JP2012117032A - Coating method, coated reactor, addition polymerization method, pre-polymerization method, pre-polymerized catalyst component for addition polymerization, and method for producing addition polymer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reactor that can suppress fouling in the reactor even when conducting chemical reactions in the reactor, and to provide an addition polymerization method.SOLUTION: This invention relates to a method for coating the inner peripheral surface of the reactor with a compound expressed by general formula [1]: (RCOO)RmM, wherein Rrepresents 1-20C hydrocarbyl group which may have a substituent, provided that if a plurality of Rexist, they may be same or different from each other; Rrepresents a hydrogen atom, hydroxy group or 1-20C hydrocarbyl group which may have a substituent, provided that if a plurality of Rexist, they may be same or different from each other; Mrepresents a metal atom selected from the group consisting of groups 1, 2, 8, 9, 10, 11, 12 and 13 of the periodic table; l denotes a number of 1 or more; and m denotes a number of 0 or more, provided that l and m are numbers satisfying 1≤l+m≤n, and n denotes a number equivalent to atomic valency of M.

Description

  The present invention relates to a coating method for a reactor, a coated reactor, an addition polymerization method, a prepolymerization method, a prepolymerized addition polymerization catalyst component, and a method for producing an addition polymer using the same.

When a chemical reaction is performed in a reactor, a fouling phenomenon in which a reaction product adheres to the reactor wall surface 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, and as a most serious situation, a runaway reaction may occur. Further, when fouling occurs, it is difficult to remove the fouling while continuing the operation. Therefore, it is necessary to open the reactor for cleaning, which may lead to a decrease in productivity.

Fouling is a significant problem especially in polymerization reactions. As a method for suppressing fouling in a polymerization reaction, the method of Patent Document 1 is known. All of these known techniques are satisfactory from the viewpoint of the quality of the reaction product because it is necessary to add a specific compound for suppressing fouling to the reaction system, and these compounds are also mixed into the reaction product. It was not a thing.

JP 2005-89583 A

  An object of the present invention is to provide a reactor capable of suppressing fouling in the reactor even when a chemical reaction is performed in the reactor, and an addition polymerization method.

The first of the present invention relates to a method of coating the inner wall surface of a reactor with a compound represented by the following general formula [1].
(R ¹ COO) _l R ² _m M ¹ [1]
(In the above general formula [1], R ¹ represents an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, and when a plurality of R ¹ are present, they are the same as each other. R ² represents a hydrogen atom, a hydroxy group, or a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent, and when there are a plurality of R ² , M ¹ may be the same as or different from each other, and M ¹ represents groups 1, 2, 8, 9, 10, 11, 12, and 12 in the periodic table. Represents a metal atom selected from the group consisting of Group 13. l represents a number of 1 or more, m represents a number of 0 or more, provided that l and m are numbers satisfying 1 ≦ l + m ≦ n, and n is Represents the number corresponding to the valence of M ¹ )

  The second of the present invention relates to the coated reactor.

A third aspect of the present invention is an addition polymerization method carried out in the reactor, wherein the transition metal compound (A) represented by the following general formula [2] or a μ-oxo type transition metal compound dimer (A ′), An activator (B), and an organoaluminum compound (C) as required, and an addition polymerization method in which an addition-polymerizable monomer is added using a primary catalyst obtained by contact. Is.
L ¹ _a M ² X ¹ _b [2]
(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 fourth aspect of the present invention relates to an addition polymerization method in which the previous addition polymerization is a preliminary polymerization.

  The fifth of the present invention relates to a prepolymerized addition polymerization catalyst component obtained by the prepolymerization method.

  A sixth 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).

  A seventh aspect of the present invention includes a transition metal compound (A) represented by the general formula [2] or a μ-oxo type transition metal compound dimer (A ′) thereof, and an activator (B). A prepolymerized addition polymerization catalyst component is obtained by prepolymerizing a monomer capable of addition polymerization using a primary catalyst obtained by contact, and the prepolymerized addition polymerization catalyst in the coated reactor according to claim 3. The present invention relates to a method for producing an addition polymer in which addition-polymerizable monomers are addition-polymerized in the presence of a component.

  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 continuously performed in the reactor, it is possible to prevent the heat transfer efficiency of the polymerization reactor from being lowered due to fouling and to stably perform the polymerization continuously.

  Hereinafter, the present invention will be described in detail.

Compound for Coating The compound for coating the inner wall surface of the olefin reactor used in the present invention is a compound represented by the following general formula [1].
(R ¹ COO) _l R ² _m M ¹ [1]
(In the above general formula [1], R ¹ represents an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, and when a plurality of R ¹ are present, they may be the same as each other. R ² represents a hydrogen atom, a hydroxy group, or a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent, and when a plurality of R ² are present, they are M ¹ may be the same as or different from each other, and M ¹ represents groups 1, 2, 8, 9, 10, 11, 12, and 13 in the periodic table. Represents a metal atom selected from the group consisting of groups, wherein l is a number of 1 or more and m is a number of 0 or more, where l and m are numbers satisfying 1 ≦ l + m ≦ n, and n is M Represents the number corresponding to the valence of ^1. )

As the hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent of R ^{1 in} the formula [1], an alkyl group having 1 to 20 carbon atoms which may have a substituent, Examples thereof include an aralkyl group having 7 to 20 carbon atoms which may have a substituent 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 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 Enyl, 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 ¹ is preferably an alkyl group having 1 to 20 carbon atoms.

R ^{2 in the} formula [1] represents a hydrogen atom, a hydroxy group, or a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent.

As the hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent of R ² , the same hydrocarbyl group as described for R ¹ is used.

R ² is preferably a hydroxy group or an alkyl group having 1 to 20 carbon atoms.

M ^{1 in the} formula [1] is selected from the group consisting of Group 1, Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, and Group 13 of the Periodic Table Represents a metal atom.

