁶⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbonoxy group, a silyl group, or an amino group, and two or more of them may be bonded to each other; (A ring may be formed.)

Specific examples of R ^{61 to} R ⁶⁶ in the general formula [9] include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a tert-butyl. Group, 2,6-dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl Group, methyl group, triethylsilyl group, diphenylmethylsilyl group, 1-methyl-1-phenylethyl group, 1,1-dimethylpropyl group, 2-chlorophenyl group and the like.

The chelating ligand used for L ² refers to a ligand having a plurality of coordination sites, and specific examples thereof include acetylacetonate, diimine, oxazoline, bisoxazoline, terpyridine, acylhydrazone, diethylenetriamine, Triethylenetetramine, porphyrin, crown ether, cryptate and the like.

If L ² have more than one among a group having a cyclopentadiene type anion skeleton, groups containing a group and hetero atom having a cyclopentadiene type anion skeleton or a group with each other containing a heteroatom, respectively, are connected directly And it may be linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Examples of such a residue include an alkylene group such as an ethylene group, a propylene group, a dimethylmethylene group and a diphenylmethylene group; a silylene group such as a silylene group, a dimethylsilylene group, a diphenylsilylene group and a tetramethyldisilylene group; a nitrogen atom; Hetero atoms such as an oxygen atom, a sulfur atom and a phosphorus atom are exemplified.

X ⁸ in the general formula [7] is a halogen atom, a hydrocarbon group (however, does not include a group having a cyclopentadiene-type anion skeleton here) or a hydrocarbon oxy group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In addition, examples of the hydrocarbon group include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group.

Examples of the alkyl group used for X ⁸ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, and a neopentyl group. Tert-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluoroalkyl group. Hexyl, perfluorooctyl, perchloropropyl, perchlorobutyl, perbromopropyl and the like.
Further, any of these alkyl groups may be substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group.

The alkyl group used for X ⁸ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group, and a tert-pentyl group. .

Examples of the aralkyl group used for X ⁸ include a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) methyl group, a (4-methylphenyl) methyl group, and a (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, (3,5 -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-trimethylphenyl) 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-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group and the like.
All of these aralkyl 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; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

The aralkyl group used for X ⁸ is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably a benzyl group.

Examples of the aryl group used for X ⁸ include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 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, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl Group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group, etc. Is mentioned.
All of these aryl 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; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

The aryl group used for X ⁸ is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group.

Examples of the hydrocarbon oxy group used for X ⁸ include an alkoxy group, an aryloxy group, an aralkyloxy group and the like, preferably an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. And an aralkyloxy group having 7 to 20 carbon atoms is preferable. Specific examples thereof include a hydrocarbon oxy group exemplified by L ¹ in the general formula [1], a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, and a (4-methylphenyl) methoxy group. , (2,3-dimethylphenyl) methoxy, (2,4-dimethylphenyl) methoxy, (2,5-dimethylphenyl) methoxy, (2,6-dimethylphenyl) methyl, (3,4- (Dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, benzyloxy group and the like. Can be. More preferred are a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, an isobutoxy group, a phenoxy group, a 2,6-di (tert-butyl) phenoxy group, and a benzyloxy group, and further preferred are a methoxy group and a phenoxy group. And a 2,6-di (tert-butyl) phenoxy group and a benzyloxy group, particularly preferably a methoxy group and a phenoxy group.

X ⁸ is more preferably a chlorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a benzyl group, an allyl group, a methallyl group, a methoxy group, an ethoxy group, or a phenoxy group. More preferably, they are a chlorine atom, a methyl group, a methoxy group, and a phenoxy group.

In the general formula [7], a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8, and is appropriately selected according to the valency of M ⁶ .

Among the metal compounds represented by the general formula [7], specific examples of the compound in which M ⁶ is a titanium atom include dimethylsilylenebis (cyclopentadienyl) titanium dichloride and dimethylsilylenebis (2-methylcyclopentadiene). Enyl) titanium dichloride, dimethylsilylenebis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) ) Titanium dichloride, dimethylsilylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-dimethylcyclopentadiene) I) Titanium dichloride, dimethylsilylenebis (3,4-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4-ethylmethyl) Cyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2 3,4-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (tetramethylcyclopentadienyl) ) Titanium dichloride, dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (tetra) Methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadiene) Enyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (fluorenyl) titanium dichloride, And the like Ren (indenyl) (fluorenyl) titanium dichloride, dimethylsilylene diethyl silylene of the above compounds, and the like diphenylsilylene compound or was changed to dimethoxyethane silylene.

Further, specific examples of the compound in which M ⁶ is a titanium atom include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, Bis (dimethylcyclopentadienyl) titanium dichloride, bis (ethylmethylcyclopentadienyl) titanium dichloride, bis (trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium dichloride, bis (pentamethyl) Cyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenyl) Indenyl) titanium dichloride, bis [2- (bis-3,5-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-tert-butylphenyl) indenyl] titanium dichloride, bis [2- (4- Trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-methylphenyl) indenyl] titanium dichloride, bis [2- (3,5-dimethylphenyl) indenyl] titanium dichloride, bis [2- (pentafluorophenyl) ) Indenyl] titanium dichloride,

Cyclopentadienyl (pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride, pentamethylcyclopentadienyl (indenyl) ) Titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-phenylindenyl) titanium dichloride, pentamethylcyclopentadienyl (2-phenylindenyl) titanium dichloride,

Ethylene bis (cyclopentadienyl) titanium dichloride, ethylenebis (2-methylcyclopentadienyl) titanium dichloride, ethylenebis (3-methylcyclopentadienyl) titanium dichloride, ethylenebis (2-n-butylcyclopentadiene) Enyl) titanium dichloride, ethylenebis (3-n-butylcyclopentadienyl) titanium dichloride, ethylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, ethylenebis (2,4-dimethylcyclopentadienyl) Titanium dichloride, ethylene bis (2,5-dimethylcyclopentadienyl) titanium dichloride, ethylene bis (3,4-dimethylcyclopentadienyl) titanium dichloride, ethylene bis (2,3-ethylmethylcyclopentadiene) I) titanium dichloride, ethylenebis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, ethylenebis (2,5-ethylmethylcyclopentadienyl) titanium dichloride, ethylenebis (3,5-ethylmethylcyclopenta Dienyl) titanium dichloride, ethylenebis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, ethylenebis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, ethylenebis (tetramethylcyclopentadiene) (Enyl) titanium dichloride, ethylene bis (indenyl) titanium dichloride, ethylene bis (4, 5, 6, 7-tetrahydroindenyl) titanium dichloride, ethylene bis (2-phenylindenyl) titanium dichloride, ethylene bis Fluorenyl) titanium dichloride,

Ethylene (cyclopentadienyl) (pentamethylcyclopentadienyl) titanium dichloride, ethylene (cyclopentadienyl) (indenyl) titanium dichloride, ethylene (methylcyclopentadienyl) (indenyl) titanium dichloride, ethylene (n-butyl) Cyclopentadienyl) (indenyl) dichloride, ethylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, ethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (methylcyclopentadienyl) (fluorenyl) titanium Dichloride, ethylene (pentamethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (n-butylcyclopentadienyl) (fluorenyl) titanium dichloride Id, ethylene (tetramethyl cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (indenyl) (fluorenyl) titanium dichloride,

Isopropylidenebis (cyclopentadienyl) titanium dichloride, isopropylidenebis (2-methylcyclopentadienyl) titanium dichloride, isopropylidenebis (3-methylcyclopentadienyl) titanium dichloride, isopropylidenebis (2-n- Butylcyclopentadienyl) titanium dichloride, isopropylidenebis (3-n-butylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,4 -Dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (3,4-dimethylcyclopentadienyl) Titanium dichloride, isopropylidenebis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,5-ethylmethylcyclo) (Pentadienyl) titanium dichloride, isopropylidenebis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2 3,5-trimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (tetramethylcyclopentadienyl) titanium dichloride, isopropylidenebis (indenyl) titanium dichloride, isopropyl Piridenbisu (4,5,6,7-tetrahydroindenyl) titanium dichloride, isopropylidene-bis (2-phenyl indenyl) titanium dichloride, isopropylidene-bis (fluorenyl) titanium dichloride,

Isopropylidene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (indenyl) titanium dichloride, isopropylidene (methylcyclopentadienyl) (indenyl) titanium dichloride, isopropylidene (N-butylcyclopentadienyl) (indenyl) dichloride, isopropylidene (tetramethylcyclopentadienyl) (indenyl) dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (methylcyclopentadiene) Enyl) (fluorenyl) titanium dichloride, isopropylidene (n-butylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (Tetramethylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (indenyl) (fluorenyl) titanium dichloride,

Cyclopentadienyl (dimethylamide) titanium dichloride, cyclopentadienyl (phenoxy) titanium dichloride, cyclopentadienyl (2,6-dimethylphenyl) titanium dichloride, cyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride , Cyclopentadienyl (2,6-di-tert-butylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-dimethylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-diisopropylphenyl) ) Titanium dichloride, pentamethylcyclopentadienyl (2,6-tert-butylphenyl) titanium dichloride, indenyl (2,6-diisopropylphenyl) titanium dichloride, fluorenyl ( , 6-diisopropylphenyl) titanium dichloride,

(Tert-butylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl- 1,2-ethanediyl titanium dichloride, (tert-butylamido) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (phenylphosphido) tetramethylcyclopentadiene Enyldimethylsilane titanium dichloride,

