JP4158698B2 - Addition polymerization catalyst component, addition polymerization catalyst and method for producing addition polymer - Google Patents

Description

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

  Olefin polymers such as polypropylene and polyethylene are used in many fields including the packaging field due to their excellent mechanical properties, chemical resistance, etc., and their excellent balance between properties and economy. . Examples of addition polymerization catalysts used in the production of these olefin polymers are conventionally represented by solid catalyst components obtained mainly using Group 4 metal compounds such as titanium trichloride and titanium tetrachloride, and organoaluminum compounds. Conventional solid catalysts (multisite catalysts) in combination with the Group 13 metal compounds that have been used have been used. However, in recent years, as an addition polymerization catalyst for obtaining an addition polymer having less stickiness and strength superior to that of an addition polymer produced by a conventional solid catalyst, it is composed of metallocene complexes such as metallocene complexes and half metallocene complexes. A so-called single-site catalyst is proposed in which a catalyst component is brought into contact with an activation co-catalyst component such as aluminoxane or tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate. Consideration to use has been made (for example, Patent Document 1, Patent Document 2, etc.). In recent years, a compound obtained by contacting diethylzinc, pentafluorophenol and water has been developed as an activation co-catalyst component, and a catalyst obtained by contacting the compound with a metallocene complex or a half metallocene complex, It has been proposed as a highly active catalyst (for example, Patent Document 3).

JP 58-19309 A Japanese translation of PCT publication No. 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 resulting addition polymer is not sufficiently satisfactory.
Under such circumstances, the problem to be solved by the present invention is that an addition polymerization catalyst component for obtaining a high molecular weight addition polymer, an addition polymerization catalyst using the addition polymerization catalyst component, and the addition An object of the present invention is to provide a method for producing an addition polymer using a polymerization catalyst.

That is, the first of the present invention relates to an olefin polymerization catalyst component obtained by contacting the following components (a) to (c).
(A): Compound represented by the following general formula [1]
BiL ¹ ₃ [1]
(B): Compound represented by the following general formula [2]
R ¹ T ¹ H [2]
(C): Compound represented by the following general formula [3]
T ² H ₂ [3]
(In the above general formulas [1] to [3], L ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group or a hydrocarbon oxy group, and the three L ^{1 s} may be the same or different from each other; T ¹ and T ² each independently represent an oxygen atom or a sulfur atom, R ¹ is table to a halogenated alkyl group or a halogenated aryl group.)
The second aspect of the present invention are those according to the olefin polymerization catalyst obtained by using the above olefin polymerization catalyst component.
The third aspect of the present invention are those according to the process for producing an olefin polymer using the above olefin polymerization catalyst.

  According to the present invention, there are provided an addition polymerization catalyst component for obtaining a high molecular weight addition polymer, an addition polymerization catalyst using the addition polymerization catalyst component, and a method for producing an addition polymer using the addition polymerization catalyst. Can be provided. The addition polymerization catalyst of the present invention exhibits high polymerization activity and is suitable for the production of addition polymers.

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

L ¹ in the general formula [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, the plurality of L ¹ may be the same or different from each other. Good. Specific examples of the halogen atom in L ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The hydrocarbon group for L ¹ is preferably an alkyl group, an aryl group, or an aralkyl group. The hydrocarbon oxy group in L ¹ is preferably an 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, or an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, and 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 Ethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl Perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl group, perchloro Dodecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromopentadecyl group And perbromoeicosyl group.
Further, any alkyl group used for L ¹ 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 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, or an isobutyl group.

Examples of the aryl group used for L ¹ include 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, 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.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups such as methyl group, ethyl group and isopropyl group; alkoxy groups such as methoxy group and ethoxy group; phenoxy group and the like An aryloxy group of the above; may be substituted with an aralkyloxy group such as a benzyloxy group.

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

Examples of the aralkyl group used for L ¹ include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (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 substituted with.

As the aralkyl group used for L ¹ , an aralkyl group having 7 to 20 carbon atoms is preferable, and a benzyl group is more preferable.

Examples of the alkoxy group used for L ¹ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, isobutoxy group, 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 A siloxy group etc. are mentioned.
These alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group It may be substituted with.

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, or a tert- It is a pentyloxy group.

Examples of the aryloxy group used for L ¹ include a phenoxy group, 2-tolyloxy group, 3-tolyloxy group, 4-tolyloxy group, 2,3-xylyloxy group, 2,4-xylyloxy group, and 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 decylphenoxy group, n-dodecylphenoxy group, n-tetradecylphenoxy group, naphthyloxy group, 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 substituted with.

The aryloxy group used for L ¹ is preferably an aryloxy group having 6 to 20 carbon atoms, and 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-metal atom of Group 15 or Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). Specific examples of the Group 15 nonmetallic atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 nonmetallic atom include an oxygen atom and a sulfur atom. It is preferably a T ^1, a nitrogen atom, an oxygen atom, particularly preferably an oxygen atom.

S in the general formula [2] represents a valence of T ^1, if T ¹ is a Group 15 atom s is 3, when T ¹ is a Group 16 atom s is 2.

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

  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; nitrated hydrocarbon groups such as nitrated aryl groups A hydrocarbon oxycarbonyl group such as an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and the like.

Specific examples of the halogenated alkyl group used for R ¹ include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a diiodomethyl group, a trifluoromethyl group, 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 1,1-bis (triiodomethyl) -2,2,2-triiodoethyl group and the like.

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, 2- 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 tribromophenyl group, 2,4,6-triiodophenyl group, pentafluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentaiodophenyl group is substituted with halogen Is mentioned.

Specific examples of the halogenated aryl group used for R ¹ include 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 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, Can be mentioned.

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

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, and particularly preferably a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, 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 , 1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 3,4,5-trifluorophenyl group or pentafluorophenyl group.

