JP2012193347A - Method for performing addition polymerization, preliminary polymerized catalytic component for addition polymerization and method for producing addition polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for performing polymerization, capable of giving an addition polymer containing less fine powder, or a preliminary polymerized addition polymerization catalytic component.SOLUTION: This method for performing the addition polymerization of an addition polymerizable monomer, includes the following processes: (1) a process of forming a mixture by mixing a solvent used for the polymerization with (D) an organic compound expressed by formula [2]; (2) a process of performing the addition polymerization of the monomer in the mixture in the presence of a catalyst formed by making a contact of (A) a compound selected from a transition metal compound expressed by formula [1] and its μ-oxo type transition metal compound dimer with (B) an activator, wherein formula [1] is LMXand formula [2] is R-O-(-R-O-)Q.

Description

  The present invention relates to an addition polymerization method, a prepolymerized catalyst component for addition polymerization, and a method for producing an addition polymer.

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

  In recent years, these addition polymers are produced by polymerizing olefins or the like using a catalyst in which a transition metal component composed of a transition metal compound and an organometallic component composed of an aluminoxane or the like are combined.

  Since these catalysts are soluble in the reaction system, when the catalyst is applied to polymerization involving the formation of addition polymer particles, the shape of the resulting addition polymer can be changed by using specific particles as one of the catalyst components. It is known that it can be shaped. For example, Patent Document 1 describes modified particles obtained using silica gel, an organic zinc compound, trifluorophenols, and water, and a catalyst formed by combining the particles, a transition metal compound, and organoaluminum. Is used to polymerize olefins.

  In addition, it is known that when a polymerization in which an addition polymer is produced in the form of particles is industrially carried out, it is effective to perform a prepolymerization step as a previous stage of the main polymerization step. For example, Patent Document 2 discloses a catalyst component for olefin polymerization obtained by prepolymerizing an olefin with a catalyst obtained by using specific particles as one of the catalyst components, and obtaining the prepolymerized catalyst component. A method for carrying out the main polymerization using is described.

JP 2003-171413 A JP 2002-293817 A

  However, in these methods, a finely powdered addition polymer or a prepolymerized catalyst component may be produced, which is not fully satisfactory from the viewpoint of stable operation and productivity of the addition polymer. It is an object of the present invention to provide a polymerization process that provides an addition polymer with a reduced fines and a prepolymerized catalyst component for addition polymerization.

The first of the present invention is a method of addition polymerization of a monomer capable of addition polymerization, which is a method having the following steps.
(1) Step of mixing a polymerization solvent and an organic compound (D) represented by formula [2] to form a mixture (2) Transition metal compound represented by formula [1] and its μ-oxo type A step of polymerizing the monomer in the mixture in the presence of a catalyst formed by contacting a compound (A) selected from the transition metal compound dimers of (1) with an activator (B) L ¹ _a M ¹ X ¹ _b [1]
M ¹ is a Group 4 transition metal atom; L ¹ is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom; X ¹ is a halogen atom, a hydrocarbyloxy group, or a hydrocarbyl A group (excluding a group having a cyclopentadiene-type anion skeleton); a is a number satisfying 0 <a ≦ 3; b is a number satisfying 0 <b ≦ 3; When larger, one L ¹ may be linked to each other L ¹ directly or through a group containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
R ¹ —O — (— R ² —O—) _n Q ¹ [2]
R ¹ is an optionally substituted hydrocarbyl group having 1 to 30 carbon atoms; R ² is an optionally substituted alkylene group having 1 to 20 carbon atoms; Q ¹ represents a hydrogen ^{atom, -C (= O) OM 2} , -R 3 -C (= O) OM 2, -S (= O) 2 OM 2, -R 3 -S (= O) 2 OM 2, ^{-P (= O) (OH)} (OM 2), - P (= O) (oR 4) (OM 2), or ^{-P (= O) (OM 2} ) be a _2; ^{M 2} represents a hydrogen atom or R ³ is an optionally substituted alkylene group having 1 to 20 carbon atoms; R ⁴ is an optionally substituted hydro carbon having 1 to 20 carbon atoms; N is a number from 1 to 100; when n is greater than 1, the plurality of R ² may be the same or different.

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

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

A fourth aspect of the present invention relates to a prepolymerized addition polymerization catalyst component having a cumulative weight fraction of 7% or less of a prepolymerized addition polymerization catalyst component having a particle size of 60 μm or less. is there.

  According to the method of the present invention, when the addition polymer or the prepolymerized catalyst component for addition polymerization can be produced, the generation of fine powder can be suppressed, so that the polymerization can be carried out stably and continuously.

  Hereinafter, the present invention will be described in detail.

Compound (A): Transition metal compound or its μ-oxo type transition metal compound dimer The compound (A) used in the present invention is selected from a transition metal compound and its μ-oxo type transition metal compound dimer. It is. Examples of the transition metal compound or a μ-oxo type transition metal compound dimer thereof include a transition metal compound represented by the following formula [1] or a dimer of the μ-oxo type transition metal compound.
L ¹ _a M ¹ X ¹ _b [1]
Wherein M ¹ is a Group 4 transition metal atom; L ¹ is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom; X ¹ is a halogen atom, a hydrocarbyloxy group, or A hydrocarbyl group (excluding a group having a cyclopentadiene type anion skeleton); a is a number satisfying 0 <a ≦ 3; b is a number satisfying 0 <b ≦ 3; when a is greater than 1, one L ¹ is linked to another L ¹ directly or via a group containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom Also good.

M ^{1 in the} formula [1] 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 [1] 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 [1] 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 [1] 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 [1] 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 ⁷ ₃ P = N- [6]
(Wherein, each R ⁷ independently represents a hydrogen atom, a halogen atom or a hydrocarbyl group, a plurality of R ⁷ may be different from one another the same, out of the plurality of R ^7, any two Two or more may be bonded to each other and may form a ring structure.)

Specific examples of R ⁷ 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.

［７］






（式中、Ｒ^８はそれぞれ独立に、水素原子、ハロゲン原子、ハイドロカルビル基、ハロゲン化ハイドロカルビル基、ハイドロカルビルオキシ基、シリル基またはアミノ基を表し、複数のＲ^８は互いに同じであっても異なっていてもよく、複数のＲ^８のうち、任意の２つ以上が互いに結合していてもよく、環構造を形成していてもよい。） Further, examples of the group containing a hetero atom include a group represented by the following formula [7].

[7]






(In the formula, each R ⁸ 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 a plurality of R ⁸ are the same as each other. Or any two or more of R ⁸ may be bonded to each other and may form a ring structure.)

Specific examples of R ⁸ 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 [1] 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 [1] 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 [1], when a plurality of L ¹ are linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom (that is, a cyclopentadiene anion When a group having a skeleton is linked via its residue, a group containing a hetero atom is linked via its residue, or a group having a cyclopentadiene-type anion skeleton and a hetero atom A group containing a hydrogen atom), and as the residue, preferably the two atoms bonded to L ¹ are a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or It is a phosphorus atom and is a divalent residue having a minimum atomic number of 3 or less for bonding two L ¹ . As the residue, alkylene groups such as methylene group, ethylene group and propylene group; substituted alkylene groups such as dimethylmethylene group (isopropylidene group) and diphenylmethylene group; silylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group And substituted silylene groups such as tetramethyldisilene group and dimethoxysilylene group; and heteroatoms such as nitrogen atom, oxygen atom, sulfur atom and phosphorus atom. Among these, a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), a diphenylmethylene group, a dimethylsilylene group, a diethylsilylene group, a diphenylsilylene group, or a dimethoxysilylene group is particularly preferable.

Examples of the halogen atom represented by X ¹ in the formula [1] 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 of X ¹ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n -Pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, and n-eicosyl group, among others, more A methyl group, ethyl group, isopropyl group, tert-butyl group, isobutyl group or amyl group is preferred. Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluorobutyl group. Mention may be made of fluorohexyl, perfluorooctyl, perchloropropyl, perchlorobutyl and perbromopropyl groups. These alkyl groups may have an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, an aralkyloxy group such as a benzyloxy group, and the like as a substituent.

Examples of the aralkyl group having 7 to 20 carbon atoms of X ¹ include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2, 3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl Group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl Group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2 3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) Methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) ) Methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, and anthracenylmethyl group More preferred is a benzyl group. These aralkyl groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. As a substituent.

