JP5147493B2 - Catalyst for addition polymerization, method for producing addition polymer using the same, modified particles, method for producing the same, and catalyst component for addition polymerization - Google Patents

Description

  The present invention relates to an addition polymerization catalyst obtained by bringing a transition metal compound (A) of Group 3 to Group 11 of the periodic table of elements or a lanthanoid series transition metal (A) and modified particles (B ′) into contact with each other. The present invention relates to a method for producing an addition polymer to be used. Furthermore, the present invention relates to a catalyst component for addition polymerization comprising the modified particles (B ′), a production method thereof, and the modified particles (B ′).

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

  In recent years, these addition polymers are obtained by polymerizing olefins or the like by using a catalyst in which a transition metal component composed of a transition metal compound (for example, a metallocene complex or a nonmetallocene compound) and an organometallic component composed of an aluminoxane are combined. It is manufactured.

  In addition, when applied to polymerization accompanied by formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.), generation of coarse particles, lumps, fine powder, etc., and reduction of bulk density of the addition polymer In addition, in order to suppress the adhesion of the addition polymer to the polymerization reactor wall, to enable stable operation, and to improve the productivity, a specific particle is used as one of the catalyst components, It is known that the shape is fixed (for example, Patent Document 1).

Patent Document 2 describes a modified particle used as a support and 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. As a modified particle, a compound (a) such as diethyl zinc, a compound (b) such as pentafluorophenol, a compound (c) such as H ₂ O, and a particle (d) such as silica are contacted. The particles obtained are described.

International Patent Application Publication No. 02/051878 Japanese Patent Laid-Open No. 2003-171212

  When an addition polymerization catalyst is applied to polymerization such as slurry polymerization, gas phase polymerization, bulk polymerization, etc., accompanied by the formation of addition polymer particles described in the above-mentioned patent publications, the polymerization reaction or polymerization reaction apparatus In order to stabilize the operation, it is required to stably maintain the dispersed state of the catalyst and the polymer particles to be generated in the polymerization reaction tank, and to suppress the generation of fouling and agglomerates.

  Under such circumstances, the present inventors stably maintain the dispersed state of the catalyst and the generated polymer particles in the polymerization reaction tank by increasing the bulk density of the resulting addition polymer, thereby fouling and lump. It has been found that the formation of chemical compounds can be suppressed and the polymerization reaction or the operation of the polymerization reactor can be stabilized.

  Therefore, an object of the present invention is to provide modified particles used in an addition polymerization catalyst capable of producing an addition polymer having a higher bulk density, a method for producing such modified particles, and such modified particles. An object of the present invention is to provide an addition polymerization catalyst component comprising particles, an addition polymerization catalyst capable of producing an addition polymer having a higher bulk density, and a method for producing an addition polymer having a higher bulk density.

The first aspect of the present invention is for addition polymerization obtained by bringing a transition metal compound (A) of Group 3 to Group 11 or a lanthanoid series of an element into contact with modified particles (B ′). A catalyst, wherein the modified particles (B ′) are
Compound (a) represented by the following formula [1],
M ¹ L ¹ _m [1]
(In the formula, M ¹ represents a typical metal atom of Group ¹ , 2, 12, 14 or 15 of the periodic table of elements, and m represents a number corresponding to the valence of M ^1. L ¹ represents a hydrogen atom, a halogen atom. It represents an atom or a hydrocarbon group, if L ¹ there are a plurality, a plurality of L ¹ may be different be the same as each other.)
Compound (b) represented by the following formula [2], and R ¹ _t-1 TH [2]
Compound (c) represented by the following formula [3],
R ² _t-2 TH ₂ [3]
(The above formula [2], in [3], R ¹ represents a group containing an electron withdrawing group or an electron withdrawing group, R ² is .R ¹ representing a hydrocarbon group or a halogenated hydrocarbon group is more than When present, a plurality of R ¹ may be the same or different from each other, T independently represents an atom of Group 15 or Group 16 of the periodic table of elements, and t represents a valence of T. (Represents the corresponding number.)
In addition, the modified particles (B) obtained by contacting the particles (d) made of a substance different from any of the compound (a), the compound (b) or the compound (c) are further represented by the following formula [4]. Compound (f) represented
M ² L ² _n [4]
(In the formula, M ² represents a typical metal atom of Groups 12 to 15 of the periodic table of elements, and n represents a number corresponding to the valence of M ^2. L ² represents a hydrogen atom, a halogen atom or a hydrocarbon group. It represents, when L ² there are a plurality, a plurality of L ² may be different be the same as each other.)
It is an object of the present invention to provide a catalyst for addition polymerization, which is a modified particle obtained by contacting the catalyst. A transition metal compound (A) other than Group 4 of the periodic table of elements, a compound not containing the organoaluminum compound (C), a typical metal atom of Group 12 of the compound (a) and M ¹ of the periodic table of the elements Other than the above, the compound (b) is other than R ¹ OH (where R ¹ represents a halogenated hydrocarbon group), the compound (c) is other than H ₂ O, the compound (f) and M ² is an element Those other than the typical metal atoms of Group 13 of the periodic table and those in which the addition polymerization catalyst is other than the olefin polymerization catalyst are reference examples.

  The second aspect of the present invention is the same modification as the first aspect described above, the transition metal compounds (A) and organoaluminum compounds (C) of Group 3 to Group 11 of the periodic table of elements or lanthanoid series Another object of the present invention is to provide an addition polymerization catalyst obtained by bringing the particles (B ′) into contact with each other.

The third aspect of the present invention is for addition polymerization obtained by bringing a transition metal compound (A) of Group 3 to Group 11 of a periodic table of elements or a lanthanoid series transition metal into contact with modified particles (B ′). A method for producing an addition polymer using a catalyst, comprising:
Compound (a) represented by the following formula [1],
M ¹ L ¹ _m [1]
(In the formula, M ¹ represents a typical metal atom of Group ¹ , 2, 12, 14 or 15 of the periodic table of elements, and m represents a number corresponding to the valence of M ^1. L ¹ represents a hydrogen atom, a halogen atom. It represents an atom or a hydrocarbon group, if L ¹ there are a plurality, a plurality of L ¹ may be different be the same as each other.)
Compound (b) represented by the following formula [2], and R ¹ _t-1 TH [2]
Compound (c) represented by the following formula [3],
R ² _t-2 TH ₂ [3]
(The above formula [2], in [3], R ¹ represents a group containing an electron withdrawing group or an electron withdrawing group, R ² is .R ¹ representing a hydrocarbon group or a halogenated hydrocarbon group is more than When present, a plurality of R ¹ may be the same or different from each other, T independently represents an atom of Group 15 or Group 16 of the periodic table of elements, and t represents a valence of T. (Represents the corresponding number.)
In addition, the modified particles (B) obtained by contacting the particles (d) made of a substance different from any of the compound (a), the compound (b) or the compound (c) are further represented by the following formula [4]. Compound (f) represented
M ² L ² _n [4]
(In the formula, M ² represents a typical metal atom of Groups 12 to 15 of the periodic table of elements, and n represents a number corresponding to the valence of M ^2. L ² represents a hydrogen atom, a halogen atom or a hydrocarbon group. It represents, when L ² there are a plurality, a plurality of L ² may be different be the same as each other.)
A method for producing an addition polymer, characterized by using a catalyst for addition polymerization obtained by bringing modified particles (B ′) obtained by contacting with a transition metal compound (A) into contact with each other Is to provide. A transition metal compound (A) other than Group 4 of the periodic table of elements, a compound not containing the organoaluminum compound (C), a typical metal atom of Group 12 of the compound (a) and M ¹ of the periodic table of the elements Other than the above, the compound (b) is other than R ¹ OH (where R ¹ represents a halogenated hydrocarbon group), the compound (c) is other than H ₂ O, the compound (f) and M ² is an element Other than the typical metal atom of Group 13 of the periodic table, the catalyst for addition polymerization other than the catalyst for olefin polymerization, and the addition polymer other than the olefin polymer are reference examples.

