JP2006233115A - Catalyst constituent for addition polymerization, preliminarily polymerized catalyst constituent for addition polymerization, catalyst for addition polymerization and method for producing addition polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst constituent for addition polymerization which is capable of producing an addition polymer with a higher polymerization activity, a preliminarily polymerized catalyst constituent for addition polymerization, a catalyst for addition polymerization using the same and method for producing an addition polymer. <P>SOLUTION: The catalyst constituent for addition polymerization is obtained by bringing a modified particle (A) which is obtained by bringing following constituents (a), (b), (c) and (d) into contact with one another, a transition metal compound (B) and further optionally an organo-aluminium compound (C) into contact with one another wherein the transition matal compound is contacted in the state of powder or slurry when the contact takes place, where (a) is a compound expressed by general formula [1]: M<SP>1</SP>L<SP>1</SP><SB>m</SB>, (b) is a compound expressed by general formula [2]: R<SP>1</SP><SB>t-1</SB>TH, (c) is a compound expressed by general formula [3]: R<SP>2</SP><SB>t-2</SB>TH<SB>2</SB>and (d) is a particle. The addition polymer is produced using the preliminarily polymerized catalyst for addition polymerization comprising the preliminarily polymerized catalyst constituent for addition polymerization. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an addition polymerization catalyst component capable of producing an addition polymer with higher polymerization activity, a prepolymerized addition polymerization catalyst component, an addition polymerization catalyst using the same, and a method for producing the addition polymer.

  Olefin polymers such as polypropylene and polyethylene are widely used in various molding fields because of their excellent mechanical properties, chemical resistance, etc., and their excellent balance between properties and economy.

  In recent years, these polymers are produced by using a so-called single-site catalyst, which is a combination of a transition metal component composed of an isolatable transition metal compound (for example, a metallocene complex or a nonmetallocene compound) and an organometallic component composed of an aluminoxane or the like. And a production method in which an olefin or the like is addition-polymerized has been proposed.

  Since ordinary single-site catalysts are soluble in the polymerization solvent, when applied to polymerization in which the addition polymer is formed into particles, such as slurry polymerization or gas phase polymerization, uniform shaped addition polymer particles can be obtained. It is difficult to produce coarse or fine particles, or bulk polymers are formed, and these adhere to the wall of the polymerization reactor, resulting in poor heat removal of the polymerization reactor, resulting in decreased productivity. For example, Patent Document 1 discloses a catalyst component for olefin polymerization using specific particles as a carrier as a means for solving the problem.

Japanese Patent Laid-Open No. 11-193306

However, as described in Patent Document 1, when a single-site catalyst is applied to polymerization in which an addition polymer is produced in the form of particles, it is effective to perform a prepolymerization step before the main polymerization step. When the prepolymerization step is performed, there is a problem that the polymerization activity in the main polymerization step decreases.
In view of such circumstances, the problem to be solved by the present invention, that is, the object of the present invention is to provide an addition polymerization catalyst component capable of producing an addition polymer with higher polymerization activity, a prepolymerized addition polymerization catalyst component, An object of the present invention is to provide a catalyst for addition polymerization using the same and a method for producing an addition polymer.

The present invention provides an addition polymerization catalyst obtained by contacting modified particles obtained by contacting the following components (a), (b), (c) and (d), a transition metal compound, or an organoaluminum compound. A component that is applied to the catalyst component for addition polymerization obtained by contacting the transition metal compound in the form of powder or slurry at the time of the contact, and the present invention uses the catalyst component for addition polymerization. A prepolymerized addition polymerization catalyst obtained by prepolymerizing an olefin, an addition polymerization catalyst obtained by contacting the prepolymerized addition polymerization catalyst component and an organoaluminum compound, and the addition polymerization catalyst. The present invention relates to a method for producing an addition polymer.
(A): Compound represented by the following general formula [1] M ¹ L ¹ _m [1]
(B): Compound represented by the following general formula [2] R ¹ _t-1 TH [2]
(C): Compound represented by the following general formula [3] R ² _t-2 TH ₂ [3]
(D): Particles (In the above general formulas [1] to [3], M ¹ represents a typical metal atom of Group ¹ , 2, 12, 14 or 15 of the periodic table, and m represents the valence of M ¹ . .L ¹ is hydrogen atom represents a number corresponding to, a halogen atom or a hydrocarbon group, if L ¹ there are a plurality, a plurality of L ¹ is optionally different from one another identical .R ¹ is represents a group containing an electron withdrawing group or an electron withdrawing group, if R ¹ there are a plurality, the plurality of R ¹ are optionally different from one another identical .R ² is a hydrocarbon group or a halogenated (T represents a number corresponding to the valence of T in each compound, and T represents an atom of Group 15 or Group 16 of the periodic table of elements, and t represents a number corresponding to the valence of T in each compound.)

  According to the present invention, there are provided an addition polymerization catalyst capable of producing an addition polymer with higher polymerization activity, a prepolymerized addition polymerization catalyst component, an addition polymerization catalyst using the same, and a method for producing the addition polymer. .

The compound (a) in the present invention is a compound represented by the following general formula [1].
M ¹ L ¹ _m [1]
(M ¹ represents a typical metal atom of Group ^{1, 2,} 12, 14 or 15 of the Periodic Table of Elements; m represents a number corresponding to the valence of M ¹ ; L ¹ represents a hydrogen atom, a halogen atom or a carbon atom; It represents a hydrogen group, if L ¹ there are a plurality, a plurality of L ¹ may be different be the same as each other.)

M ¹ in the general formula [1] is a typical metal atom of Group ¹ , 2, 12, 14 or 15 of the periodic table. Examples of M ¹ include lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, beryllium atom, magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, cadmium atom, mercury atom, germanium atom, tin Atoms, lead atoms, antimony atoms, bismuth atoms can be mentioned. Among them, preferred is a magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom or bismuth atom, particularly preferred is a magnesium atom, zinc atom, tin atom or bismuth atom, and most preferred. Is a zinc atom.

L ¹ in the general formula [1] is a hydrogen atom, a halogen atom or a hydrocarbon group. Examples of the halogen atom for L ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The hydrocarbon group for L ¹ is preferably an alkyl group, an aryl group, or an aralkyl group.

  As said alkyl group, a C1-C20 alkyl group is preferable, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl. And n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, and n-eicosyl group. Among them, more preferred is a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an isobutyl group.

Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, and a tetrafluoroethyl group. , Pentafluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, 1H, 1H-perfluoropropyl group, 1H, 1H-perfluorobutyl group, 1H, 1H-perfluoropentyl group, 1H, 1H-perfluorohexyl group, 1H, 1H-perfluorooctyl group, 1H, 1H-perfluorododecyl 1H, 1H-par Le Oro pentadecyl group, and IH, 1H-perfluoro eicosyl group, and can include fluoro and chloro, alkyl groups is replaced with bromo or iodo these alkyl groups.
Any of these alkyl groups may be substituted with an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, for example, phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group. 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, 2,3,4-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 Nyl group, tert-butylphenyl group, isobutylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n- A tetradecylphenyl group, a naphthyl group, and an anthracenyl group can be mentioned, and among them, a phenyl group is more preferable.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy group such as phenoxy group or benzyloxy group. Such an aralkyloxy group or the like may be substituted.

The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, such as a benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethyl) Phenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethyl) Phenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) Nyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl Group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (isobutylphenyl) methyl Group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, And anthracenylmethyl group. Among them, a benzyl group is more preferable.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy group such as phenoxy group or benzyloxy group. Such an aralkyloxy group or the like may be substituted.

L ¹ in the general formula [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.

T in the general formula [2] and T in the general formula [3] may be the same or different. T in these formulas is each independently an atom of Group 15 or Group 16 of the Periodic Table of Elements. Examples of the Group 15 nonmetal atom in T include a nitrogen atom and a phosphorus atom, and examples of the Group 16 nonmetal atom include an oxygen atom and a sulfur atom. T is preferably a nitrogen atom or an oxygen atom, and particularly preferably an oxygen atom.
T in the general formulas [2] and [3] is a number corresponding to the valence of T. t is 3 when T is a Group 15 nonmetallic atom and is 2 when T is a Group 16 nonmetallic atom.

R ¹ in the general formula [2] is an electron-withdrawing group or a group containing an electron-withdrawing group. As an index of electron withdrawing property of R ¹ , for example, a Hammett's rule substituent constant σ is known, and a functional group having a positive substituent constant σ can be exemplified as an electron withdrawing group.

Examples of the electron-withdrawing group of R ¹ in the general formula [2] include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group, and a phenyl group. . Examples of the group containing an electron-withdrawing group represented by R ¹ in the general formula [2] include a halogenated alkyl group, a halogenated aryl group, a (halogenated alkyl) aryl group, a cyanated aryl group, a nitrated aryl group, Examples include ester groups (alkoxycarbonyl groups, aralkyloxycarbonyl groups and aryloxycarbonyl groups), acyl groups, and acyl halide groups.

Examples of the halogenated alkyl group for R ¹ include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a 2,2,3,3,3-pentafluoropropyl group. Group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 1H, 1H-perfluorobutyl group, 1H, 1H-perfluoropentyl group, 1H, 1H-perfluorohexyl group, 1H, 1H-perfluorooctyl group, 1H, 1H-perfluorododecyl group, 1H, 1H-perfluoropentadecyl group, and 1H, 1H -Perfluoroeicosyl groups, as well as fluoro in these halogenated alkyl groups, replaced with chloro, bromo or iodo It can be mentioned alkyl group.

Examples of the halogenated aryl group for R ¹ include, for example, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4 -Difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluoro Phenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro group Fluoro-2-naphthyl group and 4,5,6,7,8-pentafluoro-2-naphthyl group Fluoro Le group chloro, and halogenated aryl group is replaced with bromo or iodo.

Examples of the (halogenated alkyl) aryl group for R ¹ include 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6- Bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, and 2,4,6-tris (trifluoromethyl) phenyl group, and these (halogenated alkyl) aryl groups Mention may be made of (halogenated) aryl groups in which fluoro is replaced by chloro, bromo or iodo.

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

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

Examples of the ester group of R ¹ include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, phenoxycarbonyl group, trifluoromethoxycarbonyl group, and pentafluorophenoxycarbonyl group. it can.

Examples of the acyl group and halogenated acyl group for R ¹ include formyl group, ethanoyl group, propanoyl group, butanoyl group, trifluoroethanoyl group, benzoyl group, pentafluorobenzoyl group, perfluoroethanoyl group, perfluoro Propanoyl, perfluorobutanoyl, perfluoropentanoyl, perfluorohexanoyl, perfluoroheptanoyl, perfluorooctanoyl, perfluorononanoyl, perfluorodecanoyl, perfluoroundeca A noyl group and a perfluorododecanoyl group can be mentioned.

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

R ² in the general formula [3] is a hydrocarbon group or a halogenated hydrocarbon group. The hydrocarbon group for R ² is preferably an alkyl group, an aryl group or an aralkyl group, and examples thereof include the groups exemplified as L ¹ in the general formula [1]. Examples of the halogenated hydrocarbon group in R ² include a halogenated alkyl group, a halogenated aryl group, and a (halogenated alkyl) aryl group, and the electron withdrawing property of R ¹ in the above general formula [2]. Examples of the halogenated alkyl group, halogenated aryl group, and (halogenated alkyl) aryl group exemplified as the group can be given.

