JP2005281212A - Aluminum compound, its manufacturing method, addition polymerization catalyst component, addition polymerization catalyst and method for manufacturing addition polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high performance compound having an ethylaluminum compound as a raw material, an addition polymerization catalyst component, an addition polymerization catalyst, and an efficient method for manufacturing an addition polymer by using the addition polymerization catalyst. <P>SOLUTION: A compound (A) is obtained by bringing (a) EtAlL<SP>1</SP><SB>2</SB>(wherein Et is an ethyl group; and L<SP>1</SP>is hydrogen, a ≥2C hydrocarbon group or a halogen) into contact with (b) R<SP>1</SP><SB>t-1</SB>TH (wherein R<SP>1</SP>is an electron-attracting group or a group containing an electron-attracting group; T is a group 15 or 16 nonmetallic atom; and t is a valence of T) and then bringing the resulting compound into contact with (c) R<SP>2</SP><SB>t-2</SB>TH<SB>2</SB>(wherein R<SP>2</SP>is a hydrocarbon group or a halogenated hydrocarbon; and T and t are the same as defined above). The addition polymerization catalyst component is composed of the compound. The addition polymerization catalyst is obtained by bringing the compound (A) into contact with a transition metal compound (B). The method for manufacturing an addition polymer uses the addition polymerization catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a compound used for the preparation of an addition polymerization catalyst classified as a single site catalyst, a catalyst component for addition polymerization, a method for producing the compound, a catalyst for addition polymerization classified as a single site catalyst, and an addition polymer. It relates to the manufacturing method.

Addition polymers such as polypropylene and polyethylene are widely used in various molding fields due to their excellent mechanical properties, chemical resistance, etc., and their excellent balance between properties and economy.
These addition polymers have heretofore been a combination of a solid catalyst component obtained mainly using a Group 4 metal compound such as titanium trichloride or titanium tetrachloride and a Group 13 metal compound typified by an organoaluminum compound. It has been produced by multisite polymerization in which olefins and the like are polymerized using a conventional solid catalyst (multisite catalyst).

  In recent years, unlike solid catalyst components that have been used for a long time, a transition metal component that can be isolated (for example, a metallocene complex or a nonmetallocene compound) is combined with an organometallic component that consists of an aluminoxane or the like. There has been proposed a method for producing an addition polymer by single-site polymerization in which an olefin or the like is polymerized using a so-called single-site catalyst. For example, Patent Document 1 reports a method using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane. The aluminoxane is usually a linear or cyclic oligomer having an —Al—O—Al— bond, obtained by reacting an alkylaluminum with water.

JP 58-19309 A

  A lot of research has been done on aluminoxanes, but most of them are only known to be methylaluminoxane or those based on methylaluminoxane (introduced with isobutyl groups or modified with modifiers). Not. For example, triethylaluminum, which is a representative compound of an ethylaluminum compound, is an aluminoxane compound that uses ethylaluminum compound as a raw material, even though it is 20 years ago and at a low price that is one tenth of that of trimethylaluminum. Is not practical. An object of the present invention is to provide a high-performance compound using an ethylaluminum compound as a raw material, a catalyst component for addition polymerization, a catalyst for addition polymerization, and an efficient method for producing an addition polymer using the catalyst for addition polymerization. is there.

In the present invention, the following (a) and the following (b) are contacted, the following (c) is contacted with the compound (A), and the following (a) and the following (b) are contacted with each other. This relates to a method for producing a compound in which (c) is contacted.
The present invention also relates to an addition polymerization catalyst component comprising the compound.
The present invention further relates to an addition polymerization catalyst obtained by contacting the compound (A) and the transition metal compound (B), and the compound (A), the transition metal compound (B), and The present invention relates to an addition polymerization catalyst obtained by bringing an organoaluminum compound (C) into contact therewith.
The present invention also relates to a method for producing an addition polymer using any of the above addition polymerization catalysts.
(A): Compound represented by the following general formula [1] EtAlL ¹ ₂ [1]
(B): Compound represented by the following general formula [2] R ¹ _t-1 TH [2]
(C): Compound represented by the following general formula [3] R ² _t-2 TH ₂ [3]
(In the general formulas [1] to [3], Et represents an ethyl group, L ¹ represents a hydrogen atom, a hydrocarbon group having 2 or more carbon atoms, or a halogen atom, and L ¹ is the same as each other. It may even be different .R ¹ is a group containing an electron withdrawing group or an electron withdrawing group, if R ¹ there are a plurality may be different even they the same as each other .R ² Represents a hydrocarbon group or a halogenated hydrocarbon group, T independently represents a non-metal atom of Group 15 or Group 16 of the periodic table, and t represents a number corresponding to the valence of T of each compound. Represents.)

According to the present invention, a high-performance compound using an ethylaluminum compound as a raw material, a catalyst component for addition polymerization, a catalyst for addition polymerization, and an efficient method for producing an addition polymer using the catalyst for addition polymerization are provided.
Hereinafter, the present invention will be described in more detail.

The compound (a) is a compound represented by the following general formula [1].
EtAlL ¹ ₂ [1]
In the general formula [1], Al represents an aluminum atom, and Et represents an ethyl group.

L ¹ in the general formula [1] represents a hydrogen atom, a halogen atom or a hydrocarbon group having 2 or more carbon atoms, and L ¹ may be the same or different from each other. 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.

  As an alkyl group here, a C2-C20 alkyl group is preferable, for example, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like are more preferable. An ethyl group, an isopropyl group, a tert-butyl group or an isobutyl group, particularly preferably an ethyl group.

  Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 2 to 20 carbon atoms substituted with a halogen atom include a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group. Group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, 1H, 1H-perfluoropropyl group, 1H, 1H-perfluorobutyl Group, 1H, 1H-perfluoropentyl group, 1H, 1H-perfluorohexyl group, 1H, 1H-perfluorooctyl group, 1H, 1H-perfluorododecyl group, 1H, 1H-perfluoropentadecyl group, 1H, 1H-perfluoroeicosyl group Or, fluoro these alkyl groups chloro, such as an alkyl group was replaced by bromo or iodo.

As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable. For example, a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, 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-tetra Methylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl Tert-butylphenyl group, isobutylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecyl group A phenyl group, a naphthyl group, an anthracenyl group, etc. are mentioned, More preferably, it is a phenyl group.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or aralkyloxy groups such as benzyloxy group Etc. may be partially substituted.

As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable. For example, a benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2 , 3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) Methyl group, (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, (isobutylphenyl) methyl group, (N-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, anthrace An nylmethyl group, etc. are mentioned, More preferably, it is a benzyl group.
Any of these aralkyl groups may be partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

L ¹ in the general formula [1] is preferably a hydrogen atom, an alkyl group, an aryl group or a halogen atom, more preferably a hydrogen atom, an alkyl group or a halogen atom, particularly preferably an alkyl group, most preferably Is an ethyl group.

The compound (b) is a compound represented by the following general formula [2].
R ¹ _t-1 TH [2]
Further, the compound (c) is a compound represented by the following general formula [3].
R ² _t-2 TH ₂ [3]
T in the above general formula [2] or [3] independently represents a nonmetallic atom of Group 15 or Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). T in the general formula [2] and T in the general formula [3] may be the same or different. Specific examples of the Group 15 nonmetal atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 nonmetal atom include an oxygen atom and a sulfur atom. T is preferably each independently a nitrogen atom or an oxygen atom, and particularly preferably T is an oxygen atom.
In the general formula [2] or [3], t represents a number corresponding to the valence of each T. When T is a Group 15 nonmetal atom, t is 3, and T is a Group 16 nonmetal. In the case of atoms, t 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, they may be the same as or different from each other. 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 sulfone group, and a phenyl group. Examples of the group containing an electron-withdrawing group include halogenated alkyl groups, halogenated aryl groups, (halogenated alkyl) aryl groups, cyanated aryl groups, nitrated aryl groups, ester groups (alkoxycarbonyl groups, aralkyloxycarbonyl groups, Aryloxycarbonyl group), acyl group, acyl halide group and the like.