T ² in the above general formula [3] represents a non-metal atom of Group 15 or Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). Specific examples of the Group 15 nonmetallic atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 nonmetallic atom 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 above 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 from each other. As the hydrocarbon group for R ² , an alkyl group, an aryl group, and an aralkyl group are preferable. The hydrocarbon group described as L ^{1 in the} general formula [1] and the halogenation described as R ^{1 in the} general formula [2]. A hydrocarbon can be illustrated.

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

  Specific examples of component (a) include bismuth (III) fluoride, bismuth (III) chloride, bismuth (III) bromide, bismuth (III) iodine and other bismuth halides (III); trialkylbismuth such as trimethylbismuth Triaryl bismuth such as triphenyl bismuth; trimethoxy bismuth, triethoxy bismuth, triisopropoxy bismuth, tri (tert-butoxy) bismuth, triisobutoxy bismuth, trineopentyloxy bismuth, tri (tert-pentyloxy) bismuth Trialkoxy bismuth such as triphenoxy bismuth, 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 (2,3,3) 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- Dodecylphenoxy) bismuth, tri (n-tetradecylphenoxy) bismuth, trinaphthyloxybismuth, trianthracenyloxybismuth, and the like; 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; pentamethoxy bismuth, pentaethoxy bismuth, etc. Pentaalkoxy bismuth; pentaaryloxy bismuth such as pentaphenoxy bismuth.

  Component (a) is preferably bismuth halide (III), trialkyl bismuth, triaryl bismuth, trialkoxy bismuth or triaryloxy bismuth, more preferably bismuth halide (III), triaryl bismuth, trialkoxy bismuth. And triaryloxybismuth, particularly preferably triarylbismuth such as triphenylbismuth.

  Specific examples of component (b) include amines such as di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, di (iodomethyl) amine, bis (difluoromethyl) amine, bis (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-trimethyl) 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- (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-dibromophene) 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-trifluoro (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.

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

  Specific examples of the component (b) include alcohols such as fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodethanol, trifluoromethanol, trichloromethanol, 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 ester 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.

  Specific examples of the component (b) include thiols such as compounds in which the oxygen atoms in the above specific examples of alcohols are substituted with sulfur atoms, for example, methanol in the specific examples of the above alcohols in methanethiol and ethanol in ethanethiol. And compounds represented by rewriting propanol with propanethiol.

  Specific examples of the compound (b) include phenols such as 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3- 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.

  Specific examples of the component (b) include thiophenols represented by rewriting the phenols in the specific examples of the phenols with thiophenols, such as compounds in which the oxygen atom in the specific examples of the phenols is substituted with a sulfur atom. And the like.

  Specific examples of the component (b) include carboxylic acids such as 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, 1,1-bis (trifluoromethyl). Examples include -2,2,2-trifluoroethanesulfonic acid.

  Component (b) is preferably an amine such as 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 (Pentafluorophenyl) amine and alcohols include trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1 -As trifluoromethylethanol, or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, 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 and 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, aralkylamine, 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 , , 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) methylamine , (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-penta 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, pentaio 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, 2 , 6-Xylylamine, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine , Perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroaniline, 3-fluoroaniline, 4- Luoaniline, 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, 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 components (a) to (c) into contact with each other. The contact treatment of components (a) to (c) is preferably performed in an inert gas atmosphere. The contact treatment temperature is usually −100 to 200 ° C., preferably −80 to 150 ° C., more preferably 10 to 150 ° C., and further preferably 40 to 100 ° C. The contact treatment time is usually 1 minute to 36 hours, preferably 10 minutes to 24 hours. Moreover, although such a contact process may use a solvent and may contact components (a)-(c) directly without using a solvent, it is preferable to perform a contact process using a solvent. Examples of the solvent used include nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents; polar solvents such as halide solvents and ether solvents. Specific examples 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 , Halogenated solvents such as chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene 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. An aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, and an ether solvent are preferable, an aromatic hydrocarbon solvent is more preferable, and toluene is more preferable.

Although it does not specifically limit as a method of making said component (a)-(c) contact, For example, the method of mentioning below can be employ | adopted.
(A): Method in which component (a) and component (b) are contacted and then component (c) is contacted.
(B): A method of contacting the component (b) after contacting the component (a) with the component (c).
(C) A method of contacting component (a) after contacting component (b) and component (c).
The method (b) or (b) is preferred. That is, the catalyst component for addition polymerization of the present invention is preferably a contact product obtained by bringing the component (a) and the component (b) into contact with the component (c). Or a compound obtained by contacting the component (b) with a contact product obtained by bringing the component (a) and the component (c) into contact with each other. More preferably, as the addition polymerization catalyst component of the present invention, the contact product obtained by bringing the component (a) and the component (b) into contact with the component (c) is obtained. A compound. In the method (a), the contact product obtained by bringing the component (a) and the component (b) into contact with each other is dissolved in a solvent to form a solution, and then the solution and the component (c) are brought into contact with each other. Is preferred. In the method of contacting the components (a) to (c), after contacting any two components selected from the components (a) to (c), the contact product is purified and selected as the purified product. A method of contacting the remaining components that have not been performed may be performed. After contacting any two components selected from the components (a) to (c), the contact product is not purified, You may perform the method of contacting the remaining components which were not selected.

  The contact treatment amount ratio of the components (a) to (c) is the molar ratio of the contact treatment amount of each component from the viewpoint of enhancing the catalyst activity. Component (a): component (b): component (c) = 1: y : When z, y is preferably 0.7 × r to 1.3 × r, more preferably 0.8 × r to 1.2 × r, and even more preferably 0.9 × r to 1.1 × r. However, 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. Yes, most preferably from 0.9 to 1.3.

  In the compound (A) of the present invention, as a result of the contact treatment of the components (a) to (c), the component (a) and / or the component (b) and / or the component (c) as raw materials It may remain.

  Specific examples of the production method of 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 3-fold molar amount with respect to triphenylbismuth is added dropwise as a toluene solution of pentafluorophenol, stirred for 10 minutes to 24 hours under reflux conditions, and then cooled to room temperature. To do. The precipitated crystals are separated by filtration and dried, and then the crystals are dissolved in toluene. An equimolar amount of water is added dropwise to the toluene solution with respect to the bismuth component in the toluene solution, followed by stirring at 80 ° C. for 1 hour. .

