JP2004244629A - Metallic compound, catalytic component for addition polymerization, catalyst for addition polymerization and method for producing addition polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metallic compound applicable as a catalyst component excellent in polymerization activity and for addition polymerization, a catalytic component for addition polymerization and a catalyst excellent in polymerization activity and for addition polymerization, and to provide a method for efficiently producing addition polymers. <P>SOLUTION: The compound is obtained by contacting M<SP>1</SP>L<SP>1</SP><SB>r</SB>(a), R<SP>1</SP><SB>s-1</SB>TH (b), and R<SP>2</SP><SB>4-n</SB>J(OH)<SB>n</SB>(c), wherein the contact treatment amount of the component (b) is 0.1-8 mol per 1 mol component (a), the contact treatment amount of the component (c) is 0.5-8 mol per 1 mol component (a). (M<SP>1</SP>is a group (12-15) metal or B; r is a number corresponding to the valence of M<SP>1</SP>; L<SP>1</SP>is H, a halogen, a hydrocarbon or a hydrocarbonoxy, T is a group 15 or 16 nonmetal; s is a number corresponding to the valence of T; R<SP>1</SP>is an electron-withdrawing group or a group containing an electron-withdrawing group; n is a number of ≥2 but ≤4; J is a group 14 nonmetal; R<SP>2</SP>is a hydrocarbon.). <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

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

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

JP-A-58-19309 Japanese Unexamined Patent Publication No. Hei 1-502036 JP 2001-181327 A

However, when the addition polymerization of olefins was carried out using the above catalyst, the polymerization activity was not sufficiently satisfactory.
Under such circumstances, the problem to be solved by the present invention is a metal compound used as a component of an addition polymerization catalyst having excellent polymerization activity and a catalyst component for addition polymerization, an addition polymerization catalyst having excellent polymerization activity, and an efficient It is an object of the present invention to provide a method for producing a novel addition polymer.

That is, the first of the present invention is a compound obtained by bringing the following components (a) to (c) into contact with each other, and the contact treatment amount of the component (b) per 1 mol of the component (a) is 0.1 to 8: Mole of the compound, wherein the amount of the component (c) to be treated is 0.5 to 8 moles per mole of the component (a).
(A): a compound represented by the following general formula [1]: M ¹ L ¹ _r [1]
(B): a compound represented by the following general formula [2] R ¹ _s-1 TH [2]
(C): a compound represented by the following general formula [3] R ² _4-n J (OH) _n [3]
(In the above general formulas [1] to [3], M ¹ represents a metal atom or a boron atom belonging to Groups 12 to 15 of the periodic table of elements, r represents a number corresponding to the valency of M ¹ , L ¹ represents a hydrogen atom, a halogen atom, the period of the hydrocarbon represents a hydrogen group or a hydrocarbon oxy group, a plurality of L ¹ if L ¹ there are a plurality or different be the same as each other, T is an element A non-metallic atom of Group 15 or 16 of the Table, s represents a number corresponding to the valence of T, R ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group, ^When there are a plurality of ¹ 's, a plurality of R ^1's may be the same or different from each other, n represents a number of 2 or more and 4 or less, and J is a non-metallic atom of Group 14 of the periodic table of the element. the stands, R ² represents a hydrocarbon group, a plurality of R ² if R ² there are a plurality of mutually identical Or different.)
The second aspect of the present invention relates to a catalyst component for addition polymerization comprising the above compound.
The third aspect of the present invention relates to a catalyst for addition polymerization using the above compound.
The fourth aspect of the present invention relates to a method for producing an addition polymer using the above addition polymerization catalyst.

  According to the present invention, a metal compound and a catalyst component for addition polymerization used as components of an addition polymerization catalyst having excellent polymerization activity, an addition polymerization catalyst having excellent polymerization activity, and a method for efficiently producing an addition polymer are provided. You.

The component (a) of the present invention is a compound represented by the following general formula [1].
M ¹ L ¹ _r [1]
M ¹ is a metal atom or a boron atom belonging to Groups 12 to 15 of the periodic table of the elements. Specific examples include zinc, cadmium, mercury, aluminum, gallium, indium, thallium, germanium, tin, lead, antimony, bismuth, and boron. M ¹ is preferably a zinc atom, an aluminum atom, a gallium atom, an indium atom, a thallium atom, an antimony atom or a bismuth atom, and more preferably an aluminum atom or a bismuth atom. r represents a number corresponding to the valency of M ¹ and is an integer of 2 to 5, preferably 3.

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

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

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

The alkyl group used in L ^1, an alkyl group having 1 to 20 carbon atoms are preferred, more preferably a methyl group, an ethyl group, an isopropyl group, n- butyl group, tert- butyl group, or isobutyl group.

Examples of the aryl group used for L ¹ include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3 , 5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl Group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group, etc. Is mentioned.
All of these aryl groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

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

Examples of the aralkyl group used for L ¹ include a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) methyl group, a (4-methylphenyl) methyl group, and a (2,3-dimethylphenyl) methyl Group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3,5 -Dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4 , 5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6 (Tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) ) Methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n -Hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group and the like.
All of these aralkyl groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

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

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

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

Examples of the aryloxy group used for L ¹ include a phenoxy group, a 2-tolyloxy group, a 3-tolyloxy group, a 4-tolyloxy group, a 2,3-xylyloxy group, a 2,4-xylyloxy group, and a 2,5-xylyloxy group 2,6-xylyloxy group, 3,4-xylyloxy group, 3,5-xylyloxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy Group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2, 3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropyl Phenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, isobutylphenoxy group, n-pentylphenoxy group, neopentylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n- Examples include a decylphenoxy group, an n-dodecylphenoxy group, an n-tetradecylphenoxy group, a naphthyloxy group, an anthracenyloxy group and the like.
Each of these aryloxy groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group; It may be substituted with a group or the like.

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

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

Specific examples of the compound (a) when M ¹ is a bismuth atom include bismuth (III) halides such as bismuth (III) fluoride, bismuth (III) chloride, bismuth (III) bromide, and bismuth (III) iodine. Trialkyl bismuth such as trimethyl bismuth; triaryl bismuth such as triphenyl bismuth; trimethoxy bismuth, triethoxy bismuth, triisopropoxy bismuth, tri (tert-butoxy) bismuth, triisobutoxy bismuth, trineopentyloxy bismuth; Trialkoxybismuth such as tri (tert-pentyloxy) bismuth; triphenoxybismuth, tri (2-tolyloxy) bismuth, tri (3-tolyloxy) bismuth, tri (4-tolyloxy) bismuth, tri (2,3-xylyloxy) ) Bismuth, tri (2,4-xylyloxy) bismuth, tri (2,5-xylyloxy) bismuth, tri (2,6-xylyloxy) bismuth, tri (3,4-xylyloxy) bismuth, tri (3,5-xylyloxy) ) Bismuth, tri (2,3,4-trimethylphenoxy) bismuth, tri (2,3,5-trimethylphenoxy) bismuth, tri (2,3,6-trimethylphenoxy) bismuth, tri (2,4,6- Trimethylphenoxy) bismuth, tri (3,4,5-trimethylphenoxy) bismuth, tri (2,3,4,5-tetramethylphenoxy) bismuth, tri (2,3,4,6-tetramethylphenoxy) bismuth Tri (2,3,5,6-tetramethylphenoxy) bismuth, tri (pentamethylphenoxy) bismuth Tris (ethylphenoxy) bismuth, tri (n-propylphenoxy) bismuth, tri (isopropylphenoxy) bismuth, tri (n-butylphenoxy) bismuth, tri (sec-butylphenoxy) bismuth, tri (tert-butylphenoxy) Bismuth, tri (isobutylphenoxy) bismuth, tri (n-pentylphenoxy) bismuth, tri (neopentylphenoxy) bismuth, tri (n-hexylphenoxy) bismuth, tri (n-octylphenoxy) bismuth, tri (n-decylphenoxy) ) Triaryloxybismuth such as bismuth, tri (n-dodecylphenoxy) bismuth, tri (n-tetradecylphenoxy) bismuth, trinaphthyloxybismuth, and trianthracenyloxybismuth; bismuth (V Bismuth (V) halides such as fluoride, bismuth (V) chloride, bismuth (V) bromide and bismuth (V) iodine; pentaalkyl bismuth such as pentamethyl bismuth; pentaaryl bismuth such as pentaphenyl bismuth; pentamethoxy bismuth; Pentaalkoxybismuth such as pentaethoxybismuth; and pentaaryloxybismuth such as pentaphenoxybismuth.

Specific examples of the compound (a) when M ¹ is an aluminum atom include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n -Trialkylaluminums such as octylaluminum; triarylaluminums such as triphenylaluminum, trinaphthylaluminum, tri (pentafluorophenyl) aluminum; trialkenylaluminums such as triallylaluminum; tri (cyclopentadienyl) aluminum; dimethylaluminum Chloride, diethylaluminum chloride, dipropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum Chloride, di-n-hexylaluminum chloride, diethylaluminum bromide, dipropylaluminum bromide, di-n-butylaluminum bromide, diisobutylaluminum bromide, di-n-hexylaluminum bromide, diethylaluminum iodide, dipropylaluminum iodide, Examples thereof include aluminum halides such as dialkylaluminum halides such as di-n-butylaluminum iodide, diisobutylaluminum iodide, and di-n-hexylaluminum iodide.