The metal atom of M ¹ 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 more preferably Group 1 of the Periodic Table And more preferably a sodium atom or a potassium atom.

  The compound represented by the general formula [1] is preferably sodium acetate, sodium propionate, sodium butyrate, sodium isobutyrate, sodium valerate, sodium isovalerate, sodium caproate, sodium enanthate, sodium caprylate, pelargon Sodium, sodium caprate, sodium laurate, sodium myristate, sodium pentadecylate, sodium palmitate, sodium stearate, sodium arachidate, potassium acetate, potassium propionate, potassium butyrate, potassium isobutyrate, potassium valerate, iso Potassium valerate, potassium caproate, potassium enanthate, potassium caprylate, potassium pelargonate, potassium caprate, potassium laurate, potassium myristate, Potassium ntadecylate, potassium palmitate, potassium stearate, potassium arachidate, calcium acetate, calcium propionate, calcium butyrate, calcium isobutyrate, calcium valerate, calcium isovalerate, calcium caproate, calcium enanthate, calcium caprylate , Calcium pelargonate, calcium caprate, calcium laurate, calcium myristate, calcium pentadecylate, calcium palmitate, calcium stearate, calcium arachidate, iron acetate, iron propionate, iron butyrate, iron isobutyrate, iron valerate, isoyoshichi Iron valerate, iron caproate, iron enanthate, iron caprylate, iron pelargonate, iron caprate, iron laurate, iron myristate, iron pentadecylate, iron palmitate, Iron teaate, iron arachidate, cobalt acetate, cobalt propionate, cobalt butyrate, cobalt isobutyrate, cobalt valerate, cobalt isovalerate, cobalt caproate, cobalt enanthate, cobalt caprylate, cobalt pelargonate, cobalt caprate , Cobalt laurate, cobalt myristate, cobalt pentadecylate, cobalt palmitate, cobalt stearate, cobalt arachidate, nickel acetate, nickel propionate, nickel butyrate, nickel isobutyrate, nickel valerate, nickel isovalerate, caproic acid Nickel, nickel enanthate, nickel caprylate, nickel pelargonate, nickel caprate, nickel laurate, nickel myristate, nickel pentadecylate, nickel palmitate, Nickel allate, nickel arachidate, copper acetate, copper propionate, copper butyrate, copper isobutyrate, copper valerate, copper isovalerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper caprate , Copper laurate, copper myristate, copper pentadecylate, copper palmitate, copper stearate, copper arachidate, zinc acetate, zinc propionate, zinc butyrate, zinc isobutyrate, zinc valerate, zinc isovalerate, caproic acid Zinc, zinc enanthate, zinc caprylate, zinc pelargonate, zinc caprate, zinc laurate, zinc myristate, zinc pentadecylate, zinc palmitate, zinc stearate, zinc arachidate, aluminum monoacetate, aluminum diacetate, Aluminum triacetate, aluminum monopropionate, aluminum dipropionate Aluminum tripropionate, aluminum monobutyrate, aluminum dibutyrate, aluminum tributyrate, aluminum monoisobutyrate, aluminum diisobutyrate, aluminum triisobutyrate, aluminum monovalerate, aluminum divalerate, aluminum trivalerate, aluminum monoisovalerate, diiso Aluminum valerate, aluminum triisovalerate, aluminum monocaproate, aluminum dicaproate, aluminum tricaproate, aluminum monoenanthate, aluminum dienanthate, aluminum trienanthate, aluminum monocaprylate, aluminum dicaprylate, aluminum tricaprylate, aluminum monopelargonate , Aluminum dipelargonate, aluminum tripelargonate, monocap Aluminum phosphate, aluminum dicaprate, aluminum tricaprate, aluminum monolaurate, aluminum dilaurate, aluminum trilaurate, aluminum monomyristate, aluminum dimyristate, aluminum trimyristate, aluminum monopentadecylate, aluminum tripentadecylate Aluminum pentadecylate, aluminum monopaltimate, aluminum dipalmitate, aluminum tripartitate, aluminum monostearate, aluminum distearate, aluminum tristearate, aluminum monoarachidate, aluminum diarachidate, aluminum triarachidate, and more preferably Is sodium acetate, sodium propionate, Sodium butyrate, sodium isobutyrate, sodium valerate, sodium isovalerate, sodium caproate, sodium enanthate, sodium caprylate, sodium pelargonate, sodium caprate, sodium laurate, sodium myristate, sodium pentadecylate, palmitic acid Sodium, sodium stearate, sodium arachidate.

Coating method As the coating method of the present invention, a coating liquid is attached to the inner wall surface of the reactor to remove the solvent, or a coating liquid is applied on a separately prepared plate and dried to prepare a film in advance. A method of attaching this to the inner wall surface of the reactor can be used.

  In the method of attaching the coating liquid to the inner wall surface of the reactor and removing the solvent, in particular, as the method of attaching the coating liquid to the inner wall surface of the reactor, various methods can be used. For example, the coating liquid is atomized with a spray gun and sprayed onto the inner wall surface of the reactor (spray coating), and the coating liquid is applied to the inner wall surface of the reactor by including it in a brush, roller, exposed surface, etc. The method of filling the reactor with the coating liquid and extracting the coating liquid after a predetermined time has passed, and the method of pouring the coating liquid on the inner wall of the reactor using a pipette, syringe, dropper, etc. can be suitably used. is there.

The coating liquid is a liquid composition containing the coating compound and a solvent. Here, as the solvent, water, non-polar solvents such as aliphatic hydrocarbyl solvents, aromatic hydrocarbyl solvents, halide solvents, ether solvents, alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid Examples include polar solvents such as derivatives, nitrile solvents, nitro compounds, amine solvents, and sulfur compounds, preferably water and alcohol solvents, and particularly preferably alcohol solvents. The concentration of the diluent is usually 0.01 wt% to 10 wt%, preferably 0.05 wt% to 1 wt%. As a method for removing the solvent, the solvent can be dried and evaporated usually by maintaining the temperature in a temperature range of room temperature to 200 ° C. and a time range of 10 minutes to 20 hours. The residual solvent is preferably removed by drying under reduced pressure or sweeping with an inert gas such as nitrogen under heating conditions as necessary.
The thickness of the coating layer in the coated reactor is usually 5 mm or less, preferably 1 mm or less.
The amount of the coating compound with respect to the inner wall area of the reactor is preferably 0.01 to 50 g / m ² , more preferably 0.1 to 5 g / m ² .