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

The compound (B) is not particularly limited as long as the compound obtained by bringing the compound (B) into contact with the compound (A) or the compound (C) becomes a compound exhibiting addition polymerization. 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]
(Wherein, a represents a number satisfying 0 <a ≦ 8, b represents a number satisfying 0 <b ≦ 8. M ⁶ represents a group 3-11 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 through a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, X ⁸ is a halogen atom, a hydrocarbon group (provided that cyclohexane Except for a group having a pentadiene-type anion skeleton) or a hydrocarbon oxy 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 of Group 3 to 11 of the Periodic Table of Elements (IUPAC 1989) or a lanthanoid series. Specific examples include scandium atoms, yttrium atoms, titanium atoms, zirconium atoms, hafnium atoms, vanadium atoms, niobium atoms, tantalum atoms, chromium atoms, iron atoms, ruthenium atoms, cobalt atoms, rhodium atoms, nickel atoms, palladium atoms. , Samarium atoms, ytterbium atoms, and the like. M ⁶ is preferably a metal atom belonging to 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 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.

Examples of the group having a cyclopentadiene type anion skeleton in L ² include η ^5- (substituted) cyclopentadienyl group, η ^5- (substituted) indenyl group, and η ^5- (substituted) fluorenyl group. If specifically exemplified, eta ⁵ - cyclopentadienyl group, eta ⁵ - methylcyclopentadienyl group, eta ^{5-tert-butylcyclopentadienyl} group, eta ^{5-1,2-dimethyl-cyclopentadienyl} Group, η ⁵ -1,3-dimethylcyclopentadienyl group, η ⁵ -1-tert-butyl-2-methylcyclopentadienyl group, η ⁵ -1-tert-butyl-3-methylcyclopentadienyl Group, η ⁵ -1-methyl-2-isopropylcyclopentadienyl group, η ⁵ -1-methyl-3-isopropylcyclopentadienyl group, η ⁵ -1,2,3-trimethylcyclopentadienyl 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} Nyl group, η ⁵ -6-methylindenyl group, η ⁵ -7-methylindenyl group, η ⁵ -2-tert-butylindenyl group, η ⁵ -3-tert-butylindenyl group, η ^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 oxygen atom, sulfur atom, nitrogen atom and phosphorus atom in the ring Group heterocyclic groups; and chelating ligands.

  Specific examples of the group containing a heteroatom include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, 2-methylphenoxy group, 2,6-dimethylphenoxy group, 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 Si 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-dihydroxynaphth Group, 2,2′-hyphenenyldiol 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 can be exemplified.

Examples of the group containing a hetero atom also include a group represented by the following general formula [8].
R ³ ₃ P = N− [8]
(Wherein 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, and two or more of them may be bonded to each other) Or may form a ring.)

Specific examples of R ³ in the general formula [8] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Examples thereof 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。） Further, examples of the group containing a hetero atom include a group represented by the following general formula [9].

(In the formula, R ^{61 to} R ⁶⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon oxy 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, and 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. Specifically, acetylacetonate, diimine, oxazoline, bisoxazoline, terpyridine, acylhydrazone, diethylenetriamine, Examples include triethylenetetramine, porphyrin, crown ether, cryptate and the like.

When there are a plurality of L ² groups, groups having a cyclopentadiene-type anion skeleton, groups having a cyclopentadiene-type anion skeleton and a group containing a hetero atom, or groups containing a hetero atom are directly connected to each other. Alternatively, they may be linked via a residue containing a carbon atom, silicon atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. Examples of such residues include alkylene groups such as ethylene group, propylene group, dimethylmethylene group, diphenylmethylene group; silylene groups such as silylene group, dimethylsilylene group, diphenylsilylene group, tetramethyldisilylene group; nitrogen atom, Hetero atoms such as oxygen atom, sulfur atom and phosphorus atom can be mentioned.

X ⁸ in the general formula [7] is a halogen atom, a hydrocarbon group (however, it does not include a group having a cyclopentadiene-type anion skeleton) 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. Examples of the hydrocarbon group herein 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 or 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 perfluoro group. Examples include a hexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group.
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, or a tert-pentyl group. .

Examples of the aralkyl group used for X ⁸ include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (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 substituted with.

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, 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, 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 substituted with.

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

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

X ⁸ is more preferably a chlorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, benzyl group, allyl group, methallyl group, methoxy group, ethoxy group, or 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, b represents a number satisfying 0 <b ≦ 8, and is appropriately selected according to the valence of M ⁶ .

Specific examples of the compound in which M ⁶ is a titanium atom among the metal compounds represented by the general formula [7] include dimethylsilylene bis (cyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-methylcyclopentadidi). Enyl) titanium dichloride, dimethylsilylene bis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3-n-butylcyclopentadienyl) ) Titanium dichloride, dimethylsilylene bis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,4-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,5-dimethylcyclopentadiene) L) Titanium dichloride, dimethylsilylene bis (3,4-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,4-ethylmethyl) Cyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2, 3,4-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (tetramethylcyclopentadienyl) ) Titanium dichloride, dimethylsilylene bis (indenyl) titanium dichloride, dimethylsilylene bis (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, dimethyl 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.