  Component (a) is preferably bismuth (III) halide, trialkylbismuth, triarylbismuth, trialkoxybismuth, triaryloxybismuth, or trialkylaluminum, and more preferably bismuth (III) halide, triaryl Bismuth, trialkoxybismuth, triaryloxybismuth, or trialkylaluminum, particularly preferably triarylbismuth or trialkylaluminum, and most preferably triphenylbismuth, trimethylaluminum, triethylaluminum, triisobutylaluminum, triisobutylaluminum, -N-hexyl aluminum or tri-n-octyl aluminum.

The component (b) of the present invention is a compound represented by the following general formula [2].
R ¹ _s-1 TH [2]
T represents a non-metallic atom of Group 15 or 16 of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989). Specific examples of the Group 15 non-metallic atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 non-metallic atom include an oxygen atom and a sulfur atom. T is preferably a nitrogen atom or an oxygen atom, and particularly preferably an oxygen atom.

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

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

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

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

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

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

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

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

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

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

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

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

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

  Specific examples of the compound (b) represented by the general formula [2] include, as amines, 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-triiodoethyl) 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-pentaiodo) Propyl) 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-tri Fluoroethyl) 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-fluoro Phenyl) 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-difluoro Phenyl) amine, bis (2,6-dichlorophenyl) amine, bis (3,5-dichlorophenyl) amine, Bis (2,6-dibromophenyl) amine, bis (3,5-dibromophenyl) amine, bis (2,6-diiodophenyl) amine, bis (3,5-diiodophenyl) amine, bis (2 4,6-trifluorophenyl) amine, bis (2,4,6-trichlorophenyl) amine, bis (2,4,6-tribromophenyl) amine, bis (2,4,6-triiodophenyl) amine , Bis (pentafluorophenyl) amine, bis (pentachlorophenyl) amine, bis (pentabromophenyl) amine, bis (pentaiodophenyl) amine, bis (2- (trifluoromethyl) phenyl) amine, bis (3- ( Trifluoromethyl) phenyl) amine, bis (4- (trifluoromethyl) phenyl) amine, bis (2,6-di (trifluoro (Romethyl) phenyl) amine, bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-tri (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 and the like.

  Examples of the phosphines as specific examples of the component (b) include compounds in which the nitrogen atom in the specific examples of the above amines is substituted with a phosphorus atom, that is, compounds in which the amine of the above compound name of the amines is replaced with phosphine. Can be

  Examples of alcohols include fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodmethanol, trifluoromethanol, trichloromethanol, tribromomethanol, triiodmethanol, 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 B-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-periodopen 1H, 1H-perfluoropentanol, 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 Octanol, 1H, 1H-perbromooctanol, 1H, 1H-periodooctanol and the like can be mentioned.

  Specific examples of component (b) include thiols, such as the above-mentioned specific examples of alcohols, in which an oxygen atom is replaced with a sulfur atom. For example, methanol, which is the compound name of the above-mentioned alcohols, is methanethiol, and ethanol is ethanethiol. Examples thereof include compounds represented by rewriting propanol to propanethiol.

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

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

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

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

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

  More preferably, component (b) is bis (trifluoromethyl) amine, bis (pentafluorophenyl) amine, trifluoromethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 1,1,3,3,3-hexafluoro-2- (trifluoromethyl) -2-propanol, 4-fluorophenol, 2,6-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; Preferably, 3,4,5-trifluorophenol, pentafluorophenol, 1,1,1,3 3,3-hexafluoro-2-propanol, or 1,1,1,3,3,3-hexafluoro-2- (trifluoromethyl) -2-propanol.

The component (c) of the present invention is a compound represented by the following general formula [3].
R ² _4-n J (OH) _n [3]
J represents a non-metallic atom of Group 14 of the Periodic Table of the Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition, 1989). Specific examples of Group 14 non-metallic atoms are carbon and silicon. J is preferably a silicon atom.

  In the above general formula [3], n is a number of 2 or more and 4 or less, preferably n is 2 or 3, and more preferably 2.

R ² in the general formula [3] represents a hydrocarbon group, and when a plurality of R ² are present, the plurality of R ² may be the same or different. Examples of the hydrocarbon group for R ² include the hydrocarbon groups described as L ^{1 in the} general formula [1] and the halogenated hydrocarbons described as R ^{1 in the} general formula [2]. Is an alkyl group or an aryl group, more preferably an aryl group, and still more preferably a phenyl group.

  Specific examples of the component (c) represented by the general formula [3] include dimethylsilanediol, diethylsilanediol, di (n-propyl) silanediol, diisopropylsilanediol, di (n-butyl) silanediol, Di (sec-butyl) silanediol, di (tert-butyl) silanediol, diisobutylsilanediol, di (n-pentyl) silanediol, dineopentyl) silanediol, di (n-hexyl) silanediol, di (n-heptyl) ) Silanediol, di (n-octyl) silanediol, di (n-decyl) silanediol, di (n-dodecyl) silanediol, di (n-pentadecyl) silanediol, di (n-eicosyl) silanediol,

Diphenylsilanediol, di (2-tolyl) silanediol, di (3-tolyl) silanediol, di (4-tolyl) silanediol, di (2,3-xylyl) silanediol, di (2,4-xylyl) Silanediol, di (2,5-xylyl) silanediol, di (2,6-xylyl) silanediol, di (3,4-xylyl) silanediol, di (3,5-xylyl) silanediol, di (2 , 3,4-trimethylphenyl) silanediol, di (2,3,5-trimethylphenyl) silanediol, di (2,3,6-trimethylphenyl) silanediol, di (2,4,6-trimethylphenyl) Silanediol, di (3,4,5-trimethylphenyl) silanediol, di (2,3,4,5-tetramethylphenyl) silanediol Di (2,3,4,6-tetramethylphenyl) silanediol, di (2,3,5,6-tetramethylphenyl) silanediol, di (pentamethylphenyl) silanediol, di (ethylphenyl) silanediol Di (n-propylphenyl) silanediol, di (isopropylphenyl) silanediol, di (n-butylphenyl) silanediol, di (sec-butylphenyl) silanediol, di (tert-butylphenyl) silanediol, (Isobutylphenyl) silanediol, di (n-pentylphenyl) silanediol, di (neopentylphenyl) silanediol, di (n-hexylphenyl) silanediol, di (n-octylphenyl) silanediol, di (n- Decylphenyl) silanediol, di (n- Decyl phenyl) silane diol, di (n- tetradecyl phenyl) silane diol, dinaphthyl silane diol, Jian tiger Se sulfonyl silane diol,

Methylsilanetriol, ethylsilanetriol, n-propylsilanetriol, isopropylsilanetriol, n-butylsilanetriol, sec-butylsilanetriol, tert-butylsilanetriol, isobutylsilanetriol, n-pentylsilanetriol, neopentylsilanetriol N-hexylsilanetriol, n-heptylsilanetriol, n-octylsilanetriol, n-decylsilanetriol, n-dodecylsilanetriol, n-pentadecylsilanetriol, n-eicosylsilanetriol,

Phenylsilanetriol, 2-tolylsilanetriol, 3-tolylsilanetriol, 4-tolylsilanetriol, 2,3-xylylsilanetriol, 2,4-xylylsilanetriol, 2,5-xylylsilanetriol, 2 2,6-xylylsilanetriol, 3,4-xylylsilanetriol, 3,5-xylylsilanetriol, 2,3,4-trimethylphenylsilanetriol, 2,3,5-trimethylphenylsilanetriol, 2, 3,6-trimethylphenylsilanetriol, 2,4,6-trimethylphenylsilanetriol, 3,4,5-trimethylphenylsilanetriol, 2,3,4,5-tetramethylphenylsilanetriol, 2,3,4 , 6-tetramethylphenylsilanetriol, 2, , 5,6-tetramethylphenylsilanetriol, pentamethylphenylsilanetriol, ethylphenylsilanetriol, n-propylphenylsilanetriol, isopropylphenylsilanetriol, n-butylphenylsilanetriol, sec-butylphenylsilanetriol, tert- Butylphenylsilanetriol, isobutylphenylsilanetriol, n-pentylphenylsilanetriol, neopentylphenylsilanetriol, n-hexylphenylsilanetriol, n-octylphenylsilanetriol, n-decylphenylsilanetriol, n-dodecylphenylsilanetriol , N-tetradecylphenylsilanetriol, naphthylsilanetriol, anthracenylsilanet Ol, tetrahydroxy silane, such as pentafluorophenyl silane triol or di (pentafluorophenyl) silane diol, and the like.