(Tert-butylamido) indenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) tetrahydroindenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyltitanium dichloride,
(Tert-butylamido) indenyldimethylsilanetitanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilanetitanium dichloride, (tert-butylamido) fluorenyldimethylsilanetitanium dichloride,

(Dimethylaminomethyl) tetramethylcyclopentadienyltitanium (III) dichloride, (dimethylaminoethyl) tetramethylcyclopentadienyltitanium (III) dichloride, (dimethylaminopropyl) tetramethylcyclopentadienyltitanium (III) dichloride , (N-pyrrolidinylethyl) tetramethylcyclopentadienyltitanium dichloride,
(B-dimethylaminoborabenzene) cyclopentadienyl titanium dichloride, cyclopentadienyl (9-mesityl boraanthracenyl) titanium dichloride,

2,2′-thiobis [4-methyl-6-tert-butylphenoxy] titanium dichloride, 2,2′-thiobis [4-methyl-6- (1-methylethyl) phenoxy] titanium dichloride, 2,2′- Thiobis (4,6-dimethylphenoxy) titanium dichloride, 2,2′-methylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2′-ethylenebis (4-methyl-6-tert-butyl) Phenoxy) titanium dichloride, 2,2′-sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2 ′-(4,4 ′, 6,6′-tetra-tert-butyl-1 , 1'biphenoxy) titanium dichloride,

(Di-tert-butyl-1,3-propanediamide) titanium dichloride, (dicyclohexyl-1,3-propanediamide) titanium dichloride, [bis (trimethylsilyl) -1,3-propanedidiamide] titanium dichloride, [bis ( tert-butyldimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-dimethylphenyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-diisopropylphenyl) -1 , 3-propanediamide] titanium dichloride, [bis (2,6-di-tert-butylphenyl) -1,3-propanediamide] titanium dichloride,
[Bis (triisopropylsilyl) naphthalenediamide] titanium dichloride, [bis (trimethylsilyl) naphthalenediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dichloride,

Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride,

[Hydrotris (3,5-dimethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium trichloride Chloride, [tris (3,5-dimethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-di-tert-butylpyrazolyl) methyl] Titanium trichloride and the like can be mentioned.

Further, specific examples of the compound in which M ⁶ is a titanium atom include dichloride of the above titanium compound as difluoride, dibromide, diiodide, dimethyl, diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di-n-propoxide. , Diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide or a compound changed to di (2,6-di-tert-butylphenoxide), and trichloride of the above titanium compound. Trifluoride, tribromide, triiodide, trimethyl, triethyl, triisopropyl, triphenyl, tribenzyl, trimethoxide, triethoxide, tri-n-propoxide, triisopropoxide, tri-n-butoxide, Riisobutokishido, tri -tert- butoxide, also such birds phenoxide or tri (2,6-di -tert- butyl phenoxide) compounds modified may be exemplified.

Specific examples of the compound in which M ⁶ is a zirconium atom or a hafnium atom among the metal compounds represented by the general formula [7] include compounds in which a titanium atom is replaced with a zirconium atom or a hafnium atom in the above titanium compound. Can be mentioned.

Among the compounds represented by the general formula [7], specific examples of the compound in which M ⁶ is a nickel atom include 2,2′-methylenebis [(4R) -4-phenyl-5,5′-dimethyloxazoline] Nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5 ′ -Di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diisopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R)- 4-phenyl-5,5'-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-dimethoxy Oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diethoxyoxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5 , 5'-Diphenyloxazoline] nickel dibromide,

Methylenebis [(4R) -4-methyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (3-methylphenyl) Oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl- 5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide,

Methylene bis [spiro {(4R) -4-methyloxazoline-5,1′-cyclobutane}] nickel dibromide, methylenebis [spiro {(4R) -4-methyloxazoline-5,1′-cyclopentane}] nickel dibromide Methylene bis [spiro {(4R) -4-methyloxazoline-5,1′-cyclohexane}] nickel dibromide, methylenebis [spiro {(4R) -4-methyloxazoline-5,1′-cycloheptane}] nickel dibromide bromide,

2,2′-methylenebis [(4R) -4-isopropyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-di-n-propyloxazoline] nickel dibromide, methylenebis [(4R) -4-isopropyl-5,5-diisopropyloxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diphenyloxazoline ] Nickel dibromide, 2,2'-methylenebis [(4R) -4 Isopropyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide Bromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methoxyphenyl) oxazo Phosphorus] nickel dibromide,
2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro} (4R) -4-isopropyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2-methylenebis [(4R) -4-isobutyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-diethyloxazoline] nickel dibromide 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5- Di-isopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl- 5,5-diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4- Sobutyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide Bromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel Dibromide,
2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro} (4R) -4-isobutyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-tert-butyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-diethyl Oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-diphenyloxazoline] nickel dibromide, 2'-methylenebis [(4R) -4-tert-butyl-5,5-dicyclohexyloxazoline] nickel dibromy 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert -Butyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di- (4-methylphenyl) Oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R ) -4-tert-Butyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4 tert- butyl-5,5-di - (4-methoxyphenyl) oxazoline] nickel dibromide,
2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyl] Oxazoline-5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2 '-Methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1'-cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-phenyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5 -Di-isopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl -5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-f Nyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide Bromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl- 5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide , 2,2'-methylenebis [(4R) -4-phenyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromo 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline- 5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [ Spiro {(4R) -4-phenyloxazoline-5,1'-cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-benzyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5 -Di-isopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl -5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-b Jill-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide Bromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibro 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline- 5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [ Spiro {(4R) -4-benzyloxazoline-5,1'-cycloheptane}] nickel dibromide, and enantiomers and diastereomers of the above nickel compounds. [Hydrotris (3,5-dimethylpyrazolyl) borate] nickel bromide, [hydrotris (3,5-diethylpyrazolyl) borate] nickel bromide, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel bromide And the like.

Further, specific examples of the compound in which M ⁶ is a nickel atom include dibromide of the above nickel compound as difluoride, dichloride, diiodide, dimethyl, diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di-n-propoxide. , Diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide or a compound changed to di (2,6-di-tert-butylphenoxide).

（式中、Ｒ⁷¹およびＲ⁷²はそれぞれ２，６−ジイソプロピルフェニル基であり、Ｘ⁹、Ｘ¹⁰、Ｒ⁷³およびＲ⁷⁴は下記の表１に表わされる置換基の組み合わせのいずれかである。） Specific examples of the compound in which M ⁶ is a nickel atom include a compound represented by the following general formula [10].

(In the formula, R ⁷¹ and R ⁷² are each a 2,6-diisopropylphenyl group, and X ⁹ , X ¹⁰ , R ⁷³ and R ⁷⁴ are any of combinations of substituents shown in Table 1 below. )

  In addition, as the metal compound represented by the general formula [7], a compound in which nickel is replaced with palladium, cobalt, rhodium, or ruthenium in the above nickel compound can also be exemplified.

Among the metal compounds represented by the general formula [7], specific examples of the compound in which M ⁶ is iron include 2,6-bis- [1- (2,6-dimethylphenylimino) ethyl] pyridine iron dichloride 2,6-bis- [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron dichloride, 2,6-bis- [1- (2-tert-butyl-phenylimino) ethyl] pyridine iron dichloride, [Hydrotris (3,5-dimethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-diethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron chloride, Dichloride of the above iron compound is dibromide, difluoride, diiodide, dimethyl, diethyl, diiso Ropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide or di (2,6-di-tert. -Butylphenoxide) and the like.

  Further, as the metal compound represented by the general formula [7], a compound in which iron is replaced with cobalt or nickel in the above-mentioned iron compound can be similarly exemplified.

  Specific examples of the μ-oxo type metal compound represented by the general formula [7] 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 (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide], µ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium Chloride], μ-oxobis [isopropylidene (methylcyclo Antadienyl) (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) titanium chloride , .Mu. Okisobisu [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 (methylcyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium methoxide] , Μ-oxobis [dimethylsi Len (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 (tetramethylcyclo Pentadienyl) (3-t rt- butyl-5-methyl-2-phenoxy) titanium methoxide],

Di-μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium], di-μ-oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) ) Titanium], di-μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium], di-μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5) -Methyl-2-phenoxy) titanium], di-μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium], di-μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium], di- -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 (tetramethylcyclopentadienyl) (3- tert-butyl-5-methyl-2-phenoxy) titanium] and the like. It is.

  Other specific examples of the compound (B) in which the metal atom is a nickel atom include nickel chloride, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, nickel perchlorate, nickel acetate, nickel trifluoroacetate. , Nickel cyanide, nickel oxalate, nickel acetylacetonate, bis (allyl) nickel, bis (1,5-cyclooctadiene) nickel, dichloro (1,5-cyclooctadiene) nickel, dichlorobis (acetonitrile) nickel, dichlorobis (Benzonitrile) nickel, carbonyltris (triphenylphosphine) nickel, dichlorobis (triethylphosphine) nickel, diacetbis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel, dichloro [1,2- Di (diphenylphosphino) ethane] nickel, bis [1,2-bis (diphenylphosphino) ethane] nickel, dichloro [1,3-bis (diphenylphosphino) propane] nickel, bis [1,3-bis ( Diphenylphosphino) propane] nickel, tetraamine nickel nitrate, tetrakis (acetonitrile) nickel tetrafluoroborate, nickel phthalocyanine and the like.