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

Examples of the compound (a) when M ¹ in the general formula [1] is a zinc atom include dimethyl zinc, diethyl zinc, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-n-hexyl zinc and the like. Dialkyl zinc; diaryl zinc such as diphenyl zinc, dinaphthyl zinc, and bis (pentafluorophenyl) zinc; dialkenyl zinc such as diallyl zinc; bis (cyclopentadienyl) zinc; methyl zinc chloride, ethyl zinc chloride, chloride Propyl zinc, -n-butyl zinc chloride, isobutyl zinc chloride, -n-hexyl chloride, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, -n-butyl zinc bromide, isobutyl zinc bromide, odor -N-hexyl zinc, methyl zinc iodide, ethyl zinc iodide, propyl zinc iodide, n-butyl iodide Le Zinc, isobutyl iodide, zinc, and halogenated alkyl zinc such as iodide n- hexyl zinc; zinc fluoride, zinc chloride, zinc bromide, and zinc halides such as zinc iodide.

  The compound (a) is preferably dialkyl zinc, more preferably dimethyl zinc, diethyl zinc, dipropyl zinc, di n-butyl zinc, diisobutyl zinc or di n-hexyl zinc, particularly preferably dimethyl zinc or diethyl. Zinc.

  Examples of the compound (b) include amines, phosphines, alcohols, thiols, phenols, thiophenols, naphthols, naphthylthiols, and carboxylic acid compounds. Examples of amine and phosphine compounds include di (fluoromethyl) amine, bis (difluoromethyl) amine, bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, and 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, bis (2-fluorophenyl) amine, bis (3-fluorophenyl) amine, bis (4-fluorophenyl) amine, bis (2,6-difluorophenyl) amine, bis (3,5- Difluorophenyl) amine, bis (2,4,6-trifluorophenyl) amine, bis (3,4,5-trifluorophenyl) Amine, bis (pentafluorophenyl) amine, bis (2- (trifluoromethyl) phenyl) amine, bis (3- (trifluoromethyl) phenyl) amine, bis (4- (trifluoromethyl) phenyl) amine, bis (2,6-di (trifluoromethyl) phenyl) amine, bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-trifluoro (trifluoromethyl) phenyl) amine, bis (2-cyanophenyl) amine, (3-cyanophenyl) amine, bis (4-cyanophenyl) amine, bis (2-nitrophenyl) amine, bis (3-nitrophenyl) amine, bis (4-nitrophenyl) Amines, bis (1H, 1H-perfluorobutyl) amine, bis (1H, 1H-perfluoropentyl) amine, (1H, 1H-perfluorohexyl) amine, bis (1H, 1H-perfluorooctyl) amine, bis (1H, 1H-perfluorododecyl) amine, bis (1H, 1H-perfluoropentadecyl) amine, and Mention may be made of bis (1H, 1H-perfluoroeicosyl) amine, as well as amines in which the fluoro of these amines is replaced by chloro, bromo or iodo. Moreover, the phosphine compound which substituted the nitrogen atom of the said amine with the phosphorus atom can also be mentioned similarly. These phosphine compounds are compounds represented by replacing “amine” in the amine with “phosphine”.

  Examples of the alcohol and thiol compound of the compound (b) include fluoromethanol, difluoromethanol, trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2, 2,2-trifluoro-1-trifluoromethylethanol, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, 1H, 1H-perfluorobutanol, 1H, 1H-perfluoropen Thanol, 1H, 1H-perfluorohexanol, 1H, 1H-perfluorooctanol, 1H, 1H-perfluorododecanol, 1H, 1H-perfluoropentadecanol, and 1H, 1H-perfluoroeicosanol, and The fluoro of these alcohols , Mention may be made of alcohol replaced by bromo or iodo. Moreover, the thiol compound which replaced the oxygen atom of the said alcohol compound with the sulfur atom can be mentioned similarly. These thiol compounds are compounds represented by substituting “nol” in the alcohol compound with “nthiol”.

  Examples of the phenol, naphthol, thiophenol, and naphthylthiol compound of the compound (b) include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, 2,3,5,6-tetrafluorophenol, pentafluorophenol, 2,3,5,6-tetrafluoro-4-trifluoromethylphenol, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol, perfluoro-1-naphthol, perfluoro-2-naphthol, 4,5,6,7,8-pentafluoro-2 Naphthol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (trifluoromethyl) ) Phenol, 2,4,6-tris (trifluoromethyl) phenol, 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, and 4-nitrophenol, and Mention may be made of phenolic compounds in which the fluoro of these phenols is replaced by chloro, bromo or iodo. Moreover, the thiophenol compound which replaced the oxygen atom of the said phenol compound with the sulfur atom can be mentioned similarly. These thiophenol compounds are compounds represented by replacing “phenol” in the above phenol compounds with “thiophenol” (in the case of naphthol, compounds represented by replacing “naphthol” with “naphthylthiol”), etc. It is.

  Examples of the carboxylic acid compound of the compound (b) include pentafluorobenzoic acid, perfluoroethanoic acid, perfluoropropanoic acid, perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid. Examples include ic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid.

  The compound (b) is preferably an amine, an alcohol, or a phenol compound. Specifically, examples of the amine include bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis ( 2,2,3,3,3-pentafluoropropyl) amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2 , 2,2-trifluoroethyl) amine, or bis (pentafluorophenyl) amine, and examples of the alcohol include trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3- Pentafluoropropanol, 2,2,2-trifluoro-1-trifluoromethylethanol, or 1,1-bis (trifluorome 2) -2,2,2-trifluoroethanol, and phenol includes 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2, 4,6-trifluorophenol, pentafluorophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol 3,5-bis (trifluoromethyl) phenol or 2,4,6-tris (trifluoromethyl) phenol.

  More preferably, the compound (b) is bis (trifluoromethyl) amine, bis (pentafluorophenyl) amine, trifluoromethanol, 2,2,2-trifluoro-1-trifluoromethylethanol, 1,1- Bis (trifluoromethyl) -2,2,2-trifluoroethanol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4, 6-trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, or 2,4,6-tris ( Trifluoromethyl) phenol, more preferably 3,5- Fluoro phenol, 3,4,5-fluorophenol, pentafluorophenol or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol.

  Examples of the compound (c) include water, hydrogen sulfide, amine, and aniline compounds. Examples of the amine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentylamine, neopentylamine, isopentylamine, and n-hexyl. Alkylamines such as amines, n-octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, and n-eicosylamine, aralkylamines such as allylamine, cyclopentadienylamine, and benzylamine , Fluoromethylamine, difluoromethylamine, trifluoromethylamine, 2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine, 2,2,2-trifluoro-1- G Fluoromethylethylamine, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, perfluorooctylamine, perfluoro Mention may be made of fluorododecylamine, perfluoropentadecylamine, and perfluoroeicosylamine, and halogenated alkylamines in which the fluoro of these amines has been replaced by chloro, bromo or iodo.

  Examples of the aniline compound of the compound (c) include aniline, naphthylamine, anthracenylamine, 2-tolylamine, 3-tolylamine, 4-tolylamine, 2,3-xylylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3,4-xylylamine, 3,5-xylylamine, 2,3,4-trimethylaniline, 2,3,5-trimethylaniline, 2,3,6-trimethylaniline, 2,4,6 -Trimethylaniline, 3,4,5-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,4,6-tetramethylaniline, 2,3,5,6-tetramethylaniline, penta Methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2,3-diethylaline Phosphorus, 2,4-diethylaniline, 2,5-diethylaniline, 2,6-diethylaniline, 3,4-diethylaniline, 3,5-diethylaniline, 2,3,4-triethylaniline, 2,3, 5-triethylaniline, 2,3,6-triethylaniline, 2,4,6-triethylaniline, 3,4,5-triethylaniline, 2,3,4,5-tetraethylaniline, 2,3,4,6 Tetraethylaniline, 2,3,5,6-tetraethylaniline, and pentaethylaniline, and these ethyls as n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, Alkyla substituted with n-hexyl, n-octyl, n-decyl, n-dodecyl, or n-tetradecyl Phosphorus, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline , And halogenated anilines such as pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-di (trifluoromethyl) aniline 3,4-di (trifluoromethyl) aniline, and 2,4,6-tri (trifluoromethyl) aniline, and (halogenated alkyl) anilines in which these fluoros are replaced by chloro, bromo or iodo be able to.

  The compound (c) is preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-octylamine, aniline, 2, 6-xylylamine, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, Perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoro Oroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3 -(Trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline or 2,4,6-tris (tri Fluoromethyl) aniline, particularly preferably water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine, perfluoropentadecylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2, 6-difluoroaniline, 3,5-difluoroa Phosphorus, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) ) Aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, or 2,4,6-tris (trifluoromethyl) aniline, most preferably water or penta Fluoroaniline.

As the particles (d), those generally used as carriers are preferably used, porous materials having a uniform particle diameter are preferable, inorganic materials or organic polymers are preferably used, and inorganic materials are more preferably used. used.
The particle (d) is preferably 2.5 or less, more preferably 2.0 or less as a volume-based geometric standard deviation of the particle diameter of the particle (d) from the viewpoint of the particle size distribution of the resulting addition polymer. More preferably, it is 1.7 or less.

Examples of the inorganic substance of the particles (d) include inorganic oxides, clays, and clay minerals. A mixture of these may be used.
As the inorganic oxide, _{e.g., SiO 2, Al 2 O 3} , MgO, ZrO 2, TiO 2, B 2 O 3, CaO, ZnO, BaO, and ThO _2, and mixtures thereof, SiO ₂ -MgO, SiO Mention may be made of _2- Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , and SiO ₂ —TiO ₂ —MgO. Among these inorganic oxides, SiO ₂ and / or Al ₂ O ₃ are preferable, and SiO ₂ (that is, silica) is particularly preferable. The inorganic oxide is a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) _2. Carbonic acid salts such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained.

Examples of the clay or clay mineral include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, vylophilite, talc, ummo group, smectite, montmorillonite group, hectorite, laponite, saponite, vermiculite, ryokdeite stone. Group, palygorskite, kaolinite, nacrite, dickite, halloysite.
Among these, preferred are smectite, montmorillonite, hectorite, laponite and saponite, and more preferred are montmorillonite and hectorite.

Among these inorganic substances, inorganic oxides are preferably used.
These inorganic substances are preferably dried and substantially free of moisture, and those dried by heat treatment are preferred. The heat treatment is usually performed at a temperature of 100 to 1500 ° C., preferably 100 to 1000 ° C., more preferably 200 to 800 ° C. for an inorganic substance whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the heat drying method include a method in which an inert gas (eg, nitrogen or argon) dried during heating is circulated and dried at a constant flow rate, and a method in which heat drying is performed under reduced pressure. Can do.

