JP2013082891A - Washing method, addition polymerization method, prepolymerization method, prepolymerized catalytic component for addition polymerization, and method for producing addition polymer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of controlling fouling in a reactor, and a method of carrying out an addition polymerization while controlling the fouling of a reactor.SOLUTION: The method for washing the inner wall surface of the reactor comprises: (1) a step of placing in the reactor a solution containing at least one compound selected from the group consisting of a compound represented by general formula [1], a compound represented by general formula [2] and a compound represented by general formula [9], and a hydrocarbon solvent; and (2) a step of removing the solution in the reactor. Formula [1] is represented by R-O-(-R-O-)-Q, formula [2] is represented by RC(=O)NR, and formura [9] is represented by ML.

Description

  The present invention relates to a method for cleaning an inner wall surface of a reactor.

When the chemical reaction is performed in the reactor, a fouling phenomenon in which the reaction product adheres to the wall surface of the reactor may occur. When fouling occurs, it becomes difficult to remove heat from the reactor wall surface, so it becomes difficult to control the reaction temperature.
Also, if fouling occurs, it is difficult to remove fouling while continuing operation, so it is necessary to open the reactor and perform cleaning, which may lead to a decrease in productivity. .

Fouling is a significant problem especially in polymerization reactions. A method of Patent Document 1 is known as a method for suppressing fouling in a polymerization reaction.

JP 2005-89583 A

  Patent Document 1 describes a method for slurry polymerization of an olefin in a hydrocarbon medium in the presence of an olefin polymerization catalyst and at least one compound selected from a specific amide, amine, and ester. However, in this method, it is necessary to add specific compounds to the reaction system in order to suppress fouling, and these compounds may be mixed into the reaction product, which is satisfactory from the viewpoint of the quality of the reaction product. It wasn't possible. An object of the present invention is to provide a method for suppressing fouling in a reactor and a method for addition polymerization while suppressing fouling in the reactor.

The first aspect of the present invention relates to the following steps (1) and (2) and, if necessary, a method for washing the inner wall surface of the reactor including step (3) after step (2).
Step (1): at least one compound selected from the compound represented by the general formula [1], the compound represented by the general formula [2], and the compound represented by the general formula [9] and a hydrocarbon solvent Adding a solution comprising: to the reactor. Step (2): A step of removing the solution in the reactor. Step (3): A step of washing the inside of the reactor with a hydrocarbon solvent.

R ¹ —O — (— R ² —O—) _m Q ¹ [1]
R ¹ C (═O) NR ⁵ ₂ [2]
M ⁴ L ³ _n [9]
(In the above general formulas [1] and [2], R ¹ represents an optionally substituted hydrocarbyl group having 1 to 30 carbon atoms. R ² may have a substituent. Represents a good alkylene group having 1 to 20 carbon atoms, Q ¹ represents a hydrogen atom, —C (═O) OM ¹ , —R ³ —C (═O) OM ¹ , —S (═O) ₂ OM ¹ , _{^{-R 3 -S (= O) 2}} OM 1, -P (= O) (OH) (OM 1), - R 3 -P (= O) (OH) (OM 1), - P (= O) (OR ⁴ ) (OM ¹ ), —R ³ —P (═O) (OR ⁴ ) (OM ¹ ), —P (═O) (OM ¹ ) ₂ , or —R ³ —P (═O) ^(OM ₁₎ represents a ₂ .M ¹ is hydrogen ^{_{atom, NH 4, NH (R 12}} OH) 3 or, ^{.R 12} good number of carbon atoms which may have a substituent represents an alkali metal atom Represents a 20 alkylene group .R ³ is .R ⁴ is carbon atoms which may have a substituent represents an alkylene group which may having 1 to 20 carbon atoms which may have a substituent 1 to 20 M represents a number of 1 to 100. R ⁵ represents a hydrogen atom or a hydrocarbyl group having 1 to 30 carbon atoms which may have a substituent.
In the general formula [9], M ⁴ is a group consisting of Group 1, Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, and Group 13 of the Periodic Table. It represents a metal atom selected more. L ³ is a hydrogen atom, a halogen atom or a hydrocarbyl group, and n is the valence of the metal atom M ⁴ . )

A second aspect of the present invention is an addition polymerization method, in which a transition metal compound represented by the following general formula [3] or a μ-oxo type transition metal compound dimer in a reactor washed by the above method is used. Addition polymerization method of addition polymerization of a monomer capable of addition polymerization using a catalyst obtained by contacting a compound (A), an activator (B), and, if necessary, an organoaluminum compound (C) It depends on.
L ¹ _a M ² X ¹ _b [3]
(In the formula, M ² is a transition metal atom of Group 4 of the periodic table. L ¹ is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ¹ are directly connected to each other. Or may be linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, wherein X ¹ is a halogen atom, a hydrocarbyl group (provided that (Excluding a group having a cyclopentadiene type anion skeleton) or a hydrocarbyloxy group, a represents a number satisfying 0 <a ≦ 3, and b represents a number satisfying 0 <b ≦ 3.)

  The third aspect of the present invention relates to a prepolymerized addition polymerization catalyst component obtained when the above addition polymerization method is prepolymerization.

  A fourth aspect of the present invention relates to a method for producing an addition polymer, characterized by using the prepolymerized addition polymerization catalyst component and, if necessary, an organoaluminum compound (C).

  According to the method of the present invention, fouling in the reactor can be suppressed even when the chemical reaction is performed in the reactor. In particular, even if the polymerization reaction is carried out continuously in the reactor, it is possible to prevent a decrease in the heat transfer efficiency of the polymerization reactor due to fouling and to stably operate continuously.

  Hereinafter, the present invention will be described in detail.

Method for Cleaning the Inner Wall Surface of the Reactor The method for cleaning the inner wall surface of the reactor of the present invention includes the following steps (1) and (2) and, if necessary, step (3) after step (2). Is the method.
Step (1): at least one compound selected from the compound represented by the general formula [1], the compound represented by the general formula [2], and the compound represented by the general formula [9] and a hydrocarbon solvent Step (2) of adding a solution containing: R ¹ —O — (— R ² —O—) _m -Q ¹ [1]
R ¹ C (═O) NR ⁵ ₂ [2]
M ⁴ L ³ _n [9]
(In the above general formulas [1] and [2], R ¹ represents an optionally substituted hydrocarbyl group having 1 to 30 carbon atoms. R ² may have a substituent. Represents a good alkylene group having 1 to 20 carbon atoms, Q ¹ represents a hydrogen atom, —C (═O) OM ¹ , —R ³ —C (═O) OM ¹ , —S (═O) ₂ OM ¹ , _{^{-R 3 -S (= O) 2}} OM 1, -P (= O) (OH) (OM 1), - R 3 -P (= O) (OH) (OM 1), - P (= O) (OR ⁴ ) (OM ¹ ), —R ³ —P (═O) (OR ⁴ ) (OM ¹ ), —P (═O) (OM ¹ ) ₂ , or —R ³ —P (═O) ^(OM ₁₎ represents a ₂ .M ¹ is hydrogen ^{_{atom, NH 4, NH (R 12}} OH) 3 or, ^{.R 12} good number of carbon atoms which may have a substituent represents an alkali metal atom Represents a 20 alkylene group .R ³ is .R ⁴ is carbon atoms which may have a substituent represents an alkylene group which may having 1 to 20 carbon atoms which may have a substituent 1 to 20 M represents a number of 1 to 100. R ⁵ represents a hydrogen atom or a hydrocarbyl group having 1 to 30 carbon atoms which may have a substituent.
In the general formula [9], M ⁴ is a group consisting of Group 1, Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, and Group 13 of the Periodic Table. It represents a metal atom selected more. L ³ is a hydrogen atom, a halogen atom or a hydrocarbyl group, and n is the valence of the metal atom M ⁴ . )

As the hydrocarbyl group having 1 to 30 carbon atoms which may have a substituent of R ^{1 in} the formula [1], an alkyl group having 1 to 30 carbon atoms which may have a substituent, Examples thereof include an aralkyl group having 7 to 30 carbon atoms which may have a substituent and an aryl group having 6 to 30 carbon atoms which may have a substituent.

  Examples of the optionally substituted alkyl group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms having a halogen atom as a substituent, and substituted silyl An alkyl group having 1 to 30 carbon atoms having a substituent as a substituent, an alkyl group having 1 to 30 carbon atoms having a substituted amino group as a substituent, and 1 to 30 carbon atoms having a hydrocarbyloxy group as a substituent And the like.

  Examples of the alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and neopentyl group. , Isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, n-triacontyl group, etc. It is.

  Examples of the alkyl group having 1 to 30 carbon atoms having a halogen atom as a substituent include, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromo Methyl group, tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloro Ethyl group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluorope group Tyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perfluorotriacontyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl Group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perchlorotriacontyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group Perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromopentadecyl group, perbromoeicosyl group, perbromotriacontyl group and the like.

  Examples of the alkyl group having 1 to 30 carbon atoms having a substituted silyl group as a substituent include, for example, trimethylsilylmethyl group, trimethylsilylethyl group, trimethylsilylpropyl group, trimethylsilylbutyl group, bis (trimethylsilyl) methyl group, and bis (trimethylsilyl) ethyl. Group, bis (trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, triphenylsilylmethyl group and the like.

  Examples of the alkyl group having 1 to 30 carbon atoms having a substituted amino group as a substituent include, for example, a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a dimethylaminobutyl group, a bis (dimethylamino) methyl group, Examples thereof include bis (dimethylamino) ethyl group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, phenylaminomethyl group, diphenylaminomethyl group and the like.

  Examples of the alkyl group having 1 to 30 carbon atoms having a hydrocarbyloxy group as a substituent include, for example, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, an n-butoxymethyl group, sec -Butoxymethyl group, tert-butoxymethyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, sec-butoxyethyl group, tert-butoxyethyl Group, phenoxyethyl group, methoxy-n-propyl group, ethoxy-n-propyl group, n-propoxy-n-propyl group, isopropoxy-n-propyl group, n-butoxy-n-propyl group, sec-butoxy- n-propyl group, tert-butoxy-n-propyl group Phenoxy-n-propyl group, methoxyisopropyl group, ethoxyisopropyl group, n-propoxyisopropyl group, isopropoxyisopropyl group, n-butoxyisopropyl group, sec-butoxyisopropyl group, tert-butoxyisopropyl group, phenoxyisopropyl group, etc. It is done.

  Examples of the aralkyl group having 7 to 30 carbon atoms which may have a substituent include an aralkyl group having 7 to 30 carbon atoms and an aralkyl group having 7 to 30 carbon atoms having a halogen atom as a substituent. It is done.

  Examples of the aralkyl group having 7 to 30 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, 4,6-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-decylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group , Anthracenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphth Nirumechiru group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group.

  Examples of the aralkyl group having 7 to 30 carbon atoms having a halogen atom as a substituent include 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2-chlorobenzyl group, and 3-chlorobenzyl. Group, 4-chlorobenzyl group, 2-bromobenzyl group, 3-bromobenzyl group, 4-bromobenzyl group, 2-iodobenzyl group, 3-iodobenzyl group, 4-iodobenzyl group and the like.

  The aryl group having 6 to 30 carbon atoms which may have a substituent includes an aryl group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms having a halogen atom as a substituent, and substituted silyl. An aryl group having 6 to 30 carbon atoms having a substituent as a substituent, an aryl group having 6 to 30 carbon atoms having a substituted amino group as a substituent, and 6 to 30 carbon atoms having a hydrocarbyloxy group as a substituent And aryl groups.

  Examples of the aryl group having 6 to 30 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, diethylphenyl group, triethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, ec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetra Examples include decylphenyl group, naphthyl group, anthracenyl group and the like.

  Examples of the aryl group having 6 to 30 carbon atoms having a halogen atom as a substituent include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group, Examples include 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group and the like.

  Examples of the aryl group having 6 to 30 carbon atoms having a substituted silyl group as a substituent include a trimethylsilylphenyl group and a bis (trimethylsilyl) phenyl group.

  Examples of the aryl group having 6 to 30 carbon atoms having a substituted amino group as a substituent include a dimethylaminophenyl group, a bis (dimethylamino) phenyl group, and a diphenylaminophenyl group.

  Examples of the aryl group having 6 to 30 carbon atoms having a hydrocarbyloxy group as a substituent include, for example, methoxyphenyl group, ethoxyphenyl group, n-propoxyphenyl group, isopropoxyphenyl group, n-butoxyphenyl group, sec -Butoxyphenyl group, tert-butoxyphenyl group, phenoxyphenyl group and the like.

R ¹ in the formula [1] is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent, and more preferably an alkyl group having 1 to 30 carbon atoms.

R ² represents an alkylene group having 1 to 20 carbon atoms which may have a substituent.

  Examples of the optionally substituted alkylene group having 1 to 20 carbon atoms include alkylene groups having 1 to 20 carbon atoms, alkylene groups having 1 to 20 carbon atoms having a halogen atom as a substituent, and substituted silyl groups. An alkylene group having 1 to 20 carbon atoms having a substituent as a substituent, an alkylene group having 1 to 20 carbon atoms having a substituted amino group as a substituent, and 1 to 20 carbon atoms having a hydrocarbyloxy group as a substituent And the like.

  Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, and dodecylene group. Tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, eicosylene group, methylmethylene group, dimethylmethylene group, ethylmethylene group, ethylmethylmethylene group, diethylmethylene group, propylenemethylene group, Examples thereof include a methylethylene group, a dimethylethylene group, a trimethylethylene group, and a tetramethylethylene group.

  Examples of the alkylene group having 1 to 20 carbon atoms having a halogen atom as a substituent include, for example, a fluoromethylene group, a difluoromethylene group, a chloromethylene group, a dichloromethylene group, a bromomethylene group, a dibromomethylene group, an iodomethylene group, di Iodomethylene, fluoroethylene, difluoroethylene, trifluoroethylene, tetrafluoroethylene, chloroethylene, dichloroethylene, trichloroethylene, tetrachloroethylene, bromoethylene, dibromoethylene, tribromoethylene, tetrabromo Ethylene group, perfluoropropylene group, perfluorobutylene group, perfluoropentylene group, perfluorohexylene group, perfluorooctylene group, perfluorododecylene group, perfluoropropylene group Tadecylene group, perfluoroeicosylene group, perchloropropylene group, perchlorobutylene group, perchloropentylene group, perchlorohexylene group, perchlorooctylene group, perchlorododecylene group, perchloropentadecylene group Perchloroeicosylene group, perbromopropylene group, perbromobutylene group, perbromopentylene group, perbromohexylene group, perbromooctylene group, perbromododecylene group, perbromopentadecylene group, And bromoeicosylene group.

  Examples of the alkylene group having 1 to 30 carbon atoms having a substituted silyl group as a substituent include, for example, trimethylsilylmethylene group, trimethylsilylethylene group, trimethylsilylpropylene group, trimethylsilylbutylene group, bis (trimethylsilyl) methylene group, and bis (trimethylsilyl) ethylene. Group, bis (trimethylsilyl) propylene group, bis (trimethylsilyl) butylene group, triphenylsilylmethyl group and the like.

  Examples of the alkylene group having 1 to 30 carbon atoms having a substituted amino group as a substituent include, for example, a dimethylaminomethylene group, a dimethylaminoethylene group, a dimethylaminopropylene group, a dimethylaminobutylene group, a bis (dimethylamino) methylene group, Examples thereof include bis (dimethylamino) ethylene group, bis (dimethylamino) propylene group, bis (dimethylamino) butylene group, phenylaminomethylene group, diphenylaminomethylene group and the like.

  Examples of the alkylene group having 1 to 20 carbon atoms having a hydrocarbyloxy group as a substituent include, for example, a methoxymethylene group, an ethoxymethylene group, an n-propoxymethylene group, an isopropoxymethylene group, an n-butoxymethylene group, sec -Butoxymethylene group, tert-butoxymethylene group, phenoxymethylene group, methoxyethylene group, ethoxyethylene group, n-propoxyethylene group, isopropoxyethylene group, n-butoxyethylene group, sec-butoxyethylene group, tert-butoxyethylene Group, phenoxyethylene group, methoxy-n-propylene group, ethoxy-n-propylene group, n-propoxy-n-propylene group, isopropoxy-n-propylene group, n-butoxy-n-propylene group, sec-butoxy- n-p Pyrene group, tert-butoxy-n-propylene group, phenoxy-n-propylene group, methoxyisopropylene group, ethoxyisopropylene group, n-propoxyisopropylene group, isopropoxyisopropylene group, n-butoxyisopropylene group, sec -Butoxy isopropylene group, tert-butoxy isopropylene group, phenoxy isopropylene group and the like can be mentioned.