  Component (c) is preferably dimethylsilanediol, diethylsilanediol, diisopropylsilanediol, di (tert-butyl) silanediol, diphenylsilanediol, di (2-tolyl) silanediol, or di (3-tolyl) silanediol. , Di (4-tolyl) silanediol, di (2,4,6-trimethylphenyl) silanediol, tetrahydroxysilane, pentafluorophenylsilanetriol, or di (pentafluorophenyl) silanediol, most preferably Diphenylsilanediol.

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

  The contact treatment of the above components (a) to (c) is preferably performed in an inert gas atmosphere. The contact treatment temperature is generally -100 to 300C, preferably -80 to 200C, and more preferably 0 to 150C. The contact treatment time is generally 1 minute to 200 hours, preferably 10 minutes to 100 hours. In such a contact treatment, a solvent may be used, or the components (a) to (c) may be directly contacted without using a solvent. The solvent used is a non-polar solvent such as an aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent which is inert to the components (a) to (c), or a polar solvent such as a halide solvent or an ether solvent. Any of them can be used, and specific examples include butane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane, benzene, toluene, xylene, dichloromethane, difluoromethane, chloroform, and 1,2- Dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, di-n -Butyl ether, methyl tert-butyl acrylate Le, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, tetrahydrofuran, tetrahydropyran and the like.

  As the contact treatment amount ratio of the components (a) to (c), assuming that the molar ratio of the contact treatment amount of each component is component (a): component (b): component (c) = 1: y: z, y Is 0.1 to 8, preferably 1 to 6, more preferably 2 to 4, and still more preferably 2.5 to 3.5. z is from 0.5 to 8, preferably from 0.6 to 6, more preferably from 0.7 to 4, and even more preferably from 0.8 to 1.2.

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

  Specific examples of the method for producing the compound (A) of the present invention will be further described with reference to the case where the component (a) is triphenylbismuth, the component (b) is pentafluorophenol, and the component (c) is diphenylsilanediol. Details are shown below. To a solution of triphenylbismuth in toluene was added dropwise pentafluorophenol in a molar amount 3 times the amount of triphenylbismuth as a toluene solution of pentafluorophenol, and the mixture was stirred at room temperature for 10 minutes to 24 hours. After stirring for minutes to 24 hours, the solution is concentrated, and the precipitated solid component is separated by filtration and dried. Toluene and diphenylsilanediol are added to the obtained solid component, and the mixture is stirred for 10 minutes to 24 hours under reflux, the solution is concentrated, and the precipitated solid component is separated by filtration and dried.

  The compound (A) of the present invention is suitably used as a catalyst component for addition polymerization (more preferably, as a catalyst component for olefin polymerization). Specific examples of the addition polymerization catalyst using the compound (A) include a compound (A) and an addition obtained by bringing a compound of Group 3 to 11 or a lanthanoid series metal compound (hereinafter, referred to as a compound (B)) into contact. Examples thereof include a polymerization catalyst, an addition polymerization catalyst obtained by contacting a compound (A), a compound (B), and an organoaluminum compound (hereinafter, referred to as a compound (C)). Is a catalyst for addition polymerization obtained by contacting the compound (A), the compound (B) and the compound (C).

The compound (B) is not particularly limited as long as the compound (B) and the compound (A), or those obtained by further contacting the compound (C) with the compound (C) exhibit addition polymerizability. As the compound (B), a metal compound represented by the following general formula [4] or a μ-oxo type metal compound thereof is preferable.
L ² _a M ² X ¹ _b [4]
Wherein a represents a number satisfying 0 <a ≦ 8, b represents a number satisfying 0 <b ≦ 8, and M ² represents a metal belonging to Groups 3 to 11 of the periodic table of elements or a lanthanoid series metal. .L ² representing the atom is a group containing a group or a hetero atom having a cyclopentadiene type anion skeleton, if L ² there is a plurality, they may be different from one another the same, a plurality of L ² May be directly connected, or may be connected via a residue containing at least one atom selected from a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. X ¹ represents a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene-type anion skeleton) or a hydrocarbon oxy group, and when there are a plurality of X ¹ , they are the same or different. May be.)

In the general formula [4], M ² is a metal atom belonging to Groups 3 to 11 of the Periodic Table of the Elements (IUPAC 1989) or a lanthanoid series. Specific examples thereof include scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, iron, ruthenium, cobalt, rhodium, nickel, and palladium atoms. , Samarium atom, ytterbium atom and the like. M ² is preferably a metal atom of Groups 3 to 11 of the periodic table, and particularly preferably a titanium atom, a zirconium atom or a hafnium atom.

In the general formula [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. Further, a plurality of L ² may be directly linked, and are linked via a residue containing at least one atom selected from a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. It may be.

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

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

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

Examples of the group containing a hetero atom include a group represented by the following general formula [5].
_{^{R 3 3 P = N- [5}} ]
(In the formula, R ³ represents a hydrogen atom, a halogen atom, or a hydrocarbon group in each case, and a plurality of R ³ may be the same or different from each other. May form a ring.)

Specific examples of R ³ in the general formula [5] include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Examples include a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cycloheptyl group, a cyclohexyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a benzyl group.

（式中、Ｒ⁴¹〜Ｒ⁴⁶はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、炭化水素オキシ基、シリル基、またはアミノ基を表し、それら２つ以上が互いに結合していてもよく、環を形成していてもよい。） Further, examples of the group containing a hetero atom include a group represented by the following general formula [6].

(Wherein, R ^{41 to} R ⁴⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbonoxy group, a silyl group, or an amino group, and two or more of them may be bonded to each other. , May form a ring.)

Specific examples of R ^{41 to} R ⁴⁶ in the general formula [6] include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a tert-butyl. Group, 2,6-dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl Group, methyl group, triethylsilyl group, diphenylmethylsilyl group, 1-methyl-1-phenylethyl group, 1,1-dimethylpropyl group, 2-chlorophenyl group, pentafluorophenyl group and the like.

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

Specific examples of the heterocyclic group used for L ² include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, and a pyridyl group is preferable.

If L ² have more than one among a group having a cyclopentadiene type anion skeleton, groups containing a group and hetero atom having a cyclopentadiene type anion skeleton or a group with each other containing a heteroatom, respectively, are connected directly And may be linked via a residue containing at least one atom selected from a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples of such a residue include an alkylene group such as a methylene group, an ethylene group, and a propylene group; a substituted alkylene group such as a dimethylmethylene group (isopropylidene group) and a diphenylmethylene group; a silylene group; a dimethylsilylene group, a diethylsilylene group; Substituted silylene groups such as diphenylsilylene group, tetramethyldisilylene group, dimethoxysilylene group; heteroatoms such as nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, etc., and particularly preferably methylene group, ethylene group, 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 (however, here does not include a group having a cyclopentadiene-type anion skeleton) or a hydrocarbon oxy group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In addition, examples of the hydrocarbon group include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group.

Examples of the alkyl group used for X ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, and a neopentyl group. , Amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluoroalkyl group. Hexyl, perfluorooctyl, perchloropropyl, perchlorobutyl, perbromopropyl and the like.
Further, any of these alkyl groups may be substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group.

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

Examples of the aralkyl group used for X ¹ include a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) methyl group, a (4-methylphenyl) methyl group, and a (2,3-dimethylphenyl) methyl Group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3,5 -Dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4 , 5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6 (Tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) ) Methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n -Hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group and the like.
All of these aralkyl groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

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

Examples of the aryl group used for X ¹ include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3 , 5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl Group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group, etc. Is mentioned.
All of these aryl groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

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

The alkenyl group used for X ¹ includes, for example, an allyl group, a methallyl group, a crotyl group, a 1,3-diphenyl-2-propenyl group and the like, and is preferably an alkenyl group having 3 to 20 carbon atoms. Preferably, it is an allyl group or a methallyl group.

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

X ¹ is more preferably a chlorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a benzyl group, an allyl group, a methallyl group, a methoxy group, an ethoxy group, or a phenoxy group. More preferably, they are a chlorine atom, a methyl group, a methoxy group, or a phenoxy group.

In the general formula [4], a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8, and is appropriately selected according to the valence of M ² .

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

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

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

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

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

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

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

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

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

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

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

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

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

(Di-tert-butyl-1,3-propanediamide) titanium dichloride, (dicyclohexyl-1,3-propanediamide) titanium dichloride, [bis (trimethylsilyl) -1,3-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) naph Range amide] titanium dichloride, [bis (tert- butyldimethylsilyl) naphthalene diamide] titanium dichloride,

Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride,

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

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

Specific examples of the compound in which M ² is a zirconium atom or a hafnium atom among the metal compounds represented by the general formula [4] include compounds in which a titanium atom in the above titanium compound is replaced with a zirconium atom or a hafnium atom. Can be mentioned.