The coated reactor of the present invention can be used for various chemical reactions, but a preferred application is an addition polymerization application.

Transition metal compound (A) or its μ-oxo type transition metal compound dimer (A ′)
The transition metal compound (A) or its μ-oxo type transition metal compound dimer (A ′) used in the present invention can be used together with the activator (B), or organically as necessary. Although it will not specifically limit if it is a transition metal compound which shows addition polymerization activity by using together with an aluminum compound (C), Usually, transition metal compounds, such as a metallocene complex, are used. The transition metal compound of the present invention is a catalyst that is distinguished from conventional solid catalysts (typically called Ziegler-Natta catalysts) using titanium trichloride or titanium tetrachloride, and is a transition metal compound such as a metallocene complex. Means a catalyst using

Specific examples of such a transition metal compound include a transition metal compound (A) represented by the following formula [2] or a dimer (A ′) of the μ-oxo type transition metal compound.
L ¹ _a M ² X ¹ _b [2]
(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 [2] 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 [2] 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 [2] 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 [2] 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 [2] include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, a 2-methylphenoxy group, a 2,6-dimethylphenoxy group, 2, 4,6-trimethylphenoxy group, 2-ethylphenoxy group, 4-n-propylphenoxy group, 2-isopropylphenoxy group, 2,6-diisopropylphenoxy group, 4-sec-butylphenoxy group, 4-tert-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 [6] can also be mentioned, for example.
R ⁵ ₃ P = N- [6]
(In the formula, each R ⁵ independently represents a hydrogen atom, a halogen atom or a hydrocarbyl group, and the plurality of R ⁵ may be the same or different from each other, and any two of the plurality of R ⁵ may be selected. Two or more may be bonded to each other and may form a ring structure.)

Specific examples of R ⁵ in the formula [6] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 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 [7].

(In the formula, each R ⁶ independently represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a halogenated hydrocarbyl group, a hydrocarbyloxy group, a silyl group, or an amino group, and the plurality of R ⁶ are the same as each other. Or any two or more of R ⁶ may be bonded to each other and may form a ring structure.)

Specific examples of R ⁶ in the above formula [7] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, phenyl group, 1-naphthyl group, 2-naphthyl group, tert-butyl group, 2,6- Dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl group, methyl group, 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 [2] 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 [2] 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 [2], 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 for X ¹ in the formula [2] 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 be substituted with an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

  Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (2,3-dimethyl). (Phenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, 3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, 3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3, , 6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group , (N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, and anthracenylmethyl group More preferably, it is a benzyl group. These aralkyl groups 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. May be substituted.

  Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5- Xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6- Trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butyl Nenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl, and anthracenyl Group, and more preferably a phenyl group. These aryl groups include fluorine atoms, chlorine atoms, bromine atoms, halogen atoms such as iodine atoms, alkoxy groups such as methoxy and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. May be substituted.

  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 [2] 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 are 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. May be substituted.

  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. May be substituted.

  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. May be substituted.

X ¹ in the formula [2] 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.

A number that satisfies a is 0 <a ≦ 3 in the formula [2], b is 0 <a number satisfying b ≦ 3, are appropriately selected depending on 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 [2] 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 Examples of the compound represented by the formula [1] in which the transition metal atom is a titanium atom, a zirconium atom or a hafnium atom include bis (cyclopentadienyl) titanium dichloride and bis (methylcyclopentadienyl) titanium dichloride. Bis (ethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, bis (1,2-dimethylcyclopentadiene) Nyl) titanium dichloride, bis (1,3-dimethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) ) Titanium dichloride, bis (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-methylcyclopentadie L) Titanium dichloride, bis (1,2,3-trimethylcyclopentadienyl) titanium dichloride, bis (1,2,4-trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium dichloride Bis (pentamethylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenylindene) Nil) 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.

Of the transition metal compounds exemplified above, the transition metal compound (A) used in the present invention is preferably a transition metal compound represented by the above formula [2]. Among these, M ² in the above formula [2] is preferably a zirconium compound, and particularly a transition metal compound having at least one group having a cyclopentadiene type anion skeleton as L ¹ in the formula [2] is preferable. Among them, L ¹ in the formula [2] 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 [2] 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 transition metal compound (A) or its μ-oxo type transition metal compound dimer (A ′), , When applied to the polymerization accompanying the formation of the generated addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.), the specific particles are used as one of the catalyst components to change the shape of the generated addition polymer. It is preferable to use a fixed shape, and the modified particles (I), (II) and (III) below can be suitably used.

(I): Modified particles obtained by contacting the following (a), (b), (c) and (d) below (a): a compound represented by the following general formula [3] M ³ L ² ₂ [3]
(B): Compound represented by the following general formula [4] R ³ _t-1 TH [4]
(C): Compound represented by the following general formula [5] R ⁴ _t-2 TH ₂ [5]
(D): Inorganic oxide particles or organic polymer particles (in the above general formulas [3] to [5], 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 ³ represents an electron-withdrawing group or a group containing an electron-withdrawing group, and R 3 ^{When a} plurality of ³ are present, they may be the same or different from each other, R ⁴ 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 above general formula [3] 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 [3], 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 is preferably an aralkyl group having 7 to 20 carbon atoms, such as a benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethyl) Phenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethyl) Phenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) Nyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl Group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (isobutylphenyl) methyl Group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, And anthracenylmethyl group. Among them, a benzyl group is more preferable. 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 [3] 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 [4] or [5] 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 [4] and T in the general formula [5] 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 general formula [4] or [5], 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 ³ in the general formula [4] represents an electron-withdrawing group or a group containing an electron-withdrawing group, and when a plurality of R ³ are present, they may be the same or different from each other. As an index of electron withdrawing property, Hammett's rule substituent constant σ and the like are known, and functional groups having positive Hammett's rule constant σ are listed as electron withdrawing groups.