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,

Ethylenebis (cyclopentadienyl) titanium dichloride, ethylenebis (2-methylcyclopentadienyl) titanium dichloride, ethylenebis (3-methylcyclopentadienyl) titanium dichloride, ethylenebis (2-n-butylcyclopentadi) 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) L) Titanium dichloride, ethylene bis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, ethylene bis (2,5-ethylmethylcyclopentadienyl) titanium dichloride, ethylene bis (3,5-ethylmethylcyclopenta) Dienyl) titanium dichloride, ethylenebis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, ethylenebis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, ethylenebis (tetramethylcyclopentadi) Enyl) titanium dichloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, ethylenebis (2-phenylindenyl) titanium dichloride, ethylenebis 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 (methylcyclopentadi) Enyl) (fluorenyl) titanium dichloride, isopropylidene (n-butylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylide (Tetramethylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (indenyl) (fluorenyl) titanium dichloride,

Cyclopentadienyl (dimethylamido) 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-Butylamide) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl- 1,2-ethanediyltitanium dichloride, (tert-butylamide) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (phenylphosphide) tetramethylcyclopentadi Enildimethylsilane 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) indenyldimethylsilane titanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilane titanium dichloride, (tert-butylamido) fluorenyldimethylsilane titanium dichloride,

(Dimethylaminomethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminoethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminopropyl) tetramethylcyclopentadienyl titanium (III) dichloride , (N-pyrrolidinylethyl) tetramethylcyclopentadienyl titanium dichloride,
(B-dimethylaminoborabenzene) cyclopentadienyl titanium dichloride, cyclopentadienyl (9-mesitylboraanthracenyl) 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-propanediamide] 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] Examples thereof include titanium trichloride.

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

Among the metal compounds represented by the general formula [7], specific examples of the compounds in which M ⁶ is a zirconium atom or a hafnium atom include compounds in which the 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,

Methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cyclobutane}] nickel dibromide, methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cyclopentane}] nickel dibromide , Methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cyclohexane}] nickel dibromide, methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cycloheptane}] nickel di 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 di Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methoxyphenyl) oxazo Phosphor] 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 di 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--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, 2'-methylenebis [(4R) -4-tert-butyl-5,5-dicyclohexyloxazoline] nickel dibromide 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-fur Nyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methylpheni) oxazoline] nickel di 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 dibrom 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-benzene Dil-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 di Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide Id, 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 so on.

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. Examples thereof include compounds changed to diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide or 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 compounds represented by the following general formula [10].

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

  In addition, examples of the metal compound represented by the general formula [7] include compounds in which nickel is replaced with palladium, cobalt, rhodium, or ruthenium in the above nickel compound.

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, Dichlorides of the above iron compounds are dibromide, difluoride, diiodide, dimethyl, diethyl, diiso Propyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide or di (2,6-di-tert) Examples thereof include compounds changed to -butylphenoxide).

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

  Specific examples of μ-oxo type metal compounds 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 (methylcyclohexane) Tantadienyl) (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 [dimethylsilane 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.

  In the compound (B), as other specific examples of the compound in which the metal atom is a nickel atom, 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- (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 (B) in which the metal atom is a vanadium atom include vanadium acetylacetonate, vanadium tetrachloride, vanadium oxytrichloride, and the like, and specific examples of the compound in which the metal atom is a samarium atom. Includes bis (pentamethylcyclopentadienyl) samarium methyltetrahydrofuran, and specific examples of the compound in which the metal atom is an ytterbium atom include bis (pentamethylcyclopentadienyl) ytterbiummethyltetrahydrofuran.

（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 use only 1 type and may combine 2 or more types. Of 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. The metal compound which is a group is preferable. The compound (B) is preferably a metal compound represented by the following general formulas [4] to [6].

(In the above general formulas [4] to [6], M ^{1 to} M ⁵ represent atoms of Group 4 of the periodic table of elements, and A ^{1 to} A ⁵ represent Group 16 of the periodic table of elements. Represents an atom, J ^{1 to} J ⁵ represent an atom belonging to Group 14 of the periodic table of elements, Cp ^{1 to} Cp ⁵ represent a group having a cyclopentadiene-type anion skeleton, 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 are each independently 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, 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 optionally combined. May form a monocyclic ring or a polycyclic ring, which 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 atom represented by M ^{1 to} M ⁵ represents a group 4 atom of the periodic table of elements (IUPAC inorganic chemical nomenclature revised edition 1989), for example, Examples thereof include a titanium atom, a zirconium atom, and a hafnium atom. Titanium atoms and zirconium atoms are preferred.

In the general formula [4] to [6], the group having a cyclopentadiene type anion skeleton represented as Cp ¹ ~ CP ^5, for example, eta ⁵ - (substituted) cyclopentadienyl group, eta ⁵ - (substituted) indenyl Group, η ^5- (substituted) fluorenyl group and the like. 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, η ⁵ -indenyl group, η ⁵ -methylindenyl group, η ⁵ -dimethylindenyl group , Η ⁵ -n-propylindenyl group, η ⁵ -isopropylindenyl group, η ⁵ -n-butylindenyl group, η ⁵ -tert-butylindenyl group, η ⁵ -phenylindenyl group, η ^5- Methylphenylindenyl group, η ⁵ -naphthylindenyl group, η ⁵ -trimethylsilylindenyl group, η ⁵ -tetrahydroindenyl group, η ⁵ -fluorenyl group, η ⁵ -methylfluorenyl group, η ⁵ -dimethylfluor 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, η ⁵ -bistrimethylsilylfluorenyl group and the like can be mentioned, preferably η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl 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 halogen atoms 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, and a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable.

As a hydrocarbon 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] Includes an alkyl group, an aralkyl group, an aryl group, and the like.

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] 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 or 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 perfluoro group. Examples include a hexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group.
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] , 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, or a tert-pentyl group.

Examples of the aralkyl 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] 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-to 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, etc. 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 substituted with.

Examples of the aralkyl 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] , Preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably a benzyl group.

As an aryl 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] 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 , Pentamethylphenyl group, ethylphenyl group, 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 substituted with.

As 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] , Preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group.

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 Aryloxy group; may be substituted with an aralkyloxy group such as benzyloxy group. Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, 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 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, for example, a monosubstituted silyl group having 1 to 20 carbon atoms such as a methylsilyl group, an ethylsilyl group or a phenylsilyl group; a disubstituted silyl group having 2 to 20 carbon atoms such as a dimethylsilyl group, a diethylsilyl group or a diphenylsilyl group. 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.

Examples of the alkoxy 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] 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, etc. are mentioned.
These alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group It may be substituted with.

