JP4218482B2 - Contact treated product, catalyst component for addition polymerization, catalyst for addition polymerization, and method for producing addition polymer - Google Patents

Description

  The present invention relates to a contact treated product useful as an addition polymerization catalyst component, an addition polymerization catalyst component comprising the contact treated product, an addition polymerization catalyst using the addition polymerization catalyst component, and the addition polymerization catalyst. The present invention relates to a method for producing an addition polymer using

  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, pentafluorophenol and water has been developed as an activation promoter component, and a catalyst obtained by contacting the compound with a metallocene complex is a highly active catalyst. (For example, patent document 3 etc.).

JP 58-19309 A Japanese translation of PCT publication No. 1-502036 JP 2001-247612 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 problems to be solved by the present invention are a contact treatment product used as a component of an addition polymerization catalyst having excellent polymerization activity, an addition polymerization catalyst component comprising the contact treatment product, and the addition polymerization catalyst. An object of the present invention is to provide a catalyst for addition polymerization using components and a method for producing an addition polymer using the catalyst for addition polymerization.

That is, the first of the present invention comprises a contact-treated product obtained by contacting the following component (a) with the following component (b), then contacting the following component (c), and further contacting the following component (d). A catalyst component for olefin polymerization, wherein the amount of contact treatment between component (b) and component (c) per component (a) satisfies the following formula (I), and component (a) component per mol ( Olefin polymerization characterized in that the contact treatment amount of b) is 0.3 to 1 mole and the contact treatment amount of component (d) per mole of component (a) is 0.01 to 0.7 mole. Catalyst components,
Or a catalyst component for olefin polymerization comprising a contact treated product obtained by bringing the following component (c) into contact with a contact treated product obtained by bringing the following components (a), (b) and (d) into contact; a) The contact treatment amount of component (b) and component (c) per mole satisfies the following formula (I), and the contact treatment amount of component (b) per mole of component (a) is 0.3 to The amount of the contact treatment of component (d) per mole of component (a) is 0.01 to 0.7 mole, and the catalyst component for olefin polymerization is characterized by 1 mole .
(A): Compound ZnL ¹ ₂ [1] represented by the following general formula [1]
(B): Compound R ¹ T ¹ H represented by the following general formula [2] [2]
(C): Compound T ² H ₂ [3] represented by the following general formula [3]
(D): Compound R ³ ₃ N [4] represented by the following general formula [4]
(In the above general formulas [1] to [3], L ¹ represents a hydrogen atom or a hydrocarbon group , and two L ^{1 s} may be the same or different from each other, and T ¹ and T ² are independent of each other. Represents an oxygen atom or a sulfur atom, R ¹ represents a halogenated alkyl group or a halogenated aryl group, In the above general formula [4], R ³ represents a hydrocarbon group, and three R ^{3 s} are the same as each other. Or different.)
| 2-y-2z | ≦ 0.2 (I)
(In the above formula (I), y represents the component (b) contact treatment amount (mol) per mole of component (a), and z represents the component (c) contact treatment amount (mol) per mole of component (a). )
The second of the present invention relates to an olefin polymerization catalyst using the above olefin polymerization catalyst component.
A third aspect of the present invention relates to a method for producing an olefin polymer using the olefin polymerization catalyst.

  According to the present invention, a contact treated product used as a component of an addition polymerization catalyst having excellent polymerization activity, an addition polymerization catalyst component comprising the contact treated product, an addition polymerization catalyst using the addition polymerization catalyst component, and the A method for producing an addition polymer using the catalyst for addition polymerization can be provided.

Component (a) of the present invention is a compound represented by the following general formula [1].
M ¹ L ¹ _r [1]
M ¹ in the above general formula [1] represents a group 3 to group 12, group 14, group 15, or lanthanoid series metal atom of the periodic table of elements (IUPAC inorganic chemical nomenclature revised edition 1989). . Specific examples thereof include scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, chromium atom, molybdenum atom, manganese atom, rhenium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom. Palladium atom, platinum atom, copper atom, silver atom, gold atom, zinc atom, cadmium atom, mercury atom, germanium atom, tin atom, lead atom, antimony atom, bismuth atom, samarium atom, ytterbium atom and the like. M ¹ is preferably a metal atom of Group 5 to Group 12, Group 14 or Group 15, more preferably a metal atom of Group 8 to Group 12, Group 14 or Group 15. More preferably a metal atom of Group 12, 14, or 15, particularly preferably a metal atom of Group 12, and most preferably a zinc atom.

R in the general formula [1] represents a valence of M ^1, for example, when M ¹ is a zinc atom r is 2.

L ¹ in the general formula [1] represents a hydrogen atom, a halogen atom, a hydrocarbon group or a hydrocarbon oxy group, and when a plurality of L ¹ are present, each L ¹ may be the same or different. 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.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups such as methyl group, ethyl group and isopropyl group; alkoxy groups such as methoxy group and ethoxy group; phenoxy group and the like An aryloxy group of the above; may be substituted with an aralkyloxy group such as a benzyloxy group.

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

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

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

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

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

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

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

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

Specific examples of the component (a) include, when M ¹ is a zinc atom, dimethyl zinc, diethyl zinc, dipropyl zinc, dinormal butyl zinc, diisobutyl zinc, dinormal hexyl zinc, diallyl zinc, bis Dialkyl zinc such as (cyclopentadienyl) zinc; Diaryl zinc such as diphenyl zinc, dinaphthyl zinc and bis (pentafluorophenyl) zinc; methyl zinc chloride, ethyl zinc chloride, propyl zinc chloride, normal butyl zinc chloride, isobutyl zinc chloride Normal hexyl chloride, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, normal butyl zinc bromide, isobutyl zinc bromide, normal hexyl bromide zinc, methyl zinc iodide, ethyl zinc iodide, iodide Propyl zinc, normal butyl zinc iodide, isobutyl iodide Zinc, halogenated alkyl zinc such as iodide-hexyl zinc, zinc fluoride, zinc chloride, zinc bromide, and halogenated zinc such as zinc iodide.

  Component (a) is preferably dialkylzinc, more preferably dimethylzinc, diethylzinc, dipropylzinc, dinormalbutylzinc, diisobutylzinc, dinormalhexylzinc, diallylzinc or bis (cyclopentadienyl) zinc. Particularly preferred is dimethyl zinc or diethyl zinc.

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

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

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

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

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 component (b) include amines such as di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, di (iodomethyl) amine, bis (difluoromethyl) amine, bis (dichloro). Methyl) 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-pe) Tachloropropyl) amine, bis (2,2,3,3,3-pentabromopropyl) amine, bis (2,2,3,3,3-pentaiodopropyl) amine, bis (2,2,2- Trifluoro-1-trifluoromethylethyl) amine, bis (2,2,2-trichloro-1-trichloromethylethyl) amine, bis (2,2,2-tribromo-1-tribromomethylethyl) amine, bis (2,2,2-triiodo-1-triiodomethylethyl) amine, bis {1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl} amine, bis {1,1-bis (Trichloromethyl) -2,2,2-trichloroethyl} amine, bis {1,1-bis (tribromomethyl) -2,2,2-tribromoethyl} amine, bis {1,1-bis ( Lyodomethyl) -2,2,2-triiodoethyl} amine, bis (2-fluorophenyl) amine, bis (3-fluorophenyl) amine, bis (4-fluorophenyl) amine, bis (2-chlorophenyl) amine, Bis (3-chlorophenyl) amine, bis (4-chlorophenyl) amine, bis (2-bromophenyl) amine, bis (3-bromophenyl) amine, bis (4-bromophenyl) amine, bis (2-iodophenyl) Amine, bis (3-iodophenyl) amine, bis (4-iodophenyl) amine, bis (2,6-difluorophenyl) amine, bis (3,5-difluorophenyl) amine, bis (2,6-dichlorophenyl) Amine, bis (3,5-dichlorophenyl) amine, bis (2,6-dibromophenyl) Amine, bis (3,5-dibromophenyl) amine, bis (2,6-diiodophenyl) amine, bis (3,5-diiodophenyl) amine, bis (2,4,6-trifluorophenyl) amine Bis (2,4,6-trichlorophenyl) amine, bis (2,4,6-tribromophenyl) amine, bis (2,4,6-triiodophenyl) amine, bis (pentafluorophenyl) amine, Bis (pentachlorophenyl) amine, bis (pentabromophenyl) amine, bis (pentaiodophenyl) amine, bis (2- (trifluoromethyl) phenyl) amine, bis {3- (trifluoromethyl) phenyl} amine, bis {4- (trifluoromethyl) phenyl} amine, bis {2,6-di (trifluoromethyl) phenyl} amine, {3,5-di (trifluoromethyl) phenyl} amine, bis {2,4,6-trifluoro (trifluoromethyl) phenyl} amine, bis (2-cyanophenyl) amine, bis (3-cyanophenyl) Examples include amine, bis (4-cyanophenyl) amine, bis (2-nitrophenyl) amine, bis (3-nitrophenyl) amine, and bis (4-nitrophenyl) amine.