  Specific examples of the electron withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a 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 ³ 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 ⁴ in the general formula [5] represents a hydrocarbyl group or a halogenated hydrocarbyl group. The hydrocarbyl group in R ⁴ 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 [3] is used. Examples of the halogenated hydrocarbyl group in R ⁴ include a halogenated alkyl group, a halogenated aryl group, and a (halogenated alkyl) aryl group. Specific examples of the electron-withdrawing group in R ³ of the above general formula [4] The same halogenated alkyl group, halogenated aryl group, and (halogenated alkyl) aryl group as those mentioned as examples are used.

R ⁴ in the general formula [5] is preferably a halogenated hydrocarbyl group, and more preferably a fluorinated hydrocarbyl group.

As the compound (a) used for 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, di-n -Dialkyl zinc such as hexyl zinc, diphenyl zinc, dinaphthyl zinc, 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, bromide n-hexyl zinc, methyl zinc iodide, ethyl zinc iodide, propyl zinc iodide, n-butyl zinc iodide And zinc halides such as zinc halides such as isobutylzinc iodide, and n-hexylzinc iodide, 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 diameter 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. Examples of the heat drying method include a method in which an inert gas (eg, nitrogen or argon) dried during heating is circulated and dried at a constant flow rate, or a method in which heat drying is performed under reduced pressure. .

  Inorganic oxides usually have hydroxy groups formed on the surface, but modified inorganic oxides in which active hydrogen of 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, after contact with trialkylaluminum, there can be mentioned dialkylamines such as diethylamine and diphenylamine, alcohols such as methanol and ethanol, and inorganic oxides contacted with phenol.

  Inorganic oxides may have increased strength due to hydrogen bonding between hydroxy groups. In that case, if all the active hydrogens of 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. Preferably by the specific surface area and 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 is preferably 0.01 to 50 mmol / g, more preferably 0.1 to 20 mmol / g, as the molar amount of the functional group per unit gram of the polymer.

  Examples of the method for producing 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 crosslinking polymerizable 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 heat drying method include a method in which an inert gas (eg, nitrogen or argon) dried during heating is circulated and dried at a constant flow rate, or a method in which heat drying is performed under reduced pressure. .

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 non-polar solvents such as aliphatic hydrocarbyl solvents and aromatic hydrocarbyl solvents, halide solvents, ether solvents, alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives, Examples include polar solvents such as nitrile solvents, nitro compounds, amine solvents, and sulfur compounds. For example, aliphatic hydrocarbyl solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane, aromatic hydrocarbyl solvents such as benzene, toluene, xylene, dichloromethane, difluoromethane, Halide solvents such as 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, tetrahydride Ether solvents such as furan and 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, alcohol solvents such as glycerin, phenol solvents such as phenol and p-cresol, acetone, ethyl methyl ketone, cyclohexanone, Carbonyl such as acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone Solvents, phosphoric acid derivatives such as hexamethyl phosphate triamide, triethyl phosphate, nitrile solvents such as acetonitrile, propionitrile, succinonitrile, benzonitrile, nitro compounds such as nitromethane, nitrobenzene, pyridine, piperidine, morpholine, etc. Sulfur compounds such as amine solvents, dimethyl sulfoxide, sulfolane and the like can be mentioned.

  When the contact product (e) 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 above methods, the solvent (s1) for producing the contact product (e) is preferably the above aliphatic hydrocarbyl solvent, aromatic hydrocarbyl solvent or ether solvent.

  A polar solvent is preferable as the solvent (s2) when the contact product (e) and the particles (d) are brought into contact with each other. As an index representing the polarity of a solvent, an ETN value (C. Reichardt, “Solvents and Solvents Effects in Organic Chemistry”, 2nd ed., VCH Verlag (1988)) is known, and 0.8 ≧ ETN ≧ A solvent satisfying the range of 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 hydrocarbyl solvents can also be used. As the hydrocarbyl solvent, the aliphatic hydrocarbyl solvent and aromatic hydrocarbyl solvent exemplified above are used. As a mixed solvent of a polar solvent and a hydrocarbyl solvent, for example, a hexane / methanol mixed solvent, a hexane / ethanol mixed solvent, a hexane / 1-propanol mixed solvent, a hexane / 2-propanol mixed solvent, a 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, Mention may be made of a xylene / methanol mixed solvent, a xylene / ethanol mixed solvent, a xylene / 1-propanol mixed solvent and a 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 a contact product (e) obtained by contacting the compounds (a), (b) and (c) with (d), that is, according to the above <1>, <3>, <7> In each method, a hydrocarbyl solvent can be used as the solvent (s1) and the solvent (s2). In this case, after the compounds (a), (b) and (c) are brought into contact, it is preferable that the time until the obtained contact product (e) is brought into contact with the particles (d) is shorter. The time is preferably 0 to 5 hours, more preferably 0 to 3 hours, and most preferably 0 to 1 hour. Moreover, the temperature in the case of bringing the contact product (e) into contact with the particles (d) 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 the typical metal atom derived from the compound (a) contained in the modified particle (I) is the number of moles of the typical metal atom contained in 1 g of the obtained particle. Thus, the amount 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 preferable to carry out a washing treatment to remove unreacted substances in advance. The solvent at that time may be the same as or different from the solvent at the time of contact. Such cleaning treatment is preferably carried out in an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  In addition, in the above washing process, the modified particles (I) are allowed to settle, and indefinite or fine particles are floating above the slurry. Preference is given to obtaining ordered and modified particles (I).