  In addition, a hydroxyl group is usually generated and present on the surface of the inorganic oxide, but as the inorganic oxide, modified inorganic oxides in which active hydrogen of the surface hydroxyl group is substituted with various substituents may be used. . Examples of the modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane, triarylchlorosilanes such as triphenylchlorosilane, dialkyldichlorosilanes such as dimethyldichlorosilane, and diphenyldichlorosilane. Diaryldichlorosilanes, alkyltrichlorosilanes such as methyltrichlorosilane, aryltrichlorosilanes such as phenyltrichlorosilane, trialkylalkoxysilanes such as trimethylmethoxysilane, triarylalkoxysilanes such as triphenylmethoxysilane and dimethyl Dialkyl dialkoxysilanes such as dimethoxysilane, diaryl dialkoxysilanes such as diphenyldimethoxysilane , Alkyltrialkoxysilanes such as methyltrimethoxysilane, aryltrialkoxysilanes such as phenyltrimethoxysilane, tetraalkoxysilanes such as tetramethoxysilane, 1,1,1,3,3,3-hexamethyl Treated with alkyldisilazane such as disilazane, alcohols such as tetrachlorosilane, methanol and ethanol, phenol, dialkylmagnesium such as dibutylmagnesium, butylethylmagnesium, and butyloctylmagnesium, alkyllithium such as butyllithium Mention may be made of inorganic oxides.

  Furthermore, after contact with a trialkylaluminum, inorganic oxides contacted with dialkylamines such as diethylamine and diphenylamine, alcohols such as methanol and ethanol, and phenol can be exemplified.

  In addition, the strength of the inorganic oxide itself may increase due to hydrogen bonding between hydroxyl groups. In that case, if all the active hydrogens of the surface hydroxyl group are substituted with various substituents, the particle strength may be lowered. Therefore, it is not always necessary to substitute all the active hydrogens on the surface hydroxyl groups of the inorganic oxide, and the substitution rate of the surface hydroxyl groups may be determined as appropriate. The method for changing the substitution rate of the surface hydroxyl group is not particularly limited. As this method, the method of changing the usage-amount of the compound used for a contact process is mentioned, for example.

The average particle diameter of the inorganic substance is preferably 5 to 1000 μm, more preferably 10 to 500 μm, and still more preferably 10 to 100 μm. The pore volume of the inorganic substance is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area is preferably a 10 to 1000 m ² / g, more preferably 100 to 500 m ² / g.

  Any organic polymer may be used as the organic polymer of the particles (d), and a mixture of plural kinds of organic polymers may be used. The organic polymer is preferably a polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group.

  The functional group having active hydrogen is not particularly limited as long as it has active hydrogen. Examples of the functional group include a primary amino group, secondary amino group, imino group, amide group, hydrazide group, amidino group, hydroxy group, hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid group, Mention may be made of sulfinic acid groups, sulfenic acid groups, thiol groups, thioformyl groups, pyrrolyl groups, imidazolyl groups, piperidyl groups, indazolyl groups and carbazolyl groups. Among them, preferred is a primary amino group, a secondary amino group, an imino group, an amide group, an imide group, a hydroxy group, a formyl group, a carboxyl group, a sulfonic acid group, or a thiol group, and particularly preferred is a primary amino group. Group, secondary amino group, amide group or hydroxy group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  The non-proton donating Lewis basic functional group is not particularly limited as long as it is a functional group having a Lewis base portion having no active hydrogen atom. Examples of the functional group include a pyridyl group, an N-substituted imidazolyl group, an N-substituted indazolyl group, a nitrile group, an azide group, an N-substituted imino group, an N, N-substituted amino group, and an N, N-substituted aminooxy group. Group, N, N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group, furyl group, carbonyl group, thiocarbonyl group, alkoxy group, alkyloxycarbonyl group, N, N-substituted carbamoyl group, thioalkoxy group , Substituted sulfinyl groups, substituted sulfonyl groups, and substituted sulfonic acid groups. A heterocyclic group is preferable, and an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring is more preferable. Particularly preferred are a pyridyl group, an N-substituted imidazolyl group and an N-substituted indazolyl group, and most preferred is a pyridyl group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  The content of the functional group having active hydrogen or the non-proton donating Lewis basic functional group in the polymer as the organic polymer is not particularly limited. The amount used is preferably 0.01 to 50 mmol / g, more preferably 0.1 to 20 mmol / g as the molar amount of the functional group per unit gram of the polymer.

  Examples of the method for producing a polymer having the functional group include homopolymerization of a monomer having a functional group having active hydrogen or a non-proton donating Lewis basic functional group and one or more polymerizable unsaturated groups. And a method of copolymerizing the monomer with another monomer having a polymerizable unsaturated group. At this time, it is preferable to copolymerize together a crosslinkable monomer having two or more polymerizable unsaturated groups.

Examples of the polymerizable unsaturated group include alkenyl groups such as vinyl group and allyl group, and alkynyl groups such as ethyne group.
Examples of the monomer having a functional group having active hydrogen and one or more polymerizable unsaturated groups include a vinyl group-containing primary amine, a vinyl group-containing secondary amine, a vinyl group-containing amide compound, and a vinyl group-containing compound. Mention may be made of hydroxy compounds. Specific examples of the monomer include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methyl. Amine, 1-ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-butene-1- Oars.
Examples of the monomer having a functional group having a Lewis base moiety having no active hydrogen atom and one or more polymerizable unsaturated groups include vinylpyridine, vinyl (N-substituted) imidazole, and vinyl (N-substituted). ) Indazole can be mentioned.

As another monomer which has a polymerizable unsaturated group, ethylene, an alpha olefin, and an aromatic vinyl compound can be mentioned, for example. Specific examples of the monomer are ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and styrene. Of these, ethylene or styrene is preferable. Two or more of these monomers may be used.
Specific examples of the crosslinking polymerizable monomer having two or more polymerizable unsaturated groups include divinylbenzene.

The average particle diameter of the organic polymer is preferably 5 to 1000 μm, more preferably 10 to 500 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area is preferably 10 to 1000 m ² / g, more preferably 50 to 500 m ² / g.

  These organic polymers are preferably dried and substantially free of moisture, and are preferably dried by heat treatment. The heat treatment is usually carried out at a temperature of 30 to 400 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. for an organic polymer whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the heat drying method include a method in which a dry inert gas (for example, nitrogen or argon) is circulated and dried at a constant flow rate during heating, and a method in which heat drying is performed under reduced pressure. be able to.

In order to obtain the modified particles (A) of the present invention, the order in which the components (a), (b), (c) and (d) are brought into contact with each other is not particularly limited. The following order can be given.
<1> A contact object obtained by contacting (a) and (b) with (c) and a contact object obtained by bringing (c) into contact with each other.
<2> A contact object obtained by bringing (a) and (b) into contact with each other and a contact object obtained by bringing (d) into contact with each other.
<3> A contact object obtained by bringing (a) and (c) a contact object into contact with (b) is brought into contact with (d).
<4> A contact object obtained by bringing (a) and (c) into contact with each other and (d) in contact with (b).
<5> A contact product obtained by contacting (b) with a contact product between (a) and (d) and (c) are brought into contact with each other.
<6> A contact object obtained by bringing (a) and (d) into contact with each other and (c) with the contact object obtained in contact with (b).
<7> A contact product obtained by contacting (b) with the contact product between (b) and (c) is brought into contact with (d).
<8> A contact product obtained by contacting (b) with the contact product between (b) and (c) and (a) are brought into contact with each other.
<9> A contact product obtained by contacting (b) with the contact product between (b) and (d) and (c) are brought into contact with each other.
<10> The contact product obtained by bringing (b) and (d) into contact with each other and (c) with the contact product are brought into contact with each other.
<11> A contact object obtained by contacting (a) with a contact object between (c) and (d) and (b) are brought into contact with each other.
<12> A contact product obtained by contacting (b) with a contact product between (c) and (d) and (a) are contacted.
The contact order is preferably <1>, <2>, <3>, <5>, <11> or <12>. Particularly preferred is <2> or <5>.

In addition, the particles obtained by contacting the components (a), (b), (c) and (d) (sometimes referred to as “intermediate solid”) are again reused as the components (a), (b) and You may make it contact with (c). The order of contacting is not particularly limited, and examples thereof include a method in which (d) is replaced with an intermediate solid in the above <1> to <12>. Among these, the following <13>, <14> or <15> is preferable.
<13> A contact product obtained by contacting the intermediate solid with (a) and (b) is contacted with (c).
<14> A contact product between the intermediate solid and (b), a contact product obtained by contacting (a), and (c) are contacted.
<15> A contact product between the intermediate solid and (c) and a contact product obtained by bringing (b) into contact with (a).
After the contact treatment, the contact treatment between the solid component obtained by the contact treatment and the components (a), (b), and (c) may be further performed once or more.

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

  As a solvent, the solvent which does not react with the said component (a), (b), (c), (d), and those contacts is used. However, as described above, when each component is brought into contact in stages, even if the solvent reacts with a certain component at a certain stage, if the solvent does not react with each component at another stage, The solvent can be used in other stages. That is, the solvents in each stage are the same or different from each other. Examples of the solvent include nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents, halide solvents, ether solvents, alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives. , Polar solvents such as nitrile solvents, nitro compounds, amine solvents, and sulfur compounds. Specific examples include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, and cyclohexane, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, Dichloromethane, difluoromethane, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, and o-dichlorobenzene Halide solvents such as, 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 solvents such as ether, tetrahydrofuran, and tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, Alcohol solvents such as cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, and glycerin, phenol solvents such as phenol and p-cresol, acetone , Ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetate Amides, and carbonyl solvents such as N-methyl-2-pyrrolidone, phosphate derivatives such as hexamethyl phosphate triamide and triethyl phosphate, nitriles such as acetonitrile, propionitrile, succinonitrile, and benzonitrile Mention may be made of system solvents, nitro compounds such as nitromethane and nitrobenzene, amine solvents such as pyridine, piperidine and morpholine, and sulfur compounds such as dimethyl sulfoxide and sulfolane.

  When the contact product (e) obtained by bringing the components (a), (b) and (c) into contact with the particles (d), that is, the above <1>, <3>, <7> In each of the methods, the solvent (s1) for producing the contact product (e) is preferably the above aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether solvent.

On the other hand, a polar solvent is preferable as the solvent (s2) when the contact product (e) and the particles (d) are brought into contact with each other. As an index representing the polarity of the solvent, E _T ^N value (C.Reichardt, "Solvents and Solvents Effects in Organic Chemistry", 2nd ed., VCH Verlag ( 1988).) And the like are known, 0.8 ≧ A solvent satisfying the range of E _T ^N ≧ 0.1 is particularly preferable. Examples of the polar solvent include dichloromethane, dichlorodifluoromethane chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, Bromobenzene, o-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol Cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, triethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrobenzene, Mention may be made of ethylenediamine, pyridine, piperidine, morpholine, dimethyl sulfoxide and sulfolane. More preferably, the solvent (s2) is 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, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, Ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol or triethylene glycol, particularly preferably di-n-butyl ether, methyl tert-butyl ether, 1,4-dioxane, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol or cyclohexanol Most preferably, it is tetrahydrofuran, methanol, ethanol, 1-propanol or 2-propanol.