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

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

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

  Specific examples of the compound (b) include phenols such as 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3- Bromophenol, 4-bromophenol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,6-dichlorophenol, 3,5-dichlorophenol 2,6-dibromophenol, 3,5-dibromophenol, 2,6-diiodophenol, 3,5-diiodophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol 2,4,6-trichlorophenol, 3,4,5-to Chlorophenol, 2,4,6-tribromophenol, 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 (trifluoro Methyl) phenol, 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol and the like.

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

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

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

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

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

Component (c) of the present invention is a compound represented by the following general formula [3].
R ² _t-2 T ² H ₂ [3]
T ² in the above general formula [3] represents a non-metal atom of Group 15 or Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). Specific examples of the Group 15 nonmetallic atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 nonmetallic atom include an oxygen atom and a sulfur atom. T ² is preferably a nitrogen atom or an oxygen atom, and particularly preferably an oxygen atom.

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

R ² in the general formula [3] represents a hydrocarbon group, R ² each is when R ² existing in plural numbers may be different be the same as each other. Examples of the hydrocarbon group in R ² include the hydrocarbon groups exemplified as L ^{1 in the} general formula [1] and the halogenated hydrocarbons exemplified as R ^{1 in the} general formula [2].

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

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

Benzylamine, (methylphenyl) methylamine [(2-methylphenyl) methylamine, (3-methylphenyl) methylamine, (4-methylphenyl) methylamine],
(Dimethylphenyl) methylamine [(2,3-dimethylphenyl) methylamine, (2,4-dimethylphenyl) methylamine, (2,5-dimethylphenyl) methylamine, (2,6-dimethylphenyl) methylamine , (3,4-dimethylphenyl) methylamine, (3,5-dimethylphenyl) methylamine], (trimethylphenyl) methylamine [(2,3,4-trimethylphenyl) methylamine, (2,3,5) -Trimethylphenyl) methylamine, (2,3,6-trimethylphenyl) methylamine, (3,4,5-trimethylphenyl) methylamine, (2,4,6-trimethylphenyl) methylamine], (tetramethyl Phenyl) methylamine [(2,3,4,5-tetramethylphenyl) methylamine, (2,3 4,6-tetramethylphenyl) methylamine, (2,3,5,6-tetramethylphenyl) methylamine], (pentamethylphenyl) methylamine, (ethylphenyl) methylamine, (n-propylphenyl) methyl Amine, (isopropylphenyl) methylamine, (n-butylphenyl) methylamine, (sec-butylphenyl) methylamine, (tert-butylphenyl) methylamine, (n-pentylphenyl) methylamine, (neopentylphenyl) Methylamine, (n-hexylphenyl) methylamine, (n-octylphenyl) methylamine, (n-decylphenyl) methylamine, (n-tetradecylphenyl) methylamine, naphthylmethylamine, anthracenylmethylamine, Fluoromethylamine Chloromethylamine, bromomethylamine, iodomethylamine, difluoromethylamine, dichloromethylamine, dibromomethylamine, diiodomethylamine, trifluoromethylamine, trichloromethylamine, tribromomethylamine, triiodomethylamine, 2, 2,2-trifluoroethylamine, 2,2,2-trichloroethylamine, 2,2,2-tribromoethylamine, 2,2,2-triiodoethylamine, 2,2,3,3,3-pentafluoropropyl Amine, 2,2,3,3,3-pentachloropropylamine, 2,2,3,3,3-pentabromopropylamine, 2,2,3,3,3-pentaiodopropylamine, 2,2 , 2-trifluoro-1-trifluoromethylethylamine, 2,2,2-tri Chloro-1-trichloromethylethylamine, 2,2,2-tribromo-1-tribromomethylethylamine, 2,2,2-triiodo-1-triiodomethylethylamine, 1,1-bis (trifluoromethyl) -2 , 2,2-trifluoroethylamine, 1,1-bis (trichloromethyl) -2,2,2-trichloroethylamine, 1,1-bis (tribromomethyl) -2,2,2-tribromoethylamine, , 1-bis (triiodomethyl) -2,2,2-triiodoethylamine,

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

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

  Component (d) of the present invention is a nonionic surfactant having no active hydrogen. The active hydrogen is a hydrogen atom bonded to any atom of nitrogen atom, oxygen atom or sulfur atom.

  Nonionic surfactants having no active hydrogen include tertiary amines, ethers, thioethers, polyethylene glycol fatty acid diesters, amine oxides, and the like.

As the component (d), a compound represented by the following general formula [4] is preferable.
R ³ _m Z [4]
In the above general formula [4], R ³ represents a hydrocarbon group, each R ³ may be the same or different, Z represents a nitrogen atom, an oxygen atom or a sulfur atom, and m represents Z Represents a valence.

  Z is preferably a nitrogen atom or an oxygen atom, and more preferably a nitrogen atom.

  m is the valence of Z. When Z is nitrogen, m is 3. When Z is an oxygen atom or a sulfur atom, m is 2.

The hydrocarbon group for R ³ is preferably a chain hydrocarbon group, more preferably an alkyl group or an alkenyl group.

As the alkyl group for R ³ , an alkyl group having 1 to 100 carbon atoms is preferable. For example, 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, Isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group N-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-docosyl group, 2- (3-methylhexyl) -7-methyldecyl group, Long chain alkyl groups derived from natural products (coconut oil, soybean oil, beef tallow, etc.) can be mentioned.

The alkenyl group represented by R ³ is preferably an alkenyl group having 1 to 100 carbon atoms, such as a 9-cis-octadecenyl group; a long-chain alkenyl group derived from natural products such as coconut oil, soybean oil, and beef tallow.

Any of the alkyl groups and alkenyl groups of R ³ may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

R ³ in the general formula [4] is preferably an alkyl group.

In the general formula [4], at least one R ³ is preferably a hydrocarbon group having 12 to 100 carbon atoms, and at least two R ³ are hydrocarbon groups having 12 to 100 carbon atoms. It is more preferable that The hydrocarbon group having 12 to 100 carbon atoms is preferably an alkyl group having 12 to 100 carbon atoms, more preferably n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n- An octadecyl group, an n-eicosyl group, an n-docosyl group, a 2- (3-methylhexyl) -7-methyldecyl group, or a long chain alkyl group derived from a natural product (coconut oil, soybean oil, beef tallow, etc.); Preferably, long-chain alkyl derived from n-octadecyl group, n-eicosyl group, n-docosyl group, 2- (3-methylhexyl) -7-methyldecyl group, or natural products (coconut oil, soybean oil, beef tallow, etc.) Group, particularly preferably an n-octadecyl group.