Examples of the aryl group having 6 to 20 carbon atoms of X ¹ include, for example, phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2 , 5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3 , 6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethyl Phenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert- Tylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, and anthracenyl Group, and more preferably a phenyl group. These aryl groups include fluorine atoms, chlorine atoms, bromine atoms, halogen atoms such as iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. You may have as a substituent.

Examples of the alkenyl group having 3 to 20 carbon atoms for X ¹ include an allyl group, a methallyl group, a crotyl group, and a 1,3-diphenyl-2-propenyl group. Among them, an allyl group is more preferable. Or a methallyl group.

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

Examples of the alkoxy group having 1 to 20 carbon atoms of X ¹ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, and an n-pentoxy group. Group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, and n-icosoxy group. Among them, methoxy group, ethoxy group, isopropoxy group are preferable. Or a tert-butoxy group. These alkoxy groups include fluorine atoms, chlorine atoms, halogen atoms such as bromine atoms and iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. You may have as a substituent.

Examples of the aralkyloxy group having 7 to 20 carbon atoms of X ¹ 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- (Limethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethyl) Phenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) ) Methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, and anthracenylmethoxy group Among them, a benzyloxy group is more preferable. These aralkyloxy groups include fluorine atoms, chlorine atoms, halogen atoms such as bromine atoms and iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. As a substituent.

Examples of the aryloxy group having 6 to 20 carbon atoms of X ¹ include, for example, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2, 4 -Dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2 -Tert-butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5 -Trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6- Limethylphenoxy 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-trimethyl Phenoxy 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-tetramethylphenol Noxy 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 And anthracenoxy group. These aryloxy groups include fluorine atoms, chlorine atoms, halogen atoms such as bromine atoms and iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. As a substituent.

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

In Formula [1], a is a number that satisfies 0 <a ≦ 3, and b is a number that satisfies 0 <b ≦ 3. a and b are appropriately selected according to the valence of M ¹ . When M ¹ is a titanium atom, a zirconium atom or a hafnium atom, a is preferably 2, and b is also preferably 2.

  Examples of the transition metal compound represented by the formula [1] 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-dimethylcyclopentadiene) Enyl) titanium dichloride, bis (1-methyl-2-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-n-butyl) Cyclopentadienyl) titanium dichlora Bis (1-methyl-3-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-isopropylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-isopropylcyclopentadiene) Enyl) titanium dichloride, bis (1-tert-butyl-2-methylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-3-methylcyclopentadienyl) 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 (Indeni ) Titanium dichloride, bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenyl indenyl) titanium dichloride,

Bis [2- (bis-3,5-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-tert-butylphenyl) indenyl] titanium dichloride, bis [2- (4-trifluoromethylphenyl) Indenyl] titanium dichloride, bis [2- (4-methylphenyl) indenyl] titanium dichloride, bis [2- (3,5-dimethylphenyl) indenyl] titanium dichloride, bis [2- (pentafluorophenyl) indenyl] titanium dichloride , Cyclopentadienyl (pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride , Pentamethylcyclopentadienyl (indenyl) titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-phenylindenyl) titanium dichloride, pentamethylcyclopentadienyl (2-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 In the above compound, “(2-phenoxy)” is replaced with “(3-phenyl-2-phenoxy)”, “(3-trimethylsilyl-2-phenoxy)”, or “(3-tert-butyldimethylsilyl-2- Compound replaced with “phenoxy)”, the above compound Also included are compounds in which “dimethylsilylene” is replaced with “methylene”, “ethylene”, “dimethylmethylene (isopropylidene)”, “diphenylmethylene”, “diethylsilylene”, “diphenylsilylene”, or “dimethoxysilylene”. .

Moreover, the following compound is also mentioned as a specific example of the transition metal compound represented by Formula [1].

In addition to these, compounds in which the titanium atom of the above compound is replaced with a zirconium atom or a hafnium atom are also included.

Furthermore, the “dichloride” in the above compound is replaced with “difluoride”, “dibromide”, “diaiodide”, “dimethyl,“ diethyl ”,“ diisopropyl ”,“ diphenyl ”,“ dibenzyl ”,“ dimethoxide ”,“ diethoxide ”. , “Di (n-propoxide)”, “di (isopropoxide)”, “diphenoxide” or “di (pentafluorophenoxide)”, and “trichloride” as “trifluoride”, “Tribromide”, “Triiodide”, “Trimethyl”, “Triethyl”, “Triisopropyl”, “Triphenyl”, “Tribenzyl”, “Trimethoxide”, “Triethoxide”, “Tri (n-propoxide)” , “Tri (isopropoxide)”, “triphenoxide”, or “to Compounds obtained by replacing the (pentafluoro phenoxide) "can be exemplified.

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

Of the transition metal compounds exemplified above, the compound (A) used in the present invention is preferably a compound in which M ¹ is zirconium, or at least one group having a cyclopentadiene-type anion skeleton as L ¹ in the formula [1]. One transition metal compound is preferable. Among them, L ¹ in the formula [1] has two groups having a cyclopentadiene type anion skeleton, and L ¹ is mutually via a group containing a carbon atom, a silicon atom, an oxygen atom, a sulfur atom or a phosphorus atom. Linked zirconium compounds are particularly preferred.

  The transition metal compound represented by the formula [1] 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.

Organic compound (D)
The organic compound (D) used in the present invention is specifically an organic compound represented by the formula [2].
R ¹ —O — (— R ² —O—) _n Q ¹ [2]
R ¹ is an optionally substituted hydrocarbyl group having 1 to 30 carbon atoms; R ² is an optionally substituted alkylene group having 1 to 20 carbon atoms; Q ¹ represents a hydrogen ^{atom, -C (= O) OM 2} , -R 3 -C (= O) OM 2, -S (= O) 2 OM 2, -R 3 -S (= O) 2 OM 2, ^{-P (= O) (OH)} (OM 2), - P (= O) (oR 4) (OM 2), or ^{-P (= O) (OM 2} ) be a _2; ^{M 2} represents a hydrogen atom or R ³ is an optionally substituted alkylene group having 1 to 20 carbon atoms; R ⁴ is an optionally substituted hydro carbon having 1 to 20 carbon atoms; N is a number from 1 to 100; when n is greater than 1, the plurality of R ² may be the same or different.

The hydrocarbyl group having 1 to 30 carbon atoms which may have a substituent of R ¹ has an alkyl group having 1 to 30 carbon atoms and a substituent which may have a substituent. Examples thereof include an aralkyl group having 7 to 30 carbon atoms which may be present, and an aryl group having 6 to 30 carbon atoms which may have a substituent.

Examples of the alkyl group having 1 to 30 carbon atoms which may have a substituent of R ¹ include an alkyl group having 1 to 30 carbon atoms and an alkyl group having 1 to 30 carbon atoms having a halogen atom as a substituent. , An alkyl group having 1 to 30 carbon atoms having a substituted silyl group as a substituent, an alkyl group having 1 to 30 carbon atoms having a substituted amino group as a substituent, and the number of carbon atoms having a hydrocarbyloxy group as a substituent Examples thereof include 1-30 alkyl groups.

Examples of the alkyl group having 1 to 30 carbon atoms of R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Neopentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n- Tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n- Tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, n-triacontyl group, etc. I can give it.

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

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

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

Examples of the alkyl group having 1 to 30 carbon atoms having the hydrocarbyloxy group of R ¹ as a substituent include, for example, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, and 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-pro Pyl 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.

Examples of the aralkyl group having 7 to 30 carbon atoms which may have a substituent of R ¹ include an aralkyl group having 7 to 30 carbon atoms and an aralkyl group having 7 to 30 carbon atoms having a halogen atom as a substituent. Etc.

Examples of the aralkyl group having 7 to 30 carbon atoms of R ¹ include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2, 3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl Group, (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 , 3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) ) Methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentyl) Phenyl) 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 Diphenylmethyl group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group.

Examples of the aralkyl group having 7 to 30 carbon atoms having the halogen atom of R ¹ as a substituent include 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2-chlorobenzyl group, 3- Examples include 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 30 carbon atoms which may have a substituent of R ¹ include an aryl group having 6 to 30 carbon atoms and an aryl group having 6 to 30 carbon atoms having a halogen atom as a substituent. An aryl group having 6 to 30 carbon atoms having a substituted silyl group as a substituent, an aryl group having 6 to 30 carbon atoms having a substituted amino group as a substituent, and a carbon atom number having a hydrocarbyloxy group as a substituent A 6-30 aryl group etc. are mentioned.