R ² in the formula [1] is preferably an alkylene group having 1 to 20 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group or a hexylene group, and more preferably Is an ethylene group.

Q ¹ is a hydrogen atom, —C (═O) OM ¹ , —R ³ —C (═O) OM ¹ , —S (═O) ₂ OM ¹ , —R ³ —S (═O) ₂ OM ¹ , ^{-P (= O) (OH)} (OM 1), - R 3 -P (= O) (OH) (OM 1), - P (= O) (OR 4) (OM 1), - R 3 - P (═O) (OR ⁴ ) (OM ¹ ), —P (═O) (OM ¹ ) ₂ , or —R ³ —P (═O) (OM ¹ ) ₂ , preferably a hydrogen atom , —R ³ —C (═O) OM ¹ , —S (═O) ₂ OM ¹ .

In the above examples, M ¹ represents a hydrogen atom, NH ₄ , NH (R ¹² OH) _3, or an alkali metal atom.

R ¹² represents an alkylene group having 1 to 20 carbon atoms which may have a substituent.

Examples of the alkylene group having 1 to 20 carbon atoms which may have a substituent of R ¹² include the same groups as those exemplified for R ² .

R ¹² is preferably an alkylene group having 1 to 20 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group or a hexylene group, and even more preferably an ethylene group.

  As an alkali metal atom, Preferably they are a sodium atom and a potassium atom, More preferably, it is a sodium atom.

R ³ represents an alkylene group having 1 to 20 carbon atoms which may have a substituent.

Examples of the alkylene group having 1 to 20 carbon atoms which may have a substituent of R ³ include the same groups as those exemplified for R ² .

R ³ is preferably an alkylene group having 1 to 20 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group or a hexylene group, and further preferably a methylene group.

R ⁴ represents a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent.

The hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent of R ⁴ has an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Examples thereof include an aralkyl group having 7 to 20 carbon atoms which may be present, and an aryl group having 6 to 20 carbon atoms which may have a substituent.

  Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms having a halogen atom as a substituent, and substituted silyl An alkyl group having 1 to 20 carbon atoms having a group as a substituent, an alkyl group having 1 to 20 carbon atoms having a substituted amino group as a substituent, and 1 to 20 carbon atoms having a hydrocarbyloxy group as a substituent And the like.

  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, n-pentyl group, and neopentyl group. , Isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, Examples thereof include n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like.

  Examples of the alkyl group having 1 to 20 carbon atoms having a halogen atom as a substituent include, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromo Methyl group, tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloro Ethyl group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluorope group Til group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, Perchlorooctyl group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group Group, perbromopentadecyl group, perbromoeicosyl group and the like.

  Examples of the alkyl group having 1 to 20 carbon atoms having a substituted silyl group as a substituent include, for example, trimethylsilylmethyl group, trimethylsilylethyl group, trimethylsilylpropyl group, trimethylsilylbutyl group, bis (trimethylsilyl) methyl group, and bis (trimethylsilyl) ethyl. Group, bis (trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, triphenylsilylmethyl group and the like.

  Examples of the alkyl group having 1 to 20 carbon atoms having a substituted amino group as a substituent include, for example, a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a dimethylaminobutyl group, a bis (dimethylamino) methyl group, Examples thereof include bis (dimethylamino) ethyl group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, phenylaminomethyl group, diphenylaminomethyl group and the like.

  Examples of the alkyl group having 1 to 20 carbon atoms having a hydrocarbyloxy group as a substituent include, for example, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, an n-butoxymethyl group, sec -Butoxymethyl group, tert-butoxymethyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, sec-butoxyethyl group, tert-butoxyethyl Group, phenoxyethyl group, methoxy-n-propyl group, ethoxy-n-propyl group, n-propoxy-n-propyl group, isopropoxy-n-propyl group, n-butoxy-n-propyl group, sec-butoxy- n-propyl group, tert-butoxy-n-propyl group Phenoxy-n-propyl group, methoxyisopropyl group, ethoxyisopropyl group, n-propoxyisopropyl group, isopropoxyisopropyl group, n-butoxyisopropyl group, sec-butoxyisopropyl group, tert-butoxyisopropyl group, phenoxyisopropyl group, etc. It is done.

  Examples of the aralkyl group having 7 to 20 carbon atoms which may have a substituent include an aralkyl group having 7 to 20 carbon atoms and an aralkyl group having 7 to 20 carbon atoms substituted with a halogen atom. .

  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, 4,6-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-decylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group , Anthracenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphth Nirumechiru group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group.

  Examples of the aralkyl group having 7 to 20 carbon atoms having a halogen atom as a substituent include, for example, 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2-chlorobenzyl group, 3-chlorobenzyl. Group, 4-chlorobenzyl group, 2-bromobenzyl group, 3-bromobenzyl group, 4-bromobenzyl group, 2-iodobenzyl group, 3-iodobenzyl group, 4-iodobenzyl group and 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.

  Examples of the aryl group having 6 to 20 carbon atoms having a halogen atom as a substituent include, for example, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, Examples include 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group and the like.

R ⁴ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably a methyl group, an ethyl group, an n-propyl group, or isopropyl. Group.

  m represents a number from 1 to 100.

  m is preferably a number of 1 to 50, more preferably a number of 1 to 30, and still more preferably a number of 1 to 12.

R ^{5 in the} formula [2] represents a hydrogen atom or a hydrocarbyl group having 1 to 30 carbon atoms which may have a substituent.

The hydrocarbyl group having 1 to 30 carbon atoms which may have a substituent in R ⁵ has an alkyl group having 1 to 30 carbon atoms and a substituent which may have a substituent. An aralkyl group having 7 to 30 carbon atoms which may be optionally substituted, and an aryl group having 6 to 30 carbon atoms which may have a substituent are preferred, and the same hydro ly as described for R ¹ in the general formula [1] A carbyl group is used.

Compound [1] includes polyoxyethylene lauryl ether, polyoxyethylene lauryl ether acetic acid, sodium polyoxyethylene lauryl ether acetate, potassium polyoxyethylene lauryl ether acetate, ammonium polyoxyethylene lauryl ether acetate, polyoxyethylene lauryl ether acetic acid. Triethanolamine, polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, potassium polyoxyethylene lauryl ether sulfate, polyoxyethylene lauryl ether ammonium sulfate, polyoxyethylene lauryl ether sulfate triethanolamine, polyoxyethylene lauryl ether phosphate Acid, polyoxyethylene lauryl ether sodium phosphate, polyoxyethylene Potassium lauryl ether phosphate, ammonium polyoxyethylene lauryl ether phosphoric acid, polyoxyethylene lauryl ether phosphate triethanolamine, and the like.

The compound [1] is preferably polyoxyethylene lauryl ether, polyoxyethylene lauryl ether acetic acid, polyoxyethylene lauryl ether sodium acetate, polyoxyethylene lauryl ether sulfate, polyoxyethylene lauryl ether sodium sulfate, and more preferably Is sodium polyoxyethylene lauryl ether acetate.

Compound [2] includes caprylic acid amide, caprylic acid diethanolamide, pelargonic acid amide, pelargonic acid diethanolamide, capric acid amide, capric acid diethanolamide, lauric acid amide, lauric acid diethanolamide, myristic acid amide, myristic acid diethanolamide. , Pentadecylic acid amide, pentadecylic acid diethanolamide, palmitic acid amide, palmitic acid diethanolamide, and the like.

The compound [2] is preferably pelargonic acid diethanolamide, capric acid diethanolamide, lauric acid diethanolamide, myristic acid diethanolamide.

Selected from the group consisting of Group 1, Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 12 and Group 13 of M ^{4 in} formula [9] The metal atom is preferably a metal atom selected from the group consisting of Group 1, Group 2, Group 12, and Group 13 of the periodic table, and particularly preferably a metal atom of Group 1.

As a halogen atom of L < ³ > of Formula [9], a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned, for example.

Examples of the hydrocarbyl group of L ^{3 in} the formula [9] include an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms.

The hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent may have an alkyl group having 1 to 20 carbon atoms which may have a substituent or a substituent. Examples thereof include an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms which may have a substituent.

  Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms having a halogen atom as a substituent, and substituted silyl An alkyl group having 1 to 20 carbon atoms having a group as a substituent, an alkyl group having 1 to 20 carbon atoms having a substituted amino group as a substituent, and 1 to 20 carbon atoms having a hydrocarbyloxy group as a substituent And the like.

  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, n-pentyl group, and neopentyl group. , Isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, Examples thereof include n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like.

  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 chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl. Group, tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl Group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group Perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl Group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromododecyl group Examples thereof include a bromopentadecyl group and a perbromoeicosyl group.

  Examples of the alkyl group having 1 to 20 carbon atoms having a substituted silyl group as a substituent include, for example, trimethylsilylmethyl group, trimethylsilylethyl group, trimethylsilylpropyl group, trimethylsilylbutyl group, bis (trimethylsilyl) methyl group, and bis (trimethylsilyl) ethyl. Group, bis (trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, triphenylsilylmethyl group and the like.

  Examples of the alkyl group having 1 to 20 carbon atoms having a substituted amino group as a substituent include, for example, a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a dimethylaminobutyl group, a bis (dimethylamino) methyl group, Examples thereof include bis (dimethylamino) ethyl group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, phenylaminomethyl group, diphenylaminomethyl group and the like.

  Examples of the alkyl group having 1 to 20 carbon atoms having a hydrocarbyloxy group as a substituent include, for example, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, an n-butoxymethyl group, sec -Butoxymethyl group, tert-butoxymethyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, sec-butoxyethyl group, tert-butoxyethyl Group, phenoxyethyl group, methoxy-n-propyl group, ethoxy-n-propyl group, n-propoxy-n-propyl group, isopropoxy-n-propyl group, n-butoxy-n-propyl group, sec-butoxy- n-propyl group, tert-butoxy-n-propyl group Phenoxy-n-propyl group, methoxyisopropyl group, ethoxyisopropyl group, n-propoxyisopropyl group, isopropoxyisopropyl group, n-butoxyisopropyl group, sec-butoxyisopropyl group, tert-butoxyisopropyl group, phenoxyisopropyl group, etc. It is done.

  Examples of the aralkyl group having 7 to 20 carbon atoms which may have a substituent include an aralkyl group having 7 to 20 carbon atoms and an aralkyl group having 7 to 20 carbon atoms having a halogen atom as a substituent. It is done.

  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, 4,6-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-decylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group , Anthracenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphth Nirumechiru group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group.

  Examples of the aralkyl group having 7 to 20 carbon atoms having a halogen atom as a substituent include, for example, 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2-chlorobenzyl group, 3-chlorobenzyl. Group, 4-chlorobenzyl group, 2-bromobenzyl group, 3-bromobenzyl group, 4-bromobenzyl group, 2-iodobenzyl group, 3-iodobenzyl group, 4-iodobenzyl group and the like.

  Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent include an aryl group having 6 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms having a halogen atom as a substituent. It is done.

  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.

  Examples of the aryl group having 6 to 20 carbon atoms having a halogen atom as a substituent include, for example, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, Examples include 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group and the like.

L ³ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group. , N-pentyl group, neopentyl group, isopentyl group, n-hexyl group.

As the compound of the formula [9], when M ⁴ is a lithium atom, for example, methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n- Examples include alkyllithium such as pentyllithium, neopentyllithium, isopentyllithium, and n-hexyllithium, aryllithium such as phenyllithium, naphthyllithium, and pentafluorophenyllithium, allyllithium, and cyclopentadienyllithium. When M ⁴ is a zinc atom, for example, dialkyl zinc such as dimethyl zinc, diethyl zinc, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-n-hexyl zinc, diphenyl zinc, dinaphthyl zinc, and bis (penta Diaryl zinc such as fluorophenyl) zinc, dialkenyl zinc such as diallyl zinc, bis (cyclopentadienyl) zinc, methyl zinc chloride, ethyl zinc chloride, propyl zinc chloride, n-butyl zinc chloride, isobutyl zinc chloride, n- chloride Hexyl zinc, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, n-butyl zinc bromide, isobutyl zinc bromide, n-hexyl zinc bromide, methyl zinc iodide, ethyl zinc iodide, propyl iodide Zinc, n-butyl zinc iodide, isobutyl zinc iodide, n-hexyl zinc iodide, etc. Halogenated alkyl zinc. When M ⁴ is an aluminum atom, for example, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like Dialkylaluminum chlorides such as dimethylaluminum chloride, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride; methylaluminum dichloride, ethylaluminum Dichloride, n-propylaluminum dichloride, n-butylaluminum dichloride, isobutyl Alkyl aluminum dichlorides such as rualuminum dichloride and n-hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n-hexylaluminum hydride Dialkyl aluminum hydride such as

  The compound of the formula [9] is preferably alkyl lithium, dialkyl zinc, or trialkyl aluminum, more preferably alkyl lithium, and still more preferably methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n -Butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, neopentyl lithium, isopentyl lithium, n-hexyl lithium, particularly preferably n-butyl lithium, sec-butyl lithium, tert-butyl Lithium.

Examples of the hydrocarbon solvent used in the step (1) include an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent. The hydrocarbon solvent may be a mixed solvent of a plurality of hydrocarbon solvents.

  The aliphatic hydrocarbon solvent is preferably an aliphatic hydrocarbon solvent having 4 to 10 carbon atoms, such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclopentane, cyclohexane. And cycloheptane.

The aromatic hydrocarbon solvent is preferably an aromatic hydrocarbon solvent having 6 to 12 carbon atoms, and examples thereof include benzene, toluene, xylene, ethylbenzene, mesitylene and the like.

  As the step (1), at least one compound selected from the compound of the formula [1], the compound of the formula [2], and the compound of the formula [9] is put in a reactor in advance, and a hydrocarbon is added thereto. A step of producing a solution in a reactor by adding a solvent, and carbonizing at least one compound selected from a compound of formula [1], a compound of formula [2], and a compound of formula [9] in a separate container beforehand Examples include a step of dissolving in a hydrogen solvent and charging the reactor.

The amount of at least one compound selected from the compound of formula [1], the compound of formula [2] and the compound of formula [9] used in step (1) is based on the inner wall area of the reactor. it is preferably in the range of 1~10000mmol / ^{m 2,} more preferably in the range of 10 to 100 / ^{m 2.}

  A method of stirring the solution in the reactor after the step (1) is preferable. Although there is no restriction | limiting in particular in stirring time, Preferably the method of stirring for 1 minute or more is mention | raise | lifted.

Examples of the step (2) include a step of extracting the solution with a syringe or a tube, a step of discharging the solution from the outlet of the reaction vessel to the outside of the reaction vessel, and the like. When step (3) is performed after step (2), step (3) may be performed in such a manner that the solution in the reactor is not completely removed and a part of the solution remains.

Examples of the hydrocarbon solvent used in the step (3) include the same hydrocarbon solvents as those described as the hydrocarbon solvent in the step (1).

As the step (3), there is a method in which a hydrocarbon solvent is added to a washed reactor, and after the washed reactor is left standing or stirred, the hydrocarbon solvent is removed. The standing time or stirring time is not particularly limited, but is preferably 1 hour or longer. Examples of the method for extracting the hydrocarbon solvent include a method for extracting with a syringe or tube, and a method for discharging the hydrocarbon solvent from the reaction vessel extraction port to the outside of the reaction vessel.

Although the washed reactor of the present invention can be used for various chemical reactions, it is preferably used for addition polymerization.

Compound (A) which is a transition metal compound or a μ-oxo type transition metal compound dimer thereof
The transition metal compound used in the present invention or the compound (A) which is a μ-oxo type transition metal compound dimer thereof may be used in combination with an activator (B) or, if necessary, organic aluminum Although it will not specifically limit if it is a transition metal compound which shows addition polymerization activity by using together with a compound (C), Usually, transition metal compounds, such as a metallocene complex, are used.