  Specific examples of the compound represented by the general formula [4] include tridecylamine, trihexadecylamine, N, N-dimethyl-n-dodecylamine, N, N-dimethyl-n-hexadecylamine, N , N-dimethyl-n-octadecylamine, N, N-dimethylcoco (coconut) alkylamine, N, N-dimethyl hydrogenated tallow (tallow) alkylamine, N, N-dimethyloleylamine, N, N-dimethylsoya (soybean ) Alkylamine, N, N-dimethyltallow (tallow) alkylamine, N, N-di-n-dodecylmethylamine, N, N-di-n-hexadecylmethylamine, N, N-di-n-octadecyl Methylamine, N, N-dicoco (palm) alkylmethylamine, N, N-dihydrogenated tallow (beef tallow) alkylmethylamine, N, N-di-n-oleylmethylamine, N, N-disoya (soybean) Examples include alkylmethylamine, N, N-ditalo (tallow) alkylmethylamine, and the like. N, N-di-n-octadecylmethylamine is preferred.

  The contact-treated product of the present invention is a contact-treated product (hereinafter referred to as contact-treated product (A)) obtained by bringing the components (a), (b), (c) and (d) into contact with each other. .

As the contact treatment amount of the components (a) to (c), when the molar ratio of the contact treatment amount of each component is component (a): component (b): component (c) = 1: y: z, y and z preferably satisfies the following formula (I), and more preferably satisfies the following formula (II).
| R-y-2z | ≦ 0.2 (I)
r = y + 2z (II)
(In the above formulas (I) and (II), r represents the valence of M ^1. )

  The amount of contact treatment of component (b) is preferably 0.01 to 1.99 mol, more preferably 0.1 to 1.8 mol, and still more preferably per mol of component (a). It is 0.2-1.5 mol, Most preferably, it is 0.3-1 mol.

  The contact treatment amount of component (d) is preferably 0.01 to 0.7 mol, more preferably 0.05 to 0.6 mol, still more preferably 0.001 mol per mol of component (a). It is 08-0.5 mol, Most preferably, it is 0.1-0.4 mol.

  The contact treatment of the components (a) to (d) is preferably performed in an inert gas atmosphere. The contact treatment temperature is usually −100 to 200 ° C., preferably −80 to 150 ° C. The contact treatment time is usually 1 minute to 36 hours, preferably 10 minutes to 24 hours.

  The contact treatment of components (a) to (d) may use a solvent, or may directly contact components (a) to (d) without using a solvent. As the solvent to be used, any of nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents that are inert with respect to components (a) to (d), or polar solvents such as ether solvents are used. Specific examples include butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane, benzene, toluene, xylene, dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether Methyl tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, tetrahydrofuran, tetrahydropyran and the like. Among the solvents, a hydrocarbon solvent is more preferable, and toluene is most preferable.

As a method of bringing the components (a) to (d) into contact, for example, the following methods can be employed.
(A): A method in which component (a) and component (b) are contacted, then component (c) is contacted, and further component (d) is contacted.
(B): A method in which component (a) and component (b) are contacted, then component (d) is contacted, and then component (c) is contacted.
(C) A method in which component (a) and component (c) are contacted, then component (b) is contacted, and component (d) is further contacted.
(D): A method in which component (a) and component (c) are contacted, then component (d) is contacted, and then component (b) is contacted.
(E) A method in which component (a) and component (d) are contacted, then component (b) is contacted, and then component (c) is contacted.
(F): A method in which component (a) and component (d) are contacted, then component (c) is contacted, and component (b) is further contacted.
(G): A method in which component (b) and component (c) are contacted, then component (a) is contacted, and component (d) is further contacted.
(H): A method in which component (b) and component (c) are contacted, then component (d) is contacted, and then component (a) is further contacted.
(I): A method in which component (b) and component (d) are contacted, then component (a) is contacted, and further component (c) is contacted.
(Nu): A method in which component (b) and component (d) are contacted, then component (c) is contacted, and further component (a) is contacted.
(L): A method in which component (c) and component (d) are contacted, then component (a) is contacted, and further component (b) is contacted.
(W): A method in which component (c) and component (d) are contacted, then component (b) is contacted, and further component (a) is contacted.
Preferably, component (a), component (b) and component (c) are contacted and then component (d) is contacted, or component (a), component (b) and component (d) are contacted After that, component (c) is brought into contact, more preferably (b) or (b).

  In the method of contacting the components (a) to (c), after contacting any component selected from the components (a) to (d), the contact-treated product is purified, and the purified product is purified. A method of contacting the remaining components not selected may be performed. After contacting any component selected from the components (a) to (d), the contact treatment product is not purified and the contact is performed. A method of bringing the remaining components not selected into contact with the treated product may be performed, and the contact treated product (A) of the present invention is a raw material that is a raw material as a result of the contact treatment of the components (a) to (d). May remain as an unreacted product.

  Specific examples of the method for producing the contact treated product (A) of the present invention are as follows. Component (a) is diethyl zinc, Component (b) is pentafluorophenol, Component (c) is water, Component (d) ) Is methyldioctadecylamine, it will be described in more detail below. Toluene as a solvent, hexane solution of diethyl zinc was added thereto, equimolar amount of pentafluorophenol with respect to diethyl zinc, and 0.5 times molar amount of water with respect to diethyl zinc were added dropwise at 70 ° C. for 10 minutes to Stir for 24 hours. Thereafter, a method of adding 0.2-fold molar amount of N, N-di-n-octadecylmethylamine to diethylzinc and stirring at 70 ° C. for 10 minutes to 24 hours can be employed.

  The contact treated product (A) of the present invention is suitably used as a catalyst component for addition polymerization. Specific examples of the addition polymerization catalyst using the addition polymerization catalyst component include a contact-treated product (A) and a group 3-12 or lanthanoid series metal compound (hereinafter referred to as compound (B) of the periodic table of elements. A catalyst for addition polymerization obtained by contacting a contact treated product (A), a compound (B) and an organoaluminum compound (hereinafter referred to as a compound (C)). Preferably, it is a catalyst for addition polymerization obtained by contacting the contact treated product (A), the compound (B) and the compound (C).

Examples of the compound (B) include a metal compound represented by the following general formula [5] and a μ-oxo type metal compound thereof.
L ² _a M ² X ¹ _b [5]
{(Wherein, a represents a number satisfying 0 <a ≦ 8, b represents a number satisfying 0 <b ≦ 8. M ² represents a group 3-12 of the periodic table of elements or a lanthanoid series) .L ² representing the metal atom is a group having a group or a hetero atom having a cyclopentadiene type anion skeleton, if L ² there is a plurality, they may be different from one another the same, a plurality of L ² May be linked via a residue having an atom selected from a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom, or X ¹ may be a halogen atom or a hydrocarbon group. (However, a group having a cyclopentadiene-type anion skeleton is excluded.) Or a hydrocarbonoxy group, and when there are a plurality of X ^{1 s} , they may be the same or different from each other.

In the general formula [5], M ² is a group 3-12 or lanthanoid series metal atom of the periodic table of elements (IUPAC inorganic chemical nomenclature revised edition 1989). Specific examples thereof include scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, technetium atom, iron atom, ruthenium atom. , Cobalt atom, rhodium atom, nickel atom, palladium atom and the like. M ² is preferably a metal atom of Group 3 to Group 11 of the periodic table, more preferably a metal atom of Group 3 to Group 7 of the periodic table, and particularly preferably Group 4 of the periodic table. Metal atom.

In the general formula [5], 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 .

In the general formula [5], L ² is a group having a cyclopentadiene-type anion skeleton or a group having a hetero atom, and a plurality of L ² may be the same or different. A plurality of L ² may be directly connected via a residue having an atom selected from a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom.

