JP2009161779A - Modified particle and method for producing the same, carrier, catalyst component for addition polymerization, catalyst for addition polymerization, and method for producing addition polymer - Google Patents

Abstract

A highly active olefin polymerization catalyst, a more efficient method for producing an olefin polymer, and a method for producing an addition polymerization catalyst component used for the preparation of the olefin polymerization catalyst.
A solid component obtained by contacting ZnL ¹ ₂ , R ¹ OH, H ₂ O, and silica in a specific contact order and a specific blending ratio, the solid component, and ZnL ² ₂ And an olefin polymerization catalyst component (A) obtained by bringing R ³ OH and H ₂ O into contact with each other in a specific contact order and a specific blending ratio,
Transition metal compound (B),
And
Organoaluminum compound (C),
A catalyst for olefin polymerization obtained by contacting the catalyst.
[Selection figure] None

Description

The present invention relates to a carrier and a modified particle useful as a catalyst component for addition polymerization, a method for producing the same, a catalyst for addition polymerization obtained using the same, 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.
These addition polymers have heretofore been a combination of a solid catalyst component obtained mainly using a Group 4 metal compound such as titanium trichloride or titanium tetrachloride and a Group 13 metal compound typified by an organoaluminum compound. It has been produced by multisite polymerization in which olefins and the like are polymerized using a conventional solid catalyst (multisite catalyst).

  In recent years, unlike solid catalyst components that have been used for a long time, olefins and the like using so-called single-site catalysts in which a transition metal compound (such as a metallocene complex or a nonmetallocene compound) that can be isolated is combined with an aluminoxane or the like. There has been proposed a method for producing an addition polymer by single-site polymerization for polymerizing. For example, Patent Document 1 reports a method using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane. It has also been reported that certain boron compounds are combined with such transition metal compounds. For example, Patent Document 2 reports a method using bis (cyclopentadienyl) zirconium dimethyl and tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate. Addition polymers obtained using these single-site catalysts generally have a narrower molecular weight distribution than those obtained with conventional solid catalysts (multi-site catalysts), and in the case of copolymers, the comonomer is copolymerized more uniformly. Therefore, it is known that an addition polymer more homogeneous than that obtained when a conventional solid catalyst is used can be obtained. In addition, from the viewpoint of processability and physical properties of the resulting addition polymer, single site catalysts and polymerization methods that slightly reduce the homogeneity of the addition polymer are also known (Patent Documents 3 to 6).

  Since ordinary single-site catalysts are soluble in the reaction system, the shape of the resulting addition polymer is inferior when applied to polymerization involving the formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.). It may lead to formation of coarse and coarse addition polymer particles, bulk addition polymer, fine powder addition polymer, etc., reduction of the bulk density of the addition polymer, adhesion of the addition polymer to the polymerization reactor wall, and the like. And in such a case, there is a problem that these causes contribute to poor heat transfer, poor heat removal, etc., resulting in a state where stable operation is difficult, resulting in reduced productivity. It is known to use specific particles as one of the catalyst components (for example, Patent Document 7).

JP 58-19309 A Japanese translation of PCT publication No. 1-502036 JP-A-5-320248 Japanese Patent Laid-Open No. 10-17617 Japanese Patent Laid-Open No. 11-12319 JP 11-343306 A International Patent Application Publication No. 02/051878

Incidentally, in the production of an addition polymer, the molecular weight of the resulting addition polymer is adjusted with hydrogen gas. That is, if a large amount of hydrogen is introduced into the polymerization system, the molecular weight generally decreases. From the viewpoint of design, it is preferable if a high molecular weight addition polymer can be obtained even in the presence of high concentration hydrogen, since the range of molecular weight design is widened.
In addition, when producing an addition polymer, the higher the production efficiency, the better. The present invention relates to particles, supports, addition polymerization catalyst components and methods for producing the particles used for the preparation of a more active addition polymerization catalyst, a more active addition polymerization catalyst, and a more efficient addition weight. It is in providing the manufacturing method of coalescence.

The present invention
A solid component obtained by bringing the following (a1), the following (b1), H ₂ O (c1), and silica (d) into contact with each other in the contact order of any of the following {1} to {4}: The catalyst component for olefin polymerization obtained by contacting the solid component with the following (a2), the following (b2), and H ₂ O (c2) in the following order of contact {5} or {6}. When the molar ratio of the amounts used of the following (a1), the following (b1), and the above (c1) is (a1) :( b1) :( c1) = 1: y ¹ : z ¹ , y ¹ And z ¹ satisfies the following formula (1) and the following formula (2), and the molar ratio of the usage amounts of the following (a2), the following (b2), and the above (c2) is (a1) : (B1) :( c1) = 1: y ² : When z ² , contact is performed at a use ratio in which y ² and z ² satisfy the following formula (3) and the following formula (4). Olefin polymerization catalyst component (A) obtained by
Transition metal compound (B),
And
Organoaluminum compound (C),
Is a catalyst for olefin polymerization obtained by contacting the catalyst.

(A1): Compound represented by the following general formula [1] ZnL ¹ ₂ [1]
(B1): Compound represented by the following general formula [2] R ¹ OH [2]
(A2): Compound represented by the following general formula [4] ZnL ² ₂ [4]
(B2): Compound represented by the following general formula [5] R ³ OH [5]
(In the above general formula [1], L ¹ represents a hydrocarbon group, and the two L ^{1 s} may be the same or different.
In the general formula [4], L ² represents a hydrocarbon group, and two L ^{2 s} may be the same or different.
In addition, the compounds (a1) and (a2) may be the same or different.
In the above general formulas [2] and [5], R ¹ and R ³ each represent a halogenated hydrocarbon group. However, R ¹ and R ³ each represent a different halogenated hydrocarbon group. )

{1}: The first contact object between the above (a1) and the above (b1) and the second contact object obtained by bringing the above (c1) into contact with the above (d).
{2}: The first contact object between the above (a1) and the above (b1) and the second contact object obtained by bringing the above (d) into contact with the above (c1).
{3}: The first contact object between the above (a1) and the above (d) and the second contact object obtained by bringing the above (b1) into contact with the above (c1).
{4}: The first contact object between (b1) and (d) above, the second contact object obtained by contacting (a1) above, and the above (c1) are brought into contact with each other.
{5}: The fourth contact product obtained by bringing the solid component into contact with the third contact product with the above (a2) and the above (b2) is brought into contact with the above (c2).
{6}: The solid contact, the third contact with (b2) above, the fourth contact obtained by contacting (a2) above, and (c2) above are brought into contact.

| 2-y ¹ -2z ¹ | ≦ 1 (1)
0.01 ≦ y ¹ ≦ 1.99 (2)
| 2-y ² −2z ² | ≦ 1 (3)
0.01 ≦ y ² ≦ 1.99 (4)
The present invention also relates to a method for producing an olefin polymer using the above olefin polymerization catalyst.
The present invention includes the above (a1), and the (b1), and H ₂ O (c1), and silica and (d) contacting in either order of contacting the {1} - {4} A step of obtaining the obtained solid component, and a step of bringing the solid component, the above (a2), the above (b2), and H ₂ O (c2) into contact with each other in the contact order of {5} or {6} And the molar ratio of the amount used of (a1), (b1) and (c1) is (a1) :( b1) :( c1) = 1: y ¹ : z ¹ , Y ¹ and z ¹ satisfy the above formula (1) and the above formula (2), and the molar ratio of the amount used of the above (a2), the above (b2) and the above (c2) is When (a1) :( b1) :( c1) = 1: y ² : z ² , y ² and z ² come into contact with each other at a use ratio that satisfies the above formula (3) and the above formula (4). A method for producing the above-mentioned catalyst component for olefin polymerization.

The compound (a1) is a compound represented by the following general formula [1].
M ¹ L ¹ _m [1]
M ¹ in the general formula [1] represents a typical metal atom of Group 1, 2, 12, 14 or 15 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). Specific examples thereof include lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, beryllium atom, magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, cadmium atom, mercury atom, germanium atom, tin atom. , Lead atom, antimony atom, bismuth atom and the like. M ¹ is preferably a magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom or bismuth atom, particularly preferably a magnesium atom, zinc atom, tin atom or bismuth atom, most preferably Is a zinc atom.
Also, m in the general formula [1] represents the number corresponding to the valence of M ^1, for example, when M ¹ is a zinc atom and m is 2.

L ¹ in the general formula [1] represents a hydrogen atom, a halogen atom or a hydrocarbon group, and when a plurality of L ¹ are present, they may be the same as or different from each other. Specific examples of the halogen atom in L ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The hydrocarbon group for L ¹ is preferably an alkyl group, an aryl group, or an aralkyl group.

  As an alkyl group here, a C1-C20 alkyl group is preferable, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, Isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like. More preferably, they are a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an isobutyl group.

Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, 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 group 1H, 1H-Perf Oropentadeshiru group, 1H, and the like 1H- perfluoro eicosyl group, fluoro and chloro these alkyl group, and the alkyl group was replaced by bromo or iodo.
Any of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable. For example, a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 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-tetra Methylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl Tert-butylphenyl group, isobutylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecyl group A phenyl group, a naphthyl group, an anthracenyl group, etc. 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 Etc. may be partially substituted.

As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable. For example, a benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2 , 3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) Methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) Methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) Methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (N-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (isobutylphenyl) methyl group, (N-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, anthrace An nylmethyl group, etc. are mentioned, More preferably, it is a benzyl group.
These aralkyl 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, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

L ¹ in the general formula [1] is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group.

The compound (b1) is a compound represented by the following general formula [2].
R ¹ _t-1 T ¹ H [2]
The compound (c1) is a compound represented by the following general formula [3].
R ² _t-2 T ¹ H ₂ [3]
T ¹ in the above general formula [2] or [3] independently represents a non-metal atom of Group 15 or Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). The T ¹ of T ¹ and the general formula in the formula [2] [3] may be different even in the same. Specific examples of the Group 15 nonmetal atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 nonmetal atom include an oxygen atom and a sulfur atom. T ¹ is preferably each independently a nitrogen atom or an oxygen atom, and particularly preferably T ¹ is an oxygen atom.
In the above general formula [2] or [3], t represents a number corresponding to the valence of each T ^{1. When} T ¹ is a Group 15 nonmetal atom, t is 3, and T ¹ is 16th. In the case of a group nonmetal atom, t is 2.

R ¹ in the general formula [2] represents an electron-withdrawing group or a group containing an electron-withdrawing group, and when a plurality of R ¹ 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 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 halogenated alkyl groups, halogenated aryl groups, (halogenated alkyl) aryl groups, cyanated aryl groups, nitrated aryl groups, ester groups (alkoxycarbonyl groups, aralkyloxycarbonyl groups, Aryloxycarbonyl group), acyl group, acyl halide group and the like.