Specific examples of the transition metal compound include a transition metal compound represented by the following formula [3] or a dimer of a μ-oxo type transition metal compound.
L ¹ _a M ² X ¹ _b [3]
(In the formula, M ² is a transition metal atom of Group 4 of the periodic table. L ¹ is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ¹ are directly connected to each other. Or may be linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, wherein X ¹ is a halogen atom, a hydrocarbyl group (provided that (Excluding a group having a cyclopentadiene type anion skeleton) or a hydrocarbyloxy group, a represents a number satisfying 0 <a ≦ 3, and b represents a number satisfying 0 <b ≦ 3.)

M ^{2 in the} formula [3] is a titanium atom, a zirconium atom, or a hafnium atom, and more preferably a zirconium atom.

Examples of the group having a cyclopentadiene-type anion skeleton of L ^{1 in} the formula [3] 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, eta ⁵ -1 2,3-trimethyl cyclopentadienyl group, eta ^{5-1,2,4-trimethyl} cyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group, 4,5, 6,7-tetrahydroindenyl group, 2-methylindenyl group, 3-methylindenyl group, 4-methylindenyl group, 5-methylindenyl group, 6-methylindenyl group, 7-methylindenyl group 2-tert-butylindenyl group, 3-tert-butylindenyl group, 4-tert-butylindenyl group, 5-tert-butylindenyl group, 6-tert-butylindenyl group, 7-tert- Butyl indenyl group, 2,3-dimethyl indenyl group, 4,7-dimethyl indenyl group, 2,4,7-trimethyl indenyl group, -Methyl-4-isopropylindenyl group, 4,5-benzindenyl group, 2-methyl-4,5-benzindenyl group, 4-phenylindenyl group, 2-methyl-5-phenylindenyl group, 2-methyl- Examples thereof include 4-phenylindenyl 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 ¹ in the formula [3] is not particularly limited, and may be any value that can be taken by the group having a cyclopentadiene type anion skeleton. 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 hetero atom of L ¹ in the formula [3] include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Examples of such a group include an alkoxy group and an aryloxy group. , A thioalkoxy group, a thioaryloxy group, an alkylamino group, an arylamino group, an alkylphosphino group, an arylphosphino group, a chelating ligand, or a ring of oxygen, sulfur, nitrogen and / or phosphorus atoms An aromatic heterocyclic group or an aliphatic heterocyclic group is preferable.

Examples of the group containing a hetero atom of L ¹ in the formula [3] include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, 2-methylphenoxy group, 2,6-dimethylphenoxy group, 2, 4,6-trimethylphenoxy group, 2-ethylphenoxy group, 4-n-propylphenoxy group, 2-isopropylphenoxy group, 2,6-diisopropylphenoxy group, 4-sec-butylphenoxy group, 4-tert-butylphenoxy group Group, 2,6-di-sec-butylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2,6-di-tert-butylphenoxy group, 4-methoxyphenoxy group, 2,6-dimethoxyphenoxy group Group, 3,5-dimethoxyphenoxy group, 2-chlorophenoxy group, 4-nitrosophenoxy 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 formula [7] can also be mentioned, for example.
R ⁸ ₃ P = N- [7]
(In the formula, each R ⁸ independently represents a hydrogen atom, a halogen atom or a hydrocarbyl group, and the plurality of R ⁸ may be the same or different from each other, and any two of the plurality of R ⁸ may be selected. Two or more may be bonded to each other and may form a ring structure.)

Specific examples of R ⁸ in the formula [7] 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 thereof include a butyl group, a cyclopropyl group, a cyclobutyl group, a cycloheptyl group, a cyclohexyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a benzyl group.

  Further, examples of the group containing a hetero atom include a group represented by the following formula [8].

(Wherein, R ⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbyl group, a halogenated hydrocarbyl group, hydrocarbyloxy group, a silyl group or an amino group, a plurality of R ⁹ is the same as each other Or any two or more of R ⁹ may be bonded to each other and may form a ring structure.)

Specific examples of R ⁹ in the above formula [8] 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, triethyl Examples include a silyl group, a diphenylmethylsilyl group, a 1-methyl-1-phenylethyl group, a 1,1-dimethylpropyl group, a 2-chlorophenyl group, and a pentafluorophenyl group.

The chelating ligand of L ¹ in the formula [3] refers to a ligand having a plurality of coordination sites. Examples of the ligand include acetylacetonate, diimine, oxazoline, bisoxazoline, Mention may be made of terpyridine, acyl hydrazones, diethylenetriamine, triethylenetetramine, porphyrin, crown ether, and cryptate.

Examples of the heterocyclic group represented by L ¹ in the formula [3] 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 formula [3], when a plurality of L ¹ 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, a cyclopentadiene anion When a group having a skeleton is linked via its residue, a group containing a hetero atom is linked via its residue, or a group having a cyclopentadiene-type anion skeleton and a hetero atom A group containing a hydrogen atom), and as the residue, preferably the two atoms bonded to L ¹ are a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or It is a phosphorus atom and is a divalent residue having a minimum atomic number of 3 or less for bonding two L ¹ . As the residue, 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, diphenylsilylene group And substituted silylene groups such as tetramethyldisilene group and dimethoxysilylene group; and heteroatoms such as nitrogen atom, oxygen atom, sulfur atom and 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 represented by X ¹ in the formula [3] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbyl group represented by 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 carbon atoms is preferable. An 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 have an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, an aralkyloxy group such as a benzyloxy group, and the like as a substituent.

  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 include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. As a substituent.

  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 Enyl, 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 include fluorine atoms, chlorine atoms, bromine atoms, halogen atoms such as iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. You may have as a substituent.

  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 hydrocarbyloxy group represented by X ¹ in the general formula [1] include an alkoxy group, an aralkyloxy group, and an aryloxy group. Among them, 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 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 aralkyloxy groups such as benzyloxy groups. You may have as a substituent.

  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 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 aralkyloxy groups such as benzyloxy groups. As a substituent.

  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 aralkyloxy groups such as benzyloxy groups. As a substituent.

X ¹ in the formula [3] is more preferably a chlorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, methoxy group, ethoxy group, n-propoxy group, 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 Formula [3], a is a number that satisfies 0 <a ≦ 3, and b is a number that satisfies 0 <b ≦ 3. a and b are 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 formula [3] in which the transition metal atom is a titanium atom, a zirconium atom or a hafnium atom include bis (cyclopentadienyl) titanium dichloride, 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-methylcyclopenta) Dienyl) titanium dichloride, bis (1,2,3-trimethylcyclopentadienyl) titanium dichloride, bis (1,2,4-trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium Dichloride, bis (pentameth Lucyclopentadienyl) 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, dimethylsilylene bis (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-ethanediyltitanium dichloride, (tert-butylamide) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (phenylphosphide) tetramethylcyclopentadi Enyldimethylsilane titanium dichloride, (tert-butylamido) indenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) tetrahydroyl Denenyl-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) fluorenyldimethylsilane titanium dichloride,

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

2,2′-thiobis [4-methyl-6-tert-butylphenoxy] titanium dichloride, 2,2′-thiobis [4-methyl-6- (1-methylethyl) phenoxy] titanium dichloride, 2,2′- Thiobis (4,6-dimethylphenoxy) titanium dichloride, 2,2'-thiobis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-methylenebis (4-methyl-6-tert-butylphenoxy) ) Titanium dichloride, 2,2'-ethylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2, 2 ′-(4,4 ′, 6,6′-tetra-tert-butyl-1,1 ′ biphenol Shi) titanium dichloride, (di -tert- butyl-1,3-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, and [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium trichloride, and these A compound in which “titanium” is replaced with “zirconium” or “hafnium”, “(2-phenoxy)” is “(3-phenyl-2-phenoxy)”, “(3-trimethylsilyl-2-phenoxy)” Or “(3-tert-butyldi Compound substituted with “methylsilyl-2-phenoxy)”, “dimethylsilylene” with “methylene”, “ethylene”, “dimethylmethylene (isopropylidene)”, “diphenylmethylene”, “diethylsilylene”, “diphenylsilylene”, or "Dimethoxysilylene" is a compound that replaces "dichloride", "difluoride", "dibromide", "diaiodide", "dimethyl," diethyl "," diisopropyl "," diphenyl "," dibenzyl "," dimethoxide "," “Diethoxide”, “di (n-propoxide)”, “di (isopropoxide)”, “diphenoxide” or “di (pentafluorophenoxide)” as well as “trichloride” as “trifluoride” ”,“ Tribromide ”,“ Tria “Iodide”, “Trimethyl”, “Triethyl”, “Triisopropyl”, “Triphenyl”, “Tribenzyl”, “Trimethoxide”, “Triethoxide”, “Tri (n-propoxide)”, “Tri (isopropoxide)” ”,“ Triphenoxide ”, or“ tri (pentafluorophenoxide) ”.

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

Among the transition metal compounds exemplified above, the transition metal compound (A) used in the present invention is preferably a compound in which M ² is zirconium, or a group having a cyclopentadiene-type anion skeleton as L ¹ in the formula [3]. A transition metal compound having at least one is preferable.
Among them, L ¹ in the formula [3] has two groups having a cyclopentadiene type anion skeleton, and L ¹ is bonded to each other through a residue containing a carbon atom, a silicon atom, an oxygen atom, a sulfur atom or a phosphorus atom. Particularly preferred are zirconium compounds linked together.

  The transition metal compound represented by the formula [3] can be produced by a production method described in JP-A-6-340684, JP-A-7-258321, International Patent Publication No. 95/00562, and the like. Is possible.

Activator (B)
The activator (B) used in the present invention may be any as long as it can activate the aforementioned transition metal compound or its μ-oxo type transition metal compound dimer (A). When performing polymerization with the formation of the generated addition polymer particles (eg slurry polymerization, gas phase polymerization, bulk polymerization, etc.), the specific particles are used as one of the catalyst components, and the shape of the generated addition polymer is fixed. It is preferable to use the modified particles of (I), (II) and (III) below.

(I): Modified particles obtained by contacting the following (a), (b), (c) and (d) below (a): a compound represented by the following general formula [4] M ³ L ² ₂ [4]
(B): Compound represented by the following general formula [5] R ⁶ _t-1 TH [5]
(C): Compound represented by the following general formula [6] R ⁷ _t-2 TH ₂ [6]
(D): Inorganic oxide particles or organic polymer particles (in the above general formulas [4] to [6], M ³ represents a typical metal atom of Group 12 of the periodic table. L ² represents a hydrogen atom or a halogen atom. Or a hydrocarbyl group, and when a plurality of L ² are present, they may be the same or different from each other, R ⁶ represents an electron-withdrawing group or a group containing an electron-withdrawing group, and R 6 ^{When a} plurality of ⁶ are present, they may be the same or different from each other, R ⁷ represents a hydrocarbyl group or a halogenated hydrocarbyl group, and each T independently represents group 15 of the periodic table. Or represents a Group 16 atom, and t represents the valence of T of each compound.)

(II): Modified particles obtained by bringing inorganic oxide particles or organic polymer particles (d) into contact with aluminoxane (e)

(III): Modified particles obtained by bringing inorganic oxide particles or organic polymer particles (d), aluminoxane (e), and a transition metal compound into contact with each other.

M ³ in the general formula [4] represents a typical metal atom of Group 12 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). Specific examples thereof include a zinc atom, a cadmium atom, and a mercury atom. M ³ is particularly preferably a zinc atom.

In the general formula [4], L ² represents a hydrogen atom, a halogen atom or a hydrocarbyl group. Examples of the halogen atom for L ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The hydrocarbyl group for L ² is preferably an alkyl group, an aryl group, or an aralkyl group.

The alkyl group of the hydrocarbyl group of L ² is preferably an alkyl group having 1 to 20 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl. Group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, and n -An eicosyl group is mentioned, More preferably, they are 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, IH, 1H-perfluoro eicosyl group, and "chloro" to "fluoro" in these alkyl group include an alkyl group is replaced with "bromo" or "iodo". 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 of the hydrocarbyl group of L ² is preferably an aryl group having 6 to 20 carbon atoms, such as a 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-butyl group Enyl group, sec-butylphenyl group, tert-butylphenyl group, isobutylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n- A dodecylphenyl group, n-tetradecylphenyl group, a naphthyl group, and an anthracenyl group are mentioned, More preferably, it is a phenyl group. These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

The aralkyl group of the hydrocarbyl group of L ² is preferably an aralkyl group having 7 to 20 carbon atoms. For example, benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4 -Methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group , (3,4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, 2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3, 4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group , (Ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group , (Isobutylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl Groups, naphthylmethyl groups, and anthracenylmethyl groups, and more preferably Is a Njiru group. All of these aralkyl groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

L ^{2 in} Formula [4] 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 [5] or [6] independently represents an atom of Group 15 or Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). T in the general formula [5] and T in the general formula [6] may be the same or different. Specific examples of the Group 15 atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 atom include an oxygen atom and a sulfur atom. T is preferably each independently a nitrogen atom or an oxygen atom, and particularly preferably T is an oxygen atom.
In the above general formula [5] or [6], t represents the valence of each T. When T is a Group 15 atom, t is 3, and when T is a Group 16 atom, t is 2. is there.

R ⁶ in the general formula [5] represents an electron-withdrawing group or a group containing an electron-withdrawing group, and when a plurality of R ⁶ are present, they may be the same or different from each other.
As an index of electron withdrawing property, the Hammett's rule substituent constant σ and the like are known, and a functional group having a positive Hammett's rule constant σ can be cited as an electron withdrawing group.

  Specific examples of the electron withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group, and a phenyl group. Examples of the group containing an electron-withdrawing group include a halogenated alkyl group, a halogenated aryl group, a (halogenated alkyl) aryl group, a cyanated aryl group, a nitrated aryl group, an ester group (an alkoxycarbonyl group, an aralkyloxycarbonyl group, Aryloxycarbonyl group) and the like.

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

  Specific examples of the halogenated aryl group include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl. Group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2 -Naphthyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,4-dichlorophenyl group, 2,6 Dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 3,4,5-trichlorophenyl group, 2,3,5,6-tetrachlorophenyl group, penta Chlorophenyl group, 2,3,5,6-tetrachloro-4-trichloromethylphenyl group, 2,3,5,6-tetrachloro-4-pentachlorophenylphenyl group, perchloro-1-naphthyl group, perchloro-2- Naphtyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,4-dibromophenyl group, 2,6-dibromophenyl group, 3,4-dibromophenyl group, 3,5-dibromo Phenyl group, 2,4,6-tribromophenyl group, 3,4,5-tribromophenyl group, 2,3,5,6-tetrabromide Phenyl group, pentabromophenyl group, 2,3,5,6-tetrabromo-4-tribromomethylphenyl group, 2,3,5,6-tetrabromo-4-pentabromophenylphenyl group, perbromo-1-naphthyl group Perbromo-2-naphthyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,4-diiodophenyl group, 2,6-diiodophenyl group, 3,4-diiodo Phenyl group, 3,5-diiodophenyl group, 2,4,6-triiodophenyl group, 3,4,5-triiodophenyl group, 2,3,5,6-tetraiodophenyl group, pentaiodophenyl Group, 2,3,5,6-tetraiodo-4-triiodomethylphenyl group, 2,3,5,6-tetraiodo-4-pentaiodophenylphenyl group, A do-1-naphthyl group, a periodo-2-naphthyl group, etc. are mentioned.

  Specific examples of the (halogenated alkyl) aryl group include 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6-bis (tri Fluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 3,4,5-tris (trifluoromethyl) phenyl group, etc. Can be mentioned.

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

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

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

R ⁶ is preferably a halogenated hydrocarbyl group, more preferably a halogenated alkyl group or a halogenated aryl group. More preferably, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2-trimethyl Fluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-tri Fluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoro Methylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-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 a pentachlorophenyl group, particularly preferably a fluoroalkyl group or a fluoroaryl group, and most preferably a trialkyl group. Fluoromethyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 3,5-difluorophenyl group , 3,4,5-trifluorophenyl group or pentafluorophenyl group.