Examples of the group having a cyclopentadiene type anion skeleton in L ² include η ^5- (substituted) cyclopentadienyl group, η ^5- (substituted) indenyl group, and η ^5- (substituted) fluorenyl group. 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 having 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; Aryloxy group; alkylamino group; arylamino group; alkylphosphino group; arylphosphino group; aromatic or aliphatic having at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom in the ring A heterocyclic group; and chelating ligands.

  Specific examples of the group having a hetero atom 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-dimethoxy Phenoxy group, 2-chlorophenoxy group, 4-nitrosophenoxy group, 4-nitrophenoxy group 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-hydroxyphenyl Group, resorcinolate group, 3-hydroxyphenyl group, 4-isopropylcatecholate group, 4-isopropyl-2-hydroxyphenyl group, 3-methoxycatecholate group, 3-methoxy-2-hydroxyphenyl group, 1,8-dihydroxy Naphthyl group, 1,2-dihydroxynaphthy Group, 2,2′-hyphenyldiol group, 1,1′-bi-2-naphthol group, 2,2′-dihydroxy-6,6′-dimethylbiphenyl group, 4,4 ′, 6,6′- Examples thereof include a tetra-tert-butyl-2,2′methylenediphenoxy group, a 4,4 ′, 6,6′-tetramethyl-2,2′-isobutylidenediphenoxy group, and the like.

In addition, examples of the group having a hetero atom also include a group represented by the following general formula [6].
R ⁴ ₃ P = N− [6]
(Wherein R ⁴ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and each R ⁴ may be the same as or different from each other, and two or more of them may be bonded to each other; May be formed.)

Specific examples of R ⁴ in the general formula [6] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Examples thereof include a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cycloheptyl group, a cyclohexyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a benzyl group.

（式中、Ｒ⁶¹〜Ｒ⁶⁶はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、炭化水素オキシ基、シリル基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。） Furthermore, examples of the group having a hetero atom also include a group represented by the following general formula [7].

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

Specific examples of R ^{61 to} R ⁶⁶ in the general formula [7] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, phenyl group, 1-naphthyl group, 2-naphthyl group, tert-butyl. Group, 2,6-dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl Group, methyl group, triethylsilyl group, diphenylmethylsilyl group, 1-methyl-1-phenylethyl group, 1,1-dimethylpropyl group, 2-chlorophenyl group and the like.

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

When there are a plurality of L ² groups, groups having a cyclopentadiene type anion skeleton, groups having a cyclopentadiene type anion skeleton and a group having a hetero atom, or groups having a hetero atom may be directly connected to each other. It may be connected through a residue having an 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 ethylene group, propylene group, dimethylmethylene group and diphenylmethylene group; silylene groups such as silylene group, dimethylsilylene group, diphenylsilylene group and tetramethyldisilylene group; nitrogen atom, Hetero atoms such as oxygen atom, sulfur atom and phosphorus atom can be mentioned.

X ¹ in the general formula [5] is a halogen atom, a hydrocarbon group (however, a group having a cyclopentadiene-type anion skeleton is not included here) or a hydrocarbon oxy group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. 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. , Tert-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluoro group. Examples include a hexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group.
Any of these alkyl groups may be substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group.

The alkyl group used for X 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 a tert-pentyl 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 hydrocarbon oxy group used for X ¹ include an alkoxy group, an aryloxy group, an aralkyloxy group, and the like, and preferably an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms. Or an aralkyloxy group having 7 to 20 carbon atoms. 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 preferred are methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, isobutoxy group, phenoxy group, 2,6-di (tert-butyl) phenoxy group or benzyloxy group, and more preferred are methoxy group, phenoxy group Group, 2,6-di (tert-butyl) phenoxy group or benzyloxy group, particularly preferably methoxy group or 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.

Specific examples of the compound in which M ² is a titanium atom among the metal compounds represented by the general formula [5] include dimethylsilylene bis (cyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-methylcyclopentadiene). 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) (indenyl) titanium dichloride, dimethylsilyl And such emissions (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'-thiobis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-methylenebis (4-methyl-6-tert-butylphenoxy) ) Titanium dichloride, 2,2'-ethylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2, 2 ′-(4,4 ′, 6,6′-tetra-tert-butyl-1,1 ′ biphenol Shi) titanium dichloride,

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

Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride,

[Hydrotris (3,5-dimethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium trichloride Chloride, [tris (3,5-dimethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-di-tert-butylpyrazolyl) methyl] Examples thereof include titanium trichloride.

Further, specific examples of the compound in which M 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). Further, the trichloride of the titanium compound is trifluoride, tribromide, triiodide, trimethyl, triethyl, triisopropyl, triphenyl, tribenzyl, trimethoxide, triethoxide, tri-n-propoxide, triisopropoxide, tri-n. Examples thereof include compounds changed to -butoxide, triisobutoxide, tri-tert-butoxide, triphenoxide or tri (2,6-di-tert-butylphenoxide).

Among the metal compounds represented by the general formula [5], 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.

Among the compounds represented by the general formula [5], 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 [(4R) -4 Isopropyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methoxyphenyl) oxazo Phosphor] Nickel dibromide,
2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-isopropyloxazoline-5,1′-cycloheptane}] nickel dibromide,

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

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

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

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

Further, specific examples of the compound in which M 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、Ｘ⁹、Ｘ¹⁰、Ｒ⁷³およびＲ⁷⁴は下記の表１に表わされる置換基の組み合わせのいずれかである。） Specific examples of the compound in which M ² is a nickel atom include compounds represented by the following general formula [8].

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

  In addition, as the metal compound represented by the general formula [5], 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 [5], as a specific example of a compound in which M ² is iron, 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 [5], a compound in which iron is replaced with cobalt or nickel in the above iron compound can be exemplified as well.

  Specific examples of the μ-oxo type metal compound represented by the general formula [5] include μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [ Isopropylidene (cyclopentadienyl) (2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ -Oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium Chloride], μ-oxobis [isopropylidene (methylcyclohexane) Tantadienyl) (2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (Methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) titanium chloride , .Mu. Okisobisu [isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide],

μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium methoxide], μ-oxobis [dimethylsilylene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) ) Titanium methoxide], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium methoxide] , Μ-oxobis [dimethylsilane Len (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl) -2-phenoxy) titanium methoxide], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2- Phenoxy) titanium methoxide], μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (tetramethylcyclo) Pentadienyl) (3-t rt- butyl-5-methyl-2-phenoxy) titanium methoxide],

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

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

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

（上記一般式［９］〜［１１］においてそれぞれ、Ｍ³〜Ｍ⁷は元素の周期律表の第４族の金属原子を表し、Ａ¹〜Ａ⁵は元素の周期律表の第１６族の原子を表し、Ｊ¹〜Ｊ⁵は元素の周期律表の第１４族の原子を表す。Ｃｐ¹〜Ｃｐ⁵はシクロペンタジエン形アニオン骨格を有する基を表す。Ｘ¹¹〜Ｘ¹⁴、Ｒ¹¹〜Ｒ¹⁶、Ｒ²¹〜Ｒ²⁶、Ｒ³¹〜Ｒ³⁶、Ｒ⁴¹〜Ｒ⁴⁶およびＲ⁵¹〜Ｒ⁵⁶はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、置換シリル基、炭化水素オキシ基、２置換アミノ基、炭化水素チオ基または炭化水素セレノ基を表し、Ｒ¹¹〜Ｒ¹⁶、Ｒ²¹〜Ｒ²⁶、Ｒ³¹〜Ｒ³⁶、Ｒ⁴¹〜Ｒ⁴⁶およびＲ⁵¹〜Ｒ⁵⁶は任意に結合して単環または多環を形成してもよい。該単環または多環は、芳香族環または非芳香族環のいずれでもよい。Ｘ¹⁵〜Ｘ¹⁷は元素の周期律表の第１６族の原子を表す。） These compounds (B) may use only 1 type and may combine 2 or more types. As the compound (B), a metal compound (metallocene metal compound) in which at least one of L ² in the general formula [5] is a group having a cyclopentadiene type anion skeleton is preferable. Examples of the metal compound include metal compounds represented by the following general formulas [9] to [11].