Examples of the alkoxy 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] And an alkoxy group having 1 to 20 carbon atoms, more preferably a methoxy group, an ethoxy group, an isopropoxy group, or a tert-butoxy group.

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] Are, for example, benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4- (Dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethyl) Enyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, 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 Group 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 such as benzyloxy group It may be substituted with a group or the like.

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 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 group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2, 6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-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 Examples thereof include a phenoxy group, an n-octylphenoxy group, an n-decylphenoxy group, an n-tetradecylphenoxy group, a naphthoxy group, and an anthracenoxy group.
All of these aryloxy 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 such as benzyloxy group It may be substituted with a group or the like.

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] 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, the hydrocarbon group or the silyl group being a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. An aryl group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group; and the like. 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. Preferred examples include alkyl groups having 1 to 20 carbon atoms such as cyclohexyl groups; aryl groups having 6 to 20 carbon atoms such as phenyl groups; aralkyl groups having 7 to 10 carbon atoms such as benzyl groups, and the like, and silyl groups Examples thereof include a trimethylsilyl group and a tert-butyldimethylsilyl group. Examples of the disubstituted amino group include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group, 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, etc. And preferably a dimethylamino group, a diethylamino group, a diisopropylamino group, a di-tert-butylamino group, or 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] For example, methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, n-pentylthio group, neopentylthio group, n-hexylthio group, n-octylthio Group, n-dodecylthio group, n-pentadecylthio group, n-eicosylthio group and the like.
These alkylthio groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group It may be substituted with.

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] And an alkylthio group having 1 to 20 carbon atoms, more preferably a methylthio group, an ethylthio group, an isopropylthio group, or a tert-butylthio group.

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] Are, 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, (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 Examples include a ruthio 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 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.

As an arylthio 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] 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 Thio group, 2-tert-butyl-3,5-dimethylphenylthio group, 2-tert-butyl-3,6-dimethylphenylthio group, 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 group, n-butylphenylthio group, sec-butylphenylthio group, tert-butylphenylthio group, n-hexylphenylthio group, n-octylphenylthio group, n-decylphenylthio group, n- A tetradecylphenylthio group, a naphthylthio group, an anthracenylthio group, etc. are mentioned.
These arylthio groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group It may be substituted with.

Examples of the arylthio 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] An arylthio group having 6 to 20 carbon atoms is preferred.

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 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, 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 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 such as 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] Are, for example, benzylseleno group, (2-methylphenyl) methylseleno group, (3-methylphenyl) methylseleno group, (4-methylphenyl) methylseleno group, (2,3-dimethylphenyl) methylseleno group, (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 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, more preferably a benzylseleno group.

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] Are, for example, phenylseleno group, 2-methylphenylseleno group, 3-methylphenylseleno group, 4-methylphenylseleno group, 2,3-dimethylphenylseleno group, 2,4-dimethylphenylseleno group, 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 A seleno group, a naphthyl seleno group, an anthracenyl seleno group, etc. are mentioned.
These arylseleno groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy such as 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 general formulas [4] to [6], 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], 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 preferably each independently a hydrogen atom, A halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, and an aryloxy group, and particularly R ¹¹ , R ²¹ , R ³¹ , R ^41, and R ⁵¹ are independently alkyl 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 are each independently a hydrogen atom, An alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group or an aryloxy group is preferred.

X ^{5 to} X ⁷ in the above general formulas [5] and [6] represent atoms of Group 16 of the periodic table of elements, and specific examples 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 group 16 atom in the periodic table of the elements shown as 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 the group 14 atom in the periodic table of elements shown as 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, 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-phenyl) 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 (η ⁵ -tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -tetramethylcyclopentadienyl) ( 3-tert-butyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (η 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 (η 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 (η ⁵ -cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (η ⁵ -cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Isopropylidene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (η ⁵ -cyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, isopropylidene (η ⁵ -cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (η 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 (η ⁵ -tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (η ⁵ -tetramethylcyclopentadi) 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 (η ⁵ -tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl -5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (η ⁵ -cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Diphenylmethylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (η ⁵ -cyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, diphenylmethylene (η ⁵ -cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (η 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 (η ⁵ -tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (η 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. Moreover, the compound etc. which changed the dichloride of the said compound into dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino), or bis (diethylamino), etc. can be mentioned. Furthermore, the compound which changed the titanium of the said compound into the zirconium or hafnium can be mentioned.

Specific examples of the metal compound represented by the general formula [4] include dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) ( 3-methyl-2-phenoxy) titanium dichloride, dimethylsilene (η ⁵ -cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (3- tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η 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 (η ⁵ -cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (η 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-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride, dimethylsilylene (η ⁵ -tetra Methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadiene) Enyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (η 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 (η ⁵ -tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -Tetramethi Rucyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2- Phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (η 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), (η ⁵ -n-butylcyclopentadienyl) , (Η ⁵ -tert-butylcyclopentadienyl), (η ⁵ -trimethylsilylcyclopentadienyl), (η ⁵ -tert-butyldimethylsilylcyclopentadienyl), (η ⁵ -indenyl), (η ⁵ - methylindenyl), (eta ⁵ - phenyl indenyl) or (eta ⁵ - such as compound change fluorenyl) and the like. Moreover, the compound etc. which changed 2-phenoxy of the said compound into 3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxy, or 3-tert-butyldimethylsilyl-2-phenoxy can be mentioned. Moreover, the compound etc. which changed the dimethylsilylene of the said compound into diethylsilylene, diphenylsilylene, or dimethoxysilylene can be mentioned. Moreover, the compound etc. which changed the dichloride of the said compound into dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino), or bis (diethylamino), etc. can be mentioned. Furthermore, the compound etc. which changed the titanium of the said compound into the zirconium or hafnium can 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}, 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 -Oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylide (Η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-methyl-2- Phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropi Redene (η 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 -Oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (η 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 -methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (η 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 the like (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 - And a compound changed to (phenylindenyl) or (η ⁵ -fluorenyl). In addition, (2-phenoxy) of the above compound is changed to (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), ( Examples thereof include compounds changed to (3-phenyl-5-methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy). Moreover, the compound etc. which changed the chloride of the said compound into methyl, benzyl, phenoxide, dimethylamino, or diethylamino can be mentioned. Furthermore, the compound etc. which changed the titanium of the said compound into the zirconium or hafnium can be mentioned.