R ⁷ in the general formula [6] represents a hydrocarbyl group or a halogenated hydrocarbyl group. The hydrocarbyl group in R ⁷ is preferably an alkyl group, an aryl group, or an aralkyl group, and the same hydrocarbyl group as described for L ² in the general formula [4] is used. Examples of the halogenated hydrocarbyl group in R ⁷ include a halogenated alkyl group, a halogenated aryl group, and a (halogenated alkyl) aryl group. Specific examples of the electron-withdrawing group in R ⁶ of the general formula [5] The same halogenated alkyl group, halogenated aryl group, and (halogenated alkyl) aryl group as those mentioned as examples are used.

R ⁷ in the general formula [6] is preferably a halogenated hydrocarbyl group, and more preferably a fluorinated hydrocarbyl group.

As the compound (a) used for obtaining the modified particles (I), when M ² is a zinc atom, for example, dimethyl zinc, diethyl zinc, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc, Dialkyl zinc such as di-n-hexyl zinc, diphenyl zinc, dinaphthyl zinc, and diaryl zinc such as bis (pentafluorophenyl) zinc, dialkenyl zinc such as diallyl zinc, bis (cyclopentadienyl) zinc, methyl zinc chloride, Ethyl zinc chloride, propyl zinc chloride, 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 N-hexylzinc bromide, methylzinc iodide, ethylzinc iodide, propylzinc iodide, n-iodide Examples include zinc halides such as butyl zinc, isobutyl zinc iodide, and n-hexyl zinc iodide, and zinc halides such as zinc fluoride, zinc chloride, zinc bromide, and 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.

  Specific examples of the compound (b) include amines such as di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, di (iodomethyl) amine, bis (difluoromethyl) amine, bis (Dichloromethyl) amine, bis (dibromomethyl) amine, bis (diiodomethyl) amine, bis (trifluoromethyl) amine, bis (trichloromethyl) amine, bis (tribromomethyl) amine, bis (triiodomethyl) amine, Bis (2,2,2-trifluoroethyl) amine, bis (2,2,2-trichloroethyl) amine, bis (2,2,2-tribromoethyl) amine, bis (2,2,2-trimethyl) Iodoethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine, bis (2,2,3,3) 3-pentachloropropyl) amine, bis (2,2,3,3,3-pentabromopropyl) amine, bis (2,2,3,3,3-pentaiodopropyl) amine, bis (2,2, 2-trifluoro-1-trifluoromethylethyl) amine, bis (2,2,2-trichloro-1-trichloromethylethyl) amine, bis (2,2,2-tribromo-1-tribromomethylethyl) amine Bis (2,2,2-triiodo-1-triiodomethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine, bis (1,1 -Bis (trichloromethyl) -2,2,2-trichloroethyl) amine, bis (1,1-bis (tribromomethyl) -2,2,2-tribromoethyl) amine, bis (1,1 Bis (triiodomethyl) -2,2,2-triiodoethyl) amine, bis (2-fluorophenyl) amine, bis (3-fluorophenyl) amine, bis (4-fluorophenyl) amine, bis (2- Chlorophenyl) amine, bis (3-chlorophenyl) amine, bis (4-chlorophenyl) amine, bis (2-bromophenyl) amine, bis (3-bromophenyl) amine, bis (4-bromophenyl) amine, bis (2 -Iodophenyl) amine, bis (3-iodophenyl) amine, bis (4-iodophenyl) amine, bis (2,6-difluorophenyl) amine, bis (3,5-difluorophenyl) amine, bis (2, 6-dichlorophenyl) amine, bis (3,5-dichlorophenyl) amine, bis (2,6-dibromophenyl) Enyl) amine, bis (3,5-dibromophenyl) amine, bis (2,6-diiodophenyl) amine, bis (3,5-diiodophenyl) amine, bis (2,4,6-trifluorophenyl) ) Amine, bis (2,4,6-trichlorophenyl) amine, bis (2,4,6-tribromophenyl) amine, bis (2,4,6-triiodophenyl) amine, bis (3,4, 5-trifluorophenyl) amine, bis (3,4,5-trichlorophenyl) amine, bis (3,4,5-tribromophenyl) amine, bis (3,4,5-triiodophenyl) amine, bis (Pentafluorophenyl) amine, bis (pentachlorophenyl) amine, bis (pentabromophenyl) amine, bis (pentaiodophenyl) amine, bis (2- ( Trifluoromethyl) phenyl) amine, bis (3- (trifluoromethyl) phenyl) amine, bis (4- (trifluoromethyl) phenyl) amine, bis (2,6-di (trifluoromethyl) phenyl) amine, Bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-tri (trifluoromethyl) phenyl) amine, bis (3,4,5-tri (trifluoromethyl) phenyl) Amine, bis (2-cyanophenyl) amine, (3-cyanophenyl) amine, bis (4-cyanophenyl) amine, bis (2-nitrophenyl) amine, bis (3-nitrophenyl) amine, bis (4- Nitrophenyl) amine and the like. Moreover, the phosphine compound by which the nitrogen atom was substituted by the phosphorus atom can be illustrated similarly. These phosphine compounds are compounds represented by rewriting the amine of the above-mentioned specific examples to phosphine.

  Specific examples of the compound (b) include alcohols such as fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodethanol, trifluoromethanol, trichloromethanol, tribromomethanol, Triiodomethanol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2,2,2-tribromoethanol, 2,2,2-triiodoethanol, 2,2,3,3 , 3-pentafluoropropanol, 2,2,3,3,3-pentachloropropanol, 2,2,3,3,3-pentabromopropanol, 2,2,3,3,3-pentaiodopropanol, 2, , 2,2-trifluoro-1-trifluorome Ethanol, 2,2,2-trichloro-1-trichloromethylethanol, 2,2,2-tribromo-1-tribromomethylethanol, 2,2,2-triiodo-1-triiodomethylethanol, 1,1 -Bis (trifluoromethyl) -2,2,2-trifluoroethanol, 1,1-bis (trichloromethyl) -2,2,2-trichloroethanol, 1,1-bis (tribromomethyl) -2, Examples include 2,2-tribromoethanol and 1,1-bis (triiodomethyl) -2,2,2-triiodoethanol. Moreover, the thiol compound by which the oxygen atom was substituted by the sulfur atom can be illustrated similarly. These thiol compounds are compounds represented by rewriting methanol in the above specific examples to methanethiol, ethanol to ethanethiol, and propanol to propanethiol.

  Specific examples of the compound (b) include phenols such as 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, 2-chlorophenol, 3-chloro Phenol, 4-chlorophenol, 2,4-dichloropheno 2,6-dichlorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol, 2,4,6-trichlorophenol, 3,4,5-trichlorophenol, 2,3,5,6-tetrachloro Phenol, pentachlorophenol, 2,3,5,6-tetrachloro-4-trichloromethylphenol, 2,3,5,6-tetrachloro-4-pentachlorophenylphenol, perchloro-1-naphthol, perchloro-2- Naphthol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2,4-dibromophenol, 2,6-dibromophenol, 3,4-dibromophenol, 3,5-dibromophenol, 2,4,6 -Tribromophenol, 3,4,5-tribromophenol, 2,3,5,6- Trabromophenol, pentabromophenol, 2,3,5,6-tetrabromo-4-tribromomethylphenol, 2,3,5,6-tetrabromo-4-pentabromophenylphenol, perbromo-1-naphthol, perbromo- 2-naphthol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,4-diiodophenol, 2,6-diiodophenol, 3,4-diiodophenol, 3,5-diiodophenol 2,4,6-triiodophenol, 3,4,5-triiodophenol, 2,3,5,6-tetraiodophenol, pentaiodophenol, 2,3,5,6-tetraiodo-4-tri Iodomethylphenol, 2,3,5,6-tetraiodo-4-pentaiodophenylphenol , Period-1-naphthol, period-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, 3,4,5-tris (trifluoromethyl) phenol, 2-cyanophenol, 3-cyano Phenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol and the like can be mentioned. Moreover, the thiophenol compound by which the oxygen atom was substituted by the sulfur atom can be illustrated similarly. These thiophenol compounds are compounds represented by rewriting phenol of the above-mentioned specific examples with thiophenol.

  The compound (b) is preferably a bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine. ) Amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine, or bis (Pentafluorophenyl) amine and alcohols include trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1 -Trifluoromethylethanol, or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, phenols Are 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol , Pentafluorophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis ( Trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol, or 3,4,5-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 (tri Fluoromethyl) 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 amine, n-octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, and n-eicosylamine, aralkylamines such as allylamine, cyclopentadienylamine, and benzylamine, fluoro Methylamine, difluoromethylamine, trifluoromethylamine, 2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine, 2,2,2-trifluoro-1-trifluoro Methylethylamine, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, perfluorooctylamine, perfluoro Dodecylamine, perfluoropentadecylamine, perfluoroeicosylamine, and halogenated alkylamines in which “fluoro” of these amines is replaced with “chloro”, “bromo”, or “iodo”.

  Examples of the aniline compound of 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, pentaethylaniline, and their "ethyl" are "n-propyl", "isopropyl", "n-butyl", "sec-butyl", " tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, Alkylaniline substituted with “n-tetradecyl”, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, Halogenated anilines such as 3,4,5-trifluoroaniline and pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6 -Di (trifluoromethyl) aniline, 3,5-di (trifluoromethyl) aniline, 2,4,6-tri (trifluoromethyl) aniline, and their “fluoro” are “chloro”, “bromo” Or (halogenated alkyl) aniline substituted with “iodo”.

  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.

  Examples of (d) include inorganic oxide particles and organic polymer particles. Among them, porous particles having a uniform particle size generally used as a carrier are preferable. As the particle size distribution of (d), from the viewpoint of the particle size distribution of the resulting addition polymer, the volume standard geometric standard deviation of the particle size of (d) is preferably 2.5 or less, more preferably It is 2.0 or less, More preferably, it is 1.7 or less.

As the inorganic oxide particles (d), any inorganic oxide may be used, and a plurality of inorganic substances may be mixed and 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 _{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 and the like. These inorganic oxides are preferably SiO ₂ and / or Al ₂ O ₃ , and particularly preferably SiO ₂ (ie, silica). The inorganic oxide includes 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.

  The inorganic oxide is preferably dried to substantially remove moisture, and the drying method is preferably heat drying. The drying temperature is usually 100 to 1500 ° C., preferably 100 to 1000 ° C., more preferably 200 to 800 ° C. for inorganic oxides whose moisture cannot be visually confirmed. The drying time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. As a method for heating and drying the inorganic oxide, for example, a method of drying an inorganic oxide by flowing an inert gas (for example, nitrogen or argon) dried during heating at a constant flow rate, or under reduced pressure. Examples include a method of heating and drying the inorganic oxide.

  Inorganic oxides usually have hydroxy groups formed on the surface, but modified inorganic oxides in which active hydrogens on the surface hydroxy groups are substituted with various substituents can be used as inorganic oxides. Good. Examples of the modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane, triarylchlorosilanes such as triphenylchlorosilane, dialkyldichlorosilanes such as dimethyldichlorosilane, and diaryldichlorosilanes such as diphenyldichlorosilane. Alkyltrichlorosilanes such as methyltrichlorosilane, aryltrichlorosilanes such as phenyltrichlorosilane, trialkylalkoxysilanes such as trimethylmethoxysilane, triarylalkoxysilanes such as triphenylmethoxysilane, and dialkyldialkoxysilanes such as dimethyldimethoxysilane , Diaryldialkoxysilanes such as diphenyldimethoxysilane, and alkyltols such as methyltrimethoxysilane Alkoxysilane, aryltrialkoxysilane such as phenyltrimethoxysilane, tetraalkoxysilane such as tetramethoxysilane, alkyldisilazane such as 1,1,1,3,3,3-hexamethyldisilazane, tetrachlorosilane, methanol and Inorganic oxides contact-treated with alcohols such as ethanol, dialkylmagnesium such as phenol, dibutylmagnesium, butylethylmagnesium and butyloctylmagnesium, and alkyllithiums such as butyllithium.

  Furthermore, the inorganic oxide which contact-treated the inorganic oxide contacted with the trialkylaluminum with dialkylamine, such as diethylamine and diphenylamine, alcohol, such as methanol and ethanol, and phenol is mentioned.

  Inorganic oxides may have increased strength due to hydrogen bonding between hydroxy groups. In that case, if all active hydrogens on the surface hydroxy group are substituted with various substituents, the particle strength may be lowered. Therefore, it is not always necessary to replace all active hydrogens on the surface hydroxy groups of the inorganic oxide, and the substitution rate of the surface hydroxy groups may be determined as appropriate. The method for changing the substitution rate of the surface hydroxy group is not particularly limited. Examples of the method include a method of changing the amount of the compound used for the contact treatment.

The average particle diameter of the inorganic oxide particles is not particularly limited, but is usually 1 to 5000 μm, preferably 5 to 1000 μm, more preferably 10 to 500 μm, and still more preferably 10 to 100 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 a 10 to 1000 m ² / g, more preferably 100 to 500 m ² / g.

  Any organic polymer may be used for the organic polymer particles of (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 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, Examples thereof include a sulfinic acid group, a sulfenic acid group, a thiol group, a thioformyl group, a pyrrolyl group, an imidazolyl group, a piperidyl group, an indazolyl group, and a carbazolyl group. Preferred are primary amino group, secondary amino group, imino group, amide group, imide group, hydroxy group, formyl group, carboxyl group, sulfonic acid group or thiol group, and particularly preferred are primary amino group, 2 A primary amino group, an amide group or a hydroxy group. These groups may be substituted with a halogen atom or a hydrocarbyl 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 pyridyl group, N-substituted imidazolyl group, N-substituted indazolyl group, nitrile group, azide group, N-substituted imino group, N, N-substituted amino group, and N, N-substituted aminooxy. 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 group, substituted sulfonyl group, and substituted sulfonic acid group. 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 hydrocarbyl 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 organic polymer is not particularly limited. The content thereof 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 gram of the organic polymer.

  Examples of the method for producing an organic polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group include, for example, a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and one or more. And a method of homopolymerizing a monomer having a polymerizable unsaturated group, or 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 monomers having a functional group having active hydrogen and one or more polymerizable unsaturated groups include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amide compounds, and vinyl group-containing hydroxy compounds. Is mentioned. Examples of the monomer include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, and N- (2-propenyl) -N-methylamine. 1-ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-buten-1-ol Is mentioned. Examples of monomers having a functional group having a Lewis base having no active hydrogen atom and one or more polymerizable unsaturated groups include vinyl pyridine, vinyl (N-substituted) imidazole, and vinyl (N-substituted) indazole. Is mentioned.

  Examples of the other monomer having a polymerizable unsaturated group include ethylene, α-olefin, aromatic vinyl compound and cyclic olefin compound. Examples of the monomer include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, styrene, norbornene, and dicyclopentadiene. Preferred is ethylene or styrene. Two or more of these monomers may be used. Examples of the crosslinkable polymerizable monomer having two or more polymerizable unsaturated groups include divinylbenzene.

The average particle diameter of the organic polymer particles is not particularly limited, but is usually 1 to 5000 μm, preferably 5 to 1000 μm, and more preferably 10 to 500 μm. Although it does not specifically limit as pore volume, Preferably it is 0.1 ml / g or more, More preferably, it is 0.3-10 ml / g. Although it does not specifically limit as a specific surface area, Preferably it is 10-1000 m < ² > / g, More preferably, it is 50-500 m < ² > / g.

  These organic polymer particles are preferably dried and substantially free of moisture, and those dried by heat drying are preferred. The drying temperature is usually 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, and more preferably 1 hour to 30 hours. Examples of the method for heating and drying the organic polymer particles include a method in which an inert gas (for example, nitrogen or argon) dried while heating the organic polymer is circulated at a constant flow rate, or the organic polymer particles are dried. The method etc. which heat-dry under reduced pressure are mentioned.

In order to obtain the modified particles (I) of the present invention, the order in which the above components (a), (b), (c) and (d) are contacted 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>.

  Such contact treatment is preferably performed 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. Such treatment may use a solvent, or may directly contact these compounds without using a solvent.