  According to a fourth aspect of the present invention, there is provided a transition metal compound (A) and an organoaluminum compound (C) of the Group 3 to Group 11 or lanthanoid series of the periodic table of elements, and the same modification as the third aspect described above. Another object of the present invention is to provide a method for producing an addition polymer using an addition polymerization catalyst obtained by bringing the particles (B ′) into contact with each other.

The fifth aspect of the present invention is the compound (a) represented by the following formula [1],
M ¹ L ¹ _m [1]
(In the formula, M ¹ represents a typical metal atom of Group ¹ , 2, 12, 14 or 15 of the periodic table of elements, and m represents a number corresponding to the valence of M ^1. L ¹ represents a hydrogen atom, a halogen atom. It represents an atom or a hydrocarbon group, if L ¹ there are a plurality, a plurality of L ¹ may be different be the same as each other.)
Compound (b) represented by the following formula [2], and R ¹ _t-1 TH [2]
Compound (c) represented by the following formula [3],
R ² _t-2 TH ₂ [3]
(The above formula [2], in [3], R ¹ represents a group containing an electron withdrawing group or an electron withdrawing group, R ² is .R ¹ representing a hydrocarbon group or a halogenated hydrocarbon group is more than When present, a plurality of R ¹ may be the same or different from each other, T independently represents an atom of Group 15 or Group 16 of the periodic table of elements, and t represents a valence of T. (Represents the corresponding number.)
In addition, the modified particles (B) obtained by contacting the particles (d) made of a substance different from any of the compound (a), the compound (b) or the compound (c) are further represented by the following formula [4]. Compound (f) represented
M ² L ² _n [4]
(In the formula, M ² represents a typical metal atom of Groups 12 to 15 of the periodic table of elements, and n represents a number corresponding to the valence of M ^2. L ² represents a hydrogen atom, a halogen atom or a hydrocarbon group. It represents, when L ² there are a plurality, a plurality of L ² may be different be the same as each other.)
It is an object to provide modified particles obtained by contacting the particles. In the compound (a), M ¹ is other than the typical metal atom of Group 12 of the periodic table of the element, and the compound (b) is other than R ¹ OH (where R ¹ represents a halogenated hydrocarbon group), A compound (c) other than H ₂ O and a compound (f) other than a typical metal atom of Group 13 of the periodic table in which M ² is an element are reference examples.

The sixth aspect of the present invention is the compound (a) represented by the following formula [1],
M ¹ L ¹ _m [1]
(In the formula, M ¹ represents a typical metal atom of Group ¹ , 2, 12, 14 or 15 of the periodic table of elements, and m represents a number corresponding to the valence of M ^1. L ¹ represents a hydrogen atom, a halogen atom. It represents an atom or a hydrocarbon group, if L ¹ there are a plurality, a plurality of L ¹ may be different be the same as each other.)
Compound (b) represented by the following formula [2], and R ¹ _t-1 TH [2]
Compound (c) represented by the following formula [3],
R ² _t-2 TH ₂ [3]
(The above formula [2], in [3], R ¹ represents a group containing an electron withdrawing group or an electron withdrawing group, R ² is .R ¹ representing a hydrocarbon group or a halogenated hydrocarbon group is more than When present, a plurality of R ¹ may be the same or different from each other, T independently represents an atom of Group 15 or Group 16 of the periodic table of elements, and t represents a valence of T. (Represents the corresponding number.)
And a step of contacting particles (d) comprising a substance different from any of compound (a), compound (b) or compound (c) to obtain modified particles (B), and the following formula [4] Compound (f) represented by
M ² L ² _n [4]
(In the formula, M ² represents a typical metal atom of Groups 12 to 15 of the periodic table of elements, and n represents a number corresponding to the valence of M ^2. L ² represents a hydrogen atom, a halogen atom or a hydrocarbon group. It represents, when L ² there are a plurality, a plurality of L ² may be different be the same as each other.)
It is an object of the present invention to provide a method for producing modified particles, which comprises a step of bringing the modified particles into contact with the obtained modified particles (B). In the compound (a), M ¹ is other than the typical metal atom of Group 12 of the periodic table of the element, and the compound (b) is other than R ¹ OH (where R ¹ represents a halogenated hydrocarbon group), A compound (c) other than H ₂ O and a compound (f) other than a typical metal atom of Group 13 of the periodic table in which M ² is an element are reference examples.

The seventh aspect of the present invention is a compound (a) represented by the following formula [1],
M ¹ L ¹ _m [1]
(In the formula, M ¹ represents a typical metal atom of Group ¹ , 2, 12, 14 or 15 of the periodic table of elements, and m represents a number corresponding to the valence of M ^1. L ¹ represents a hydrogen atom, a halogen atom. It represents an atom or a hydrocarbon group, if L ¹ there are a plurality, a plurality of L ¹ may be different be the same as each other.)
Compound (b) represented by the following formula [2], and R ¹ _t-1 TH [2]
Compound (c) represented by the following formula [3],
R ² _t-2 TH ₂ [3]
(The above formula [2], in [3], R ¹ represents a group containing an electron withdrawing group or an electron withdrawing group, R ² is .R ¹ representing a hydrocarbon group or a halogenated hydrocarbon group is more than When present, a plurality of R ¹ may be the same or different from each other, T independently represents an atom of Group 15 or Group 16 of the periodic table of elements, and t represents a valence of T. (Represents the corresponding number.)
In addition, the modified particles (B) obtained by contacting the particles (d) made of a substance different from any of the compound (a), the compound (b) or the compound (c) are further represented by the following formula [4]. Compound (f) represented
M ² L ² _n [4]
(In the formula, M ² represents a typical metal atom of Groups 12 to 15 of the periodic table of elements, and n represents a number corresponding to the valence of M ^2. L ² represents a hydrogen atom, a halogen atom or a hydrocarbon group. It represents, when L ² there are a plurality, a plurality of L ² may be different be the same as each other.)
It is an object of the present invention to provide a catalyst component for addition polymerization comprising modified particles (B ′) obtained by bringing them into contact with each other. In the compound (a), M ¹ is other than the typical metal atom of Group 12 of the periodic table of the element, and the compound (b) is other than R ¹ OH (where R ¹ represents a halogenated hydrocarbon group), Compound (c) other than H ₂ O, Compound (f) where M ² is an element other than a typical metal atom of Group 13 of the periodic table, and addition polymerization catalyst component other than olefin polymerization catalyst component Is a reference example.

  According to the present invention, the addition polymerization catalyst component used for the production of a higher bulk density addition polymer, the addition polymerization catalyst for producing a higher bulk density addition polymer, and the higher bulk density addition polymer A manufacturing method is provided. In the present invention, as described in the various aspects of the present invention described above, particularly the sixth aspect, by employing a two-step particle modification process, the particles thus modified are used. It becomes possible to produce an addition polymer having a higher bulk density by using the produced catalyst for addition polymerization.