  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 ² ) —O—} _b and / or the general formula E ³ {-Al (E ³ ) —O—} _c Linear aluminoxane having a structure represented by AlE ³ ₂ is preferably used.
(However, E ¹ , E ² , and E ³ are each a hydrocarbyl group, and all E ¹ , all E ^2, and all E ³ may be the same or different. Z is Represents a hydrogen atom or a halogen atom, and all Zs may be the same or different, a is a number satisfying 0 <a ≦ 3, b is a number of 2 or more, and c is a number of 1 or more. Represents.)
The hydrocarbyl group in E ^1, E ² or E ^3,, preferably hydrocarbyl groups of 1 to 8 carbon atoms, the alkyl group is more preferable.

Specific examples of E ² and E ³ 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. b is a number of 2 or more, and c is a number of 1 or more. Preferably, E ² and E ³ are a methyl group or an isobutyl group, b is 2 to 40, and c 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 obtained by dissolving a trialkylaluminum (for example, trimethylaluminum) in an appropriate organic solvent (benzene, aliphatic hydrocarbyl, etc.) is made to contact 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.

  As the particles (d) used for the modified particles (II), the same particles as (d) used for the modified particles (I) can be used.

Alumoxane (e) and particles (d) can be contacted by any method to produce modified particles (II). Specifically, it is 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 modified particles (I) can be used, and those that do not react with the aluminoxane (e) are preferable, and solvents that dissolve the aluminoxane (e) are 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.

  Although the temperature and time to contact can be taken arbitrarily, the temperature is usually -100 ° C to 200 ° C, preferably -50 ° C to 150 ° C, more preferably -20 ° C to 120 ° C. In particular, the reaction is preferably performed at a low temperature in order to suppress heat generation at the initial stage of the reaction. The amount of contact can be arbitrarily selected, but the aluminoxane (e) per unit gram of the particles (d) is usually 0.01 to 100 mmol, preferably 0.1 to 20 mmol, more preferably 1 to 20 in terms of aluminum atom. 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 (A) represented by the above general formula [2] or its μ-oxo type transition metal compound dimer (A ′) is used.
Contact of the alumoxane (e), the particles (d) and the transition metal compound can be carried out by any method to produce the modified particles (III). In that case, it is preferable to use a solvent, and any of the above-mentioned solvents can be used as the solvent, and those that do not react with the aluminoxane (e) and the transition metal compound are preferable. The aluminoxane (e) and the transition metal compound A solvent that dissolves 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.

  Although the temperature and time to contact can be taken arbitrarily, the temperature is usually -100 ° C to 200 ° C, preferably -50 ° C to 150 ° C, more preferably -20 ° C to 120 ° C. In particular, the reaction is preferably performed at a low temperature in order to suppress heat generation at the initial stage of the reaction. The amount of contact can be arbitrarily selected, but the aluminoxane (e) per unit gram of the particles (d) is usually 0.01 to 100 mmol, preferably 0.1 to 20 mmol, more preferably 1 to 20 in terms of aluminum atom. 10 mmol. Moreover, the transition metal compound (A) per unit gram of the particles (d) is usually 0.1 to 1000 μmol, preferably 1 to 500 μmol, and more preferably 10 to 200 μmol in terms of transition metal atom.

Organoaluminum compound (C)
As the organoaluminum compound (C) used in the present invention, a known organoaluminum compound can be used. Preferably, it is an organoaluminum compound represented by the following general formula [8].
R ⁷ _d AlY _3-d [8]
(Wherein R ⁷ represents a hydrocarbyl group, and all R ⁷ 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 ⁷ in the general formula [8] representing the organoaluminum compound 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 [8] 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-butylaluminum Alkylaluminum dichlorides such as mudichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n- Dialkyl aluminum hydrides such as hexyl aluminum hydride; alkyl (dialkoxy) aluminum such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, methyl (di-tert-butoxy) aluminum; dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum Di, 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)
In the prepolymerization and addition polymer production of the present invention, 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 alkoxy silicons, 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, alkoxysilicones or ethers are preferable. Examples of the nitrogen-containing compound include amines, nitriles, isocyanates, and the like, and amines are preferable.

The alkoxysilicons Motorui general formula _R ⁸ _r Si ^(OR 9) in _4-r (wherein, ^{R 8} represents a hydrocarbyl group, a hydrogen atom or a hetero atom-containing substituent group having a carbon number 1 to 20, R ⁹ represents a hydrocarbyl group having 1 to 20 carbon atoms, and r represents a number satisfying 0 ≦ r <4, and all R ⁸ and all R ⁹ may be the same or different. It is preferable to use an alkoxysilicon compound represented by the following formula.

When R ⁸ or R ⁹ is a hydrocarbyl group, a linear alkyl group such as methyl group, ethyl group, propyl group, butyl group, 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 ⁸ 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 alkoxysilicones, R ⁸ and R ⁹ are preferably alkyl groups, and r is preferably a number satisfying 4> r ≧ 2.