（上記一般式［７］〜［９］においてそれぞれ、Ｍ^３〜Ｍ^７はそれぞれ独立に元素の周期律表の第４族の原子を表し、Ａ¹〜Ａ⁵はそれぞれ独立に元素の周期律表の第１６族の原子を表し、Ｊ¹〜Ｊ⁵はそれぞれ独立に元素の周期律表の第１４族の原子を表す。Ｃｐ¹〜Ｃｐ⁵はシクロペンタジエン形アニオン骨格を有する基を表す。Ｘ^２〜Ｘ^５、Ｒ¹¹〜Ｒ¹⁶、Ｒ²¹〜Ｒ²⁶、Ｒ³¹〜Ｒ³⁶、Ｒ⁵¹〜Ｒ⁵⁶およびＲ⁶¹〜Ｒ⁶⁶はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、置換シリル基、炭化水素オキシ基、２置換アミノ基、炭化水素チオ基、または炭化水素セレノ基を表し、Ｒ¹¹〜Ｒ¹⁶、Ｒ²¹〜Ｒ²⁶、Ｒ³¹〜Ｒ³⁶、Ｒ⁵¹〜Ｒ⁵⁶およびＲ⁶¹〜Ｒ⁶⁶は任意に結合して単環または多環を形成してもよい。該単環または多環は、芳香族環を形成してもよく非芳香族環を形成していてもよい。Ｘ⁶〜Ｘ⁸は元素の周期律表の第１６族の原子を表す。） Further, among the metal compounds represented by the general formula [4], specific examples of the compound in which M ² is a titanium atom include metal compounds represented by the following general formulas [7] to [9].

(In the general formulas [7] to [9], M ^{3 to} M ⁷ each independently represent an atom of Group 4 of the periodic table of the element, and A ^{1 to} A ⁵ each independently represent the periodic rule of the element. It represents an atom belonging to Group 16 of the table, J ^{1 to} J ⁵ each independently represent an atom belonging to Group 14 of the periodic table, and Cp ^{1 to} Cp ⁵ each represent a group having a cyclopentadiene-type anion skeleton. X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, Represents a substituted silyl group, a hydrocarbon oxy group, a disubstituted amino group, a hydrocarbon thio group, or a hydrocarbon seleno group, and R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ⁶¹ to R ⁶⁶ may form a monocyclic or polycyclic linked arbitrarily. monocyclic or polycyclic, the Aromatic good .X ⁶ to X ⁸ be in even better form a non-aromatic ring to form a ring represents an atom of Group 16 of the periodic table of elements.)

In the above general formulas [7] to [9], the metal atoms represented by M ^{3 to} M ⁷ represent atoms of Group 4 of the periodic table of elements (IUPAC revised edition of inorganic chemical nomenclature 1989). Examples include a titanium atom, a zirconium atom, and a hafnium atom. Preferably, it is a titanium atom or a zirconium atom.

In the general formulas [7] to [9], examples of the group having a cyclopentadiene-type anion skeleton represented by Cp ^{1 to} Cp ⁵ include, for example, η ^5- (substituted) cyclopentadienyl group, η ^5- (substituted) indenyl And η ^5- (substituted) fluorenyl groups. If specifically exemplified, for example, eta ⁵ - cycloalkyl Bae Ntajieniru group, eta ⁵ - methylcyclopentadienyl group, eta ⁵ - dimethyl cyclopentadienyl group, eta ⁵ - trimethyl cyclopentadienyl group, eta ⁵ - tetra methylcyclopentadienyl group, eta ⁵ - Echirushikuro Bae Ntajieniru group, eta ^5-n-propyl cyclopentadienyl group, eta ⁵ - isopropyl cyclopentadienyl group, eta ^{5-n-butylcyclopentadienyl} group, eta ^{5-sec-butylcyclopentadienyl} group, eta ^{5-tert-Buchirushikuro} Bae Ntajieniru group, eta ⁵ - phenyl cycloalkyl Bae Ntajieniru group, eta ⁵ - trimethylsilylcyclopentadienyl Bae Ntajieniru group, eta ^{5-tert-butyldimethylsilyl} cyclo Bae Ntajieniru group, eta ⁵ - indenyl group, eta ⁵ - methylindenyl group, eta ⁵ - dimethyl indenyl group , Eta ^5-n-propyl indenyl group, eta ⁵ - isopropylindenyl group, eta ^5-n-butyl indenyl group, eta ^5-tert-butyl indenyl group, eta ⁵ - phenyl indenyl group, eta ⁵ - methylphenyl indenyl group, eta ⁵ - naphthyl indenyl group, eta ⁵ - trimethylsilyl indenyl group, eta ⁵ - tetrahydroindenyl group, eta ⁵ - fluorenyl group, eta ⁵ - methyl fluorenyl group, eta ⁵ - dimethyl full Oreniru group, eta ^{5-tert-butyl-fluorenyl} group, eta ⁵ - di-tert-butyl-fluorenyl group, eta ⁵ - phenyl fluorenyl group, eta ⁵ - diphenyl fluorenyl group, eta ⁵ - trimethylsilyl fluorenyl group, eta ⁵ - bis trimethylsilyl fluorenyl group and the like, preferably eta ⁵ - cyclopentadienyl group, eta ⁵ - methyl cyclopentadienyl group , Eta ^{5-n-butylcyclopentadienyl} group, eta ^{5-tert-butylcyclopentadienyl} group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - indenyl group, eta ⁵ - tetrahydroindenyl group, η ⁵ -fluorenyl group.

As the halogen atom in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9], , A fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like are exemplified, preferably a chlorine atom and a bromine atom, and more preferably a chlorine atom.

As a hydrocarbon group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Represents an alkyl group, an aralkyl group, an aryl group and the like.

The alkyl groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] include For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, tert-pentyl group, n-hexyl Group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluoroalkyl group. Hexyl, perfluorooctyl, perchloropropyl, perchlorobutyl, perbromopropyl and the like.
Further, any of these alkyl groups may be substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group.

The alkyl groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] include , Preferably an alkyl group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group, or a tert-pentyl group.

The aralkyl groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] include For example, benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) ) Methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2 , 3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6- (Limethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethyl (Phenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) ) Methyl, (tert-butylphenyl) methyl, (n-pentylphenyl) methyl, (neopentylphenyl) methyl, (n-hexylphenyl) methyl, (n-octylphenyl) methyl, (n -Decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group and the like. It is.
All of these aralkyl groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

The aralkyl groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] include , Preferably an aralkyl group having 7 to 20 carbon atoms, more preferably a benzyl group.

The aryl groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] include For example, phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3, 4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl Group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group , Pentamethylphenyl group, ethylphenyl group, n-propylphenyl group Isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group , N-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group and the like.
All of these aryl groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

The aryl groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] include , Preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group.

Substituted silyl groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9]; Is a silyl group substituted with a hydrocarbon group, and the hydrocarbon group is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group or an ethoxy group; a phenoxy group or the like. An aryloxy group; it may be substituted with an aralkyloxy group such as a benzyloxy group; Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, Preferable examples include an alkyl group having 1 to 20 carbon atoms such as a cyclohexyl group and an aryl group such as a phenyl group.

As a substituted silyl group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Is a mono-substituted silyl group having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group; a disubstituted silyl group having 2 to 20 carbon atoms such as dimethylsilyl group, diethylsilyl group and diphenylsilyl group A trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyl Dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl group Such as trisubstituted silyl group having 3 to 20 carbon atoms, such groups are preferably exemplified, more preferably trimethylsilyl group, tert- butyldimethylsilyl group or triphenylsilyl group.

Hydrocarbon oxy groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Examples thereof include an alkoxy group, an aralkyloxy group, and an aryloxy group.

Examples of the alkoxy group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] include For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n -Octyloxy group, n-dodecyloxy group, n-pentadecyloxy group, n-eicosyloxy group and the like.
Each of these alkoxy groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group. It may be replaced by, for example.

Examples of the alkoxy groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] include And an alkoxy group having 1 to 20 carbon atoms is preferable, and a methoxy group, an ethoxy group, an isopropoxy group, or a tert-butoxy group is more preferable.

As an aralkyloxy group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Is, for example, benzyloxy, (2-methylphenyl) methoxy, (3-methylphenyl) methoxy, (4-methylphenyl) methoxy, (2,3-dimethylphenyl) methoxy, (2,4- A (dimethylphenyl) methoxy group, a (2,5-dimethylphenyl) methoxy group, a (2,6-dimethylphenyl) methoxy group, a (3,4-dimethylphenyl) methoxy group, a (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy, (2,3,5-trimethylphenyl) methoxy, (2,3,6-trimethylphenyl) methoxy, (2,4,5-trimethyl) (Phenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2 3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) Methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octyl) Phenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenyl meth Such as shea group.
All of these aralkyloxy groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

As the aralkyloxy group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Is preferably an aralkyloxy group having 7 to 20 carbon atoms, and more preferably a benzyloxy group.

As the aryloxy group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Are, for example, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2, 6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert- Butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, , 3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3 , 5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4 5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3,4,6-trimethylphenoxy group, 2,6 Di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert -Butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n- Hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, naphthoxy, anthracenoxy and the like.
Each of these aryloxy groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group; It may be substituted with a group or the like.