Moreover, as said solvent (s2), the mixed solvent of these polar solvents and hydrocarbon solvents can also be used. As the hydrocarbon solvent, the aliphatic hydrocarbon solvent and aromatic hydrocarbon solvent exemplified above are used. Examples of the mixed solvent of the polar solvent and the hydrocarbon solvent include hexane / methanol mixed solvent, hexane / ethanol mixed solvent, hexane / 1-propanol mixed solvent, hexane / 2-propanol mixed solvent, heptane / methanol mixed solvent, heptane. / Ethanol mixed solvent, heptane / 1-propanol mixed solvent, heptane / 2-propanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, toluene / 1-propanol mixed solvent, toluene / 2-propanol mixed solvent, xylene And xylene / ethanol mixed solvent, xylene / 1-propanol mixed solvent, and xylene / 2-propanol mixed solvent. Preferably in hexane / methanol mixed solvent, hexane / ethanol mixed solvent, heptane / methanol mixed solvent, heptane / ethanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, xylene / methanol mixed solvent, xylene / ethanol mixed solvent is there. More preferred are a hexane / methanol mixed solvent, a hexane / ethanol mixed solvent, a toluene / methanol mixed solvent or a toluene / ethanol mixed solvent. Most preferred is a toluene / ethanol mixed solvent.
The preferable range of the ethanol fraction in the toluene / ethanol mixed solvent is 10 to 50% by volume, more preferably 15 to 30% by volume.

  A method of contacting the contact product (e) obtained by contacting the components (a), (b) and (c) with (d), ie, <1>, <3> and <7> above In each method, a hydrocarbon solvent can be used as both the solvent (s1) and the solvent (s2). In this case, after the components (a), (b) and (c) are contacted, it is preferable that the time until the obtained contact product (e) and the particles (d) are contacted is short. The time is preferably 0 to 5 hours, more preferably 0 to 3 hours, and most preferably 0 to 1 hour. Moreover, the temperature at the time of contacting a contact product (e) and particle | grains (d) is -100 degreeC-40 degreeC normally, Preferably it is -20 degreeC-20 degreeC, Most preferably, it is -10 degreeC- 10 ° C.

  In the case of <2>, <5>, <6>, <8>, <9>, <10>, <11>, <12> above, any of the above nonpolar solvents and polar solvents may be used. it can. Preferably, it is a nonpolar solvent. This is because the contact product of (a) and (c) and the contact product of (a) and (b) and the contact product of (c) are generally dissolved in a nonpolar solvent. It is considered that when (d) is present in the reaction system when these contact products are produced, the produced contact products are deposited on the surface of (d) and are more easily immobilized. It is.

The amount of each component (a), (b), (c) used is not particularly limited. The amount of each compound used preferably satisfies the following relational expression (1) when the amount of (a) used is 1 mol.
| Valence of M ¹ -molar amount of (b) -2 × molar amount of (c) | ≦ 1 (1)
The molar amount of the component (b) when the amount of the component (a) used is 1 mol is preferably 0.01 to 1.99 mol, more preferably 0.1 to 1.8 mol, More preferably, it is 0.2-1.5 mol, Most preferably, it is 0.3-1 mol. The preferred use amount, more preferred use amount, more preferred use amount, and most preferred use amount of the component (c) are calculated by the valence of M ¹ , the use amount of the component (b), and the above relational expression (1), respectively. The

  The amount of components (a) and (d) used is such that typical metal atoms derived from component (a) contained in the modified particles (A) are converted into typical metal atoms contained in 1 g of the resulting modified particles. The number of moles is preferably 0.1 mmol or more, and more preferably 0.5 to 20 mmol.

  In order to make the reaction proceed faster, it is preferable to add a heating step at a higher temperature after the contact treatment as described above. In the heating step, it is preferable to use a solvent having a high boiling point in order to obtain a higher temperature. When performing the heating step, the solvent used in the contact step may be replaced with another solvent having a higher boiling point.

  In the modified particles (A) of the present invention, the components (a), (b), (c) and / or (d) as raw materials remain as unreacted materials as a result of such contact treatment. May be. However, it is preferable to carry out a washing treatment to remove unreacted substances in advance. The solvent at that time may be the same as or different from the solvent at the time of contact. Such cleaning treatment is preferably carried out in an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  Further, after such contact treatment or washing treatment, it is preferable to distill off the solvent from the product, and then to dry under reduced pressure for 1 to 24 hours at a temperature of 0 ° C. or higher. More preferably, it is 1 hour to 24 hours at a temperature of 0 ° C. to 200 ° C., more preferably 1 hour to 24 hours at a temperature of 10 ° C. to 200 ° C., particularly preferably 2 at a temperature of 10 ° C. to 160 ° C. Time to 18 hours, most preferably 4 to 18 hours at a temperature of 15 ° C to 160 ° C.

  Specific examples of the method for producing the modified particles (A) of the present invention are as follows: the compound (a) is diethyl zinc, the compound (b) is pentafluorophenol, the compound (c) is water, The case where (d) is silica will be described in more detail below. Tetrahydrofuran was used as a solvent, a hexane solution of diethylzinc was added thereto, the mixture was cooled to 3 ° C., and an equimolar amount of pentafluorophenol was added dropwise to diethylzinc, followed by stirring at room temperature for 10 minutes to 24 hours. Thereafter, 0.5-fold molar amount of water is added dropwise with respect to diethyl zinc, and the mixture is stirred at room temperature for 10 minutes to 24 hours. Thereafter, the solvent is distilled off, followed by drying at 120 ° C. under reduced pressure for 8 hours. Tetrahydrofuran and silica are added to the solid component obtained by the above operation, and the mixture is stirred at 40 ° C. for 2 hours. The solid component is washed with tetrahydrofuran and then dried at 120 ° C. under reduced pressure for 8 hours. Thus, the modified particles (A) of the present invention can be produced.

  The transition metal compound (B) used in the addition polymerization catalyst of the present invention is added by using it together with the modified particles (A) described below (or further together with the organoaluminum compound (C)). Although it will not specifically limit if it is a transition metal compound which shows polymerization activity, Usually, the transition metal compound which forms a single site catalyst is used. The single-site catalyst in the present invention is a catalyst that is distinguished from conventional solid catalysts, and includes not only a single-site catalyst in a narrow sense that can produce an addition polymer with a narrow molecular weight distribution and high homogeneity, but also a single site in a narrow sense. It also means a catalyst which can be produced by a production method similar to the catalyst and which can produce an addition polymer having a broad molecular weight distribution and low homogeneity.

As the transition metal compound (B), a transition metal compound of Group 3 to 11 of the Periodic Table of the Elements or a lanthanoid series is usually used, and the transition metal compound represented by the following general formula [4] or a μ-oxo type thereof Dimers of these transition metal compounds are preferred.
L ² _a M ² X ¹ _b [4]
(In the formula, M ² is a transition metal atom of Group 3 to 11 of the Periodic Table of Elements or a lanthanoid series. L ² is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ² may be directly connected to each other, or may be connected via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, X ¹ is a halogen atom, carbonized A hydrogen group (excluding a group having a cyclopentadiene type anion skeleton) or a hydrocarbon oxy group, a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8. Represents.)

As M ^{2 in the} general formula [4], for example, scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium Atoms, nickel atoms, palladium atoms, samarium atoms, ytterbium atoms and the like can be mentioned. Among them, preferred is a titanium atom, zirconium atom, hafnium atom, vanadium atom, chromium atom, iron atom, cobalt atom or nickel atom, particularly preferred is a titanium atom, zirconium atom or hafnium atom, and most preferred is a zirconium atom. It is.

Examples of the group having a cyclopentadiene-type anion skeleton of L ^{2 in} the general formula [4] include (substituted) cyclopentadienyl group, (substituted) indenyl group, and (substituted) fluorenyl group. Specifically, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, tert-butylcyclopentadienyl group, 1,2-dimethylcyclopenta Dienyl group, 1,3-dimethylcyclopentadienyl group, 1-methyl-2-ethylcyclopentadienyl group, 1-methyl-3-ethylcyclopentadienyl group, 1-tert-butyl-2-methyl Cyclopentadienyl group, 1-tert-butyl-3-methylcyclopentadienyl group, 1-methyl-2-isopropylcyclopentadienyl group, 1-methyl-3-isopropylcyclopentadienyl group, 1-methyl 2-n-butylcyclopentadienyl group, 1-methyl-3-n-butylcyclopentadienyl group, 1,2, -Trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group, 4,5,6,7-tetrahydroindene Nyl group, 2-methylindenyl group, 3-methylindenyl group, 4-methylindenyl group, 5-methylindenyl group, 6-methylindenyl group, 7-methylindenyl group, 2-tert-butyl Indenyl group, 3-tert-butylindenyl group, 4-tert-butylindenyl group, 5-tert-butylindenyl group, 6-tert-butylindenyl group, 7-tert-butylindenyl group, 2 , 3-dimethylindenyl group, 4,7-dimethylindenyl group, 2,4,7-trimethylindenyl group, 2-methyl 4-isopropylindenyl group, 4,5-benzindenyl group, 2-methyl-4,5-benzindenyl group, 4-phenylindenyl group, 2-methyl-5-phenylindenyl group, 2-methyl-4-phenyl Examples thereof include indenyl group, 2-methyl-4-naphthylindenyl group, fluorenyl group, 2,7-dimethylfluorenyl group and 2,7-di-tert-butylfluorenyl group.

The polydentate η of the group having a cyclopentadiene type anion skeleton used for L ² is not particularly limited, and may be any value that the group having a cyclopentadiene type anion skeleton can take. For example, 5 seats, 4 seats, 3 seats, 2 seats and single seats are mentioned, preferably 5 seats, 3 seats or single seats, more preferably 5 seats or 3 seats.

Examples of the hetero atom in the group containing the L ² hetero atom in the general formula [4] include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Examples of such a group include an alkoxy group, aryloxy Group, thioalkoxy group, thioaryloxy group, alkylamino group, arylamino group, alkylphosphino group, arylphosphino group, chelating ligand, or oxygen atom, sulfur atom, nitrogen atom and / or phosphorus atom An aromatic heterocyclic group or an aliphatic heterocyclic group in the ring is preferable.

Examples of the group containing a hetero atom of L ² in the general formula [4] include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, a 2-methylphenoxy group, a 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-butyl Phenoxy group, 2,6-di-sec-butylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2,6-di-tert-butylphenoxy group, 4-methoxyphenoxy group, 2,6-dimethoxy Phenoxy group, 3,5-dimethoxyphenoxy group, 2-chlorophenoxy group, 4-nitrosopheno Si group, 4-nitrophenoxy group, 2-aminophenoxy group, 3-aminophenoxy group, 4-aminothiophenoxy group, 2,3,6-trichlorophenoxy group, 2,4,6-trifluorophenoxy group, thiomethoxy Group, dimethylamino group, diethylamino group, dipropylamino group, diphenylamino group, isopropylamino group, tert-butylamino group, pyrrolyl group, dimethylphosphino group, 2- (2-oxy-1-propyl) phenoxy group, Catechol, resorcinol, 4-isopropylcatechol, 3-methoxycatechol, 1,8-dihydroxynaphthyl group, 1,2-dihydroxynaphthyl group, 2,2′-biphenyldiol group, 1,1′-bi-2-naphthol Group, 2,2′-dihydroxy-6,6′-dimethylbiphenyl group, 4,4 ′ 6,6'-tetra -tert- butyl 2,2 'methylenedianiline phenoxy group, and 4,4', mention may be made of 6,6'-tetramethyl-2,2'-isobutenyl dust Denji phenoxy group.