  Specific examples of the halogenated alkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, 2 , 2,2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 1H, 1H-perfluorobutyl group, 1H, 1H -Perfluoropentyl group, 1H, 1H-perfluorohexyl group, 1H, 1H-perfluorooctyl group, 1H, 1H-perfluorododecyl group, 1H, 1H-perfluoropentadecyl group, 1H, 1H-perfluoroeico And alkyl groups obtained by changing the fluoro of these halogenated alkyl groups to chloro, bromo or iodo. It is.

  Specific examples of the halogenated aryl group include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl. Group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2 -Naphthyl group, 4,5,6,7,8-pentafluoro-2-naphthyl group, etc., and fluoro of these halogenated aryl groups B, and halogenated aryl groups that have changed bromo or iodo and the like.

  Specific examples of the (halogenated alkyl) aryl group include 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group, 2,6-bis (tri Fluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, etc., and fluoro of these (halogenated alkyl) aryl groups is chloro, (Halogenated alkyl) aryl group changed to bromo or iodo and the like.

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

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

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

  Specific examples of acyl groups include formyl, ethanoyl, propanoyl, butanoyl, trifluoroethanoyl, benzoyl, pentafluorobenzoyl, perfluoroethanoyl, perfluoropropanoyl, perfluorobutanoyl. Group, perfluoropentanoyl group, perfluorohexanoyl group, perfluoroheptanoyl group, perfluorooctanoyl group, perfluorononanoyl group, perfluorodecanoyl group, perfluoroundecanoyl group, perfluorododecanoyl group Etc.

R ¹ is preferably a halogenated hydrocarbon 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 Tylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2-naphthyl group, 4,5,6,7,8-pentafluoro 2-naphthyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, 2,2,2-trichloroethyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,2-trichloro -1-trichloromethylethyl group, 1,1-bis (trichloromethyl) -2,2,2-trichloroethyl group, 4-chlorophenyl group, 2,6-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4 , 6-trichlorophenyl group, 3,4,5-trichlorophenyl group or pentachlorophenyl group, particularly preferably a fluoroalkyl group. Is a fluoroaryl group, most preferably a trifluoromethyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2- A trifluoroethyl group, a 3,5-difluorophenyl group, a 3,4,5-trifluorophenyl group or a pentafluorophenyl group;

R ² in the general formula [3] represents a hydrocarbon group or a halogenated hydrocarbon group. As the hydrocarbon group for R ² , an alkyl group, an aryl group, or an aralkyl group is preferable, and the same hydrocarbon group as described for L ¹ in the general formula [1] is used. Examples of the halogenated hydrocarbon group for R ² include a halogenated alkyl group, a halogenated aryl group, and a (halogenated alkyl) aryl group. Specific examples of the electron-withdrawing group for R ¹ in the general formula [2] The same halogenated alkyl group, halogenated aryl group and (halogenated alkyl) aryl group as those mentioned above are used.

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

The compound (a2) is a compound represented by the following general formula [4].
M ² L ² _n [4]
M ² , L ² and n in the general formula [4] are the same as M ¹ L ¹ and m in the general formula [1], respectively, and the compound (a2) is the same as the compound (a1). May be different.

The compound (b2) is a compound represented by the following general formula [5].
R ³ _t-1 T ² H [5]
Compound (c2) is a compound represented by the following general formula [6].
R ⁴ _t-2 T ² H ₂ [6]
T ² in the above general formula [5] or [6] independently represents a non-metal atom of Group 15 or Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). The T ² in T ² and general formula [6] in the general formula [5] may be different even in the same. Specific examples of the Group 15 nonmetal atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 nonmetal atom include an oxygen atom and a sulfur atom. T ² is preferably each independently a nitrogen atom or an oxygen atom, and particularly preferably T ² is an oxygen atom.
In the general formula [5] or [6], t represents a number corresponding to the valence of each T ^{2. When} T ² is a Group 15 nonmetal atom, t is 3, and T ² is 16th. In the case of a group nonmetal atom, t is 2.

R ³ in the general formula [5] is the same as R ¹ in the general formula [2], and R ⁴ in the general formula [6] is the same as R ² in the general formula [3]. ) May be the same as or different from the compound (b1), and the compound (c2) may be the same as or different from the compound (c1).

When the compound (a1) or (a2) is specifically exemplified, specific examples when M ¹ is a zinc atom include dimethyl zinc, diethyl zinc, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-n. Dialkyl zinc such as hexyl zinc; diaryl zinc such as diphenyl zinc, dinaphthyl zinc and bis (pentafluorophenyl) zinc; dialkenyl zinc such as diallyl zinc; bis (cyclopentadienyl) zinc; methyl zinc chloride, ethyl zinc chloride, Propyl zinc chloride, -n-butyl zinc chloride, isobutyl zinc chloride, -n-hexyl chloride, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, -n-butyl zinc bromide, isobutyl zinc bromide, -N-hexylzinc bromide, methylzinc iodide, ethylzinc iodide, propylzinc iodide, iodide-n-butyl Le zinc iodide isobutyl zinc, halogenated alkyl zinc such as iodide -n- hexyl zinc; zinc fluoride, zinc chloride, zinc bromide, and halogenated zinc such as zinc iodide.

  Compound (a1) or (a2) is preferably dialkylzinc, more preferably dimethylzinc, diethylzinc, dipropylzinc, di-n-butylzinc, diisobutylzinc, or di-n-hexylzinc, Particularly preferred is dimethyl zinc or diethyl zinc.

  Specific examples of the compound (b1) or (b2) include amines such as di (fluoromethyl) amine, bis (difluoromethyl) amine, bis (trifluoromethyl) amine, bis (2,2,2- Trifluoroethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1- Bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine, bis (2-fluorophenyl) amine, bis (3-fluorophenyl) amine, bis (4-fluorophenyl) amine, bis (2, 6-difluorophenyl) amine, bis (3,5-difluorophenyl) amine, bis (2,4,6-trifluorophenyl) amine, bis (3 4,5-trifluorophenyl) amine, bis (pentafluorophenyl) amine, bis (2- (trifluoromethyl) phenyl) amine, bis (3- (trifluoromethyl) phenyl) amine, bis (4- (tri Fluoromethyl) phenyl) amine, bis (2,6-di (trifluoromethyl) phenyl) amine, bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-tri (tri) Fluoromethyl) 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, bis (1H, 1H-perfluorobutyl) amine, bis (1H, 1H- -Fluoropentyl) amine, bis (1H, 1H-perfluorohexyl) amine, bis (1H, 1H-perfluorooctyl) amine, bis (1H, 1H-perfluorododecyl) amine, bis (1H, 1H-perfluoro Pentadecyl) amine, bis (1H, 1H-perfluoroeicosyl) amine, and amines in which the fluoro of these amines is changed to chloro, bromo or iodo. 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.

  Examples of alcohols include fluoromethanol, difluoromethanol, trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1- Trifluoromethylethanol, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, 1H, 1H-perfluorobutanol, 1H, 1H-perfluoropentanol, 1H, 1H-perfluorohexanol 1H, 1H-perfluorooctanol, 1H, 1H-perfluorododecanol, 1H, 1H-perfluoropentanol, 1H, 1H-perfluoroeicosanol, etc., and the fluoro of these alcohols are chloro, bromo or Alcohol changed to iodine That. 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 the above specific examples of diols with thiols.

  Examples of phenols include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 2, 4,6-trifluorophenol, 3,4,5-trifluorophenol, 2,3,5,6-tetrafluorophenol, pentafluorophenol, 2,3,5,6-tetrafluoro-4-trifluoromethyl Phenol, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol, perfluoro-1-naphthol, perfluoro-2-naphthol, 4,5,6,7,8-pentafluoro-2-naphthol , 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) Enol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (trifluoromethyl) phenol, 2,4,6-tris (trifluoromethyl) phenol, 2 -Cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, etc., and phenols obtained by changing the fluoro of these phenols to chloro, bromo or iodo It is done. 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 phenols of the above-described specific examples to thiophenol (in the case of naphthol, compounds represented by rewriting naphthol to naphthylthiol) and the like.

  Examples of halogenated carboxylic acids include pentafluorobenzoic acid, perfluoroethanoic acid, perfluoropropanoic acid, perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluorohepta. Examples include nomic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, perfluorododecanoic acid, and the like.

  Preferably as the compound (b1) or (b2), the amine is preferably bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis (2,2,3,3,3). -Pentafluoropropyl) amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) Examples of amines or bis (pentafluorophenyl) amines 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, Enols include 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 or 2,4,6-tris (trifluoromethyl) phenol.

  More preferably, the compound (b1) or (b2) is bis (trifluoromethyl) amine, bis (pentafluorophenyl) amine, trifluoromethanol, 2,2,2-trifluoro-1-trifluoromethylethanol, 1 , 1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2 , 4,6-trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, or 2,4,6 -Tris (trifluoromethyl) phenol, more preferred Ku is a 3,5-difluorophenol, 3,4,5-fluorophenol, pentafluorophenol or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol. Most preferred is pentafluorophenol, 3,5-difluorophenol, 3,4,5-trifluorophenol, or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol. In particular, pentafluorophenol is used as the compound (b1), 3,5-difluorophenol, 3,4,5-trifluorophenol, or 1,1-bis (trifluoromethyl) -2,2, as the compound (b2). 2-trifluoroethanol is preferably used.

  Specific examples of the compound (c1) or (c2) include water, hydrogen sulfide, and amines such as alkylamine, arylamine, aralkylamine, halogenated alkylamine, halogenated arylamine, or (halogenated alkyl) aryl. Examples of amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentylamine, neopentylamine, isopentylamine, n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, n-eicosylamine, allylamine, cyclopentadienylamine, aniline, 2-tolylamine, 3-tri Amine, 4-tolylamine, 2,3-xylylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3,4-xylylamine, 3,5-xylylamine, naphthylamine, anthracenylamine, benzylamine , (2-methylphenyl) methylamine, (3-methylphenyl) methylamine, (4-methylphenyl) methylamine, (2,3-dimethylphenyl) methylamine, (2,4-dimethylphenyl) methylamine, (2,5-dimethylphenyl) methylamine, (2,6-dimethylphenyl) methylamine, (3,4-dimethylphenyl) methylamine, (3,5-dimethylphenyl) methylamine, (2,3,4) -Trimethylphenyl) methylamine, (2,3,5-trimethylphenyl) Methylamine, (2,3,6-trimethylphenyl) methylamine, (3,4,5-trimethylphenyl) methylamine, (2,4,6-trimethylphenyl) methylamine, (2,3,4,5) -Tetramethylphenyl) methylamine, (2,3,4,6-tetramethylphenyl) methylamine, (2,3,5,6-tetramethylphenyl) methylamine, (pentamethylphenyl) methylamine, (ethyl Phenyl) methylamine, (n-propylphenyl) methylamine, (isopropylphenyl) methylamine, (n-butylphenyl) methylamine, (sec-butylphenyl) methylamine, (tert-butylphenyl) methylamine, (n -Pentylphenyl) methylamine, (neopentylphenyl) methylamine, (n- (Hexylphenyl) methylamine, (n-octylphenyl) methylamine, (n-decylphenyl) methylamine, (n-tetradecylphenyl) methylamine, naphthylmethylamine, anthracenylmethylamine, fluoromethylamine, difluoromethyl Amine, trifluoromethylamine, 2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine, 2,2,2-trifluoro-1-trifluoromethylethylamine, 1, 1-bis (trifluoromethyl) -2,2,2-trifluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, perfluorooctylamine, perfluorododecylamine, perf Oro pentadecyl amine, and the like perfluoro eicosyl amine, chloro and fluoro these amines, and amines that have changed bromo or iodo.