As an aryloxy group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Is preferably an aryloxy group having 6 to 20 carbon atoms.

Disubstituted amino groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Is an amino group substituted with two hydrocarbon groups or an amino group substituted with two silyl groups, wherein the hydrocarbon group or the silyl group is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or the like. May be substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group. Here, examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, and an n-hexyl group. , An alkyl group having 1 to 20 carbon atoms such as a cyclohexyl group; an aryl group having 6 to 20 carbon atoms such as a phenyl group; an aralkyl group having 7 to 10 carbon atoms such as a benzyl group; Examples thereof include a trimethylsilyl group and a tert-butyldimethylsilyl group. Examples of such a disubstituted amino group include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-sec-butylamino group, and a di-tert-butylamino group. Group, diisobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group and the like. And preferably a dimethylamino group, a diethylamino group, a diisopropylamino group, a di-tert-butylamino group, and a bistrimethylsilylamino group.

Hydrocarbon thio groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Examples thereof include an alkylthio group, an aralkylthio group, and an arylthio group.

The alkylthio groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] include For example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, n-pentylthio, neopentylthio, n-hexylthio, n-octylthio Group, n-dodecylthio group, n-pentadecylthio group, n-eicosylthio group and the like.
Each of these alkylthio groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group. It may be replaced by, for example.

The alkylthio groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] include And an alkylthio group having 1 to 20 carbon atoms is preferable, and a methylthio group, an ethylthio group, an isopropylthio group, or a tert-butylthio group is more preferable.

As an aralkylthio group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Is, for example, benzylthio, (2-methylphenyl) methylthio, (3-methylphenyl) methylthio, (4-methylphenyl) methylthio, (2,3-dimethylphenyl) methylthio, (2,4-dimethyl (Phenyl) methylthio group, (2,5-dimethylphenyl) methylthio group, (2,6-dimethylphenyl) methylthio group, (3,4-dimethylphenyl) methylthio group, (3,5-dimethylphenyl) methylthio group, 2,3,4-trimethylphenyl) methylthio group, (2,3,5-trimethylphenyl) methylthio group, (2,3,6-trimethylphenyl) methylthio group, ( , 4,5-trimethylphenyl) methylthio group, (2,4,6-trimethylphenyl) methylthio group, (3,4,5-trimethylphenyl) methylthio group, (2,3,4,5-tetramethylphenyl) Methylthio group, (2,3,4,6-tetramethylphenyl) methylthio group, (2,3,5,6-tetramethylphenyl) methylthio group, (pentamethylphenyl) methylthio group, (ethylphenyl) methylthio group, (N-propylphenyl) methylthio group, (isopropylphenyl) methylthio group, (n-butylphenyl) methylthio group, (sec-butylphenyl) methylthio group, (tert-butylphenyl) methylthio group, (n-hexylphenyl) methylthio group Group, (n-octylphenyl) methylthio group, (n-decylphenyl) Chiruchio group, naphthylmethyl thio group, anthracenylmethyl thio group.
All of these aralkylthio groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

As an aralkylthio group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Is preferably an aralkylthio group having 7 to 20 carbon atoms, more preferably a benzylthio group.

The arylthio groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] include For example, phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2,3-dimethylphenylthio, 2,4-dimethylphenylthio, 2,5-dimethylphenyl Thio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 2-tert-butyl-3-methylphenylthio group, 2-tert-butyl-4 -Methylphenylthio group, 2-tert-butyl-5-methylphenylthio group, 2-tert-butyl-6-methylphenylthio group, 2,3,4-trimethylphenylthio group, 2,3 -Trimethylphenylthio group, 2,3,6-trimethylphenylthio group, 2,4,5-trimethylphenylthio group, 2,4,6-trimethylphenylthio group, 2-tert-butyl-3,4-dimethyl Phenylthio group, 2-tert-butyl-3,5-dimethylphenylthio group, 2-tert-butyl-3,6-dimethylphenylthio group, 2,6-di-tert-butyl-3-methylphenylthio group , 2-tert-butyl-4,5-dimethylphenylthio group, 2,6-di-tert-butyl-4-methylphenylthio group, 3,4,5-trimethylphenylthio group, 2,3,4 5-tetramethylphenylthio group, 2-tert-butyl-3,4,5-trimethylphenylthio group, 2,3,4,6-tetramethylphenylthio group, 2-te t-butyl-3,4,6-trimethylphenylthio group, 2,6-di-tert-butyl-3,4-dimethylphenylthio group, 2,3,5,6-tetramethylphenylthio group, 2- tert-butyl-3,5,6-trimethylphenylthio group, 2,6-di-tert-butyl-3,5-dimethylphenylthio group, pentamethylphenylthio group, ethylphenylthio group, n-propylphenylthio Group, isopropylphenylthio group, n-butylphenylthio group, sec-butylphenylthio group, tert-butylphenylthio group, n-hexylphenylthio group, n-octylphenylthio group, n-decylphenylthio group, n -A tetradecylphenylthio group, a naphthylthio group, an anthracenylthio group and the like.
All of these arylthio groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group. It may be replaced by, for example.

The arylthio groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] include And an arylthio group having 6 to 20 carbon atoms is preferable.

Hydrocarbon seleno groups in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Examples thereof include an alkylseleno group, an aralkylseleno group, and an arylseleno group.

As an alkylseleno group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Are, for example, methylseleno group, ethylseleno group, n-propylseleno group, isopropylseleno group, n-butylseleno group, sec-butylseleno group, tert-butylseleno group, n-pentylseleno group, neopentylseleno group, n-hexylseleno group , N-octylseleno group, n-dodecylseleno group, n-pentadecylseleno group, n-eicosylseleno group and the like.
All of these alkylseleno groups are halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; alkoxy groups such as a methoxy group and an ethoxy group; aryloxy groups such as a phenoxy group; aralkyloxy groups such as a benzyloxy group. It may be substituted with a group or the like.

As an alkylseleno group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Is preferably an alkylseleno group having 1 to 20 carbon atoms, more preferably a methylseleno group, an ethylseleno group, an isopropylseleno group, or a tert-butylseleno group.

As an aralkylseleno group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Is, for example, a benzylseleno group, a (2-methylphenyl) methylseleno group, a (3-methylphenyl) methylseleno group, a (4-methylphenyl) methylseleno group, a (2,3-dimethylphenyl) methylseleno group, a (2,4- (Dimethylphenyl) methylseleno group, (2,5-dimethylphenyl) methylseleno group, (2,6-dimethylphenyl) methylseleno group, (3,4-dimethylphenyl) methylseleno group, (3,5-dimethylphenyl) methylseleno group, (2,3,4-trimethylphenyl) methylseleno group, (2,3,5-trimethylphenyl) methylseleno group, (2,3,6-trimethyl Enyl) methylseleno group, (2,4,5-trimethylphenyl) methylseleno group, (2,4,6-trimethylphenyl) methylseleno group, (3,4,5-trimethylphenyl) methylseleno group, (2,3,4 , 5-tetramethylphenyl) methylseleno group, (2,3,4,6-tetramethylphenyl) methylseleno group, (2,3,5,6-tetramethylphenyl) methylseleno group, (pentamethylphenyl) methylseleno group, (Ethylphenyl) methylseleno group, (n-propylphenyl) methylseleno group, (isopropylphenyl) methylseleno group, (n-butylphenyl) methylseleno group, (sec-butylphenyl) methylseleno group, (tert-butylphenyl) methylseleno group, (N-hexylphenyl) methylseleno group, (n Octylphenyl) methylseleno group, (n- decylphenyl) methylseleno group, naphthylmethyl seleno group, anthracenylmethyl seleno group.
All of these aralkylseleno groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

As an aralkylseleno group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Is preferably an aralkylseleno group having 7 to 20 carbon atoms, more preferably a benzylseleno group.

