JP4341409B2 - Metal compound, catalyst component for addition polymerization, catalyst for addition polymerization, and method for producing addition polymer - Google Patents

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

JP 58-19309 A Japanese translation of PCT publication No. 1-502036 JP 2001-181327 A

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

That is, the first of the present invention is a compound obtained by contacting the following components (a) to (c), and the contact treatment amount of the component (b) per mole of the component (a) is 0.1 to 8: And the amount of contact treatment of component (c) per mole of component (a) is 0.5 to 8 moles.
M ¹ L ¹ _r [1]
(B): Compound represented by the following general formula [2] R ¹ O H [2]
(C): Compound represented by the following general formula [3] R ² _4-n Si (OH) _n [3]
(In the above general formulas [1] to [3], M ¹ represents an aluminum atom or a bismuth atom , r represents a number corresponding to the valence of M ¹ , and L ¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group. Or a hydrocarbon oxy group, and when a plurality of L ¹ are present, the plurality of L ¹ may be the same or different from each other, and R ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group. And when a plurality of R ¹ are present, the plurality of R ¹ may be the same or different from each other, n represents a number of 2 or more and 4 or less, R ² represents a hydrocarbon group, and R ² represents When there are a plurality of R ^{2 s} , they may be the same or different.)
The second of the present invention relates to an olefin polymerization catalyst comprising the above compound.
The third aspect of the present invention are those according to the process for producing an olefin polymer using the above olefin polymerization catalyst.

  According to the present invention, there are provided a metal compound and an addition polymerization catalyst component used as a component of an addition polymerization catalyst having excellent polymerization activity, an addition polymerization catalyst having excellent polymerization activity, and an efficient method for producing an addition polymer. 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 boron atom belonging to Groups 12 to 15 of the periodic table of elements. Specifically, they are zinc atom, cadmium atom, mercury atom, aluminum atom, gallium atom, indium atom, thallium atom, germanium atom, tin atom, lead atom, antimony atom, bismuth atom and boron atom. 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 valence of M ¹ , is an integer of 2 to 5, and is 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 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The hydrocarbon group for L ¹ is preferably an alkyl group, an aryl group, or an aralkyl group. The hydrocarbon oxy group in L ¹ is preferably an alkoxy group or an aryloxy group.

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

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

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

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

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

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

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

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

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

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

The aryloxy group used for L ¹ is preferably an aryloxy group having 6 to 20 carbon atoms, and more preferably a phenoxy group.

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

Specific examples of the compound (a) when M ¹ is a bismuth atom include bismuth halides (III) such as bismuth (III) fluoride, bismuth (III) chloride, bismuth (III) bromide, bismuth (III) iodo 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, Trialkoxy bismuth such as tri (tert-pentyloxy) bismuth; triphenoxy bismuth, 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) bisma , Tri (ethylphenoxy) bismuth, tri (n-propylphenoxy) bismuth, tri (isopropylphenoxy) bismuth, tri (n-butylphenoxy) bismuth, tri (sec-butylphenoxy) bismuth, tri (tert-butylphenoxy) Bismuth, tri (isobutylphenoxy) bismuth, tri (n-pentylphenoxy) bismuth, tri (neopentylphenoxy) bismuth, tri (n-hexylphenoxy) bismuth, tri (n-octylphenoxy) bismuth, tri (n-decylphenoxy) ) Triaryloxybismuth such as bismuth, tri (n-dodecylphenoxy) bismuth, tri (n-tetradecylphenoxy) bismuth, trinaphthyloxybismuth, trianthracenyloxybismuth; bismuth (V Halogenated bismuth (V) such as fluoride, bismuth (V) chloride, bismuth (V) bromide, bismuth (V) iodine; pentaalkyl bismuth such as pentamethyl bismuth; pentaaryl bismuth such as pentaphenyl bismuth; pentamethoxy bismuth; And pentaalkoxybismuth such as pentaethoxybismuth; 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. -Trialkylaluminum such as octylaluminum; Triarylaluminum such as triphenylaluminum, trinaphthylaluminum and tri (pentafluorophenyl) aluminum; Trialkenylaluminum such as triallylaluminum; Tri (cyclopentadienyl) aluminum; Dimethylaluminum Chloride, diethylaluminum chloride, dipropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminium Chloride, di-n-hexyl aluminum chloride, diethyl aluminum bromide, dipropyl aluminum bromide, di-n-butyl aluminum bromide, diisobutyl aluminum bromide, di-n-hexyl aluminum bromide, diethyl aluminum iodide, dipropyl aluminum 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, trialkyl bismuth, triaryl bismuth, trialkoxy bismuth, triaryloxy bismuth, or trialkylaluminum, more preferably bismuth (III) halide or triaryl. Bismuth, trialkoxybismuth, triaryloxybismuth, or trialkylaluminum, particularly preferably triarylbismuth or trialkylaluminum, most preferably triphenylbismuth, trimethylaluminum, triethylaluminum, triisobutylaluminum, trialkylaluminum -N-hexylaluminum or tri-n-octylaluminum.

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-metal atom of Group 15 or Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). Specific examples of the Group 15 nonmetal atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 nonmetal atom include an oxygen atom and a sulfur atom. T is preferably a nitrogen atom or an oxygen atom, and particularly preferably an oxygen atom.

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

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

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

Specific examples of the halogenated alkyl group used for R ¹ include fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, diiodomethyl group trifluoromethyl group, and trichloromethyl group. 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 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2- Bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 2,6-dichlorophenyl group, 3,5-dichlorophenyl group, 2,6-dibromophenyl group, 3,5-dibromophenyl group, 2,6-diiodophenyl group, 3,5-diiodophenyl group, 2, 4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,4,6-trichlorophenyl group, 2,4, -Aryl group in which hydrogen of aromatic ring such as tribromophenyl group, 2,4,6-triiodophenyl group, pentafluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentaiodophenyl group is substituted with halogen Is mentioned.

Specific examples of the halogenated aryl group used for R ¹ include 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6 An aryl group substituted with a halogenated alkyl group such as bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, Can be mentioned.

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

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

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

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

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

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

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

  Specific examples of the compound (b) represented by the general formula [2] include amines such as di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, and 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, (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.