Specific examples of the metal compound represented by the general formula [6] include di-μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {isopropylidene ( η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (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-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η 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 -methylcyclohexane) 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. In addition, (2-phenoxy) of the above compound is changed to (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), ( Examples thereof include compounds changed to (3-phenyl-5-methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy). Furthermore, the compound etc. which changed the titanium of the said compound into the zirconium or hafnium can be mentioned.

As the compound (C) used in the addition polymerization catalyst of the present invention, a known organoaluminum 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 Y, the plurality of Y 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. Group or normal hexyl group.

  Specific examples when 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 preferably a chlorine atom.

  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 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 n-pentoxy group, and a neopentoxy group. 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 or an iodine atom; an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group.

  As an alkoxy group in Y of General formula [12], a C1-C24 alkoxy group is preferable, More preferably, they are a methoxy group, an ethoxy group, and a tert-butoxy group.

Examples of the aryloxy group in 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, etc. are mentioned.
Any of these aryloxy groups may be substituted with 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; 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 in Y in the general formula [12] include a benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3- (Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethyl) (Tilphenyl) 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) ) 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 or an iodine atom; an alkoxy group such as a methoxy group or 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, more preferably a benzyloxy group.

  Specific examples of the organoaluminum compound represented by the general formula [12] include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum and the like. Dialkylaluminum chlorides such as alkylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dinormalpropylaluminum chloride, dinormalbutylaluminum chloride, diisobutylaluminum chloride, dinormalhexylaluminum chloride; methylaluminum dichloride, ethylaluminum dichloride, normalpropylaluminum dichloride Alkyl aluminum dichloride such as normal butyl aluminum dichloride, isobutyl aluminum dichloride, normal hexyl aluminum dichloride; dimethyl aluminum hydride, diethyl aluminum hydride, dinormal propyl aluminum hydride, di normal butyl aluminum hydride, diisobutyl aluminum hydride, dinormal hexyl aluminum hydride, etc. Dialkylaluminum hydrides; trialkoxyaluminums such as trimethoxyaluminum, triethoxyaluminum, tri (t-butoxy) aluminum; alkyls such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum Alkoxy) aluminum; Dialkyl (alkoxy) aluminum such as dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, dimethyl (t-butoxy) aluminum; triphenoxyaluminum, tris (2,6-diisopropylphenoxy) aluminum 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 amount ratio (molar ratio) of the compound (A) to the compound (B) is not particularly limited, but the molar ratio of the compound (A) to the compound (B) is Usually, compound (A): compound (B) = 1: 1 to 10000: 1, preferably compound (A): compound (B) = 1: 1 to 5000: 1, more preferably compound (A). : Compound (B) = 1: 1 to 1000: 1. When the compound component (C) is used, the amount 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 compound (C) with compound (A) and compound (B) may be used. It may be used after being put in. Any two of them may be pre-contacted and then another compound contacted.

Examples of the addition polymerizable monomer that can be used in the production of the addition polymer using the addition polymerization catalyst of the present invention include 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 thereof 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-decene and vinylcyclohexane; 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 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-endome Diolefins such as lenhexahydronaphthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene; norbornene, 5-methylnorbornene 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclodone Decene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorborn , Cyclic olefins such as 5-cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; alkenylbenzene (styrene, 2-phenylpropylene, 2 -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 butyl styrene, p-secondary butyl styrene, etc.), bis Alkenylbenzene (divinylbenzene, etc.), alkenylnaphthalene (1- Alkenyl aromatic hydrocarbons such as vinylnaphthalene; 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, etc.) and metal salts thereof (sodium, potassium, lithium, zinc, magnesium, calcium, etc.), 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, etc.), unsaturated dicarboxylic acid (maleic acid) , Itaconic acid, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc.), unsaturated carboxylic acid glycidyl esters (acrylic acid) Polar monomers such as glycidyl, glycidyl methacrylate, monoglycidyl itaconate, etc.) and cyclic ethers (ethylene oxide, propylene oxide, 1-hexene oxide, cyclohexene oxide, styrene oxide, tetrahydrofuran, etc.).

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

  The addition polymerization catalyst of the present invention is particularly suitable as an olefin polymerization catalyst, and is preferably used in a method for producing an olefin polymer. Such an olefin polymer is preferably a copolymer of ethylene and an α-olefin, particularly preferably a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and among them, a linear low density polyethylene (LLDPE) is preferred.

  The polymerization method of the addition polymerizable monomer in the production of the addition polymer of the present invention is not particularly limited. For example, aliphatic hydrocarbon (butane, pentane, hexane, heptane, octane, etc.), aromatic Solvent polymerization or slurry polymerization using hydrocarbons (benzene, toluene, etc.) or halogenated hydrocarbons (methylene dichloride, etc.) as solvents; bulk polymerization in which polymerization is performed in liquid monomer; polymerization in gaseous monomer Gas phase polymerization for carrying out; high pressure method for carrying out polymerization in a supercritical fluid state under high temperature and high pressure. As the polymerization mode, either batch type or continuous type is possible.

  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 solution dissolved in a hydrocarbon solvent from which components for deactivating the catalyst such as moisture and oxygen are sufficiently removed, or a method of supplying in a suspended or slurry state, etc. Can be mentioned.

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

  The polymerization temperature is usually -100 ° C to 350 ° C, preferably -20 ° C to 300 ° C, more preferably 160 ° C to 300 ° C. The polymerization pressure is usually 0.1 to 350 MPa, preferably 0.1 to 300 MPa, and more preferably 0.1 to 200 MPa. In general, the polymerization time is appropriately determined depending on the kind of the target addition polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours. 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 an Example was measured with the following method.