As the arylseleno group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Are, for example, phenylseleno, 2-methylphenylseleno, 3-methylphenylseleno, 4-methylphenylseleno, 2,3-dimethylphenylseleno, 2,4-dimethylphenylseleno, 2,5- Dimethylphenylseleno group, 2,6-dimethylphenylseleno group, 3,4-dimethylphenylseleno group, 3,5-dimethylphenylseleno group, 2-tert-butyl-3-methylphenylseleno group, 2-tert-butyl -4-methylphenylseleno group, 2-tert-butyl-5-methylphenylseleno group, 2-tert-butyl-6-methylphenylseleno group, 2,3,4-tri Tylphenylseleno group, 2,3,5-trimethylphenylseleno group, 2,3,6-trimethylphenylseleno group, 2,4,5-trimethylphenylseleno group, 2,4,6-trimethylphenylseleno group, 2 -Tert-butyl-3,4-dimethylphenylseleno group, 2-tert-butyl-3,5-dimethylphenylseleno group, 2-tert-butyl-3,6-dimethylphenylseleno group, 2,6-di- tert-butyl-3-methylphenylseleno group, 2-tert-butyl-4,5-dimethylphenylseleno group, 2,6-di-tert-butyl-4-methylphenylseleno group, 3,4,5-trimethyl Phenylseleno group, 2,3,4,5-tetramethylphenylseleno group, 2-tert-butyl-3,4,5-trimethylphenylseleno group Group, 2,3,4,6-tetramethylphenylseleno group, 2-tert-butyl-3,4,6-trimethylphenylseleno group, 2,6-di-tert-butyl-3,4-dimethylphenylseleno Group, 2,3,5,6-tetramethylphenylseleno group, 2-tert-butyl-3,5,6-trimethylphenylseleno group, 2,6-di-tert-butyl-3,5-dimethylphenylseleno Group, pentamethylphenylseleno group, ethylphenylseleno group, n-propylphenylseleno group, isopropylphenylseleno group, n-butylphenylseleno group, sec-butylphenylseleno group, tert-butylphenylseleno group, n-hexylphenyl Seleno group, n-octylphenylseleno group, n-decylphenylseleno group, n-tetradecylphenyl Examples thereof include a luseleno group, a naphthylseleno group, and an anthracenylseleno group.
All of these arylseleno groups include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; alkoxy groups such as a methoxy group and an ethoxy group; aryloxy groups such as a phenoxy group; and aralkyloxy groups such as a benzyloxy group. It may be substituted with a group or the like.

As the arylseleno group in X ^{2 to} X ⁵ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{51 to} R ⁵⁶ and R ^{61 to} R ⁶⁶ in the general formulas [7] to [9] Is preferably an arylseleno group having 6 to 20 carbon atoms.

In the general formulas [7] to [9], preferably, X ^{2 to} X ⁵ are each independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group, or a disubstituted amino group, and more preferably a halogen atom. An atom, an alkyl group, an alkoxy group or an aryloxy group.

In the general formulas [7] to [9], preferably, R ^{11 to} R ¹⁴ , R ^{21 to} R ²⁴ , R ^{31 to} R ³⁴ , R ^{51 to} R ⁵⁴ and R ^{61 to} R ⁶⁴ are each independently a hydrogen atom, halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, alkoxy group, aralkyloxy group, an aryloxy group, in particular ^{R 11, R 21, R 31} , R 51 and R ⁶¹ are alkyl each independently It is preferably a group, an aralkyl group, an aryl group or a substituted silyl group.

In the general formulas [7] to [9], R ¹⁵ , R ¹⁶ , R ²⁵ , R ²⁶ , R ³⁵ , R ³⁶ , R ⁵⁵ , R ⁵⁶ , R ⁶⁵ and R ⁶⁶ each independently represent a hydrogen atom, It is preferably an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group or an aryloxy group.

X ^{6 to} X ⁸ in the general formulas [8] and [9] represent atoms of Group 16 of the periodic table of the elements, and specific examples thereof include an oxygen atom, a sulfur atom, and a selenium atom. Is an oxygen atom or a sulfur atom, more preferably an oxygen atom.

In the general formulas [7] to [9], examples of atoms of Group 16 of the periodic table of the elements represented by A ^{1 to} A ⁵ include an oxygen atom, a sulfur atom, and a selenium atom. Preferably, it is an oxygen atom.

In the general formulas [7] to [9], examples of the atoms belonging to Group 14 of the periodic table of the elements represented by J ^{1 to} J ⁵ include a carbon atom, a silicon atom, and a germanium atom. Preferably, they are a carbon atom and a silicon atom.

Specific examples of the metal compound represented by the general formula [7] include methylene (η ⁵ -cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride and methylene (η ⁵ -cyclopentadienyl) ) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -cyclopenta Dienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (η ⁵ -cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (η ⁵ − Cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-f Phenoxy) titanium dichloride, methylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl - 5-chloro-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) ( 3-tert-butyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethyl Cyclopentadienyl) (3- Eniru 2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadiene dienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (Η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

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

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

Specific examples of the metal compound represented by the general formula [7], dimethylsilylene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) ( 3-methyl-2-phenoxy) titanium dichloride, dimethylsilene (η ⁵ -cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (3- tert- butyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert- butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl ) (3,5-di-tert-butyl-2-fe) Carboxymethyl) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert-butyldimethyl silyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl ) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (Η ⁵ -Cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride, dimethylsilylene (η ⁵ -tetra methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl enyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetra Methyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert - butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ -Tetramethyi Lecyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2- phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (1-naphthoxy - 2-yl) titanium dichloride, etc. and the compound (eta ⁵ - cyclopentadienyl) (eta ⁵ - methylcyclopentadienyl), (eta ⁵ - dimethyl cyclopentadienyl), (eta ⁵ - trimethylcyclopentadienyl dienyl), (eta ^5-n-butyl cyclopentadienyl) , (Eta ^{5-tert-butylcyclopentadienyl),} (η ⁵ - trimethylsilyl cyclopentadienyl), (η ⁵ -tert- butyldimethylsilyl cyclopentadienyl), (η ⁵ - indenyl), (eta ⁵ - methylindenyl), (eta ⁵ - phenyl indenyl) or (eta ⁵ - such as compound change fluorenyl) and the like. Further, there can be mentioned, for example, compounds in which 2-phenoxy in the above compound is changed to 3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxy, or 3-tert-butyldimethylsilyl-2-phenoxy. Further, a compound in which dimethylsilylene of the above compound is changed to diethylsilylene, diphenylsilylene, or dimethoxysilylene can be given. Further, there may be mentioned compounds in which dichloride of the above compound is changed to dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino) or bis (diethylamino). Further, compounds obtained by changing titanium in the above compounds to zirconium or hafnium can also be mentioned.

Specific examples of the metal compound represented by the general formula [8] include μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium chloride} and μ-oxobis {isopropylidene (η ⁵ − Cyclopentadienyl) (2-phenoxy) titanium methoxide {, μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ - Okisobisu {isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, .mu. Okisobisu {isopropylidene (eta ⁵ - methylcyclopentadienyl) (2-phenoxy) titanium chloride｝, μ-oxobis ｛isopropylidide (Η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium methoxide {, μ-oxobis} isopropylidene (η ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-methyl-2- phenoxy) titanium chloride}, .mu. Okisobisu {isopropylidene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, .mu. Okisobisu {isopropylidene (eta ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride ク ロ, μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide｝, μ-oxobis ｛isopropylide isopropylidene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) ) Titanium methoxide

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

Specific examples of the metal compound represented by the general formula [9] include di-μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium} and di-μ-oxobis {isopropylidene ( eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di -μ- Okisobisu {isopropylidene (eta ⁵ - cyclopentadienyl) (2-phenoxy) titanium {, Di-μ-oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (η ⁵ − tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di -μ- Okisobisu {isopropylidene (eta ⁵ Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium},

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

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

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

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

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

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

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

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

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

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

（式中、Ｒ⁷¹およびＲ⁷²はそれぞれ２，６−ジイソプロピルフェニル基であり、Ｒ⁷³およびＲ⁷⁴はそれぞれ独立に水素原子またはメチル基であるか、あるいはＲ⁷³とＲ⁷⁴とがいっしょになってアセナフテン基であり、Ｘ⁸およびＸ⁹はそれぞれ独立にフッ素原子、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、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、イソブトキシ基、フェノキシ基である。） Further, specific examples of the compound in which M ² is a nickel atom include a compound represented by the following general formula [10].

(Wherein, R ⁷¹ and R ⁷² are each a 2,6-diisopropylphenyl group, and R ⁷³ and R ⁷⁴ are each independently a hydrogen atom or a methyl group, or R ⁷³ and R ⁷⁴ are taken together. X ⁸ and X ⁹ are each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, Benzyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and phenoxy.)

  Further, as the metal compound represented by the general formula [4], a compound in which nickel in the above nickel compound is replaced with palladium, cobalt, rhodium, or ruthenium can be similarly exemplified.

Among the metal compounds represented by the general formula [4], specific examples of the compound in which M ² is iron include 2,6-bis- [1- (2,6-dimethylphenylimino) ethyl] pyridine iron dichloride 2,6-bis- [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron dichloride, 2,6-bis- [1- (2-tert-butyl-phenylimino) ethyl] pyridine iron dichloride, [Hydrotris (3,5-dimethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-diethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron chloride, Dichloride of the above iron compound is dibromide, difluoride, diiodide, dimethyl, diethyl, diiso Ropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide or di (2,6-di-tert. -Butylphenoxide) and the like.

  In addition, as the metal compound represented by the general formula [4], a compound in which iron is replaced with cobalt or nickel in the above-described iron compound can also be exemplified.

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

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

  The metal compound used for the above compound (B) may be used alone or in combination of two or more.

The compound (B) is preferably a metal compound represented by the above general formula [4], and more preferably a metal compound wherein M ² in the above general formula [4] is an atom belonging to Group 4 of the periodic table. And more preferably a metal compound having at least one group having a cyclopentadiene-type anion skeleton as L ² in the general formula [3].