Examples of the aryl group having 6 to 30 carbon atoms of R ¹ include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2 , 5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3 , 6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethyl Phenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl Group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, Examples thereof include an n-tetradecylphenyl group, a naphthyl group, and an anthracenyl group.

Examples of the aryl group having 6 to 30 carbon atoms having the halogen atom of R ¹ as a substituent include, for example, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl. Group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group and the like.

Examples of the aryl group having 6 to 30 carbon atoms having the substituted silyl group of R ¹ as a substituent include a trimethylsilylphenyl group and a bis (trimethylsilyl) phenyl group.

Examples of the aryl group having 6 to 30 carbon atoms having the substituted amino group of R ¹ as a substituent include a dimethylaminophenyl group, a bis (dimethylamino) phenyl group, and a diphenylaminophenyl group.

Examples of the aryl group having 6 to 30 carbon atoms having the hydrocarbyloxy group of R ¹ as a substituent include, for example, a methoxyphenyl group, an ethoxyphenyl group, an n-propoxyphenyl group, an isopropoxyphenyl group, and n-butoxyphenyl. Group, sec-butoxyphenyl group, tert-butoxyphenyl group, phenoxyphenyl group and the like.

R ¹ in the formula [2] is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent, and more preferably an alkyl group having 1 to 30 carbon atoms.

R ² represents an optionally substituted alkylene group having 1 to 20 carbon atoms, and a plurality of R ² may be the same as or different from each other.

The alkylene group having 1 to 20 carbon atoms which may have a substituent of R ² includes an alkylene group having 1 to 20 carbon atoms and an alkylene group having 1 to 20 carbon atoms having a halogen atom as a substituent. , An alkylene group having 1 to 20 carbon atoms having a substituted silyl group as a substituent, an alkylene group having 1 to 20 carbon atoms having a substituted amino group as a substituent, and the number of carbon atoms having a hydrocarbyloxy group as a substituent Examples thereof include 1 to 20 alkylene groups.

Examples of the alkylene group having 1 to 20 carbon atoms of R ² include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, and an undecylene group. , Dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, eicosylene group, methylmethylene group, dimethylmethylene group, ethylmethylene group, ethylmethylmethylene group, diethylmethylene group, propylene Examples include a methylene group, a methylethylene group, a dimethylethylene group, a trimethylethylene group, and a tetramethylethylene group.

Examples of the alkylene group having 1 to 20 carbon atoms having the halogen atom of R ² as a substituent include, for example, a fluoromethylene group, a difluoromethylene group, a chloromethylene group, a dichloromethylene group, a bromomethylene group, a dibromomethylene group, and an iodomethylene. Group, diiodomethylene group, fluoroethylene group, difluoroethylene group, trifluoroethylene group, tetrafluoroethylene group, chloroethylene group, dichloroethylene group, trichloroethylene group, tetrachloroethylene group, bromoethylene group, dibromoethylene group, tribromoethylene group , Tetrabromoethylene group, perfluoropropylene group, perfluorobutylene group, perfluoropentylene group, perfluorohexylene group, perfluorooctylene group, perfluorododecylene group, perful Olopentadecylene group, perfluoroeicosylene group, perchloropropylene group, perchlorobutylene group, perchloropentylene group, perchlorohexylene group, perchlorooctylene group, perchlorododecylene group, perchloropenta group Decylene group, perchloroeicosylene group, perbromopropylene group, perbromobutylene group, perbromopentylene group, perbromohexylene group, perbromooctylene group, perbromododecylene group, perbromopentadecylene group Group, perbromoeicosylene group, and the like.

Examples of the alkylene group having 1 to 30 carbon atoms having the substituted silyl group of R ^{2 as} a substituent include, for example, trimethylsilylmethylene group, trimethylsilylethylene group, trimethylsilylpropylene group, trimethylsilylbutylene group, bis (trimethylsilyl) methylene group, bis ( Trimethylsilyl) ethylene group, bis (trimethylsilyl) propylene group, bis (trimethylsilyl) butylene group, triphenylsilylmethyl group and the like.

Examples of the alkylene group having 1 to 30 carbon atoms having the substituted amino group of R ^{2 as} a substituent include dimethylaminomethylene group, dimethylaminoethylene group, dimethylaminopropylene group, dimethylaminobutylene group, and bis (dimethylamino). Examples include methylene group, bis (dimethylamino) ethylene group, bis (dimethylamino) propylene group, bis (dimethylamino) butylene group, phenylaminomethylene group, diphenylaminomethylene group and the like.

Examples of the alkylene group having 1 to 20 carbon atoms having the hydrocarbyloxy group of R ² as a substituent include, for example, a methoxymethylene group, an ethoxymethylene group, an n-propoxymethylene group, an isopropoxymethylene group, and an n-butoxymethylene group. Group, sec-butoxymethylene group, tert-butoxymethylene group, phenoxymethylene group, methoxyethylene group, ethoxyethylene group, n-propoxyethylene group, isopropoxyethylene group, n-butoxyethylene group, sec-butoxyethylene group, tert -Butoxyethylene group, phenoxyethylene group, methoxy-n-propylene group, ethoxy-n-propylene group, n-propoxy-n-propylene group, isopropoxy-n-propylene group, n-butoxy-n-propylene group, sec -Butoxy- n-propylene group, tert-butoxy-n-propylene group, phenoxy-n-propylene group, methoxyisopropylene group, ethoxyisopropylene group, n-propoxyisopropylene group, isopropoxyisopropylene group, n-butoxyisopropylene group , Sec-butoxyisopropylene group, tert-butoxyisopropylene group, phenoxyisopropylene group and the like.

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

Q ¹ represents a hydrogen ^{atom, -C (= O) OM 2} , -R 3 -C (= O) OM 2, -S (= O) 2 OM 2, -R 3 -S (= O) 2 OM 2, ^{-P (= O) (OH)} (OM 2), - represents a ^{P (= O) (oR 4} ) (OM 2), or ^{-P (= O) (OM 2} ) 2.

Q ¹ is preferably a hydrogen atom, —C (═O) OM ² , —R ³ —C (═O) OM ² , —S (═O) ₂ OM ² , —R ³ —S (═O) _2. OM ² , more preferably a hydrogen atom, —R ³ —C (═O) OM ² , —S (═O) ₂ OM ² .

In the above examples, M ² represents an alkali metal atom.

M ² is preferably a sodium atom or a potassium atom, and more preferably a sodium atom.

In the above examples, R ³ represents an alkylene group having 1 to 20 carbon atoms which may have a substituent.

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

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

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

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

Examples of the alkyl group having 1 to 20 carbon atoms that may have a substituent of R ⁴ include an alkyl group having 1 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms having a halogen atom as a substituent. , An alkyl group having 1 to 20 carbon atoms having a substituted silyl group as a substituent, an alkyl group having 1 to 20 carbon atoms having a substituted amino group as a substituent, and the number of carbon atoms having a hydrocarbyloxy group as a substituent Examples thereof include 1 to 20 alkyl groups.

Examples of the alkyl group having 1 to 20 carbon atoms of R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , 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- Examples include tetradecyl group, 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 the halogen atom of R ⁴ as a substituent include, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, and bromomethyl. Group, dibromomethyl group, tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl Group, trichloroethyl group, tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perful Oropentyl 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 the substituted silyl group of R ^{4 as} a substituent include, for example, trimethylsilylmethyl group, trimethylsilylethyl group, trimethylsilylpropyl group, trimethylsilylbutyl group, bis (trimethylsilyl) methyl group, bis ( Examples thereof include trimethylsilyl) ethyl group, bis (trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, and triphenylsilylmethyl group.

Examples of the alkyl group having 1 to 20 carbon atoms having the substituted amino group of R ^{4 as} a substituent include dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminopropyl group, dimethylaminobutyl group, and bis (dimethylamino). Examples thereof include a methyl group, a bis (dimethylamino) ethyl group, a bis (dimethylamino) propyl group, a bis (dimethylamino) butyl group, a phenylaminomethyl group, and a diphenylaminomethyl group.

Examples of the alkyl group having 1 to 20 carbon atoms having the hydrocarbyloxy group of R ⁴ as a substituent include, for example, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, and 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-pro Pyl 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.

The aralkyl group having 7 to 20 carbon atoms which may have a substituent of R ⁴ includes 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. Etc.