  As anilines, 2,3,4-trimethylaniline, 2,3,5-trimethylaniline, 2,3,6-trimethylaniline, 2,4,6-trimethylaniline, 3,4,5-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,4,6-tetramethylaniline, 2,3,5,6-tetramethylaniline, pentamethylaniline, ethylaniline, n-propylaniline, isopropylaniline N-butylaniline, sec-butylaniline, tert-butylaniline, n-pentylaniline, neopentylaniline, n-hexylaniline, n-octylaniline, n-decylaniline, n-dodecylaniline, n-tetradecylaniline 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline 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-di (trifluoromethyl) aniline, 3,5-di (trifluoromethyl) aniline, 2,4,6-tri (trifluoromethyl) Aniline and the like, and anilines obtained by changing the fluoro of these anilines to chloro, bromo or iodo.

  Compound (c1) or (c2) 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, Fluorohexylamine, perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroaniline, 3-fluoro Niline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoro Methyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline or 2,4 6-tris (trifluoromethyl) aniline, particularly preferably water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine, perfluoropentadecylamine, 2-fluoroaniline, 3-fluoroaniline, 4- Fluoroaniline, 2,6-difluoroaniline, 3, -Difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (tri Fluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, or 2,4,6-tris (trifluoromethyl) aniline, most preferably water Or it is pentafluoroaniline.

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

Examples of inorganic substances that can be used as the particles (d) include inorganic oxides, and clays and clay minerals can also be used. These may be mixed and used.
Specific examples of the inorganic oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, and mixtures thereof such as SiO ₂ — Examples thereof include 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. Among these inorganic oxides, SiO ₂ and / or Al ₂ O ₃ are preferable, and SiO ₂ (that is, silica) is particularly preferable. The inorganic oxide 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 , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Examples of clay or clay mineral include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, bayophyllite, talc, unmo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite, Halloysite and the like.
Among these, preferred are smectite, montmorillonite, hectorite, laponite and saponite, and more preferred are montmorillonite and hectorite.

Of these inorganic substances, inorganic oxides are preferably used.
These inorganic substances are preferably dried to substantially remove moisture, and those dried by heat treatment are preferred. The heat treatment is usually carried out at a temperature of 100 to 1,500 ° C., preferably 100 to 1,000 ° C., more preferably 200 to 800 ° C. for an inorganic substance whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Further, during heating, for example, a method of circulating a dry inert gas (for example, nitrogen or argon) at a constant flow rate or a method of reducing the pressure can be used, but the method is not limited thereto.

  In addition, a hydroxyl group is usually formed on the surface of an inorganic oxide, but a modified inorganic oxide in which active hydrogen of the surface hydroxyl group is substituted with various substituents may be used as the inorganic oxide. good. Specific examples of the modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane, triarylchlorosilanes such as triphenylchlorosilane, dialkyldichlorosilanes such as dimethyldichlorosilane, and diaryldisilanes such as diphenyldichlorosilane. Dialkyldialkoxy such as chlorosilane, alkyltrichlorosilane such as methyltrichlorosilane, aryltrichlorosilane such as phenyltrichlorosilane, trialkylalkoxysilane such as trimethylmethoxysilane, triarylalkoxysilane such as triphenylmethoxysilane, and dimethyldimethoxysilane Silanes, diaryl dialkoxysilanes such as diphenyldimethoxysilane, and alkyltria such as methyltrimethoxysilane Aryltrialkoxysilanes such as coxisilane, phenyltrimethoxysilane, tetraalkoxysilanes such as tetramethoxysilane, alkyldisilazanes such as 1,1,1,3,3,3-hexamethyldisilazane, tetrachlorosilane, methanol, ethanol And inorganic oxides obtained by contact treatment with alcohols such as phenol, dialkylmagnesium such as dibutylmagnesium, butylethylmagnesium and butyloctylmagnesium, and alkyllithiums such as butyllithium.

  Further, specific examples of the modified inorganic oxide include inorganic oxides that have been contacted with a trialkylaluminum and then contacted with a dialkylamine such as diethylamine or diphenylamine, an alcohol such as methanol or ethanol, or phenol.

  In addition, the inorganic oxide itself 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 replace 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. Examples of the method for changing the substitution rate of the surface hydroxyl group include a method for changing the amount of the compound used for the contact treatment, but the method is not limited to these exemplified methods and there is no particular limitation.

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

  As the organic polymer that can be used as the particles (d), any organic polymer may be used, and a plurality of types of organic polymers may be used as a mixture. As the organic polymer, a polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group is preferable.

  The functional group having active hydrogen is not particularly limited as long as it has active hydrogen. Specific examples include primary amino group, secondary amino group, imino group, amide group, hydrazide group, amidino group, and hydroxy group. , Hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid group, sulfinic acid group, sulfenic acid group, thiol group, thioformyl group, pyrrolyl group, imidazolyl group, piperidyl group, indazolyl group, carbazolyl group, etc. . Preferred are a primary amino group, a secondary amino group, an imino group, an amide group, an imide group, a hydroxy group, a formyl group, a carboxyl group, a sulfonic acid group, or a thiol group. Particularly preferred are a primary amino group, a secondary amino group, an amide group or a hydroxy group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  The non-proton-donating Lewis basic functional group is not particularly limited as long as it is a functional group having a Lewis base part that does not have an active hydrogen atom. Specific examples include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted group. Indazolyl group, nitrile group, azide group, N-substituted imino group, N, N-substituted amino group, 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, substituted sulfonic acid group and the like. Preferred is a heterocyclic group, and more preferred is an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring. Particularly preferred are a pyridyl group, an N-substituted imidazolyl group and an N-substituted indazolyl group, and most preferred is a pyridyl group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

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

  The polymer having such a functional group is obtained by, for example, homopolymerizing a monomer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated groups, or It can be obtained by copolymerizing this and 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.

Such a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated groups include the above-described functional group having active hydrogen and one or more polymerizable groups. A monomer having a saturated group, or a monomer having a functional group having a Lewis base having no active hydrogen atom and one or more polymerizable unsaturated groups may be used. Examples of such polymerizable unsaturated groups include alkenyl groups such as vinyl groups and allyl groups, and alkynyl groups such as ethyne groups.
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. Can be mentioned. Specific examples include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, 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, etc. Can be mentioned.
Specific examples of the monomer having a functional group having a Lewis base moiety having no active hydrogen atom and one or more polymerizable unsaturated groups include vinylpyridine, vinyl (N-substituted) imidazole, and vinyl (N-substituted) indazole. Can be mentioned.

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

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

  These organic polymers are preferably dried to substantially remove moisture, and those dried by heat treatment are preferred. The heat treatment is usually carried out at a temperature of 30 to 400 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. for an organic polymer whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Further, during heating, for example, a method of circulating a dry inert gas (for example, nitrogen or argon) at a constant flow rate or a method of reducing the pressure can be used, but the method is not limited thereto.

The modified particles of the present invention comprise (a1), (b1), (c1) and (d), and (a2), (b2) and (c2). It is a modified particle obtained by contact. The order in which (a1), (b1), (c1) and (d) are brought into contact is not particularly limited, and the following order may be mentioned.
<1> A contact product obtained by contacting (a1) and (b1) with a contact product (c1) is brought into contact with (d).
<2> A contact product obtained by contacting (a) with (a1) and (b1) and (d) is brought into contact with (c1).
<3> A contact object obtained by bringing (a1) and (c1) a contact object into contact with (b1) is brought into contact with (d).
<4> A contact product obtained by contacting (a) with (a1) and (c1) and (d) is brought into contact with (b1).
<5> A contact product obtained by contacting (b1) with a contact product between (a1) and (d) and (c1) are brought into contact with each other.
<6> A contact object obtained by contacting (a1) and (d) with a contact object obtained by bringing (c1) into contact with (b1).
<7> The contact product obtained by bringing (b1) and (c1) into contact with (a1) is brought into contact with (d).
<8> A contact product obtained by bringing (b1) and (c1) into contact with (d) and a contact product obtained by bringing (d) into contact with each other.
<9> A contact object obtained by bringing (b1) and (d) a contact object into contact with (a1) is contacted with (c1).
<10> The contact product obtained by bringing (b1) and (d) the contact product into contact with (c1) is brought into contact with (a1).
<11> A contact object obtained by bringing (a1) into contact with a contact object between (c1) and (d) and (b1) are brought into contact with each other.
<12> A contact object obtained by bringing (b1) into contact with a contact object between (c1) and (d) and (a1) are brought into contact with each other.
The contact order is preferably <1>, <2>, <3>, <5>, <11> or <12>.

A solid component obtained by contacting (a1), (b1), (c1) and (d) (sometimes referred to as “intermediate solid”), and (a2), (b2) and (c2) The order of contacting is not particularly limited. In the above <1> to <12>, (d) is an intermediate solid, (a1) is (a2), (b1) is (b2), ( A method in which c1) is replaced with (c2), respectively. Among these, the following <13>, <14> or <15> is preferable.
<13> A contact product between the intermediate solid and (a2) and a contact product obtained by bringing (b2) into contact with (c2).
<14> A contact product between the intermediate solid and (b2) and a contact product obtained by bringing (a2) into contact with (c2).
<15> The contact product obtained by bringing the contact product between the intermediate solid and (c2) and (b2) into contact with (a2).

  After the contact treatment, the contact treatment between the solid component obtained by the contact treatment and (a2), (b2), and (c2) may be further performed once or more.

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

  As the solvent, a solvent that does not react with each of the components to be contacted when the solvent is used and the contact product obtained by contact is usually used. As described above, when each component is brought into contact stepwise, for example, even if the solvent reacts with (a1), the contact obtained by contacting (a1) with other components The product may no longer react with the solvent, and in such a case, the solvent can be used as a solvent in the contact operation using the contact product as one component. Solvents are exemplified below, but they may be properly used as described above. Examples of solvents that can be used include nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents, or 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. Specific examples include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, and cyclohexane, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, dichloromethane, difluoromethane, 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, tetrahydrofuran, Ether solvents such as trahydropyran, 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, glycerol and other alcohol solvents, phenol, p-cresol and other phenol solvents, acetone, ethyl methyl ketone, cyclohexanone, anhydrous Carbonyl solvents such as acetic acid, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, Phosphoric acid derivatives such as samethyl phosphate triamide and triethyl phosphate, nitrile solvents such as acetonitrile, propionitrile, succinonitrile and benzonitrile, nitro compounds such as nitromethane and nitrobenzene, amine solvents such as pyridine, piperidine and morpholine, And sulfur compounds such as dimethyl sulfoxide and sulfolane.