As the compound (C) used in the addition polymerization catalyst of the present invention, a known organic aluminum compound can be used. Preferably, it is an organoaluminum compound represented by the following general formula [11].
R ⁶ _d AlY _3-d [11]
(Wherein, d is .R ⁶ representing the number satisfying the 0 <d ≦ 3 represents a hydrocarbon group, if R ⁶ have more than one plurality of R ⁶ may be the same or different Y represents a hydrogen atom, a halogen atom, or a hydrocarbon oxy group, and when there are a plurality of Ys, the plurality of Ys may be the same or different.)

R ⁶ in the general formula [11] is preferably a hydrocarbon group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, an n-hexyl group, a 2-methylhexyl group, and an n-octyl group. -Butyl, isobutyl, n-hexyl, or n-octyl.

  Specific examples of the case where Y in the general formula [11] is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.

  As the hydrocarbon oxy group for Y in the general formula [11], an alkoxy group, an aralkyloxy group, or an aryloxy group is preferable.

Examples of the alkoxy group for Y in the general formula [11] include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, and a neopentoxy group. Group, n-hexyloxy group, n-octyloxy group, n-dodecyloxy group, n-pentadecyloxy group, n-eicosyloxy group and the like.
Any of these alkoxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group.

  The alkoxy group for Y in the general formula [11] is preferably an alkoxy group having 1 to 24 carbon atoms, more preferably a methoxy group, an ethoxy group, or a tert-butoxy group.

Examples of the aryloxy group for Y in the general formula [11] include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxy group, and a 2,4-dimethylphenoxy group Group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5- Trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4 5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, N-methylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n -Decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like.
Any of these aryloxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group.

  The aryloxy group for Y in the general formula [11] is preferably an aryloxy group having 6 to 24 carbon atoms.

Examples of the aralkyloxy group for Y in the general formula [11] include a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, a (4-methylphenyl) methoxy group, and a (2,3- (Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethyl (Tylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy Group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) A) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like.
Any of these aralkyloxyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group.

  The aralkyloxy group for Y in the general formula [11] is preferably an aralkyloxy group having 7 to 24 carbon atoms, and more preferably a benzyloxy group.

  Specific examples of the organoaluminum compound represented by the general formula [11] include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-aluminum. Trialkylaluminums such as -n-octylaluminum; dialkylaluminums such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminumchloride Chloride; methyl aluminum dichloride, ethyl aluminum dichloride, n-propyl aluminum dichloride, n-butyl aluminum Alkyl aluminum dichlorides such as aluminum dichloride, isobutyl aluminum dichloride and n-hexyl aluminum dichloride; dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, di-n- Dialkyl aluminum hydride such as hexyl aluminum hydride; alkyl (dialkoxy) aluminum such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum and methyl (di-tert-butoxy) aluminum; dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum , Dimethyl (tert-butoxy) aluminum and the like Alkyl (alkoxy) aluminum; alkyl (diaryloxy) aluminum such as methyl (diphenoxy) aluminum, methylbis (2,6-diisopropylphenoxy) aluminum, methylbis (2,6-diphenylphenoxy) aluminum; dimethyl (phenoxy) aluminum, dimethyl ( Examples thereof include dialkyl (aryloxy) aluminums such as 2,6-diisopropylphenoxy) aluminum and dimethyl (2,6-diphenylphenoxy) aluminum.

  Among these, preferably trialkyl aluminum, more preferably trimethyl aluminum, triethyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum or tri-n-octyl aluminum, particularly Preferably, it is triisobutylaluminum or tri-n-octylaluminum.

  The above organoaluminum compounds may be used alone or in combination of two or more.

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

  As the catalyst for addition polymerization of the present invention, a reaction product obtained by previously contacting component (A) and component (B), and optionally component (C) may be used. May be used. Any two of the components may be pre-contacted and then the other component contacted.

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

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

  The addition polymerization catalyst of the present invention is particularly suitable as an olefin polymerization catalyst, and is suitably used in a method for producing an olefin polymer. As such an olefin polymer, a copolymer of ethylene and an α-olefin is particularly preferred, and a copolymer of ethylene and an α-olefin having a polyethylene crystal structure is particularly preferred. Here, the α-olefin is preferably an α-olefin having 3 to 8 carbon atoms, and specific examples thereof include 1-butene, 1-hexene and 1-octene.

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

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

  When the compounds (A) to (C) are used in the form of a solution, suspension or slurry, the concentrations of the compounds (A) and (C) are usually 0.0001 to 100 mmol / liter in terms of metal atoms. , Preferably 0.01 to 10 mmol / l. The concentration of the compound (B) is usually 0.0001 to 100 mmol / L, preferably 0.01 to 10 mmol / L in terms of metal atoms.

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

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

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

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

(3) Molecular weight and molecular weight distribution Measured by gel permeation chromatography (GPC) under the following conditions. A calibration curve was created using standard polystyrene. The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Model: Millipore Waters 150C column: TSK-GEL GMH-HT 7.5 × 600 × 2 tubes Measurement temperature: 140 ° C.
Solvent: orthodichlorobenzene,
Measurement concentration: 5mg / 5ml

(4) Melt flow rate = MFR: It is a melt flow rate value measured at 190 ° C. under a load of 21.18 N (2.16 kg) in accordance with the method specified in JIS K7210-1995 (unit: g / 10 minutes). .
In the above melt flow rate measurement, a polymer in which an antioxidant was previously blended at 1000 ppm was used.

[Example 1]
(1) Preparation of Bismuth Compound 9.88 g (22.4 mmol) of triphenylbismuth and 100 ml of toluene were placed in a 300 ml four-necked flask purged with argon, and stirred at room temperature. To this, a solution of 12.6 g (68.5 mmol) of pentafluorophenol in 100 ml of toluene was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 15.5 hours. Thereafter, the reaction was carried out sequentially for 4 hours under refluxing conditions of toluene, 18 hours at room temperature, 7 hours under refluxing conditions of toluene, and 17 hours at room temperature. The resulting yellow needle-like crystals were separated by filtration and dried under reduced pressure at room temperature to obtain 12.6 g of yellow crystals (hereinafter, referred to as compound A1).
Next, 0.967 g (1.14 mmol) of compound A1 and 30 ml of toluene were placed in a 100 ml four-necked flask purged with argon. At room temperature, 0.243 g (1.13 mmol) of diphenylsilanediol and 10 ml of toluene were added thereto. The mixture was stirred for 6 hours under reflux conditions. When the stirring was stopped and the mixture was allowed to stand, a white precipitate was formed, and the supernatant was a yellow transparent liquid. The volatile component was distilled off under reduced pressure and dried to obtain a white crystal.

(2) Production of Addition Polymer An autoclave with an internal volume of 400 ml with a stirrer was vacuum-dried and replaced with argon. 190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer were charged, and the reactor was heated to 70 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 0.6 MPa. After the inside of the system was stabilized, 0.25 ml (250 μmol) of triisobutylaluminum (1 mmol / ml toluene solution) was charged, and ethylenebis (indenyl) zirconium was added. 0.5 ml (1 μmol) of dichloride (2 μmol / ml toluene solution) was added, followed by 43.3 mg of the white crystals obtained in the above (1). The polymerization was carried out at 70 ° C. for 30 minutes while feeding ethylene so as to keep the total pressure constant. As a result, 2.06 g of an ethylene / 1-hexene copolymer was obtained. The polymerization activity was 4.1 × 10 ⁶ g / molZr / hour,
CB = 15.5, Mw = 92000, Mw / Mn = 2.5.

[Example 2]
(1) Preparation of Bismuth Compound 31.9 g (72.5 mmol) of triphenylbismuth and 200 ml of toluene were placed in a 500 ml four-necked flask purged with argon, and stirred at room temperature. To this, 109 ml (217 mmol as pentafluorophenol) of a toluene solution of pentafluorophenol having a concentration of 2.00 mmol / mL was added dropwise. After completion of the dropwise addition, the reaction was carried out sequentially for 2 hours under refluxing conditions of toluene, 14 hours at room temperature, 7 hours under refluxing conditions of toluene, 91 hours at room temperature, and 3 hours under refluxing conditions of toluene. The yellow needle crystals generated by storage at 0 ° C. were separated by filtration and dried at 40 ° C. under reduced pressure to obtain 50.2 g of yellow crystals (hereinafter, referred to as compound A2).
Next, 22.4 g (29.6 mmol) of compound A2 and 400 ml of toluene were placed in a 1000 ml four-necked flask purged with argon. At room temperature, 6.37 g (29.4 mmol) of diphenylsilanediol and 100 ml of toluene were added at room temperature. The mixture was stirred for 6 hours under reflux conditions. When the stirring was stopped and the mixture was allowed to stand, a white precipitate was formed, and the supernatant was a yellow transparent liquid. Immediately after the completion of the reflux, the supernatant was withdrawn and transferred to a 1-liter four-necked flask. Immediately after the solid began to precipitate, the mixture was allowed to stand for 2 days. The supernatant was extracted again, and volatile components were distilled off under reduced pressure at 50 ° C., followed by drying to obtain 8.22 g of a pale yellow viscous solid. The result of elemental analysis of the pale yellow viscous solid was Bi = 0.77 mmol / g and F = 7.4 mmol / g.