Examples of the aralkyl group having 7 to 20 carbon atoms of R ⁴ include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2, 3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl Group, (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 , 3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) ) Methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentyl) Phenyl) 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 Diphenylmethyl group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group.

Examples of the aralkyl group having 7 to 20 carbon atoms having the halogen atom of R ⁴ as a substituent include, for example, 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2-chlorobenzyl group, 3- Examples include 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 of R ⁴ 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-tetramethyl Phenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert- Butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl, and And anthracenyl group.

Examples of the aryl group having 6 to 20 carbon atoms substituted by the halogen atom of R ⁴ include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl. Group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group and the like.

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

  n represents a number from 1 to 100.

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

  Examples of the organic compound (D) include polyoxyethylene lauryl ether, polyoxyethylene lauryl ether acetic acid, sodium polyoxyethylene lauryl ether acetate, potassium polyoxyethylene lauryl ether acetate, polyoxyethylene lauryl ether ammonium acetate, polyoxyethylene lauryl ether Triethanolamine acetate, polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, potassium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, polyoxyethylene lauryl ether sulfate triethanolamine, polyoxyethylene lauryl ether Phosphoric acid, polyoxyethylene lauryl ether sodium phosphate, polyoxy Potassium Ji Ren lauryl ether phosphate, ammonium polyoxyethylene lauryl ether phosphoric acid, polyoxyethylene lauryl ether phosphate triethanolamine, and the like.

  The organic compound (D) is preferably polyoxyethylene lauryl ether, polyoxyethylene lauryl ether acetic acid, polyoxyethylene lauryl ether sodium acetate, polyoxyethylene lauryl ether sulfate, polyoxyethylene lauryl ether sodium sulfate, and more preferably Is sodium polyoxyethylene lauryl ether acetate.

Activator (B)
The activator (B) used in the present invention may be any one that can activate the compound (A). When applying a catalyst to polymerization that involves the formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.), the shape of the resulting addition polymer is fixed using specific particles as one of the catalyst components. It is preferable to make it. As specific particles, the following modified particles (I), (II) or (III) can be preferably 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 ⁵ _t-1 TH [4]
(C): Compound represented by the following general formula [5] R ⁶ _u-2 T′H ₂ [5]
(D): Inorganic oxide particles or organic polymer particles (M ³ is a Group 12 element; L ² is a hydrogen atom, a halogen atom or a hydrocarbyl group, and the two L ² may be the same as each other R ⁵ may be an electron-withdrawing group or a group containing an electron-withdrawing group; when t-1 is greater than 1, a plurality of R ⁵ may be the same or different from each other R ⁶ is a hydrocarbyl group or a halogenated hydrocarbyl group; T is a Group 15 element or Group 16 element; t is a number corresponding to the valence of T; A group element or a group 16 element; u is a number corresponding to the valence of T ′.)

(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 transition metal compound (A) into contact with each other.

M ³ in the formula [3] represents a group 12 element 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 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 the alkyl groups of L ² may have a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a substituent. 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 have, as a substituent, 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. You may have a group etc. as a substituent.

As the aralkyl group of L ^2, an aralkyl group having 7 to 20 carbon atoms is preferable. For example, benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl Group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4) -Dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6) -Trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethyl) Phenyl) 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. You may have a group etc. as a substituent.

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 Formula [4] represents a Group 15 element or a Group 16 element in the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). Specific examples of the Group 15 element include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 element include an oxygen atom and a sulfur atom. T is preferably a nitrogen atom or an oxygen atom, and particularly preferably an oxygen atom.
In the formula [4], t represents the valence of T. When T is a Group 15 element, t is 3, and when T is a Group 16 element, t is 2.

T ′ in the formula [5] represents a group 15 element or a group 16 element in the periodic table of elements (IUPAC inorganic chemical nomenclature revised edition 1989). Specific examples of the Group 15 element include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 element include an oxygen atom and a sulfur atom. T ′ is preferably a nitrogen atom or an oxygen atom, and particularly preferably an oxygen atom.
In formula [5], u represents the valence of T ′. When T ′ is a Group 15 element, u is 3, and when T ′ is a Group 16 element, u is 2.

R ⁵ in the general formula [4] represents an electron-withdrawing group or a group containing an electron-withdrawing group, and when a plurality of R ⁵ are present, they may be the same as or different from each other.
As an index of electron withdrawing property, Hammett's rule substituent constant σ and the like are known, and functional groups having positive Hammett's rule constant σ are listed as electron withdrawing groups.

Specific examples of the electron-withdrawing group for R ⁵ 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 represented by R ⁵ 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, and a trichloromethyl group. , Tribromomethyl group, triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2-tri Iodoethyl 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-tric Loromethylethyl 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 for R ⁵ 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, pentafluoro Phenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro group Fluoro-2-naphthyl group, 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-tetra Chlorophenyl group, pentachlorophenyl group, 2,3,5,6-tetrachloro-4-trichloromethylphenyl group, 2,3,5,6-tetrachloro-4-pentachlorophenylphenyl group, perchloro-1-naphthyl group, Perchloro-2-naphthyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,4-dibromophenyl group, 2,6-dibromophenyl group, 3,4-dibromophenyl group, 3 , 5-Dibromophenyl group, 2,4,6-tribromophenyl group, 3,4,5-tribromophenyl group, 2,3,5,6-teto Bromophenyl 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-di Iodophenyl group, 3,5-diiodophenyl group, 2,4,6-triiodophenyl group, 3,4,5-triiodophenyl group, 2,3,5,6-tetraiodophenyl group, pentaiodo Phenyl group, 2,3,5,6-tetraiodo-4-triiodomethylphenyl group, 2,3,5,6-tetraiodo-4-pentaiodophenylphenyl group, Yodo-1-naphthyl group, Payodo-2-naphthyl group and the like.

Specific examples of the (halogenated alkyl) aryl group for R ⁵ include 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6- Bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 3,4,5-tris (trifluoromethyl) phenyl Groups and the like.

Specific examples of the cyanated aryl group for R ⁵ include a 2-cyanophenyl group, a 3-cyanophenyl group, a 4-cyanophenyl group, and the like.

Specific examples of the nitrated aryl group for R ⁵ include a 2-nitrophenyl group, a 3-nitrophenyl group, and a 4-nitrophenyl group.

Specific examples of the ester group for R ⁵ include a methoxycarbonyl group, an ethoxycarbonyl group, a normal propoxycarbonyl group, an isopropoxycarbonyl group, a phenoxycarbonyl group, a trifluoromethoxycarbonyl group, and a pentafluorophenoxycarbonyl group.

R ⁵ 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 ⁶ in the general formula [5] represents a hydrocarbyl group or a halogenated hydrocarbyl group. The hydrocarbyl group in R ⁶ 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 [5] is used. Examples of the halogenated hydrocarbyl group in R ⁶ include a halogenated alkyl group, a halogenated aryl group, and a (halogenated alkyl) aryl group. Specific examples of the electron withdrawing group in R ⁵ 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 ⁶ 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 ³ 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 hydroxyl groups formed on the surface, but modified inorganic oxides in which active hydrogen of the surface hydroxyl groups are substituted with various substituents may be used as inorganic oxides. 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, Diaryl dialkoxysilanes such as diphenyldimethoxysilane, 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 hydroxyl groups. In that case, if all the active hydrogens of the surface hydroxyl group are substituted with various substituents, the particle strength may be lowered. Therefore, it is not always necessary to substitute all the active hydrogens on the surface hydroxyl groups of the inorganic oxide, and the substitution rate of the surface hydroxyl groups may be determined as appropriate. The method for changing the substitution rate of the surface hydroxyl group is not particularly limited. 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 have a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms as a substituent.

  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 crosslinkable monomer having two or more polymerizable unsaturated groups.

  Examples of the polymerizable unsaturated group include alkenyl groups such as vinyl group and allyl group, and alkynyl groups such as ethyne group. Examples of monomers having a functional group having active hydrogen and one or more polymerizable unsaturated groups include vinyl group-containing primary amines, vinyl group-containing secondary amines, vinyl group-containing amide compounds, and vinyl group-containing hydroxy compounds. Is mentioned. Examples of the monomer include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, and N- (2-propenyl) -N-methylamine. 1-ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-buten-1-ol Is mentioned. Examples of monomers having a functional group having a Lewis base having no active hydrogen atom and one or more polymerizable unsaturated groups include vinyl pyridine, vinyl (N-substituted) imidazole, and vinyl (N-substituted) indazole. Is mentioned.