Moreover, as group containing the said hetero atom, group represented by following General formula [5] can also be mentioned, for example.
R ³ ₃ P = N− [5]
(In the formula, each R ³ independently represents a hydrogen atom, a halogen atom or a hydrocarbon group, and the plurality of R ³ may be the same or different from each other, and the plurality of R ³ are bonded to each other. Or a ring structure may be formed.)

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

（式中、Ｒ⁴はそれぞれ独立に水素原子、ハロゲン原子、炭化水素基、ハロゲン化炭化水素基、炭化水素オキシ基、シリル基またはアミノ基を表し、複数のＲ⁴は互いに同じであっても異なっていてもよく、複数のＲ⁴は互いに結合していてもよく、環構造を形成していてもよい。） Further, examples of the group containing a hetero atom include a group represented by the following general formula [6].

(Wherein R ⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon oxy group, a silyl group or an amino group, and a plurality of R ⁴ may be the same as each other) They may be different, and a plurality of R ⁴ may be bonded to each other and may form a ring structure.)

Specific examples of R ⁴ in the general formula [6] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, phenyl group, 1-naphthyl group, 2-naphthyl group, tert-butyl group, 2, 6-dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl group, methyl group , Triethylsilyl group, diphenylmethylsilyl group, 1-methyl-1-phenylethyl group, 1,1-dimethylpropyl group, 2-chlorophenyl group, and pentafluorophenyl group.

The chelating ligand of L ² in the general formula [4] refers to a ligand having a plurality of coordination sites. Examples of the ligand include acetylacetonate, diimine, oxazoline, and bisoxazoline. Terpyridine, acylhydrazone, diethylenetriamine, triethylenetetramine, porphyrin, crown ether, and cryptate.

Examples of the heterocyclic group of L ² in the general formula [4] include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, and among them, a pyridyl group is preferable.

In the general formula [4], when a plurality of L ² are linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom (that is, cyclopentadiene form) When a group having an anion skeleton is linked via the residue, a group containing a hetero atom is linked via the residue, or a group having a cyclopentadiene anion skeleton is heterogeneous If the group containing an atom are linked via the residues), as preferably the residues, two L ² and the atoms connecting the carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom Alternatively, it is a divalent residue which is a phosphorus atom and has a minimum atomic number of 3 or less for bonding two L ² . Examples of the residue include alkylene groups such as methylene group, ethylene group and propylene group; substituted alkylene groups such as dimethylmethylene group (isopropylidene group) and diphenylmethylene group; silylene group, dimethylsilylene group, diethylsilylene group, diphenyl Examples thereof include substituted silylene groups such as a silylene group, a tetramethyldisilylene group, and a dimethoxysilylene group; and heteroatoms such as a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Among these, a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), a diphenylmethylene group, a dimethylsilylene group, a diethylsilylene group, a diphenylsilylene group, or a dimethoxysilylene group is particularly preferable.

Examples of the halogen atom for X ¹ in the general formula [4] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group for X ¹ include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Among them, an alkyl group having 1 to 20 carbon atoms, preferably 7 to 7 carbon atoms is preferable. A aralkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkenyl group having 3 to 20 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, and n-pentyl group. , Neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, and n-eicosyl group, and more preferably methyl. Group, ethyl group, isopropyl group, tert-butyl group, isobutyl group or amyl group.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluorobutyl group. Mention may be made of fluorohexyl, perfluorooctyl, perchloropropyl, perchlorobutyl and perbromopropyl groups.
These alkyl groups may be substituted with an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (2,3-dimethyl). (Phenyl) 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, , 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, and anthracenylmethyl group More preferably, it is a benzyl group.
These aralkyl groups are halogen atoms such as fluorine, chlorine, bromine and iodine atoms, alkoxy groups such as methoxy and ethoxy groups, aryloxy groups such as phenoxy groups or benzyloxy groups. It may be substituted with an aralkyloxy group or the like.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 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-butyl Nenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl, and anthracenyl Group, and more preferably a phenyl group.
These aryl groups are fluorine atoms, chlorine atoms, bromine atoms, halogen atoms such as iodine atoms, alkoxy groups such as methoxy and ethoxy groups, aryloxy groups such as phenoxy groups, or aralkyl groups such as benzyloxy groups. It may be substituted with an oxy group or the like.

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

Examples of the hydrocarbon oxy group represented by X ¹ in the general formula [4] include an alkoxy group, an aralkyloxy group, and an aryloxy group. Among these, an alkoxy group having 1 to 20 carbon atoms is preferable, An aralkyloxy group having 7 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms.

Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, and neopentoxy. Group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, and n-icosoxy group, and among them, preferably methoxy group, ethoxy group, isopropoxy group, or tert. -Butoxy group.
These alkoxy groups include halogen atoms such as fluorine, chlorine, bromine and iodine atoms, alkoxy groups such as methoxy and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyl groups such as benzyloxy groups. It may be substituted with an oxy group or the like.

Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3 -Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group , (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group , (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethyl) Ruphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) Methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy Group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, and anthracenylmethoxy group Among them, a benzyloxy group is more preferable.
These aralkyloxy groups include halogen atoms such as fluorine, chlorine, bromine and iodine atoms, alkoxy groups such as methoxy and ethoxy groups, aryloxy groups such as phenoxy groups, and benzyloxy groups. It may be substituted with an aralkyloxy group or the like.

Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, and 2,4-dimethylphenoxy group. Group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert- Butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy Group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethyl Ruphenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6- Di-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group 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 Group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group , Isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group And anthracenoxy group.
These aryloxy groups include fluorine atoms, chlorine atoms, halogen atoms such as bromine atoms and iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and benzyloxy groups. It may be substituted with an aralkyloxy group or the like.

X ¹ in the general formula [4] is more preferably a chlorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, n-butoxy group, trifluoromethoxy group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5, 6-tetrafluoro-4-pentafluorophenylphenoxy group or benzyl group.

In the general formula [4], a is a number satisfying 0 <a ≦ 8, b is a number satisfying 0 <b ≦ 8, and is appropriately selected according to the valence of M ² . When M ² is a titanium atom, a zirconium atom or a hafnium atom, a is preferably 2, and b is also preferably 2.

  Examples of the compound represented by the general formula [4] in which the transition metal atom is a titanium atom, a zirconium atom, or a hafnium atom include bis (cyclopentadienyl) titanium dichloride and bis (methylcyclopentadienyl) titanium dichloride. Bis (ethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, bis (1,2-dimethylcyclopentadienyl) Titanium dichloride, bis (1,3-dimethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) titanium Dichloride, screw 1-methyl-2-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-isopropylcyclopentadienyl) Titanium dichloride, bis (1-methyl-3-isopropylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-2-methylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-3-methyl) Cyclopentadienyl) titanium dichloride, bis (1,2,3-trimethylcyclopentadienyl) titanium dichloride, bis (1,2,4-trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) ) Titanium dichloride, screw (pen Methylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenylindenyl) titanium dichloride ,

Bis [2- (bis-3,5-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-tert-butylphenyl) indenyl] titanium dichloride, bis [2- (4-trifluoromethylphenyl) Indenyl] titanium dichloride, bis [2- (4-methylphenyl) indenyl] titanium dichloride, bis [2- (3,5-dimethylphenyl) indenyl] titanium dichloride, bis [2- (pentafluorophenyl) indenyl] titanium dichloride , Cyclopentadienyl (pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride , Pentamethylcyclopentadienyl (indenyl) titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-phenylindenyl) titanium dichloride, pentamethylcyclopentadienyl (2-phenylindene) Nil) titanium dichloride,

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

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

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

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

Dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl -2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2) -Phenoxy Titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-chloro-) 2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride Id, dimethylsilylene (cyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) 5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopenta Dienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (methyl) Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilyl Down (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, Dimethylsilylene (n- Tilcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) ( 3,5-diamil- -Phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (1-naphthoxy-2-yl) titanium Dichloride,

Dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5) -Methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3 -Tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (tert-butylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene ( tert-butylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethyl Len (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadieni) ) (3,5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (1- Naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy) -2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (trimethylsilylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadi) Enyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl) Rudimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-diamil-2-phenoxy) titanium dichloride Dimethylsilylene (indenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) ( -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl -5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-diamil-2-phenoxy) ) Titanium dichloride, dimethylsilylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (1-naphthoxy-2-yl) titanium dichloride,

(Tert-Butylamide) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl- 1,2-ethanediyl titanium dichloride,
(Tert-Butylamide) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (phenylphosphide) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (tert- Butylamido) indenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) tetrahydroindenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyl titanium dichloride, (tert- Butylamido) indenyldimethylsilane titanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilane titanium dichloride (Tert- butylamido) fluorenyl dimethylsilane titanium dichloride,

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

2,2′-thiobis [4-methyl-6-tert-butylphenoxy] titanium dichloride, 2,2′-thiobis [4-methyl-6- (1-methylethyl) phenoxy] titanium dichloride, 2,2′- Thiobis (4,6-dimethylphenoxy) titanium dichloride, 2,2'-thiobis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-methylenebis (4-methyl-6-tert-butylphenoxy) ) Titanium dichloride, 2,2'-ethylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2, 2 ′-(4,4 ′, 6,6′-tetra-tert-butyl-1,1 ′ biphenol Shi) titanium dichloride, (di -tert- butyl-1,3-propane diamide) titanium dichloride, (dicyclohexyl-1,3-propane diamide) titanium dichloride,

[Bis (trimethylsilyl) -1,3-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, [hydrotris (3,5 Dimethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium trichloride, [tris (3 5-dimethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium trichloride, etc. Compounds in which titanium in these compounds is replaced with zirconium or hafnium, (2-phenoxy) is replaced with (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert-butyldimethylsilyl- 2-pheno Compound in which dimethylsilylene is replaced with methylene, ethylene, dimethylmethylene (isopropylidene), diphenylmethylene, diethylsilylene, diphenylsilylene, or dimethoxysilylene, dichloride is difluoride, dibromide, diiodide, dimethyl, diethyl , Diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di (n-propoxide), di (isopropoxide), diphenoxide, or di (pentafluorophenoxide), and trichloride, trifluoride, tribromide , Triiodide, trimethyl, triethyl, triisopropyl, triphenyl, tribenzyl, trimethoxide, triethoxide, tri (n-propoxide And compounds substituted with tri (pentafluorophenoxide), tri (isopropoxide), triphenoxide, or tri (pentafluorophenoxide).