  Specific examples of the component (b) include phosphines such as compounds in which the nitrogen atom in the specific examples of the above amines is substituted with a phosphorus atom, that is, compounds in which the amine having the compound name of the above amines is rewritten with phosphine, and the like. It is done.

  As alcohols, fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodomethanol, trifluoromethanol, trichloromethanol, tribromomethanol, triiodomethanol, 2,2,2 -Trifluoroethanol, 2,2,2-trichloroethanol, 2,2,2-tribromoethanol, 2,2,2-triiodoethanol, 1,1,1,3,3,3-hexafluoro-2 -Propanol, 1,1,1,3,3,3-hexachloro-2-propanol, 1,1,1,3,3,3-hexabromo-2-propanol, 1,1,1,3,3,3 -Hexaiodo-2-propanol, 1,1,1,3,3,3-hexafur Ro-2- (trifluoromethyl) -2-propanol, 1,1,1,3,3,3-hexachloro-2- (trichloromethyl) -2-propanol, 1,1,1,3,3,3 -Hexabromo-2- (tribromomethyl) -2-propanol, 1,1,1,3,3,3-hexaiodo-2- (triiodomethyl) -2-propanol, 1H, 1H, 3H-perfluoropropanol 1H, 1H, 3H-perchloropropanol, 1H, 1H, 3H-perbromopropanol, 1H, 1H, 3H-periodopropanol, 1H, 1H-perfluoropropanol, 1H, 1H-perchloropropanol, 1H, 1H -Perbromopropanol, 1H, 1H-Periodopropanol, 1H, 1H, 4H-perfluorobutanol, 1H, 1H 4H-perchlorobutanol, 1H, 1H, 4H-perbromobutanol, 1H, 1H, 4H-periodobutanol, 1H, 1H-perfluorobutanol, 1H, 1H-perchlorobutanol, 1H, 1H-perbromobutanol, 1H, 1H-Periodobutanol, 1H, 1H, 5H-Perfluoropentanol, 1H, 1H, 5H-Perchloropentanol, 1H, 1H, 5H-Perbromopentanol, 1H, 1H, 5H-Periodo pen Tanol, 1H, 1H-perfluoropentanol, 1H, 1H-perchloropentanol, 1H, 1H-perbromopentanol, 1H, 1H-periodopentanol, 1H, 1H, 6H-perfluorohexanol, 1H, 1H, 6H-perchlorohexanol, 1H, 1H, 6H- Perbromohexanol, 1H, 1H, 6H-Periodohexanol, 1H, 1H-Perfluorohexanol, 1H, 1H-Perchlorohexanol, 1H, 1H-Perbromohexanol, 1H, 1H-Periodohexanol, 1H, 1H, 8H-perfluorooctanol, 1H, 1H, 8H-perchlorohexanol, 1H, 1H, 8H-perbromooctanol, 1H, 1H, 8H-periodooctanol, 1H, 1H-perfluorooctanol, 1H, 1H-perchloro Examples include octanol, 1H, 1H-perbromooctanol, 1H, 1H-periodooctanol and the like.

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

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

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

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

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

  Component (b) is preferably an amine such as bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis (2,2,3,3,3-pentafluoropropyl). ) Amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine, or bis (Pentafluorophenyl) amine and alcohols include trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1 -As trifluoromethylethanol, or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, phenols 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, Pentafluorophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (tri Fluoromethyl) phenol or 2,4,6-tris (trifluoromethyl) phenol and carboxylic acids are pentafluorobenzoic acid, or trifluoroacetic acid and sulfonic acids are trifluoromethanesulfonic acid.

  More preferably as component (b), bis (trifluoromethyl) amine, bis (pentafluorophenyl) amine, trifluoromethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 1, 1,1,3,3,3-hexafluoro-2- (trifluoromethyl) -2-propanol, 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.

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 nonmetallic atom belonging to Group 14 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). Specific examples of group 14 non-metallic atoms are carbon atoms and silicon atoms. 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, more preferably 2.

R ² in the above general formula [3] represents a hydrocarbon group, and when a plurality of R ² are present, the plurality of R ² may be the same or different from each other. Examples of the hydrocarbon group in R ² include the hydrocarbon group described as L ^{1 in the} general formula [1], the halogenated hydrocarbon described as R ^{1 in the} general formula [2], and the like. Is an alkyl group or an aryl group, more preferably an aryl group, 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) ) Silane diol, di (n-octyl) silane diol, di (n-decyl) silane diol, di (n-dodecyl) silane diol, di (n-pentadecyl) silane diol, di (n-eicosyl) silane diol,

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, di (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,

Methyl silane triol, ethyl silane triol, n-propyl silane triol, isopropyl silane triol, n-butyl silane triol, sec-butyl silane triol, tert-butyl silane triol, isobutyl silane triol, n-pentyl silane triol, neopentyl silane triol 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 , 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, anthracenylsilane 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, 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 this invention is a compound (henceforth a compound (A)) obtained by making said component (a)-(c) contact. Although it does not specifically limit as a method of making components (a)-(c) contact, For example, the method of mentioning below can be employ | adopted.
(A): Method in which component (a) and component (b) are contacted and then component (c) is contacted.
(B): A method of contacting the component (b) after contacting the component (a) with the component (c).
(C) A method of contacting component (a) after contacting component (b) and component (c).
The method (b) or (b) is preferred, that is, the compound (A) of the present invention is preferably a contact product obtained by bringing the component (a) and the component (b) into contact with the component (c). Or a compound obtained by contacting the component (b) with a contact product obtained by bringing the component (a) and the component (c) into contact with each other.
In the method of contacting the components (a) to (c), after contacting any two components selected from the components (a) to (c), the contact product is purified and selected as the purified product. A method of contacting the remaining components that have not been performed may be performed. After contacting any two components selected from the components (a) to (c), the contact product is not purified, You may perform the method of contacting the remaining components which were not selected.

  The contact treatment of the components (a) to (c) is preferably performed in an inert gas atmosphere. The contact treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C., more preferably 0 to 150 ° C. The contact treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours. Moreover, such a contact treatment may use a solvent, and may directly contact components (a) to (c) without using a solvent. The solvent used is a nonpolar solvent such as an aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent that is inert to the components (a) to (c), or a polar solvent such as a halide solvent or an ether solvent. Any of these can be used. Specific examples include butane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane, benzene, toluene, xylene, dichloromethane, difluoromethane, chloroform, 1,2- Dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, di-n -Butyl ether, methyl tert-butyl ether 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), if the molar ratio of the contact treatment amount of each component is component (a): component (b): component (c) = 1: y: z, y Is 0.1-8, preferably 1-6, more preferably 2-4, and even more preferably 2.5-3.5. z is 0.5 to 8, preferably 0.6 to 6, more preferably 0.7 to 4, and still more preferably 0.8 to 1.2.