  As the solvent, a solvent inert to the above-mentioned compounds (a), (b), (c), (d) and their contact products is used. However, as described above, when each compound is brought into contact in stages, even if the solvent reacts with a compound at one stage, the solvent is not a solvent that reacts with each compound at another stage. The solvent can be used at 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, and nitrile solvents. Examples include solvents, nitro compounds, amine solvents, and polar solvents such as sulfur compounds. For example, aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane, aromatic hydrocarbon solvents such as benzene, toluene, xylene, dichloromethane, difluoromethane, chloroform, Halide solvents such as 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, tetra Ether solvents such as dropyran, 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, alcohol solvents such as glycerin, phenol solvents such as phenol, p-cresol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, Carbonyl solvents such as ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethyl Phosphoric acid derivatives such as luric acid triamide and phosphoric acid triethyl, nitrile solvents such as acetonitrile, propionitrile, succinonitrile and benzonitrile, 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 (f) obtained by bringing the compounds (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 (f) is preferably the above-mentioned aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether solvent.

A polar solvent is preferable as the solvent (s2) when the contact product (f) 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 (f) obtained by bringing the compounds (a), (b) and (c) into contact with (d), that is, the above-mentioned <1>, <3>, <7> In each method, a hydrocarbon solvent can be used as both the solvent (s1) and the solvent (s2). In this case, after the compounds (a), (b) and (c) are contacted, it is preferable that the time until the obtained contact product (f) 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. The temperature when the contact product (f) and the particles (d) are contacted is usually -100 ° C to 40 ° C, preferably -20 ° C to 20 ° C, and most preferably -10 ° C to 10 ° C.

  In the case of <2>, <5>, <6>, <8>, <9>, <10>, <11>, <12>, 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. This is because it is considered that the contact product produced is deposited on the surface of (d) and is more easily immobilized when (d) is present in the reaction system when these contact products are produced. is there.

The amount of each compound (a), (b), (c) used is not particularly limited, but the molar ratio of the amount of each compound used is (a) :( b) :( c) = 1: y: z It is preferable that y and z substantially satisfy the following formula (1).
| My-2z | <1 (1)
(In the above formula (1), m represents the valence of M ^3. )
In the above formula (1), y is preferably a number of 0.01 to 1.99, more preferably a number of 0.10 to 1.80, and still more preferably a number of 0.20 to 1.50. Yes, most preferably a number from 0.30 to 1.00, and the same preferred range of z in the above formula (1) is determined by m, y and the above formula (1).

  The amount of the compounds (a) and (d) used is such that a typical metal atom derived from the compound (a) contained in the modified particle (I) is contained in 1 g of the resulting modified particle (I). The amount of typical metal atoms is preferably 0.05 mmol or more, and more preferably 0.1 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 (I), as a result of such contact treatment, the starting compounds (a), (b), (c) and / or (d) may remain as unreacted substances. . However, it is preferred to wash the resulting modified particles (I) to remove unreacted material from the resulting modified particles (I). The solvent used when washing the modified particles (I) may be the same as or different from the solvent used when producing the modified particles (I). It is preferable to wash the modified particles (I) under an inert gas atmosphere. The washing temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The washing time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  In addition, during the above washing treatment, the modified particles (I) in the solvent are allowed to settle, and the amorphous solvent or fine powder particles are suspended in the upper part of the slurry. It is preferable to obtain modified particles (I) having a uniform shape.

  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., and 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 (I) are as follows: M ³ is a zinc atom, compound (b) is 3,4,5-trifluorophenol, and compound (c) is water, The case where (d) is silica will be described in more detail below. Tetrahydrofuran is used as a solvent, and a hexane solution of diethylzinc is added thereto, followed by cooling to 3 ° C., and an equimolar amount of 3,4,5-trifluorophenol is added dropwise thereto relative to diethylzinc for 10 minutes at room temperature. After stirring for 24 hours, 0.5 times molar amount of water is further added dropwise 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 (I) of the present invention can be produced.

As the aluminoxane (e) used for the preparation of the modified particles (II), a cyclic aluminoxane having a structure represented by the general formula {—Al (E ¹ ) —O—} _c and / or the general formula E ² A linear aluminoxane having a structure represented by {—Al (E ² ) —O—} _d AlE ² ₂ is preferably used.
(However, E ¹ and E ² are each a hydrocarbyl group, and all E ¹ and all E ² may be the same or different. C is a number of 2 or more, d is Represents a number of 1 or more.)
As a hydrocarbyl group in E < ¹ > or E < ² >, a C1-C8 hydrocarbyl group is preferable and an alkyl group is more preferable.

Specific examples of E ¹ and E ² include alkyl groups such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group, and neopentyl group. c is a number of 2 or more, and d is a number of 1 or more. Preferably, E ¹ and E ² are a methyl group or an isobutyl group, c is 2 to 40, and d is 1 to 40.

  The above aluminoxane can be made by various methods. There is no restriction | limiting in particular about the method, What is necessary is just to make according to a well-known method. For example, a solution in which a trialkylaluminum (eg, trimethylaluminum) is dissolved in a suitable organic solvent (benzene, aliphatic hydrocarbyl, etc.) can be made by contacting with water. Moreover, the method of making the metal salt (for example, copper sulfate hydrate etc.) containing crystal water contact the trialkylaluminum (for example, trimethylaluminum etc.) can be illustrated. The aluminoxane obtained by such a method is usually considered to be a mixture of a cyclic aluminoxane and a linear aluminoxane.

  The particles (d) used for obtaining the modified particles (II) are the same particles as (d) used for the modified particles (I).

The modified particles (II) can be produced by contacting the aluminoxane (e) and the particles (d) by any method. Specifically, modified particles (II) can be produced by dispersing particles (d) in a solvent and adding aluminoxane (e) thereto.
As the solvent in this case, any of the solvents described in the description of the method for producing the modified particles (I) can be used, and a solvent that does not react with the aluminoxane (e) is preferable, and the solvent that dissolves the aluminoxane (e). Is more preferable. Specifically, an aromatic hydrocarbyl solvent such as toluene or xylene or an aliphatic hydrocarbyl solvent such as hexane, heptane, or octane is preferable, and toluene or xylene is more preferable.

  The temperature and time for bringing the aluminoxane (e) into contact with the particles (d) can be arbitrarily selected, but the temperature is usually −100 ° C. to 200 ° C., preferably −50 ° C. to 150 ° C., more preferably −20 ° C. to 120 ° C. In particular, it is preferable to react these at a low temperature in order to suppress heat generation at the initial stage of the reaction. The amount of contact between the aluminoxane (e) and the particles (d) is arbitrary, but the aluminoxane (e) per unit gram of the particles (d) is usually 0.01 to 100 mmol, preferably 0.1 -20 mmol, more preferably 1-10 mmol.

The modified particles (III) are obtained using a transition metal compound during the preparation of the modified particles (II).
As the transition metal compound, the transition metal compound represented by the above general formula [3] or its μ-oxo type transition metal compound dimer (A) is used.
The modified particles (III) can be obtained by contacting the aluminoxane (e), the particles (d) and the transition metal compound by any method. It is preferable to use a solvent when contacting the aluminoxane (e), the particles (d) and the transition metal compound. Any of the solvents described above can be used as the solvent, and a solvent that does not react with the aluminoxane (e) and the transition metal compound is preferable, and a solvent that dissolves the aluminoxane (e) and the transition metal compound is more preferable. Specifically, an aromatic hydrocarbyl solvent such as toluene or xylene or an aliphatic hydrocarbyl solvent such as hexane, heptane, or octane is preferable, and toluene or xylene is more preferable.

  The temperature and time for contacting the aluminoxane (e), the particles (d) and the transition metal compound are arbitrary, but the temperature is usually -100 ° C to 200 ° C, preferably -50 ° C to 150 ° C, more preferably -20 ° C. ~ 120 ° C. In particular, it is preferable to react these at a low temperature in order to suppress heat generation at the initial stage of the reaction. The amount in which the aluminoxane (e), the particles (d) and the transition metal compound are brought into contact with each other is arbitrary, but the aluminoxane (e) per unit gram of the particles (d) is usually 0.01 to 100 mmol in terms of aluminum atoms, preferably It is 0.1-20 mmol, More preferably, it is 1-10 mmol. Moreover, the transition metal compound per unit gram of the particles (d) is usually 0.1 to 1000 μmol, preferably 1 to 500 μmol, more preferably 10 to 200 μmol in terms of transition metal atom.

Organoaluminum compound (C)
The organoaluminum compound (C) used in the present invention is a known organoaluminum compound. An organoaluminum compound represented by the following general formula [9] is preferable.
R ¹⁰ _d AlY _3-d [9]
(Wherein R ¹⁰ represents a hydrocarbyl group, and all R ¹⁰ may be the same or different. Y represents a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, or an aryloxy group. And all Y may be the same or different, and d represents a number satisfying 0 <d ≦ 3.)

R ¹⁰ in the general formula [9] is preferably a hydrocarbyl group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, 2-methylhexyl group, n-octyl group and the like, preferably ethyl group, n -A butyl group, an isobutyl group, an n-hexyl group or an n-octyl group.

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

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

  The aralkyloxy group in Y is preferably an aralkyloxy group having 7 to 24 carbon atoms. Specific examples include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4 -Methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, 2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6- Limethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy Group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group , (Tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group , Anthracenylmethoxy group and the like, preferably a benzyloxy group That.

  Specific examples of the organoaluminum compound represented by the general formula [9] include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri -Trialkylaluminum such as n-octylaluminum; Dialkylaluminum such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride Chloride: methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, n-butylaluminium Alkyl aluminum dichlorides such as dichloride, isobutyl aluminum dichloride, n-hexyl aluminum dichloride; dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, di-n-hexyl Dialkyl aluminum hydrides such as aluminum hydride; alkyl (dialkoxy) aluminum such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, methyl (di-tert-butoxy) aluminum; dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, Dials such as dimethyl (tert-butoxy) aluminum Alkyl (diaryloxy) aluminum such as methyl (diphenoxy) aluminum, methylbis (2,6-diisopropylphenoxy) aluminum, methylbis (2,6-diphenylphenoxy) aluminum; dimethyl (phenoxy) aluminum, dimethyl ( Examples include dialkyl (aryloxy) aluminum such as 2,6-diisopropylphenoxy) aluminum and dimethyl (2,6-diphenylphenoxy) aluminum.

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

Electron donating compound (D)
When the prepolymerized addition polymerization catalyst component of the present invention is produced, when the compound (A), the activator (B), and optionally the organoaluminum compound (C) are contacted, an electron donating compound (D ) May be brought into contact with these.
In the production of the addition polymer of the present invention, the compound (A), the activator (B), and optionally the organoaluminum compound (C) are contacted with the electron donating compound (D). You may make it contact.
When producing the addition polymer of the present invention, the prepolymerized addition polymerization catalyst component and the electron donating compound (D) may be contacted.
The electron-donating compound (D) is preferably a compound containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, and examples thereof include an oxygen-containing compound, a nitrogen-containing compound, a phosphorus-containing compound and a sulfur-containing compound. Compounds or nitrogen-containing compounds are preferred. Examples of the oxygen-containing compound include alkoxysilanes, ethers, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, acid amides of organic acids or inorganic acids, acid anhydrides, and the like. Of these, alkoxysilanes or ethers are preferred. Examples of the nitrogen-containing compound include amines, nitriles, isocyanates, and the like, and amines are preferable.

The alkoxysilanes of the general formula _R ¹¹ _r Si ^{(OR 12)} in _4-r ^{(wherein, R 11} represents a hydrocarbyl group, a hydrogen atom or a hetero atom-containing substituent group having a carbon number 1 to 20, R ¹² represents a hydrocarbyl group having 1 to 20 carbon atoms, and r represents a number satisfying 0 ≦ r <4, and all R ¹¹ and all R ¹² may be the same or different. The alkoxysilane compound represented by this is preferably used.

When R ¹¹ or R ¹² is a hydrocarbyl group, a linear alkyl group such as methyl group, ethyl group, propyl group, butyl group or pentyl group, isopropyl group, sec-butyl group, tert-butyl group, tert- Examples thereof include branched alkyl groups such as amyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, cycloalkenyl groups such as cyclopentenyl group, and aryl groups such as phenyl group and tolyl group. When R ¹¹ is a heteroatom-containing substituent, examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. Specifically, dimethylamino group, methylethylamino group, diethylamino group, ethyl n-propylamino group, di-n-propylamino group, pyrrolyl group, pyridyl group, pyrrolidinyl group, piperidyl group, perhydroindolyl group, perhydro Examples thereof include an isoindolyl group, a perhydroquinolyl group, a perhydroisoquinolyl group, a perhydrocarbazolyl group, a perhydroacridinyl group, a furyl group, a pyranyl group, a perhydrofuryl group, and a thienyl group.
As alkoxysilanes, R ¹¹ and R ¹² are preferably alkyl groups, and r is preferably a number satisfying 4> r ≧ 2.

  Specific examples of the alkoxysilanes include tetramethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, normalpropyltrimethoxysilane, isopropyltrimethoxysilane, normalbutyltrimethoxysilane, isobutyltrimethoxysilane, sec-butyltrimethyl. Methoxysilane, tert-butyltrimethoxysilane, normal pentyltrimethoxysilane, tert-amyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dinormalbutyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, methyl Ethyl dimethoxysilane, methyl normal propyl dimethoxy silane, methyl normal butyl dimethoxy silane, methyl isobutyl Methoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylnormalpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butylnormalbutyldimethoxysilane, tert-butylisobutyldimethoxysilane, tert-amyl Methyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amylnormalpropyldimethoxysilane, tert-amylnormalbutyldimethoxysilane, isobutylisopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylmethyldimethoxysilane, cyclobutylethyldimethoxysilane, Cyclobutylisopropyldimethoxysilane, cyclobutylnor Rubutyldimethoxysilane, cyclobutylisobutyldimethoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylnormalpropyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylnormalbutyldimethoxysilane, cyclopentylisobutyldimethoxysilane , Cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylnormalpropyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylnormalbutyldimethoxysilane, silane Cyclohexyl isobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylethyldimethoxysilane, phenylnormalpropyldimethoxysilane, phenylisopropyldimethoxysilane, phenyl Normal butyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, 2-norbornanemethyldimethoxysilane, bis (perhydroquinolino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, (Perhydroquinolino) Hydroisoquinolino) dimethoxysilane, (perhydroquinolino) methyldimethoxysilane, (perhydroisoquinolino) methyldimethoxysilane, (perhydroquinolino) ethyldimethoxysilane, (perhydroisoquinolino) ethyldimethoxysilane, Hydroquinolino) (n-propyl) dimethoxysilane, (perhydroisoquinolino) (n-propyl) dimethoxysilane, ((perhydroquinolino) (tert-butyl) dimethoxysilane, (perhydroisoquinolino) (tert- Butyl) dimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, trinormalpropylmethoxysilane, triisopropylmethoxysilane, trinormalbutylmethoxysilane, triisobutylmethoxysilane, tri-t rt- butyl methoxysilane, and the like. Examples thereof also include compounds in which methoxy in these compounds is replaced with ethoxy, propoxy, normal butoxy, isobutoxy, tert-butoxy, or phenoxy. Dialkyl dialkoxy silane or trialkyl monoalkoxy silane is preferable, and trialkyl monoalkoxy silane is more preferable.

  Examples of ethers include dialkyl ethers, alkylaryl ethers, diaryl ethers, diether compounds, cyclic ethers and cyclic diethers.

  Specific examples include dimethyl ether, diethyl ether, dinormal propyl ether, diisopropyl ether, dinormal butyl ether, diisobutyl ether, di-tert-butyl ether, dicyclohexyl ether, diphenyl ether, methyl ethyl ether, methyl normal propyl ether, methyl isopropyl ether, methyl. Normal butyl ether, methyl isobutyl ether, methyl tert-butyl ether, methyl cyclohexyl ether, methyl phenyl ether, ethylene oxide, propylene oxide, oxetane, tetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1, 2-diethoxyethane, 1,2-diisobutoxyethane, , 2-dimethoxypropane, 1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl- 1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2, 2-dipropyl-1,3-dimethoxypropane, 2-isopropyl 2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1 , 3-dimethoxypropane, 1,2-dimethoxybenzene, 1.3-dimethoxybenzene, 1,4-dimethoxybenzene, 1,3-dioxolane, 1,4-dioxane, 1,3-dioxane, and the like. it can. Preferred are diethyl ether, dinormal butyl ether, methyl normal butyl ether, methyl phenyl ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, 1,3-dioxolane, and more preferred are diethyl ether and dinormal butyl ether. Or tetrahydrofuran.