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

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

  These organic polymer particles are preferably dried and substantially free of moisture, and those dried by heat drying are preferred. The drying temperature is usually 30 to 400 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. for an organic polymer whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, and more preferably 1 hour to 30 hours. Examples of the 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 (f) obtained by bringing the compounds (a), (b) and (c) into contact with the particles (d), that is, the above-mentioned <1>, <3> and <7> In each method, the above-mentioned aliphatic hydrocarbyl solvent, aromatic hydrocarbyl solvent or ether solvent is preferable as the solvent (s1) in the production of the contact product (f).

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

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

  In the case of <2>, <5>, <6>, <8>, <9>, <10>, <11>, <12>, 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.

There are no particular restrictions on the amount of each of the compounds (a), (b), and (c) that are brought into contact with each other, but the molar ratio of the amount of each compound that is brought into contact with each other is: (a) :( b) :( c) = When the molar ratio is 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 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—} _e 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. 2 represents a number of 2 or more, and c represents a number of 1 or more.)
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. e 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, e 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.

The modified particles (II) can be produced by contacting the alumoxane (e) and the particles (d) by any method. 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.

  The temperature and time for bringing the aluminoxane (e) into contact with the particles (d) can be arbitrarily selected, but the temperature is usually −100 ° C. to 200 ° C., preferably −50 ° C. to 150 ° C., more preferably −20 ° C. ~ 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 the compound (A) at the time of preparing the modified particles (II).
As the compound (A), a transition metal compound represented by the formula [1] or a μ-oxo type transition metal compound dimer thereof is used.
Contact of alumoxane (e), particles (d) and compound (A) can be carried out by any method to produce 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 (A) are preferable, and the aluminoxane (e) and A solvent that dissolves the compound (A) is more preferable. Specifically, an aromatic hydrocarbyl solvent such as toluene or xylene or an aliphatic hydrocarbyl solvent such as hexane, heptane, or octane is preferable, and toluene or xylene is more preferable.

  The temperature and time for contacting the aluminoxane (e), the particles (d) and the compound (A) can be arbitrarily selected, but the temperature is usually −100 ° C. to 200 ° C., preferably −50 ° C. to 150 ° C., more preferably. Is −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 in which the aluminoxane (e), the particles (d) and the compound (A) are contacted is arbitrary, but the aluminoxane (e) per unit gram of the particles (d) is usually 0.01 to 100 mmol, preferably in terms of aluminum atoms. Is 0.1-20 mmol, more preferably 1-10 mmol. Further, the amount of the compound (A) per unit gram of the particles (d) is usually 0.1 to 1000 μmol, preferably 1 to 500 μmol, more preferably 10 to 200 μmol in terms of transition metal atom.

Organoaluminum compound (C)
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 formula [8].
R ⁹ _d AlY _3-d [8]
(Wherein R ⁹ represents a hydrocarbyl group, and all R ⁹ may be the same or different. Y represents a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, or an aryloxy group. And all Y may be the same or different, and d represents a number satisfying 0 <d ≦ 3.)

R ⁹ in Formula [8] 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 formula [8] include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri- Trialkylaluminum such as n-octylaluminum; dialkylaluminum chloride such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride Methyl aluminum dichloride, ethyl aluminum dichloride, n-propyl aluminum dichloride, n-butyl aluminum Alkyl aluminum dichlorides such as chloride, isobutyl aluminum dichloride, n-hexyl aluminum dichloride; dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, di-n-hexyl Dialkyl aluminum hydrides such as aluminum hydride; alkyl (dialkoxy) aluminum such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, methyl (di-tert-butoxy) aluminum; dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum, Dials such as dimethyl (tert-butoxy) aluminum Al (alkoxy) 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 (E)
In the production of the prepolymerized addition polymerization catalyst component and the addition polymer of the present invention, the electron donating compound (E) may be brought into contact with the catalyst or the prepolymerized addition polymerization catalyst component. The electron-donating compound (E) 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.

As alkoxysilicons, the general formula R ¹⁰ _r Si (OR ¹¹ ) _4-r (wherein R ¹⁰ represents a hydrocarbyl group having 1 to 20 carbon atoms, a hydrogen atom or a heteroatom-containing substituent; ¹¹ represents a hydrocarbyl group having 1 to 20 carbon atoms, and r represents a number satisfying 0 ≦ r <4, and all R ¹⁰ and all R ¹¹ may be the same or different. It is preferable to use an alkoxysilicon compound represented by the following formula.

When R ¹⁰ or R ¹¹ 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 ¹⁰ 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 alkoxysilicons, R ¹⁰ and R ¹¹ 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 thereof also include compounds in which methoxy in these compounds is replaced with ethoxy, propoxy, normal butoxy, isobutoxy, tert-butoxy, or phenoxy. Dialkyl dialkoxy silane or trialkyl monoalkoxy silane is preferable, and trialkyl monoalkoxy silane is more preferable.

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

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

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

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

  As the electron donating compound (E), alkoxysilicones, ethers or amines are preferably used. Furthermore, amines are more preferably used. These electron donating compounds (E) 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 two methods.
The first is a method for producing an addition polymer including the following steps.
(1) Step of mixing a polymerization solvent and an organic compound (D) to form a mixture (2) Addition polymerization of a monomer capable of addition polymerization in the presence of a catalyst in the mixture to produce an addition polymer Process
The second is a method for producing an addition polymer including the following steps.
(1) Step of mixing a polymerization solvent and an organic compound (D) to form a mixture (2) Prepolymerized addition by prepolymerizing a monomer capable of addition polymerization in the mixture in the presence of a catalyst Step of obtaining a polymerization catalyst component (3) Step of producing an addition polymer by addition polymerization of a monomer capable of addition polymerization in the presence of a prepolymerized addition polymerization catalyst component

  Examples of the solvent for polymerization include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbon solvents such as benzene and toluene, and halogenated hydrocarbon solvents such as dichloromethane. Can be mentioned. 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.

  This invention has the process of mixing the solvent for polymerization, and the organic compound (D) represented by Formula [2], and forming a mixture.

  The amount of the organic compound (D) relative to the polymerization solvent is preferably usually in the range of 0.1 to 1000 mg / L, more preferably in the range of 1 to 100 mg / L, and 1.5 to 40 mg. More preferably, it is in the range of / L.

The polymerization solvent and the organic compound (D) may be mixed in the polymerization reactor. After mixing the polymerization solvent and the organic compound (D) in advance, the mixture is added to the polymerization reactor. Also good. Further, the organic compound (D) may be mixed after introducing a monomer into the polymerization solvent.
In a preferred method, a polymerization solvent and an organic compound (D) are mixed to form a mixture, and the mixture is mixed with the compound (A), the activator (B), and the organic compound (C) as necessary. A catalyst is formed, and then a monomer is introduced into the mixture and polymerized by the catalyst.

  The method of mixing the polymerization solvent and the organic compound (D) is not particularly limited. For example, the polymerization solvent and the organic compound (D) are mixed as they are, and the organic compound (D) is once mixed with the polymerization solvent. A method of mixing the mixture with the polymerization solvent after mixing with the same solvent, a method of mixing the organic compound (D) with a solvent different from the polymerization solvent, and then mixing the mixture with the polymerization solvent, organic Examples thereof include a method of adding the compound (D) to the polymerization solvent together with an inert gas stream, a method of adding the organic compound (D) to the polymerization solvent together with the monomer gas stream, and the like.

When mixing the polymerization solvent and the organic compound (D), the polymerization solvent is preferably stirred.

  The temperature at which the polymerization solvent and the organic compound (D) are mixed is not particularly limited, but is usually 0 ° C to 150 ° C, preferably 5 ° C to 100 ° C, more preferably 10 ° C to 80 ° C.

  The mixture formed by mixing the polymerization solvent and the organic compound (D) can be used for polymerization immediately after it is formed, or the mixture of the polymerization solvent and the organic compound (D) is mixed. After forming, it can be used for polymerization after a while. In the latter case, it is preferable to use the mixture for the polymerization preferably within 5 hours, more preferably within 3 hours, and even more preferably within 1 hour after forming the mixture.