  Specific examples of the halogenated alkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, 2 , 2,2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 1H, 1H-perfluorobutyl group, 1H, 1H -Perfluoropentyl group, 1H, 1H-perfluorohexyl group, 1H, 1H-perfluorooctyl group, 1H, 1H-perfluorododecyl group, 1H, 1H-perfluoropentadecyl group, 1H, 1H-perfluoroeico And alkyl groups obtained by changing the fluoro of these halogenated alkyl groups to chloro, bromo or iodo. It is.

  Specific examples of the halogenated aryl group include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl. Group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2 -Naphthyl group, 4,5,6,7,8-pentafluoro-2-naphthyl group, etc., and fluoro of these halogenated aryl groups B, and halogenated aryl groups that have changed bromo or iodo and the like.

  Specific examples of the (halogenated alkyl) aryl group include 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6-bis (tri Fluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, etc., and fluoro of these (halogenated alkyl) aryl groups is chloro, (Halogenated alkyl) aryl group changed to bromo or iodo and the like.

  Specific examples of the cyanated aryl group include 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group and the like.

  Specific examples of the nitrated aryl group include 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group and the like.

  Specific examples of the ester group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, phenoxycarbonyl group, trifluoromethoxycarbonyl group, pentafluorophenoxycarbonyl group and the like.

  Specific examples of acyl groups include formyl, ethanoyl, propanoyl, butanoyl, trifluoroethanoyl, benzoyl, pentafluorobenzoyl, perfluoroethanoyl, perfluoropropanoyl, perfluorobutanoyl. Group, perfluoropentanoyl group, perfluorohexanoyl group, perfluoroheptanoyl group, perfluorooctanoyl group, perfluorononanoyl group, perfluorodecanoyl group, perfluoroundecanoyl group, perfluorododecanoyl group Etc.

R ¹ is preferably a halogenated hydrocarbon group, more preferably a halogenated alkyl group or a halogenated aryl group. More preferably, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2-trimethyl Fluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-tri Fluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoro Tylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2-naphthyl group, 4,5,6,7,8-pentafluoro 2-naphthyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, 2,2,2-trichloroethyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,2-trichloro -1-trichloromethylethyl group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group, 4-chlorophenyl group, 2,6-dichlorophenyl group, 3.5-dichlorophenyl group, 2,4 , 6-trichlorophenyl group, 3,4,5-trichlorophenyl group or pentachlorophenyl group, particularly preferably a fluoroalkyl group. Is a fluoroaryl group, most preferably a trifluoromethyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2- A trifluoroethyl group, a 3,5-difluorophenyl group, a 3,4,5-trifluorophenyl group or a pentafluorophenyl group;

R ² in the general formula [3] represents a hydrocarbon group or a halogenated hydrocarbon group. As the hydrocarbon group for R ² , an alkyl group, an aryl group, or an aralkyl group is preferable, and the same hydrocarbon group as described for L ¹ in the general formula [1] is used. Examples of the halogenated hydrocarbon group for R ² include a halogenated alkyl group, a halogenated aryl group, and a (halogenated alkyl) aryl group. Specific examples of the electron-withdrawing group for R ¹ in the general formula [2] The same halogenated alkyl group, halogenated aryl group and (halogenated alkyl) aryl group as those mentioned above are used.

R ² in the general formula [3] is preferably a halogenated hydrocarbon group, and more preferably a fluorinated hydrocarbon group.

  Specific examples of the compound (a) include trialkylaluminums such as triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum; Triarylaluminum such as aluminum, trinaphthylaluminum, tri (pentafluorophenyl) aluminum; Trialkenylaluminum such as triallyl aluminum; Tri (cyclopentadienyl) aluminum; Diethylaluminum chloride, dipropylaluminum chloride, di-n- Butyl aluminum chloride, diisobutyl aluminum chloride, di-n-hexyl aluminum chloride, di-n-octyl aluminum chloride Id, diethylaluminum bromide, dipropylaluminum bromide, di-n-butylaluminum bromide, diisobutylaluminum bromide, di-n-hexylaluminum bromide, di-n-octylaluminum bromide, diethylaluminum iodide, dipropylaluminum iodide, Dialkylaluminum halides such as di-n-butylaluminum iodide, diisobutylaluminum iodide, di-n-hexylaluminum iodide, di-n-octylaluminum iodide; ethylaluminum dichloride, propylaluminum dichloride, n-butylaluminum Dichloride, isobutyl aluminum dichloride, n-hexyl aluminum dichlora N-octyl aluminum dichloride, ethyl aluminum dibromide, propyl aluminum dibromide, n-butyl aluminum dibromide, isobutyl aluminum dibromide, n-hexyl aluminum dibromide, n-octyl aluminum dibromide, ethyl aluminum diiodide, Examples include dihalogenated alkylaluminums such as propylaluminum diaiodide, n-butylaluminum diaiodide, isobutylaluminum diaiodide, n-hexylaluminum diaiodide, and n-octylaluminum diaiodide.

  The compound (a) is preferably trialkylaluminum, more preferably triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, or tri-n-octylaluminum. Particularly preferred is triethylaluminum, triisobutylaluminum, or tri-n-octylaluminum, and most preferred is triethylaluminum.

  Specific examples of the compound (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) 3-pentachloropropyl) amine, bis (2,2,3,3,3-pentabromopropyl) amine, bis (2,2,3,3,3-pentaiodopropyl) amine, bis (2,2, 2-trifluoro-1-trifluoromethylethyl) amine, bis (2,2,2-trichloro-1-trichloromethylethyl) amine, bis (2,2,2-tribromo-1-tribromomethylethyl) amine Bis (2,2,2-triiodo-1-triiodomethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine, bis (1,1 -Bis (trichloromethyl) -2,2,2-trichloroethyl) amine, bis (1,1-bis (tribromomethyl) -2,2,2-tribromoethyl) amine, bis (1,1 Bis (triiodomethyl) -2,2,2-triiodoethyl) amine, bis (2-fluorophenyl) amine, bis (3-fluorophenyl) amine, bis (4-fluorophenyl) amine, bis (2- Chlorophenyl) amine, bis (3-chlorophenyl) amine, bis (4-chlorophenyl) amine, bis (2-bromophenyl) amine, bis (3-bromophenyl) amine, bis (4-bromophenyl) amine, bis (2 -Iodophenyl) amine, bis (3-iodophenyl) amine, bis (4-iodophenyl) amine, bis (2,6-difluorophenyl) amine, bis (3,5-difluorophenyl) amine, bis (2, 6-dichlorophenyl) amine, bis (3,5-dichlorophenyl) amine, bis (2,6-dibromophenyl) Enyl) 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 (3,4, 5-trifluorophenyl) amine, bis (3,4,5-trichlorophenyl) amine, bis (3,4,5-tribromophenyl) amine, bis (3,4,5-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) amine, Bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-trifluoro (trifluoromethyl) phenyl) amine, bis (2-cyanophenyl) amine, (3-cyanophenyl) amine Bis (4-cyanophenyl) amine, bis (2-nitrophenyl) amine, bis (3-nitrophenyl) amine, bis (4-nitrophenyl) amine, bis (1H, 1H-perfluorobutyl) amine, bis (1H, 1H-perfluoropentyl) amine, bis (1H, 1H-perfluorohexyl) amine, bis (1H, H-perfluorooctyl) amine, bis (1H, 1H-perfluorododecyl) amine, bis (1H, 1H-perfluoropentadecyl) amine, bis (1H, 1H-perfluoroeicosyl) amine, bis (1H, 1H-perchlorobutyl) amine, bis (1H, 1H-perchloropentyl) amine, bis (1H, 1H-perchlorohexyl) amine, bis (1H, 1H-perchlorooctyl) amine, bis (1H, 1H- Perchlorododecyl) amine, bis (1H, 1H-perchloropentadecyl) amine, bis (1H, 1H-perchloroeicosyl) amine, bis (1H, 1H-perbromobutyl) amine, bis (1H, 1H- Perbromopentyl) amine, bis (1H, 1H-perbromohexyl) amine, bis (1H, 1H-par) -Bromooctyl) amine, bis (1H, 1H-perbromododecyl) amine, bis (1H, 1H-perbromopentadecyl) amine, bis (1H, 1H-perbromoeicosyl) amine and the like. Moreover, the phosphine compound by which the nitrogen atom was substituted by the phosphorus atom can be illustrated similarly. These phosphine compounds are compounds represented by rewriting the amine of the above-mentioned specific examples to phosphine.