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

  A specific example of the production method of the compound (A) of the present invention is further described in 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 toluene solution of triphenylbismuth, pentafluorophenol, which is a 3-fold molar amount with respect to triphenylbismuth, is dropped as a toluene solution of pentafluorophenol, and stirred at room temperature for 10 minutes to 24 hours. The mixture is stirred for 24 minutes for 24 minutes, the solution is concentrated, and the precipitated solid component is filtered off 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 conditions. 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). As a specific example of the catalyst for addition polymerization using the compound (A), an addition obtained by contacting the compound (A) and a Group 3-11 or lanthanoid series metal compound (hereinafter referred to as compound (B)). A polymerization catalyst, a compound (A), a compound (B), and an organoaluminum compound (hereinafter referred to as compound (C)) may be mentioned as an addition polymerization catalyst, which is preferable from the viewpoint of enhancing the catalytic activity. 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 bringing them into contact 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 group 3-11 of the periodic table of elements or a lanthanoid series metal. .L ² representing the atom is a group containing a group or a hetero atom having a cyclopentadiene type anion skeleton, if L ² there is a plurality, they may be different from one another the same, a plurality of L ² May be directly linked, or 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. 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 may be the same or different from each other. May be.)

In the general formula [4], M ² is a metal atom of Group 3 to 11 of the periodic table of elements (IUPAC 1989) or a lanthanoid series. Specific examples thereof include scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom. , Samarium atoms, ytterbium atoms, and the like. M 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. A plurality of L ² may be directly linked and 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. May be.

Examples of the group having a cyclopentadiene type anion skeleton in L ² include η ^5- (substituted) cyclopentadienyl group, η ^5- (substituted) indenyl group, and η ^5- (substituted) fluorenyl group. Specifically, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ -tert-butylcyclopentadienyl group, η ⁵ -1,2-dimethylcyclopentadienyl Group, η ⁵ -1,3-dimethylcyclopentadienyl group, η ⁵ -1-tert-butyl-2-methylcyclopentadienyl group, η ⁵ -1-tert-butyl-3-methylcyclopentadienyl Group, η ⁵ -1-methyl-2-isopropylcyclopentadienyl group, η ⁵ -1-methyl-3-isopropylcyclopentadienyl group, η ⁵ -1,2,3-trimethylcyclopentadienyl group, eta ^{5-1,2,4-trimethyl} cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - indenyl group, eta ⁵ Tetrahydroindenyl group, eta ^{5-2-methylindenyl} group, eta ^{5-3-methylindenyl} group, eta ^{5-4-methylindenyl} group, eta ^{5-5-Mechiruinde} Nyl group, η ⁵ -6-methylindenyl group, η ⁵ -7-methylindenyl group, η ⁵ -2-tert-butylindenyl group, η ⁵ -3-tert-butylindenyl group, η ^5- 4-tert-butyl indenyl group, η ⁵ -5-tert-butyl indenyl group, η ⁵ -6-tert-butyl indenyl group, η ⁵ -7-tert-butyl indenyl group, η ⁵ -2, 3-dimethyl-indenyl group, eta ^{5-4,7-dimethyl-indenyl} group, eta ^{5-2,4,7-trimethyl} indenyl group, eta ^{5-2-methyl-4-isopropylindenyl} group, eta ⁵ - 4,5 benzindenyl group, eta ^5-2-methyl - , 5-benzindenyl group, eta ^5-4-phenyl indenyl group, eta ^{5-2-methyl-5-phenyl} indenyl group, eta ^{5-2-methyl-4-phenyl} indenyl group, eta ^5-2-methyl 4-naphthyl indenyl group, eta ⁵ - fluorenyl group, eta ^{5-2,7-dimethyl} fluorenyl group, eta ^5-2,7-di -tert- butyl fluorenyl groups, and their substitution products Is mentioned.

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

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

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

Specific examples of R ³ in the general formula [5] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Examples thereof include 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].

(In the formula, R ^{41 to} R ⁴⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon oxy group, a silyl group, or an amino group, and two or more of them may be bonded to each other. And 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, and tert-butyl. Group, 2,6-dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl Group, methyl group, triethylsilyl group, diphenylmethylsilyl group, 1-methyl-1-phenylethyl group, 1,1-dimethylpropyl group, 2-chlorophenyl group, pentafluorophenyl group and the like.

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

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.

When there are a plurality of L ² groups, groups having a cyclopentadiene-type anion skeleton, groups having a cyclopentadiene-type anion skeleton and a group containing a hetero atom, or groups containing a hetero atom are directly connected to each other. It 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 residues include alkylene groups such as methylene group, ethylene group, propylene group; substituted alkylene groups such as dimethylmethylene group (isopropylidene group) and diphenylmethylene group; silylene group; dimethylsilylene group, 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 preferred are 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, it does not include a group having a cyclopentadiene-type anion skeleton) or a hydrocarbon oxy group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group herein include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group.

Examples of the alkyl group used for X 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 or an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluoro group. Examples include a hexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group.
Any of these alkyl groups may be substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group.

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

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

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

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

Examples of the hydrocarbon oxy group used for X ¹ include an alkoxy group, an aryloxy group, an aralkyloxy group, etc., and an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or carbon. Aralkyloxy groups having 7 to 20 atoms are preferred. Specific examples thereof include the hydrocarbon oxy group exemplified by L ¹ in the general formula [1], (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, and (4-methylphenyl) methoxy group. , (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methyl group, (3,4- Dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, benzyloxy group, etc. Can do. More preferably 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, and more preferably a methoxy 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, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, benzyl group, allyl group, methallyl group, methoxy group, ethoxy group, or phenoxy group. More preferably, they are a chlorine atom, a methyl group, a methoxy group, or a phenoxy group.