  Specific examples of the compound in which the metal atom is a vanadium atom in the compound (B) include vanadium acetylacetonate, vanadium tetrachloride, and vanadium oxytrichloride. Specific examples of the compound in which the metal atom is a samarium atom Is bis (pentamethylcyclopentadienyl) samarium methyltetrahydrofuran, and specific examples of the compound in which the metal atom is an ytterbium atom include bis (pentamethylcyclopentadienyl) ytterbium methyltetrahydrofuran.

（上記一般式［４］〜［６］においてそれぞれ、Ｍ¹〜Ｍ⁵は元素の周期律表の第４族の原子を表し、Ａ¹〜Ａ⁵は元素の周期律表の第１６族の原子を表し、Ｊ¹〜Ｊ⁵は元素の周期律表の第１４族の原子を表す。Ｃｐ¹〜Ｃｐ⁵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〜Ｘ⁴、Ｒ¹¹〜Ｒ¹⁶、Ｒ²¹〜Ｒ²⁶、Ｒ³¹〜Ｒ³⁶、Ｒ⁴¹〜Ｒ⁴⁶およびＲ⁵¹〜Ｒ⁵⁶はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、置換シリル基、炭化水素オキシ基、２置換アミノ基、炭化水素チオ基、炭化水素セレノ基を表し、Ｒ¹¹〜Ｒ¹⁶、Ｒ²¹〜Ｒ²⁶、Ｒ³¹〜Ｒ³⁶、Ｒ⁴¹〜Ｒ⁴⁶およびＲ⁵¹〜Ｒ⁵⁶は任意に結合して単環または多環を形成してもよい。該単環または多環は、芳香族環を形成してもよく非芳香族環を形成していてもよい。Ｘ⁵〜Ｘ⁷は元素の周期律表の第１６族の原子を表す。） These compounds (B) may be used alone or in a combination of two or more. Among the metal compounds exemplified above, the compound (B) used in the present invention is preferably a metal compound represented by the above general formula [7]. Among them, a metal compound in which M ⁶ in the general formula [7] is a metal atom belonging to Groups 3 to 11 of the periodic table is preferable, and at least one of L ² in the general formula [7] has a cyclopentadiene-type anion skeleton. Preferred are metal compounds that are groups. The compound (B) is preferably a metal compound represented by the following general formulas [4] to [6].

(In the general formulas [4] to [6], M ^{1 to} M ⁵ each represent an atom belonging to Group 4 of the periodic table of the element, and A ^{1 to} A ⁵ represent atoms belonging to Group 16 of the periodic table of the element. It represents an atom, J ¹ through J ⁵ are .X ¹ ~X ⁴ .Cp ¹ ~Cp ⁵ representing an atom of the group XIV of the periodic table of the elements representing a group having a cyclopentadiene type anion skeleton, R ¹¹ ~ R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted silyl group, a hydrocarbon oxy group, Represents a disubstituted amino group, a hydrocarbon thio group, or a hydrocarbon seleno group, and R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ are arbitrarily bonded; The monocyclic or polycyclic ring may form an aromatic ring or a non-aromatic ring. X ⁵ to X ⁷ represents an atom of Group 16 of the periodic table of elements.)

In the above general formulas [4] to [6], the metal atoms represented by M ^{1 to} M ⁵ represent atoms belonging to Group 4 of the periodic table of elements (Revised edition of IUPAC inorganic chemical nomenclature 1989). Examples include a titanium atom, a zirconium atom, and a hafnium atom. Preferably, they are a titanium atom and a zirconium atom.

In the general formulas [4] to [6], examples of the group having a cyclopentadiene-type anion skeleton represented by Cp ^{1 to} Cp ⁵ include η ^5- (substituted) cyclopentadienyl group and η ^5- (substituted) indenyl And η ^5- (substituted) fluorenyl groups. If specifically exemplified, for example, eta ⁵ - cycloalkyl Bae Ntajieniru group, eta ⁵ - methylcyclopentadienyl group, eta ⁵ - dimethyl cyclopentadienyl group, eta ⁵ - trimethyl cyclopentadienyl group, eta ⁵ - tetra methylcyclopentadienyl group, eta ⁵ - Echirushikuro Bae Ntajieniru group, eta ^5-n-propyl cyclopentadienyl group, eta ⁵ - isopropyl cyclopentadienyl group, eta ^{5-n-butylcyclopentadienyl} group, eta ^{5-sec-butylcyclopentadienyl} group, eta ^{5-tert-Buchirushikuro} Bae Ntajieniru group, eta ⁵ - phenyl cycloalkyl Bae Ntajieniru group, eta ⁵ - trimethylsilylcyclopentadienyl Bae Ntajieniru group, eta ^{5-tert-butyldimethylsilyl} cyclo Bae Ntajieniru group, eta ⁵ - indenyl group, eta ⁵ - methylindenyl group, eta ⁵ - dimethyl indenyl group , Eta ^5-n-propyl indenyl group, eta ⁵ - isopropylindenyl group, eta ^5-n-butyl indenyl group, eta ^5-tert-butyl indenyl group, eta ⁵ - phenyl indenyl group, eta ⁵ - methylphenyl indenyl group, eta ⁵ - naphthyl indenyl group, eta ⁵ - trimethylsilyl indenyl group, eta ⁵ - tetrahydroindenyl group, eta ⁵ - fluorenyl group, eta ⁵ - methyl fluorenyl group, eta ⁵ - dimethyl full Oreniru group, eta ^{5-tert-butyl-fluorenyl} group, eta ⁵ - di-tert-butyl-fluorenyl group, eta ⁵ - phenyl fluorenyl group, eta ⁵ - diphenyl fluorenyl group, eta ⁵ - trimethylsilyl fluorenyl group, eta ⁵ - bis trimethylsilyl fluorenyl group and the like, preferably eta ⁵ - cyclopentadienyl group, eta ⁵ - methyl cyclopentadienyl group , Eta ^{5-n-butylcyclopentadienyl} group, eta ^{5-tert-butylcyclopentadienyl} group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - indenyl group, eta ⁵ - tetrahydroindenyl group, η ⁵ -fluorenyl group.

As the halogen atom in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6], , A fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like are exemplified, preferably a chlorine atom and a bromine atom, and more preferably a chlorine atom.

As hydrocarbon groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Represents an alkyl group, an aralkyl group, an aryl group and the like.

Examples of the alkyl groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] include For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, tert-pentyl group, n-hexyl Group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluoroalkyl group. Hexyl, perfluorooctyl, perchloropropyl, perchlorobutyl, perbromopropyl and the like.
Further, any of these alkyl groups may be substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group.

Examples of the alkyl group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] include , Preferably an alkyl group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group, and a tert-pentyl group.

The aralkyl groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] include For example, 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, (3,5-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-g (Methylphenyl) 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- (Decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group and the like. It is.
All of these aralkyl 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; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

The aralkyl groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] include , Preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably a benzyl group.

The aryl groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] include For example, phenyl group, 2-tolyl 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 A pentamethylphenyl group, an ethylphenyl group, an n-propylphenyl group, Sopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl Group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group and the like.
All of these aryl 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; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

The aryl groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] include , Preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group.

The substituted silyl groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6]; Is a silyl group substituted with a hydrocarbon group, and the hydrocarbon group is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group or an ethoxy group; a phenoxy group or the like. An aryloxy group; it may be substituted with an aralkyloxy group such as a benzyloxy group; Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, Preferable examples include an alkyl group having 1 to 20 carbon atoms such as a cyclohexyl group and an aryl group such as a phenyl group.

As a substituted silyl group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Is a mono-substituted silyl group having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group; a disubstituted silyl group having 2 to 20 carbon atoms such as dimethylsilyl group, diethylsilyl group and diphenylsilyl group A trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyl Dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl Such as trisubstituted silyl group having 3 to 20 carbon atoms are preferably mentioned, such as, more preferably a trimethylsilyl group, tert- butyldimethylsilyl group, a triphenylsilyl group.

Hydrocarbon oxy groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Examples thereof include an alkoxy group, an aralkyloxy group, and an aryloxy group.

The alkoxy groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] include For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n -Octyloxy group, n-dodecyloxy group, n-pentadecyloxy group, n-eicosyloxy group and the like.
Each of these alkoxy groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group. It may be replaced by, for example.

Examples of the alkoxy groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] include And an alkoxy group having 1 to 20 carbon atoms is preferable, and a methoxy group, an ethoxy group, an isopropoxy group and a tert-butoxy group are more preferable.

As an aralkyloxy group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Is, for example, benzyloxy, (2-methylphenyl) methoxy, (3-methylphenyl) methoxy, (4-methylphenyl) methoxy, (2,3-dimethylphenyl) methoxy, (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 Enyl) 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, naphthylmethoxy group, anthracenylmethoxy And the like.
All of these aralkyloxy 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; aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

As the aralkyloxy group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Is preferably an aralkyloxy group having 7 to 20 carbon atoms, more preferably a benzyloxy group.

As an aryloxy group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Are, for example, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2, 6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert- Butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy 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, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3, 5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5 -Trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3,4,6-trimethylphenoxy group, 2,6-di -Tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert- Butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexyl Phenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like.
Each of these aryloxy groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group; It may be substituted with a group or the like.

As the aryloxy group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Is preferably an aryloxy group having 6 to 20 carbon atoms.