  When the contact (e) obtained by bringing (a1), (b1) and (c1) into contact with the particles (d), that is, in the case of <1>, <3> and <7> above In the above, the solvent (s1) for producing the contact product (e) is preferably the above aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether solvent.

On the other hand, a polar solvent is preferable as the solvent (s2) for bringing the contact product (e) into contact with the particles (d). 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 E _T ^N ≧ 0.1 is particularly preferred.

  Moreover, as said solvent (s2), the mixed solvent of these polar solvents and hydrocarbon solvents can also be used. As the hydrocarbon solvent, the aliphatic hydrocarbon solvent and aromatic hydrocarbon solvent exemplified above are used.

  (A1), (b1) and (c1) in contact with the contact product (e) obtained by contacting (d), that is, in the case of <1>, <3>, <7> above A hydrocarbon solvent can be used as the solvent (s1) and the solvent (s2). In this case, the contact product (e) obtained after contacting (a1), (b1) and (c1). It is preferable that the time interval until the particles (d) are brought into contact with each other is short. The time interval is preferably 0 to 5 hours, more preferably 0 to 3 hours, and most preferably 0 to 1 hour. Moreover, the temperature at the time of making a contact thing (e) and particle | grains (d) contact 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. A nonpolar solvent is more preferred. This is because the contact product between (a1) and (c1) or the contact product between (a1) and (b1) and (c1) is generally soluble in a nonpolar solvent. Since it is low, when (d) is present in the reaction system when these contact products are produced, it is more stable that the produced contact product is deposited on the surface of (d) than in a nonpolar solvent. It is preferable because it is considered that the fixation becomes easier.

  For the same reason as described above, when the intermediate solid is brought into contact with (a2), (b2) and (c2), both the nonpolar solvent and the polar solvent can be used. More preferred.

The amount of each compound (a1), (b1), (c1) used is not particularly limited, but the molar ratio of the amount of each compound used is (a1) :( b1) :( c1) = 1: y: z It is preferable that y and z substantially satisfy the following formula (1).
| M−y−2z | ≦ 1 (1)
(In the above formula (1), m represents a number corresponding to the valence of M ^1. )
In the above formula (1), y is preferably a number of 0.01 to 1.99, more preferably a number of 0.10 to 1.80, and still more preferably a number of 0.20 to 1.50. Yes, most preferably a number from 0.30 to 1.00, and the same preferred range of z in the above formula (1) is determined by m, y and the above formula (1).

  The amount of each compound (a2), (b2), (c2) used is also the same as the amount used (a1), (b1), (c1).

  In the actual contact treatment of each compound, even if the use of each compound is intended to completely satisfy the above formula (1), the amount used may fluctuate slightly and remain unreacted. In consideration of the amount of the compound to be used, etc., it is usual to slightly increase or decrease the amount used as appropriate. Here, “substantially satisfying the formula (1)” is obtained by bringing each compound into contact with each other at a molar ratio satisfying the above formula (1) without completely satisfying the above formula (1). It is meant to be included when attempting to obtain such objects.

In the preparation of the modified particles of the present invention, the amount of (d) used for (a1) is derived from (a1) contained in the particles obtained by contacting (a1) and (d). It is preferable that the amount of the typical metal atom to be converted is 0.1 mmol or more in terms of the number of moles of the typical metal atom contained in 1 g of the obtained particles, and more preferably 0.5 to 20 mmol. And may be determined as appropriate within the range.
The amount of (a2) used may be appropriately determined in the same manner as the amount of (d) used for (a1). When (a2) and (a1) have the same typical metal atom, the ratio of the usage fee between (a2) and (a1) may be determined as appropriate within the range that finally becomes the above range.

  After the contact treatment as described above, heating is also preferably performed in order to further advance the reaction. In heating, it is preferable to use a solvent having a higher boiling point in order to obtain a higher temperature. For this reason, the solvent used for the contact treatment may be replaced with another solvent having a higher boiling point.

  As the modified particles of the present invention, as a result of such contact treatment, the raw materials (a1), (b1), (c1), (a2), (b2), (c2) and / or (d ) May remain as an unreacted substance. However, when applying to the polymerization accompanied by the formation of addition polymer particles, it is preferable to perform a washing treatment to remove unreacted substances in advance. The solvent at that time may be the same as or different from the solvent at the time of contact. Such cleaning treatment is preferably carried out in an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

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

Specific examples of the method for producing the modified particles of the present invention are as follows: M ¹ and M ² are zinc atoms, compound (b1) is pentafluorophenol, compound (b2) is trifluorophenol, The case where (c1) and (c2) are water and the particle (d) is silica is shown in more detail below. Toluene is used as a solvent, silica is added thereto, the mixture is cooled to 5 ° C., 2 mmol of 1,1,1,3,3,3-hexamethyldisilazane is added to 1 g of silica, and the mixture is stirred for 10 minutes to 24 hours. After that, 2.50 mmol of diethylzinc per 1 g of silica is added, and 1.25 mmol of pentafluorophenol per 1 g of silica is added dropwise, followed by stirring at room temperature for 10 minutes to 24 hours. Thereafter, 1.88 mmol of water per 1 g of silica is further added dropwise and stirred at room temperature for 10 minutes to 24 hours. Thereafter, 2.50 mmol of diethylzinc per 1 g of silica is added, and 1.25 mmol of trifluorophenol is added dropwise per 1 g of silica, followed by stirring at room temperature for 10 minutes to 24 hours. Thereafter, 1.88 mmol of water per 1 g of silica is further added dropwise and stirred at room temperature for 10 minutes to 24 hours. Thereafter, the solvent is retained and drying is performed under reduced pressure. Thus, the modified particles of the present invention can be produced.

The modified particles of the present invention can be used as a support for supporting a catalyst component for addition polymerization composed of a transition metal compound that forms a single site catalyst, and is suitably used for polymerization accompanied by formation of addition polymer particles. The modified particles of the present invention are useful as an addition polymerization catalyst component (especially an olefin polymerization catalyst component). Specific examples of the addition polymerization catalyst of the present invention include the above-mentioned modified particles (A) and addition polymerization catalysts obtained by contacting the transition metal compound (B). Examples include addition polymerization catalysts obtained by bringing modified particles (A), transition metal compounds (B), and organoaluminum compounds (C) into contact, and the latter is more preferred because it is more active.
Hereinafter, the addition polymerization catalyst will be described in more detail.

(B) Transition metal compound As the transition metal compound (B) used in the addition polymerization catalyst of the present invention, a transition metal compound forming a single site catalyst is used, and the modified particles (A) (or further organic There is no particular limitation as long as it is a transition metal compound exhibiting addition polymerization activity by using aluminum compound (C)) as an activation promoter component. In addition, the single site catalyst here is a concept distinguished from the conventional solid catalyst, and in the case of copolymerization, not only a single site catalyst in a narrow sense that can provide an addition polymer having a narrow molecular weight distribution and a narrow composition distribution. As long as the catalyst can be obtained by a preparation method similar to the single-site catalyst in such a narrow sense, an addition polymer having a broad molecular weight distribution and a catalyst capable of obtaining an addition polymer having a wide composition distribution in the case of copolymerization are also included. .

Such a transition metal compound (B) is preferably a group 3-11 or lanthanoid series transition metal compound represented by the following general formula [7] or its μ-oxo type transition metal compound dimer. The body is more preferred.
L ³ _a M ³ X ¹ _b [7]
(In the above general formula [7], M ³ represents a transition metal atom of Groups 3 to 11 or lanthanoid series of the periodic table. L ³ represents a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom. , L ³ may be the same as or different from each other, and a plurality of L ³ are directly connected to each other or contain a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom X ¹ is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton) or a hydrocarbon oxy group, and a is 0 <a ≦. B represents a number satisfying 8, and b represents a number satisfying 0 <b ≦ 8.

In the general formula [7], M ³ is a transition metal atom of Group 3 to 11 or lanthanoid series of the periodic table (IUPAC 1989). Specific examples thereof include scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom. , Samarium atoms, ytterbium atoms, and the like. M ³ in the general formula [7] is preferably a titanium atom, zirconium atom, hafnium atom, vanadium atom, chromium atom, iron atom, cobalt atom or nickel atom, particularly preferably a titanium atom, zirconium atom or hafnium atom. And most preferably a zirconium atom.

In the general formula [7], L ³ is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ³ may be the same or different. The plurality of L ³ may be directly connected to each other, or may be connected via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom.

Examples of the group having a cyclopentadiene-type anion skeleton in L ³ include η ^5- (substituted) cyclopentadienyl group, η ^5- (substituted) indenyl group, η ^5- (substituted) fluorenyl group and the like. Specifically, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ -ethylcyclopentadienyl group, η ⁵ -n-butylcyclopentadienyl group, η ⁵ -Tert-butylcyclopentadienyl group, η ⁵ -1,2-dimethylcyclopentadienyl group, η ⁵ -1,3-dimethylcyclopentadienyl group, η ⁵ -1-methyl-2-ethylcyclopenta Dienyl group, η ⁵ -1-methyl-3-ethylcyclopentadienyl group, η ⁵ -1-tert-butyl-2-methylcyclopentadienyl group, η ⁵ -1-tert-butyl-3-methyl Cyclopentadienyl group, η ⁵ -1-methyl-2-isopropylcyclopentadienyl group, η ⁵ -1-methyl-3-isopropylcyclopentadienyl group, η ⁵ -1-methyl-2-n-butyl Cyclopentadienyl group, η ⁵ -1-methyl-3-n-butylcyclopentadienyl group, η ⁵ -1,2,3-trimethylcyclopentadienyl group, η ⁵ -1,2,4-trimethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - indenyl group, eta ^{5-4,5,6,7-tetrahydroindenyl} group, η ⁵ -2-methylindenyl group, η ⁵ -3-methylindenyl group, η ⁵ -4-methylindenyl group, η ⁵ -5-methylindenyl group, η ⁵ -6-methylindenyl group, eta ^{5-7-methylindenyl} group, η ⁵ -2-tert- butyl indenyl group, η ⁵ -3-tert- butyl indenyl group, η ⁵ -4-tert- butylindenyl group, eta ⁵ -5 -Tert-butylindenyl group, η ^5-6 -tert-butylindenyl group, η ⁵ -7-tert-butylindenyl group, η ⁵ -2,3-dimethylindenyl group, η ⁵ -4,7-dimethylindenyl group, η ^5- 2,4,7-trimethylindenyl group, η ⁵ -2-methyl-4-isopropylindenyl group, η ⁵ -4,5-benzindenyl group, η ⁵ -2-methyl-4,5-benzindenyl group, η ^5-4-phenyl indenyl group, eta ^{5-2-methyl-5-phenyl} indenyl group, eta ^{5-2-methyl-4-phenyl} indenyl group, eta ^{5-2-methyl-4-naphthyl} indenyl group , Η ⁵ -fluorenyl group, η ⁵ -2,7-dimethylfluorenyl group, η ⁵ -2,7-di-tert-butylfluorenyl group, and substituted products thereof.
In the present specification, “η ⁵ −” may be omitted for the names of transition metal compounds.