  Specific examples of the alkoxysilicones 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 of these compounds include compounds in which methoxy 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), alkoxysilicones, 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) A method for producing an addition polymer by addition polymerization of a monomer in the presence of a primary catalyst in the coated reactor of the present invention (2) In the presence of a primary catalyst in the coated reactor of the present invention, A method of producing a prepolymerized addition polymerization catalyst component by prepolymerizing the monomer and producing an addition polymer by subjecting the monomer to addition polymerization in the presence of the prepolymerized addition polymerization catalyst component in an uncoated reactor ( 3) A prepolymerized addition polymerization catalyst component is obtained by prepolymerizing a monomer in the presence of a primary catalyst in an uncoated reactor, and the prepolymerized addition polymerization catalyst component is obtained in a coated reactor of the present invention. Method for producing addition polymer by addition polymerization of monomer in the presence (4) Prepolymerized by prepolymerizing monomer in the presence of primary catalyst in the coated reactor of the present invention Obtain a polymerization catalyst component, the presence of the prepolymerized spent addition polymerization catalyst component in the coating already reactor of the present invention, a method of producing an addition polymer of a monomer addition polymerization to

Primary catalyst The primary catalyst in the present invention comprises the above component (A) or its μ-oxo type transition metal compound dimer (A ′), component (B), and optionally component (C). Obtained by contacting with As the contact amount ratio of each component, the contact amount of component (A) or (A ′) is usually 0.1 to 1000 μmol / g, preferably 1 to 500 μmol / g, relative to component (B). Yes, more preferably 10 to 300 μmol / g. The contact amount of component (C) is usually 0.01 to 10000 mmol / g, preferably 0.1 to 1000 mmol / g, more preferably 0.5 to component (A) or (A ′). ~ 200 mmol / g.

  As the contact method of each component, a reaction product obtained by previously contacting the component (A) or (A ′), the component (B) and the component (C) may be used, and charged separately into the reactor. May be used. Any of them may be contacted in advance and then the remaining components may be contacted. Among these contact methods, a method of separately charging the polymerization reactor is preferable. Further, the component (A) or (A ′) may be added in a slurry state in which the component (A) or (A ′) is suspended in a powder or a solvent.

  The contact of each component may or may not be present in the presence of a solvent. Since it is possible to form active sites more efficiently using a solvent, it is preferable that a solvent is present. As the solvent used for the contact, any solvent can be used as long as it does not deactivate the generated active sites. Further, a solvent in which the component (A) or (A ′) dissolves upon contact is more preferable. Specifically, aliphatic hydrocarbyl solvents such as butane, pentane, hexane, and octane, benzene, and toluene Aromatic hydrocarbyl solvents such as xylene, halogenated hydrocarbyl solvents such as dichloromethane, polar solvents such as 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.), it is preferable that the resulting addition polymer is not soluble in a solvent, and specifically, an aliphatic hydrocarbyl 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. For example, a prepolymerization method in the presence of a primary catalyst can be exemplified. Examples of the polymerization solvent used in the prepolymerization method in the presence of the primary catalyst include aliphatic hydrocarbyl solvents such as butane, pentane, hexane, heptane, and octane, and aromatic hydrocarbyl such as benzene and toluene. Mention may be made of carbyl solvents and halogenated hydrocarbyl 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 pre-polymerization (also referred to as pre-polymerization 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 monomer is addition-polymerized using a primary catalyst, and a monomer is addition-polymerized using a prepolymerized addition polymerization catalyst component. And a method (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, relative to the component (A) or (A ′). Is 30 to 1000 mmol / 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 in which each component is supplied in a solid state, a solution state in which a component that deactivates a catalyst component such as moisture and oxygen is sufficiently removed, a solution in a hydrocarbyl solvent, or a suspension or The method etc. which supply in the state made into the slurry can be mentioned. Examples of the hydrocarbyl solvent at this time include aliphatic hydrocarbyl solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbyl solvents such as benzene and toluene, and dichloromethane. A halogenated hydrocarbyl solvent can be mentioned, and among them, an aliphatic hydrocarbyl solvent or an aromatic hydrocarbyl solvent is preferable, and an aliphatic hydrocarbyl 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. Examples of polymerization solvents used for solution polymerization or slurry polymerization include aliphatic hydrocarbyl solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbyl solvents such as benzene and toluene, and dichloromethane. Mention may be made of such halogenated hydrocarbyl 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. The elemental analysis of the modified particles and the properties of the olefin polymer in the examples were measured by the following methods.

(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) MFR: Melt flow rate value measured at 190 ° C. under a load of 21.18 N (2.16 kg) according to the method defined in JIS K7210-1995 (unit: g / 10 minutes).

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

(4) Prepolymerized addition polymerization The cumulative weight fraction of particles having a particle size of 60 μm or less Preliminarily polymerized addition using a laser diffraction particle size distribution analyzer HELOS & RODOS system manufactured by SYMPATEC under the following measurement conditions The polymerization catalyst component was dispersed in a dry state, the particle size distribution was measured, and the amount of prepolymerized addition polymerization catalyst component having a particle size of 60 μm or less was calculated in terms of volume.

(Measurement condition)
Range: R4 1.8-350μm
Trigger condition: Reference duration 2 seconds
: Time base 100ms
: Start channel 15 ≧ 0.5%
: Stop 2s, channel 15 ≦ 0.5%, 10s real time Dispersion condition: RODOS (dry airflow type dispersion unit) direct throwing type
: Feeder VIBRI
: Feed 50%
: Injector 4mm
: Dispersion pressure 1.5bar

[Example 1]
(1) 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%.

(2) Production of coated reactor Sodium butyrate ([CH ₃ (CH ₂ ) ₂ COO] Na) whose concentration was adjusted to 1 mg / ml on the inner wall of a reactor with a stirrer having an internal volume of 3 liters heated to 90 ° C. After 50 ml of ethanol solution was applied with a pipette, it was dried under reduced pressure at 90 ° C. for about 1 hour, and the solvent ethanol was evaporated to coat the inner wall surface. The amount of the coating compound relative to the inner wall area of the reactor was 486 mg / m ² .

(3) The prepolymerized and coated reactor was dried under reduced pressure and then replaced with argon, followed by evacuation, and 480 g of butane and 191 mg (358 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. After stirring at 50 ° C. for 1 hour, the mixture was cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the modified particles (B) obtained in (1) above were added, and then a hexane solution of triisobutylaluminum (C) adjusted to a concentration of 1.0 mmol / ml 3 Pre-polymerization was started by adding 0.5 ml (3.5 mmol). 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: 0.182 mol%) was switched to, while supplying at 0.81 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 2 hours. It was. The monomer and butane were purged and the prepolymerized addition polymerization catalyst component was recovered. The recovered amount was 121.3 g, and the degree of polymerization per modified particle (B) was 17.4 g / g. No polymer adhered to the inner wall of the reactor. As a result of the particle size distribution measurement, the content of particles having a particle size of 60 μm or less in the prepolymerized addition polymerization catalyst component was 4.1%.