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

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

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

Specific examples of the compound in which M 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,

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

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

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

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

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

(Tert-Butylamide) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl- 1,2-ethanediyltitanium dichloride, (tert-butylamido) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (phenylphosphide) tetramethylcyclopentadi Enildimethylsilane titanium dichloride,

(Tert-Butylamido) indenyl-1,2-ethanediyltitanium dichloride, (tert-Butylamido) tetrahydroindenyl-1,2-ethanediyltitanium dichloride, (tert-Butylamido) fluorenyl-1,2-ethanediyltitanium dichloride, (Tert-butylamido) indenyldimethylsilane titanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilane titanium dichloride, (tert-butylamido) fluorenyldimethylsilane titanium dichloride,

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

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

(Di-tert-butyl-1,3-propanediamide) titanium dichloride, (dicyclohexyl-1,3-propanediamide) titanium dichloride, [bis (trimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis ( tert-butyldimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-dimethylphenyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-diisopropylphenyl) -1 , 3-propanediamide] titanium dichloride, [bis (2,6-di-tert-butylphenyl) -1,3-propanediamide] titanium dichloride, [bis (triisopropylsilyl) naphthalenediamide] titanium dichloride, [bis ( Trimethylsilyl) naphth 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] Examples thereof include titanium trichloride.

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

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

（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。） Furthermore, among the metal compounds represented by the general formula [4], specific examples of the compounds in which M ² is a titanium atom include metal compounds represented by the following general formulas [7] to [9].

(In the above general formulas [7] to [9], M ^{3 to} M ⁷ each independently represent an atom of Group 4 of the periodic table of elements, and A ^{1 to} A ⁵ each independently represent the periodic rule of the element. Represents an atom of Group 16 in the table, and J ^{1 to} J ⁵ each independently represents an atom of Group 14 of the periodic table of elements, and Cp ^{1 to} Cp ⁵ 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 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, Represents a substituted silyl group, hydrocarbon oxy group, disubstituted amino group, hydrocarbon thio group, or hydrocarbon seleno group, 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 general formulas [7] to [9], the metal atom represented by M ^{3 to} M ⁷ represents an atom belonging to Group 4 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989), for example, Examples thereof include a titanium atom, a zirconium atom, and a hafnium atom. Preferably, they are 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 η ^5- (substituted) cyclopentadienyl group and η ^5- (substituted) indenyl. Group, η ^5- (substituted) fluorenyl group and the like. If specifically exemplified, for example, eta ⁵ - cycloalkyl Bae Ntajieniru group, eta ⁵ - methylcyclopentadienyl group, eta ⁵ - dimethyl cyclopentadienyl group, eta ⁵ - trimethyl cyclopentadienyl group, eta ⁵ - tetra methylcyclopentadienyl group, eta ⁵ - Echirushikuro Bae Ntajieniru group, eta ^5-n-propyl cyclopentadienyl group, eta ⁵ - isopropyl cyclopentadienyl group, eta ^{5-n-butylcyclopentadienyl} group, eta ^{5-sec-butylcyclopentadienyl} group, eta ^{5-tert-Buchirushikuro} Bae Ntajieniru group, eta ⁵ - phenyl cycloalkyl Bae Ntajieniru group, eta ⁵ - trimethylsilylcyclopentadienyl Bae Ntajieniru group, eta ^{5-tert-butyldimethylsilyl} cyclo Bae Ntajieniru Group, η ⁵ -indenyl group, η ⁵ -methylindenyl group, η ⁵ -dimethylindenyl group , Η ⁵ -n-propylindenyl group, η ⁵ -isopropylindenyl group, η ⁵ -n-butylindenyl group, η ⁵ -tert-butylindenyl group, η ⁵ -phenylindenyl group, η ^5- Methylphenylindenyl group, η ⁵ -naphthylindenyl group, η ⁵ -trimethylsilylindenyl group, η ⁵ -tetrahydroindenyl group, η ⁵ -fluorenyl group, η ⁵ -methylfluorenyl group, η ⁵ -dimethylfluor Oreniru group, eta ^{5-tert-butyl-fluorenyl} group, eta ⁵ - di-tert-butyl-fluorenyl group, eta ⁵ - phenyl fluorenyl group, eta ⁵ - diphenyl fluorenyl group, eta ⁵ - trimethylsilyl Fluorenyl group, η ⁵ -bistrimethylsilylfluorenyl group and the like can be mentioned, preferably η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group , Η ⁵ -n-butylcyclopentadienyl group, η ⁵ -tert-butylcyclopentadienyl group, η ⁵ -tetramethylcyclopentadienyl group, η ⁵ -indenyl group, η ⁵ -tetrahydroindenyl group, η ⁵ -fluorenyl group.

As halogen atoms 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 preferable, and a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable.

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

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

As the alkyl 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], , 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.

As the aralkyl 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] 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 group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n -Decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc. It is.
All of these aralkyl groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group It may be substituted with.

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

As 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] 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 substituted with.

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

The 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 Aryloxy group; may be substituted with an aralkyloxy group such as benzyloxy group. Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, Preferable examples include an alkyl group having 1 to 20 carbon atoms such as a cyclohexyl group and an aryl group such as a phenyl group.

As substituted silyl groups in X ^{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 monosubstituted silyl group having 1 to 20 carbon atoms such as a methylsilyl group, an ethylsilyl group or a phenylsilyl group; a disubstituted silyl group having 2 to 20 carbon atoms such as a dimethylsilyl group, a diethylsilyl group or a diphenylsilyl group. Trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyl Dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl Such as trisubstituted silyl group having 3 to 20 carbon atoms, 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] For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n -Octyloxy group, n-dodecyloxy group, n-pentadecyloxy group, n-eicosyloxy group, etc. are mentioned.
These alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group It may be substituted with.

Examples of the alkoxy group in X ^{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] , 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] Are, for example, benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4- (Dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethyl) 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, anthracenylmeth Such as sheet group, and the like.
All of these aralkyloxy groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy such as benzyloxy group It may be substituted with a group or the like.

As an aralkyloxy group in X ^{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, more preferably a benzyloxy group.