(In the above general formulas [9] to [11], M ^{3 to} M ⁷ represent group 4 metal atoms of the periodic table of elements, and A ^{1 to} A ⁵ represent Group 16 of the periodic table of elements. J ^{1 to} J ⁵ represent atoms of Group 14 of the periodic table of elements, Cp ^{1 to} Cp ⁵ represent groups having a cyclopentadiene-type anion skeleton, X ^{11 to} X ¹⁴ , R ¹¹ the ^{~R 16, R 21 ~R 26,} R 31 ~R 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, a substituted silyl group, a hydrocarbon oxy group R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ^46, and R ^{51 to} R ⁵⁶ are arbitrarily represented by a disubstituted amino group, a hydrocarbon thio group, or a hydrocarbon seleno group. They may combine to form a monocycle or polycycle, which may be either an aromatic ring or a non-aromatic ring. ¹⁵ to X ¹⁷ represents an atom of Group 16 of the periodic table of elements.)

In the general formula [9] ~ [11], M 3 is to be a metal atom represented by ~M ^7, shows a fourth group of metal atoms of the Periodic Table of the Elements (IUPAC Inorganic Chemistry Nomenclature revised edition 1989), Examples thereof include a titanium atom, a zirconium atom, and a hafnium atom. Preferably, it is a titanium atom or a zirconium atom.

In the general formulas [9] to [11], 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 or η ⁵ -fluorenyl group.

The general formula [9] The halogen atom in ^{X 11 ~X 14, R 11 ~R} 16, R 21 ~R 26, R 31 ~R 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ to [11] , A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., are exemplified, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

Formula [9] to the hydrocarbon groups in ^{X 11 ~X 14, R 11 ~R} 16, R 21 ~R 26, R 31 ~R 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ of [11] Includes an alkyl group, an aralkyl group, an aryl group, and the like.

The general formula [9] The alkyl group in ^{X 11 ~X 14, R 11 ~R} 16, R 21 ~R 26, R 31 ~R 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ to [11] 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.

The general formula [9] The alkyl group in ^{X 11 ~X 14, R 11 ~R} 16, R 21 ~R 26, R 31 ~R 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ to [11] , Preferably an alkyl group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group or a tert-pentyl group.

Examples of the aralkyl group in X ^{11 to} X ¹⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [9] to [11] 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- Trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) ) Methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) Methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n- Decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc. It is.
All of these aralkyl groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group It may be substituted with.

Examples of the aralkyl group in X ^{11 to} X ¹⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [9] to [11] , Preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably a benzyl group.

The general formula [9] The aryl group in ^{X 11 ~X 14, R 11 ~R} 16, R 21 ~R 26, R 31 ~R 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ to [11] 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.

The general formula [9] The aryl group in ^{X 11 ~X 14, R 11 ~R} 16, R 21 ~R 26, R 31 ~R 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ to [11] , Preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group.

General formula [9] and a substituted silyl group in ^{X 11 ~X 14, R 11 ~R} 16, R 21 ~R 26, R 31 ~R 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ to [11] 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; optionally 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 ^{11 to} X ¹⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ^46, and R ^{51 to} R ⁵⁶ in the general formulas [9] to [11] 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 Preferable examples include trisubstituted silyl groups having 3 to 20 carbon atoms such as ruthenium group, and more preferred are trimethylsilyl group, tert-butyldimethylsilyl group and triphenylsilyl group.

Formula ^{[9] X 11 ~X 14,} R 11 ~R 16, R 21 ~R 26, R 31 ~R 36, hydrocarbon oxy group in R ⁴¹ to R ⁴⁶ and R ⁵¹ to R ⁵⁶ to [11] Examples thereof include an alkoxy group, an aralkyloxy group, and an aryloxy group.

The general formula [9] The ^{X 11 ~X 14, R 11 ~R} 16, R 21 ~R 26, alkoxy group in ^{R 31 ~R 36, R 41 ~R} 46 and R ⁵¹ to R ⁵⁶ to [11] 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.

The general formula [9] The ^{X 11 ~X 14, R 11 ~R} 16, R 21 ~R 26, alkoxy group in ^{R 31 ~R 36, R 41 ~R} 46 and R ⁵¹ to R ⁵⁶ to [11] , 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.

Formula [9] to the ^{X 11 ~X 14, R 11 ~R} 16, aralkyloxy group in ^{R 21 ~R 26, R 31 ~R} 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ of [11] 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) Ruphenyl) 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 shea group.
All of these aralkyloxy groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy such as benzyloxy group It may be substituted with a group or the like.

Formula [9] to the ^{X 11 ~X 14, R 11 ~R} 16, aralkyloxy group in ^{R 21 ~R 26, R 31 ~R} 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ of [11] Is preferably an aralkyloxy group having 7 to 20 carbon atoms, more preferably a benzyloxy group.

Formula [9] to the ^{X 11 ~X 14, R 11 ~R} 16, R 21 ~R 26, an aryloxy group in ^{R 31 ~R 36, R 41 ~R} 46 and R ⁵¹ to R ⁵⁶ of [11] Are, for example, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2, 6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert- Butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl- 3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group 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 a hexylphenoxy group, an n-octylphenoxy group, an n-decylphenoxy group, an n-tetradecylphenoxy group, a naphthoxy group, and an anthracenoxy group.
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.

Formula [9] to the ^{X 11 ~X 14, R 11 ~R} 16, R 21 ~R 26, an aryloxy group in ^{R 31 ~R 36, R 41 ~R} 46 and R ⁵¹ to R ⁵⁶ of [11] Is preferably an aryloxy group having 6 to 20 carbon atoms.

Formula [9] ~ [11] X 11 ~X 14, R 11 ~R 16, R 21 ~R 26, R 31 ~R 36, R 41 ~R 46 and a disubstituted amino group in R ⁵¹ to R ⁵⁶ of the 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.

Formula ^{[9] X 11 ~X 14,} R 11 ~R 16, R 21 ~R 26, R 31 ~R 36, hydrocarbon thio group in R ⁴¹ to R ⁴⁶ and R ⁵¹ to R ⁵⁶ to [11] Examples thereof include an alkylthio group, an aralkylthio group, and an arylthio group.

Examples of the alkylthio group in X ^{11 to} X ¹⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ^46, and R ^{51 to} R ⁵⁶ in the general formulas [9] to [11] For example, methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, n-pentylthio group, neopentylthio group, n-hexylthio group, n-octylthio Group, n-dodecylthio group, n-pentadecylthio group, n-eicosylthio group and the like.
These alkylthio groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; aralkyloxy groups such as benzyloxy group It may be substituted with.

Examples of the alkylthio group in X ^{11 to} X ¹⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [9] to [11] And an alkylthio group having 1 to 20 carbon atoms, more preferably a methylthio group, an ethylthio group, an isopropylthio group, or a tert-butylthio group.