(4) 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. Furthermore, 359.8 mg of the prepolymerized addition polymerization catalyst component obtained in the above (3) was added. Polymerization was carried out at 70 ° C. for 3 hours while feeding an ethylene / hydrogen mixed gas (hydrogen 0.304 mol%) so as to keep the total pressure constant. As a result, 16 g of an olefin polymer was obtained. The polymerization activity per activator (B) was 760 g / g. Moreover, the obtained olefin polymer was MFR = 3.57 and SR = 1.48.

[Example 2]
(1) Production of coated reactor Coated reaction as in Example 1 (2) except that sodium stearate ([CH ₃ (CH ₂ ) ₁₆ COO] Na) was used instead of sodium butyrate A vessel was manufactured. The amount of the coating compound relative to the inner wall area of the reactor was 486 mg / m ² .

(2) The pre-polymerized and coated reactor was dried under reduced pressure and then replaced with argon, followed by evacuation, and 480 g of butane and 202 mg (378 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. After stirring at 50 ° C. for 1 hour, 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 (1) were added, and then hexane of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml Preliminary polymerization was started by adding 3.5 ml (3.5 mmol) of the solution. 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: 0.195 mol%) was switched to, while supplying at 0.81 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 2 hours. It was. The monomer and butane were purged and the prepolymerized addition polymerization catalyst component was recovered. The recovered amount was 120.6 g, and the degree of polymerization per modified particle (B) was 17.3 g / g. Further, 1.1 g of the recovered prepolymerized addition polymerization catalyst component was recovered as a deposit on the inner wall of the reactor. As a result of the particle size distribution measurement, the content of particles having a particle size of 60 μm or less in the prepolymerized addition polymerization catalyst component was 4.4%.

(3) 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 = 1.81 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, 356.2 mg of the prepolymerized addition polymerization catalyst component obtained in the above (2) 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, 80 g of an olefin polymer was obtained. The polymerization activity per activator (B) was 3890 g / g. Moreover, the obtained olefin polymer was MFR = 3.40 and SR = 1.47.

[Example 3]
(1) Production of coated reactor Coated reaction as in Example 1 (2) except that calcium stearate ([CH ₃ (CH ₂ ) ₁₆ COO] ₂ Ca) was used instead of sodium butyrate A vessel was manufactured. The amount of the coating compound relative to the inner wall area of the reactor was 486 mg / m ² .

(2) The prepolymerized reactor was dried under reduced pressure, and then replaced with argon, followed by vacuum, and 480 g of butane and 213 mg (399 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. After stirring at 50 ° C for 1 hour, 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 (1) were added, and then hexane of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml Preliminary polymerization was started by adding 3.5 ml (3.5 mmol) of the solution. 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: 0.193 mol%) was switched to, while supplying at 0.81 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 2 hours. It was. The monomer and butane were purged and the prepolymerized addition polymerization catalyst component was recovered. The recovered amount was 129.1 g, and the degree of polymerization per modified particle (B) was 18.5 g / g. Further, 5.1 g of the recovered prepolymerized addition polymerization catalyst component was recovered as a deposit on the inner wall of the reactor. As a result of the particle size distribution measurement, the content of particles having a particle size of 60 μm or less in the prepolymerized addition polymerization catalyst component was 5.9%.

(3) 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. Furthermore, 380.7 mg of the prepolymerized addition polymerization catalyst component obtained in the above (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, 131 g of an olefin polymer was obtained. The polymerization activity per activator (B) was 6370 g / g. Moreover, the obtained olefin polymer was MFR = 1.42 and SR = 1.41.

[Example 4]
(1) Production of coated reactor Coated as in Example 1 (2) except that zinc stearate ([CH ₃ (CH ₂ ) ₁₆ COO] ₂ Zn) was used instead of sodium butyrate A reactor was manufactured. The amount of the coating compound relative to the inner wall area of the reactor was 486 mg / m ² .

(2) The pre-polymerized and coated reactor was dried under reduced pressure and then replaced with argon, followed by evacuation, and 480 g of butane and 220 mg (412 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. After stirring at 50 ° C. for 1 hour, 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 (1) were added, and then hexane of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml Preliminary polymerization was started by adding 3.5 ml (3.5 mmol) of the solution. 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: 0.195 mol%) was switched to, while supplying at 0.81 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 2 hours. It was. The monomer and butane were purged and the prepolymerized addition polymerization catalyst component was recovered. The recovered amount was 127.2 g, and the degree of polymerization per modified particle (B) was 18.4 g / g. Further, 3.8 g of the recovered prepolymerized addition polymerization catalyst component was recovered as a deposit on the inner wall of the reactor. As a result of the particle size distribution measurement, the content of particles having a particle size of 60 μm or less in the prepolymerized addition polymerization catalyst component was 10.5%.

(3) 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 = 1.90 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 the above (2) 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, 105 g of an olefin polymer was obtained. The polymerization activity per activator (B) was 5120 g / g. Moreover, the obtained olefin polymer was MFR = 2.05 and SR = 1.43.

[Example 5]
(1) Preparation of coated reactor Example 1 (2) with the exception that aluminum monostearate ([CH ₃ (CH ₂ ) ₁₆ COO] (OH) ₂ Al) was used instead of sodium butyrate. A coated reactor was prepared as well. The amount of the coating compound relative to the inner wall area of the reactor was 486 mg / m ² .