  Examples of the compound represented by the general formula [4] whose transition metal atom is a nickel atom include 2,2′-methylenebis [(4R) -4-phenyl-5,5′-dimethyloxazoline] nickel dibromide. 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-di- n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diisopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl -5,5'-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5 -Dimethoxyoxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diethoxyoxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl -5,5'-diphenyloxazoline] nickel dibromide,

2,2′-methylenebis [(4R) -4-methyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-methyl-5, 5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-methyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2 , 2′-methylenebis [(4R) -4-methyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-methyl-5,5 -Di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-methyl-5,5-di- (4-methoxyphenyl) Xazoline] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-methyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4 -Methyloxazoline-5,1'-cyclopentane}] nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cyclohexane}] nickel dibromide, 2,2 '-Methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cycloheptane}] nickel dibromide,

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], 2,2′-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- Sopropyl-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) o Oxazoline] nickel dibromide,

2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-isopropyloxazoline-5,1′-cycloheptane}] nickel dibromide, 2,2-methylenebis [(4R) -4-isobutyl-5,5-dimethyloxazoline] nickel dibromide, 2,2 '-Methylenebis [(4R) -4-isobutyl-5,5-diethyloxazoline] Ckell dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl- 5,5-di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R)- 4-isobutyl-5,5-diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2, 2′-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methylphenyl) oxa Phosphorus] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) — 4-isobutyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methoxyphenyl) oxazoline ] Nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methoxyphenyl) 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-diethyloxazo ] 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-methylphenyl) oxazoline] nickel Dibromide, 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 di Bromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide Ido,

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 Ido,

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 the enantiomers of the above compounds, the asymmetric carbon configuration of one oxazoline ring of the bisoxazoline type compound is reversed. And dibromide to difluoride, dichloride, diiodide, dimethiide Can diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di -n- propoxide, diisopropoxide, diphenoxide or compounds obtained by replacing the di (pentafluorophenyl phenoxide), and the like.

（式中、Ｒ⁵とＲ⁶はいずれも２，６−ジイソプロピルフェニル基を表し、Ｒ⁷およびＲ⁸はそれぞれ独立に水素原子またはメチル基あるいはＲ⁷とＲ⁸とが互いに結合したアセナフテン基を表し、Ｘ²はそれぞれ独立に、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、フェニル基、ベンジル基、メトキシ基、エトキシ基、またはフェノキシ基を表す。）
また、上記のニッケル化合物において、ニッケルをパラジウム、コバルト、ロジウム、またはルテニウムに置き換えた化合物も同様に例示することができる。 Examples of the compound represented by the general formula [4] in which the transition metal atom is a nickel atom include compounds represented by the following structural formula.

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

  Examples of the compound represented by the general formula [4] whose transition metal atom is iron include 2,6-bis- [1- (2,6-dimethylphenylimino) ethyl] pyridine iron dichloride, 2,6 -Bis- [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron dichloride and 2,6-bis- [1- (2-tert-butyl-phenylimino) ethyl] pyridine iron dichloride, and these And compounds in which the dichloride of the compound is replaced with difluoride, dibromide, diiodide, dimethyl, diethyl, dimethoxide, diethoxide, or diphenoxide.

Examples of the μ-oxo type transition metal compound of the transition metal compound represented by the general formula [4] include, for example, μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ- Oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride] , Μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2- Phenoxy) titanium chloride], μ-oxobis [ Sopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], [Mu] -oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], [mu] -oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2 -Phenoxy) chita Chloride], and μ-oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], and chlorides of these compounds to fluoride, bromide, iodide , Methyl, ethyl, isopropyl, phenyl, benzyl, methoxide, ethoxide, n-propoxide, isopropoxide, phenoxide, or pentafluorophenoxide.

As transition metal compounds (B) other than the compound represented by the general formula [4], [hydrotris (3,5-dimethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-diethylpyrazolyl) borate] nickel chloride, And [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel chloride and compounds in which the chloride of these compounds is replaced with bromide, iodide, methyl, ethyl, allyl, methallyl, methoxide, or ethoxide Can be mentioned.
In addition, in the above nickel compound, a compound in which nickel is replaced with iron or cobalt can be similarly exemplified.

  Examples of the compound in which the transition metal atom is a nickel atom include nickel chloride, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, nickel perchlorate, nickel acetate, nickel trifluoroacetate, nickel cyanide, Nickel oxalate, nickel acetylacetonate, bis (allyl) nickel, bis (1,5-cyclooctadiene) nickel, dichloro (1,5-cyclooctadiene) nickel, dichlorobis (acetonitrile) nickel, dichlorobis (benzonitrile) Nickel, carbonyltris (triphenylphosphine) nickel, dichlorobis (triethylphosphine) nickel, diacetbis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel, dichloro [1,2-bi (Diphenylphosphino) ethane] nickel, bis [1,2-bis (diphenylphosphino) ethane] nickel, dichloro [1,3-bis (diphenylphosphino) propane] nickel, bis [1,3-bis (diphenyl) Mention may be made of phosphino) propane] nickel, tetraamine nickel nitrate, tetrakis (acetonitrile) nickel tetrafluoroborate, and nickel phthalocyanine.

Similarly, examples of the compound whose transition metal atom is a vanadium atom include vanadium acetylacetonate, vanadium tetrachloride, and vanadium oxytrichloride.
Examples of the compound in which the transition metal atom is a samarium atom include bis (pentamethylcyclopentadienyl) samarium methyltetrahydrofuran.
Examples of the compound in which the transition metal atom is an ytterbium atom include bis (pentamethylcyclopentadienyl) ytterbium methyltetrahydrofuran.

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

Of the transition metal compounds exemplified above, the transition metal compound (B) used in the present invention is preferably a transition metal compound represented by the above general formula [4]. Among these, a transition metal compound in which M ² in the general formula [4] is a group 4 atom is preferable, and in particular, a transition metal having at least one group having a cyclopentadiene type anion skeleton as L ² in the general formula [4]. Compounds are preferred. Among them, a zirconium compound is more preferable, and L ² in the general formula [4] has two groups having a cyclopentadiene type anion skeleton, and L ² is a carbon atom, a silicon atom, an oxygen atom, a sulfur atom or a phosphorus atom. Zirconium compounds linked via a residue containing are particularly preferred.

  The transition metal compound represented by the general formula [4] can be produced, for example, by the production method described in JP-A-6-340684, JP-A-7-258321, and International Patent Publication No. 95/00562. It is.

A known organoaluminum compound can be used as the organoaluminum compound (C). Preferably, it is an organoaluminum compound represented by the following general formula [7].
R ⁹ _d AlY _3-d [7]
(In the formula, R ⁹ represents a hydrocarbon group, and all R ⁹ may be the same or different. Y represents a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, or an aryloxy group. And all Y may be the same or different, and d represents a number satisfying 0 <d ≦ 3.)

R ⁹ in the general formula [7] is preferably a hydrocarbon group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, 2-methylhexyl group, and n-octyl group. An ethyl group, n-butyl group, isobutyl group, n-hexyl group or n-octyl group is preferred.

Moreover, as a halogen atom in Y, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned, for example, Preferably it is a chlorine atom.
As the alkoxy group in Y, an alkoxy group having 1 to 24 carbon atoms is preferable, and specifically, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group. , Tert-butoxy group, n-pentoxy group, and n-icosoxy group, preferably methoxy group, ethoxy group, or tert-butoxy group.

  The aralkyloxy group for Y is preferably an aralkyloxy group having 7 to 24 carbon atoms. Examples of the aralkyloxy group include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, and (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, (2,4,4) 5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) meth Si 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, and anthracenylmethoxy group, preferably benzyloxy It is a group.

  The aryloxy group for Y is preferably an aryloxy group having 6 to 24 carbon atoms. Examples of the aryloxy group include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5- Dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2, 3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy Group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group 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 Group, n-tetradecylphenoxy group, naphthoxy group, and anthracenoxy group.

  Examples of the organoaluminum compound (C) represented by the general formula [7] include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, and tri-n-hexylaluminum. , And trialkylaluminums such as tri-n-octylaluminum, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, and di-n-hexylaluminum Dialkylaluminum chloride such as chloride, methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride Id, n-butyl aluminum dichloride, isobutyl aluminum dichloride, and alkyl aluminum dichlorides such as n-hexyl aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl Aluminum hydrides, and dialkylaluminum hydrides such as di-n-hexylaluminum hydride, methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, and alkyl (dialkoxy) aluminum such as methyl (di-tert-butoxy) aluminum, Dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum And dialkyl (alkoxy) aluminum such as dimethyl (tert-butoxy) aluminum, methyl (diphenoxy) aluminum, methylbis (2,6-diisopropylphenoxy) aluminum, and methylbis (2,6-diphenylphenoxy) aluminum Alkyl (diaryloxy) aluminum, and dialkyl (aryloxy) aluminum such as dimethyl (phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, and dimethyl (2,6-diphenylphenoxy) aluminum Can do.

Among them, preferred is trialkylaluminum, more preferred is trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum, particularly preferred. Triisobutylaluminum or tri-n-octylaluminum.
These organoaluminum compounds may be used alone or in combination of two or more.

  As the use amount ratio of each catalyst component of the catalyst component for addition polymerization of the present invention, the transition metal compound (B) is usually 0.1 to 1000 μmol / g with respect to the modified particles (A), Preferably it is 1-500 micromol / g, More preferably, it is 10-300 micromol / g. Similarly, the organoaluminum compound (C) is usually 0.1 to 10000 mmol / g, preferably 0.5 to 1000 mmol / g, more preferably 1 to 500 mmol / g.

  The order in which the catalyst components and monomers such as the modified particles (A), the transition metal compound (B) and the organoaluminum compound (C) are supplied to the polymerization reactor is not particularly limited. As a method for supplying to the polymerization reactor, for example, (1) a method of supplying simultaneously, (2) a method of supplying sequentially, and (3) a method of supplying after contacting any of the catalyst components in advance. Can be mentioned.

  The transition metal compound (B) is supplied to the polymerization reactor in a solid state such as powder or in a slurry state suspended in a solvent. The solvent to be used is not particularly limited, and examples thereof include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbon solvents such as benzene and toluene, and halogenated hydrocarbons such as dichloromethane. Mention may be made of solvents. A solvent having a low solubility in the transition metal compound (B) is preferably used. Similarly to the transition metal compound (B), the modified particles (A) are also supplied to the polymerization reactor in a solid state such as powder or in a slurry state. The organoaluminum compound (C) is supplied to the polymerization reactor as a solution of the above solvent.

  The polymerization method is not particularly limited, but solution polymerization using a solvent, slurry polymerization and the like are preferable. Examples of the solvent used for solution polymerization or slurry polymerization include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbon solvents such as benzene and toluene, and dichloromethane. Mention may be made of halogenated hydrocarbon solvents. In addition, the monomer itself can be used as a polymerization solvent, and examples of the monomer include ethylene, propylene, 1-butene and 1-hexene. The polymerization method can be either batch polymerization or continuous polymerization, and the polymerization may be performed in two or more stages with different reaction conditions. In general, the polymerization time is appropriately determined depending on the kind of the target olefin polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours.

  Slurry polymerization can be performed according to known methods and conditions. A preferred method of this method is to continuously or intermittently supply monomers (and comonomers), diluents, and other feeds to the polymerization reactor as necessary, and the resulting addition polymer slurry from the polymerization reactor. It is a method of extracting continuously or intermittently. Examples of the polymerization reactor include a loop reactor, a reactor with a stirrer, and a reactor in which a plurality of reactors with a stirrer having different types and polymerization reaction conditions are connected in series, in parallel, or a combination thereof. .