Hereinafter, the present invention will be described in detail.
One preferred embodiment of the first and second aspects of the present invention is an addition polymerization catalyst in which the compound (f) is an organoaluminum compound or an organozinc compound. Thus, the catalyst for addition polymerization which can manufacture an addition polymer with a high bulk density is obtained by using an organoaluminum compound or an organozinc compound as a compound (f).

  Another preferred embodiment of the first and second aspects of the present invention includes an addition polymerization catalyst in which the transition metal compound (A) is a transition metal compound having at least one cyclopentadiene-type anion skeleton. Thus, by using a transition metal compound having at least one cyclopentadiene-type anion skeleton as the transition metal compound (A), a catalyst for addition polymerization capable of producing an addition polymer having a higher bulk density is obtained. It is done.

  In addition, as a preferred embodiment of the third and fourth aspects of the present invention described above, a method for producing an olefin polymer can be mentioned. In such an embodiment, a method for producing an olefin polymer having a higher bulk density can be provided by using the excellent catalyst for addition polymerization in the third and fourth aspects.

  Another preferred embodiment of the third and fourth aspects of the present invention includes a method for producing an addition polymer, wherein the addition polymer is a copolymer of ethylene and an α-olefin. Thus, by using an excellent catalyst for addition polymerization, a method for producing a copolymer of ethylene and α-olefin having a higher bulk density can be provided.

  In the preferred embodiments of the third and fourth aspects of the present invention, an addition polymer production method using the above-described addition polymerization catalyst as the preferred embodiments of the first and second aspects may be included. In addition, the above-described preferred aspects of the first and second aspects can also be included in the fifth to seventh aspects of the present invention.

Transition metal compound (A)
As the transition metal compound (A) used in the addition polymerization catalyst of the present invention, modified particles (B ′) obtained by bringing the compound (f) into contact with the modified particles (B) described below and Although it will not specifically limit if it is a transition metal compound which shows addition polymerization activity by using together (or further together with organoaluminum compound (C)), Usually, for example, transition metal compounds such as metallocene complexes and nonmetallocene compounds are used. Is done. The addition polymerization catalyst of the present invention is a catalyst that is distinguished from the conventional solid catalyst using titanium trichloride or titanium tetrachloride (usually a catalyst called Ziegler-Natta catalyst), which is a metallocene complex or a nonmetallocene compound. It means a catalyst using a transition metal compound such as

As the transition metal compound (A), a transition metal compound of Group 3 to Group 11 of the periodic table of elements or a lanthanoid series is usually used, and a transition metal compound represented by the following formula [5] or a μ-oxo thereof Dimers of type transition metal compounds are preferred.
L ² _a M ² X ¹ _b [5]
(In the formula, M ² represents a transition metal atom of Group 3 to Group 11 of the periodic table of elements or a lanthanoid series. L ² represents a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, L ^{2 in the above} 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, and X ¹ is a halogen atom. Represents a hydrocarbon group (excluding a group having a cyclopentadiene type anion skeleton) or a hydrocarbon oxy group, a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8. Represents.)

As M ^{2 in the} formula [5], for example, scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom Nickel atom, palladium atom, samarium atom, ytterbium atom and the like. Among them, preferred is a titanium atom, zirconium atom, hafnium atom, vanadium atom, chromium atom, iron atom, cobalt atom or nickel atom, more preferred is a titanium atom, zirconium atom or hafnium atom, and particularly preferred is a zirconium atom. It is.

Examples of the group having a cyclopentadiene-type anion skeleton of L ^{2 in} the formula [5] include (substituted) cyclopentadienyl group, (substituted) indenyl group, and (substituted) fluorenyl group. Specifically, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, tert-butylcyclopentadienyl group, 1,2-dimethylcyclopenta Dienyl group, 1,3-dimethylcyclopentadienyl group, 1-methyl-2-ethylcyclopentadienyl group, 1-methyl-3-ethylcyclopentadienyl group, 1-tert-butyl-2-methyl Cyclopentadienyl group, 1-tert-butyl-3-methylcyclopentadienyl group, 1-methyl-2-isopropylcyclopentadienyl group, 1-methyl-3-isopropylcyclopentadienyl group, 1-methyl 2-n-butylcyclopentadienyl group, 1-methyl-3-n-butylcyclopentadienyl group, η5-1, , 3-trimethylcyclopentadienyl group, η5-1,2,4-trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group, 4, 5, 6, 7-tetrahydroindenyl group, 2-methylindenyl group, 3-methylindenyl group, 4-methylindenyl group, 5-methylindenyl group, 6-methylindenyl group, 7-methylindenyl group, 2 -Tert-butyl indenyl group, 3-tert-butyl indenyl group, 4-tert-butyl indenyl group, 5-tert-butyl indenyl group, 6-tert-butyl indenyl group, 7-tert-butyl indenyl group Nyl group, 2,3-dimethylindenyl group, 4,7-dimethylindenyl group, 2,4,7-trimethylindenyl group, 2 Methyl-4-isopropylindenyl group, 4,5-benzindenyl group, 2-methyl-4,5-benzindenyl group, 4-phenylindenyl group, 2-methyl-5-phenylindenyl group, 2-methyl-4 -Phenylindenyl group, 2-methyl-4-naphthylindenyl group, fluorenyl group, 2,7-dimethylfluorenyl group and 2,7-di-tert-butylfluorenyl group can be exemplified.

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

Examples of the hetero atom in the group containing the hetero atom of L ² in the formula [5] include an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom. Examples of such a group include an alkoxy group and an aryloxy group. , A thioalkoxy group, a thioaryloxy group, an alkylamino group, an arylamino group, an alkylphosphino group, an arylphosphino group, a chelating ligand, or a ring of oxygen, sulfur, nitrogen and / or phosphorus atoms An aromatic heterocyclic group or an aliphatic heterocyclic group is preferable.

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

Moreover, as group containing the said hetero atom, group represented by following formula [6] can also be mentioned, for example.
R ³ ₃ P = N- [6]
(In the formula, each R ³ independently represents a hydrogen atom, a halogen atom or a hydrocarbon group, and the plurality of R ³ may be the same or different from each other, and any two of the plurality of R ³ may be selected. The above may be bonded to each other and may form a ring structure.)

Specific examples of R ³ in the formula [6] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert- Examples thereof include a butyl group, a cyclopropyl group, a cyclobutyl group, a cycloheptyl group, a cyclohexyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a benzyl group.

（式中、Ｒ^４はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン化炭化水素基、炭化水素オキシ基、シリル基またはアミノ基を表し、複数のＲ^４は互いに同じであっても異なっていてもよく、複数のＲ^４のうち、任意の２つ以上が互いに結合していてもよく、環構造を形成していてもよい。） Further, examples of the group containing a hetero atom include a group represented by the following formula [7].

(In the formula, each R ⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon oxy group, a silyl group or an amino group, and the plurality of R ⁴ are the same as each other. And any two or more of R ⁴ may be bonded to each other and may form a ring structure.)

Specific examples of R ⁴ in the above formula [7] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, phenyl group, 1-naphthyl group, 2-naphthyl group, tert-butyl group, 2,6- Dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl group, methyl group, triethyl Examples include a silyl group, a diphenylmethylsilyl group, a 1-methyl-1-phenylethyl group, a 1,1-dimethylpropyl group, a 2-chlorophenyl group, and a pentafluorophenyl group.