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] Are, for example, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2, 6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert- Butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, , 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- Examples include hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like.
These aryloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy such as benzyloxy 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, the hydrocarbon group or the silyl group being a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. An aryl group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group; and the like. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, and an n-hexyl group. Preferred examples include alkyl groups having 1 to 20 carbon atoms such as cyclohexyl groups; aryl groups having 6 to 20 carbon atoms such as phenyl groups; aralkyl groups having 7 to 10 carbon atoms such as benzyl groups, and the like, and silyl groups Examples thereof include a trimethylsilyl group and a tert-butyldimethylsilyl group. Examples of the disubstituted amino group include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group, di-tert-butylamino group. Group, diisobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group, etc. And preferably a dimethylamino group, a diethylamino group, a diisopropylamino group, a di-tert-butylamino group, or a bistrimethylsilylamino group.

Hydrocarbon thio groups in X ^{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.

As the alkylthio 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] For example, methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, n-pentylthio group, neopentylthio group, n-hexylthio group, n-octylthio Group, n-dodecylthio group, n-pentadecylthio group, n-eicosylthio group and the like.
These alkylthio groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group It may be substituted with.

As the alkylthio 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] , 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] Are, for example, benzylthio, (2-methylphenyl) methylthio, (3-methylphenyl) methylthio, (4-methylphenyl) methylthio, (2,3-dimethylphenyl) methylthio, (2,4-dimethyl) Phenyl) methylthio group, (2,5-dimethylphenyl) methylthio group, (2,6-dimethylphenyl) methylthio group, (3,4-dimethylphenyl) methylthio group, (3,5-dimethylphenyl) methylthio group, 2,3,4-trimethylphenyl) methylthio group, (2,3,5-trimethylphenyl) methylthio group, (2,3,6-trimethylphenyl) methylthio group, , 4,5-trimethylphenyl) methylthio group, (2,4,6-trimethylphenyl) methylthio group, (3,4,5-trimethylphenyl) methylthio group, (2,3,4,5-tetramethylphenyl) Methylthio group, (2,3,4,6-tetramethylphenyl) methylthio group, (2,3,5,6-tetramethylphenyl) methylthio group, (pentamethylphenyl) methylthio group, (ethylphenyl) methylthio group, (N-propylphenyl) methylthio group, (isopropylphenyl) methylthio group, (n-butylphenyl) methylthio group, (sec-butylphenyl) methylthio group, (tert-butylphenyl) methylthio group, (n-hexylphenyl) methylthio Group, (n-octylphenyl) methylthio group, (n-decylphenyl) 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 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.

As the arylthio 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] For example, phenylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-methylphenylthio group, 2,3-dimethylphenylthio group, 2,4-dimethylphenylthio group, 2,5-dimethylphenyl Thio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 2-tert-butyl-3-methylphenylthio group, 2-tert-butyl-4 -Methylphenylthio group, 2-tert-butyl-5-methylphenylthio group, 2-tert-butyl-6-methylphenylthio group, 2,3,4-trimethylphenylthio group, 2,3, -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, etc. are mentioned.
These arylthio groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group It may be substituted with.

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

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] Is, for example, methylseleno group, ethylseleno group, n-propylseleno group, isopropylseleno group, n-butylseleno group, sec-butylseleno group, tert-butylseleno group, n-pentylseleno group, neopentylseleno group, n-hexylseleno group N-octylseleno group, n-dodecylseleno group, n-pentadecylseleno group, n-eicosylseleno group and the like.
These alkylseleno groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy such as benzyloxy group It may be substituted with a group or the like.

As an 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] Are, for example, benzylseleno group, (2-methylphenyl) methylseleno group, (3-methylphenyl) methylseleno group, (4-methylphenyl) methylseleno group, (2,3-dimethylphenyl) methylseleno group, (2,4- (Dimethylphenyl) methylseleno group, (2,5-dimethylphenyl) methylseleno group, (2,6-dimethylphenyl) methylseleno group, (3,4-dimethylphenyl) methylseleno group, (3,5-dimethylphenyl) methylseleno group, (2,3,4-trimethylphenyl) methylseleno group, (2,3,5-trimethylphenyl) methylseleno group, (2,3,6-trimethyl) Phenyl) 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 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 an 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 group, 2-methylphenylseleno group, 3-methylphenylseleno group, 4-methylphenylseleno group, 2,3-dimethylphenylseleno group, 2,4-dimethylphenylseleno group, 2,5- Dimethylphenylseleno group, 2,6-dimethylphenylseleno group, 3,4-dimethylphenylseleno group, 3,5-dimethylphenylseleno group, 2-tert-butyl-3-methylphenylseleno group, 2-tert-butyl -4-methylphenylseleno group, 2-tert-butyl-5-methylphenylseleno group, 2-tert-butyl-6-methylphenylseleno group, 2,3,4-tri Tilphenylseleno group, 2,3,5-trimethylphenylseleno group, 2,3,6-trimethylphenylseleno group, 2,4,5-trimethylphenylseleno group, 2,4,6-trimethylphenylseleno group, 2 -Tert-butyl-3,4-dimethylphenylseleno group, 2-tert-butyl-3,5-dimethylphenylseleno group, 2-tert-butyl-3,6-dimethylphenylseleno group, 2,6-di- tert-butyl-3-methylphenylseleno group, 2-tert-butyl-4,5-dimethylphenylseleno group, 2,6-di-tert-butyl-4-methylphenylseleno group, 3,4,5-trimethyl Phenylseleno group, 2,3,4,5-tetramethylphenylseleno group, 2-tert-butyl-3,4,5-trimethylphenylseleno Group, 2,3,4,6-tetramethylphenylseleno group, 2-tert-butyl-3,4,6-trimethylphenylseleno group, 2,6-di-tert-butyl-3,4-dimethylphenylseleno Group, 2,3,5,6-tetramethylphenylseleno group, 2-tert-butyl-3,5,6-trimethylphenylseleno group, 2,6-di-tert-butyl-3,5-dimethylphenylseleno Group, pentamethylphenylseleno group, ethylphenylseleno group, n-propylphenylseleno group, isopropylphenylseleno group, n-butylphenylseleno group, sec-butylphenylseleno group, tert-butylphenylseleno group, n-hexylphenyl Seleno group, n-octylphenylseleno group, n-decylphenylseleno group, n-tetradecylpheny Examples thereof include a ruseleno group, a naphthylseleno group, and an anthracenylseleno group.
These arylseleno groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy such as benzyloxy group It may be substituted with a group or the like.

As an arylseleno group in X ^{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 general formulas [7] to [9], X ^{2 to} X ⁵ are preferably 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], 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 are each independently a hydrogen atom, An alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group or an aryloxy group is preferred.