  The polymerization temperature is usually about 0 ° C to about 150 ° C, preferably 30 ° C to 100 ° C. The polymerization pressure is usually about 0.1 MPa to about 10 MPa, preferably 0.5 MPa to 5 MPa.

The molecular weight of the addition polymer can be controlled by the polymerization temperature or a molecular weight regulator such as hydrogen.
Each catalyst component and monomer (and comonomer) can be fed to the polymerization reactor in any order by any known method. Examples of the supply method to the polymerization reactor include (1) a method of supplying simultaneously and (2) a method of supplying sequentially. Each catalyst component may be pre-contacted in an inert atmosphere prior to contact with the monomer (and comonomer).

  The polymerization temperature is not particularly limited as long as it is lower than the melting temperature of the produced addition polymer, but it is preferably 0 ° C to 150 ° C, particularly preferably 30 ° C to 100 ° C. Hydrogen may be added as a molecular weight modifier for the purpose of adjusting the melt fluidity of the produced addition polymer. In the polymerization, an inert gas may coexist in the mixed gas.

  When the addition polymerization catalyst of the present invention is applied to polymerization in which the addition polymer is formed into particles, such as slurry polymerization or gas phase polymerization, in order to generate addition polymer particles having a uniform shape and stably operate It is effective to perform a prepolymerization step as a pre-stage of the main polymerization step.

  As the use amount ratio of each component used in the prepolymerization used in the present invention, the use amount of the transition metal compound (B) is usually 0.1 to 1000 μmol / g with respect to the modified particles (A). Yes, preferably 1 to 500 μmol / g, more preferably 10 to 300 μmol / g. The amount of the organoaluminum compound (C) used is usually from 0.03 to 100,000 μmol / g, preferably from 0.3 to 50,000 μmol / g, more preferably from 3 to 50,000, based on the modified particles (A). 30000 μmol / g.

  In the present invention, as the monomer used for the prepolymerization, any olefin having 2 to 20 carbon atoms can be used, and two or more olefins can be used at the same time. Examples of the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene and 4-methyl. -2-pentene, vinylcyclohexane and the like.

  When a preliminary copolymer is formed by using two or more types of monomers at the same time for the preliminary polymerization, examples of the combination of monomers constituting the copolymer include ethylene and propylene, ethylene and 1-butene, and ethylene and 1-hexene. And a combination of propylene and 1-butene.

  In the prepolymerization of the present invention, the order in which the catalyst components and monomers such as the modified particles (A), the transition metal compound (B) and the organoaluminum compound (C) are supplied to the polymerization reactor is not particularly limited. As a method for supplying to the polymerization reactor, for example, (1) a method of supplying simultaneously, (2) a method of supplying sequentially, and (3) a method of supplying after contacting any of the catalyst components in advance. Can be mentioned.

  The transition metal compound (B) is supplied to the polymerization reactor in a solid state such as powder or in a slurry state suspended in a solvent of the transition metal compound (B). The solvent to be used is not particularly limited, and examples thereof include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbon solvents such as benzene and toluene, and halogenated hydrocarbons such as dichloromethane. Mention may be made of solvents. Similarly to the transition metal compound (B), the modified particles (A) are also supplied to the polymerization reactor in a solid state such as powder or in a slurry state. The organoaluminum compound (C) is supplied to the polymerization reactor as a solution of the above solvent.

  The prepolymerization method is not particularly limited. Examples of the method include a prepolymerization method in the presence of a polymerization solvent. Examples of the polymerization solvent used in the prepolymerization method in the presence of the polymerization solvent include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane, and aromatic hydrocarbon solvents such as benzene and toluene. And halogenated hydrocarbon solvents such as dichloromethane. In addition, the monomer itself can be used as a polymerization solvent, and examples of the monomer include ethylene, propylene, 1-butene and 1-hexene.

  The prepolymerization method can be either batch polymerization or continuous polymerization. The prepolymerization temperature and prepolymerization time are generally determined appropriately depending on the type of the target prepolymer, the amount of polymer to be produced, and the reaction apparatus. Usually, the prepolymerization temperature is −20 ° C. to 80 ° C., preferably The temperature can range from 0 ° C. to 50 ° C., and the prepolymerization time is usually from 1 minute to 24 hours, preferably from 30 minutes to 12 hours. Further, in the prepolymerization, the molecular weight of the prepolymer can be adjusted by coexisting a molecular weight regulator such as hydrogen.

  After the prepolymerized addition polymerization catalyst component is formed by prepolymerization, the obtained prepolymerized addition polymerization catalyst component may be used in the main polymerization as it is, or after the following treatment is performed. Also good. When the prepolymerized addition polymerization catalyst component is formed by a method of prepolymerization in the presence of a solvent, the prepolymerized addition polymerization catalyst component is in a solution or slurry liquid state, or removed from a monomer, removed by solvent, filtered, Processing such as washing and drying is performed and used in the main polymerization in a solid state.

  The amount of polymer produced by prepolymerization (also referred to as prepolymerization degree) is usually in the range of 0.1 to 1000 g, preferably in the range of 0.5 to 500 g, per 1 g of the modified particles (A). The prepolymerization is particularly preferably carried out so as to be in the range of 1 to 100 g.

  In the present invention, when the addition polymer is produced (main polymerization), the prepolymerized addition polymerization catalyst component thus obtained may be used as it is as the addition polymerization catalyst, or the prepolymerization of the present invention. You may use the catalyst for addition polymerization obtained by making a spent addition polymerization catalyst component and an organoaluminum compound contact. The latter is preferable from the viewpoint of excellent polymerization activity. As the organoaluminum compound in the latter case, the organoaluminum compound described as the compound (C) is used. When the organoaluminum compound is used in this way, the amount used is usually 0.1 to 10,000 mmol / g, preferably 0.5 to 1000 mmol / g, based on the modified particles (A). More preferably, it is 1-500 mmol / g.

  When the addition polymerization catalyst is an addition polymerization catalyst obtained by contacting the prepolymerized addition polymerization catalyst component of the present invention and the organoaluminum compound (C), the prepolymerized addition polymerization catalyst component and the organoaluminum The compound (C) can be used by being charged into the polymerization reactor in any order at the time of polymerization. Alternatively, the compound (C) may be used after being brought into contact with the polymerization reactor in advance.

  The method for supplying the prepolymerized addition polymerization catalyst component and organoaluminum compound (C) of the present invention to the catalyst preparation reactor or the polymerization reactor for the main polymerization is not particularly limited. Examples of the method include a method of supplying each component in a solid state, a solution state in which a component that deactivates a catalyst component such as moisture and oxygen is sufficiently removed, or a suspension or slurry. The method etc. which supply in the state made into the thing can be mentioned. Examples of the hydrocarbon solvent at this time include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbon solvents such as benzene and toluene, and halogenated carbonization such as dichloromethane. Hydrogen can be mentioned, and among them, an aliphatic hydrocarbon or an aromatic hydrocarbon is preferable.

  The polymerization method in this polymerization is not particularly limited. Examples of the method include (1) a gas phase polymerization method in which polymerization is performed in a gaseous monomer, (2) a solution polymerization method in which polymerization is performed in a solvent, or a slurry polymerization method (suspension polymerization method), (3) A bulk polymerization method using a monomer as a solvent can be mentioned. Examples of polymerization solvents used for solution polymerization or slurry polymerization include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbon solvents such as benzene and toluene, and dichloromethane. Mention may be made of halogenated hydrocarbon solvents. The polymerization method may be either batch polymerization or continuous polymerization, and the polymerization may be further divided into two or more stages having different reaction conditions. The polymerization time of the main polymerization is generally determined by the kind of the target addition polymer and the polymerization reactor, and is usually 1 minute to 20 hours.

The prepolymerized addition polymerization catalyst component and addition polymerization catalyst of the present invention are particularly suitable for polymerization in which the addition polymer is formed into particles in the main polymerization, such as slurry polymerization, gas phase polymerization, and bulk polymerization. Is done.
Slurry polymerization can be performed according to known methods and conditions. A preferred method of this method is to continuously or intermittently supply monomers (and comonomers), diluents, and other feeds to the polymerization reactor as necessary, and the resulting addition polymer slurry from the polymerization reactor. It is a method of extracting continuously or intermittently. Examples of the polymerization reactor include a loop reactor, a reactor with a stirrer, and a reactor in which a plurality of reactors with a stirrer having different types and polymerization reaction conditions are connected in series, in parallel, or a combination thereof. .

  Examples of the diluent include inert diluents (medium) such as paraffin, cycloparaffin, and aromatic hydrocarbon. The medium, as well as the polymerization temperature and pressure, are selected such that the catalyst is held in suspension, the medium and at least some of the monomers and comonomers are maintained in the liquid phase, and the monomers and comonomers can be contacted. . The polymerization temperature is usually about 0 ° C to about 150 ° C, preferably 30 ° C to 100 ° C. The polymerization pressure is usually about 0.1 MPa to about 10 MPa, preferably 0.5 MPa to 5 MPa.

The molecular weight of the addition polymer can be controlled by the polymerization temperature or a molecular weight regulator such as hydrogen.
Each catalyst component and monomer (and comonomer) can be fed to the polymerization reactor in any order by any known method. Examples of the supply method to the polymerization reactor include (1) a method of supplying simultaneously and (2) a method of supplying sequentially. Each catalyst component may be pre-contacted in an inert atmosphere prior to contact with the monomer (and comonomer).

The gas phase polymerization can be performed according to known methods and conditions. The reactor for gas phase polymerization is a fluidized bed type reaction vessel, preferably a fluidized bed type reaction vessel having an enlarged portion. The reactor may be provided with a stirring blade in the reaction vessel.
As a method of supplying each catalyst component to the polymerization tank, for example, a method of supplying an inert gas such as nitrogen and argon, hydrogen, or ethylene in the absence of moisture, or a solution dissolved in a solvent or The method of supplying with the diluted slurry can be mentioned. Each catalyst component may be supplied individually, or may be supplied by contacting arbitrary components in advance in an arbitrary order.

  The polymerization temperature is not particularly limited as long as it is lower than the melting temperature of the produced addition polymer, but it is preferably 0 ° C to 150 ° C, particularly preferably 30 ° C to 100 ° C. Hydrogen may be added as a molecular weight modifier for the purpose of adjusting the melt fluidity of the produced addition polymer. In the polymerization, an inert gas may coexist in the mixed gas.

The method for producing an addition polymer of the present invention is a method for producing an addition polymer in which addition-polymerizable monomers are subjected to addition polymerization in the presence of the aforementioned catalyst for addition polymerization of the present invention.
Examples of the monomer in the method for producing an addition polymer of the present invention include olefins having 2 to 20 carbon atoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, and polar monomers, and two or more kinds at the same time. These monomers can also be used.

  Examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene, 1-octene and 1-nonene. Olefins such as 1,5-decene and vinylcyclohexane; 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4 -Methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, norbornadiene , 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydride Diolefins such as naphthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, and 1,3-cyclohexadiene; norbornene, 5-methyl-2 -Norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2-norbornene, tetracyclododecene, tricyclodecene, tricycloundecene, penta Cyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-Ethoxycarbonyl-2-norbol , 5-methyl-5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, and 8-cyanotetracyclodone Cyclic olefins such as decene; styrene, alkenylbenzene (eg, 2-phenylpropylene, 2-phenylbutene, and 3-phenylpropylene), alkylstyrene (eg, p-methylstyrene, m-methylstyrene, o-methylstyrene) P-ethylstyrene, m-ethylstyrene, o-ethylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3 -Methyl-5-ethylstyrene, 1,1-diphenyl ester And alkenyl aromatic hydrocarbons such as bisalkenylbenzene (eg, divinylbenzene), alkenylnaphthalene (eg, 1-vinylnaphthalene), and the like. And α, β-unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo (2,2,1) -5-heptene-2, 3-dicarboxylic acid), metal salts of such α, β-unsaturated carboxylic acids, such as sodium, potassium, lithium, zinc, magnesium and calcium, α, β-unsaturated carboxylic acid esters (eg acrylic Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, tert-acrylate Butyl, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate), unsaturated dicarboxylic acids (eg, maleic acid and itaconic acid ), Vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate), and unsaturated carboxylic acid glycidyl esters (eg, acrylic acid) Polar monomers such as glycidyl, glycidyl methacrylate, and monoglycidyl itaconate).

  The present invention is applied to homopolymerization or copolymerization of these monomers. Examples of the combination of monomers constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, and propylene and 1-butene.

  The catalyst for addition polymerization of the present invention is suitably used for production of an olefin polymer. The olefin polymer is particularly preferably a copolymer of ethylene and an α-olefin, and particularly preferably a copolymer of ethylene and an α-olefin having a polyethylene crystal structure. The α-olefin is preferably an α-olefin having 3 to 8 carbon atoms, and examples thereof include 1-butene, 1-hexene, and 1-octene.

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

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

(2) Melt flow rate, MFR
It is a melt flow rate value measured in accordance with the method defined in JIS K7210-1995 at a load of 21.18 N (2.16 kgf) at 190 ° C. (unit: g / 10 minutes).

(3) Swell ratio, SR
It is a value obtained by dividing the strand diameter obtained at the time of MFR measurement by 2.095 mm which is the inner diameter of the die.

(4) Melt flow rate ratio, MFRR
According to the method defined in JIS K7210-1995, the melt flow rate value measured at 190 ° C. and a load of 211.82 N (21.60 kgf) is the melt flow rate value measured at a load of 21.18 N (2.16 kgf). The value divided by (MFR).
For all the melt flow rate measurements, a polymer in which 1000 ppm of Irganox 1076 manufactured by Ciba Specialty Chemical Co., Ltd. was previously used as an antioxidant was used.

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

(6) Elemental analysis zinc: A sample was poured into a sulfuric acid aqueous solution (1 mol / L), and then ultrasonic waves were applied to extract metal components. The obtained liquid portion was quantified by ICP emission spectrometry.
The combustion gas generated by burning the sample in a flask filled with fluorine: oxygen was absorbed into an aqueous sodium hydroxide solution (10%), and the obtained aqueous solution was quantified using an ion electrode method.

[Example 1]
(1) Treatment of particles (d)
In a reactor equipped with a stirrer substituted with nitrogen, 24 kg of toluene as a solvent and silica heat-treated at 300 ° C. under nitrogen flow as particles (d) (Sypolol 948 manufactured by Devison, average particle size 55 μm, pore volume 1.67 ml / G, specific surface area 325 m ² / g) 2.8 kg was added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.91, 1 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.43 kg of toluene as a solvent was kept at a reactor temperature of 5 ° C. It was dripped in 33 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 95 ° C. for 3 hours. Thereafter, the obtained solid product was washed 6 times with 21 kg of toluene. Thereafter, 6.9 kg of toluene was added and allowed to stand overnight.

(2) Preparation of modified particles (A) To the toluene slurry obtained in Example 1 (1) above, 2.05 kg of a 50 wt% diethylzinc hexane solution as component (a) and hexane 1 as a solvent. .3 kg was added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 0.77 kg of pentafluorophenol and 1.17 kg of toluene as component (b) was added dropwise over 61 minutes while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 0.11 kg of water as component (c) was added dropwise over 1.5 hours while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1.5 hours and at 55 ° C. for 2 hours. Thereafter, 1.4 kg of a 50 wt% diethylzinc hexane solution at room temperature as a component (a) and 0.8 kg of hexane as a solvent were added. After cooling to 5 ° C., 0.42 kg of 3,4,5-trifluorophenol as the component (b) and 0.77 kg of toluene as the solvent were added in 60 minutes while maintaining the reactor temperature at 5 ° C. It was dripped. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 0.077 kg of water as component (c) was added dropwise over 1.5 hours while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 1.5 hours, at 40 ° C for 2 hours, and further at 80 ° C for 2 hours. Stirring was stopped and the supernatant liquid was extracted until the remaining amount reached 16 liters, and 11.6 kg of toluene was added as a solvent and stirred. The temperature was raised to 95 ° C. and stirred for 4 hours. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Thereafter, the particles (A) modified by drying were obtained. As a result of elemental analysis, zinc was 2.9 mmol / g and fluorine was 4.0 mmol / g.

(3) Preliminary polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added as a molecular weight regulator so that its partial pressure became 0.01 MPa, and butane as a polymerization solvent. Of 500 g, and the temperature was raised to 50 ° C. Thereafter, ethylene was added as a monomer so that the partial pressure became 0.2 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.03 mol%. To this was added 1.5 ml of a hexane solution of triisobutylaluminum prepared at a concentration of 1 mmol / ml. Next, 247 mg of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added as a transition metal compound (B) in a powder state. Subsequently, 3.11 g of the modified particles (A) obtained in Example 1 (2) were charged as a solid catalyst component, and then 15 ml of hexane was charged as a solvent. Polymerization was carried out for 40 minutes while feeding an ethylene / hydrogen mixed gas (hydrogen 1.03 mol%) so as to keep the total pressure constant. After purging ethylene, butane, etc. in the autoclave and replacing with argon, it was transferred to a 300 ml three-necked flask under an argon atmosphere. The mixture was vacuum-dried at 40 ° C. for 30 minutes to obtain 43.7 g of a prepolymerized addition polymerization catalyst component. The degree of prepolymerization was 14.1 g / g-solid catalyst component.

(4) Main polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added as a molecular weight regulator so that its partial pressure was 0.020 MPa, and 1- 55 g of butene and 695 g of butane as a polymerization solvent were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was 0.98 mol% hydrogen. To this, 1.0 ml of a hexane solution of triisobutylaluminum prepared as an organoaluminum compound (C) at a concentration of 1 mmol / ml was added. Next, 66.8 mg of the prepolymerized addition polymerization catalyst component obtained in (3) above was added. Polymerization was carried out at 70 ° C. for 1 hour while feeding an ethylene / hydrogen mixed gas (hydrogen 0.463 mol%) so as to keep the total pressure constant. As a result, 83.1 g of an addition polymer having a good particle property was obtained. The polymerization activity per solid catalyst component was 17500 g / g-solid catalyst component. The obtained addition polymer had SCB = 16.4, Mw = 90400, Mw / Mn = 7.1, MFR = 1.34 (g / 10 min), MFRR = 56, SR = 1.35. It was.

[Comparative Example 1]
(1) Preliminary polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon is evacuated, hydrogen is added as a molecular weight regulator so that its partial pressure becomes 0.01 MPa, and butane as a polymerization solvent. 500 g was charged and the temperature was raised to 50 ° C. Thereafter, ethylene was added as a monomer so that the partial pressure became 0.2 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was 0.88 mol% hydrogen. To this, a mixed solution of 253 mg of racemic-ethylenebis (1-indenyl) zirconium diphenoxide and 1.40 ml of 1 mmol / ml hexane solution of triisobutylaluminum and 4.0 ml of hexane was added as a transition metal compound (B). Subsequently, 3.26 g of the modified particles (A) obtained in Example 1 (2) were charged as a solid catalyst component, and then 15 ml of hexane was charged as a solvent. Polymerization was carried out for 40 minutes while feeding an ethylene / hydrogen mixed gas (hydrogen 1.03 mol%) so as to keep the total pressure constant. After purging ethylene, butane, etc. in the autoclave and replacing with argon, it was transferred to a 300 ml three-necked flask under an argon atmosphere. It was vacuum dried at 40 ° C. for 30 minutes to obtain 43.4 g of a prepolymerized addition polymerization catalyst component. The degree of prepolymerization was 13.3 g / g-solid catalyst component.

(2) Main polymerization The prepolymerized addition polymerization catalyst component was changed to 70.9 mg of the prepolymerized addition polymerization catalyst component obtained in Comparative Example 1 (1), and the gas in the system by gas chromatography analysis Polymerization was carried out in the same manner as in Example 1 (4) except that the composition was 0.74 mol% hydrogen.
As a result, 48.0 g of addition polymer was obtained. The polymerization activity per solid catalyst component was 9000 g / g-solid catalyst component. The obtained addition polymer had SCB = 14.2, MFR = 2.04 (g / 10 min), MFRR = 45, SR = 1.46.

As described above in detail, according to the present invention, an addition polymerization catalyst component capable of producing an addition polymer with higher polymerization activity, a prepolymerized addition polymerization catalyst component, an addition polymerization catalyst, and a method for producing the addition polymer Is provided.

Claims (6)

The modified particles (A) obtained by contacting the following components (a), (b), (c) and (d), the transition metal compound (B), or the organoaluminum compound (C) A catalyst component for addition polymerization obtained by contacting the transition metal compound (B) in a powder or slurry state at the time of the contact.
(A): Compound represented by the following general formula [1] M ¹ L ¹ _m [1]
(B): Compound represented by the following general formula [2] R ¹ _t-1 TH [2]
(C): Compound represented by the following general formula [3] R ² _t-2 TH ₂ [3]
(D): Particles (In the above general formulas [1] to [3], M ¹ represents a typical metal atom of Group ¹ , 2, 12, 14 or 15 of the periodic table of elements, and m represents an atom of M ¹ . .L ¹ which represents a number corresponding to the valence is hydrogen atom, a halogen atom or a hydrocarbon group, if L ¹ there are a plurality, a plurality of L ¹ is optionally different from one another identical .R ¹ represents a group containing an electron withdrawing group or an electron withdrawing group, if R ¹ there are a plurality, the plurality of R ¹ are optionally different from one another identical .R ² is a hydrocarbon group or halogen T represents a group 15 or 16 atom of the periodic table, and t represents a number corresponding to the valence of T in each compound.)   A prepolymerized addition polymerization catalyst component obtained by prepolymerizing an olefin using the addition polymerization catalyst component according to claim 1.   An addition polymerization catalyst obtained by contacting the prepolymerized addition polymerization catalyst component according to claim 2 and an organoaluminum compound.   A method for producing an addition polymer using the catalyst for addition polymerization according to claim 3.   The method for producing an addition polymer according to claim 4, wherein the addition polymer is an olefin polymer. The method for producing an addition polymer according to claim 4, wherein the addition polymer is a copolymer of ethylene and an α-olefin.