The chelating ligand of L ² in the formula [5] refers to a ligand having a plurality of coordination sites. Examples of the ligand include acetylacetonate, diimine, oxazoline, bisoxazoline, Mention may be made of terpyridine, acyl hydrazones, diethylenetriamine, triethylenetetramine, porphyrin, crown ether, and cryptate.

Examples of the heterocyclic group of L ² in the formula [5] include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, and among them, a pyridyl group is preferable.

In the formula [5], when a plurality of L ² are linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom (that is, a cyclopentadiene anion When a group having a skeleton is linked via its residue, a group containing a hetero atom is linked via its residue, or a group having a cyclopentadiene-type anion skeleton and a hetero atom If the group containing is connected via its residues), preferably as a residue, the two L ² and the atoms connecting the carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or It is a phosphorus atom and is a divalent residue having a minimum number of atoms of 3 or less for bonding two L ² . As the residue, alkylene groups such as methylene group, ethylene group and propylene group; substituted alkylene groups such as dimethylmethylene group (isopropylidene group) and diphenylmethylene group; silylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group And substituted silylene groups such as tetramethyldisilene group and dimethoxysilylene group; and heteroatoms such as nitrogen atom, oxygen atom, sulfur atom and phosphorus atom. Among these, a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), a diphenylmethylene group, a dimethylsilylene group, a diethylsilylene group, a diphenylsilylene group, or a dimethoxysilylene group is particularly preferable.

Examples of the halogen atom for X ¹ in the formula [5] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group for X ¹ include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Among them, an alkyl group having 1 to 20 carbon atoms, preferably 7 to 7 carbon atoms is preferable. A aralkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkenyl group having 3 to 20 carbon atoms.

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

  Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (2,3-dimethyl). (Phenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, 3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, 3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3, , 6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group , (N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, naphthylmethyl group, and anthracenylmethyl group More preferably, it is a benzyl group. These aralkyl groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or aralkyloxy groups such as benzyloxy group, etc. May be substituted.

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

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

Examples of the hydrocarbon oxy group represented by X ¹ in the general formula [5] include an alkoxy group, an aralkyloxy group, and an aryloxy group. Among them, an alkoxy group having 1 to 20 carbon atoms is preferable, An aralkyloxy group having 7 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms.

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

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

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

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

A number that satisfies a is 0 <a ≦ 8 in the formula [5], b is 0 <a number satisfying b ≦ 8, are selected appropriately depending on the valence of M ^2. When M ² is a titanium atom, a zirconium atom or a hafnium atom, a is preferably 2, and b is also preferably 2.

  Examples of the compound represented by the formula [5] in which the transition metal atom is a titanium atom, a zirconium atom or a hafnium atom include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, Bis (ethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, bis (1,2-dimethylcyclopentadienyl) titanium Dichloride, bis (1,3-dimethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) titanium dichloride , Screw (1 Methyl-2-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-isopropylcyclopentadienyl) titanium dichloride Bis (1-methyl-3-isopropylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-2-methylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-3-methylcyclopenta) Dienyl) titanium dichloride, bis (1,2,3-trimethylcyclopentadienyl) titanium dichloride, bis (1,2,4-trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium Dichloride, bis (pentameth Lucyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenylindenyl) titanium dichloride ,

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

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

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

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

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

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

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

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

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

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

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

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

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

(Tert-Butylamide) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl- 1,2-ethanediyltitanium dichloride, (tert-butylamide) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilane titanium dichloride, (phenylphosphide) tetramethylcyclopentadi Enyldimethylsilane titanium dichloride, (tert-butylamido) indenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) tetrahydroyl Denenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyl titanium dichloride, (tert-butylamido) indenyldimethylsilane titanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilane titanium Dichloride, (tert-butylamido) fluorenyldimethylsilane titanium dichloride,

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

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

[Bis (trimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-dimethylphenyl) -1,3 -Propanediamide] titanium dichloride, [bis (2,6-diisopropylphenyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-di-tert-butylphenyl) -1,3-propanediamide] Titanium dichloride, [bis (triisopropylsilyl) naphthalenediamide] titanium dichloride, [bis (trimethylsilyl) naphthalenediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dichloride, [hydrotris (3,5 Dimethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium trichloride, [tris (3 5-dimethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, and [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium trichloride, and these A compound in which “titanium” is replaced with “zirconium” or “hafnium”, “(2-phenoxy)” is “(3-phenyl-2-phenoxy)”, “(3-trimethylsilyl-2-phenoxy)” Or “(3-tert-butyldi Compound substituted with “methylsilyl-2-phenoxy)”, “dimethylsilylene” with “methylene”, “ethylene”, “dimethylmethylene (isopropylidene)”, “diphenylmethylene”, “diethylsilylene”, “diphenylsilylene”, or "Dimethoxysilylene" is a compound that replaces "dichloride", "difluoride", "dibromide", "diaiodide", "dimethyl," diethyl "," diisopropyl "," diphenyl "," dibenzyl "," dimethoxide "," “Diethoxide”, “di (n-propoxide)”, “di (isopropoxide)”, “diphenoxide” or “di (pentafluorophenoxide)” as well as “trichloride” as “trifluoride” ”,“ Tribromide ”,“ Tria “Iodide”, “Trimethyl”, “Triethyl”, “Triisopropyl”, “Triphenyl”, “Tribenzyl”, “Trimethoxide”, “Triethoxide”, “Tri (n-propoxide)”, “Tri (isopropoxide)” ”,“ Triphenoxide ”, or“ tri (pentafluorophenoxide) ”.

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

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

2,2′-methylenebis [(4R) -4-isopropyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di-n-propyloxazoline], 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diisopropyloxazoline ] Nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5- Diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4- Sopropyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methoxyphenyl) o Oxazoline] nickel dibromide,

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

2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-isobutyloxazoline-5,1′-cycloheptane}] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-diethyloxazo ] Nickel dibromide, 2,2'-methylenebis [(4R) -4--4-tert-butyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-diphenyloxazoline] nickel dibromide, 2, 2'-methylenebis [(4R) -4-tert-butyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- ( 2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl -5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (4-methylphenyl) oxazoline ] Nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (4 -Methoxyphenyl) oxazoline] nickel dibromide,

2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyl Oxazoline-5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2 '-Methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1'-cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-phenyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5 -Di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl -5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-fur Nyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide Ido,

2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-phenyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-benzyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5 -Di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl -5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzene Dil-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide Ido,

2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-benzyloxazoline-5,1′-cycloheptane}] nickel dibromide, and the enantiomers of the above compounds, the configuration of the asymmetric carbon of one oxazoline ring of the bisoxazoline type compound is reversed. As well as “dibromide” as “difluoride”, “dichloride”, “diaiod” Id "," dimethyl "," diethyl "," diisopropyl "," diphenyl "," dibenzyl "," dimethoxide "," diethoxide "," di-n-propoxide "," diisopropoxide "," diphenoxide " Or a compound substituted with “di (pentafluorophenoxide)”.

（式中、Ｒ^５とＲ^６はいずれも２，６−ジイソプロピルフェニル基を表し、Ｒ^７およびＲ^８はそれぞれ独立に水素原子またはメチル基あるいはＲ^７とＲ^８とが互いに結合したアセナフテン基を表し、Ｘ^２はそれぞれ独立に、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、フェニル基、ベンジル基、メトキシ基、エトキシ基、またはフェノキシ基を表す。）
また、上記のニッケル化合物において、「ニッケル」を「パラジウム」、「コバルト」、「ロジウム」、または「ルテニウム」に置き換えた化合物も同様に例示することができる。 Examples of the compound represented by the formula [5] whose transition metal atom is a nickel atom include compounds represented by the following structural formula.