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

In the general formulas [7] to [9], examples of the group 16 atom in 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 group 14 atom in the periodic table of elements shown as J ^{1 to} J ⁵ include a carbon atom, a silicon atom, and a germanium atom. Preferably, they are a carbon atom and a silicon atom.

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

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

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

Specific examples of the metal compound represented by the general formula [7] include dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) ( 3-methyl-2-phenoxy) titanium dichloride, dimethylsilene (η ⁵ -cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (3- tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) ) (3,5-di-tert-butyl-2-fe Carboxymethyl) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert-butyldimethyl Silyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) ) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (Η ⁵ -Cyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -cyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride, dimethylsilylene (η ⁵ -tetra Methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadiene) Enyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetra Methyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert -Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -Tetramethi Rucyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2- Phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (1-naphthoxy- 2-yl) titanium dichloride, etc. and the compound (eta ⁵ - cyclopentadienyl) (eta ⁵ - methylcyclopentadienyl), (eta ⁵ - dimethyl cyclopentadienyl), (eta ⁵ - trimethylcyclopentadienyl Dienyl), (η ⁵ -n-butylcyclopentadienyl) , (Η ⁵ -tert-butylcyclopentadienyl), (η ⁵ -trimethylsilylcyclopentadienyl), (η ⁵ -tert-butyldimethylsilylcyclopentadienyl), (η ⁵ -indenyl), (η ⁵ - methylindenyl), (eta ⁵ - phenyl indenyl) or (eta ⁵ - such as compound change fluorenyl) and the like. Moreover, the compound etc. which changed 2-phenoxy of the said compound into 3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxy, or 3-tert-butyldimethylsilyl-2-phenoxy can be mentioned. Moreover, the compound etc. which changed the dimethylsilylene of the said compound into diethylsilylene, diphenylsilylene, or dimethoxysilylene can be mentioned. Moreover, the compound etc. which changed the dichloride of the said compound into dimethyl, dibenzyl, dimethoxide, diphenoxide, bis (dimethylamino), or bis (diethylamino), etc. can be mentioned. Furthermore, the compound etc. which changed the titanium of the said compound into the zirconium or hafnium can be mentioned.

Specific examples of the metal compound represented by the general formula [8] include μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η ⁵ − Cyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ -Oxobis {isopropylidene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylide (Η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-methyl-2- Phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropi Redene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) ) Titanium methoxide},

μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium methoxide}, μ -Oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene ( eta ⁵ - cyclopentadienyl) (2-phenol Shi) titanium methoxide}, .mu. Okisobisu {dimethylsilylene (eta ⁵ - cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, .mu. Okisobisu {dimethylsilylene (eta ⁵ -methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) Titanium chloride}, μ-oxobis {dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy ) Titanium chloride}, μ-oxobis {dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide} and the like (η ⁵ − cyclopentadienyl) (η ⁵ - dimethyl cyclopentadienyl), (η ⁵ - trimethyl cyclopentadienyl), (η ⁵ -n- butylcyclopentadienyl), (η ⁵ -tert- butyl cyclopentadiene dienyl), (η ⁵ - trimethylsilyl cyclopentadienyl), (η ⁵ -tert- butyldimethylsilyl cyclopentadienyl), (η ⁵ - indenyl), (η ⁵ - methylindenyl), (η ⁵ - And a compound changed to (phenylindenyl) or (η ⁵ -fluorenyl). In addition, (2-phenoxy) of the above compound is changed to (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), ( Examples thereof include compounds changed to (3-phenyl-5-methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy). Moreover, the compound etc. which changed the chloride of the said compound into methyl, benzyl, phenoxide, dimethylamino, or diethylamino can be mentioned. Furthermore, the compound etc. which changed the titanium of the said compound into the zirconium or hafnium can be mentioned.

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

Di-μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η ⁵ -cyclopentadienyl) (3-tert-butyl-5 -Methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η ⁵ -methylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η ⁵ -methylcyclohexane) Pentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (η ⁵ -tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di -μ- Okisobisu {dimethylsilylene (eta ⁵ - tetramethylcyclopentadienyl) (3-tert Butyl-5-methyl-2-phenoxy) titanium}, etc. and the above compound (eta ⁵ - cyclopentadienyl) (eta ⁵ - dimethyl cyclopentadienyl), (eta ⁵ - trimethyl cyclopentadienyl) ( eta ^5-n-butyl cyclopentadienyl), (eta ^{5-tert-butylcyclopentadienyl),} (eta ⁵ - trimethylsilyl cyclopentadienyl), (eta ^{5-tert-butyldimethylsilyl} cyclopentadienyl) , and the like - (fluorenyl eta ⁵⁾ compound has been changed to (eta ⁵ - indenyl), (eta ⁵ - - methylindenyl), (eta ^5-phenyl indenyl) or. In addition, (2-phenoxy) of the above compound is changed to (3-methyl-2-phenoxy), (3,5-dimethyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), ( Examples thereof include compounds changed to (3-phenyl-5-methyl-2-phenoxy) or (3-trimethylsilyl-5-methyl-2-phenoxy). Furthermore, the compound etc. which changed the titanium of the said compound into the zirconium or hafnium can be mentioned.

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

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

Methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cyclobutane}] nickel dibromide, methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cyclopentane}] nickel dibromide , Methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cyclohexane}] nickel dibromide, methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cycloheptane}] nickel di bromide,

2,2′-methylenebis [(4R) -4-isopropyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di-n-propyloxazoline] nickel dibromide, methylenebis [(4R) -4-isopropyl-5,5-diisopropyloxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diphenyloxazoline ] Nickel dibromide, 2,2'-methylenebis [(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-methoxyphen) 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 , 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--4-tert-butyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-diphenyloxazoline] nickel dibromide, 2, 2'-methylenebis [(4R) -4-tert-butyl-5,5-dicyclohexyloxazoline] nickel di Romide, 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-fur Nyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methylpheni) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl- 5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibrom 2,2'-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1'-cyclobutane}] nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-phenyloxazoline- 5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [ Spiro {(4R) -4-phenyloxazoline-5,1'-cycloheptane}] nickel dibromide,

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

Further, specific examples of the compound in which M 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. Examples thereof include a compound changed to diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide or di (2,6-di-tert-butylphenoxide).