  Examples of the hetero atom in the group containing a hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Examples of such a group include an alkoxy group, an aryloxy group, a thioalkoxy group, a thioaryloxy group, and an alkyl group. Amino group, arylamino group, alkylphosphino group, arylphosphino group, chelating ligand, or aromatic or aliphatic heterocyclic group having an oxygen atom, sulfur atom, nitrogen atom and / or phosphorus atom in the ring Is preferred.

  Specific examples of groups containing heteroatoms include methoxy, ethoxy, propoxy, butoxy, phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethyl. Phenoxy group, 2-ethylphenoxy group, 4-n-propylphenoxy group, 2-isopropylphenoxy group, 2,6-diisopropylphenoxy group, 4-sec-butylphenoxy group, 4-tert-butylphenoxy group, 2,6 -Di-sec-butylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2,6-di-tert-butylphenoxy group, 4-methoxyphenoxy group, 2,6-dimethoxyphenoxy group, 3,5 -Dimethoxyphenoxy group, 2-chlorophenoxy group, 4-nitrosophenoxy group, 4-nitrophene Xy 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'-te La -tert- butyl 2,2 'methylenedianiline phenoxy group, 4,4', 6,6'-tetramethyl-2,2'-isobutenyl dust Denji phenoxy group and the like.

Examples of the group containing a hetero atom also include a group represented by the following general formula [8].
R ⁵ ₃ P = N- [8]
(Wherein R ⁵ represents a hydrogen atom, a halogen atom or a hydrocarbon group in each case, and they may be the same or different from each other, and two or more of them may be bonded to each other; A ring may be formed.)

Specific examples of R ⁵ in the general formula [8] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Examples thereof include, but are not limited to, a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cycloheptyl group, a cyclohexyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a benzyl group.

（式中、Ｒ⁶ はそれぞれの場合に水素原子、ハロゲン原子、炭化水素基、ハロゲン化炭化水素基、炭化水素オキシ基、シリル基またはアミノ基を表し、それらは互いに同じであっても異なっていても良く、それら２つ以上が互いに結合していても良く、環を形成していても良い。） Further, examples of the group containing a hetero atom include a group represented by the following general formula [9].

(Wherein R ⁶ represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon oxy group, a silyl group or an amino group in each case, and they may be the same or different from each other. Or two or more of them may be bonded to each other and may form a ring.)

Specific examples of R ⁶ in the general formula [9] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, phenyl group, 1-naphthyl group, 2-naphthyl group, tert-butyl group, 2 , 6-dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl group, methyl Group, triethylsilyl group, diphenylmethylsilyl group, 1-methyl-1-phenylethyl group, 1,1-dimethylpropyl group, 2-chlorophenyl group, pentafluorophenyl group, etc., but are not limited thereto is not.

  The chelating ligand refers to a ligand having a plurality of coordination sites. Specifically, acetylacetonate, diimine, oxazoline, bisoxazoline, terpyridine, acylhydrazone, diethylenetriamine, triethylenetetramine, Porphyrin, crown ether, cryptate and the like can be mentioned.

  Specific examples of the heterocyclic group include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, preferably a pyridyl group.

A group having a cyclopentadiene type anion skeleton, a group having a cyclopentadiene type anion skeleton and a group containing a hetero atom, or a group containing a hetero atom may be directly connected to each other, such as a carbon atom, silicon It may be linked via a residue containing an atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom. Such a residue is preferably a divalent residue in which two atoms bonded to L ³ are a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, and more preferably 2 A divalent atom having two atoms bonded to L ³ is a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom, and the minimum number of atoms between the two atoms bonded to L ³ is 3 or less. Residue (this includes the case where there is a single atom bound to two L ³ ). Specifically, alkylene groups such as methylene group, ethylene group and propylene group, substituted alkylene groups such as dimethylmethylene group (isopropylidene group) and diphenylmethylene group, or silylene group, dimethylsilylene group, diethylsilylene group and diphenylsilylene. Group, a substituted silylene group such as tetramethyldisilylene group and dimethoxysilylene group, or a hetero atom such as nitrogen atom, oxygen atom, sulfur atom and phosphorus atom, particularly preferably a methylene group, an ethylene group and a dimethylmethylene group. (Isopropylidene group), diphenylmethylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group or dimethoxysilylene group.

X ¹ in the general formula [7] is a halogen atom, a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton), or a hydrocarbon oxy group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The hydrocarbon group here does not include a group having a cyclopentadiene type anion skeleton. Examples of the hydrocarbon group include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Preferably, the alkyl group has 1 to 20 carbon atoms, the aralkyl group has 7 to 20 carbon atoms, and the number of carbon atoms. An aryl group having 6 to 20 carbon atoms or an alkenyl group having 3 to 20 carbon atoms is preferable.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, Neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group, etc. are mentioned, more preferably methyl group, ethyl group, isopropyl Group, tert-butyl group, isobutyl group or amyl group.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 1 to 10 carbon atoms 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, Examples thereof include a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group.
Any of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (2,3-dimethylphenyl). ) Methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (3 , 5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3 , 4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4) 6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, ( Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc. More preferred is a benzyl group.
These aralkyl 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, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, and 2,5-xylyl group. 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-trimethyl Phenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2 , 3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butyl group Nyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, anthracenyl group More preferred 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 Etc. may be partially substituted.

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

  The hydrocarbon oxy group herein includes an alkoxy group, an aralkyloxy group, an aryloxy group, and the like, and preferably an alkoxy group having 1 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, or carbon. An aryloxy group having 6 to 20 atoms is preferred.

Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, and a neopentoxy group. , N-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group, etc., more preferably methoxy group, ethoxy group, isopropoxy group, or tert-butoxy group. .
These alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3- (Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethyl) Phenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) Methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy Group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group and the like. More preferably, it is a benzyloxy group.
These aralkyloxy 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, and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, and 2,4-dimethylphenoxy group. 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl -4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethyl Phenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di -Tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3 , 4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, Isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, Anthracenoxy group etc. are mentioned.
These aryloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

X ¹ is more preferably chlorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, trifluoro Methoxy group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6-tetrafluoro-4- A pentafluorophenylphenoxy group or a benzyl group.

In the general formula [7], a represents a number satisfying 0 <a ≦ 8, b represents a number satisfying 0 <b ≦ 8, and is appropriately selected according to the valence of M ³ . When M ³ is a titanium atom, a zirconium atom or a hafnium atom, a is preferably 2, and b is also preferably 2.

  Among the transition metal compounds represented by the general formula [7], specific examples of the compound in which the transition metal atom is a titanium atom, a zirconium atom or a hafnium atom include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclohexane). Pentadienyl) titanium dichloride, bis (ethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, bis (1,2- Dimethylcyclopentadienyl) titanium dichloride, bis (1,3-dimethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-ethyl) Cyclopentadienyl) titanium Chloride, bis (1-methyl-2-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-isopropylcyclo) Pentadienyl) titanium dichloride, bis (1-methyl-3-isopropylcyclopentadienyl) 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 (tetramethyl) Cyclopentadienyl) titanium dichlor Id, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenyl) Indenyl) titanium dichloride,

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

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

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

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

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

(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 Denyl-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-propanedidiamide] 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 -Dimethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium trichloride, [tris (3 , 5-dimethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium trichloride, Compounds in which titanium is changed to zirconium or hafnium, dimethylsilylene is methylene, ethylene, dimethylmethylene (isopropylidene), diphenylmethylene, diethylsilylene, diphenylsilylene, or dimethoxysilylene Or dichloride, diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide, di (pentafluorophenoxide), or The compound changed to di (2,6-di-tert-butylphenoxide), trichloride, triethoxide, tri-n-propoxide, triisopropoxide, tri-n-butoxide, triisobutoxide, tri-tert- Examples thereof include compounds changed to butoxide, triphenoxide, tri (pentafluorophenoxide), or tri (2,6-di-tert-butylphenoxide).

  Further, among the transition metal compounds represented by the general formula [7], dimethylsilylene (cyclopentadienyl) (2-phenoxy) is a specific example of a compound in which the transition metal atom is a titanium atom, a zirconium atom or a hafnium atom. Titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopenta) Dienyl) (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-butyldimethyl) Silyl-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) ( , 5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (1-naphthoxy-2-yl) titanium Dichloride, etc., compounds in which the titanium of these compounds is changed to zirconium or hafnium, cyclopentadienyl of these compounds is changed to methylcyclopentadienyl, n-butylcyclopentadienyl, tert-butylcyclopentadienyl, tetra Compound changed to methylcyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl, or fluorenyl, (2-phenoxy) to (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or Compound changed to (3-tert-butyldimethylsilyl-2-phenoxy), Compound changed from dimethylsilylene to methylene, ethylene, dimethylmethylene (isopropylidene), diphenylmethylene, diethylsilylene, diphenylsilylene, or dimethoxysilylene, dichloride Diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide, di (pentafluorophenoxide), or di (2,6-di A compound changed to -tert-butylphenoxide) can also be exemplified.

  Among the transition metal compounds represented by the general formula [7], specific examples of the compound in which the transition metal atom is a nickel atom include 2,2′-methylenebis [(4R) -4-phenyl-5,5′- Dimethyloxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diethyloxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5 '-Di-n-propyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diisopropyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4 -Phenyl-5,5'-dicyclohexyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R)- -Phenyl-5,5'-dimethoxyoxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diethoxyoxazoline] nickel dichloride, 2,2'-methylenebis [(4R ) -4-phenyl-5,5′-diphenyloxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (2-methylphenyl) oxazoline] nickel dichloride, 2 , 2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methylphenyl) oxazoline] nickel dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5- Di- (4-methylphenyl) oxazoline] nickel dichloride, 2,2'-methylenebis [(4R)- -Phenyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel Dichloride, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dichloride,

2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclobutane}] nickel dichloride, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1 '-Cyclopentane}] nickel dichloride, 2,2'-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1'-cyclohexane}] nickel dichloride, 2,2'-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cycloheptane}] nickel dichloride, and the enantiomers of the above compounds. Further, compounds in which the steric configuration of the asymmetric carbon of one oxazoline ring of the bisoxazoline type compound is reversed, or -4-phenyl of these compounds is replaced with -4-methyl, -4-isopropyl, -4- Compound changed to isobutyl, -4-tert-butyl or -4-benzyl, dichloride, diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide , Diphenoxide, di (pentafluorophenoxide), or a compound changed to di (2,6-di-tert-butylphenoxide).