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

  Examples of the compound represented by the formula [5] whose transition metal atom is iron include 2,6-bis- [1- (2,6-dimethylphenylimino) ethyl] pyridine iron dichloride, 2,6- Bis- [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron dichloride and 2,6-bis- [1- (2-tert-butyl-phenylimino) ethyl] pyridine iron dichloride, and these Examples include compounds in which “dichloride” of the compound is replaced with “difluoride”, “dibromide”, “diaiodide”, “dimethyl”, “diethyl”, “dimethoxide”, “diethoxide”, or “diphenoxide”. .

  Examples of the μ-oxo type transition metal compound of the transition metal compound represented by the formula [5] 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 [isopro Liden (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) titanium chlora And [mu] -oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], and "chloride" of these compounds as "fluoride" , “Bromide”, “iodide”, “methyl”, “ethyl”, “isopropyl”, “phenyl”, “benzyl”, “methoxide”, “ethoxide”, “n-propoxide”, “isopropoxide”, Mention may be made of compounds substituted with “phenoxide” or “pentafluorophenoxide”.

  As the transition metal compound (B) other than the compound represented by the formula [5], [hydrotris (3,5-dimethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-diethylpyrazolyl) borate] nickel chloride, and [Hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel chloride, as well as the “chloride” of these compounds can be referred to as “bromide”, “iodide”, “methyl”, “ethyl”, “allyl”, Mention may be made of compounds substituted with “methallyl”, “methoxide” or “ethoxide”. In addition, in the above nickel compound, a compound in which “nickel” is replaced with “iron” or “cobalt” can be exemplified similarly.

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

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

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

Of the transition metal compounds exemplified above, the transition metal compound (B) used in the present invention is preferably a transition metal compound represented by the above formula [5]. Among them, a transition metal compound in which M ² in the above formula [5] 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 ² in the formula [5] preferable. Among them, a zirconium compound is more preferable, and L ² in the formula [5] has two groups having a cyclopentadiene type anion skeleton, and L ² contains a carbon atom, a silicon atom, an oxygen atom, a sulfur atom or a phosphorus atom. Zirconium compounds linked via the containing residues are particularly preferred.

  The transition metal compound represented by the formula [5] can be produced by a production method described in JP-A-6-340684, JP-A-7-258321, International Patent Publication No. 95/00562, and the like. Is possible.

Particle (B)
The modified particles (B) used in the present invention are:
Compound (a) represented by the following formula [1],
M ¹ L ¹ _m [1]
(In the formula, M ¹ represents a typical metal atom of Group ¹ , 2, 12, 14 or 15 of the periodic table of elements, and m represents a number corresponding to the valence of M ^1. L ¹ represents a hydrogen atom, a halogen atom. It represents an atom or a hydrocarbon group, if L ¹ there are a plurality, a plurality of L ¹ may be different be the same as each other.)
Compound (b) represented by the following formula [2], and R ¹ _t-1 TH [2]
Compound (c) represented by the following formula [3],
R ² _t-2 TH ₂ [3]
(The above formula [2], in [3], R ¹ represents a group containing an electron withdrawing group or an electron withdrawing group, R ² is .R ¹ representing a hydrocarbon group or a halogenated hydrocarbon group is more than When present, a plurality of R ¹ may be the same or different from each other, T independently represents an atom of Group 15 or Group 16 of the periodic table of elements, and t represents a valence of T. (Represents the corresponding number.)
In addition, modified particles obtained by bringing particles (d) made of a substance different from any of compound (a), compound (b), and compound (c) into contact with each other.

The compound (a) used for such particles (B) is a compound represented by the following formula [1].
M ¹ L ¹ m [1]
In the above formula [1], M 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.

  The aryl group is preferably an aryl group having 6 to 20 carbon atoms, such as a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2, 3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-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.

  The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms. 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 (b) used for the particles (B) is a compound represented by the following general formula [2].
R ¹ _t-1 TH [2]
Moreover, the compound (c) used for particle | grains (B) is a compound represented by following General formula [3].
_{^{R 2 t-2 TH 2 [}} 3]

  T in the above general formula [2] or [3] independently represents a nonmetallic atom of Group 15 or Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). T in the general formula [2] and T in the general formula [3] may be the same or different. 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 is preferably each independently a nitrogen atom or an oxygen atom, and particularly preferably T is an oxygen atom. T in the general formula [2] or [3] represents a number corresponding to the valence of each T. When T is a Group 15 nonmetal atom, t is 3, and T is a Group 16 nonmetal. In the case of an 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, the Hammett's rule substituent constant σ and the like are known, and a functional group having a positive Hammett's rule constant σ can be cited as an electron withdrawing group.

  Specific examples of the electron withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group, and a phenyl group. Examples of the group containing an electron-withdrawing group include a halogenated alkyl group, a halogenated aryl group, a (halogenated alkyl) aryl group, a cyanated aryl group, a nitrated aryl group, an ester group (an alkoxycarbonyl group, an aralkyloxycarbonyl group, Aryloxycarbonyl group), 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 in which the fluoro of these halogenated alkyl groups is changed 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. The hydrocarbon group for R ² is preferably an alkyl group, an aryl group, or an aralkyl group, and the same hydrocarbon group as that 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.

When the compound (a) 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-hexyl zinc and the like. Dialkyl zinc; diaryl zinc such as diphenyl zinc, dinaphthyl zinc and bis (pentafluorophenyl) zinc; dialkenyl zinc such as diallyl zinc; bis (cyclopentadienyl) zinc; methyl zinc chloride, ethyl zinc chloride, propyl zinc chloride, -N-butyl zinc chloride, isobutyl zinc chloride, -n-hexyl chloride, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, n-butyl zinc bromide, isobutyl zinc bromide, bromide-n -Hexyl zinc, methyl zinc iodide, ethyl zinc iodide, propyl zinc iodide, iodide-n-butyl zinc, iodide Examples thereof include alkyl zinc halides such as isobutyl zinc and zinc n-hexyl iodide; zinc halides such as zinc fluoride, zinc chloride, zinc bromide and zinc iodide.

  The compound (a) is preferably dialkylzinc, more preferably dimethylzinc, diethylzinc, dipropylzinc, di-n-butylzinc, diisobutylzinc, or di-n-hexylzinc, particularly preferably dimethylzinc. Zinc or diethyl zinc.

  Specific examples of the compound (b) 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 (trifluoro) Methyl) -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-trifluoro) Olophenyl) amine, bis (pentafluorophenyl) amine, bis (2- (trifluoromethyl) phenyl) amine, bis (3- (trifluoromethyl) phenyl) amine, bis (4- (trifluoromethyl) phenyl) amine Bis (2,6-di (trifluoromethyl) phenyl) amine, bis (3,5-di (trifluoromethyl) phenyl) amine, bis (2,4,6-tri (trifluoromethyl) phenyl) amine Bis (2-cyanophenyl) amine, (3-cyanophenyl) amine, bis (4-cyanophenyl) amine, bis (2-nitrophenyl) amine, bis (3-nitrophenyl) amine, bis (4-nitro Phenyl) amine, bis (1H, 1H-perfluorobutyl) amine, bis (1H, 1H-perfluoropen ) Amine, bis (1H, 1H-perfluorohexyl) amine, bis (1H, 1H-perfluorooctyl) amine, bis (1H, 1H-perfluorododecyl) amine, bis (1H, 1H-perfluoropentadecyl) ) Amine, bis (1H, 1H-perfluoroeicosyl) amine, and the like, 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-perfluoropentadecanol, 1H, 1H-perfluoroeicosanol, etc., and fluoro of these alcohols are chloro, bromo Or alcohol changed to iodine It is. 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.