(2) The pre-polymerized and coated reactor was dried under reduced pressure and then replaced with argon, followed by evacuation, and 480 g of butane and 220 mg (412 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) were added. After stirring at 50 ° C for 1 hour, 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 (1) were added, and then hexane of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml Preliminary polymerization was started by adding 3.5 ml (3.5 mmol) of the solution. 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 0.81 g / min, the temperature was raised to 50 ° C. over 30 minutes, followed by prepolymerization at 50 ° C. for 2 hours. It was. The monomer and butane were purged and the prepolymerized addition polymerization catalyst component was recovered. The recovered amount was 129.3 g, and the degree of polymerization per modified particle (B) was 18.3 g / g. Further, 2.1 g of the recovered prepolymerized addition polymerization catalyst component was recovered as a deposit on the inner wall of the reactor. As a result of the particle size distribution measurement, the content of particles having a particle size of 60 μm or less in the prepolymerized addition polymerization catalyst component was 3.9%.

(3) 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. Furthermore, 367.1 mg of the prepolymerized addition polymerization catalyst component obtained in (2) above 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, 120 g of an olefin polymer was obtained. The polymerization activity per activator (B) was 5960 g / g. Further, the obtained olefin polymer had MFR = 1.94 and SR = 1.43.

[Comparative Example 1]
(1) Prepolymerization 198 mg (372 μmol) of ethylenebis (indenyl) zirconium diphenoxide (A) and 7.0 g of modified particles (B) were added and ethylene was used in a reactor without coating. / Preliminary polymerization was carried out in the same manner as in Example 1 (3) except that a gas having a hydrogen concentration of 0.183 mol% was used as the hydrogen mixed gas. The recovered amount was 130.3 g, and the degree of polymerization per modified particle (B) was 18.6 g / g. In addition, 7.1 g of the recovered prepolymerized addition polymerization catalyst component was recovered as a deposit on the inner wall of the reactor. As a result of the particle size distribution measurement, the content of particles having a particle size of 60 μm or less in the prepolymerized addition polymerization catalyst component was 11.0%.

(2) 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 = 1.90 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, 384.1 mg of the prepolymerized addition polymerization catalyst component obtained in the above (1) was added. Polymerization was carried out at 70 ° C. for 3 hours while feeding an ethylene / hydrogen mixed gas (hydrogen 0.315 mol%) so as to keep the total pressure constant. As a result, 104 g of an olefin polymer was obtained. The polymerization activity per activator (B) was 5170 g / g. Moreover, the obtained olefin polymer was MFR = 1.86 and SR = 1.42.

Claims (13)

A method of coating the inner wall surface of a reactor with a compound represented by the following general formula [1].
(R ¹ COO) _l R ² _m M ¹ [1]
(In the above general formula [1], R ¹ represents an optionally substituted hydrocarbyl group having 1 to 20 carbon atoms, and when a plurality of R ¹ are present, they are the same as each other. R ² represents a hydrogen atom, a hydroxy group, or a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent, and when there are a plurality of R ² , M ¹ may be the same as or different from each other, and M ¹ represents groups 1, 2, 8, 9, 10, 11, 12, and 12 in the periodic table. Represents a metal atom selected from the group consisting of Group 13. l represents a number of 1 or more, m represents a number of 0 or more, provided that l and m are numbers satisfying 1 ≦ l + m ≦ n, and n is Represents the number corresponding to the valence of M ¹ )   The method of coating according to claim 1, wherein the reactor is a reactor for addition polymerization.   Coated reactor obtained by the method according to claim 1 or 2. It is the addition polymerization method performed with the coated reactor of Claim 3, Comprising: The transition metal compound (A) represented by following General formula [2], or its mu-oxo type transition metal compound dimer (A ') And an addition polymerization method in which a monomer capable of addition polymerization is subjected to addition polymerization using a primary catalyst obtained by contacting the activator (B).
L ¹ _a M ² X ¹ _b [2]
(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.)   Primary catalyst obtained by contacting transition metal compound (A) or its μ-oxo type dimer (A ′), activator (B) and organoaluminum compound (C) The addition polymerization method according to claim 4, wherein a monomer capable of addition polymerization is subjected to addition polymerization. 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 [3] M ³ L ² ₂ [3]
(B): Compound represented by the following general formula [4] R ³ _t-1 TH [4]
(C): Compound represented by the following general formula [5] R ⁴ _t-2 TH ₂ [5]
(D): Inorganic oxide particles or organic polymer particles (in the above general formulas [3] to [5], 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 ³ represents an electron-withdrawing group or a group containing an electron-withdrawing group, and R 3 ^{When a} plurality of ³ are present, they may be the same or different from each other, R ⁴ 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 4 to 6, wherein the addition polymerization is preliminary polymerization.   A prepolymerized addition polymerization catalyst component obtained by the method according to claim 7.   A method for producing an addition polymer using the prepolymerized addition polymerization catalyst component according to claim 8.   A method for producing an addition polymer using the prepolymerized addition polymerization catalyst component according to claim 8 and the organoaluminum compound (C).   A primary product obtained by contacting a transition metal compound (A) represented by the general formula [2] or its μ-oxo type transition metal compound dimer (A ′) with an activator (B). A prepolymerized addition polymerization catalyst component is obtained by prepolymerizing a monomer capable of addition polymerization using a catalyst, and the addition polymerization is carried out in the presence of the prepolymerized addition polymerization catalyst component in the coated reactor according to claim 3. A method for producing an addition polymer in which possible monomers are addition-polymerized.   A primary product obtained by contacting a transition metal compound (A) represented by the general formula [2] or its μ-oxo type transition metal compound dimer (A ′) with an activator (B). A prepolymerized addition polymerization catalyst component is obtained by prepolymerizing a monomer capable of addition polymerization using a catalyst, and the prepolymerized addition polymerization catalyst component and the organoaluminum compound ( A method for producing an addition polymer in which addition-polymerizable monomers are added in the presence of C).   The method for producing an addition polymer according to any one of claims 9 to 12, wherein the addition polymer is a copolymer of ethylene and an α-olefin.