  Further, specific examples of the nickel compound include [hydrotris (3,5-dimethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-diethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-di-tert- Butylpyrazolyl) borate] nickel chloride and chlorides of these compounds are ethoxide, n-propoxide, isopropoxide, n-butoxide, isobutoxide, tert-butoxide, phenoxide, pentafluorophenoxide, or 2,6-dioxide Examples thereof include compounds changed to -tert-butylphenoxide.

（式中、Ｒ⁷ とＲ⁸ はそれぞれ２，６−ジイソプロピルフェニル基であり、Ｒ⁹ およびＲ¹⁰ はそれぞれ水素原子またはメチル基あるいはＲ⁹ とＲ¹⁰ とがいっしょになってアセナフテン基であり、Ｘ² はフッ素原子、塩素原子、臭素原子、よう素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、フェニル基、ベンジル基、メトキシ基、エトキシ基、またはフェノキシ基である。）
また、上記のニッケル化合物において、ニッケルをパラジウム、コバルト、ロジウム、またはルテニウムに置き換えた化合物も同様に例示することができる。 Examples of the nickel compound include compounds represented by the following structural formula.

(Wherein R ⁷ and R ⁸ are each a 2,6-diisopropylphenyl group, R ⁹ and R ¹⁰ are each a hydrogen atom or a methyl group, or R ⁹ and R ¹⁰ together are an acenaphthene group; X ² is fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methoxy group, ethoxy group, or phenoxy group .)
In addition, in the above nickel compound, compounds in which nickel is replaced with palladium, cobalt, rhodium, or ruthenium can be exemplified as well.

  Among the transition metal compounds represented by the general formula [7], specific examples of the compound in which the transition metal atom is iron include 2,6-bis- [1- (2,6-dimethylphenylimino) ethyl] pyridine. Iron dichloride, 2,6-bis- [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron dichloride, 2,6-bis- [1- (2-tert-butyl-phenylimino) ethyl] pyridine iron Dichloride, etc. or dichloride can be diethoxide, di-n-propoxide, diisopropoxide, di-n-butoxide, diisobutoxide, di-tert-butoxide, diphenoxide, di (pentafluorophenoxide), or di ( Examples thereof include compounds changed to 2,6-di-tert-butylphenoxide).

  Further, specific examples of the iron compound include [hydrotris (3,5-dimethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-diethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-di-tert- Butylpyrazolyl) borate] iron chloride and the like, and chlorides of these compounds include ethoxide, n-propoxide, isopropoxide, n-butoxide, isobutoxide, tert-butoxide, phenoxide, pentafluorophenoxide, or 2,6- The compound changed into di-tert-butyl phenoxide can be illustrated. In addition, in the above iron compound, a compound in which iron is replaced with cobalt or nickel can also be exemplified.

  Specific examples of the transition metal compound of the transition metal compound represented by the general formula [7] include μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], Μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2 -Phenoxy) titanium chloride], μ-oxobis [ Sopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], [Mu] -oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], [mu] -oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2 -Phenoxy) chita Chloride], and the like can be exemplified μ- Okisobisu [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride]. Also, the chloride of these compounds is changed to ethoxide, n-propoxide, isopropoxide, n-butoxide, isobutoxide, tert-butoxide, phenoxide, pentafluorophenoxide, or 2,6-di-tert-butylphenoxide. The compound etc. which were made can be illustrated.

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

Of the transition metal compounds exemplified above, the transition metal compound (B) used in the present invention is preferably a transition metal compound represented by the above general formula [7]. Among these, a transition metal compound in which M ³ in the general formula [7] is a Group 4 atom is preferable, and in particular, a transition metal compound having at least one group having a cyclopentadiene-type anion skeleton as L ³ in the general formula [7]. Is preferred.

(C) Organoaluminum compound As the organoaluminum compound (C) used in the addition polymerization catalyst of the present invention, a known organoaluminum compound can be used. Preferably, it is an organoaluminum compound represented by the following general formula [10].
R ¹¹ _c AlY _3-c [10]
(Wherein R ¹¹ represents a hydrocarbon group, and all R ¹¹ may be the same or different. Y represents a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group or an aryloxy group; All Y may be the same or different, and c represents a number satisfying 0 <c ≦ 3.)

R ¹¹ in the general formula [10] representing the organoaluminum compound is preferably a hydrocarbon group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, 2-methylhexyl group, n-octyl group and the like, preferably ethyl group, n -A butyl group, an isobutyl group, an n-hexyl group or an n-octyl group.

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

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

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

  Specific examples of the organoaluminum compound represented by the general formula [10] include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri -Trialkylaluminum such as n-octylaluminum; Dialkylaluminum such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride Chloride; methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, n-butylaluminum Alkyl aluminum dichlorides such as um dichloride, isobutyl aluminum dichloride, n-hexyl aluminum dichloride; dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, di-n- Dialkyl aluminum hydrides such as hexyl aluminum hydride; alkyl (dialkoxy) aluminum such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, methyl (di-tert-butoxy) aluminum; dimethyl (methoxy) aluminum, dimethyl (ethoxy) aluminum Dimethyl (tert-butoxy) aluminum, etc. Alkyl (alkoxy) aluminum; alkyl (diaryloxy) aluminum such as methyl (diphenoxy) aluminum, methyl bis (2,6-diisopropylphenoxy) aluminum, methyl bis (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.

The usage-amount of a component (B) is 1 * 10 < ^-6 > -1 * 10 < ^-3 > mol normally with respect to 1g of a component (A), Preferably it is 5 * 10 < ^-6 > -5 * 10 <^-4> mol. Moreover, the usage-amount of a component (C) is 0.01-10 as molar ratio (C) / (B) of the aluminum atom of a component (C) organoaluminum compound with respect to the transition metal atom of a component (B) transition metal compound. 000 is preferable, 0.1 to 5,000 is more preferable, and 1 to 2,000 is most preferable.

  As the addition polymerization catalyst of the present invention, a reaction product obtained by bringing the component (A) and the component (B), and optionally the component (C) into contact with each other in advance may be used. It may be used after being put in. When components (A), (B) and (C) are used, any two of them may be contacted in advance and then another component may be contacted.

  The method for supplying each catalyst component to the catalyst preparation reactor or the polymerization reactor is not particularly limited. A method of supplying each component in a solid state, a method of supplying a solution dissolved in a hydrocarbon solvent from which components for deactivating catalyst components such as moisture and oxygen are sufficiently removed, or a method of supplying in a suspended or slurry state Etc. Examples of the solvent at this time include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbon solvents such as benzene and toluene, and halogenated hydrocarbons such as methylene chloride. Hydrocarbons or aromatic hydrocarbons are preferred.

  When supplying each catalyst component in a solution state or in a suspended or slurry state, the concentration of the component (A) is usually 0.01 to 1000 g / liter, preferably 0.1 to 500 g / liter. The concentration of the component (C) is usually 0.0001 to 100 mol / liter, preferably 0.01 to 10 mol / liter in terms of Al atoms. The concentration of component (B) is usually 0.0001 to 1000 mmol / liter, preferably 0.01 to 50 mmol / liter in terms of transition metal atoms.

  The polymerization method is not particularly limited, and gas phase polymerization in a gaseous monomer, solution polymerization using a solvent, slurry polymerization, and the like are possible. Solvents used for solution polymerization or slurry polymerization include aliphatic hydrocarbon solvents such as butane, hexane, pentane, heptane and octane, aromatic hydrocarbon solvents such as benzene and toluene, or halogenated hydrocarbon solvents such as methylene chloride. It is also possible to use olefin itself as a solvent (bulk polymerization). The polymerization method may be either batch polymerization or continuous polymerization, and the polymerization may be performed in two or more stages with different reaction conditions. In general, the polymerization time is appropriately determined depending on the kind of the target olefin polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours.

The present invention is particularly suitably applied to polymerization involving formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.).
The slurry polymerization may be performed according to a known slurry polymerization method and polymerization conditions, but is not limited thereto. A preferred polymerization method in the slurry process is a continuous reactor in which monomers (and comonomers), feeds, diluents, etc. are continuously added as required, and the polymer product is continuously or at least periodically removed. included. Examples of the reactor include a method using a loop reactor and a method using a stirring reactor. In addition, a plurality of stirred reactors having different reactors or different reaction conditions may be used in series or in parallel or a combination thereof.

  As the diluent, for example, an inert diluent (medium) such as paraffin, cycloparaffin or aromatic hydrocarbon can be used. The temperature in the polymerization reactor or reaction zone can usually range from about 0 ° C to about 150 ° C, preferably from 30 ° C to 100 ° C. The pressure can usually be changed from about 0.1 MPa to about 10 MPa, preferably 0.5 MPa to 5 MPa. A pressure can be applied to maintain the catalyst in suspension, maintain the medium and at least some of the monomer and comonomer in a liquid phase, and allow the monomer and comonomer to contact. Accordingly, the medium, temperature, and pressure may be selected such that the addition polymer is produced as solid particles and recovered in that form.

The molecular weight of the addition polymer can be controlled by various known means such as adjusting the temperature of the reaction zone and introducing hydrogen.
Each catalyst component, monomer (and comonomer) can be added to the reactor or reaction zone in any order by any known method. For example, a method of simultaneously adding each catalyst component and monomer (and comonomer) to the reaction zone, a method of adding them sequentially, and the like can be used. If desired, each catalyst component can be pre-contacted in an inert atmosphere prior to contact with the monomer (and comonomer).

The gas phase polymerization may be performed according to a known gas phase polymerization method and polymerization conditions, but is not limited thereto. As the gas phase polymerization reaction apparatus, a fluidized bed type reaction vessel, preferably a fluidized bed type reaction vessel having an enlarged portion is used. There is no problem even in a reactor equipped with a stirring blade in the reaction vessel.
As a method for supplying each component to the polymerization tank, a solution or a slurry is usually supplied using an inert gas such as nitrogen or argon, hydrogen, ethylene or the like in the absence of moisture, or dissolved or diluted in a solvent. A method such as supplying in a state can be used. Each catalyst component may be supplied individually, or may be supplied by contacting arbitrary components in advance in an arbitrary order.

  As polymerization conditions, the temperature is less than the temperature at which the polymer melts, preferably 0 ° C. to 150 ° C., particularly preferably 30 ° C. to 100 ° C. Furthermore, hydrogen may be added as a molecular weight regulator for the purpose of adjusting the melt fluidity of the final product. In the polymerization, an inert gas may coexist in the mixed gas.

  In the present invention, the prepolymerization described below may be performed before such polymerization (main polymerization).

  In the prepolymerization, a small amount of one or more olefins is supplied in the presence of the modified particles (A) and the transition metal compound (B) or in the presence of the organoaluminum compound (C). It is preferably carried out in a slurry state. Examples of the solvent used for the slurry include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Further, when slurrying, a liquid olefin can be used instead of part or all of the inert hydrocarbon solvent.