  As phenols, 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 phenol of the above-mentioned 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, and perfluorododecanoic acid.

  The compound (b) is preferably a bis (trifluoromethyl) amine, bis (2,2,2-trifluoroethyl) amine, bis (2,2,3,3,3-pentafluoropropyl) amine. ) Amine, bis (2,2,2-trifluoro-1-trifluoromethylethyl) amine, bis (1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl) amine, or bis (Pentafluorophenyl) amine and alcohols include trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1 -Trifluoromethylethanol, or 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethanol, phenols Are 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, pentafluorophenol, 2- (trifluoro Methyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-bis (trifluoromethyl) phenol, 3,5-bis (trifluoromethyl) phenol or 2,4 6-Tris (trifluoromethyl) phenol.

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

  Specific examples of the compound (c) include water, hydrogen sulfide, and amines such as alkylamine, arylamine, aralkylamine, halogenated alkylamine, halogenated arylamine, or (halogenated alkyl) arylamine. As amines, 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, benzylamine, 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, perfluoro Examples include pentadecylamine, perfluoroeicosylamine, and amines obtained by changing the fluoro of these amines to chloro, bromo, or iodo.

  Examples of anilines include aniline, naphthylamine, anthracenylamine, 2-tolylamine, 3-tolylamine, 4-tolylamine, 2,3-xylylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3 , 4-xylylamine, 3,5-xylylamine, 2,3,4-trimethylaniline, 2,3,5-trimethylaniline, 2,3,6-trimethylaniline, 2,4,6-trimethylaniline, 3,4 , 5-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,4,6-tetramethylaniline, 2,3,5,6-tetramethylaniline, pentamethylaniline, etc. 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2,3-diethylaniline, 2, -Diethylaniline, 2,5-diethylaniline, 2,6-diethylaniline, 3,4-diethylaniline, 3,5-diethylaniline, 2,3,4-triethylaniline, 2,3,5-triethylaniline, 2,3,4-triethylaniline, 2,4,6-triethylaniline, 3,4,5-triethylaniline, 2,3,4,5-tetraethylaniline, 2,3,4,6-tetraethylaniline, 2 , 3,5,6-tetraethylaniline, pentaethylaniline and the like, and these ethyls are converted into n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n- And anilines changed to octyl, n-decyl, n-dodecyl, or n-tetradecyl, and the like. Roaniline, 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.

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

  As the particles (d) used for the particles (B), 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, Inorganic substances are more preferably used. 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 Diaryl dialkoxysilanes such as silane, 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 obtained by contact with trialkylaluminum and then contact treatment with dialkylamines such as diethylamine and diphenylamine, alcohols such as methanol and ethanol, and phenols.

  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, 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. . A primary amino group, secondary amino group, imino group, amide group, imide group, hydroxy group, formyl group, carboxyl group, sulfonic acid group or thiol group is preferred. 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 portion 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.

  Examples of the monomer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group and one or more polymerizable unsaturated groups include the 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 (B) of the present invention are modified particles obtained by bringing the compounds (a), (b), (c) and the particles (d) into contact with each other. The order in which the compounds (a), (b), (c) and the particles (d) are brought into contact with each other is not particularly limited, and examples thereof include the following order.
<1> A contact object obtained by contacting (a) and (b) with (c) and a contact object obtained by bringing (c) into contact with each other.
<2> A contact object obtained by bringing (a) and (b) into contact with each other and a contact object obtained by bringing (d) into contact with each other.
<3> A contact object obtained by bringing (a) and (c) a contact object into contact with (b) is brought into contact with (d).
<4> A contact object obtained by bringing (a) and (c) into contact with each other and (d) in contact with (b).
<5> A contact product obtained by contacting (b) with a contact product between (a) and (d) and (c) are brought into contact with each other.
<6> A contact object obtained by bringing (a) and (d) into contact with each other and (c) with the contact object obtained in contact with (b).
<7> A contact product obtained by contacting (b) with the contact product between (b) and (c) is brought into contact with (d).
<8> A contact product obtained by contacting (b) with the contact product between (b) and (c) and (a) are brought into contact with each other.
<9> A contact product obtained by contacting (b) with the contact product between (b) and (d) and (c) are brought into contact with each other.
<10> The contact product obtained by bringing (b) and (d) into contact with each other and (c) with the contact product are brought into contact with each other.
<11> A contact product obtained by contacting (a) with a contact product between (c) and (d) and (b) are brought into contact with each other.
<12> A contact product obtained by contacting (b) with a contact product between (c) and (d) and (a) are brought into contact with each other.
The contact order is preferably <1>, <2>, <3>, <5>, <11> or <12>. Particularly preferred is <2> or <5>.

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

  Such contact treatment is preferably carried out in an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours. Further, such treatment may use a solvent, or these compounds may be directly treated without using 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 (a), contact obtained by contacting (a) 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, Examples thereof include sulfur compounds such as dimethyl sulfoxide and sulfolane.

  When the contact (e) obtained by bringing the compounds (a), (b) and (c) into contact with the particles (d), that is, in the above <1>, <3> and <7> In the case, as the solvent (s1) in producing the contact product (e), the above aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether solvent is preferable.

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. Examples of such polar solvents are dichloromethane, dichlorodifluoromethane chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene. O-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, Tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cycl Hexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, triethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrobenzene, ethylenediamine Pyridine, piperidine, morpholine, dimethyl sulfoxide, sulfolane and the like. More preferably, the solvent (s2) is dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl). Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, ethylene Glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol or triethylene glycol, particularly preferably di-n-butyl ether, methyl tert-butyl ether, 1,4-dioxane, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol or cyclohexanol Most preferably, it is tetrahydrofuran, methanol, ethanol, 1-propanol or 2-propanol.

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

  A method of contacting the contact (e) obtained by bringing the compounds (a), (b) and (c) into contact with the particles (d), that is, <1>, <3> and <7> above In some cases, a hydrocarbon solvent can be used as the solvent (s1) and the solvent (s2). In this case, the contact product obtained after contacting the compounds (a), (b) and (c) It is preferable that the time interval until the (e) and the particles (d) are brought into contact 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 contacting a contact thing (e) and particle | grains (d) is -100 degreeC-40 degreeC normally, Preferably it is -20 degreeC-20 degreeC, Most preferably, it is -10 degreeC-10. ° C.

  In the case of <2>, <5>, <6>, <8>, <9>, <10>, <11>, <12> above, any of the above nonpolar solvents and polar solvents may be used. A nonpolar solvent is more preferred. This is because a contact product between the compound (a) and the compound (c) or a contact product between the compound (a) and the compound (b) and the compound (c) is generally a nonpolar solvent. Therefore, when particles (d) are present in the reaction system when these contacts are formed, the formed contacts are deposited on the surface of (d) rather than in a nonpolar solvent. Is preferable because it is considered to be more easily immobilized.

The amount of each compound used in the above (a), (b) and (c) is not particularly limited, but the molar ratio (a) :( b) :( c) of each compound used is 1: y: z. Then, it is preferable that y and z substantially satisfy the following formula (1).
| M−y−2z | ≦ 1 (1)
(In the formula, m represents the valence of M ¹ in the above formula [1].)
In the above formula (1), y is preferably a number of 0.01 to 1.99, more preferably a number of 0.1 to 1.8, and still more preferably a number of 0.2 to 1.5. Yes, most preferably a number from 0.3 to 1, and the same preferred range of z in the above formula (1) is determined by m, y and the above formula (1).