（式中、Ｒ⁷¹およびＲ⁷²はそれぞれ２，６−ジイソプロピルフェニル基であり、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。） Specific examples of the compound in which M ² is a nickel atom include compounds represented by the following general formula [10].

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

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

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

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

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

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

  The metal compound used for the above-mentioned 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], more preferably a metal in which M ² in the above general formula [4] is a Group 4 atom in the periodic table. More preferably, it is 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 organoaluminum 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 Y, the plurality of Y 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 methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, 2-methylhexyl group, n-octyl group and the like, preferably ethyl group, n -A butyl group, an isobutyl group, an n-hexyl group, or an n-octyl group.

  Specific examples when Y in the general formula [11] is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom.

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

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

  As an alkoxy group in Y of general formula [11], a C1-C24 alkoxy group is preferable, More preferably, they are a methoxy group, an ethoxy group, or a tert- butoxy group.

Examples of the aryloxy group in Y of 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, etc. are mentioned.
Any of these aryloxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group.

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

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

  The aralkyloxy group in Y of 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, tri -Trialkylaluminum such as n-octylaluminum; Dialkylaluminum such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride Chloride; methyl aluminum dichloride, ethyl aluminum dichloride, n-propyl aluminum dichloride, n-butyl aluminum Alkyl aluminum dichlorides such as um dichloride, isobutyl aluminum dichloride, 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 hydrides such as hexyl aluminum hydride; alkyl (dialkoxy) aluminum such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, methyl (di-tert-butoxy) aluminum; dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum Dimethyl (tert-butoxy) aluminum, etc. Alkyl (alkoxy) aluminum; alkyl (diaryloxy) aluminum such as methyl (diphenoxy) aluminum, methyl bis (2,6-diisopropylphenoxy) aluminum, methyl bis (2,6-diphenylphenoxy) aluminum; dimethyl (phenoxy) aluminum, dimethyl ( Examples include dialkyl (aryloxy) aluminum such as 2,6-diisopropylphenoxy) aluminum and dimethyl (2,6-diphenylphenoxy) aluminum.

  Among these, trialkylaluminum is preferable, and trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum is particularly preferable. Triisobutylaluminum or tri-n-octylaluminum is preferred.

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

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

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

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

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

  The addition polymerization catalyst of the present invention is particularly suitable as an olefin polymerization catalyst, and is preferably used in a method for producing an olefin polymer. Such an olefin polymer is particularly preferably a copolymer of ethylene and an α-olefin, and among them, a copolymer of ethylene and an α-olefin having a polyethylene crystal structure is preferable. Here, the α-olefin is preferably an α-olefin having 3 to 8 carbon atoms, specifically, 1-butene, 1-hexene, 1-octene and the like.

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

  The method for supplying the compounds (A) to (C) to the reactor is not particularly limited. A method of supplying each compound in a solid state, a solution dissolved in a hydrocarbon solvent from which components for deactivating the catalyst such as moisture and oxygen are sufficiently removed, or a method of supplying in a suspended or slurry state, etc. Can be mentioned.

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

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

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

(1) α-olefin unit content in copolymer (short chain branching degree)
The α-olefin unit content (short chain branching degree) in the obtained polymer was determined from the infrared absorption spectrum. Measurement and calculation were carried out by utilizing 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 measured in the tetralin solution at 135 degreeC using the Ubbelohde viscometer.

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

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

[Example 1]
(1) Preparation of bismuth compound In a 300 ml four-necked flask purged with argon, 9.88 g (22.4 mmol) of triphenylbismuth and 100 ml of toluene were added and stirred at room temperature. To this was added dropwise a solution of 12.6 g (68.5 mmol) of pentafluorophenol in 100 ml of toluene. After completion of dropping, the mixture was stirred at room temperature for 15.5 hours. Thereafter, the reaction was carried out sequentially for 4 hours under toluene reflux conditions, 18 hours at room temperature, 7 hours under toluene reflux conditions, and 17 hours at room temperature. The resulting yellow needle crystals were filtered off 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. To this, 0.243 g (1.13 mmol) of diphenylsilanediol and 10 ml of toluene were added at room temperature. Stirring was performed for 6 hours under reflux conditions. When stirring was stopped and the mixture was allowed to stand, a white precipitate was formed, and the supernatant was a yellow transparent liquid. Volatile components were distilled off under reduced pressure and dried to obtain white crystals.

(2) Production of addition polymer An autoclave with a stirrer having an internal volume of 400 ml was vacuum-dried and replaced with argon, and then 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 rise, the feed was made while adjusting the ethylene pressure to 0.6 MPa. After the system was stabilized, 0.25 ml (250 μmol) of triisobutylaluminum (1 mmol / ml toluene solution) was added, 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 white crystals obtained in (1) above. 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 / mol Zr / hour, S
CB = 15.5, Mw = 92000, and 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 substituted with argon and stirred at room temperature. 109 ml of a toluene solution of pentafluorophenol having a concentration of 2.00 mmol / mL (217 mmol as pentafluorophenol) was added dropwise thereto. After completion of the dropping, the reaction was carried out sequentially for 2 hours under toluene reflux conditions, 14 hours at room temperature, 7 hours under toluene reflux conditions, 91 hours at room temperature, and 3 hours under toluene reflux conditions. The yellow needle-like crystals produced by storage at 0 ° C. were filtered off and dried under reduced pressure at 40 ° C. 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. To this, 6.37 g (29.4 mmol) of diphenylsilanediol and 100 ml of toluene were added at room temperature. Stirring was performed for 6 hours under reflux conditions. When 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 reflux, the supernatant was extracted and transferred to a 1 liter four-necked flask. Since solid started to precipitate immediately, it was left to stand for 2 days. The supernatant was taken out again, and the volatile component was distilled off at 50 ° C. under reduced pressure, followed by drying to obtain 8.22 g of a pale yellow viscous solid. The elemental analysis results of the pale yellow viscous solid were Bi = 0.77 mmol / g, F = 7.4 mmol / g.