As an aralkylthio group in X ^{11 to} X ¹⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [9] to [11] Are, for example, benzylthio, (2-methylphenyl) methylthio, (3-methylphenyl) methylthio, (4-methylphenyl) methylthio, (2,3-dimethylphenyl) methylthio, (2,4-dimethyl) Phenyl) methylthio group, (2,5-dimethylphenyl) methylthio group, (2,6-dimethylphenyl) methylthio group, (3,4-dimethylphenyl) methylthio group, (3,5-dimethylphenyl) methylthio group, 2,3,4-trimethylphenyl) methylthio group, (2,3,5-trimethylphenyl) methylthio group, (2,3,6-trimethylphenyl) methylthio group, 2,4,5-trimethylphenyl) methylthio group, (2,4,6-trimethylphenyl) methylthio group, (3,4,5-trimethylphenyl) methylthio group, (2,3,4,5-tetramethylphenyl) ) Methylthio group, (2,3,4,6-tetramethylphenyl) methylthio group, (2,3,5,6-tetramethylphenyl) methylthio group, (pentamethylphenyl) methylthio group, (ethylphenyl) methylthio group , (N-propylphenyl) methylthio group, (isopropylphenyl) methylthio group, (n-butylphenyl) methylthio group, (sec-butylphenyl) methylthio group, (tert-butylphenyl) methylthio group, (n-hexylphenyl) Methylthio group, (n-octylphenyl) methylthio group, (n-decylphenyl) 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 ^{11 to} X ¹⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [9] to [11] Is preferably an aralkylthio group having 7 to 20 carbon atoms, more preferably a benzylthio group.

Examples of the arylthio group in X ^{11 to} X ¹⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [9] to [11] For example, phenylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-methylphenylthio group, 2,3-dimethylphenylthio group, 2,4-dimethylphenylthio group, 2,5-dimethylphenyl Thio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 2-tert-butyl-3-methylphenylthio group, 2-tert-butyl-4 -Methylphenylthio group, 2-tert-butyl-5-methylphenylthio group, 2-tert-butyl-6-methylphenylthio group, 2,3,4-trimethylphenylthio group, 2,3, 5-trimethylphenylthio group, 2,3,6-trimethylphenylthio group, 2,4,5-trimethylphenylthio group, 2,4,6-trimethylphenylthio group, 2-tert-butyl-3,4- Dimethylphenylthio 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.

Examples of the arylthio group in X ^{11 to} X ¹⁴ , R ^{11 to} R ¹⁶ , R ^{21 to} R ²⁶ , R ^{31 to} R ³⁶ , R ^{41 to} R ⁴⁶ and R ^{51 to} R ⁵⁶ in the general formulas [9] to [11] An arylthio group having 6 to 20 carbon atoms is preferred.

Formula ^{[9] X 11 ~X 14,} R 11 ~R 16, R 21 ~R 26, R 31 ~R 36, hydrocarbon seleno group in R ⁴¹ to R ⁴⁶ and R ⁵¹ to R ⁵⁶ to [11] Examples thereof include an alkylseleno group, an aralkylseleno group, and an arylseleno group.

Formula [9] to the ^{X 11 ~X 14, R 11 ~R} 16, alkylseleno group in ^{R 21 ~R 26, R 31 ~R} 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ of [11] 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.

Formula [9] to the ^{X 11 ~X 14, R 11 ~R} 16, alkylseleno group in ^{R 21 ~R 26, R 31 ~R} 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ of [11] 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.

Formula [9] to the ^{X 11 ~X 14, R 11 ~R} 16, aralkyl seleno group in ^{R 21 ~R 26, R 31 ~R} 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ of [11] 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.

Formula [9] to the ^{X 11 ~X 14, R 11 ~R} 16, aralkyl seleno group in ^{R 21 ~R 26, R 31 ~R} 36, R 41 ~R 46 and R ⁵¹ to R ⁵⁶ of [11] Is preferably an aralkylseleno group having 7 to 20 carbon atoms, more preferably a benzylseleno group.

Formula [9] to the ^{X 11 ~X 14, R 11 ~R} 16, R 21 ~R 26, arylseleno group in ^{R 31 ~R 36, R 41 ~R} 46 and R ⁵¹ to R ⁵⁶ of [11] 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 Methylphenylseleno 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-tetradecylphenol Rusereno group, Nafuchirusereno group, anthracenyl seleno 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.

Formula [9] to the ^{X 11 ~X 14, R 11 ~R} 16, R 21 ~R 26, arylseleno group in ^{R 31 ~R 36, R 41 ~R} 46 and R ⁵¹ to R ⁵⁶ of [11] Is preferably an arylseleno group having 6 to 20 carbon atoms.

In the general formulas [9] to [11], X ^{11 to} X ¹⁴ 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 , X ^{11 to} X ¹⁴ are each independently a halogen atom, an alkyl group, an alkoxy group or an aryloxy group.

In the general formulas [9] to [11], R ^{11 to} R ¹⁴ , R ^{21 to} R ²⁴ , R ^{31 to} R ³⁴ , R ^{41 to} R ⁴⁴ and R ^{51 to} R ⁵⁴ are preferably each independently a hydrogen atom, A halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group or an aryloxy group, and particularly R ¹¹ , R ²¹ , R ³¹ , R ⁴¹ and R ⁵¹ are each independently alkyl It is preferably a group, an aralkyl group, an aryl group, or a substituted silyl group.

In the general formulas [9] to [11], R ¹⁵ , R ¹⁶ , R ²⁵ , R ²⁶ , R ³⁵ , R ³⁶ , R ⁴⁵ , R ⁴⁶ , R ⁵⁵ and R ⁵⁶ are each independently a hydrogen atom, An alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group or an aryloxy group is preferred.

X ^{15 to} X ¹⁷ in the above general formulas [10] and [11] represent atoms of Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). Specific examples include oxygen atoms, A sulfur atom and a selenium atom are mentioned, Preferably they are an oxygen atom or a sulfur atom, More preferably, it is an oxygen atom.

In the general formulas [9] to [11], as the group 16 atom of the periodic table of elements shown as A ^{1 to} A ⁵ (IUPAC inorganic chemical nomenclature revised edition 1989), for example, an oxygen atom, a sulfur atom, Examples include selenium atoms. Preferably, it is an oxygen atom.

In the general formulas [9] to [11], the group 14 atom of the periodic table of elements shown as J ^{1 to} J ⁵ (IUPAC inorganic chemical nomenclature revised edition 1989) includes, for example, a carbon atom, a silicon atom, Examples include germanium atoms. Preferably, they are a carbon atom or a silicon atom.

Specific examples of the metal compound represented by the general formula [9] 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 [9] 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 [10] 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 {isopropylidene} Den (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 Liden (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 [11] 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-oxobis {isopropylidene (η ⁵ -tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium},

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

As the compound (C) used in the addition polymerization catalyst of the present invention, a known organoaluminum compound can be used. Preferably, it is an organoaluminum compound represented by the following general formula [12].
R ⁵ _d AlY _3-d [12]
(Wherein, d is 0 <.R ⁵ representing a number satisfying d ≦ 3 represents a hydrocarbon group, if R ⁵ have multiple, R ⁵ each may be different even in the same Y represents a hydrogen atom, a halogen atom or a hydrocarbon oxy group, and when there are a plurality of Y, each Y may be the same or different.)

R ⁵ in the general formula [12] is preferably a hydrocarbon group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms. Specific examples include a methyl group, an ethyl group, a normal propyl group, a normal butyl group, an isobutyl group, a normal hexyl group, a 2-methylhexyl group, a normal octyl group, and the like, preferably an ethyl group, a normal butyl group, and an isobutyl group. Group or normal hexyl group.

  Specific examples when Y in the general formula [12] is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably a chlorine atom.

  The hydrocarbon oxy group for Y in the general formula [12] is preferably an alkoxy group, an aralkyloxy group or an aryloxy group.

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

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

Examples of the aryloxy group for Y in the general formula [12] include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxy group, and a 2,4-dimethylphenoxy group. Group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5- Trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4, 5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, N-methylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n -Decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group, etc. are mentioned.
Any of these aryloxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group.

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

Examples of the aralkyloxy group in Y in the general formula [12] include a benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3- (Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethyl) (Tilphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy Group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) ) Methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like.
Any of these aralkyloxyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group.