  Specific examples of the carboxylic acid esters include mono- and polyvalent carboxylic acid esters, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, aromatics. Carboxylic acid esters can be mentioned. Specific examples include methyl acetate, ethyl acetate, normal butyl acetate, isobutyl acetate, tert-butyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, Methyl benzoate, ethyl benzoate, normal butyl benzoate, isobutyl benzoate, tert-butyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, dimethyl succinate, diethyl succinate, succinic acid Dinormal butyl, dimethyl malonate, diethyl malonate, dinormal butyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dinormal butyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, phthalate Diethyl phthalate, dinormal phthalate, diisopropyl phthalate, dinormal butyl phthalate, diisobutyl phthalate, di-tert-butyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, diphthalate Normal octyl, di (2-ethylhexyl) phthalate, diisodecyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, dimethyl isophthalate, diethyl isophthalate, dinormal butyl isophthalate, diisobutyl isophthalate, di-tert-butyl isophthalate, Examples thereof include dimethyl terephthalate, diethyl terephthalate, di-normal butyl terephthalate, diisobutyl terephthalate, and di-tert-butyl terephthalate. Preferred are methyl acetate, ethyl acetate, methyl benzoate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, di-normal butyl phthalate, diisobutyl phthalate, dimethyl terephthalate or diethyl terephthalate, more preferably benzoic acid Methyl, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate or dimethyl terephthalate.

  Examples of amines include trihydrocarbylamine, and examples include trimethylamine, triethylamine, tripropylamine, trinormalbutylamine, triisobutylamine, trihexylamine, trioctylamine, tridodecylamine, and triphenylamine. Triethylamine or trioctylamine is preferable.

  As the electron donating compound (D), alkoxysilanes, ethers or amines are preferably used. Furthermore, amines are more preferably used. These electron donating compounds (D) may be used alone or in combination of two or more.

The method for producing an addition polymer of the present invention includes the following four methods.
(1) Method for producing an addition polymer by addition polymerization of a monomer in the presence of a catalyst in the cleaned reactor of the present invention (2) Prepolymerization of the monomer in the presence of a catalyst in the cleaned reactor of the present invention To obtain a prepolymerized addition polymerization catalyst component, and to produce an addition polymer by addition polymerization of monomers in the presence of the prepolymerized addition polymerization catalyst component in a reactor separate from the washed reactor (3) A prepolymerized addition polymerization catalyst component is obtained by prepolymerizing the monomer in the presence of a catalyst in a reactor different from the washed reactor of the present invention, and the prepolymerization is performed in the washed reactor of the present invention. (4) Prepolymerized addition polymerization by prepolymerizing a monomer in the presence of a catalyst in the washed reactor of the present invention in the presence of a spent addition polymerization catalyst component Obtaining the catalyst component, cleaning of the present invention The presence of the prepolymerized spent addition polymerization catalyst component in a reactor, a method of producing an addition polymer of a monomer addition polymerization to

Catalyst The catalyst according to the present invention is obtained by bringing the compound (A), the activator (B), and, if necessary, the organoaluminum compound (C) into contact with each other. As the contact amount ratio of each component, the contact amount of the compound (A) is usually 0.1 to 1000 μmol / g, preferably 1 to 500 μmol / g with respect to the activator (B). Preferably it is 10-300 micromol / g. The contact amount of the organoaluminum (C) is usually 0.01 to 10000 mmol / g, preferably 0.1 to 1000 mmol / g, more preferably 0.5 to 200 mmol / g with respect to the compound (A). It is.

Although the method of making a compound (A), an activator (B), and an organoaluminum compound (C) contact is not specifically limited, For example, the method of following <1>-<3> is mentioned.
<1> A method in which a contact product obtained by bringing the above components into contact with each other is introduced into a polymerization tank.
<2> A method in which each of the above components is separately supplied to a polymerization tank and brought into contact with the polymerization tank.
<3> A method in which a part of each of the above components is brought into contact with each other before being introduced into the polymerization tank to obtain a preliminary contact product, and the preliminary contact product and the remaining components are contacted in the polymerization tank.
The contact method is preferably <2> described above. The compound (A) may be charged into the polymerization tank in a slurry state in which the compound (A) is suspended in a powder or solvent.

The order in which the compound (A), the activator (B) and the organoaluminum compound (C) are brought into contact with each other is not particularly limited, and examples thereof include the following order <4> to <9>.
<4> A contact product obtained by bringing the compound (A) and the activator (B) into contact with the organoaluminum compound (C).
<5> A contact product obtained by bringing the compound (A) and the organoaluminum compound (C) into contact with the activator (B).
<6> The contact product obtained by bringing the activator (B) and the organoaluminum compound (C) into contact with the compound (A).
<7> A contact product obtained by contacting the compound (A) and the organoaluminum compound (C), and a contact product obtained by contacting the activator (B) and the organoaluminum compound (C). Make contact.
<8> A contact product obtained by contacting the compound (A) and the activator (B), and a contact product obtained by contacting the activator (B) and the organoaluminum compound (C). Make contact.
<9> A contact product obtained by bringing the compound (A) into contact with the organoaluminum compound (C) and a contact product obtained by bringing the compound (A) into contact with the activator (B) are brought into contact with each other. .
The contact order is preferably <4> described above.

In addition, when the components are brought into contact with each other, a solvent may be used. It is preferable to use a solvent because active sites can be efficiently formed. As a solvent used in the contact, any solvent that does not deactivate the generated active sites may be used. Further, a solvent in which the component (A) is dissolved is more preferable. Specifically, an aliphatic hydrocarbon solvent such as butane, pentane, hexane, and octane, and an aromatic hydrocarbon solvent such as benzene, toluene, and xylene, and dichloromethane are used. Polar solvents such as halogenated hydrocarbon solvents, ethers, esters and ketones can also be used.
When used for polymerization for forming particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.), a solvent in which the produced addition polymer does not dissolve is preferable, and specifically, an aliphatic hydrocarbon solvent is preferable. Moreover, the monomer may exist at the time of contact.

  The temperature at the time of contacting each component can be arbitrarily set. Usually, −50 ° C. to 100 ° C., preferably −30 ° C. to 80 ° C., more preferably −10 ° C. to 60 ° C. is preferable. The contact time can be arbitrarily set. Usually, it is continuously charged (substantially 0 minutes) to 24 hours, preferably 1 minute to 12 hours, more preferably 3 minutes to 10 hours.

  It is preferable to perform stirring when contacting each component.

The prepolymerization method and the prepolymerized addition polymerization catalyst component prepolymerization method are not particularly limited, but solution polymerization using a solvent, slurry polymerization and the like are preferable. Examples of the polymerization solvent used in the prepolymerization method in the presence of a catalyst include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane, 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, and the polymerization may be performed in two or more stages with different reaction conditions. In general, the polymerization time is appropriately determined depending on the kind of the target olefin polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours. The prepolymerization temperature is usually −50 ° C. to 100 ° C., preferably −30 ° C. to 80 ° C., more preferably −10 ° C. to 60 ° C. Moreover, you may change temperature on the way. Moreover, the pressure at the time of prepolymerization is usually 0.001 MPa to 5 MPa, preferably 0.01 MPa to 2 MPa.

  The monomer charging method can be arbitrarily selected. 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 combinations 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, 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 prepolymerized addition polymerization catalyst component obtained may be used for the main polymerization as it is, or may be used after the following treatment. . When a prepolymerized addition polymerization catalyst component is formed by a method of prepolymerization in the presence of a solvent, the prepolymerized addition polymerization catalyst component may be used in a solution or slurry liquid state, or it is removed from a monomer or a solvent. , Filtration, washing, drying, etc. may be performed and used in the main polymerization in the 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, particularly preferably, per 1 g of component (B). The prepolymerization is carried out so as to be in the range of 1 to 100 g.

Addition polymerization method and addition polymer In the present invention, when an addition polymer is produced, a method of addition polymerization of a monomer using a catalyst and a method of addition polymerization of a monomer using a prepolymerized addition polymerization catalyst component ( Main polymerization).
When the prepolymerized addition polymerization catalyst component is used, the prepolymerized addition polymerization catalyst component may be used as it is, or the prepolymerized addition polymerization catalyst component and the organoaluminum compound (C) may be used in contact with each other. Good. The latter is preferable from the viewpoint of excellent polymerization activity. As the organoaluminum compound in the latter case, the organoaluminum compound exemplified as the compound (C) is used. When the organoaluminum compound is used in this way, the amount used is usually 1 to 10000 mol / mol, preferably 10 to 5000 mol / mol, more preferably 30 to 1000 mmol / mol, relative to the component (A). g.

  When the prepolymerized addition polymerization catalyst component and the organoaluminum compound (C) are used in contact with each other, the prepolymerized addition polymerization catalyst component and the organoaluminum compound (C) are charged into the polymerization reactor in any order during polymerization. Alternatively, they may be brought into contact with each other in advance before being used in the polymerization reactor.

  The method for supplying the prepolymerized addition polymerization catalyst component of the present invention and the organoaluminum compound (C) 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. A hydrogen solvent can be mentioned, Among these, an aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent is preferable, and an aliphatic hydrocarbon solvent is more preferable.

  Examples of the addition polymerization 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 ) Bulk polymerization using monomers as solvents can be mentioned. Polymerization solvents used for solution polymerization or slurry polymerization include, for example, 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 can 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 of the present invention is particularly suitably applied to polymerization in which an addition polymer is produced in the form of particles in the main polymerization, such as slurry polymerization, gas phase polymerization, and bulk polymerization.
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 hydrocarbyl. The medium, as well as the polymerization temperature and pressure, are selected so as to keep the catalyst in suspension, maintain the medium and at least some monomer and comonomer in the liquid phase, and allow the monomer and comonomer to contact. . 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 reactor, preferably a fluidized bed reactor having an enlarged portion. The reactor may be provided with a stirring blade in the reactor.
As a method of supplying each catalyst component to the reactor, 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 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.

  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 hydrocarbyls, and polar monomers. The above 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 hydrocals such as bisalkenylbenzene (eg divinylbenzene), alkenylnaphthalene (eg 1-vinylnaphthalene), and the like. And α, β-unsaturated carboxylic acids such as 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, Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, acrylic acid ert-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, And polar monomers such as glycidyl acrylate, 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 prepolymerized addition polymerization catalyst component of the present invention is suitably used for the 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. Elemental analysis of the modified particles used in the examples was measured by the following method.

(1) Elemental analysis Zn: The sample was poured into a sulfuric acid aqueous solution (1M), and then ultrasonic waves were applied to extract metal components. The obtained liquid portion was quantified by ICP emission spectrometry.
F: Combustion gas generated by burning a sample in a flask filled with oxygen was absorbed in an aqueous sodium hydroxide solution (10%), and the obtained aqueous solution was quantified using an ion electrode method.
(2) Melt flow rate (MFR, unit: g / 10 minutes)
In the method defined in JIS K7210-1995, measurement was performed by the A method under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(3) Swell ratio (SR)
In the measurement of the melt flow rate of (2), the strand of the ethylene polymer extruded at a length of about 15 to 20 mm from the orifice under the conditions of a temperature of 190 ° C. and a load of 21.18 N is cooled in air and solid A strand was obtained. Next, the diameter D (unit: mm) of the strand at a position of about 5 mm from the upstream end of extrusion of the strand was measured, and the value obtained by dividing the diameter D by the orifice diameter 2.095 mm (D ₀ ) (D / D ₀ ) was calculated and used as the swell ratio.

[Example 1]
(1) Cleaning the reactor for addition polymerization
Step (1) Kaoakipo RLM-100 nV in 500ml flask was substituted with nitrogen (manufactured by Kao _{Corporation, C 12 H 25 -O - (} - C 2 H 4 -O) 10 23.5% aqueous solution of -COONa) 3. 0 g was added and water was removed by drying under reduced pressure. Then, hexane was added to _200ml, C ₁₂ H ₂₅ -O _- adjusting the - _{(C 2 H} 4 -O) for 10 -COONa 5 mmol / l solution. 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, charged with 360 g of butane, and then C ₁₂ H ₂₅ —O — (— C ₂ H ₄ —O) ₁₀ —COONa prepared earlier 200 ml (1.0 mmol) of hexane solution was added and stirred at room temperature for 1 hour.
Step _{(2) C 12 H 25 -O} - and the - _{(C 2 H} 4 -O) for 10 -COONa butane solution was purged from withdrawal outlet of the autoclave.
Step (3) 800 ml of hexane was charged into the autoclave and stirred at room temperature for 15 minutes. The hexane in the autoclave was extracted out of the autoclave by inserting a tube into the autoclave and pumping it.
(2) Production of modified particles (B) In the same manner as the preparation of component (A) in Example 1 (1) and (2) of JP-A-2009-79180, Quality particles (B) were produced. As a result of elemental analysis, Zn = 11 wt% and F = 6.4 wt%.

(3) Prepolymerization The autoclave washed for the first batch was dried under reduced pressure and then replaced with argon, followed by evacuation, and 480 g of butane and 182 mg (342 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 6.8 g of the modified particles (B) obtained in (2) above were added, and then a hexane solution of triisobutylaluminum (C) adjusted to a concentration of 1.0 mmol / ml 3 0.5 ml (3.5 mmol) was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.213 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, no fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 128.5 g, and the degree of polymerization per modified particle (B) was 18.9 g / g.

(4) Prepolymerization In the second batch above (3), after the hexane slurry was extracted, the autoclave was dried under reduced pressure, replaced with argon, and then evacuated. (371 μmol) was added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 6.9 g of the modified particles (B) obtained in (2) above were added, and then a hexane solution of triisobutylaluminum (C) adjusted to a concentration of 1.0 mmol / ml 3 0.5 ml (3.5 mmol) was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.215 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a very thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 127.6 g, and the degree of polymerization per modified particle (B) was 18.4 g / g.

(5) Prepolymerization In the third batch (4) above, the autoclave after extracting the hexane slurry under reduced pressure was dried under reduced pressure, then replaced with argon, and then evacuated. 387 μmol) was added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the modified particles (B) obtained in (2) above were added, and then a hexane solution of triisobutylaluminum (C) adjusted to a concentration of 1.0 mmol / ml 3 0.5 ml (3.5 mmol) was added.
First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.222 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 117.0 g. When the autoclave was opened and the fouling adhering to the inner wall was recovered, the recovered amount of fouling was 14.9 g. The ratio of the recovered amount of fouling to the sum of the prepolymerized addition polymerization catalyst component and the recovered amount of fouling was 11.3 wt%. The degree of polymerization per modified particle (B) was 18.7 g / g.

(6) 1st batch prepolymerization catalyst main polymerization
After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 5 liters substituted with argon was evacuated, hydrogen was added at a partial pressure of 0.037 MPa, 154 g of hexene-1 and 1046 g of butane were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added 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 hydrogen = 1.93 mol%. To this, 2.0 ml of a hexane solution of triisobutylaluminum prepared at a concentration of 1 mmol / ml was added. Next, 1.0 ml of a toluene solution of triethylamine prepared at a concentration of 0.1 mmol / ml was added. Further, 391.2 mg of the prepolymerized addition polymerization catalyst component obtained in Example 1 (3) was added.
Polymerization was carried out at 70 ° C. for 3 hours while feeding an ethylene / hydrogen mixed gas (hydrogen 0.293 mol%) so as to keep the total pressure constant. As a result, 78 g of an olefin polymer was obtained. The polymerization activity per modified particle (B) was 3750 g / g. The obtained olefin polymer had MFR = 3.54 and SR = 1.47.