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

Although the method of making a compound (A), an activator (B), and an organoaluminum compound (C) contact is not specifically limited, For example, the method of following <13>-<15> is mentioned.
<13> A method in which a contact product obtained by bringing the components into contact with each other is charged into a polymerization reactor.
<14> A method in which each of the above components is separately supplied to a polymerization reactor and brought into contact with the polymerization reactor.
<15> A method in which a part of each of the above components is brought into contact with each other before being charged into the polymerization reactor to obtain a preliminary contact product, and the preliminary contact product and the remaining components are contacted in the polymerization reactor.
The contact method is preferably <14> described above. You may throw into a polymerization reactor in the slurry state which suspended the compound (A) in the powder or the solvent.
In addition, in the polymerization reactor in which a mixture obtained by mixing the polymerization solvent and the organic compound (D) is present, each component, a contact product obtained by contacting each component, or a preliminary contact product The charging method is preferred.

The order in which the compound (A), the activator (B), and the organoaluminum compound (C) are brought into contact with each other is not particularly limited.
The contact thing obtained by making a <16> compound (A) and an activator (B) contact is made to contact an organoaluminum compound (C).
<17> A contact product obtained by bringing the compound (A) and the organoaluminum compound (C) into contact with the activator (B).
The contact thing obtained by making a <18> activator (B) and an organoaluminum compound (C) contact is made to contact a compound (A).
<19> A contact product obtained by contacting the compound (A) with the organoaluminum compound (C), and a contact product obtained by bringing the activator (B) and the organoaluminum compound (C) into contact with each other. Make contact.
<20> a contact product obtained by contacting the compound (A) and the activator (B), and a contact product obtained by contacting the activator (B) and the organoaluminum compound (C). Make contact.
<21> A contact product obtained by bringing the compound (A) into contact with the organoaluminum compound (C) and a contact product obtained by bringing the compound (A) into contact with the activator (B) are brought into contact with each other. .
The contact order is preferably <16> or <17> described above.

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

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

  It is preferable to perform stirring when contacting each component.

Addition polymerization method using a catalyst The addition polymerization method using a catalyst is a method in which a monomer is addition polymerized using a catalyst in the presence of a solvent. Examples of the addition polymerization method using a catalyst include a solution polymerization method in which a monomer is polymerized in a solvent, a slurry polymerization method (suspension polymerization method), or a bulk polymerization method in which a monomer that is a liquid is polymerized. A slurry polymerization method or a bulk polymerization method.

  Addition polymerization using a catalyst can be carried out batchwise or continuously. The polymerization time for addition polymerization using a catalyst is generally determined by the type of the target addition polymer and the polymerization reactor used, and is usually from 1 minute to 20 hours.

  Addition polymerization using a catalyst can be carried out according to known methods and conditions. A preferable method of this method is to continuously or intermittently supply a monomer, a solvent, other feeds, and the like to the polymerization reactor as necessary, and to continuously or intermittently form the resulting addition polymer from the polymerization reactor. It is a method of extracting. As the polymerization reactor, 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 can be used.

  The polymerization solvent and the polymerization temperature and pressure are selected so that the solvent and at least some of the monomer can be maintained in the liquid phase and the monomer and catalyst can be contacted. The polymerization temperature is usually about −50 ° C. to about 150 ° C. The polymerization pressure is usually about 0.001 MPa to about 10 MPa.

  In addition polymerization using a catalyst, the catalyst, the components used for obtaining the catalyst, and the monomer can be supplied to the polymerization reactor in any order by a known method. As these supply methods to the polymerization reactor, for example, (1) the catalyst or the catalyst is obtained in a polymerization reactor containing a mixture obtained by mixing the polymerization solvent and the organic compound (D). For example, a method of supplying the components and the monomer used simultaneously for the purpose, and (2) a method of supplying the catalyst or the components used for obtaining the catalyst and the monomer sequentially.

  The molecular weight of the resulting addition polymer can be controlled by the polymerization temperature or a molecular weight regulator such as hydrogen.

Prepolymerization method and prepolymerized catalyst component for addition polymerization Among the addition polymerization methods of the present invention, a method for obtaining a prepolymerized catalyst component for addition polymerization by prepolymerizing a monomer capable of addition polymerization using a catalyst Is particularly referred to as a prepolymerization method. In addition, the prepolymerized catalyst component for addition polymerization may be referred to as a prepolymerized catalyst component.

  The prepolymerization can be performed by the same method and conditions as the above addition polymerization. The prepolymerization can be performed batchwise or continuously. Further, the prepolymerization can be carried out in two or more stages having different reaction conditions. In general, the prepolymerization time is appropriately determined depending on the type of the target olefin polymer and the reaction apparatus, and 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.

  In the prepolymerization of the present invention, the catalyst, the components used for obtaining the catalyst, and the monomer can be supplied to the polymerization reactor by the same method as in the above addition polymerization. Preferably, it is a method of supplying the compound (A) as a powder to the polymerization reactor.

  In the prepolymerization, the molecular weight of the prepolymer can be adjusted by coexisting a molecular weight regulator such as hydrogen.

  In the present invention, since the prepolymerized catalyst component is formed in the presence of the polymerization solvent, the prepolymerized catalyst component may be used in the main polymerization together with the polymerization solvent. The prepolymerized catalyst component is separated from the polymerization solvent, and the separated prepolymerized catalyst component is subjected to treatments such as de-monomer, solvent evaporation, filtration, washing, and drying to obtain a solid-state prepolymerized catalyst. Components may be obtained and used for the main polymerization.

  The fine powder content in the prepolymerized catalyst component is preferably as low as possible from the viewpoint of improving the operational stability of the main polymerization using the prepolymerized catalyst component. The fine powder content in the prepolymerized catalyst component is evaluated by, for example, a particle content of 60 μm or less. The content of particles of 60 μm or less in the prepolymerized catalyst component is preferably 7.0% or less, more preferably 5.0% or less, still more preferably 2.0% or less, particularly preferably. Is 0.8% or less. The fine powder content in the prepolymerized catalyst component can be adjusted by, for example, the median diameter of the activator (B) used in the prepolymerization, SPAN, and the type of organic compound (D) mixed with the polymerization solvent. .

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

Main polymerization In the present invention, addition polymerization using a prepolymerized catalyst component is referred to as main polymerization. In the main polymerization, the obtained prepolymerized catalyst component may be used as it is as an addition polymerization catalyst, or a contact product of a prepolymerized catalyst component and an organoaluminum compound is used as an addition polymerization catalyst. Also 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 manner, the amount used is usually 1 to 10000 mol / mol, preferably 10 to 5000 mol / mol, more preferably 30 to 1000 mol / mol, relative to the compound (A). mol.

  When the prepolymerized catalyst component and the organoaluminum compound (C) are used in contact with each other, the prepolymerized catalyst component and the organoaluminum compound (C) should be put into a polymerization reactor in any order for use. In addition, they may be used after being brought into contact with each other before being charged into the polymerization reactor.

  The method for supplying the prepolymerized 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 a prepolymerized catalyst component and an organoaluminum compound (C) are supplied in a solid state, and a hydrocarbyl solvent in which components that deactivate catalyst components such as moisture and oxygen are sufficiently removed. And a method in which the catalyst component preliminarily polymerized and the organoaluminum compound (C) are dissolved, or supplied in a suspended or slurried state. 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.

  The polymerization method in this polymerization is not particularly limited. Examples of the method include (1) a gas phase polymerization method for polymerizing gaseous monomers, (2) a solution polymerization method for polymerizing monomers in a solvent, or a slurry polymerization method (suspension polymerization method), (3) The bulk polymerization method which superposes | polymerizes the monomer which is a liquid can be mentioned. The main polymerization can be carried out batchwise or continuously. Furthermore, the main polymerization can be carried out in two or more stages with 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 to be used, and is usually 1 minute to 20 hours.

  When the main polymerization is solution polymerization, slurry polymerization, or bulk polymerization, the polymerization can be performed according to known methods and conditions. A preferred method of the polymerization method is to continuously or intermittently supply monomers, diluents and other feeds to the polymerization reactor as necessary, and to continuously or intermittently form the resulting addition polymer from the polymerization reactor. It is a method to extract automatically. 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. .

When the main polymerization is gas phase polymerization, the gas phase polymerization can be performed according to known methods and conditions. The reactor for gas phase polymerization is a fluidized bed type reaction vessel, preferably a fluidized bed type reaction vessel having an enlarged portion. The reactor may have a stirring blade in the reaction vessel.
As a method for supplying the prepolymerized catalyst component to the reactor, for example, a method in which the catalyst component is usually supplied together with an inert gas such as nitrogen and argon, hydrogen, or ethylene in a moisture-free state, or a prepolymerized catalyst component is used. The catalyst component may be supplied as a solution in a solvent or a diluted slurry.