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

(2) Production of addition polymer An autoclave with a stirrer having an internal volume of 400 ml was vacuum-dried and replaced with argon. Then, 185 ml of 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 raising the temperature and feeding while adjusting the ethylene pressure to 2.5 MPa, the system was stabilized, and then 0.30 ml (300 μmol) of triisobutylaluminum (1 mmol / ml toluene solution) was added to compound B1 and triisobutylaluminum. Hexane solution (concentration of compound B1 is 0.5 μmol / ml, Al / Ti = 50) mixed with 1.0 ml (that is, compound B1 is 0.5 μmol, triisobutylaluminum is 25 μmol), followed by 5 ml of a 50 μmol Bi / ml toluene solution of the pale yellow viscous solid obtained in the above (1) (that is, Bi compound of 250 μmol) was added. 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 / mol Ti / hour.

[Comparative Example 1]
The autoclave with a stirrer having an internal volume of 400 ml 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 rise, the feed was made while adjusting the ethylene pressure to 0.6 MPa. After the system was stabilized, 0.25 ml (250 μmol) of triisobutylaluminum (1 mmol / ml toluene solution) was added, and ethylenebis (indenyl) zirconium was added. 0.5 ml (1 μmol) of dichloride (2 μmol / ml toluene solution) was added, followed by 49.8 mg (113 μmol) of triphenylbismuth. 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 ethylene / 1-hexene copolymer was obtained.

[Comparative Example 2]
The autoclave with a stirrer having an internal volume of 400 ml 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 rise, the feed was made while adjusting the ethylene pressure to 0.6 MPa. After the system was stabilized, 0.25 ml (250 μmol) of triisobutylaluminum (1 mmol / ml toluene solution) was added, 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 compound A1 synthesized in Example 1 (1) was added. 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 ethylene / 1-hexene copolymer was obtained.

[Comparative Example 3]
(1) Preparation of bismuth compound 1.06 g (1.25 mmol) of compound A1 synthesized in Example 1 (1) and 30 ml of toluene were placed in a 100 ml four-necked flask substituted with argon. To this, 0.125 g (0.578 mmol) of diphenylsilanediol and 10 ml of toluene were added at room temperature. Stirring was performed under reflux conditions for 3 hours. When allowed to stand overnight at room temperature, needle-like crystals were formed. After the crystals were filtered off and dried under reduced pressure, 70.2 mg of these crystals were placed in a separately prepared flask, and 10 ml of toluene was added to form a slurry.

(2) Production of addition polymer An autoclave with a stirrer having an internal volume of 400 ml was vacuum-dried and replaced with argon, and then 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 rise, the feed was made while adjusting the ethylene pressure to 0.6 MPa. After the system was stabilized, 0.25 ml (250 μmol) of triisobutylaluminum (1 mmol / ml toluene solution) was added, and ethylenebis (indenyl) zirconium was added. 0.5 ml (1 μmol) of dichloride (2 μmol / ml toluene solution) was added, and then 5 ml of the slurry obtained in the above (1) was added. 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 ethylene / 1-hexene copolymer was obtained.

[Example 3]
(1)
A 100 ml four-necked flask purged with nitrogen was charged with 17.5 ml of toluene and 12.5 ml (25.0 mmol) of a toluene solution of triethylaluminum (2.00 mol / liter) 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 dropping, the mixture was stirred at 5 ° C. for 1.5 hours. Thereafter, 5.3 g (24.5 mmol) of diphenylsilanediol was added. Then, it stirred at 5 degreeC for 1 hour, 40 degreeC for 1 hour, and 80 degreeC for 2 hours. A dark green slurry solution was obtained. (From the amount charged, the Al atom equivalent concentration is 0.75 mol / l)

(2) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer having an internal volume of 3 liters substituted with argon was evacuated, charged with 1000 ml of toluene and 30 g of 1-butene, and heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 0.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was 1-butene = 5.66 mol%. To this, 0.9 ml of a hexane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 0.25 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide adjusted to a concentration of 2 μmol / ml was added, and then the dark green slurry solution obtained in Example 3 (1) above. 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. Then, after deashing and washing with a hydrochloric acid / methanol solution, vacuum drying was performed 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 (12)

A compound obtained by contacting the following components (a) to (c), wherein the contact treatment amount of component (b) per 1 mol of component (a) is 0.1 to 8 mol, and component (a) 1 The compound whose contact processing amount of the component (c) per mol is 0.5-8 mol.
(A): Compound represented by the following general formula [1] M ¹ L ¹ _r [1]
(B): Compound represented by the following general formula [2] R ¹ O H [2]
(C): Compound represented by the following general formula [3] R ² _4-n Si (OH) _n [3]
(In the above general formulas [1] to [3], M ¹ represents an aluminum atom or a bismuth atom , r represents a number corresponding to the valence of M ¹ , and L ¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group. Or a hydrocarbon oxy group, and when a plurality of L ¹ are present, the plurality of L ¹ may be the same or different from each other, and R ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group. And when a plurality of R ¹ are present, the plurality of R ¹ may be the same or different from each other, n represents a number of 2 or more and 4 or less, R ² represents a hydrocarbon group, and R ² represents When there are a plurality of R ^{2 s} , they may be the same or different.) The compound according to claim 1 , wherein R ^{1 in} component (b) is a halogenated hydrocarbon group. The compound according to claim 1 or 2 , wherein component (b) is a fluorinated phenol. 4. A compound according to claim 3 , wherein the fluorinated phenol is pentafluorophenol. The compound according to claim 1 or 2 , wherein component (b) is a fluorinated alcohol. 6. A compound according to claim 5 , wherein the fluorinated alcohol is 1,1,1,3,3,3-hexafluoro-2-propanol. The compound according to any one of claims 1 to 6 , wherein M ^{1 of the} component (a) is a bismuth atom. The compound according to any one of claims 1 to 6 , wherein M ^{1 of the} component (a) is an aluminum atom. A catalyst for olefin polymerization comprising contacting the compound (A) according to any one of claims 1 to 8 and a Group 4 metal compound (B) having at least one group having a cyclopentadiene type anion skeleton . The compound (A) according to any one of claims 1 to 8 , a group 4 metal compound (B) having at least one group having a cyclopentadiene-type anion skeleton , and an organoaluminum compound (C) are contacted. Olefin polymerization catalyst. The manufacturing method of the olefin polymer using the catalyst for olefin polymerization of Claim 9 or 10 . The process according to claim 1 1 olefin polymer according olefin polymer is a copolymer of ethylene and α- olefin.