Disubstituted amino groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Is an amino group substituted with two hydrocarbon groups or an amino group substituted with two silyl groups, wherein the hydrocarbon group or the silyl group is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or the like. May be substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group. Here, examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, and an n-hexyl group. , An alkyl group having 1 to 20 carbon atoms such as a cyclohexyl group; an aryl group having 6 to 20 carbon atoms such as a phenyl group; an aralkyl group having 7 to 10 carbon atoms such as a benzyl group; Examples thereof include a trimethylsilyl group and a tert-butyldimethylsilyl group. Examples of such a disubstituted amino group include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-sec-butylamino group, and a di-tert-butylamino group. Group, diisobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group and the like. And preferably a dimethylamino group, a diethylamino group, a diisopropylamino group, a di-tert-butylamino group, and a bistrimethylsilylamino group.

Hydrocarbon thio groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Examples thereof include an alkylthio group, an aralkylthio group, and an arylthio group.

Examples of the alkylthio group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] include For example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, n-pentylthio, neopentylthio, n-hexylthio, n-octylthio Group, n-dodecylthio group, n-pentadecylthio group, n-eicosylthio group and the like.
Each of these alkylthio groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group. It may be replaced by, for example.

Examples of the alkylthio group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] include And an alkylthio group having 1 to 20 carbon atoms is preferable, and a methylthio group, an ethylthio group, an isopropylthio group, or a tert-butylthio group is more preferable.

As an aralkylthio group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Is, for example, benzylthio, (2-methylphenyl) methylthio, (3-methylphenyl) methylthio, (4-methylphenyl) methylthio, (2,3-dimethylphenyl) methylthio, (2,4-dimethyl (Phenyl) methylthio group, (2,5-dimethylphenyl) methylthio group, (2,6-dimethylphenyl) methylthio group, (3,4-dimethylphenyl) methylthio group, (3,5-dimethylphenyl) methylthio group, 2,3,4-trimethylphenyl) methylthio group, (2,3,5-trimethylphenyl) methylthio group, (2,3,6-trimethylphenyl) methylthio group, (2 4,5-trimethylphenyl) methylthio group, (2,4,6-trimethylphenyl) methylthio group, (3,4,5-trimethylphenyl) methylthio group, (2,3,4,5-tetramethylphenyl) methylthio group Group, (2,3,4,6-tetramethylphenyl) methylthio group, (2,3,5,6-tetramethylphenyl) methylthio group, (pentamethylphenyl) methylthio group, (ethylphenyl) methylthio group, n-propylphenyl) methylthio group, (isopropylphenyl) methylthio group, (n-butylphenyl) methylthio group, (sec-butylphenyl) methylthio group, (tert-butylphenyl) methylthio group, (n-hexylphenyl) methylthio group , (N-octylphenyl) methylthio group, (n-decylphenyl) methyl And a luthio group, a naphthylmethylthio group and an anthracenylmethylthio group.
All of these aralkylthio 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; aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

As an aralkylthio group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Is preferably an aralkylthio group having 7 to 20 carbon atoms, more preferably a benzylthio group.

The arylthio groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] include For example, phenylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-methylphenylthio group, 2,3-dimethylphenylthio group, 2,4-dimethylphenylthio group, 2,5-dimethylphenyl Thio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 2-tert-butyl-3-methylphenylthio group, 2-tert-butyl-4 -Methylphenylthio group, 2-tert-butyl-5-methylphenylthio group, 2-tert-butyl-6-methylphenylthio group, 2,3,4-trimethylphenylthio group, 2,3,5 Trimethylphenylthio group, 2,3,6-trimethylphenylthio group, 2,4,5-trimethylphenylthio group, 2,4,6-trimethylphenylthio group, 2-tert-butyl-3,4-dimethylphenyl A thio group, a 2-tert-butyl-3,5-dimethylphenylthio group, a 2-tert-butyl-3,6-dimethylphenylthio group, a 2,6-di-tert-butyl-3-methylphenylthio group, 2-tert-butyl-4,5-dimethylphenylthio group, 2,6-di-tert-butyl-4-methylphenylthio group, 3,4,5-trimethylphenylthio group, 2,3,4,5 -Tetramethylphenylthio group, 2-tert-butyl-3,4,5-trimethylphenylthio group, 2,3,4,6-tetramethylphenylthio group, 2-tert -Butyl-3,4,6-trimethylphenylthio group, 2,6-di-tert-butyl-3,4-dimethylphenylthio group, 2,3,5,6-tetramethylphenylthio group, 2-tert -Butyl-3,5,6-trimethylphenylthio group, 2,6-di-tert-butyl-3,5-dimethylphenylthio group, pentamethylphenylthio group, ethylphenylthio group, n-propylphenylthio group , Isopropylphenylthio, n-butylphenylthio, sec-butylphenylthio, tert-butylphenylthio, n-hexylphenylthio, n-octylphenylthio, n-decylphenylthio, n- Examples include a tetradecylphenylthio group, a naphthylthio group, and an anthracenylthio group.
All of these arylthio 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; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

The arylthio groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] include And an arylthio group having 6 to 20 carbon atoms is preferable.

Hydrocarbon seleno groups in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Examples thereof include an alkylseleno group, an aralkylseleno group, and an arylseleno group.

As the alkylseleno group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Are, for example, methylseleno group, ethylseleno group, n-propylseleno group, isopropylseleno group, n-butylseleno group, sec-butylseleno group, tert-butylseleno group, n-pentylseleno group, neopentylseleno group, n-hexylseleno group , N-octylseleno group, n-dodecylseleno group, n-pentadecylseleno group, n-eicosylseleno group and the like.
All of these alkylseleno groups are halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; alkoxy groups such as a methoxy group and an ethoxy group; aryloxy groups such as a phenoxy group; aralkyloxy groups such as a benzyloxy group. It may be substituted with a group or the like.

As an alkylseleno group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Is preferably an alkylseleno group having 1 to 20 carbon atoms, more preferably a methylseleno group, an ethylseleno group, an isopropylseleno group, or a tert-butylseleno group.

As an aralkylseleno group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Is, for example, a benzylseleno group, a (2-methylphenyl) methylseleno group, a (3-methylphenyl) methylseleno group, a (4-methylphenyl) methylseleno group, a (2,3-dimethylphenyl) methylseleno group, a (2,4- (Dimethylphenyl) methylseleno group, (2,5-dimethylphenyl) methylseleno group, (2,6-dimethylphenyl) methylseleno group, (3,4-dimethylphenyl) methylseleno group, (3,5-dimethylphenyl) methylseleno group, (2,3,4-trimethylphenyl) methylseleno group, (2,3,5-trimethylphenyl) methylseleno group, (2,3,6-trimethylphenyl) (Nyl) methylseleno group, (2,4,5-trimethylphenyl) methylseleno group, (2,4,6-trimethylphenyl) methylseleno group, (3,4,5-trimethylphenyl) methylseleno group, (2,3,4 , 5-tetramethylphenyl) methylseleno group, (2,3,4,6-tetramethylphenyl) methylseleno group, (2,3,5,6-tetramethylphenyl) methylseleno group, (pentamethylphenyl) methylseleno group, (Ethylphenyl) methylseleno group, (n-propylphenyl) methylseleno group, (isopropylphenyl) methylseleno group, (n-butylphenyl) methylseleno group, (sec-butylphenyl) methylseleno group, (tert-butylphenyl) methylseleno group, (N-hexylphenyl) methylseleno group, (n-O (Cutylphenyl) methylseleno group, (n-decylphenyl) methylseleno group, naphthylmethylseleno group, anthracenylmethylseleno group and the like.
All of these aralkylseleno 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; aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

As an aralkylseleno group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Is preferably an aralkylseleno group having 7 to 20 carbon atoms, and more preferably a benzylseleno group.

As the arylseleno group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Are, for example, phenylseleno, 2-methylphenylseleno, 3-methylphenylseleno, 4-methylphenylseleno, 2,3-dimethylphenylseleno, 2,4-dimethylphenylseleno, 2,5- Dimethylphenylseleno group, 2,6-dimethylphenylseleno group, 3,4-dimethylphenylseleno group, 3,5-dimethylphenylseleno group, 2-tert-butyl-3-methylphenylseleno group, 2-tert-butyl -4-methylphenylseleno group, 2-tert-butyl-5-methylphenylseleno group, 2-tert-butyl-6-methylphenylseleno group, 2,3,4-trime Ruphenylseleno group, 2,3,5-trimethylphenylseleno group, 2,3,6-trimethylphenylseleno group, 2,4,5-trimethylphenylseleno group, 2,4,6-trimethylphenylseleno group, 2 -Tert-butyl-3,4-dimethylphenylseleno group, 2-tert-butyl-3,5-dimethylphenylseleno group, 2-tert-butyl-3,6-dimethylphenylseleno group, 2,6-di- tert-butyl-3-methylphenylseleno group, 2-tert-butyl-4,5-dimethylphenylseleno group, 2,6-di-tert-butyl-4-methylphenylseleno group, 3,4,5-trimethyl Phenylseleno group, 2,3,4,5-tetramethylphenylseleno group, 2-tert-butyl-3,4,5-trimethylphenylseleno group 2,3,4,6-tetramethylphenylseleno group, 2-tert-butyl-3,4,6-trimethylphenylseleno group, 2,6-di-tert-butyl-3,4-dimethylphenylseleno group 2,3,5,6-tetramethylphenylseleno group, 2-tert-butyl-3,5,6-trimethylphenylseleno group, 2,6-di-tert-butyl-3,5-dimethylphenylseleno group Pentamethylphenylseleno group, ethylphenylseleno group, n-propylphenylseleno group, isopropylphenylseleno group, n-butylphenylseleno group, sec-butylphenylseleno group, tert-butylphenylseleno group, n-hexylphenylseleno Group, n-octylphenylseleno group, n-decylphenylseleno group, n-tetradecylphenyl Examples include a seleno group, a naphthylseleno group, an anthracenylseleno group, and the like.
All of these arylseleno groups include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; alkoxy groups such as a methoxy group and an ethoxy group; aryloxy groups such as a phenoxy group; and aralkyloxy groups such as a benzyloxy group. It may be substituted with a group or the like.