  Examples of alcohols include fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodomethanol, trifluoromethanol, trichloromethanol, tribromomethanol, triiodomethanol, 2,2,2 -Trifluoroethanol, 2,2,2-trichloroethanol, 2,2,2-tribromoethanol, 2,2,2-triiodoethanol, 1,1,1,3,3,3-hexafluoro-2 -Propanol, 1,1,1,3,3,3-hexachloro-2-propanol, 1,1,1,3,3,3-hexabromo-2-propanol, 1,1,1,3,3,3 -Hexaiodo-2-propanol, 1,1,1,3,3,3-hexafur Ro-2- (trifluoromethyl) -2-propanol, 1,1,1,3,3,3-hexachloro-2- (trichloromethyl) -2-propanol, 1,1,1,3,3,3 -Hexabromo-2- (tribromomethyl) -2-propanol, 1,1,1,3,3,3-hexaiodo-2- (triiodomethyl) -2-propanol, 1H, 1H, 3H-perfluoropropanol 1H, 1H, 3H-perchloropropanol, 1H, 1H, 3H-perbromopropanol, 1H, 1H, 3H-periodopropanol, 1H, 1H-perfluoropropanol, 1H, 1H-perchloropropanol, 1H, 1H -Perbromopropanol, 1H, 1H-Periodopropanol, 1H, 1H, 4H-perfluorobutanol, 1H, 1H 4H-perchlorobutanol, 1H, 1H, 4H-perbromobutanol, 1H, 1H, 4H-periodobutanol, 1H, 1H-perfluorobutanol, 1H, 1H-perchlorobutanol, 1H, 1H-perbromobutanol, 1H, 1H-Periodobutanol, 1H, 1H, 5H-Perfluoropentanol, 1H, 1H, 5H-Perchloropentanol, 1H, 1H, 5H-Perbromopentanol, 1H, 1H, 5H-Periodo pen Tanol, 1H, 1H-perfluoropentanol, 1H, 1H-perchloropentanol, 1H, 1H-perbromopentanol, 1H, 1H-periodopentanol, 1H, 1H, 6H-perfluorohexanol, 1H, 1H, 6H-perchlorohexanol, 1H, 1H, 6H- Perbromohexanol, 1H, 1H, 6H-Periodohexanol, 1H, 1H-Perfluorohexanol, 1H, 1H-Perchlorohexanol, 1H, 1H-Perbromohexanol, 1H, 1H-Periodohexanol, 1H, 1H, 8H-perfluorooctanol, 1H, 1H, 8H-perchlorohexanol, 1H, 1H, 8H-perbromooctanol, 1H, 1H, 8H-periodooctanol, 1H, 1H-perfluorooctanol, 1H, 1H-perchloro Examples include octanol, 1H, 1H-perbromooctanol, 1H, 1H-periodooctanol, and the like. Moreover, the thiol compound by which the oxygen atom was substituted by the sulfur atom can be illustrated similarly. These thiol compounds are compounds represented by rewriting “Nol” in the above specific examples to “Nthiol”.

  As phenols, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 2, 4,6-trifluorophenol, 3,4,5-trifluorophenol, 2,3,5,6-tetrafluorophenol, pentafluorophenol, 2,3,5,6-tetrafluoro-4-trifluoromethyl Phenol, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol, perfluoro-1-naphthol, perfluoro-2-naphthol, 4,5,6,7,8-pentafluoro-2-naphthol 2-chlorophenol, 3-chlorophenol, 4-chlorophenol 2,4-dichlorophenol, 2,6-dichlorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol, 2,4,6-trichlorophenol, 3,4,5-trichlorophenol, 2,3, 5,6-tetrachlorophenol, pentachlorophenol, 2,3,5,6-tetrachloro-4-trichloromethylphenol, 2,3,5,6-tetrachloro-4-pentachlorophenylphenol, perchloro-1- Naphthol, perchloro-2-naphthol, 4,5,6,7,8-pentachloro-2-naphthol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2,4-dibromophenol, 2,6- Dibromophenol, 3,4-dibromophenol, 3,5-dibromophenol, 2,4, -Tribromophenol, 3,4,5-tribromophenol, 2,3,5,6-tetrabromophenol, pentabromophenol, 2,3,5,6-tetrabromo-4-tribromomethylphenol, 2, 3,5,6-tetrabromo-4-pentabromophenylphenol, perbromo-1-naphthol, perbromo-2-naphthol, 4,5,6,7,8-pentabromo-2-naphthol, 2-iodophenol, 3- Iodophenol, 4-iodophenol, 2,4-diiodophenol, 2,6-diiodophenol, 3,4-diiodophenol, 3,5-diiodophenol, 2,4,6-triiodophenol, 3,4,5-triiodophenol, 2,3,5,6-tetraiodophenol, pentaiodophenol, 2,3,5,6-tetraiodo-4-triiodomethylphenol, 2,3,5,6-tetraiodo-4-pentaiodophenylphenol, periododo-1-naphthol, periodio-2-naphthol, 4,5, 6,7,8-pentaiodo-2-naphthol, 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-nitro Phenol, 4-nitrophenol, etc. are mentioned. Moreover, the thiophenol compound by which the oxygen atom was substituted by the sulfur atom can be illustrated similarly. These thiophenol compounds are compounds represented by rewriting “phenol” in the above specific examples to “thiophenol” (in the case of naphthol, compounds represented by rewriting “naphthol” to “naphthylthiol”) Etc.

  Examples of the halogenated carboxylic acid include pentafluorobenzoic acid, perfluoroethanoic acid, perfluoropropanoic acid, perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluorohepta. Examples include nomic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid.

  The compound (b) is preferably a bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine. ) 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, 1,1,1,3,3,3-hexafluoro-2-propanol, 1,1,1 , 3,3,3-hexafluoro-2- (trifluoromethyl) -2-propanol, 1H, 1H, 6H-perfluorohexanol, 1H, 1H-par Fluorohexanol, 1H, 1H, 8H-perfluorooctanol, or 1H, 1H-perfluorooctanol, phenols include 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 (trifluoromethyl) phenol or 2,4,6-tris (trifluoromethyl) phenol.

  More preferably, the compound (b) is bis (trifluoromethyl) amine, bis (pentafluorophenyl) amine, trifluoromethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 1, 1,1,3,3,3-hexafluoro-2- (trifluoromethyl) -2-propanol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 3 , 4,5-trifluorophenol, pentafluorophenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, or 2,4,6-tris (trifluoromethyl) phenol More preferably, 1,1,1,3,3,3-hexafluoro-2-propanol, 1,1,1 3,3,3-hexafluoro-2- (trifluoromethyl) -2-propanol, 3,5-difluorophenol, or 3,4,5-trifluoro phenol, pentafluorophenol.

  Specific examples of the compound (c) are water, hydrogen sulfide, alkylamine, arylamine, aralkylamine, halogenated alkylamine, halogenated arylamine, or (halogenated alkyl) arylamine, 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-tolylua 2,3-xylylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3,4-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 Decyl aniline, n- dodecyl aniline, n- tetradecyl aniline, naphthylamine, anthracenyl amine,

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,

Perfluoropropylamine, perchloropropylamine, perbromopropylamine, periodopropylamine, perfluorobutylamine, perchlorobutylamine, perbromobutylamine, periodobutylamine, perfluoropentylamine, perchloropentylamine, perbromopentylamine , Periodopentylamine, perfluorohexylamine, perchlorohexylamine, perbromohexylamine, periodohexylamine, perfluorooctylamine, perchlorooctylamine, perbromooctylamine, periodooctylamine, perfluorododecylamine Perchlorododecylamine, perbromododecylamine, periodododecylamine, perfluoropentadecylamine, perchlor Pentadecyl amine, perbromododecyl amine, perfluoro-iodo pentadecyl amine, perfluoro eicosyl amine, perchlorethylene eicosyl amine, perfluoro-bromo eicosyl amine, perfluoro-iodo eicosyl amine,

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, 3,4,5-trifluoroaniline, 3,4,5-trichloroaniline, 3,4,5- Ribromoaniline, 3,4,5-triiodoaniline, pentafluoroaniline, pentachloroaniline, pentabromoaniline, pentaiodoaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (Trifluoromethyl) aniline, 2,6-di (trifluoromethyl) aniline, 3,5-di (trifluoromethyl) aniline, 2,4,6-trifluoro (trifluoromethyl) aniline and the like can be mentioned.