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

(2) Production of addition polymer An autoclave with an internal volume of 400 ml with a stirrer was vacuum-dried and replaced with argon, 185 ml of Isopar E as a solvent and 15 ml of 1-hexene as a comonomer were charged, and the reactor was heated to 180 ° C. . After the temperature was raised, feed was performed while adjusting the ethylene pressure to 2.5 MPa. After the inside of the system was stabilized, 0.30 ml (300 μmol) of triisobutylaluminum (1 mmol / ml toluene solution) was added, and the compound B1 and triisobutylaluminum were added. Hexane solution (concentration of compound B1 is 0.5 μmol / ml, Al / Ti = 50) mixed with 1.0 ml (that is, 0.5 μmol of compound B1 and 25 μmol of triisobutylaluminum), and subsequently, 5 ml of a 50 μmol Bi / ml toluene solution of the pale yellow viscous solid obtained in the above (1) (that is, 250 μmol of the Bi compound) was charged. Polymerization was carried out at 180 ° C. for 2 minutes while feeding ethylene so as to keep the total pressure constant. As a result, 0.172 g of an ethylene / 1-hexene copolymer was obtained. The polymerization activity was 1.0 × 10 ⁷ g / molTi / hour.

[Comparative Example 1]
An autoclave with a stirrer having an inner volume of 400 ml was vacuum-dried and purged with argon, and then 190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer were charged, and the reactor was heated to 70 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 0.6 MPa. After the inside of the system was stabilized, 0.25 ml (250 μmol) of triisobutylaluminum (1 mmol / ml toluene solution) was charged, and ethylenebis (indenyl) zirconium was added. 0.5 ml (1 μmol) of dichloride (2 μmol / ml toluene solution) was charged, followed by 49.8 mg (113 μmol) of triphenylbismuth. The polymerization was carried out at 70 ° C. for 30 minutes while feeding ethylene so as to keep the total pressure constant. As a result, only a trace amount of the ethylene / 1-hexene copolymer was obtained.

[Comparative Example 2]
An autoclave with a stirrer having an inner volume of 400 ml was vacuum-dried and purged with argon, and then 190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer were charged, and the reactor was heated to 70 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 0.6 MPa. After the inside of the system was stabilized, 0.25 ml (250 μmol) of triisobutylaluminum (1 mmol / ml toluene solution) was charged, and ethylenebis (indenyl) zirconium was added. 0.5 ml (1 μmol) of dichloride (2 μmol / ml toluene solution) was added, and then 60.9 mg (71.6 μmol) of the compound A1 synthesized in Example 1 (1) was added. The polymerization was carried out at 70 ° C. for 30 minutes while feeding ethylene so as to keep the total pressure constant. As a result, only a trace amount of the ethylene / 1-hexene copolymer was obtained.

[Comparative Example 3]
(1) Preparation of Bismuth Compound In a 100 ml four-necked flask purged with argon, 1.06 g (1.25 mmol) of the compound A1 synthesized in Example 1 (1) and 30 ml of toluene were placed. At room temperature, 0.125 g (0.578 mmol) of diphenylsilanediol and 10 ml of toluene were added thereto. The mixture was stirred for 3 hours under reflux conditions. When allowed to stand at room temperature overnight, needle crystals were formed. After the crystals were separated by filtration and dried under reduced pressure, 70.2 mg of the crystals were placed in a separately prepared flask, and 10 ml of toluene was added to obtain a slurry.

(2) Production of Addition Polymer An autoclave with an internal volume of 400 ml with a stirrer was vacuum-dried and replaced with argon. 190 ml of hexane as a solvent and 10 ml of 1-hexene as a comonomer were charged, and the reactor was heated to 70 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 0.6 MPa. After the inside of the system was stabilized, 0.25 ml (250 μmol) of triisobutylaluminum (1 mmol / ml toluene solution) was charged, and ethylenebis (indenyl) zirconium was added. 0.5 ml (1 μmol) of dichloride (2 μmol / ml toluene solution) was added, followed by 5 ml of the slurry obtained in the above (1). The polymerization was carried out at 70 ° C. for 30 minutes while feeding ethylene so as to keep the total pressure constant. As a result, only a trace amount of the ethylene / 1-hexene copolymer was obtained.

[Example 3]
(1)
17.5 ml of toluene and 12.5 ml (25.0 mmol) of a toluene solution of triethylaluminum (2.00 mol / l) were placed in a 100 ml four-necked flask purged with nitrogen, and cooled to 5 ° C. To this, 3.5 ml (33.3 mmol) of 1,1,1,3,3,3-hexafluoro-2-propanol was added dropwise over 0.25 hours. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 1.5 hours. Thereafter, 5.3 g (24.5 mmol) of diphenylsilanediol was added. Thereafter, the mixture was stirred at 5 ° C for 1 hour, at 40 ° C for 1 hour, and at 80 ° C for 2 hours. A dark green slurry solution was obtained. (Based on the charged amount, the concentration in terms of Al atom is 0.75 mol / l)

(2) Polymerization After drying under reduced pressure, the inside of a 3-liter autoclave equipped with a stirrer and purged with argon was evacuated, 1000 ml of toluene and 30 g of 1-butene were charged, and the temperature was raised 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 1-butene = 5.66 mol%. 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mmol / ml was added thereto. 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 dark green slurry solution obtained in Example 3 (1) above was added. 0.6 ml was charged. Polymerization was carried out at 70 ° C. for 20 minutes while feeding ethylene gas so as to keep the total pressure constant. Thereafter, after deashing and washing with a hydrochloric acid / methanol solution, drying was performed under reduced pressure to obtain 49 g of an olefin polymer. The polymerization activity per zirconium atom was 2.9 × 10 ⁸ g / molZr / hour, and the obtained olefin polymer had SCB = 17.1 and MFR = 4.7.

Claims (17)

A compound obtained by bringing the following components (a) to (c) into contact with each other, wherein the amount of the component (b) contacted per mol of the component (a) is 0.1 to 8 mol; A compound wherein the contact treatment amount of the component (c) is 0.5 to 8 mol per mol.
(A): a compound represented by the following general formula [1]: M ¹ L ¹ _r [1]
(B): a compound represented by the following general formula [2] R ¹ _s-1 TH [2]
(C): a compound represented by the following general formula [3] R ² _4-n J (OH) _n [3]
(In the above general formulas [1] to [3], M ¹ represents a metal atom or a boron atom belonging to Groups 12 to 15 of the periodic table of elements, r represents a number corresponding to the valency of M ¹ , L ¹ represents a hydrogen atom, a halogen atom, the period of the hydrocarbon represents a hydrogen group or a hydrocarbon oxy group, a plurality of L ¹ if L ¹ there are a plurality or different be the same as each other, T is an element A non-metallic atom of Group 15 or 16 of the Table, s represents a number corresponding to the valence of T, R ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group, ^When there are a plurality of ¹ 's, a plurality of R ^1's may be the same or different from each other, n represents a number of 2 or more and 4 or less, and J is a non-metallic atom of Group 14 of the periodic table of the element. the stands, R ² represents a hydrocarbon group, a plurality of R ² if R ² there are a plurality of mutually identical Or different.)   The compound according to claim 1, wherein T in component (b) is a nitrogen atom or an oxygen atom. 3. The compound according to claim 1, wherein R ^{1 of} component (b) is a halogenated hydrocarbon group.   The compound according to any one of claims 1 to 3, wherein component (b) is a fluorinated phenol.   The compound according to claim 4, wherein the fluorinated phenol is pentafluorophenol.   The compound according to any one of claims 1 to 3, wherein component (b) is a fluorinated alcohol.   The compound according to claim 6, wherein the fluorinated alcohol is 1,1,1,3,3,3-hexafluoro-2-propanol. The compound according to any one of claims 1 to 7, wherein M ^{1 in} component (a) is a bismuth atom. The compound according to any one of claims 1 to 7, wherein M ^{1 of} component (a) is an aluminum atom.   The compound according to any one of claims 1 to 9, wherein J of component (c) is a silicon atom.   A catalyst component for addition polymerization, comprising the compound according to claim 1.   An addition polymerization catalyst obtained by contacting the compound (A) according to any one of claims 1 to 10 with a Group 3 to 11 or lanthanoid-based metal compound (B).   An addition polymerization catalyst obtained by contacting the compound (A) according to any one of claims 1 to 10, a Group 3 to 11 or lanthanoid-based metal compound (B), and an organoaluminum compound (C).   The catalyst for addition polymerization according to claim 12 or 13, wherein the Group 3-11 or lanthanoid-based metal compound (B) is a compound having at least one group having a cyclopentadiene-type anion skeleton.   A method for producing an addition polymer using the addition polymerization catalyst according to any one of claims 12 to 14.   The method for producing an addition polymer according to claim 15, wherein the addition polymer is an olefin polymer. The method for producing an addition polymer according to claim 16, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.