(7) Second batch prepolymerization catalyst Main polymerization
After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 5 liters substituted with argon was evacuated, hydrogen was added at a partial pressure of 0.037 MPa, 154 g of hexene-1 and 1046 g of butane were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added 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 hydrogen = 1.91 mol%. To this, 2.0 ml of a hexane solution of triisobutylaluminum prepared at a concentration of 1 mmol / ml was added. Next, 1.0 ml of a toluene solution of triethylamine prepared at a concentration of 0.1 mmol / ml was added. Further, 375.4 mg of the prepolymerized addition polymerization catalyst component obtained in Example 1 (4) was added.
Polymerization was carried out at 70 ° C. for 3 hours while feeding an ethylene / hydrogen mixed gas (hydrogen 0.309 mol%) so as to keep the total pressure constant. As a result, 115 g of an olefin polymer was obtained. The polymerization activity per modified particle (B) was 5650 g / g. Moreover, the obtained olefin polymer was MFR = 1.8 and SR = 1.42.

[Example 2]
(1) Cleaning the reactor for addition polymerization
Step (1) 300 mg of Chemistat 2500 (manufactured by Sanyo Chemical Industries, C ₁₂ H ₂₅ CON (C ₂ H ₄ OH) ₂ ) was added to a 500 ml flask purged with nitrogen, then 50 ml of hexane was added, and C ₁₂ H was added. A 20 mmol / l solution of ₂₅ CON (C ₂ H ₄ OH) ₂ was prepared. After drying under reduced pressure, the inside of an autoclave with a stirrer having an internal volume of 3 liters substituted with argon was evacuated, charged with 450 g of butane, and then 50 ml of a hexane solution of C ₁₂ H ₂₅ CON (C ₂ H ₄ OH) ₂ prepared previously ( 1.0 mmol) and stirred at room temperature for 1 hour.
Step (2) A butane solution of C ₁₂ H ₂₅ CON (C ₂ H ₄ OH) ₂ was purged from the outlet of the autoclave.
Step (3) 800 ml of hexane was charged into the autoclave and stirred at room temperature for 15 minutes. The hexane in the autoclave was extracted out of the autoclave by inserting a tube into the autoclave and pumping it.

(2) Preliminary polymerization After drying under reduced pressure in the first batch, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, and 480 g of butane and 181 mg (338 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. It was. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 6.9 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml. 3.5 ml (3.5 mmol) of hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.173 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a very thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 126.9 g, and the degree of polymerization per modified particle (B) was 18.3 g / g.

(3) Prepolymerization In the second batch above (2), after the hexane slurry was extracted, the autoclave was dried under reduced pressure, replaced with argon and then evacuated, and 480 g of butane and 178 mg of ethylenebis (indenyl) zirconium diphenoxide (A). (333 μmol) was added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.1 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.168 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 107.8 g. When the autoclave was opened and the fouling adhering to the inner wall was recovered, the recovered amount of fouling was 12.9 g. The ratio of the recovered amount of fouling to the sum of the prepolymerized addition polymerization catalyst component and the recovered amount of fouling was 10.7 wt%. The degree of polymerization per modified particle (B) was 17.0 g / g.

[Example 3]
(1) for addition polymerization reactor cleaning process (1) Emulgen 108 (manufactured by Kao _{Corporation, C 12 H 25 -O C 2} H 4 -O) 6 -H - - () in 500ml flask was substituted with nitrogen 450 mg was added, and then 50 ml of hexane was added to prepare a 20 mmol / l solution of C ₁₂ H ₂₅ —O — (— C ₂ H ₄ —O) ₆ —H. 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, charged with 450 g of butane, and then C ₁₂ H ₂₅ —O — (— C ₂ H ₄ —O) ₆ —H prepared previously. 50 ml (1.0 mmol) of hexane solution was added and stirred at room temperature for 1 hour.
Step (2) A butane solution of C ₁₂ H ₂₅ —O — (— C ₂ H ₄ —O) ₆ —H was purged from the outlet of the autoclave.
Step (3) 800 ml of hexane was charged into the autoclave and stirred at room temperature for 15 minutes. The hexane in the autoclave was extracted out of the autoclave by inserting a tube into the autoclave and pumping it.

(2) Preliminary polymerization After drying under reduced pressure in the first batch, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, and 480 g of butane and 211 mg (396 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. It was. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the mixture was switched to an ethylene / hydrogen mixed gas (hydrogen concentration: 0.238 mol%), and the temperature was raised to 50 ° C. over 30 minutes while feeding at 0.58 g / min, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a very thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 128.0 g, and the degree of polymerization per modified particle (B) was 18.4 g / g.

(3) Prepolymerization In the second batch, the autoclave after extracting the hexane slurry in (2) above was dried under reduced pressure and then replaced with argon, and then vacuumed. (371 μmol) was added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.237 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 106.2 g. When the autoclave was opened and the fouling adhering to the inner wall was recovered, the recovered amount of fouling was 22.4 g. The ratio of the recovered amount of fouling to the sum of the prepolymerized addition polymerization catalyst component and the recovered amount of fouling was 17.4 wt%. The degree of polymerization per modified particle (B) was 18.0 g / g.

[Example 4]
(1) for addition polymerization reactor cleaning process (1) Emal 270 J (manufactured by Kao Corporation in 500ml flask was replaced by _{nitrogen, C 12 H 25 -O - (} - C 2 H 4 -O) 2 -SO 3 Na ) was added 540 mg, then hexane was added to _{50ml, C 12 H 25 -O -} (- adjusting the _{C 2 H 4 -O) 2 -SO} 3 Na in 20 mmol / l solution. 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, charged with 450 g of butane, and then C ₁₂ H ₂₅ —O — (— C ₂ H ₄ —O) ₂ —SO prepared previously. ₃ Na hexane was added 50 ml (1.0 mmol), and stirred at room temperature for 1 hour.
Step (2) A butane solution of C ₁₂ H ₂₅ —O — (— C ₂ H ₄ —O) ₂ —SO ₃ Na was purged from the outlet of the autoclave.
Step (3) 800 ml of hexane was charged into the autoclave and stirred at room temperature for 15 minutes. The hexane in the autoclave was extracted out of the autoclave by inserting a tube into the autoclave and pumping it.

(2) Preliminary polymerization After drying under reduced pressure in the first batch, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, and 480 g of butane and 196 mg (367 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. It was. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.237 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, no fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 127.2 g, and the degree of polymerization per modified particle (B) was 18.2 g / g.

(3) Prepolymerization In the second batch above (2), after the hexane slurry was extracted, the autoclave was dried under reduced pressure, replaced with argon, and then evacuated. (383 μmol) was added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the mixture was switched to an ethylene / hydrogen mixed gas (hydrogen concentration: 0.190 mol%), and the temperature was raised to 50 ° C. over 30 minutes while feeding at 0.58 g / min, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a very thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 121.8 g. When the autoclave was opened and the fouling adhering to the inner wall was recovered, the recovered amount of fouling was 5.3 g. The ratio of the recovered amount of fouling to the sum of the prepolymerized addition polymerization catalyst component and the recovered amount of fouling was 4.2 wt%. The degree of polymerization per modified particle (B) was 18.0 g / g.

[Example 5]
(1) Cleaning the reactor for addition polymerization
Step (1) Kaoakipo RLM-100 nV in 500ml flask was substituted with nitrogen (manufactured by Kao _{Corporation, C 12 H 25 -O - (} - C 2 H 4 -O) 10 23.5% aqueous solution of -COONa) 3. 0 g was added and water was removed by drying under reduced pressure. Then, hexane was added to _200ml, C ₁₂ H ₂₅ -O _- adjusting the - _{(C 2 H} 4 -O) for 10 -COONa 5 mmol / l solution. 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, charged with 600 ml of hexane, and then C ₁₂ H ₂₅ —O — (— C ₂ H ₄ —O) ₁₀ —COONa prepared earlier. 200 ml (1.0 mmol) of hexane solution was added and stirred at room temperature for 1 hour.
Step (2) A hexane solution of C ₁₂ H ₂₅ —O — (— C ₂ H ₄ —O) ₁₀ —COONa was drawn out of the autoclave by inserting a tube into the autoclave and feeding it.

(2) Preliminary polymerization The autoclave after the first batch was dried under reduced pressure and then replaced with argon, then evacuated, and 480 g of butane and 205 mg (385 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.1 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the mixture was switched to an ethylene / hydrogen mixed gas (hydrogen concentration: 0.216 mol%) and the temperature was raised to 50 ° C. over 30 minutes while supplying at 0.58 g / min, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a very thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 119.7 g, and the degree of polymerization per modified particle (B) was 16.9 g / g.

(4) Prepolymerization In the second batch above (2), after the hexane slurry was extracted, the autoclave was dried under reduced pressure and then replaced with argon and then vacuumed. (371 μmol) was added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.215 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 98.3 g, and the degree of polymerization per modified particle (B) was 14.0 g / g.

(5) Prepolymerization In the third batch (3) above, the autoclave after extracting the hexane slurry under reduced pressure was dried under reduced pressure, then replaced with argon, and then vacuumed. 359 μmol) was added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 6.9 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml. 3.5 ml (3.5 mmol) of hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.222 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a thick fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 93.0 g. When the autoclave was opened and the fouling adhering to the inner wall was recovered, the recovered amount of fouling was 64.5 g. The ratio of the recovered amount of fouling to the sum of the prepolymerized addition polymerization catalyst component and the recovered amount of fouling was 40.9 wt%. The degree of polymerization per modified particle (B) was 22.7 g / g.

[Comparative Example 1]

(1) Preliminary polymerization After drying under reduced pressure in the first batch, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, and 480 g of butane and 179 mg (334 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. It was. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.184 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered.
The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 111.6 g, and the degree of polymerization per modified particle (B) was 15.9 g / g.

(2) Prepolymerization In the second batch, the autoclave after the hexane slurry was extracted in the above (1) was dried under reduced pressure and then replaced with argon, followed by evacuation. (361 μmol) was added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.1 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.221 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a thick fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 64.3 g. When the autoclave was opened and the fouling adhering to the inner wall was recovered, the recovered amount of fouling was 79.9 g. The ratio of the recovered amount of fouling to the sum of the prepolymerized addition polymerization catalyst component and the recovered amount of fouling was 55.4 wt%. The degree of polymerization per modified particle (B) was 20.4 g / g.

１＝Ｃ_１２Ｈ_２５−Ｏ−（−Ｃ_２Ｈ_４−Ｏ）_１０−ＣＯＯＮａ
２＝Ｃ_１２Ｈ_２５ＣＯＮ（Ｃ_２Ｈ_４ＯＨ）_２
３＝Ｃ_１２Ｈ_２５−Ｏ−（−Ｃ_２Ｈ_４−Ｏ）_６−Ｈ
４＝Ｃ_１２Ｈ_２５−Ｏ−（−Ｃ_２Ｈ_４−Ｏ）_２−ＳＯ_３Ｎａ

_{1 = C 12 H 25 -O -} (- C 2 H 4 -O) 10 -COONa
_{2 = C 12 H 25 CON (} C 2 H 4 OH) 2
_{3 = C 12 H 25 -O -} (- C 2 H 4 -O) 6 -H
_{4 = C 12 H 25 -O -} (- C 2 H 4 -O) 2 -SO 3 Na

[Example 6]
(1) Washing step of addition polymerization reactor (1) 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, charged with 480 g of butane, and then adjusted to a concentration of 1.6 mmol / ml 3.125 ml (5.0 mmol) of the n-butyllithium hexane solution added was added and stirred at room temperature for 1 hour.
Step (2) A butane solution of n-butyllithium was purged from the outlet of the autoclave.
Step (3) 800 ml of hexane was charged into the autoclave and stirred at room temperature for 15 minutes. The hexane in the autoclave was extracted out of the autoclave by inserting a tube into the autoclave and pumping it.
(2) Production of modified particles (B) In the same manner as the preparation of component (A) in Example 1 (1) and (2) of JP-A-2009-79180, Quality particles (B) were produced. As a result of elemental analysis, Zn = 11 wt% and F = 6.4 wt%.

(3) Preliminary polymerization The autoclave washed for the first batch was dried under reduced pressure and then replaced with argon, then evacuated, and 480 g of butane and 198 mg (370 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.1 g of the modified particles (B) obtained in (2) above were added, and then a hexane solution of triisobutylaluminum (C) adjusted to a concentration of 1.0 mmol / ml 3 0.5 ml (3.5 mmol) was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.223 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, no fouling was adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 129.1 g, and the degree of polymerization per modified particle (B) was 18.2 g / g.

(4) Prepolymerization In the second batch above (3), the autoclave after extracting the hexane slurry was dried under reduced pressure, then replaced with argon and then evacuated, and 480 g of butane and 208 mg of ethylenebis (indenyl) zirconium diphenoxide (A). (389 μmol) was added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the modified particles (B) obtained in (2) above were added, and then a hexane solution of triisobutylaluminum (C) adjusted to a concentration of 1.0 mmol / ml 3 0.5 ml (3.5 mmol) was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Subsequently, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.189 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a very thin fouling was adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 127.6 g, and the degree of polymerization per modified particle (B) was 18.3 g / g.

(5) Prepolymerization Third batch The autoclave from which the hexane slurry was extracted in (4) above was dried under reduced pressure, then replaced with argon, and then vacuumed to give 480 g of butane and 200 mg of ethylenebis (indenyl) zirconium diphenoxide (A). (374 μmol) was added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 6.9 g of the modified particles (B) obtained in (2) above were added, and then a hexane solution of triisobutylaluminum (C) adjusted to a concentration of 1.0 mmol / ml 3 0.5 ml (3.5 mmol) was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the mixture was switched to an ethylene / hydrogen mixed gas (hydrogen concentration: 0.187 mol%), and the temperature was raised to 50 ° C. over 30 minutes while feeding at 0.58 g / min, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a thin fouling was adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 112.5 g.
When the autoclave was opened and the fouling adhering to the inner wall was recovered, the recovered amount of fouling was 14.3 g. The ratio of the recovered amount of fouling to the sum of the prepolymerized addition polymerization catalyst component and the recovered amount of fouling was 11.3 wt%. The degree of polymerization per modified particle (B) was 18.3 g / g.

(6) 1st batch prepolymerization catalyst main polymerization
After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 5 liters substituted with argon was evacuated, hydrogen was added at a partial pressure of 0.037 MPa, 154 g of hexene-1 and 1046 g of butane were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added 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 hydrogen = 1.99 mol%. To this, 2.0 ml of a hexane solution of triisobutylaluminum prepared at a concentration of 1 mmol / ml was added. Next, 1.0 ml of a toluene solution of triethylamine prepared at a concentration of 0.1 mmol / ml was added. Further, 376.7 mg of the prepolymerized addition polymerization catalyst component obtained in Example 1 (3) was added.
Polymerization was carried out at 70 ° C. for 3 hours while feeding an ethylene / hydrogen mixed gas (hydrogen 0.288 mol%) so as to keep the total pressure constant. As a result, 133 g of an olefin polymer was obtained. The polymerization activity per modified particle (B) was 6400 g / g. Moreover, the obtained olefin polymer was MFR = 1.82 and SR = 1.42.

(7) Second batch prepolymerization catalyst Main polymerization
After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 5 liters substituted with argon was evacuated, hydrogen was added at a partial pressure of 0.037 MPa, 154 g of hexene-1 and 1046 g of butane were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added 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 hydrogen = 1.99 mol%. To this, 2.0 ml of a hexane solution of triisobutylaluminum prepared at a concentration of 1 mmol / ml was added. Next, 1.0 ml of a toluene solution of triethylamine prepared at a concentration of 0.1 mmol / ml was added. Furthermore, 369.7 mg of the prepolymerized addition polymerization catalyst component obtained in Example 1 (4) was added.
Polymerization was carried out at 70 ° C. for 3 hours while feeding an ethylene / hydrogen mixed gas (hydrogen 0.274 mol%) so as to keep the total pressure constant. As a result, 153 g of an olefin polymer was obtained. The polymerization activity per modified particle (B) was 7540 g / g. The obtained olefin polymer had MFR = 1.44 and SR = 1.41.