  The compound (c) is preferably 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-fluoro Oroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3 -(Trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline or 2,4,6-tris (tri Fluoromethyl) aniline, particularly preferably water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine, perfluoropentadecylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2, 6-difluoroaniline, 3,5-difluoroa Phosphorus, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) ) Aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, or 2,4,6-tris (trifluoromethyl) aniline, most preferably water or penta Fluoroaniline.

The compound of this invention is a compound obtained by making said (a), (b) and (c) contact. The order in which (a), (b) and (c) are brought into contact is not particularly limited. For example, the following order can be adopted.
<1> A contact object obtained by bringing (a) and (b) into contact with each other and (c) are brought into contact with each other.
<2> A contact object obtained by bringing (a) and (c) into contact with each other and (b) are brought into contact with each other.
<3> A contact obtained by contacting (b) and (c) is brought into contact with (a).
The contact order is preferably <1> or <2>, that is, the compound of the present invention is preferably a contact product obtained by bringing (a) and (b) into contact with (c). It is a compound obtained by making the compound obtained or (b) and the contact thing obtained by making (a) and (c) contact.

  Such contact treatment is preferably carried out in an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours. Further, such treatment may use a solvent, or these compounds may be directly treated without using them.

  As the solvent, a solvent that does not react with each of the components to be contacted when the solvent is used and the contact product obtained by contact is usually used. As described above, when each component is brought into contact stepwise, for example, even if the solvent reacts with (a), contact obtained by contacting (a) with other components In some cases, the product no longer reacts with the solvent. In such a case, the solvent can be used as a solvent in the contact operation using the contact product as one component. Solvents are exemplified below, but they may be properly used as described above. Examples of solvents that can be used include nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents, or halide solvents, ether solvents, carbonyl solvents, phosphoric acid derivatives, nitrile solvents, nitro compounds, amines Polar solvents such as system solvents and sulfur compounds. Specific examples include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, decane, 2,2,4-trimethylpentane and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; dichloromethane, difluoro Halides such as methane, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene Solvent: 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, tetrahydro Ether solvents such as lan, tetrahydropyran; acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Carbonyl solvents such as 2-pyrrolidone; Phosphoric acid derivatives such as hexamethyl phosphate triamide and triethyl phosphate; Nitrile solvents such as acetonitrile, propionitrile, succinonitrile, and benzonitrile; Nitro compounds such as nitromethane and nitrobenzene Amine solvents such as pyridine, piperidine and morpholine; sulfur compounds such as dimethyl sulfoxide and sulfolane.

Although there is no restriction | limiting in particular in the usage-amount of said compound (a), (b), (c), The molar ratio of the usage-amount of each compound is set to (a) :( b) :( c) = 1: y. : When the molar ratio of z is satisfied, it is preferable that y and z substantially satisfy the following formula (1).
3-y-2z ≦ 1 (1)
In the above formula (1), y is preferably a number of 0.01 to 2.99, more preferably a number of 0.10 to 2.80, and still more preferably a number of 0.20 to 2.50. Yes, most preferably a number between 0.25 and 1.75, and a similar preferred range for z in the above formula (1) is determined by y and the above formula (1).

  In the actual contact treatment of each compound, even if the use of each compound is intended to completely satisfy the above formula (1), the amount used may fluctuate slightly and remain unreacted. In consideration of the amount of the compound to be used, etc., it is usual to slightly increase or decrease the amount used as appropriate. Here, “substantially satisfying the formula (1)” is obtained by bringing each compound into contact with each other at a molar ratio satisfying the above formula (1) without completely satisfying the above formula (1). It is meant to be included when attempting to obtain such objects.

  Heating is also preferably performed after the contact treatment as described above in order to further advance the reaction. In heating, it is preferable to use a solvent having a higher boiling point in order to obtain a higher temperature. For this purpose, the solvent used for the contact treatment may be replaced with another solvent having a higher boiling point.

  In order to further advance the reaction, it is also preferable to remove by-products generated by the reaction from the reaction system during the contact treatment as described above or heating after the contact treatment. The removal method may be determined as appropriate according to the physical properties of the by-product.For example, in the case of gas, the reaction system is not a closed system, but can be removed by providing a degassing part or the like. A method of heating to a temperature and removing the vaporized compound from the degassing part can be mentioned.

  As a compound of the present invention, as a result of such contact treatment, the raw materials (a), (b) and / or (c) may remain as unreacted substances.

  Moreover, after such a contact treatment, the solvent may be distilled off from the product, and then drying may be performed at a temperature of 25 ° C. or higher under reduced pressure for 0.5 to 24 hours.

  When using the compound of this invention, you may use it in the solution state melt | dissolved in the solvent, and you may use it in the solid state which removed the solvent. What is necessary is just to select the form at the time of use suitably for the process using the compound of this invention, a use condition, etc. suitably.

The compound (A) of the present invention is useful as a catalyst component for addition polymerization (in particular, a catalyst component for olefin polymerization). Specific examples of the addition polymerization catalyst of the present invention include the addition polymerization catalyst obtained by bringing the compound (A) and the transition metal compound (B) into contact with each other, and the compound (A). , Transition metal compound (B), and organoaluminum compound (C), and a catalyst for addition polymerization obtained by bringing the latter into contact with each other.
Hereinafter, the addition polymerization catalyst will be described in more detail.

(B) Transition metal compound As the transition metal compound (B) used in the addition polymerization catalyst of the present invention, a transition metal compound forming a single site catalyst is used, and the compound (A) (or further an organoaluminum compound (C) is used. )) Is not particularly limited as long as it is a transition metal compound exhibiting addition polymerization activity by using it as a promoter component for activation. In addition, the single site catalyst here is a concept distinguished from the conventional solid catalyst, and in the case of copolymerization, not only a single site catalyst in a narrow sense that can provide an addition polymer having a narrow molecular weight distribution and a narrow composition distribution. As long as the catalyst can be obtained by a preparation method similar to the single-site catalyst in such a narrow sense, an addition polymer having a broad molecular weight distribution and a catalyst capable of obtaining an addition polymer having a wide composition distribution in the case of copolymerization are also included. .

The transition metal compound (B) is preferably a group 3-11 or lanthanoid series transition metal compound, or a transition metal compound represented by the following general formula [4] or its μ-oxo type transition metal compound dimer The body is more preferred.
L ² _a M ¹ X ¹ _b [4]
(In the above general formula [4], M ¹ represents a group 3-11 of the periodic table or a lanthanoid series transition metal atom. L ² represents a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom. , L ² may be the same as or different from each other, and a plurality of L ² are directly connected to each other or contain a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom X ¹ is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton) or a hydrocarbon oxy group, and a is 0 <a ≦. B represents a number satisfying 8, and b represents a number satisfying 0 <b ≦ 8.

(B) Transition Metal Compound In the general formula [4], M ¹ is a group 3-11 or lanthanoid series transition metal atom in the periodic table (IUPAC 1989). Specific examples thereof include scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom. , Samarium atoms, ytterbium atoms, and the like. M ¹ in the general formula [4] is preferably a titanium atom, zirconium atom, hafnium atom, vanadium atom, chromium atom, iron atom, cobalt atom or nickel atom, particularly preferably a titanium atom, zirconium atom or hafnium atom. And most preferably a zirconium atom.