(1) α-olefin unit content in copolymer (short chain branching degree)
The α-olefin unit content (short chain branching degree) in the obtained polymer was determined from the infrared absorption spectrum. Measurement and calculation were carried out using 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] The intrinsic viscosity [η] was measured in a tetralin solution at 135 ° C. using an Ubbelohde viscometer.

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

(4) Molecular weight and molecular weight distribution It measured on the following conditions by the gel permeation chromatography (GPC). A calibration curve was prepared 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: Model 150C manufactured by Millipore Waters Inc .: TSK-GEL GMH-HT (7.5 × 600) 2 Measurement temperature: 140 ° C.
Solvent: orthodichlorobenzene,
Measurement concentration: 5 mg / 5 ml

(5) Melting point (mp)
It measured on condition of the following using the differential scanning calorimeter (Seiko Electronics Co., Ltd. product SSC-5200).
Condition adjustment: After 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 conditioning, the temperature was raised from 10 ° C. to 160 ° C. at 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 placed. At room temperature, 75.3 ml (pentafluorophenol 209 mmol) of a toluene solution of pentafluorophenol having a concentration of 2.77 mol / L was dropped. After completion of dropping, 150 ml of toluene was further added. Stirring was performed for 12 hours under reflux conditions. The yellow crystals deposited by standing at room temperature were filtered off and dried under reduced pressure to obtain 46.1 g of yellow crystals. The elemental analysis results of the yellow crystals 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 placed. To this, 4.2 μl (0.23 mmol) of H ₂ O was added at room temperature, and then 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.

<Synthesis of Compound (B) (Dimethylsilylene (η 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 (methyllithium 4.1 mmol) of methyllithium ether solution having a concentration of 1.05 mol / L was added dropwise at −78 ° C. . By raising the temperature to 20 ° C. and confirming the end of gas generation, the formation of lithium methoxide was confirmed, and the mixture was cooled again to −78 ° C. Anhydrous ether of 0.919 g (2.0 mmol) of dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride prepared in advance in another Schlenk tube The 20 ml suspension was transferred to the previous reaction solution and then gradually warmed to room temperature. After concentration of the reaction solution, 20 ml of toluene was added, and insoluble matters were filtered off. The filtrate was concentrated and dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide (hereinafter referred to as Compound B1) having the following structural formula. Was obtained as yellow crystals. (0.86g, 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>
An autoclave with a stirrer having an internal volume of 400 ml was vacuum-dried and replaced with argon, then 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 rise, the ethylene pressure was adjusted to 2.5 MPa and fed, and after the system was stabilized, 0.3 ml of a triisobutylaluminum toluene solution (300 μmol of triisobutylaluminum) having a concentration of 1 mol / L was added, and compound B1 0.5 ml of a heptane solution (compound B1 having a concentration of 1 μmol / ml, triisobutylaluminum having a concentration of 50 μmol / ml, and a molar ratio of Al atoms to Ti atoms being adjusted to 50) mixed with bismuth and triisobutylaluminum. (In other words, 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 carried out for 2 minutes. As a result of the polymerization, 0.04 g of an ethylene / 1-hexene copolymer was obtained. 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)>
In the preparation of the compound A1 slurry, the same procedure as in the preparation of the compound (A) in Example 1 was performed 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 is referred to as Compound A2 slurry). Calculated from the liquid volume, it was 57.8 μmol-Bi / ml.

<Production of addition polymer>
It replaced with the compound A1 slurry and performed similarly to manufacture of the addition polymer of Example 1 except using 4.3 ml (250 micromol-Bi) of compound A2 slurries. As a result of polymerization, 0.30 g of an ethylene / 1-hexene copolymer was obtained. The polymerization activity was 6.0 × 10 ⁵ g / mol-Ti / 2 min, [η] = 1.94 dl / g, Mw = 130,000, Mw / Mn = 1.7, and SCB = 29.5.

[Example 3]
<Preparation of compound (A)>
In the preparation of the compound A1 slurry, the same procedure as in the preparation of the compound (A) in Example 1 was performed 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. It was 61.7 micromol-Bi / ml when calculating from the liquid amount.

<Production of addition polymer>
It replaced with the compound A1 slurry and performed similarly to manufacture of the addition polymer of Example 1 except using 4.1 ml (250 micromol-Bi) of a compound A3 slurry. As a result of the polymerization, 0.64 g of 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)>
In preparing the compound A1 slurry, the same procedure as in the preparation of the compound (A) in Example 1 was carried out 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 referred to as Compound A4 slurry). Calculated from the liquid volume, it was 60.6 μmol-Bi / ml.

<Production of addition polymer>
It replaced with the compound A1 slurry and performed similarly to manufacture of the addition polymer of Example 1 except using 4.1 ml (250 micromol-Bi) of a compound A4 slurry. As a result of the polymerization, 2.05 g of 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)>
In preparing the compound A1 slurry, the same procedure as in the preparation of the compound (A) in Example 1 was conducted 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 is referred to as Compound A5 slurry). Calculated from the liquid volume, it was 53.7 μmol-Bi / ml.

<Production of addition polymer>
It replaced with the compound A1 slurry and performed similarly to manufacture of the addition polymer of Example 1 except using 4.7 ml (250 micromol-Bi) of compound A5 slurries. 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)>
In preparing the compound A1 slurry, the same procedure as in the preparation of the compound (A) in Example 1 was conducted, 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 referred to as Compound A6 slurry). Calculated from the liquid volume, it was 60.3 μmol-Bi / ml.

<Production of addition polymer>
It replaced with the compound A1 slurry and performed similarly to manufacture of the addition polymer of Example 1 except using 4.1 ml (250 micromol-Bi) of compound A6 slurries. As a result of the polymerization, 1.33 g of an ethylene / 1-hexene copolymer was obtained. The polymerization activity was 2.7 × 10 ⁶ g / mol-Ti / 2 minutes, and Mw = 100000.