  In the case where the main polymerization is gas phase polymerization, the polymerization temperature of the gas phase polymerization is not particularly limited as long as it is lower than the melting temperature of the addition polymer to be produced. ~ 100 ° C. Hydrogen may be added as a molecular weight modifier for the purpose of adjusting the melt fluidity of the produced addition polymer. Further, when the gaseous monomer is polymerized, an inert gas may coexist in the gas.

Addition-polymerizable monomer The method for producing an addition polymer of the present invention is a method for producing an addition polymer in which addition-polymerizable monomer is addition-polymerized in the presence of the above-mentioned catalyst or a prepolymerized catalyst for addition polymerization. .
As a monomer in the manufacturing method of the addition polymer of this invention, a C2-C20 olefin, diolefin, cyclic olefin, alkenyl aromatic hydrocarbyl, and a polar monomer can be mentioned, for example. Two or more types of 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 monomer is preferably an olefin having 2 to 20 carbon atoms. 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. The monomer used in the prepolymerization is particularly preferably ethylene.

When two or more types of monomers are used, it is preferable to use ethylene and α-olefin. As a combination of monomers used, ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, ethylene and 1-butene and 1-hexene, ethylene and 1-butene and 1- A combination of octene, ethylene and 1-hexene and 1-octene, propylene and 1-butene, propylene and 1-hexene, and propylene and 1-octene.

  The addition polymer obtained by the production method of the present invention 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. It is. 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 properties of the addition polymer in the examples were measured by the following methods.

(1) Elemental analysis Zn: After throwing the sample into a sulfuric acid aqueous solution (1M), ultrasonic waves were applied to the sulfuric acid aqueous solution containing the sample to extract metal components from the sample into the sulfuric acid aqueous solution. Zn was quantified by ICP emission analysis in the liquid portion of the sulfuric acid aqueous solution containing the metal component.
F: Combustion gas generated by burning a sample in a flask filled with oxygen was absorbed into an aqueous sodium hydroxide solution (10%), and F was quantified using the ion electrode method for the obtained aqueous solution.

(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) Preliminarily polymerized catalyst component for addition polymerization having a particle size of 60 μm or less Preliminary polymerization using a laser diffraction particle size distribution measuring device HELOS & RODOS system manufactured by SYMPATEC under the following measurement conditions The added addition polymerization catalyst component was dispersed in a dry state, and its particle size distribution was measured. The amount of the 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 activator (B) Modified particles were produced in the same manner as the preparation of component (A) in Example 1 (1) and (2) of JP-A-2009-79180. . As a result of elemental analysis, Zn = 11 wt% and F = 6.4 wt%.

(2) Prepolymerization After drying under reduced pressure, an autoclave with a stirrer with an internal volume of 3 liters substituted with nitrogen was evacuated to prepare 480 g of butane and a concentration of 10 mg / ml sodium polyoxyethylene lauryl acetate (n = 10) ( 1.0 mL of a hexane solution of Kao Akipo RLM-100NV (D) manufactured by Kao Corporation was added. Subsequently, 192 mg (360 μmol) of ethylene bis (indenyl) zirconium diphenoxide (A) was added to the autoclave, stirred at 50 ° C. for 1 hour, and then cooled to 30 ° C. Next, 1 g of ethylene was added, 7.0 g of the activator (B) obtained in (1) above was added, and a hexane solution of triisobutylaluminum (C) prepared to a concentration of 1.0 mmol / ml. Pre-polymerization was started by adding 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: 0.193 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 catalyst component for addition polymerization was recovered. The recovered amount was 131.7 g, and the degree of polymerization per activator (B) was 18.7 g / g. As a result of measuring the particle size distribution of the prepolymerized catalyst component, the amount of particles having a particle size of 60 μm or less contained in the prepolymerized catalyst component was 1.9%.

[Example 2]
(1) Prepolymerized ethylenebis (indenyl) zirconium diphenoxide (A) 200 mg (374 μmol) and sodium polyoxyethylene lauryl acetate (n = 10) prepared at a concentration of 10 mg / ml (Kao Akipo RLM- manufactured by Kao Corporation) 100NV) Prepolymerization was carried out in the same manner as in Example 1 (2) except that 2.0 ml of a hexane solution of (D) was added. The recovered amount was 131.2 g, and the degree of polymerization per activator (B) was 18.7 g / g. As a result of measuring the particle size distribution of the prepolymerized catalyst component, the amount of particles having a particle size of 60 μm or less contained in the prepolymerized catalyst component was 0.8%.
(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 at 70 ° C. The temperature was raised to. 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 = 1.86 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, 381.3 mg of the prepolymerized catalyst component obtained in (1) above was added. Polymerization was carried out at 70 ° C. for 3 hours while feeding an ethylene / hydrogen mixed gas (hydrogen 0.295 mol%) so as to keep the total pressure constant. As a result, 72 g of an olefin polymer was obtained. The polymerization activity per activator (B) was 3500 g / g. Moreover, the obtained olefin polymer was MFR = 2.12 and SR = 1.45.

[Example 3]
(1) 195 mg (365 μmol) of prepolymerized ethylenebis (indenyl) zirconium diphenoxide (A) and polyoxyethylene sodium lauryl acetate (n = 10) prepared at a concentration of 10 mg / ml (Kao Akipo RLM- manufactured by Kao Corporation) 100NV) Prepolymerization was carried out in the same manner as in Example 1 (2) except that 5.0 ml of a hexane solution of (D) was added. The recovered amount was 129.2 g, and the degree of polymerization per activator (B) was 18.2 g / g. As a result of measuring the particle size distribution of the prepolymerized catalyst component, the amount of particles having a particle size of 60 μm or less contained in the prepolymerized catalyst component was 1.5%.
(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 at 70 ° C. The temperature was raised to. 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 = 1.86 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, 374.2 mg of the prepolymerized 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 0.300 mol%) so as to keep the total pressure constant. As a result, 98.5 g of an olefin polymer was obtained. The polymerization activity per activator (B) was 4780 g / g. Moreover, the obtained olefin polymer was MFR = 1.19 and SR = 1.39.

[Example 4]
(1) 205 mg (384 μmol) of prepolymerized ethylenebis (indenyl) zirconium diphenoxide (A) and polyoxyethylene sodium lauryl acetate (n = 10) prepared at a concentration of 10 mg / ml (Kao Akipo RLM- manufactured by Kao Corporation) 100NV) Prepolymerization was carried out in the same manner as in Example 1 (2) except that 30.0 ml of a hexane solution of (D) was added. The recovered amount was 143.9 g, and the degree of polymerization per activator (B) was 20.4 g / g. As a result of measuring the particle size distribution of the prepolymerized catalyst component, the amount of particles having a particle size of 60 μm or less contained in the prepolymerized catalyst component was 0.4%.
(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 at 70 ° C. The temperature was raised to. 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 = 1.92 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, 409.8 mg of the prepolymerized catalyst component obtained in (1) above was added. Polymerization was carried out at 70 ° C. for 3 hours while feeding an ethylene / hydrogen mixed gas (hydrogen 0.300 mol%) so as to keep the total pressure constant. As a result, 3.7 g of an olefin polymer was obtained. The polymerization activity per activator (B) was 200 g / g. Moreover, the obtained olefin polymer was MFR = 5.

[Example 5]
(1) Prepolymerized ethylenebis (indenyl) zirconium diphenoxide (A) 195 mg (365 μmol) and polyoxyethylene sodium lauryl sulfate (n = 2) prepared at a concentration of 10 mg / ml (Emar 270J, manufactured by Kao Corporation) Prepolymerization was carried out in the same manner as in Example 1 (2) except that 5.0 ml of the hexane solution of (D) was added. The recovered amount was 123.0 g, and the degree of polymerization per activator (B) was 17.5 g / g. As a result of measuring the particle size distribution of the prepolymerized catalyst component, the amount of particles having a particle size of 60 μm or less contained in the prepolymerized catalyst component was 5.3%.
(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 at 70 ° C. The temperature was raised to. 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 = 1.86 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, 355.0 mg of the prepolymerized 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 0.309 mol%) so as to keep the total pressure constant. As a result, 21.3 g of an olefin polymer was obtained. The polymerization activity per activator (B) was 1000 g / g. Moreover, the obtained olefin polymer was MFR = 6.54 and SR = 1.52.