In the general formula [4], 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. The plurality of L ² may be directly connected to each other, or may be connected 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, η ^5- (substituted) fluorenyl group and the like. Specifically, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ -ethylcyclopentadienyl group, η ⁵ -n-butylcyclopentadienyl group, η ⁵ -Tert-butylcyclopentadienyl group, η ⁵ -1,2-dimethylcyclopentadienyl group, η ⁵ -1,3-dimethylcyclopentadienyl group, η ⁵ -1-methyl-2-ethylcyclopenta Dienyl group, η ⁵ -1-methyl-3-ethylcyclopentadienyl group, η ⁵ -1-tert-butyl-2-methylcyclopentadienyl group, η ⁵ -1-tert-butyl-3-methyl Cyclopentadienyl group, η ⁵ -1-methyl-2-isopropylcyclopentadienyl group, η ⁵ -1-methyl-3-isopropylcyclopentadienyl group, η ⁵ -1-methyl-2-n-butyl Cyclopentadienyl group, η ⁵ -1-methyl-3-n-butylcyclopentadienyl group, η ⁵ -1,2,3-trimethylcyclopentadienyl group, η ⁵ -1,2,4-trimethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - indenyl group, eta ^{5-4,5,6,7-tetrahydroindenyl} group, η ⁵ -2-methylindenyl group, η ⁵ -3-methylindenyl group, η ⁵ -4-methylindenyl group, η ⁵ -5-methylindenyl group, η ⁵ -6-methylindenyl group, eta ^{5-7-methylindenyl} group, η ⁵ -2-tert- butyl indenyl group, η ⁵ -3-tert- butyl indenyl group, η ⁵ -4-tert- butylindenyl group, eta ⁵ -5 -Tert-butylindenyl group, η ^5-6 -tert-butylindenyl group, η ⁵ -7-tert-butylindenyl group, η ⁵ -2,3-dimethylindenyl group, η ⁵ -4,7-dimethylindenyl group, η ^5- 2,4,7-trimethylindenyl group, η ⁵ -2-methyl-4-isopropylindenyl group, η ⁵ -4,5-benzindenyl group, η ⁵ -2-methyl-4,5-benzindenyl group, η ^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 , Η ⁵ -fluorenyl group, η ⁵ -2,7-dimethylfluorenyl group, η ⁵ -2,7-di-tert-butylfluorenyl group, and substituted products thereof.
In the present specification, “η ⁵ −” may be omitted for the names of transition metal compounds.

  Examples of the hetero atom in the group containing a hetero atom 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, a thioaryloxy group, and an alkyl group. Amino group, arylamino group, alkylphosphino group, arylphosphino group, chelating ligand, or aromatic or aliphatic heterocyclic group having an oxygen atom, sulfur atom, nitrogen atom and / or phosphorus atom in the ring Is preferred.

  Specific examples of groups containing heteroatoms include methoxy, ethoxy, propoxy, butoxy, phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethyl. Phenoxy 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-nitrophene Xy 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, catechol, resorcinol, 4- Isopropylcatechol, 3-methoxycatechol, 1,8-dihydroxynaphthyl group, 1,2-dihydroxynaphthyl group, 2,2′-biphenyldiol group, 1,1′-bi-2-naphthol group, 2,2 ′ -Dihydroxy-6,6'-dimethylbiphenyl group, 4,4 ', 6,6'-te La -tert- butyl 2,2 'methylenedianiline phenoxy group, 4,4', 6,6'-tetramethyl-2,2'-isobutenyl dust Denji phenoxy group and the like.

Moreover, as group containing the said hetero atom, group represented by the following general formula [5] can also be illustrated.
R ³ ₃ P = N− [5]
(Wherein R ³ represents a hydrogen atom, a halogen atom or a hydrocarbon group in each case, and they may be the same or different from each other, and two or more of them may be bonded to each other; A ring may be formed.)

Specific examples of R ³ in the general formula [5] 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, but are not limited to, 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、Ｒ⁴ はそれぞれの場合に水素原子、ハロゲン原子、炭化水素基、ハロゲン化炭化水素基、炭化水素オキシ基、シリル基またはアミノ基を表し、それらは互いに同じであっても異なっていても良く、それら２つ以上が互いに結合していても良く、環を形成していても良い。） Further, examples of the group containing a hetero atom include a group represented by the following general formula [6].

(Wherein R ⁴ represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon oxy group, a silyl group or an amino group in each case, and they may be the same or different from each other. Or two or more of them may be bonded to each other and may form a ring.)

Specific examples of R ⁴ in the general formula [6] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, phenyl group, 1-naphthyl group, 2-naphthyl group, 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, pentafluorophenyl group, etc., but are not limited thereto is not.

  The chelating ligand refers to a ligand having a plurality of coordination sites. Specifically, acetylacetonate, diimine, oxazoline, bisoxazoline, terpyridine, acylhydrazone, diethylenetriamine, triethylenetetramine, Porphyrin, crown ether, cryptate and the like can be mentioned.

  Specific examples of the heterocyclic group include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, preferably a pyridyl group.

A group having a cyclopentadiene type anion skeleton, a group having a cyclopentadiene type anion skeleton and a group containing a hetero atom, or a group containing a hetero atom may be directly connected to each other, such as a carbon atom, silicon It may be linked via a residue containing an atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. Such a residue is preferably a divalent residue in which the atoms bonded to two L ² are a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, and more preferably 2 one of L ² and the atoms connecting the carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, the minimum number of atoms between the atoms connecting the two L ² is a divalent of 3 or less Residue (this includes the case where there is a single atom bound to two L ² ). Specifically, alkylene groups such as methylene group, ethylene group and propylene group, substituted alkylene groups such as dimethylmethylene group (isopropylidene group) and diphenylmethylene group, or silylene group, dimethylsilylene group, diethylsilylene group and diphenylsilylene. Group, a substituted silylene group such as tetramethyldisilylene group and dimethoxysilylene group, or a hetero atom such as nitrogen atom, oxygen atom, sulfur atom and phosphorus atom, particularly preferably a methylene group, an ethylene group and a dimethylmethylene group. (Isopropylidene group), diphenylmethylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group or dimethoxysilylene group.

X ¹ in the general formula [4] is a halogen atom, a hydrocarbon group (excluding 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. The hydrocarbon group here does not include a group having a cyclopentadiene type anion skeleton. Examples of the hydrocarbon group include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Preferably, the alkyl group has 1 to 20 carbon atoms, the aralkyl group has 7 to 20 carbon atoms, and the number of carbon atoms. An aryl group having 6 to 20 carbon atoms or an alkenyl group having 3 to 20 carbon atoms is preferable.

Examples of the alkyl group having 1 to 20 carbon atoms include 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, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group, etc. are mentioned, more preferably methyl group, ethyl group, isopropyl Group, tert-butyl group, isobutyl group or amyl group.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 1 to 10 carbon atoms 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, Examples thereof include a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group.
Any of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

Examples of the aralkyl group having 7 to 20 carbon atoms 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, etc. More preferred is a benzyl group.
These aralkyl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, and 2,5-xylyl group. 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-trimethyl Phenyl 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-butyl group Nyl 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 More preferred is a phenyl group.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or aralkyloxy groups such as benzyloxy group Etc. may be partially substituted.

  Examples of the alkenyl group having 3 to 20 carbon atoms include an allyl group, a methallyl group, a crotyl group, a 1,3-diphenyl-2-propenyl group, and more preferably an allyl group or a methallyl group.

  The hydrocarbon oxy group herein includes an alkoxy group, an aralkyloxy group, an aryloxy group, and the like, and preferably an alkoxy group having 1 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, or carbon. An aryloxy group having 6 to 20 atoms is preferred.

Examples of the alkoxy group having 1 to 20 carbon atoms 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. , N-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group, etc., more preferably methoxy group, ethoxy group, isopropoxy group, or tert-butoxy group. .
These alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

Examples of the aralkyloxy group having 7 to 20 carbon atoms include 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) Phenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) Methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy Group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like. More preferably, it is a benzyloxy group.
These aralkyloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, and 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-trimethyl Phenoxy 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-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, Anthracenoxy group etc. are mentioned.
These aryloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

X ¹ is more preferably chlorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, trifluoro Methoxy group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4- A pentafluorophenylphenoxy group or a benzyl group.

In the general formula [4], 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 ¹ . When M ¹ is a titanium atom, a zirconium atom or a hafnium atom, a is preferably 2, and b is also preferably 2.