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

[Comparative Example 2]
<Manufacture of zinc compounds>
A 5-liter four-necked flask purged with nitrogen was charged with 1.5 liters of tetrahydrofuran and 1.35 L of ZnEt _{2 in} a concentration of 2.0 mol / L (ZnEt ₂ 2.75 mol) and cooled to 5 ° C. in an ice bath. A solution prepared by dissolving 203.3 g (1.1 mol) of pentafluorophenol in 300 ml of tetrahydrofuran was added dropwise thereto. After completion of dropping, 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 the temperature was lowered 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 dropping, 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 drying was performed at 120 ° C. under reduced pressure 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>
It replaced with the compound A1 slurry and performed similarly to manufacture of the addition polymer of Example 1 except using 58.5 mg (376 micromol) of zinc compounds manufactured by the said method. As a result of the polymerization, only a trace amount of ethylene / 1-hexene copolymer was obtained.

[Comparative Example 3]
<Production of addition polymer>
The same procedure as in the production of the addition polymer of Example 1 was conducted except that 3 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was used in place of the compound A1 slurry. As a result of the polymerization, 2.18 g of ethylene / 1-hexene copolymer was obtained. 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)>
In a 5 L four-necked flask purged with argon, 255 g (579 mmol) of triphenylbismuth and 1.6 L of toluene were placed. To this, 653 ml (pentafluorophenol 1.82 mol) of a toluene solution of pentafluorophenol having a concentration of 2.79 mol / L was dropped. Stirring was performed for 12 hours under reflux conditions. Yellow crystals precipitated by standing at room temperature were filtered off and dried under reduced pressure to obtain 447 g of yellow crystals.
In a 2 L four-necked flask purged with argon, 178 g of the yellow crystals and 1.0 L of toluene were added 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, followed by stirring at 80 ° C. for 1 hour. A white powder precipitated in the liquid by the stirring. After cooling to room temperature, the mixture was allowed to stand to settle the precipitate, and the supernatant was extracted. The precipitate in the flask was washed once with 500 ml of toluene and washed 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 internal volume of 400 ml was vacuum-dried and replaced with argon, and then 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 rise, the ethylene pressure was adjusted to 2.5 MPa and fed, and after the system was stabilized, 0.3 ml of a triisobutylaluminum toluene solution (300 μmol of triisobutylaluminum) having a concentration of 1 mol / L was added, and compound B1 0.5 ml of a heptane solution (compound B1 having a concentration of 1 μmol / ml, triisobutylaluminum having a concentration of 50 μmol / ml, and a molar ratio of Al atoms to Ti atoms being adjusted to 50) mixed with bismuth and 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 wt% was further charged to initiate polymerization. Polymerization was carried out 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 = 16000, Mw / Mn = 1.8, SCB = 25, melting point 92.7 ° C. It was.

Claims (15)

An olefin polymerization catalyst component obtained by contacting the following components (a) to (c).
(A): Compound represented by the following general formula [1]
BiL ¹ ₃ [1]
(B): Compound represented by the following general formula [2]
R ¹ T ¹ H [2]
(C): Compound represented by the following general formula [3]
T ² H ₂ [3]
(In the above general formulas [1] to [3], L ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group or a hydrocarbon oxy group, and the three L ^{1 s} may be the same or different from each other; T ¹ and T ² each independently represent an oxygen atom or a sulfur atom, R ¹ is table to a halogenated alkyl group or a halogenated aryl group.) A catalyst component for olefin polymerization according to claim 1 T ² is an acid atom of components T ¹ and components (b) (c). The catalyst component for olefin polymerization according to claim 1 or 2 , wherein the component (b) is a fluorinated phenol. The olefin polymerization catalyst component according to claim 3 , wherein the fluorinated phenol is pentafluorophenol. Component (a) per mole of the contact treatment of the component (b) is from 2.1 to 3.9 mol, it claims 1-4 contact treatment amount of the component (c) is from 0.1 to 2 moles The catalyst component for olefin polymerization according to any one of the above. The catalyst component for olefin polymerization according to any one of claims 1 to 5 , wherein the component (c) is brought into contact with a contact product obtained by bringing the component (a) and the component (b) into contact with each other. After the components (a) and (b) a contact product obtained by contacting was dissolved in a solution in a solvent, claim 1-6 comprising contacting the solution with component (c) The catalyst component for olefin polymerization described in 1. Claims and an olefin polymerization catalyst component according to any one of 1-7, an olefin polymerization catalyst comprising contacting a Group 3 to 11 or lanthanide series metal compound (B). Claim 1 and a catalyst component for olefin polymerization according to any one of 7, a Group 3 to 11 or lanthanide series metal compound, an olefin polymerization catalyst comprising contacting an organoaluminum compound. The olefin polymerization catalyst according to claim 8 or 9 , wherein the Group 3-11 or lanthanoid series metal compound is a metallocene metal compound. The olefin polymerization catalyst according to claim 10 , wherein the metallocene metal compound is a monocyclopentadienyl metal compound. The catalyst for olefin polymerization according to claim 11 , wherein the monocyclopentadienyl metal compound is a metal compound represented by any one of the following general formulas [4] to [6].

(In the above general formulas [4] to [6], M ^{1 to} M ⁵ represent atoms of Group 4 of the periodic table of elements, and A ^{1 to} A ⁵ represent Group 16 of the periodic table of elements. Represents an atom, J ^{1 to} J ⁵ represent an atom belonging to Group 14 of the periodic table of elements, Cp ^{1 to} Cp ⁵ represent a group having a cyclopentadiene-type anion skeleton, 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 are each independently 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, 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 optionally combined. May form a monocyclic ring or a polycyclic ring, which 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.) Process for producing an olefin polymer using the olefin polymerization catalyst according to any one of claims 8-12. The method for producing an olefin polymer according to claim 13 , wherein the polymerization temperature of the olefin polymer is 160 to 300 ° C. The method for producing an olefin polymer according to claim 13 or 14 , wherein the olefin polymer is a copolymer of ethylene and an α-olefin.