[Example 6]
(1) Prepolymerized hexane solution of polyoxyethylene lauryl ether (Emulgen 108 manufactured by Kao Corporation) (D) prepared by preparing 191 mg (359 μmol) of prepolymerized ethylenebis (indenyl) zirconium diphenoxide (A) and a concentration of 10 mg / ml Was added in the same manner as in Example 1 (2) except that 5.0 ml was added. The recovered amount was 123.2 g, and the degree of polymerization per activator (B) was 17.5 g / g. As a result of measuring the particle size distribution of the prepolymerized catalyst component, the amount of particles having a particle size of 60 μm or less contained in the prepolymerized catalyst component was 2.4%.
(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 at 70 ° C. The temperature was raised to. 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 = 1.89 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, 352.1 mg of the prepolymerized 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 0.309 mol%) so as to keep the total pressure constant. As a result, 26.8 g of an olefin polymer was obtained. The polymerization activity per activator (B) was 1300 g / g. The obtained olefin polymer had MFR = 4.14 and SR = 1.48.
[Comparative Example 1]
(1) 198 mg (372 μmol) of prepolymerized ethylenebis (indenyl) zirconium diphenoxide (A), 7.0 g of the activator (B) obtained in Example 1 (1) above, and an organic compound Preliminary polymerization was carried out in the same manner as in Example 1 (2) except that (D) was not added. The recovered amount was 130.3 g, and the degree of polymerization per activator (B) was 18.6 g / g. As a result of measuring the particle size distribution of the prepolymerized catalyst component, the amount of particles having a particle size of 60 μm or less contained in the prepolymerized 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 at 70 ° C. The temperature was raised to. 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 = 1.86 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, 378.3 mg of the prepolymerized 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 0.301 mol%) so as to keep the total pressure constant. As a result, 76.0 g of an olefin polymer was obtained. The polymerization activity per activator (B) was 3720 g / g. Moreover, the obtained olefin polymer was MFR = 2.44 and SR = 1.45.

Claims (12)

A method of addition polymerization of a monomer capable of addition polymerization, the method comprising the following steps.
(1) Step of mixing a polymerization solvent and an organic compound (D) represented by formula [2] to form a mixture (2) Transition metal compound represented by formula [1] and its μ-oxo type A step of subjecting the monomer to addition polymerization in the mixture in the presence of a catalyst formed by contacting a compound (A) selected from the transition metal compound dimers of (1) with an activator (B) L ¹ _a M ¹ X ¹ _b [1]
M ¹ is a Group 4 transition metal atom; L ¹ is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom; X ¹ is a halogen atom, a hydrocarbyloxy group, or a hydrocarbyl A group (excluding a group having a cyclopentadiene-type anion skeleton); a is a number satisfying 0 <a ≦ 3; b is a number satisfying 0 <b ≦ 3; When larger, one L ¹ may be linked to each other L ¹ directly or through a group containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
R ¹ —O — (— R ² —O—) _n Q ¹ [2]
R ¹ is an optionally substituted hydrocarbyl group having 1 to 30 carbon atoms; R ² is an optionally substituted alkylene group having 1 to 20 carbon atoms; Q ¹ represents a hydrogen ^{atom, -C (= O) OM 2} , -R 3 -C (= O) OM 2, -S (= O) 2 OM 2, -R 3 -S (= O) 2 OM 2, ^{-P (= O) (OH)} (OM 2), - P (= O) (oR 4) (OM 2), or ^{-P (= O) (OM 2} ) be a _2; ^{M 2} represents a hydrogen atom or R ³ is an optionally substituted alkylene group having 1 to 20 carbon atoms; R ⁴ is an optionally substituted hydro carbon having 1 to 20 carbon atoms; N is a number from 1 to 100; when n is greater than 1, the plurality of R ² may be the same or different. A method of addition polymerization of a monomer capable of addition polymerization, the method comprising the following steps.
(1) Step of mixing a polymerization solvent and an organic compound (D) represented by formula [2] to form a mixture (2) Transition metal compound represented by formula [1] and its μ-oxo type In the presence of the catalyst formed by contacting the compound (A) selected from the transition metal compound dimer, the activator (B), and the organoaluminum compound (C), the monomer is added in the mixture. Step of addition polymerization L ¹ _a M ¹ X ¹ _b [1]
M ¹ is a Group 4 transition metal atom; L ¹ is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom; X ¹ is a halogen atom, a hydrocarbyloxy group, or a hydrocarbyl A group (excluding a group having a cyclopentadiene-type anion skeleton); a is a number satisfying 0 <a ≦ 3; b is a number satisfying 0 <b ≦ 3; When larger, one L ¹ may be linked to each other L ¹ directly or through a group containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
R ¹ —O — (— R ² —O—) _n Q ¹ [2]
R ¹ is an optionally substituted hydrocarbyl group having 1 to 30 carbon atoms; R ² is an optionally substituted alkylene group having 1 to 20 carbon atoms; Q ¹ represents a hydrogen ^{atom, -C (= O) OM 2} , -R 3 -C (= O) OM 2, -S (= O) 2 OM 2, -R 3 -S (= O) 2 OM 2, ^{-P (= O) (OH)} (OM 2), - P (= O) (oR 4) (OM 2), or ^{-P (= O) (OM 2} ) be a _2; ^{M 2} represents a hydrogen atom or R ³ is an optionally substituted alkylene group having 1 to 20 carbon atoms; R ⁴ is an optionally substituted hydro carbon having 1 to 20 carbon atoms; N is a number from 1 to 100; when n is greater than 1, the plurality of R ² may be the same or different. The activator (B) is a modified particle obtained by bringing the following (a), (b), (c) and (d) below into contact with each other. Method.
(A): Compound represented by formula [3] M ³ L ² ₂ [3]
(B): Compound represented by formula [4] R ⁵ _t-1 TH [4]
(C): Compound represented by formula [5] R ⁶ _u-2 T′H ₂ [5]
(D): Inorganic oxide particles or organic polymer particles M ³ are Group 12 elements; L ² is a hydrogen atom, a halogen atom or a hydrocarbyl group, and two L ² are the same or different from each other R ⁵ is an electron-withdrawing group or a group containing an electron-withdrawing group; when t-1 is greater than 1, a plurality of R ⁵ may be the same or different from each other; R ⁶ is a hydrocarbyl group or halogenated hydrocarbyl group; T is a Group 15 element or Group 16 element; t is a number corresponding to the valence of T; T ′ is Group 15 Element or a Group 16 element; u is a number corresponding to the valence of T ′. Q ¹ in the formula [2] is a hydrogen atom, —C (═O) OM ² , —R ³ —C (═O) OM ² , —S (═O) ₂ OM ² , or —R ³ —S ( ═O) ₂ OM ² , M ² is a hydrogen atom or an alkali metal atom, and R ³ is an alkylene group having 1 to 20 carbon atoms which may have a substituent. The method according to any one. The addition polymerization method according to claim 4, wherein Q ¹ in the formula [2] is a hydrogen atom, —R ³ —C (═O) OM ² , or —S (═O) ₂ OM ² .   The addition polymerization method according to any one of claims 1 to 5, which is a method performed in a slurry.   A method for producing an addition polymer, the method comprising addition polymerization of a monomer capable of addition polymerization by the method according to claim 1.   A method for producing a prepolymerized catalyst component for addition polymerization, the method comprising producing a prepolymerized catalyst component for addition polymerization by the method according to claim 1.   A prepolymerized catalyst component for addition polymerization, wherein the prepolymerized catalyst component is obtained by the method of claim 8, and the cumulative amount of the prepolymerized catalyst component having a particle size of 60 μm or less is obtained. A prepolymerized catalyst component having a weight fraction of 7% or less.   A method for producing an addition polymer, wherein a monomer capable of addition polymerization is polymerized in the presence of a prepolymerized catalyst component for addition polymerization obtained by the method according to claim 8.   A method for producing an addition polymer, wherein a monomer capable of addition polymerization is polymerized in the presence of a mixture of a prepolymerized catalyst component for addition polymerization obtained by the method according to claim 8 and an organoaluminum compound (C). how to.   The method according to claim 10 or 11, wherein the addition-polymerizable monomers are ethylene and α-olefin.