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

  Specific examples of the organoaluminum compound represented by the general formula [12] include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum and the like. Dialkylaluminum chlorides such as alkylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dinormalpropylaluminum chloride, dinormalbutylaluminum chloride, diisobutylaluminum chloride, dinormalhexylaluminum chloride; methylaluminum dichloride, ethylaluminum dichloride, normalpropylaluminum dichloride Alkyl aluminum dichloride such as normal butyl aluminum dichloride, isobutyl aluminum dichloride, normal hexyl aluminum dichloride; dimethyl aluminum hydride, diethyl aluminum hydride, dinormal propyl aluminum hydride, di normal butyl aluminum hydride, diisobutyl aluminum hydride, dinormal hexyl aluminum hydride, etc. Dialkylaluminum hydrides; trialkoxyaluminums such as trimethoxyaluminum, triethoxyaluminum and tri (t-butoxy) aluminum; alkyls such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum and methyl (di-t-butoxy) aluminum ( Alkoxy) aluminum; Dialkyl (alkoxy) aluminum such as dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, dimethyl (t-butoxy) aluminum; triphenoxyaluminum, tris (2,6-diisopropylphenoxy) aluminum, tris (2, Triaryloxyaluminum such as 6-diphenylphenoxy) aluminum; alkyl (diaryloxy) aluminum such as methyl (diphenoxy) aluminum, methylbis (2,6-diisopropylphenoxy) aluminum, methylbis (2,6-diphenylphenoxy) aluminum, dimethyl (Phenoxy) aluminum; dimethyl (2,6-diisopropylphenoxy) aluminum, dimethyl (2,6-diphenylpheno) Examples thereof include dialkyl (aryloxy) aluminum such as xyl) aluminum.

  Among these, trialkylaluminum is preferable, trimethylaluminum, triethylaluminum, trinormalbutylaluminum, triisobutylaluminum or trinormalhexylaluminum is particularly preferable, and triisobutylaluminum or trinormalhexylaluminum is particularly preferable. is there.

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

In the addition polymerization catalyst of the present invention, the ratio of the contact treatment amount between the contact treated product (A) and the compound (B) is not particularly limited, but M ¹ metal atom / compound of the contact treated product (A). The metal atom (molar ratio) of (B) is usually 1 to 10,000, preferably 10 to 5000, more preferably 100 to 3000, and particularly preferably 500 to 2000. When using the compound (C), the Al atom of the compound (C) / the metal atom (molar ratio) of the compound (B) is usually 1 to 10,000, preferably 10 to 5000, more preferably 100 to 1000.

  As the catalyst for addition polymerization of the present invention, a contact-treated product (A) and a compound (B), and in some cases, a contact-treated product obtained by previously contacting the compound (C) may be used. They may be used separately in the inside. Any two of them may be pre-contacted and then another component contacted.

  Examples of the addition polymerizable monomer used in the production of the addition polymer using the addition polymerization catalyst of the present invention include olefins, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, polar monomers, and the like. Two or more types of monomers can also be used.

  Specific examples of these addition polymerizable monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene, 1 Olefins such as octene, 1-nonene, 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, , 8-endomethylenehexahydronaphthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene and other diolefins; norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8- Methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonyl Isobornyl norbornene, 5-cyanonorbornene, 8-methoxycarbonyl tetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyano tetracyclododecene, etc. decene cyclic olefin;

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 butylstyrene, alkenyl aromatic hydrocarbons such as p-secondary butylstyrene, bisalkenylbenzene (divinylbenzene, etc.), alkenylnaphthalene (1-vinylnaphthalene, etc.); α, β-unsaturated carboxylic acid (acrylic acid, methacrylic acid) , Fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicycl (2,2,1) -5-heptene-2,3-dicarboxylic acid and the like) and metal salts thereof (such as sodium, potassium, lithium, zinc, magnesium, calcium, etc.), α, β- Saturated carboxylic acid ester (methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, methacryl Isopropyl acid, n-butyl methacrylate, isobutyl methacrylate, etc.), unsaturated dicarboxylic acids (maleic acid, itaconic acid, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate) , Vinyl stearate, vinyl trifluoroacetate Nyl, etc.), unsaturated carboxylic acid glycidyl esters (glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc.), cyclic ethers (ethylene oxide, propylene oxide, 1-hexene oxide, cyclohexene oxide, styrene oxide, tetrahydrofuran) Etc.) and the like.

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

  The addition polymerization catalyst of the present invention is particularly suitable as an olefin polymerization catalyst and is preferably used for the production of 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, and specific examples include propylene, 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. The polymerization mode can be either a batch type or a continuous type, and the polymerization may be performed in two or more stages with different reaction conditions.

  The method for supplying the contact treated product (A), compound (B) and compound (C) to the reactor is not particularly limited. A method of supplying each catalyst component 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. Is mentioned. Examples of the hydrocarbon solvent include aliphatic hydrocarbons (butane, pentane, hexane, heptane, octane, etc.), aromatic hydrocarbons (benzene, toluene, etc.), halogenated hydrocarbons (methylene dichloride, etc.) used in the solvent polymerization. ) Etc.

  When the catalyst components of the contact treated product (A), compound (B) and compound (C) are used in a solution, suspension or slurry, the concentrations of the contact treated product (A) and compound (C) are metal atoms. In terms of conversion, it is usually 0.0001 to 100 mol / liter, 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 Polymer The α-olefin unit content in the obtained polymer was determined from an infrared absorption spectrum. The measurement and calculation were carried out using characteristic absorption derived from α-olefin according to the method described in the literature (Die Makromoleculare Chemie, 177, 449 (1976) McRae, MA, Madams, WF). It was represented by the number of short chain branches per unit (degree of short chain branching). The infrared absorption spectrum was measured using an infrared spectrophotometer (FT-IR7300 manufactured by JASCO Corporation).

(2) Molecular weight and molecular weight distribution of polymer The measurement was performed by gel permeation chromatography (GPC) under the following conditions. 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: Millicoater 150C column: Tosoh TSK-GEL GMH-HT (7.5 × 600) × 2 Measurement temperature: 140 ° C.
Solvent: Orthodichlorobenzene Sample concentration: 5mg / 5ml
Detector: Differential refractometer

[Example 1]
(1) Preparation purged with argon 100ml four-necked flask of toluene 40 ml, ZnEt ₂ in hexane (ZnEt ₂ concentration: 2.02M) of the contact treatment product placed 1 ml, this pentafluorophenol toluene solution (pentafluorophenol Concentration: 2.77M) 0.292 ml was added dropwise at room temperature. Thereafter, 29.1 μl (1.615 mmol) of H ₂ O was added dropwise with a microsyringe at room temperature. After completion of dropping, the mixture was stirred at 70 ° C. for 1 hour. The contents became a yellow slurry. To this, 116.3 mg (0.217 mmol) of N, N-di-n-octadecylmethylamine and 10 ml of toluene were added. When the mixture was stirred at 70 ° C. for 1 hour, a yellow slurry (hereinafter referred to as slurry (1)) was obtained. From the calculated value, the Zn concentration in the slurry (1) was 40 μmol-Zn / ml.

(2) Polymerization An 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 autoclave was heated to 70 ° C. After the temperature rise, the ethylene pressure was fed while adjusting the pressure to 6 kg / cm ² , and after the system was stabilized, 250 μmol of triisobutylaluminum was added, followed by 0.05 μmol of ethylenebis (indenyl) zirconium dichloride, 2.5 ml (100 μmol-Zn) of the slurry (1) was charged and polymerization was performed for 30 minutes. As a result, 9.79 g of ethylene / 1-hexene copolymer was obtained. The polymerization activity was 3.9 × 10 ⁸ g / mol-Zr / h, the degree of short chain branching was 15.42, Mw = 63000, and Mw / Mn = 2.0.