As an arylseleno group in X ^{1 to} X ⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [4] to [6] Is preferably an arylseleno group having 6 to 20 carbon atoms.

In the general formulas [4] to [6], preferably, X ^{1 to} X ⁴ are each independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group, or a disubstituted amino group, and more preferably a halogen atom. An atom, an alkyl group, an alkoxy group or an aryloxy group.

In the general formulas [4] to [6], preferably, R ^{11 to} R ¹⁴ , R ^{21 to} R ²⁴ , R ^{31 to} R ³⁴ , R ^{41 to} R ⁴⁴ and R ^{51 to} R ⁵⁴ are each independently a hydrogen atom, halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, alkoxy group, aralkyloxy group, an aryloxy group, in particular ^{R 11, R 21, R 31} , R 41 and R ⁵¹ are alkyl each independently It is preferably a group, an aralkyl group, an aryl group or a substituted silyl group.

In the general formulas [4] to [6], R ¹⁵ , R ¹⁶ , R ²⁵ , R ²⁶ , R ³⁵ , R ³⁶ , R ⁴⁵ , R ⁴⁶ , R ⁵⁵ and R ⁵⁶ each independently represent a hydrogen atom, It is preferably an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group or an aryloxy group.

X ^{5 to} X ⁷ in the general formulas [5] and [6] represent atoms of Group 16 of the periodic table of the elements, and specific examples thereof include an oxygen atom, a sulfur atom, and a selenium atom. Is an oxygen atom or a sulfur atom, more preferably an oxygen atom.

In the general formulas [4] to [6], examples of the atoms belonging to Group 16 of the periodic table of the elements represented by A ^{1 to} A ⁵ include an oxygen atom, a sulfur atom, and a selenium atom. Preferably, it is an oxygen atom.

In the general formulas [4] to [6], examples of atoms belonging to Group 14 of the periodic table of the elements represented by J ^{1 to} J ⁵ include a carbon atom, a silicon atom, and a germanium atom. Preferably, they are a carbon atom and a silicon atom.

Specific examples of the metal compound represented by the general formula [4] include methylene (η ⁵ -cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride and methylene (η ⁵ -cyclopentadienyl) ) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -cyclopenta Dienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (η ⁵ − Cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-f Phenoxy) titanium dichloride, methylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl - 5-chloro-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) ( 3-tert-butyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethyl Cyclopentadienyl) (3- Eniru 2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadiene dienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (Η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (eta ⁵ - cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (3-trimethylsilyl -5 -Methyl-2-phenoxy ) Titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert-butyl 5-chloro-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl Enyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene ( η ⁵ Tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl 5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (eta ⁵ - cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-trimethylsilyl -5 -Methyl- - phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - cyclopentadienyl) (3-tert -Butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -tetramethylcyclo pentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, Phenylmethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl 2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium di Crowlers De etc. and the above compounds - the (eta ⁵ cyclopentadienyl) (eta ⁵ - methylcyclopentadienyl), (eta ⁵ - dimethyl cyclopentadienyl), (eta ⁵ - trimethyl cyclopentadienyl) ( eta ^5-n-butyl cyclopentadienyl), (eta ^{5-tert-butylcyclopentadienyl),} (eta ⁵ - trimethylsilyl cyclopentadienyl), (eta ^{5-tert-butyldimethylsilyl} cyclopentadienyl) , and the like - (fluorenyl eta ⁵⁾ compound has been changed to (eta ⁵ - indenyl), (eta ⁵ - - methylindenyl), (eta ^5-phenyl indenyl) or. Further, there may be mentioned compounds in which dichloride of the above compound is changed to dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino) or bis (diethylamino). Further, there may be mentioned compounds in which titanium in the above compounds is changed to zirconium or hafnium.

Specific examples of the metal compound represented by the general formula [4], dimethylsilylene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) ( 3-methyl-2-phenoxy) titanium dichloride, dimethyl cyclohexylene (eta ⁵ - cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (3- tert- butyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert- butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl ) (3,5-di-tert-butyl-2-fe) Carboxymethyl) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert-butyldimethyl silyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl ) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (Η ⁵ -Cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride, dimethylsilylene (η ⁵ -tetra methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl enyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetra Methyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert - butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ -Tetramethyi Lecyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2- phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (1-naphthoxy - 2-yl) titanium dichloride, etc. and the compound (eta ⁵ - cyclopentadienyl) (eta ⁵ - methylcyclopentadienyl), (eta ⁵ - dimethyl cyclopentadienyl), (eta ⁵ - trimethylcyclopentadienyl dienyl), (eta ^5-n-butyl cyclopentadienyl) , (Eta ^{5-tert-butylcyclopentadienyl),} (η ⁵ - trimethylsilyl cyclopentadienyl), (η ⁵ -tert- butyldimethylsilyl cyclopentadienyl), (η ⁵ - indenyl), (eta ⁵ - methylindenyl), (eta ⁵ - phenyl indenyl) or (eta ⁵ - such as compound change fluorenyl) and the like. Further, there can be mentioned, for example, compounds in which 2-phenoxy in the above compound is changed to 3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxy, or 3-tert-butyldimethylsilyl-2-phenoxy. Further, a compound in which dimethylsilylene of the above compound is changed to diethylsilylene, diphenylsilylene, or dimethoxysilylene can be given. Further, there may be mentioned compounds in which dichloride of the above compound is changed to dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino) or bis (diethylamino). Further, compounds obtained by changing titanium in the above compounds to zirconium or hafnium can also be mentioned.

Specific examples of the metal compound represented by the general formula [5] include μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium chloride} and μ-oxobis {isopropylidene (η ⁵ − Cyclopentadienyl) (2-phenoxy) titanium methoxide {, μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ - Okisobisu {isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, .mu. Okisobisu {isopropylidene (eta ⁵ - methylcyclopentadienyl) (2-phenoxy) titanium chloride｝, μ-oxobis ｛isopropylidide (Η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium methoxide {, μ-oxobis} isopropylidene (η ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-methyl-2- phenoxy) titanium chloride}, .mu. Okisobisu {isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, .mu. Okisobisu {isopropylidene (eta ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride ク ロ, μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide｝, μ-oxobis ｛isopropylide isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) ) Titanium methoxide

μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium methoxide}, μ - Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, .mu. Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium methoxide, μ-oxobis {dimethylsilylene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene ( eta ⁵ - cyclopentadienyl) (2-phenol Shi) titanium methoxide}, .mu. Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, .mu. Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, .mu. Okisobisu {dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (2-phenoxy) Titanium chloride｝, μ-oxobis ｛dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide｝, μ-oxobis ｛dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy ) Titanium chloride {, μ-oxobis {dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, and (η ⁵ − cyclopentadienyl) (η ⁵ - dimethyl cyclopentadienyl), (η ⁵ - trimethyl cyclopentadienyl), (η ⁵ -n- butylcyclopentadienyl), (η ⁵ -tert- butyl cyclopentadiene dienyl), (η ⁵ - trimethylsilyl cyclopentadienyl), (η ⁵ -tert- butyldimethylsilyl cyclopentadienyl), (η ⁵ - indenyl), (η ⁵ - methylindenyl), (η ⁵ - Compounds changed to (phenylindenyl) or (η ⁵ -fluorenyl) can be mentioned. Further, (2-phenoxy) of the above compound is replaced with (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), ( Compounds changed to (3-phenyl-5-methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy) can be exemplified. Further, there may be mentioned, for example, compounds in which the chloride of the above compound is changed to methyl, benzyl, phenoxide, dimethylamino or diethylamino. Further, there may be mentioned a compound in which titanium of the above compound is changed to zirconium or hafnium.

Specific examples of the metal compound represented by the general formula [6] include di-μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium} and di-μ-oxobis {isopropylidene ( eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di -μ- Okisobisu {isopropylidene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium {, Di-μ-oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (η ⁵ − tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di -μ- Okisobisu {isopropylidene (eta ⁵ Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium},

Di -μ- Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium}, di -μ- Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5 -Methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η ⁵ -methylcyclo) Pentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di -μ- Okisobisu {dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert Butyl-5-methyl-2-phenoxy) titanium}, etc. and the above compound (eta ⁵ - cyclopentadienyl) (eta ⁵ - dimethyl cyclopentadienyl), (eta ⁵ - trimethyl cyclopentadienyl) ( eta ^5-n-butyl cyclopentadienyl), (eta ^{5-tert-butylcyclopentadienyl),} (eta ⁵ - trimethylsilyl cyclopentadienyl), (eta ^{5-tert-butyldimethylsilyl} cyclopentadienyl) , and the like - (fluorenyl eta ⁵⁾ compound has been changed to (eta ⁵ - indenyl), (eta ⁵ - - methylindenyl), (eta ^5-phenyl indenyl) or. Further, (2-phenoxy) of the above compound is replaced with (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), ( Compounds changed to (3-phenyl-5-methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy) can be exemplified. Further, there may be mentioned a compound in which titanium of the above compound is changed to zirconium or hafnium.