  Among the transition metal compounds represented by the general formula [4], specific examples of the compound in which the transition metal atom is a titanium atom, a zirconium atom or a hafnium atom include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclohexane). Pentadienyl) titanium dichloride, bis (ethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, bis (1,2- Dimethylcyclopentadienyl) titanium dichloride, bis (1,3-dimethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-ethyl) Cyclopentadienyl) titanium Chloride, bis (1-methyl-2-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-isopropylcyclo) Pentadienyl) titanium dichloride, bis (1-methyl-3-isopropylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-2-methylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl) -3-methylcyclopentadienyl) titanium dichloride, bis (1,2,3-trimethylcyclopentadienyl) titanium dichloride, bis (1,2,4-trimethylcyclopentadienyl) titanium dichloride, bis (tetramethyl) Cyclopentadienyl) titanium dichlor Id, bis (pentamethylcyclopentadienyl) 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-phenylindene) Nil) titanium dichloride,

Dimethylsilylene bis (cyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-n- Butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4 -Dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3,4-dimethylcyclopentadienyl) Titanium dichloride, dimethylsilylene bis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,5-ethylmethylcyclo) Pentadienyl) 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,

Dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2-tert-butylindenyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylindenyl) titanium Dichloride, dimethylsilylenebis (2,4,7-trimethylindenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-isopropylindenyl) titanium dichloride, dimethylsilylenebis (4,5-benzindenyl) titanium dichloride, dimethyl Silylene bis (2-methyl-4,5-benzindenyl) titanium dichloride, dimethylsilylene bis (2-phenylindenyl) titanium dichloride, dimethylsilylene bis (4-phenyl) Indenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-5-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-naphthyl) Indenyl) titanium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (tetra Methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadiene) Enyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilyl (Indenyl) (fluorenyl) titanium dichloride, dimethylsilylenebis (fluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (fluorenyl) ) Titanium dichloride,

Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, 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-dimethyl) Phenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-tert-butylphenyl) thi Njikuroraido, indenyl (2,6-diisopropylphenyl) titanium dichloride, fluorenyl (2,6-diisopropylphenyl) titanium dichloride,

(Tert-Butylamide) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl- 1,2-ethanediyl titanium dichloride,
(Tert-Butylamide) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (phenylphosphide) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (tert- Butylamido) indenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) tetrahydroindenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyl titanium dichloride, (tert- Butylamido) indenyldimethylsilane titanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilane titanium dichloride (Tert- butylamido) fluorenyl dimethylsilane 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'-thiobis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-methylenebis (4-methyl-6-tert-butylphenoxy) ) Titanium dichloride, 2,2'-ethylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2, 2 ′-(4,4 ′, 6,6′-tetra-tert-butyl-1,1 ′ biphenol Shi) titanium dichloride, (di -tert- butyl-1,3-propane diamide) titanium dichloride, (dicyclohexyl-1,3-propane diamide) titanium dichloride,

[Bis (trimethylsilyl) -1,3-propanedidiamide] titanium dichloride, [bis (tert-butyldimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-dimethylphenyl) -1, 3-propanediamide] titanium dichloride, [bis (2,6-diisopropylphenyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-di-tert-butylphenyl) -1,3-propanediamide ] Titanium dichloride, [bis (triisopropylsilyl) naphthalenediamide] titanium dichloride, [bis (trimethylsilyl) naphthalenediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dichloride, [hydrotris (3 -Dimethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium trichloride, [tris (3 , 5-dimethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium trichloride, Compounds in which titanium is changed to zirconium or hafnium, dimethylsilylene is methylene, ethylene, dimethylmethylene (isopropylidene), diphenylmethylene, diethylsilylene, diphenylsilylene, or dimethoxysilylene Or dichloride, diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide, di (pentafluorophenoxide), or The compound changed to di (2,6-di-tert-butylphenoxide), trichloride, triethoxide, tri-n-propoxide, triisopropoxide, tri-n-butoxide, triisobutoxide, tri-tert- Examples thereof include compounds changed to butoxide, triphenoxide, tri (pentafluorophenoxide), or tri (2,6-di-tert-butylphenoxide).

  Further, among the transition metal compounds represented by the general formula [4], dimethylsilylene (cyclopentadienyl) (2-phenoxy) is a specific example of a compound in which the transition metal atom is a titanium atom, a zirconium atom or a hafnium atom. Titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopenta) Dienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) ) (3,5-di tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethyl) Silyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert- Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) ( , 5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (1-naphthoxy-2-yl) titanium Dichloride, etc., compounds in which titanium of these compounds is changed to zirconium or hafnium, cyclopentadienyl of these compounds is changed to methylcyclopentadienyl, n-butylcyclopentadienyl, tert-butylcyclopentadienyl, tetra Compound changed to methylcyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl, or fluorenyl, (2-phenoxy) to (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or Compound changed to (3-tert-butyldimethylsilyl-2-phenoxy), Compound changed from dimethylsilylene to methylene, ethylene, dimethylmethylene (isopropylidene), diphenylmethylene, diethylsilylene, diphenylsilylene, or dimethoxysilylene, dichloride Diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide, di (pentafluorophenoxide), or di (2,6-di A compound changed to -tert-butylphenoxide) can also be exemplified.

  Among the transition metal compounds represented by the general formula [4], specific examples of the compound in which the transition metal atom is a nickel atom include 2,2′-methylenebis [(4R) -4-phenyl-5,5′- Dimethyloxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diethyloxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5 '-Di-n-propyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diisopropyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4 -Phenyl-5,5'-dicyclohexyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R)- -Phenyl-5,5'-dimethoxyoxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diethoxyoxazoline] nickel dichloride, 2,2'-methylenebis [(4R ) -4-phenyl-5,5′-diphenyloxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (2-methylphenyl) oxazoline] nickel dichloride, 2 , 2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methylphenyl) oxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5- Di- (4-methylphenyl) oxazoline] nickel dichloride, 2,2'-methylenebis [(4R)- -Phenyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel Dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dichloride,

2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclobutane}] nickel dichloride, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1 '-Cyclopentane}] nickel dichloride, 2,2'-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1'-cyclohexane}] nickel dichloride, 2,2'-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cycloheptane}] nickel dichloride, and the enantiomers of the above compounds. Further, compounds in which the steric configuration of the asymmetric carbon of one oxazoline ring of the bisoxazoline type compound is reversed, or -4-phenyl of these compounds is replaced with -4-methyl, -4-isopropyl, -4- Compound changed to isobutyl, -4-tert-butyl or -4-benzyl, dichloride, diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide , Diphenoxide, di (pentafluorophenoxide), or a compound changed to di (2,6-di-tert-butylphenoxide).

  Further, specific examples of the nickel compound include [hydrotris (3,5-dimethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-diethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-di-tert- Butylpyrazolyl) borate] nickel chloride and chlorides of these compounds are ethoxide, n-propoxide, isopropoxide, n-butoxide, isobutoxide, tert-butoxide, phenoxide, pentafluorophenoxide, or 2,6-dioxide Examples thereof include compounds changed to -tert-butylphenoxide.

（式中、Ｒ⁵ とＲ⁶ はそれぞれ２，６−ジイソプロピルフェニル基であり、Ｒ⁷ およびＲ⁸ はそれぞれ水素原子またはメチル基あるいはＲ⁷ とＲ⁸ とがいっしょになってアセナフテン基であり、Ｘ² はフッ素原子、塩素原子、臭素原子、よう素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、フェニル基、ベンジル基、メトキシ基、エトキシ基、またはフェノキシ基である。）
また、上記のニッケル化合物において、ニッケルをパラジウム、コバルト、ロジウム、またはルテニウムに置き換えた化合物も同様に例示することができる。 Examples of the nickel compound include compounds represented by the following structural formula.

(Wherein R ⁵ and R ⁶ are each a 2,6-diisopropylphenyl group, R ⁷ and R ⁸ are each a hydrogen atom or a methyl group, or R ⁷ and R ⁸ together are an acenaphthene group, X ² is fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methoxy group, ethoxy group, or phenoxy group .)
In addition, in the above nickel compound, compounds in which nickel is replaced with palladium, cobalt, rhodium, or ruthenium can be exemplified as well.

Of the transition metal compounds represented by the general formula [4], specific examples of the compound in which the transition metal atom 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 and the like, and dichloride are converted into diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diiso Examples thereof include compounds changed to butoxide, di-tert-butoxide, diphenoxide, di (pentafluorophenoxide), or di (2,6-di-tert-butylphenoxide).