  The amount used when each compound is used again is the same as the amount used above.

  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 the compound (d) used for the compound (a) is the compound contained in the particles obtained by contacting the compound (a) with the compound (d). The amount of typical metal atoms derived from (a) is preferably 0.1 mmol or more, and 0.5 to 20 mmol, in terms of the number of moles of typical metal atoms contained in 1 g of the obtained particles. Therefore, it may be appropriately determined so as to be within this range.

  Heating is also preferably performed after the contact treatment as described above 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 purpose, 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 of the compounds (a), (b), (c) and / or particles (d) remain as unreacted substances. Also good. However, when applied to polymerization involving 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 modified particles of the present invention are as follows: M ¹ is a zinc atom, compound (b) is pentafluorophenol, compound (c) is water, and particle (d) is silica. This is shown in more detail below. Tetrahydrofuran was used as a solvent, a hexane solution of diethylzinc was added thereto, the mixture was cooled to 3 ° C., and an equimolar amount of pentafluorophenol was added dropwise to diethylzinc, followed by stirring at room temperature for 10 minutes to 24 hours. Thereafter, 0.5-fold molar amount of water is added dropwise with respect to diethyl zinc, and the mixture is stirred at room temperature for 10 minutes to 24 hours. Thereafter, the solvent is distilled off, followed by drying at 120 ° C. under reduced pressure for 8 hours. Tetrahydrofuran and silica are added to the solid component obtained by the above operation, and the mixture is stirred at 40 ° C. for 2 hours. The solid component is washed with tetrahydrofuran and then dried at 120 ° C. under reduced pressure for 8 hours. Thus, the modified particles of the present invention can be produced.

Modified particles (B ')
The modified particle (B ′) in the present invention is obtained by adding the compound (f) represented by the following formula [4] to the above particle (B).
M ² L ² _n [4]
(In the formula, M ² represents a typical metal atom of Groups 12 to 15 of the periodic table of elements, and n represents a number corresponding to the valence of M ^2. L ² represents a hydrogen atom, a halogen atom or a hydrocarbon group. It represents, when L ² there are a plurality, a plurality of L ² may be different be the same as each other.)
Is a modified particle obtained by contacting with.

The compound (f) of the present invention is a compound represented by the following general formula [4].
M ² L ² _n [4]
M ^{2 in the} above general formula [4] represents a typical metal atom of Groups 12 to 15 of the periodic table of elements, and n represents a number corresponding to the valence of M ² . L ² represents a hydrogen atom, a halogen atom or a hydrocarbon group, if L ² there are a plurality, a plurality of L ² may be different be the same as each other.

M ² in the general formula [4] represents a typical metal atom of Groups 12 to 15 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). Specific examples thereof include zinc atom, cadmium atom, mercury atom, aluminum atom, gallium atom, indium atom, thallium atom, germanium atom, tin atom, lead atom, antimony atom, bismuth atom and the like. M2 is preferably a zinc atom, aluminum atom, gallium atom, germanium atom, tin atom or bismuth atom, particularly preferably a zinc atom, aluminum atom, tin atom or bismuth atom, most preferably a zinc atom or aluminum atom. is there. Further, n in the general formula [4] represents the number corresponding to the valence of M ^2, for example, M ² is, in the case of zinc atoms n is 2, in the case of the aluminum atoms and n is 3.

L ² in the general formula [4] represents a hydrogen atom, a halogen atom or a hydrocarbon group, and those listed as L ¹ in the general formula [1] can be used.

L ² in the general formula [4] is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group.

When the compound (f) is specifically exemplified, specific examples when M ² is a zinc atom include dimethyl zinc, diethyl zinc, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-n-hexyl zinc and the like. Dialkyl zinc; diaryl zinc such as diphenyl zinc, dinaphthyl zinc and bis (pentafluorophenyl) zinc; dialkenyl zinc such as diallyl zinc; bis (cyclopentadienyl) zinc; methyl zinc chloride, ethyl zinc chloride, propyl zinc chloride, -N-butyl zinc chloride, isobutyl zinc chloride, -n-hexyl chloride, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, n-butyl zinc bromide, isobutyl zinc bromide, bromide-n -Hexyl zinc, methyl zinc iodide, ethyl zinc iodide, propyl zinc iodide, iodide-n-butyl zinc, iodide Examples thereof include alkyl zinc halides such as isobutyl zinc and zinc n-hexyl iodide; zinc halides such as zinc fluoride, zinc chloride, zinc bromide and zinc iodide.

Specific examples when M ² is an aluminum atom include, for example, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n. -Dialkylaluminum chlorides such as trialkylaluminum such as octylaluminum, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, and di-n-hexylaluminum chloride , Methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, n-butylal Alkylaluminum dichlorides such as minium dichloride, isobutylaluminum dichloride, and n-hexylaluminum dichloride, dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, and di- Dialkylaluminum hydrides such as n-hexylaluminum hydride, methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, and alkyl (dialkoxy) aluminum such as methyl (di-tert-butoxy) aluminum, dimethyl (methoxy) aluminum, dimethyl ( Ethoxy) aluminum and dimethyl (tert- Dialkyl (alkoxy) aluminum such as (toxi) aluminum, alkyl (diaryloxy) aluminum such as methyl (diphenoxy) aluminum, methylbis (2,6-diisopropylphenoxy) aluminum, and methylbis (2,6-diphenylphenoxy) aluminum, and Examples include dimethyl (phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, and dialkyl (aryloxy) aluminum such as dimethyl (2,6-diphenylphenoxy) aluminum.

  Compound (f) is preferably dialkylzinc or trialkylaluminum, more preferably dimethylzinc, diethylzinc, dipropylzinc, di-n-butylzinc, diisobutylzinc, or di-n-hexylzinc, Trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum. Particularly preferred is dimethylzinc or diethylzinc, triisobutylaluminum or tri-n-octylaluminum.

  These organic zinc compounds and organoaluminum compounds may be used alone or in combination of two or more.

  The method for contacting the particles (B) and the compound (f) in the present invention is not particularly limited, but the 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. More preferably, it is 0-100 degreeC. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours, more preferably 30 minutes to 10 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. Examples of solvents that can be used include nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents, or polar solvents such as halide solvents and ether solvents. 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 tiger tetrahydropyran and the like. Nonpolar solvents are preferred.

  The concentration of the compound (f) when contacting in the solvent is not particularly limited, but is preferably 0.0001 to 100 mol / L, and more preferably 0.001 to 10 mol / L. The amount of (f) with respect to (B) when contacting the modified particles (B) and compound (f) is not particularly limited, but is preferably 0.01 to 100 mmol / g, more preferably Is 0.1 to 10 mol / g. The order of addition is not particularly limited, and the modified particles (B) may be charged into the solution of the compound (f), or the compound (f) may be charged into the slurry of the modified particles (B). good.

  There is no problem even if the cleaning operation is performed after the contact, and the solvent used in the cleaning operation may be the solvent used for the contact or may be changed. Further, the temperature may be changed during cleaning. Further, drying may be performed after contact, or the slurry may be used as it is.