  The amount of the organoaluminum compound (C) used during the prepolymerization can be selected in a wide range such as 0.5 to 700 mol per mol of the transition metal compound (B), preferably 0.8 to 500 mol, 1 to 200 mol is particularly preferred.

  The amount of the prepolymerized olefin is usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g, per 1 g of the modified particles.

  The slurry concentration at the time of prepolymerization is preferably 0.1 to 50 g-modified particle / liter-solvent, particularly 0.5 to 20 g-modified particle / liter-solvent is preferable. . The prepolymerization temperature is preferably -20 ° C to 100 ° C, particularly preferably 0 ° C to 80 ° C. Further, the partial pressure of olefin in the gas phase part during prepolymerization is preferably 0.001 MPa to 2 MPa, and particularly preferably 0.01 MPa to 1 MPa. For olefins that are liquid at prepolymerization pressure and temperature, Not as long. Further, the prepolymerization time is not particularly limited, but usually 2 minutes to 15 hours is preferable.

  As a method of supplying the modified particles (A), the transition metal compound (B), the organoaluminum compound (C), and the olefin, when the prepolymerization is performed, the modified particles (A) And a transition metal compound (B), or a method of supplying an olefin after contact with an organoaluminum compound (C), if necessary, the above modified particles ( A), a method of supplying an organoaluminum compound (C) after contacting a transition metal compound (B) and an olefin, an organoaluminum compound (C) and a transition metal compound (B) in the presence of an olefin After contacting, any method such as a method of supplying the modified particles (A) may be used, but the modified particles (A) and the organoaluminum compound (C) are combined. Contact It is preferable that the olefin is present in advance when to. In addition, as a method for supplying olefin, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure, or a method of supplying all the predetermined amount of olefin first is used. good. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the resulting polymer.

  In the present invention, the prepolymerized product is used as a catalyst component or a catalyst. The prepolymerized catalyst component according to the present invention is obtained by prepolymerizing an olefin in the presence of a primary catalyst obtained by contacting the modified particles (A) and the transition metal compound (B). In the presence of a primary catalyst obtained by contacting the prepolymerized addition polymerization catalyst component or the modified particles (A), the transition metal compound (B), and the organoaluminum compound (C). It is a prepolymerized addition polymerization catalyst component obtained by prepolymerizing olefin. The prepolymerized catalyst according to the present invention is obtained by prepolymerizing an olefin in the presence of a primary catalyst obtained by contacting the modified particles (A) and the transition metal compound (B). In the presence of a primary catalyst obtained by contacting the above-mentioned modified particles (A), transition metal compound (B), and organoaluminum compound (C). It is a catalyst for addition polymerization obtained in this way. The catalyst using the prepolymerized addition polymerization catalyst component according to the present invention is an addition polymerization catalyst obtained by contacting the prepolymerized addition polymerization catalyst component and the organoaluminum compound (C).

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

  Specific examples thereof 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-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-endomethylenehexahydronaphthalene, , 3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene, and other diolefins; norbornene, 5-methyl-2-norbornene, 5- Ethyl-2-norbornene, 5-butyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2-norbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, penta Cyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-ethoxycarbonyl- 2-norbornene, 5-methyl-5-methyl Cyclic olefins such as xyloxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; styrene, 2 -Alkenylbenzene such as phenylpropylene, 2-phenylbutene, 3-phenylpropylene, 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-diphenylethylene, p-th Alkyls such as tertiary butyl styrene and p-secondary butyl styrene Alkenyl aromatic hydrocarbons such as bisalkenylbenzene such as len and divinylbenzene, alkenylnaphthalene such as 1-vinylnaphthalene; acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2, 2,1) α, β-unsaturated carboxylic acid such as 5-heptene-2,3-dicarboxylic acid, and metal salts thereof such as sodium, potassium, lithium, zinc, magnesium, calcium, methyl acrylate, acrylic acid Ethyl, n-propyl acrylate, isopropyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid Α, β- such as isobutyl Unsaturated carboxylic acid esters, unsaturated dicarboxylic acids such as maleic acid, itaconic acid, vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, And polar monomers such as unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate.

  The present invention is applied to homopolymerization or copolymerization of these monomers. Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, propylene and 1-butene, ethylene and propylene and butene, ethylene and propylene. And 1-hexene are exemplified, but the present invention should not be limited thereto.

  The addition polymerization catalyst of the present invention is particularly suitable as an olefin polymerization catalyst, and is preferably used in a method for producing an olefin polymer. Such an olefin polymer is particularly preferably a copolymer of ethylene and an α-olefin, and among them, a copolymer of ethylene and an α-olefin having a polyethylene crystal structure is preferable. The α-olefin herein is preferably an α-olefin having 3 to 8 carbon atoms, and specific examples include 1-butene, 1-hexene, 1-octene and the like.

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

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

(2) Melt flow rate = MFR: 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) Melt flow rate ratio = MFRR: According to the method defined in JIS K7210-1995, the melt flow rate value measured at 190 ° C. and a load of 211.82 N (21.60 kg) was calculated as a load of 21.18 N (2. It is a value divided by the melt flow rate value (MFR) measured at 16 kg).
For all the melt flow rate measurements, a polymer containing 1000 ppm of an antioxidant in advance was used.

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

(6) Intrinsic viscosity = [η]: Measured in a tetralin solution at 135 ° C. using an Ubbelohde viscometer (unit: dl / g).

[Example 1]
(1) Treatment of Silica A 200 ml four-necked flask purged with nitrogen was heat-treated at 300 ° C. under a nitrogen stream (Sypolol 948 manufactured by Devison; average particle size = 60 μm; pore volume = 1.70 ml / g; (Specific surface area = 292 m ² / g) 10.0 g was added, and then 100 ml of toluene was added while washing out silica adhering to the flask wall. After cooling to 5 ° C., a mixed solution of 4.2 ml of 1,1,1,3,3,3-hexamethyldisilazane and 6 ml of toluene was added dropwise over 30 minutes. After completion of dropping, the inside of the dropping funnel was washed with 3.0 ml of toluene, and stirred at 5 ° C. for 1 hour and at 95 ° C. for 3 hours. Thereafter, 65 ml of the supernatant was extracted. Thereafter, 86 ml of toluene was added as a washing operation, the temperature was raised to 95 ° C., and then 86 ml of the supernatant was extracted six times. Thereafter, 55 ml of toluene and 12 ml of hexane were added and left overnight.

(2)
To the slurry obtained in Example 1 (1) above, 8.4 ml (30.0 mmol) of diethylzinc in hexane (3.57 mol / liter) was added and cooled to 5 ° C. To this, 7.5 ml (15.0 mmol) of a toluene solution of pentafluorophenol (2.0 mol / liter) was added dropwise over 60 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour. Then, it heated at 40 degreeC and stirred for 1 hour. After the 5 ° C. in an ice bath _and H 2 O 0.41 ml of (22.5 mmol) was added dropwise over 1.5 hours. After completion of dropping, the mixture was stirred at 5 ° C. for 1.5 hours and at 55 ° C. for 2 hours. Then, it was left overnight.

(3) Synthesis of Component (A) To the slurry obtained in Example 1 (2) above, 5.6 ml (20.0 mmol) of diethylzinc in hexane (3.57 mol / liter) was added and cooled to 5 ° C. . To this, 5.0 ml (10.0 mmol) of a 3,4,5-trifluorophenol toluene solution (2.0 mol / liter) was added dropwise over 60 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour. Then, it heated at 40 degreeC and stirred for 1 hour. After the 5 ° C. in an ice bath _and H 2 O 0.27 ml of (15.0 mmol) was added dropwise over 1.5 hours. After completion of dropping, the mixture was stirred at 5 ° C. for 1.5 hours and at 40 ° C. for 2 hours. Then, it was left overnight.
Furthermore, after stirring at 80 ° C. for 2 hours, 87 ml of the supernatant was extracted, 48 ml of toluene was added, and the mixture was stirred at 95 ° C. for 4 hours. Thereafter, 48 ml of the supernatant was extracted. Thereafter, as a washing operation with toluene, 86 ml of toluene was added, the temperature was raised to 95 ° C., and 86 ml of the supernatant was extracted four times. Next, as a washing operation with hexane, 93 ml of hexane was added, stirred for several minutes at room temperature, and then 93 ml of the supernatant was extracted twice, then 93 ml of hexane was added, stirred for several minutes at room temperature, and then a filter was used. The operation of removing the supernatant was performed. Thereafter, the solid component was dried at room temperature under reduced pressure for 1 hour to obtain 17.5 g of component (1).

(4) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added so that the partial pressure was 0.048 MPa, 690 g of butane, 60 g of 1-butene The temperature was raised to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.63 mol% and 1-butene = 2.66 mol%. To this, 0.9 ml of a hexane solution of triisobutylaluminum whose concentration was adjusted to 1 mmol / ml was added. Next, 1.0 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added, and then component (1) 5 obtained in Example 1 (3) above was added. .8 mg was charged as a solid catalyst component. Polymerization was carried out at 70 ° C. for 20 minutes while feeding a mixed gas of ethylene and hydrogen containing 0.45 mol% of hydrogen so as to keep the total pressure constant. As a result, 88 g of an olefin polymer having a good particle property was obtained. The polymerization activity per zirconium atom was 2.6 × 10 ⁸ g / molZr / hour, and the polymerization activity per solid catalyst component was 45500 g / g solid catalyst component / hour. Moreover, the obtained olefin polymer was SCB = 15.8 and MFR = 5.65.

[Example 2]
(1) Treatment of silica Example 1 (1) except that the amount of silica was changed to 10.14 g and that the last added “55 ml of toluene and 12 ml of hexane” was added instead of 55 ml of toluene. The silica was treated in the same manner.

(2)
Using the slurry obtained in (1) above, the amount of hexane solution of diethyl zinc (2.00 mol / liter) was changed to 20.0 ml (40.0 mmol), and a toluene solution of pentafluorophenol (2. The treatment was performed in the same manner as in Example 1 (2) except that the amount of (0 mol / liter) was changed to 10.0 ml (20.0 mmol).

(3)
Using the slurry obtained in (2) above, the amount of diethylzinc in hexane (2.00 mol / liter) was changed to 5.0 ml (10.0 mmol), and 3,4,5-trifluorophenol The treatment was performed in the same manner as in Example 1 (3) except that the amount of the toluene solution (2.0 mol / liter) was changed to 2.5 ml (5.0 mmol). As a result, 17.63 g of component (2) was obtained.