Furthermore, as a specific example of an iron compound,
[Hydrotris (3,5-dimethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-diethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron chloride, etc. The chlorides of these compounds were changed to ethoxide, n-propoxide, isopropoxide, n-butoxide, isobutoxide, tert-butoxide, phenoxide, pentafluorophenoxide, or 2,6-di-tert-butylphenoxide. A compound can be illustrated. In addition, in the above iron compound, a compound in which iron is replaced with cobalt or nickel can also be exemplified.

  Specific examples of the transition metal compound of the transition metal compound represented by the general formula [4] include μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], Μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2 -Phenoxy) titanium chloride], μ-oxobis [ Sopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], [Mu] -oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], [mu] -oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2 -Phenoxy) chita Chloride], and the like can be exemplified μ- Okisobisu [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride]. Also, change the chloride of these compounds to ethoxide, n-propoxide, isopropoxide, n-butoxide, isobutoxide, tert-butoxide, phenoxide, pentafluorophenoxide, or 2,6-di-tert-butylphenoxide. The compound etc. which were made can be illustrated.

  These transition metal compounds may be used alone or in combination of two or more.

Among the transition metal compounds exemplified above, the transition metal compound (B) used in the present invention is preferably a transition metal compound represented by the above general formula [4]. Among them, a transition metal compound in which M ¹ in the general formula [4] is a Group 4 atom is preferable, and in particular, a transition metal compound having at least one group having a cyclopentadiene-type anion skeleton as L ² in the general formula [4]. Is preferred.

(C) Organoaluminum compound As the organoaluminum 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 [7].
R ¹⁰ _c AlY _3-c [7]
(Wherein R ¹⁰ represents a hydrocarbon group, and all R ¹⁰ may be the same or different. Y represents a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group or an aryloxy group; All Y may be the same or different, and c represents a number satisfying 0 <c ≦ 3.)

R ¹⁰ in the general formula [7] representing the organoaluminum compound 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 methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, 2-methylhexyl group, n-octyl group and the like, preferably ethyl group, n -A butyl group, an isobutyl group, an n-hexyl group or an n-octyl group.

Specific examples when Y is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom.
The alkoxy group in Y is preferably an alkoxy group having 1 to 24 carbon atoms. Specific examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert. -Butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadexoxy group, n-icosoxy group, etc., preferably methoxy group, ethoxy group or tert group -Butoxy group.

  The aryloxy group in Y is preferably an aryloxy group having 6 to 24 carbon atoms. Specific examples thereof include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3 -Dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4 -Trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5 -Trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group N-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like.

  The aralkyloxy group in Y is preferably an aralkyloxy group having 7 to 24 carbon atoms. Specific examples include 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- Limethylphenyl) methoxy group, (3,4,5-trimethylphenyl) 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, preferably a benzyloxy group That.

  Specific examples of the organoaluminum compound represented by the general formula [7] include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri -Trialkylaluminum such as n-octylaluminum; Dialkylaluminum such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride Chloride: methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, n-butylaluminum Alkylaluminum dichlorides such as mudichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n- Dialkyl aluminum hydrides such as hexyl aluminum hydride; alkyl (dialkoxy) aluminum such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, methyl (di-tert-butoxy) aluminum; dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum Di, such as dimethyl (tert-butoxy) aluminum Alkyl (diaryloxy) aluminum such as methyl (diphenoxy) aluminum, methylbis (2,6-diisopropylphenoxy) aluminum, methylbis (2,6-diphenylphenoxy) aluminum; dimethyl (phenoxy) aluminum, dimethyl ( Examples include dialkyl (aryloxy) aluminum such as 2,6-diisopropylphenoxy) aluminum and dimethyl (2,6-diphenylphenoxy) aluminum.

Of these, trialkylaluminum is preferable, trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum is particularly preferable. Is triisobutylaluminum or tri-n-octylaluminum.
These organoaluminum compounds may be used alone or in combination of two or more.

The usage-amount of a component (B) is 1 * 10 < ^-6 > -1 * 10 < ^-3 > mol normally with respect to 1g of a component (A), Preferably it is 5 * 10 < ^-6 > -5 * 10 <^-4> mol. Moreover, the usage-amount of a component (C) is 0.01-10 as molar ratio (C) / (B) of the aluminum atom of a component (C) organoaluminum compound with respect to the transition metal atom of a component (B) transition metal compound. 000 is preferable, 0.1 to 5,000 is more preferable, and 1 to 2,000 is most preferable.

  As the addition polymerization catalyst of the present invention, a reaction product obtained by bringing the component (A) and the component (B), and optionally the component (C) into contact with each other in advance may be used. It may be used after being put in. When the components (A), (B) and (C) are used, any two of them may be contacted in advance, and then the other component may be contacted.

  The method of supplying each catalyst component to the catalyst preparation reactor or the polymerization reactor is not particularly limited. A method of supplying each component in a solid state, a method of supplying a solution dissolved in a hydrocarbon solvent from which components for deactivating catalyst components such as moisture and oxygen are sufficiently removed, or a method of supplying in a suspended or slurry state Etc. Examples of the solvent at this time include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbon solvents such as benzene and toluene, and halogenated hydrocarbons such as methylene chloride. Hydrocarbons or aromatic hydrocarbons are preferred.

  When supplying each catalyst component in a solution state or in a suspended or slurried state, the concentration of the component (A) is usually 0.01 to 1000 g / liter, preferably 0.1 to 500 g / liter. The concentration of the component (C) is usually 0.0001 to 100 mol / liter, preferably 0.01 to 10 mol / liter in terms of Al atoms. The concentration of the component (B) is usually 0.0001 to 1000 mmol / liter, preferably 0.01 to 50 mmol / liter in terms of transition metal atoms.

  The polymerization method is not particularly limited, and gas phase polymerization in a gaseous monomer, solution polymerization using a solvent, slurry polymerization, and the like are possible. Solvents used for solution polymerization or slurry polymerization include aliphatic hydrocarbon solvents such as butane, hexane, pentane, heptane and octane, aromatic hydrocarbon solvents such as benzene and toluene, and halogenated hydrocarbon solvents such as methylene chloride. It is also possible to use olefin itself as a solvent (bulk polymerization). The polymerization method may be either batch polymerization or continuous polymerization, and the polymerization may be performed in two or more stages with different reaction conditions. In general, the polymerization time is appropriately determined depending on the kind of the target olefin polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours.

The method for producing an addition polymer of the present invention is a method for producing an addition polymer in which addition-polymerizable monomers are subjected to addition polymerization in the presence of the aforementioned catalyst for addition polymerization of the present invention.
Examples of the monomer used for polymerization include olefins having 2 to 20 carbon atoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, polar monomers, and the like, 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, norbornadiene, 5 -Methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, , 3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene, and other diolefins; norbornene, 5-methyl-2-norbornene, 5- Ethyl-2-norbornene, 5-butyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2-norbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, penta Cyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-ethoxycarbonyl- 2-norbornene, 5-methyl-5-methyl Cyclic olefins such as xyloxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; styrene, 2 -Alkenylbenzene such as phenylpropylene, 2-phenylbutene, 3-phenylpropylene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, α- Methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, 1,1-diphenylethylene, p-th Alkyls such as tertiary butyl styrene and p-secondary butyl styrene Alkenyl aromatic hydrocarbons such as bisalkenylbenzene such as len and divinylbenzene, alkenylnaphthalene such as 1-vinylnaphthalene; acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2, 2,1) α, β-unsaturated carboxylic acid such as 5-heptene-2,3-dicarboxylic acid, and metal salts thereof such as sodium, potassium, lithium, zinc, magnesium, calcium, methyl acrylate, acrylic acid Ethyl, n-propyl acrylate, isopropyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid Α, β- such as isobutyl Unsaturated carboxylic acid esters, unsaturated dicarboxylic acids such as maleic acid, itaconic acid, vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, Examples thereof include polar monomers such as unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate.

  The present invention is applied to homopolymerization or copolymerization of these monomers. Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, propylene and 1-butene, ethylene and propylene and butene, ethylene and propylene. And 1-hexene are exemplified, but the present invention should not be limited to these.

  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 particularly preferably a copolymer of ethylene and an α-olefin, and among them, a copolymer of ethylene and an α-olefin having a polyethylene crystal structure is preferable. The α-olefin herein is preferably an α-olefin having 3 to 8 carbon atoms, and specific examples include 1-butene, 1-hexene, 1-octene and the like.

  Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these. The measured value of each item in an Example was measured with the following method.

(1) The content of repeating units derived from α-olefin in the copolymer is a calibration curve from the characteristic absorption of ethylene and α-olefin using an infrared spectrophotometer (FT-IR7300, manufactured by JASCO Corporation). And expressed as the number of short chain branches per 1000 carbon atoms (SCB).

(2) Melt flow rate = MFR: Melt flow rate value measured at 190 ° C. under a load of 21.18 N (2.16 kg) in accordance with the method defined in JIS K7210-1995 (unit: g / 10 minutes) .
For the measurement of the melt flow rate, a polymer containing 1000 ppm of an antioxidant in advance was used.

[Example 1]
(1)
A 200 ml four-necked flask purged with nitrogen was charged with 97.0 ml of toluene and 2.7 ml (20.0 mmol) of triethylaluminum and cooled to 5 ° C. To this, 2.8 ml (26.6 mmol) of 1,1,1,3,3,3-hexafluoro-2-propanol was added dropwise over 1.5 hours. After completion of dropping, the mixture was stirred at 5 ° C. for 1.5 hours. Then, it heated at 40 degreeC and stirred for 2 hours. Then, it was left overnight. Then, it cooled to 5 degreeC. To this, 0.35 ml (19.5 mmol) of H ₂ O was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 5 ° C for 1.5 hours, at 40 ° C for 2 hours, and at 80 ° C for 2 hours. A dark green slurry solution was obtained. (From the amount charged, the concentration in terms of Al atom is 0.2 mol / l)

(2) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer having an internal volume of 3 liters substituted with argon was evacuated, charged with 1000 ml of toluene and 30 g of 1-butene, and heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 0.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0 mol% and 1-butene = 6.71 mol%. To this, 0.9 ml of a hexane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 0.25 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide adjusted to a concentration of 2 μmol / ml was added, and then the slurry solution obtained in Example 1 (1) above. 0 ml was charged. Polymerization was carried out at 70 ° C. for 40 minutes while feeding ethylene gas so as to keep the total pressure constant. Then, after deashing and washing with a hydrochloric acid / methanol solution, drying under reduced pressure was performed to obtain 86 g of an olefin polymer. The polymerization activity per zirconium atom was 2.6 × 10 ⁸ g / molZr / hour, and the obtained olefin polymer had SCB = 23.5 and MFR = 2.4.

[Comparative Example 1]
Instead of the slurry solution obtained in Example 1 (1), 2.0 ml of a toluene solution (0.2 mol / l) of PMAO manufactured by Tosoh Finechem was used, and the gas composition in the system by gas chromatography analysis. However, polymerization was performed in the same manner as in Example 1 (2) except that hydrogen was 0 mol% and 1-butene was 8.18 mol%.
As a result, 39 g of an olefin polymer was obtained. The polymerization activity per zirconium atom was 1.2 × 10 ⁸ g / molZr / hour, and the obtained olefin polymer had SCB = 16.1 and MFR = 5.6.

[Comparative Example 2]
(1)
A 200-ml four-necked flask purged with nitrogen was charged with 90.0 ml of toluene and 10.0 ml (20.0 mmol) of a toluene solution of trimethylaluminum (2.00 mol / liter) and cooled to 5 ° C. To this, 0.35 ml (19.5 mmol) of H ₂ O was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 5 ° C for 1.5 hours, at 40 ° C for 2 hours, and at 80 ° C for 2 hours. A weak white slurry solution was obtained. (From the amount charged, the concentration in terms of Al atom is 0.2 mol / l)

(2) Polymerization Instead of the slurry solution obtained in Example 1 (1), 2.0 ml of the slurry solution obtained in Comparative Example 2 (1) was used, and the system was analyzed by gas chromatography analysis. Polymerization was carried out in the same manner as in Example 1 (2) except that the gas composition was hydrogen = 0 mol% and 1-butene = 7.31 mol%.
As a result, 53 g of an olefin polymer was obtained. The polymerization activity per zirconium atom was 1.6 × 10 ⁸ g / molZr / hour, and the obtained olefin polymer had SCB = 15.7 and MFR = 4.8.

[Reference Example 1]
(1)
Except that the amount of toluene initially charged was changed to 97.0 ml, and 2.7 ml (20 mmol) of triethylaluminum was used instead of 10.0 ml of a toluene solution of trimethylaluminum (2.00 mol / liter), Synthesis was performed in the same manner as in Comparative Example 2 (1).

(2) Polymerization Instead of the slurry solution obtained in Example 1 (1), 2.0 ml of the slurry solution obtained in Reference Example 1 (1) was used, and the system was analyzed by gas chromatography analysis. Polymerization was carried out in the same manner as in Example 1 (2) except that the gas composition was hydrogen = 0 mol% and 1-butene = 8.20 mol%.
As a result, 26 g of an olefin polymer was obtained. The polymerization activity per zirconium atom was 8.1 × 10 ⁷ g / molZr / hour, and the obtained olefin polymer had SCB = 14.8 and MFR = 5.0.

As described above in detail, according to the present invention, a high-performance compound using an ethylaluminum compound as a raw material, a catalyst component for addition polymerization, a catalyst for addition polymerization, and an efficient addition polymer using the catalyst for addition polymerization A method is provided. According to the present invention, the industrial utility value of the present invention is very large, such as the provision of a compound using a cheap compound such as triethylaluminum as a promoter component used for a single site catalyst.

Claims (10)

A compound obtained by contacting the following (a), the following (b), and the following (c).
(A): Compound represented by the following general formula [1] EtAlL ¹ ₂ [1]
(B): Compound represented by the following general formula [2] R ¹ _t-1 TH [2]
(C): Compound represented by the following general formula [3] R ² _t-2 TH ₂ [3]
(In the general formulas [1] to [3], Et represents an ethyl group, L ¹ represents a hydrogen atom, a hydrocarbon group having 2 or more carbon atoms, or a halogen atom, and L ¹ is the same as each other. It may even be different .R ¹ is a group containing an electron withdrawing group or an electron withdrawing group, if R ¹ there are a plurality may be different even they the same as each other .R ² Represents a hydrocarbon group or a halogenated hydrocarbon group, T independently represents a non-metal atom of Group 15 or Group 16 of the periodic table, and t represents a number corresponding to the valence of T of each compound. Represents.)   2. The compound according to claim 1, wherein the compound represented by the general formula [1] is triethylaluminum. The manufacturing method of the compound which makes following (a), following (b), and following (c) contact.
(A): Compound represented by the following general formula [1] EtAlL ¹ ₂ [1]
(B): Compound represented by the following general formula [2] R ¹ _t-1 TH [2]
(C): Compound represented by the following general formula [3] R ² _t-2 TH ₂ [3]
(In the general formulas [1] to [3], Et represents an ethyl group, L ¹ represents a hydrogen atom, a hydrocarbon group having 2 or more carbon atoms, or a halogen atom, and L ¹ is the same as each other. It may even be different .R ¹ is a group containing an electron withdrawing group or an electron withdrawing group, if R ¹ there are a plurality may be different even they the same as each other .R ² Represents a hydrocarbon group or a halogenated hydrocarbon group, T independently represents a non-metal atom of Group 15 or Group 16 of the periodic table, and t represents a number corresponding to the valence of T of each compound. Represents.)   A catalyst component for addition polymerization comprising the compound according to claim 1 or 2.   A catalyst for addition polymerization obtained by contacting the compound (A) according to claim 1 or 2 and the transition metal compound (B).   A catalyst for addition polymerization obtained by contacting the compound (A) according to claim 1 or 2, the transition metal compound (B), and the organoaluminum compound (C).   The catalyst for addition polymerization according to claim 5 or 6, wherein the transition metal compound (B) is a transition metal compound having at least one group having a cyclopentadiene-type anion skeleton.   The manufacturing method of the addition polymer using the catalyst for addition polymerization in any one of Claims 5-7.   The method for producing an addition polymer according to claim 8, wherein the addition polymer is an olefin polymer. The method for producing an addition polymer according to claim 8, wherein the addition polymer is a copolymer of ethylene and an α-olefin.