[Example 2]
(1) Preparation of contact processed material
As a result of carrying out in the same manner as in Example 1 (1) except that the amount of N, N-di-n-octadecylmethylamine added was 224.6 mg (0.419 mmol), a yellow slurry (hereinafter, slurry ( 2). From the calculated value, the Zn concentration in the slurry (2) was 40 μmol-Zn / ml.

(2) Polymerization Polymerization was performed in the same manner as in Example 1 (2) except that the slurry (2) was used instead of the slurry (1). As a result, 4.40 g of ethylene / 1-hexene copolymer was obtained. The polymerization activity was 1.8 × 10 ⁸ g / mol-Zr / h, the degree of short chain branching was 10.2, Mw = 71000, and Mw / Mn = 2.0.

[Example 3]
(1) Preparation purged with argon 100ml four-necked flask of toluene 40 ml, ZnEt ₂ in hexane (ZnEt ₂ concentration: 2.02M) of the contact treatment product placed 1 ml, this pentafluorophenol toluene solution (pentafluorophenol Concentration: 2.77M) 0.292 ml was added dropwise at room temperature. Thereafter, 32.8 μl (1.82 mmol) of H ₂ O was added dropwise with a microsyringe at room temperature. After completion of dropping, the mixture was stirred at 70 ° C. for 1 hour. The contents became a yellow slurry. To this, 226.1 mg (0.422 mmol) of N, N-di-n-octadecylmethylamine and 10 ml of toluene were added. When the mixture was stirred at 70 ° C. for 1 hour, a yellow transparent solution (hereinafter referred to as solution (3)) was obtained. From the calculated value, the Zn concentration in the solution (3) was 40 μmol-Zn / ml.

(2) Polymerization Polymerization was carried out in the same manner as in Example 1 (2) except that the solution (3) was used instead of the slurry (1). As a result, 6.04 g of ethylene / 1-hexene copolymer was obtained. The polymerization activity was 2.4 × 10 ⁸ g / mol-Zr / h.

[Example 4]
(1) Polymerization Polymerization was conducted in the same manner as in Example 3 (2) except that the amount of ethylenebis (indenyl) zirconium dichloride was changed to 0.2 μmol. As a result, 10.5 g of ethylene / 1-hexene copolymer was obtained. The polymerization activity was 1.0 × 10 ⁸ g / mol Zr / h, and the degree of short chain branching was 18.43.

[Comparative Example 1]
(1) Synthesis of zinc compounds
As a result of carrying out in the same manner as in Example 1 (1) except that N, N-di-n-octadecylmethylamine was not used, a yellow slurry (hereinafter referred to as slurry (4)) was obtained. From the calculated value, the Zn concentration in the slurry (4) was 40 μmol-Zn / ml.

(2) Polymerization Polymerization was performed in the same manner as in Example 1 (2) except that the slurry (4) was used instead of the slurry (1). As a result, 1.49 g of ethylene / 1-hexene copolymer was obtained. The polymerization activity was 6.0 × 10 ⁷ g / mol-Zr / h, the degree of short chain branching was 11.12, Mw = 72000, and Mw / Mn = 2.2.

The present invention is used for production of addition polymers such as olefin polymers.

Claims (8)

A catalyst component for olefin polymerization comprising a contact-treated product obtained by bringing the following component (a) and the following component (b) into contact with each other and then contacting the following component (c) with the following component (d). The contact treatment amount of component (b) and component (c) per mole of component (a) satisfies the following formula (I), and the contact treatment amount of component (b) per mole of component (a) is 0.00. A catalyst component for olefin polymerization, which is 3 to 1 mol, and the amount of contact treatment of component (d) per mol of component (a) is 0.01 to 0.7 mol.
(A): Compound ZnL ¹ ₂ [1] represented by the following general formula [1]
(B): Compound R ¹ T ¹ H represented by the following general formula [2] [2]
(C): Compound T ² H ₂ [3] represented by the following general formula [3]
(D): Compound R ³ ₃ N [4] represented by the following general formula [4]
(In the above general formulas [1] to [3], L ¹ represents a hydrogen atom or a hydrocarbon group , and two L ^{1 s} may be the same or different from each other, and T ¹ and T ² are independent of each other. Represents an oxygen atom or a sulfur atom, R ¹ represents a halogenated alkyl group or a halogenated aryl group, In the above general formula [4], R ³ represents a hydrocarbon group, and three R ^{3 s} are the same as each other. Or different.)
| 2-y-2z | ≦ 0.2 (I)
(In the above formula (I), y represents the component (b) contact treatment amount (mol) per mole of component (a), and z represents the component (c) contact treatment amount (mol) per mole of component (a). ) A catalyst component for olefin polymerization comprising a contact-treated product obtained by bringing the following component (c) into contact with a contact-treated product obtained by bringing the following components (a), (b) and (d) into contact with each other. ) The contact treatment amount of component (b) and component (c) per mole satisfies the following formula (I), and the contact treatment amount of component (b) per mole of component (a) is 0.3 to 1 A catalyst component for olefin polymerization, characterized in that the amount of contact treatment of component (d) per mole of component (a) is 0.01 to 0.7 mol.
(A): Compound represented by the following general formula [1]
ZnL ¹ ₂                      [1]
(B): Compound represented by the following general formula [2]
R ¹ T ¹ H [2]
(C): Compound represented by the following general formula [3]
T ² H ₂                        [3]
(D): Compound represented by the following general formula [4]
R ^Three _Three N [4]
(In the above general formulas [1] to [3], L ¹ Represents a hydrogen atom or a hydrocarbon group, and two L ¹ May be the same or different from each other, and T ¹ And T ² Each independently represents an oxygen atom or a sulfur atom; ¹ Represents a halogenated alkyl group or a halogenated aryl group. In the general formula [4], R ^Three Represents a hydrocarbon group and three R ^Three May be the same as or different from each other. )
| 2-y-2z | ≦ 0.2 (I)
(In the above formula (I), y represents the component (b) contact treatment amount (mol) per mole of component (a), and z represents the component (c) contact treatment amount (mol) per mole of component (a). ) The catalyst component for olefin polymerization according to claim 1 or 2 , wherein at least one of R ³ is a hydrocarbon group having 12 to 100 carbon atoms. The catalyst component for olefin polymerization according to any one of claims 1 to 3, wherein T ¹ and T ² are oxygen atoms. An olefin polymerization catalyst obtained by contacting the catalyst component for olefin polymerization according to any one of claims 1 to 4 and a metal compound of Group 3 to 11 or a lanthanoid series of the periodic table of elements. Claim 1-4 olefin polymerization catalyst component according to any metal compound of the third to Group 11 or lanthanide series of the Periodic Table of the Elements, and an organoaluminum compound into contact formed by olefin polymerization catalyst. Of the 3 to 1 or the lanthanoid series of the Periodic Table of Elements the metal compound according to claim 5 or 6 which is a metal compound or a μ- oxo type metal compound represented by the following general formula [5] Olefin polymerization catalyst.
L ² _a M ² X ¹ _b [5]
(Period in the formula, a is a number satisfying 0 <a ≦ 3, b is table a number satisfying 0 <b ≦ 3, and, .M ² representing a number satisfying a + b ≦ 4 elemental .L ² representing a group 4 metal atom of the periodic table is a group having a cyclopentadiene type anion skeleton, if L ² there is a plurality, they may be different from one another the same, a plurality of L ² may be linked via a residue having an atom selected from a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom, or X ¹ may be a halogen atom, a hydrocarbon Represents a group (excluding a group having a cyclopentadiene-type anion skeleton) or a hydrocarbon oxy group, and when there are a plurality of X ^{1 s} , they may be the same or different. Process for producing an olefin polymer using the olefin polymerization catalyst according to any one of claims 5-7.