(4) Polymerization The solid catalyst component was changed to 6.0 mg of the component (2) obtained in Example 2 (3) above, and the gas composition in the system by gas chromatography analysis was hydrogen = 1.79 mol. %, 1-butene = 2.70 mol%, and the polymerization was carried out in the same manner as in Example 1 (4) except that the polymerization time was 60 minutes.
As a result, 93 g of an olefin polymer having a good particle property was obtained. The polymerization activity per zirconium atom was 9.3 × 10 ⁷ g / molZr / hour, and the polymerization activity per solid catalyst component was 15500 g / g solid catalyst component / hour. The obtained olefin polymer had SCB = 17.5, MFR = 1.78, MFRR = 63, SR = 1.34, and [η] = 1.14.

[Example 3]
(1) Treatment of silica Silica was treated in the same manner as in Example 2 (1) except that the amount of silica was changed to 10.37 g.

(2) Synthesis of component (A) The slurry obtained in (1) above was used, and the treatment was performed in the same manner as in Example 2 (2).

(3) Synthesis of Component (A) Using the slurry obtained in (2) above, except that the same amount of 3,5-difluorophenol was used instead of 3,4,5-trifluorophenol, The treatment was carried out in the same manner as in Example 2 (3). As a result, 17.33 g of component (3) was obtained.

(4) Polymerization The solid catalyst component was changed to 6.5 mg of the component (3) obtained in Example 3 (3) above, and the gas composition in the system by gas chromatography analysis was hydrogen = 1.67 mol. %, 1-butene = 2.49 mol%, and the polymerization was carried out in the same manner as in Example 1 (4) except that the polymerization time was 60 minutes.
As a result, 65 g of an olefin polymer having a good particle property was obtained. The polymerization activity per zirconium atom was 6.5 × 10 ⁷ g / mol Zr / hour, and the polymerization activity per solid catalyst component was 10,000 g / g solid catalyst component / hour. The obtained olefin polymer had SCB = 16.8, MFR = 0.94, MFRR = 70, SR = 1.28.

[Comparative Example 1]
(1) Silica treatment Silica heated at 300 ° C. under nitrogen flow in a nitrogen-substituted 3 liter four-necked flask (Sypolol 948 manufactured by Devison; average particle size = 61 μm; pore volume = 1.70 ml / g) Specific surface area = 291 m ² / g) was added 203 g, and then 1.2 liters of toluene was added while washing off the silica adhering to the wall of the flask. After cooling to 5 ° C., a mixed solution of 84.4 ml of 1,1,1,3,3,3-hexamethyldisilazane and 115 ml of toluene was added dropwise over 25 minutes. After completion of the dropping, the mixture was stirred at 5 ° C. for 1 hour and then at 95 ° C. for 3 hours and filtered. Thereafter, the filter was washed four times with 1.2 liters of toluene at 95 ° C. Then, after adding 1.2 liters of toluene, it was left still overnight.

(2) Synthesis of Component (A) 0.550 liter (1.10 mol) of diethylzinc in hexane (2.00 mol / liter) was added to the slurry obtained in Comparative Example 1 (1) and cooled to 5 ° C. did. A solution prepared by dissolving 105 g (0.570 mol) of pentafluorophenol in 173 ml of toluene was added dropwise thereto over 65 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour. Then, it heated at 40 degreeC and stirred for 1 hour. After the 5 ° C. in an ice bath _and H 2 O 14.9 g of (0.828mol) was added dropwise for 90 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1.5 hours and at 40 ° C. for 2 hours. Then, it left still overnight at room temperature. Then, after stirring at 80 ° C. for 2 hours, the mixture is allowed to stand to settle the solid component, and when the interface between the precipitated solid component layer and the upper slurry portion is seen, the upper slurry portion is removed, and then the remaining liquid After filtering the components with a filter, 1.7 liters of toluene was added and stirred at 95 ° C. for 2 hours. Thereafter, the mixture was stirred four times with 1.7 liters of toluene at 95 ° C. and twice with 1.7 liters of hexane at room temperature, and then allowed to stand to precipitate the solid component. When the interface with the slurry portion was seen, the upper slurry portion was removed, and the remaining liquid component was then filtered through a filter. Thereafter, the solid component was dried at room temperature under reduced pressure for 3 hours to obtain 386 g of a component (4). As a result of elemental analysis, they were Zn = 2.4 mmol / g and F = 6.8 mmol / g.

(3) Polymerization The solid catalyst component was changed to 11.2 mg of component (4) obtained in Comparative Example 1 (2) above, and the gas composition in the system by gas chromatography analysis was hydrogen = 2.11 mol. %, 1-butene = 2.73 mol%, the hydrogen content in the fed ethylene and hydrogen mixed gas was 0.37 mol%, and the polymerization time was 60 minutes. Was polymerized in the same manner as in Example 1 (4).
As a result, 47 g of an olefin polymer having a good particle property was obtained. The polymerization activity per zirconium atom was 4.7 × 10 ⁷ g / molZr / hour, and the polymerization activity per solid catalyst component was 4200 g / g solid catalyst component / hour. Moreover, the obtained olefin polymer was SCB = 16.8, MFR = 1.06, MFRR = 74, SR = 1.30.

Claims (7)

A solid component obtained by bringing the following (a1), the following (b1), H ₂ O (c1), and silica (d) into contact with each other in the contact order of any of the following {1} to {4}: The catalyst component for olefin polymerization obtained by contacting the solid component with the following (a2), the following (b2), and H ₂ O (c2) in the following order of contact {5} or {6}. When the molar ratio of the amounts used of the following (a1), the following (b1), and the above (c1) is (a1) :( b1) :( c1) = 1: y ¹ : z ¹ , y ¹ And z ¹ satisfies the following formula (1) and the following formula (2), and the molar ratio of the usage amounts of the following (a2), the following (b2), and the above (c2) is (a1) : (B1) :( c1) = 1: y ² : When z ² , contact is performed at a use ratio in which y ² and z ² satisfy the following formula (3) and the following formula (4). Olefin polymerization catalyst component (A) obtained by
Transition metal compound (B),
And
Organoaluminum compound (C),
A catalyst for olefin polymerization obtained by contacting the catalyst.

(A1): Compound represented by the following general formula [1] ZnL ¹ ₂ [1]
(B1): Compound represented by the following general formula [2] R ¹ OH [2]
(A2): Compound represented by the following general formula [4] ZnL ² ₂ [4]
(B2): Compound represented by the following general formula [5] R ³ OH [5]
(In the above general formula [1], L ¹ represents a hydrocarbon group, and the two L ^{1 s} may be the same or different.
In the general formula [4], L ² represents a hydrocarbon group, and two L ^{2 s} may be the same or different.
In addition, the compounds (a1) and (a2) may be the same or different.
In the above general formulas [2] and [5], R ¹ and R ³ each represent a halogenated hydrocarbon group. However, R ¹ and R ³ each represent a different halogenated hydrocarbon group. )

{1}: The first contact object between the above (a1) and the above (b1) and the second contact object obtained by bringing the above (c1) into contact with the above (d).
{2}: The first contact object between the above (a1) and the above (b1) and the second contact object obtained by bringing the above (d) into contact with the above (c1).
{3}: The first contact object between the above (a1) and the above (d) and the second contact object obtained by bringing the above (b1) into contact with the above (c1).
{4}: The first contact object between (b1) and (d) above, the second contact object obtained by contacting (a1) above, and the above (c1) are brought into contact with each other.
{5}: The fourth contact product obtained by bringing the solid component into contact with the third contact product with the above (a2) and the above (b2) is brought into contact with the above (c2).
{6}: The solid contact, the third contact with (b2) above, the fourth contact obtained by contacting (a2) above, and (c2) above are brought into contact.

| 2-y ¹ -2z ¹ | ≦ 1 (1)
0.01 ≦ y ¹ ≦ 1.99 (2)
| 2-y ² −2z ² | ≦ 1 (3)
0.01 ≦ y ² ≦ 1.99 (4)   The contact order of (a1), (b1), (c1), and (d) is {3}, and the contact order of the solid component, (a2), and (b2) is {5} The olefin polymerization catalyst according to claim 1.   The olefin polymerization catalyst according to claim 1 or 2, wherein the transition metal compound (B) is a transition metal compound having at least one group having a cyclopentadiene-type anion skeleton.   The manufacturing method of the olefin polymer using the catalyst for olefin polymerization in any one of Claims 1-3.   The method for producing an olefin polymer according to claim 4, wherein the olefin polymer is a copolymer of ethylene and α-olefin. A solid component obtained by bringing the following (a1), the following (b1), H ₂ O (c1), and silica (d) into contact with each other in the following order of contact {1} to {4}: And a step of bringing the solid component into contact with the following (a2), the following (b2), and H ₂ O (c2) in the following order of {5} or {6}. When the molar ratio of the amount used of (a1), the following (b1), and the above (c1) is (a1) :( b1) :( c1) = 1: y ¹ : z ¹ , y ¹ and z ¹ Satisfies the following formula (1) and the following formula (2), and the molar ratio of the amount used of the following (a2), the following (b2), and the above (c2) is (a1) :( b1 ): (C1) = 1: y ² : When z ² , y ² and z ² are in contact with each other at a use ratio satisfying the following formula (3) and the following formula (4). A method for producing a catalyst component for olefin polymerization.

(A1): Compound represented by the following general formula [1] ZnL ¹ ₂ [1]
(B1): Compound represented by the following general formula [2] R ¹ OH [2]
(A2): Compound represented by the following general formula [4] ZnL ² ₂ [4]
(B2): Compound represented by the following general formula [5] R ³ OH [5]
(In the above general formula [1], L ¹ represents a hydrocarbon group, and the two L ^{1 s} may be the same or different.
In the general formula [4], L ² represents a hydrocarbon group, and two L ^{2 s} may be the same or different.
In addition, the compounds (a1) and (a2) may be the same or different.
In the above general formulas [2] and [5], R ¹ and R ³ each represent a halogenated hydrocarbon group. However, R ¹ and R ³ each represent a different halogenated hydrocarbon group. )

{1}: The first contact object between the above (a1) and the above (b1) and the second contact object obtained by bringing the above (c1) into contact with the above (d).
{2}: The first contact object between the above (a1) and the above (b1) and the second contact object obtained by bringing the above (d) into contact with the above (c1).
{3}: The first contact object between the above (a1) and the above (d) and the second contact object obtained by bringing the above (b1) into contact with the above (c1).
{4}: The first contact object between (b1) and (d) above, the second contact object obtained by contacting (a1) above, and the above (c1) are brought into contact with each other.
{5}: The fourth contact product obtained by bringing the solid component into contact with the third contact product with the above (a2) and the above (b2) is brought into contact with the above (c2).
{6}: The solid contact, the third contact with (b2) above, the fourth contact obtained by contacting (a2) above, and (c2) above are brought into contact.

| 2-y ¹ -2z ¹ | ≦ 1 (1)
0.01 ≦ y ¹ ≦ 1.99 (2)
| 2-y ² −2z ² | ≦ 1 (3)
0.01 ≦ y ² ≦ 1.99 (4)   The contact order of (a1), (b1), (c1), and (d) is {3}, and the contact order of the solid component, (a2), and (b2) is {5} The manufacturing method according to claim 6.