As the compound (C) used in the addition polymerization catalyst of the present invention, a known organic aluminum compound can be used. Preferably, it is an organoaluminum compound represented by the following general formula [12].
R ¹⁸ _d AlY _3-d [12]
(Wherein, d is .R ¹⁸ representing the number satisfying the 0 <d ≦ 3 represents a hydrocarbon group, if R ¹⁸ is plural, plural R ¹⁸ may be different even in the same Y represents a hydrogen atom, a halogen atom, or a hydrocarbon oxy group, and when there are a plurality of Ys, the plurality of Ys may be the same or different.)

R ¹⁸ in the general formula [12] is preferably a hydrocarbon group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms. Specific examples include a methyl group, an ethyl group, a normal propyl group, a normal butyl group, an isobutyl group, a normal hexyl group, a 2-methylhexyl group, a normal octyl group, and the like, preferably an ethyl group, a normal butyl group, and an isobutyl group. Or a normal hexyl group.

  Specific examples of the case where Y in the general formula [12] is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.

  As the hydrocarbon oxy group for Y in the general formula [12], an alkoxy group, an aralkyloxy group, and an aryloxy group are preferable.

Examples of the alkoxy group for Y in the general formula [12] include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, and neopentoxy. Group, n-hexyloxy group, n-octyloxy group, n-dodecyloxy group, n-pentadecyloxy group, n-eicosyloxy group and the like.
Any of these alkoxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group.

  As the alkoxy group for Y in the general formula [12], an alkoxy group having 1 to 24 carbon atoms is preferable, and a methoxy group, an ethoxy group, and a tert-butoxy group are more preferable.

Examples of the aryloxy group for Y in the general formula [12] include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxy group, and a 2,4-dimethylphenoxy group 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, N-methylphenoxy 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.
Any of these aryloxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group.

  The aryloxy group for Y in the general formula [12] is preferably an aryloxy group having 6 to 24 carbon atoms.

Examples of the aralkyloxy group for Y in the general formula [12] include a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, a (4-methylphenyl) methoxy group, and a (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-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) (Tylphenyl) methoxy group, (2,3,4,5-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) A) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like.
Any of these aralkyloxyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group.

  The aralkyloxy group for Y in the general formula [12] is preferably an aralkyloxy group having 7 to 24 carbon atoms, and more preferably a benzyloxy group.

  Specific examples of the organoaluminum compound represented by the general formula [12] include trimethylaluminum, triethylaluminum, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, trinormal hexyl aluminum, and trinormal octyl aluminum. Alkyl aluminum; Dialkyl aluminum chloride such as dimethyl aluminum chloride, diethyl aluminum chloride, dinormal propyl aluminum chloride, dinormal butyl aluminum chloride, diisobutyl aluminum chloride, dinormal hexyl aluminum chloride; methyl aluminum dichloride, ethyl aluminum dichloride, normal propyl aluminum dichloride Alkyl aluminum dichlorides such as normal butyl aluminum dichloride, isobutyl aluminum dichloride and normal hexyl aluminum dichloride; dimethyl aluminum hydride, diethyl aluminum hydride, dinormal propyl aluminum hydride, dinormal butyl aluminum hydride, diisobutyl aluminum hydride, dinormal hexyl aluminum hydride and the like Dialkylaluminum hydride; trialkoxyaluminum such as trimethoxyaluminum, triethoxyaluminum, tri (t-butoxy) aluminum; alkyl (such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, methyl (di-t-butoxy) aluminum Dialkyl (alkoxy) aluminum such as dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, dimethyl (t-butoxy) aluminum; triphenoxyaluminum, tris (2,6-diisopropylphenoxy) aluminum, tris (2 Triaryloxyaluminum such as 6-diphenylphenoxy) aluminum; alkyl (diaryloxy) aluminum such as methyl (diphenoxy) aluminum, methylbis (2,6-diisopropylphenoxy) aluminum, methylbis (2,6-diphenylphenoxy) aluminum, dimethyl (Phenoxy) aluminum; dimethyl (2,6-diisopropylphenoxy) aluminum, dimethyl (2,6-diphenylpheno) Examples thereof include dialkyl (aryloxy) aluminum such as xyl) aluminum.

Of these, trialkylaluminum is preferable, trimethylaluminum, triethylaluminum, trinormalbutylaluminum, triisobutylaluminum and trinormalhexylaluminum are particularly preferable, and triisobutylaluminum and trinormalhexylaluminum are particularly preferable. is there.
The above organoaluminum compounds may be used alone or in combination of two or more.

  In the addition polymerization catalyst of the present invention, the use ratio (molar ratio) of compound (A) to compound (B) is not particularly limited, but the molar ratio of compound (A) to compound (B) is Usually, compound (A): compound (B) = 1: 1 to 10,000: 1, preferably compound (A): compound (B) = 1: 1 to 5000: 1, and more preferably compound (A). : Compound (B) = 1: 1 to 1000: 1. When the compound component (C) is used, the ratio (molar ratio) of the compound (B) to the compound (C) is usually compound (B): compound (C) = 0.1: 1 to 1: 10000. , Preferably compound (B): compound (C) = 1: 1 to 1: 1000.

  As the addition polymerization catalyst of the present invention, a reaction product obtained by previously contacting the compound (A) and the compound (B), and optionally the compound (C) may be used. May be used. Any two of them may be contacted beforehand and then another compound.

The addition polymerizable monomer that can be used in the production of the addition polymer using the addition polymerization catalyst of the present invention includes olefins having 2 to 100 carbon atoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, polar Any of the monomers can be used, and two or more monomers can be used at the same time.
Specific examples of these include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene, 1-octene and 1-nonene. Olefins such as 1,5-decene and vinylcyclohexane; 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene and 4-methyl -1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl -2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomene Diolefins such as lenhexahydronaphthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, and 1,3-cyclohexadiene; norbornene, 5-methylnorbornene , 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclod Decene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorborn Cyclic olefins such as benzene, 5-cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, and 8-cyanotetracyclododecene; alkenylbenzene (styrene, 2-phenylpropylene, -Phenylbutene, 3-phenylpropylene, etc.), alkylstyrene (p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene , 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, p-tertiary butylstyrene, p-secondary butylstyrene, etc.), bis Alkenylbenzene (such as divinylbenzene), alkenylnaphthalene (1- Alkenyl aromatic hydrocarbons such as vinyl naphthalene and the like; α, β-unsaturated carboxylic acids (acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1)- 5-heptene-2,3-dicarboxylic acid and the like and metal salts thereof (such as sodium, potassium, lithium, zinc, magnesium and calcium), α, β-unsaturated carboxylic acid esters (methyl acrylate, Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, Isobutyl methacrylate), unsaturated dicarboxylic acid (maleic , Itaconic acid, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc.), glycidyl esters of unsaturated carboxylic acids (acrylic acid) Polar monomers such as glycidyl, glycidyl methacrylate, and monoglycidyl itaconate; and cyclic ethers (such as ethylene oxide, propylene oxide, 1-hexene oxide, cyclohexene oxide, styrene oxide, and tetrahydrofuran).

  The catalyst for addition polymerization of the present invention can be applied to homopolymerization or copolymerization of these addition-polymerizable monomers. Specific examples of the combination of the addition-polymerizable monomers constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, and propylene and 1-butene.

  The addition polymerization catalyst of the present invention is particularly suitable as an olefin polymerization catalyst, and is suitably used in a method for producing an olefin polymer. As such an olefin polymer, a copolymer of ethylene and an α-olefin is preferable, and a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is particularly preferable. (LLDPE) is preferred.

  The method for polymerizing the addition polymerizable monomer in the production of the addition polymer of the present invention is not particularly limited, and examples thereof include aliphatic hydrocarbons (butane, pentane, hexane, heptane, octane, etc.), and aromatic hydrocarbons. Solvent or slurry polymerization using hydrocarbons (benzene, toluene, etc.) or halogenated hydrocarbons (methylene dichloride, etc.) as solvent; bulk polymerization in which polymerization is carried out in liquid monomers; polymerization in gaseous monomers Gas phase polymerization; a high pressure method in which polymerization is performed in a supercritical fluid state under high temperature and high pressure. The polymerization system may be either a batch system or a continuous system.

  The method for supplying the compounds (A) to (C) to the reactor is not particularly limited. A method of supplying each compound in a solid state, a method of dissolving in a hydrocarbon solvent in which components for deactivating the catalyst such as water and oxygen are sufficiently removed, or a method of supplying the compound in a suspended or slurry state, etc. No.

  When the compounds (A) to (C) are used in a solution, the concentration of each of the compounds (A) and (C) is usually 0.0001 to 100 mmol / liter, preferably 0.01 to 10 mmol in terms of metal atoms. / Liter. The concentration of the compound (B) is usually 0.0001 to 100 mmol / L, preferably 0.01 to 10 mmol / L in terms of metal atoms.

  The polymerization temperature is usually from -100 ° C to 350 ° C, preferably from -20 ° C to 300 ° C, more preferably from 160 ° C to 300 ° C. The polymerization pressure is usually 0.1 to 350 MPa, preferably 0.1 to 300 MPa, more preferably 0.1 to 200 MPa. Generally, the polymerization time is appropriately determined depending on the type of the desired addition polymer and the reaction apparatus, but can range from 1 minute to 20 hours. Further, in order to adjust the molecular weight of the addition polymer, a chain transfer agent such as hydrogen may be added.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The measured value of each item in the examples was measured by the following method.