(8) Pre-polymerization catalyst for the third batch
After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 5 liters substituted with argon was evacuated, hydrogen was added at a partial pressure of 0.037 MPa, 154 g of hexene-1 and 1046 g of butane were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added 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 hydrogen = 1.96 mol%. To this, 2.0 ml of a hexane solution of triisobutylaluminum prepared at a concentration of 1 mmol / ml was added. Next, 1.0 ml of a toluene solution of triethylamine prepared at a concentration of 0.1 mmol / ml was added. Further, 369.8 mg of the prepolymerized addition polymerization catalyst component obtained in Example 1 (5) was added.
Polymerization was carried out at 70 ° C. for 3 hours while feeding an ethylene / hydrogen mixed gas (hydrogen 0.271 mol%) so as to keep the total pressure constant. As a result, 74 g of an olefin polymer was obtained. The polymerization activity per modified particle (B) was 3670 g / g. Moreover, the obtained olefin polymer was MFR = 3.76 and SR = 1.47.

[Example 7]
(1) Washing step of addition polymerization reactor (1) 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, charged with 480 g of butane, and then adjusted to a concentration of 1.0 mmol / ml 5.0 ml (5.0 mmol) of the hexane solution of triisobutylaluminum was added and stirred at room temperature for 1 hour.
Step (2) A butane solution of triisobutylaluminum was purged from the outlet of the autoclave.
Step (3) 800 ml of hexane was charged into the autoclave and stirred at room temperature for 15 minutes. The hexane in the autoclave was extracted out of the autoclave by inserting a tube into the autoclave and pumping it.

(2) Prepolymerization The autoclave washed for the first batch was dried under reduced pressure and then replaced with argon, then evacuated, and 480 g of butane and 182 mg (342 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the mixture was switched to an ethylene / hydrogen mixed gas (hydrogen concentration: 0.187 mol%), and the temperature was raised to 50 ° C. over 30 minutes while feeding at 0.58 g / min, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a very thin fouling was adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 122.5 g, and the degree of polymerization per modified particle (B) was 17.3 g / g.

(3) Prepolymerization In the second batch, the autoclave after extracting the hexane slurry in (2) above was dried under reduced pressure and then replaced with argon, and then vacuumed. (349 μmol) was added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.1 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.217 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 98.8 g. When the autoclave was opened and the fouling adhering to the inner wall was recovered, the recovered amount of fouling was 32.6 g. The ratio of the recovered amount of fouling to the sum of the prepolymerized addition polymerization catalyst component and the recovered amount of fouling was 24.8 wt%. The degree of polymerization per modified particle (B) was 18.9 g / g.

(4) 1st batch prepolymerization catalyst main polymerization
After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 5 liters substituted with argon was evacuated, hydrogen was added at a partial pressure of 0.037 MPa, 154 g of hexene-1 and 1046 g of butane were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added 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 hydrogen = 2.00 mol%. To this, 2.0 ml of a hexane solution of triisobutylaluminum prepared at a concentration of 1 mmol / ml was added. Next, 1.0 ml of a toluene solution of triethylamine prepared at a concentration of 0.1 mmol / ml was added. Furthermore, 354.7 mg of the prepolymerized addition polymerization catalyst component obtained in Example 2 (2) was added.
Polymerization was carried out at 70 ° C. for 3 hours while feeding an ethylene / hydrogen mixed gas (hydrogen 0.298 mol%) so as to keep the total pressure constant. As a result, 110 g of an olefin polymer was obtained. The polymerization activity per modified particle (B) was 5390 g / g. Further, the obtained olefin polymer had MFR = 2.16 and SR = 1.43.

[Example 8]
(1) Washing of addition polymerization reactor The autoclave with a stirrer having an internal volume of 3 liters was washed in the same manner as in Example 1 (1) Washing of the addition polymerization reactor.

(2) Preliminary polymerization First batch The washed autoclave was dried under reduced pressure and then replaced with argon, then evacuated, and 480 g of butane and 203 mg (381 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.1 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the mixture was switched to an ethylene / hydrogen mixed gas (hydrogen concentration: 0.212 mol%) and the temperature was raised to 50 ° C. over 30 minutes while supplying at 0.58 g / min, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, no fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 124.2 g, and the degree of polymerization per modified particle (B) was 17.4 g / g.

(3) Washing of addition polymerization reactor The autoclave with a stirrer having an internal volume of 3 liters was washed in the same manner as in Example 1 (1) Washing of the addition polymerization reactor.

(4) Preliminary polymerization The autoclave after the second batch was dried under reduced pressure, and then replaced with argon. Then, vacuum was applied, and 480 g of butane and 159 mg (298 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the modified particles (B) obtained in (2) above were added, and then a hexane solution of triisobutylaluminum (C) adjusted to a concentration of 1.0 mmol / ml 3 0.5 ml (3.5 mmol) was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.173 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, no fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 122.7 g, and the degree of polymerization per modified particle (B) was 17.5 g / g.

(5) Washing of addition polymerization reactor The autoclave with a stirrer having an internal volume of 3 liters was washed in the same manner as in Example 1 (1) Washing of the addition polymerization reactor.

(6) Preliminary polymerization Third batch The washed autoclave was dried under reduced pressure and then replaced with argon, then evacuated, and 480 g of butane and 182 mg (341 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the modified particles (B) obtained in (2) above were added, and then a hexane solution of triisobutylaluminum (C) adjusted to a concentration of 1.0 mmol / ml 3 0.5 ml (3.5 mmol) was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Subsequently, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.189 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a very thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 130.9 g. When the autoclave was opened and the fouling adhering to the inner wall was recovered, the recovered amount of fouling was 0.7 g. The ratio of the recovered amount of fouling to the sum of the prepolymerized addition polymerization catalyst component and the recovered amount of fouling was 0.5 wt%. The degree of polymerization per modified particle (B) was 18.7 g / g.

[Example 9]
(1) Cleaning the reactor for addition polymerization
Step (1) 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, charged with 800 ml of hexane, and then added with a hexane solution of n-butyllithium prepared to a concentration of 1.6 mmol / ml 125 ml (5.0 mmol) was added and stirred at room temperature for 1 hour.
Step (2) A hexane solution of n-butyllithium was extracted from the autoclave by inserting a tube into the autoclave and pumping it.
(2) Preliminary polymerization The autoclave washed for the first batch was dried under reduced pressure and then replaced with argon, then evacuated, and 480 g of butane and 199 mg (373 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 6.9 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml. 3.5 ml (3.5 mmol) of hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.230 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a very thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 119.9 g, and the degree of polymerization per modified particle (B) was 17.3 g / g.

(3) Prepolymerization In the second batch, the autoclave after extracting the hexane slurry in (2) above was dried under reduced pressure and then replaced with argon, then evacuated, 480 g of butane and 197 mg of ethylenebis (indenyl) zirconium diphenoxide (A). (368 μmol) was added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.1 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the mixture was switched to an ethylene / hydrogen mixed gas (hydrogen concentration: 0.233 mol%), and the temperature was raised to 50 ° C. over 30 minutes while supplying at 0.58 g / min, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 93.9 g. When the autoclave was opened and the fouling adhering to the inner wall was recovered, the recovered amount of fouling was 39.8 g. The ratio of the recovered amount of fouling to the sum of the prepolymerized addition polymerization catalyst component and the recovered amount of fouling was 29.8 wt%. The degree of polymerization per modified particle (B) was 18.9 g / g.

[Comparative Example 2]

(1) Preliminary polymerization After drying under reduced pressure in the first batch, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, and 480 g of butane and 179 mg (334 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. It was. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.184 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a thin fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered.
The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 111.6 g, and the degree of polymerization per modified particle (B) was 15.9 g / g.

(2) Pre-polymerization 2nd batch The autoclave after extracting the hexane slurry in (1) above was dried under reduced pressure and then replaced with argon, then vacuumed, 480 g of butane and 193 mg of ethylenebis (indenyl) zirconium diphenoxide (A). (361 μmol) was added. After stirring at 50 ° C. for 2 hours, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.1 g of the modified particles (B) obtained in Example 1 (2) above were added, and then the concentration of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml was added. A 3.5 ml (3.5 mmol) hexane solution was added. First, prepolymerization was performed at 30 ° C. for 30 minutes while supplying ethylene at 0.13 g / min. Next, the ethylene / hydrogen mixed gas (hydrogen concentration: 0.221 mol%) was switched to, while supplying at 0.58 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 3 hours. It was. After purging the monomer and butane and cooling the temperature of the autoclave to room temperature, 800 ml of hexane was charged into the autoclave, and the prepolymerized addition polymerization catalyst component in the autoclave was recovered as a hexane slurry. When the inside of the autoclave after extracting the hexane slurry was observed with a fiberscope camera, a thick fouling adhered to the inner wall of the autoclave. The collected hexane slurry was filtered. The recovered amount of the prepolymerized addition polymerization catalyst component after filtration was 64.3 g. When the autoclave was opened and the fouling adhering to the inner wall was recovered, the recovered amount of fouling was 79.9 g. The ratio of the recovered amount of fouling to the sum of the prepolymerized addition polymerization catalyst component and the recovered amount of fouling was 55.4 wt%. The degree of polymerization per modified particle (B) was 20.4 g / g.

nBuLi＝ｎ−ブチルリチウム、TIBA＝トリイソブチルアルミニウム

nBuLi = n-butyllithium, TIBA = triisobutylaluminum

Claims (12)

A method of cleaning the inner wall surface of a reactor including the following steps (1) and (2).
Step (1): at least one compound selected from the compound represented by the general formula [1], the compound represented by the general formula [2], and the compound represented by the general formula [9] and a hydrocarbon solvent Step (2) of adding a solution containing: to the reactor: step of removing the solution in the reactor

R ¹ —O — (— R ² —O—) _m Q ¹ [1]
R ¹ C (═O) NR ⁵ ₂ [2]
M ⁴ L ³ _n [9]
(In the above general formulas [1] and [2], R ¹ represents an optionally substituted hydrocarbyl group having 1 to 30 carbon atoms. R ² may have a substituent. Represents a good alkylene group having 1 to 20 carbon atoms, Q ¹ represents a hydrogen atom, —C (═O) OM ¹ , —R ³ —C (═O) OM ¹ , —S (═O) ₂ OM ¹ , _{^{-R 3 -S (= O) 2}} OM 1, -P (= O) (OH) (OM 1), - R 3 -P (= O) (OH) (OM 1), - P (= O) (OR ⁴ ) (OM ¹ ), —R ³ —P (═O) (OR ⁴ ) (OM ¹ ), —P (═O) (OM ¹ ) ₂ , or —R ³ —P (═O) ^(OM ₁₎ represents a ₂ .M ¹ is hydrogen ^{_{atom, NH 4, NH (R 12}} OH) 3 or, ^{.R 12} good number of carbon atoms which may have a substituent represents an alkali metal atom Represents a 20 alkylene group .R ³ is .R ⁴ is carbon atoms which may have a substituent represents an alkylene group which may having 1 to 20 carbon atoms which may have a substituent 1 to 20 M represents a number of 1 to 100. R ⁵ represents a hydrogen atom or a hydrocarbyl group having 1 to 30 carbon atoms which may have a substituent.
In the general formula [9], M ⁴ is a group consisting of Group 1, Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, and Group 13 of the Periodic Table. It represents a metal atom selected more. L ³ is a hydrogen atom, a halogen atom or a hydrocarbyl group, and n is the valence of the metal atom M ⁴ . ) The method of Claim 1 including the following process (3) after a process (2).
Step (3): Step of washing the inside of the reactor with a hydrocarbon solvent A compound (A) which is a transition metal compound represented by the following general formula [3] or a μ-oxo type transition metal compound dimer in the reactor washed by the method according to claim 1 or 2 And an activator (B), the addition polymerization method of addition polymerization of a monomer capable of addition polymerization using a catalyst obtained by contact.
L ¹ _a M ² X ¹ _b [3]
(In the formula, M ² is a transition metal atom of Group 4 of the periodic table. L ¹ is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ¹ are directly connected to each other. Or may be linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, wherein X ¹ is a halogen atom, a hydrocarbyl group (provided that (Excluding a group having a cyclopentadiene type anion skeleton) or a hydrocarbyloxy group, a represents a number satisfying 0 <a ≦ 3, and b represents a number satisfying 0 <b ≦ 3.) A compound (A) which is a transition metal compound represented by the following general formula [3] or a μ-oxo type transition metal compound dimer in the reactor washed by the method according to claim 1 or 2 And addition polymerization of a monomer capable of addition polymerization using a catalyst obtained by contacting the activator (B) with the organoaluminum compound (C).
L ¹ _a M ² X ¹ _b [3]
(In the formula, M ² is a transition metal atom of Group 4 of the periodic table. L ¹ is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ¹ are directly connected to each other. Or may be linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, wherein X ¹ is a halogen atom, a hydrocarbyl group (provided that (Excluding a group having a cyclopentadiene type anion skeleton) or a hydrocarbyloxy group, a represents a number satisfying 0 <a ≦ 3, and b represents a number satisfying 0 <b ≦ 3.) The activator (B) is a modified particle (B) obtained by bringing the following (a), (b), (c) and (d) below into contact with each other. Of addition polymerization.
(A): Compound represented by the following general formula [4] M ³ L ² ₂ [4]
(B): Compound represented by the following general formula [5] R ⁶ _t-1 TH [5]
(C): Compound represented by the following general formula [6] R ⁷ _t-2 TH ₂ [6]
(D): Inorganic oxide particles or organic polymer particles (in the above general formulas [4] to [6], M ³ represents a typical metal atom of Group 12 of the periodic table. L ² represents a hydrogen atom or a halogen atom. Or a hydrocarbyl group, and when a plurality of L ² are present, they may be the same or different from each other, R ⁶ represents an electron-withdrawing group or a group containing an electron-withdrawing group, and R 6 ^{When a} plurality of ⁶ are present, they may be the same or different from each other, R ⁷ represents a hydrocarbyl group or a halogenated hydrocarbyl group, and each T independently represents group 15 of the periodic table. Or represents a group 16 atom, and t represents a number corresponding to the valence of T of each compound.)   The addition polymerization method according to any one of claims 3 to 5, wherein the addition polymerization is preliminary polymerization.   A prepolymerized addition polymerization catalyst component obtained by the method according to claim 6.   A method for producing an addition polymer, which comprises addition polymerization of a monomer capable of addition polymerization using the prepolymerized addition polymerization catalyst component according to claim 7.   A method for producing an addition polymer, which comprises addition polymerization of a monomer capable of addition polymerization using the prepolymerized addition polymerization catalyst component according to claim 7 and the organoaluminum compound (C). A catalyst obtained by contacting a transition metal compound represented by the general formula [3] or a μ-oxo type transition metal compound dimer (A) and an activating agent (B) is used. The addition-polymerizable monomer is prepolymerized to obtain a prepolymerized addition polymerization catalyst component, and in the presence of the prepolymerized addition polymerization catalyst component in the reactor washed by the method according to claim 1 or 2, A method for producing an addition polymer, which comprises addition polymerization of a monomer capable of addition polymerization.
L ¹ _a M ² X ¹ _b [3]
(In the formula, M ² is a transition metal atom of Group 4 of the periodic table. L ¹ is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ¹ are directly connected to each other. Or may be linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, wherein X ¹ is a halogen atom, a hydrocarbyl group (provided that (Excluding a group having a cyclopentadiene type anion skeleton) or a hydrocarbyloxy group, a represents a number satisfying 0 <a ≦ 3, and b represents a number satisfying 0 <b ≦ 3.) A catalyst obtained by contacting a transition metal compound represented by the general formula [3] or a μ-oxo type transition metal compound dimer (A) and an activating agent (B) is used. A prepolymerized addition polymerization catalyst component is obtained by prepolymerizing a monomer capable of addition polymerization, and the prepolymerized addition polymerization catalyst component and organoaluminum in a reactor washed by the method according to claim 1 or 2. A method for producing an addition polymer in which addition-polymerizable monomers are addition-polymerized in the presence of the compound (C).
L ¹ _a M ² X ¹ _b [3]
(In the formula, M ² is a transition metal atom of Group 4 of the periodic table. L ¹ is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ¹ are directly connected to each other. Or may be linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, wherein X ¹ is a halogen atom, a hydrocarbyl group (provided that (Excluding a group having a cyclopentadiene type anion skeleton) or a hydrocarbyloxy group, a represents a number satisfying 0 <a ≦ 3, and b represents a number satisfying 0 <b ≦ 3.)   The method for producing an addition polymer according to any one of claims 8 to 11, wherein the addition-polymerizable monomer is ethylene and α-olefin.