(1) Content of α-olefin unit in copolymer (short-chain branching degree)
The α-olefin unit content (degree of short-chain branching) in the obtained polymer was determined from an infrared absorption spectrum. The measurement and the calculation were carried out by utilizing the characteristic absorption derived from α-olefin according to the method described in the literature (Die Makromoleculare Chemie, 177, 449 (1976) McRae, MA, Madams, WF). The infrared absorption spectrum was measured using an infrared spectrophotometer (FT-IR7300, manufactured by JASCO Corporation).
The degree of short chain branching (SCB) was expressed as the number of short chain branches per 1000 carbons.

(2) Measurement of intrinsic viscosity [η] It was measured in a tetralin solution at 135 ° C using an Ubbelohde viscometer.

(3) Measurement of ¹³ C-NMR
JEOL JNM-EX270 (67.5 MHz, ¹³ C) was used for ¹³ C-NMR measurement. The measurement was performed at room temperature using the deuterated solvent described in the examples.

(4) Molecular weight and molecular weight distribution Measured by gel permeation chromatography (GPC) under the following conditions. A calibration curve was created using standard polystyrene. The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Model: Millipore Waters 150C type column: TSK-GEL GMH-HT (7.5 × 600) Two measurement temperature: 140 ° C.
Solvent: orthodichlorobenzene,
Measurement concentration: 5mg / 5ml

(5) Melting point (mp)
The measurement was performed using a differential scanning calorimeter (SSC-5200 manufactured by Seiko Instruments Inc.) under the following conditions.
Conditioning: raising the temperature from 40 ° C. to 150 ° C. at 10 ° C./min, holding at 150 ° C. for 5 minutes, then lowering the temperature from 150 ° C. to 10 ° C. at 5 ° C./min, and holding at 10 ° C. for 10 minutes .
Melting point measurement: Immediately after condition adjustment, the temperature was raised from 10 ° C to 160 ° C at a rate of 5 ° C / min.

[Example 1]
<Preparation of compound (A)>
In a 500 ml four-necked flask purged with argon, 29.6 g (67.3 mmol) of triphenylbismuth and 100 ml of toluene were put. At room temperature, 75.3 ml (209 mmol of pentafluorophenol) of a 2.77 mol / L solution of pentafluorophenol in toluene was added dropwise at room temperature. After the addition, 150 ml of toluene was further added. The mixture was stirred for 12 hours under reflux conditions. The yellow crystals precipitated by standing at room temperature were separated by filtration and dried under reduced pressure to obtain 46.1 g of yellow crystals. The elemental analysis results of the yellow crystal were Bi = 1.2 mmol / g, F = 17 mmol / g, and C = 25 mmol / g.
In a 100 ml four-necked flask purged with argon, 0.991 g (1.19 mmol-Bi) of the yellow crystals and 20 ml of toluene were added. At room temperature, 4.2 μl (0.23 mmol) of H ₂ O was added, and the mixture was stirred at 80 ° C. for 1 hour to obtain a slurry (hereinafter, referred to as compound A1 slurry). Calculated from the liquid volume, it was 58.3 μmol-Bi / ml.

<Compound (B) - Synthesis of (dimethylsilylene (eta ^{5-tetramethylcyclopentadienyl)} (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide)>
In a Schlenk tube, 0.131 g (4.1 mmol) of methanol was dissolved in 10 ml of anhydrous ether, and 3.9 ml (4.1 mmol of methyllithium) of a methyllithium ether solution having a concentration of 1.05 mol / L was added dropwise at -78 ° C. . The temperature was raised to 20 ° C., and the completion of gas generation was confirmed, whereby the formation of lithium methoxide was confirmed, and the mixture was cooled again to −78 ° C. Dimethylsilylene prepared in advance in another Schlenk tube (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) anhydrous ether titanium dichloride 0.919 g (2.0 mmol) The 20 ml suspension was transferred to the previous reaction solution, and then gradually heated to room temperature. After concentrating the reaction solution, 20 ml of toluene was added, and insolubles were filtered off. The filtrate was concentrated, dimethylsilylene the following structural formula (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide (hereinafter, referred to as Compound B1.) Was obtained as yellow crystals. (0.86 g, 95%)
¹ H-NMR (270 MHz, C ₆ D ₆ ) δ 7.26 (m, 2H), 4.13 (s, 6H), 2.33 (s, 3H), 1.97 (s, 6H), 1. 89 (s, 6H), 1.59 (s, 9H), 0.55 (s, 6H)

<Production of addition polymer>
After the autoclave with an internal volume of 400 ml with a stirrer was vacuum-dried and purged with argon, 185 ml of cyclohexane as a solvent and 15 ml of 1-hexene as a comonomer were charged, and the reactor was heated to 180 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 2.5 MPa. After the inside of the system was stabilized, 0.3 ml of a toluene solution of triisobutylaluminum having a concentration of 1 mol / L (300 μmol of triisobutylaluminum) was charged, and Compound B1 was added. 0.5 ml of a heptane solution (mixture of compound B1 having a concentration of 1 μmol / ml, concentration of triisobutylaluminum of 50 μmol / ml, and a molar ratio of Al atoms to Ti atoms of 50) in which the mixture of the above and triisobutylaluminum was mixed. (That is, 0.5 μmol of compound B1 and 25 μmol of triisobutylaluminum) were added, and 4.3 ml of compound A1 slurry (250 μmol-Bi) was further added to initiate polymerization. Polymerization was performed for 2 minutes. As a result of the polymerization, 0.04 g of an ethylene / 1-hexene copolymer was obtained. The polymerization activity was 8.0 × 10 ⁴ g / mol-Ti / 2 minutes, Mw = 120,000, and Mw / Mn = 1.7.

[Example 2]
<Preparation of compound (A)>
The preparation of the compound A1 slurry was performed in the same manner as in the preparation of the compound (A) in Example 1 except that 0.983 g (1.18 mmol-Bi) of yellow crystals and 10.4 μl (0.577 mmol) of H ₂ O were used. Hereinafter, this will be referred to as compound A2 slurry.) Calculated from the liquid volume, it was 57.8 μmol-Bi / ml.

<Production of addition polymer>
The production was performed in the same manner as in the production of the addition polymer of Example 1, except that 4.3 ml (250 μmol-Bi) of the compound A2 slurry was used instead of the compound A1 slurry. As a result of the polymerization, 0.30 g of an ethylene / 1-hexene copolymer was obtained. Polymerization activity 6.0 × 10 ⁵ g / mol-Ti / 2 min, [η] = 1.94 dl / g, Mw = 130,000, Mw / Mn = 1.7, SCB = 29.5.

[Example 3]
<Preparation of compound (A)>
The preparation of the compound A1 slurry was carried out in the same manner as in the preparation of the compound (A) in Example 1, except that 1.05 g (1.26 mmol-Bi) of yellow crystals and 15.6 μl (0.866 mmol) of H ₂ O were used. Hereinafter, this is referred to as compound A3 slurry). When calculated from the liquid volume, it was 61.7 μmol-Bi / ml.

<Production of addition polymer>
The production was performed in the same manner as in the production of the addition polymer in Example 1, except that 4.1 ml (250 μmol-Bi) of the compound A3 slurry was used instead of the compound A1 slurry. As a result of the polymerization, 0.64 g of an ethylene / 1-hexene copolymer was obtained. Polymerization activity 1.3 × 10 ⁶ g / mol-Ti / 2 min, [η] = 1.93 dl / g, Mw = 120,000, Mw / Mn = 1.8, SCB = 30.2, melting point 86.5 ° C. Met.

[Example 4]
<Preparation of compound (A)>
The preparation of the compound A1 slurry was carried out in the same manner as in the preparation of the compound (A) in Example 1, except that 1.03 g (1.24 mmol-Bi) of yellow crystals and 21.8 μl (1.21 mmol) of H ₂ O were used. Hereinafter, this will be referred to as compound A4 slurry.) Calculated from the liquid volume, it was 60.6 μmol-Bi / ml.

<Production of addition polymer>
The production was performed in the same manner as in the production of the addition polymer of Example 1, except that 4.1 ml (250 μmol-Bi) of the compound A4 slurry was used instead of the compound A1 slurry. As a result of the polymerization, 2.05 g of an ethylene / 1-hexene copolymer was obtained. Polymerization activity 4.1 × 10 ⁶ g / mol-Ti / 2 min, [η] = 1.81 dl / g, Mw = 120,000, Mw / Mn = 1.7, SCB = 29.5, melting point 89.3 ° C. Met.

[Example 5]
<Preparation of compound (A)>
The preparation of the compound A1 slurry was carried out in the same manner as in the preparation of the compound (A) in Example 1, except that 0.913 g (1.10 mmol-Bi) of yellow crystals and 23.2 μl (1.29 mmol) of H ₂ O were used. Hereinafter, this will be referred to as compound A5 slurry.) Calculated from the liquid volume, it was 53.7 μmol-Bi / ml.

<Production of addition polymer>
The procedure of Example 1 was repeated, except that 4.7 ml of the compound A5 slurry (250 μmol-Bi) was used instead of the compound A1 slurry. As a result of the polymerization, 1.98 g of an ethylene / 1-hexene copolymer was obtained. The polymerization activity was 4.0 × 10 ⁶ g / mol-Ti / 2 minutes.

[Example 6]
<Preparation of compound (A)>
The preparation of the compound A1 slurry was carried out in the same manner as in the preparation of the compound (A) in Example 1, except that 1.02 g (1.21 mmol-Bi) of yellow crystals and 32.6 μl (1.81 mmol) of H ₂ O were used. Hereinafter, this will be referred to as compound A6 slurry). Calculated from the liquid volume, it was 60.3 μmol-Bi / ml.

<Production of addition polymer>
The production was performed in the same manner as in the production of the addition polymer of Example 1, except that 4.1 ml (250 μmol-Bi) of the compound A6 slurry was used instead of the compound A1 slurry. As a result of the polymerization, 1.33 g of an ethylene / 1-hexene copolymer was obtained. Polymerization activity was 2.7 × 10 ⁶ g / mol-Ti / 2 min, Mw = 100000.

[Comparative Example 1]
<Production of addition polymer>
The preparation of the compound (A) of Example 1 was repeated except that 50 μmol-Bi of yellow crystals obtained by contacting triphenylbismuth with pentafluorophenol was used instead of the compound A1 slurry. Performed as in production. As a result of the polymerization, only a trace amount of an ethylene / 1-hexene copolymer was obtained.

[Comparative Example 2]
<Production of zinc compound>
Nitrogen-substituted five-liter, four-necked flask of tetrahydrofuran 1.5 liters put concentration 2.0 mol / L hexane solution of _{ZnEt 2 1.35L (ZnEt 2 2.75mol)} , cooled to 5 ° C. in an ice bath. To this, a solution in which 203.3 g (1.1 mol) of pentafluorophenol was dissolved in 300 ml of tetrahydrofuran was added dropwise. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1 hour. Thereafter, the temperature was raised to 45 ° C., and the mixture was further stirred for 1 hour. After lowering the temperature to 20 ° C., 45.2 g (2.51 mol) of H ₂ O was added dropwise at room temperature. The contents became cloudy. After completion of the dropwise addition, the mixture was further stirred for 1 hour, heated to 45 ° C., and stirred for 1 hour. After standing at room temperature overnight, tetrahydrofuran was distilled off under reduced pressure, and dried under reduced pressure at 120 ° C. for 8 hours to obtain 430.0 g of a yellow powder. As a result of elemental analysis, Zn = 6.42 mmol / g and F = 13.7 mmol / g.

<Production of addition polymer>
Production was carried out in the same manner as in Example 1 except that 58.5 mg (376 μmol) of the zinc compound produced by the above method was used instead of the compound A1 slurry. As a result of the polymerization, only a trace amount of an ethylene / 1-hexene copolymer was obtained.

[Comparative Example 3]
<Production of addition polymer>
Production was carried out in the same manner as in Example 1, except that 3 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was used instead of the compound A1 slurry. As a result of the polymerization, 2.18 g of an ethylene / 1-hexene copolymer was obtained. The polymerization activity was 4.4 × 10 ⁶ g / mol-Ti / 2 min, [η] = 0.97 dl / g, Mw = 57000, Mw / Mn = 2.0, and SCB = 33.6.

[Example 7]
<Preparation of compound (A)>
255 g (579 mmol) of triphenylbismuth and 1.6 L of toluene were placed in a 5 L four-necked flask purged with argon. At room temperature, 653 ml of a 2.79 mol / L solution of pentafluorophenol in toluene (1.82 mol of pentafluorophenol) was added dropwise at room temperature. The mixture was stirred for 12 hours under reflux conditions. The yellow crystals precipitated by standing at room temperature were separated by filtration and dried under reduced pressure to obtain 447 g of yellow crystals.
178 g of the yellow crystals and 1.0 L of toluene were placed in a 2 L four-necked flask purged with argon, and stirred at 80 ° C. for 25 minutes to completely dissolve the yellow crystals. Next, 4.2 ml (233 mmol) of H ₂ O was added dropwise over 25 minutes, and the mixture was stirred at 80 ° C. for 1 hour. A white powder was precipitated in the liquid by the stirring. After cooling to room temperature, the precipitate was allowed to stand to sediment and the supernatant was removed. The precipitate in the flask was washed once with 500 ml of toluene and twice with 500 ml of hexane, and then dried under reduced pressure to obtain 99.0 g of a white compound (hereinafter, referred to as compound A7).
<Production of addition polymer>
An autoclave with a stirrer having an inner volume of 400 ml was vacuum-dried and purged with argon, 185 ml of toluene as a solvent and 15 ml of 1-hexene as a comonomer were charged, and the reactor was heated to 180 ° C. After the temperature was raised, the feed was performed while adjusting the ethylene pressure to 2.5 MPa. After the inside of the system was stabilized, 0.3 ml of a toluene solution of triisobutylaluminum having a concentration of 1 mol / L (300 μmol of triisobutylaluminum) was charged, and the compound B1 was added. 0.5 ml of a heptane solution (concentration of compound B1 was 1 μmol / ml, concentration of triisobutylaluminum was 50 μmol / ml, and the molar ratio of Al atom to Ti atom was adjusted to 50) in which was mixed with triisobutylaluminum. (In other words, 0.5 μmol of compound B1 and 25 μmol of triisobutylaluminum) were charged, and 5.0 ml of a toluene slurry of compound A7 having a concentration of 4.98% by weight was further charged to initiate polymerization. Polymerization was performed for 2 minutes. As a result of the polymerization, 0.86 g of an ethylene / 1-hexene copolymer was obtained. Polymerization activity 1.7 × 10 ⁶ g / mol-Ti / 2 min, [η] = 2.08 dl / g, Mw = 160,000, Mw / Mn = 1.8, SCB = 25, melting point 92.7 ° C. Was.

Claims (18)

A catalyst component for addition polymerization obtained by contacting the following components (a) to (c).
(A): Compound represented by the following general formula [1] BiL ¹ _r [1]
(B): a compound represented by the following general formula [2] R ¹ _s-1 T ¹ H [2]
(C): a compound represented by the following general formula [3] R ² _t-2 T ² H ₂ [3]
(In the above general formulas [1] to [3], r represents a valence of Bi, L ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group or a hydrocarbon oxy group, and when a plurality of L ¹ are present, A plurality of L ¹ may be the same or different, T ¹ and T ² each independently represent a non-metallic atom of Group 15 or 16 of the periodic table of the element, and s is T ¹ the valence, t represents the valence of T ^2, R ¹ represents a group containing an electron withdrawing group or an electron withdrawing group, R ¹ there are a plurality of when R ¹ existing in plural numbers the same as each other or different even, R ² represents a hydrocarbon group, a plurality of R ² is when R ² existing in plural numbers may be different be the same as each other.) The catalyst component for addition polymerization according to claim 1, wherein T ¹ of component (b) and T ^{2 of} component (c) are a nitrogen atom or an oxygen atom. For addition polymerization catalyst component according to claim 1 or 2 R ¹ is a halogenated hydrocarbon groups of component (b).   The catalyst component for addition polymerization according to any one of claims 1 to 3, wherein the component (b) is a fluorinated phenol.   The catalyst component for addition polymerization according to claim 4, wherein the fluorinated phenol is pentafluorophenol.   The catalyst component for addition polymerization according to any one of claims 1 to 5, wherein Bi of the component (a) is trivalent.   The amount of the contact treatment of the component (b) per mol of the component (a) is 0.7 × r to 1.3 × r mol (where r represents the valence of Bi). The catalyst component for addition polymerization according to any one of claims 1 to 6, wherein the contact treatment amount is 0.1 to 2 mol.   The catalyst component for addition polymerization according to any one of claims 1 to 7, wherein component (c) is brought into contact with a contact product obtained by bringing component (a) into contact with component (b).   9. A solution obtained by dissolving a contact product obtained by bringing component (a) and component (b) into contact with a solvent, and then bringing the solution into contact with component (c). The catalyst component for addition polymerization according to 1.   An addition polymerization catalyst obtained by contacting the addition polymerization catalyst component according to any one of claims 1 to 9 with a Group 3 to Group 11 or lanthanoid-based metal compound (B).   An addition polymerization catalyst obtained by contacting the catalyst component for addition polymerization according to any one of claims 1 to 9, a Group 3 to 11 or lanthanoid-based metal compound, and an organoaluminum compound.   The catalyst for addition polymerization according to claim 10 or 11, wherein the Group 3-11 or lanthanoid-based metal compound is a metallocene-based metal compound.   The catalyst for addition polymerization according to claim 12, wherein the metallocene-based metal compound is a monocyclopentadienyl metal compound. The catalyst for addition polymerization according to claim 13, wherein the monocyclopentadienyl metal compound is a metal compound represented by any of the following general formulas [4] to [6].

(In the general formulas [4] to [6], M ^{1 to} M ⁵ each represent an atom belonging to Group 4 of the periodic table of the element, and A ^{1 to} A ⁵ represent atoms belonging to Group 16 of the periodic table of the element. It represents an atom, J ¹ through J ⁵ are .X ¹ ~X ⁴ .Cp ¹ ~Cp ⁵ representing an atom of the group XIV of the periodic table of the elements representing a group having a cyclopentadiene type anion skeleton, R ¹¹ ~ R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted silyl group, a hydrocarbon oxy group, Represents a disubstituted amino group, a hydrocarbon thio group, or a hydrocarbon seleno group, and R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ are arbitrarily bonded; The monocyclic or polycyclic ring may form an aromatic ring or a non-aromatic ring. X ⁵ to X ⁷ represents an atom of Group 16 of the periodic table of elements.)   A method for producing an addition polymer using the addition polymerization catalyst according to claim 10.   The method for producing an addition polymer according to claim 15, wherein the polymerization temperature of the addition polymer is 160 to 300 ° C.   17. The method for producing an addition polymer according to claim 15, wherein the addition polymer is an olefin polymer. The method for producing an addition polymer according to claim 17, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.