  The addition polymerization catalyst obtained by bringing the transition metal compound (A) into contact with the modified particles (B ′) becomes more active when the organoaluminum compound (C) is further brought into contact as a catalyst component. Excellent and preferred. That is, a preferred addition polymerization catalyst of the present invention is an addition polymerization catalyst obtained by bringing the transition metal compound (A), the modified particles (B ′), and the organoaluminum compound (C) into contact with each other. It is.

Organoaluminum compound (C)
A known organoaluminum compound can be used as the organoaluminum compound (C). An organoaluminum compound represented by the following formula [7] is preferable.
R ⁸ _d AlY _3-d [7]
(Wherein R ⁸ represents a hydrocarbon group, and R ⁸ may be the same or different. Y represents a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, or an aralkyloxy group; May be the same or different, d represents a number satisfying 0 <d ≦ 3.)

R ⁸ in the above formula [7] is preferably a hydrocarbon group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, 2-methylhexyl group, and n-octyl group. An ethyl group, n-butyl group, isobutyl group, n-hexyl group or n-octyl group is preferred.

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

  The aryloxy group for Y is preferably an aryloxy group having 6 to 24 carbon atoms. Examples of the aryloxy group include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5- Dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2, 3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy , Ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group , N-tetradecylphenoxy group, naphthoxy group, and anthracenoxy group.

  The aralkyloxy group for Y is preferably an aralkyloxy group having 7 to 24 carbon atoms. Examples of the aralkyloxy group include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, and (2,3-dimethylphenyl) methoxy group. , (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5- (Dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,4) 5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) meth Si group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (N-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy Group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group, and anthracenylmethoxy group, preferably benzyloxy It is a group.

  Examples of the organoaluminum compound (C) represented by the formula [7] include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, And trialkylaluminum such as tri-n-octylaluminum, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, and di-n-hexylaluminum chloride Dialkylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, n- Alkyl aluminum dichlorides such as til aluminum dichloride, isobutyl aluminum dichloride, and n-hexyl aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, and di Dialkylaluminum hydrides such as n-hexylaluminum hydride, methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, and alkyl (dialkoxy) aluminum such as methyl (di-tert-butoxy) aluminum, dimethyl (methoxy) aluminum, dimethyl (Ethoxy) aluminum and dimethyl ( alkyl (diaryloxy) aluminum such as dialkyl (alkoxy) aluminum such as ert-butoxy) aluminum, methyl (diphenoxy) aluminum, methylbis (2,6-diisopropylphenoxy) aluminum, and methylbis (2,6-diphenylphenoxy) aluminum, In addition, dimethyl (phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, dialkyl (aryloxy) aluminum such as dimethyl (2,6-diphenylphenoxy) aluminum, and the like can be given.

  Among them, preferred is trialkylaluminum, more preferred is trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum, particularly preferred. Triisobutylaluminum or tri-n-octylaluminum.

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

Production Method of Addition Polymer As the ratio of the amount of each catalyst component used in the production method of the addition polymer of the present invention, the transition metal compound (A) is usually 0. It is 1-1000 micromol / g, Preferably it is 1-500 micromol / g, More preferably, it is 10-300 micromol / g. Similarly, the organoaluminum compound (C) is usually 0.1 to 10000 mmol / g, preferably 0.5 to 1000 mmol / g, more preferably 1 to 500 mmol / g.

  As a catalyst for addition polymerization of the present invention, a reaction product obtained by previously contacting component (C) with component (A) and component (B ′) may be used in some cases. May be used separately. Any of them may be contacted in advance and then the remaining components may be contacted.

  The method of 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 slurried state, the concentration of the component (B) is usually 0.01 to 1000 g / liter, preferably 0.1 to 500 g / liter. The concentration of component (D) is usually 0.0001 to 100 mol / liter, preferably 0.01 to 10 mol / liter in terms of aluminum atoms. The concentration of component (A) is usually 0.0001 to 1000 mmol / liter, preferably 0.01 to 50 mmol / liter, in terms of transition metal atoms. The concentration of component (C) is usually 0.00001 to 10 mol / liter, preferably 0.001 to 1 mol / liter.

  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, pentane, hexane, 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 can be either batch polymerization or continuous polymerization, and the polymerization may be performed in two or more stages with different reaction conditions. In general, the polymerization time is appropriately determined depending on the kind of the target olefin polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours.

  The 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 method is a continuous reactor in which monomers (and comonomers), feeds, diluents and the like are continuously added as necessary, and the polymer product is continuously or at least periodically removed. included. Examples of the reactor include a method using a loop reactor, a plurality of stirred reactors having different reactors or different reaction conditions 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 modifier 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, preliminary polymerization may be performed before such polymerization (main polymerization) is performed.

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; 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, 5-methyl-2- Norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphth Diolefins such as len, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene; norbornene, 5-methylnorbornene, 5- Ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8 -Ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbo Cyclic olefins such as nene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; styrene, 2-phenylpropylene, 2-phenylbutene, 3-phenylpropylene Alkenylbenzene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3 , 4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, p-tertiary butyl styrene, alkyl styrene such as p-secondary butyl styrene, bisalkenyl benzene such as divinylbenzene, Alkene such as alkenylnaphthalene such as 1-vinylnaphthalene Nyl aromatic hydrocarbons; α, β such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid -Unsaturated carboxylic acids and their metal salts such as sodium, potassium, lithium, zinc, magnesium, calcium, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, t-butyl acrylate, acrylic acid Such as 2-ethylhexyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, α, β-unsaturated carboxylic acid esters, maleic acid, itaconic acid, etc. Unsaturated dicarboxylic acid, vinyl acetate, vinyl propionate, capro Polar monomers such as vinyl esters such as vinyl acid, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc. Is mentioned.

  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, and propylene and 1-butene. It should not be limited to these.

  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.

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

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

Melt flow rate (MFR)
MFR is a melt flow rate value (unit: g / 10 minutes) measured at 190 ° C. under a load of 21.18 N (2.16 kg) according to the method defined in JIS K7210-1995. For all melt flow rate measurements, a polymer in which 1000 ppm of an antioxidant was blended in advance was used.

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

Melt flow rate ratio (MFRR)
The MFRR was measured according to the method specified in JIS K7210-1995, with the melt flow rate value measured at 190 ° C. and a load of 211.82 N (21.60 kg) measured at a load of 21.18 N (2.16 kg). The value divided by.

Bulk density According to the method defined in JIS K6721-1966, the bulk density was dropped freely from a bulk density meter, the weight in a predetermined volume was measured, and the bulk density was calculated as the weight per unit volume.

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

Example 1
(1) Treatment of silica
In a 50 liter reactor equipped with a nitrogen-replaced stirrer, 27.7 liters of toluene as a solvent and silica heat treated at 300 ° C. under a nitrogen stream as particles (d) (Sypolol 948 manufactured by Devison; average particle size = 58 μm; pore volume = 1.60 ml / g; specific surface area = 316 m ² / g) 2.81 kg was added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 906 g of 1,1,1,3,3,3-hexamethyldisilazane and 1.62 liters of toluene was maintained while maintaining the reactor temperature at 5 ° C. ± 1 ° C. 32. Dropped in minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 95 ° C. for 3 hours. Then, the obtained solid product was washed 6 times with 95 liters of toluene. Next, 8.2 liters of toluene was added to make a slurry.

(2) Preparation of modified particles (B) To the toluene slurry obtained in Example 1 (1) above, 1.75 kg of a hexane solution of 50.13 wt% diethylzinc as compound (a) was added, Stir. Then, after cooling to 5 ° C., 2.19 kg of a toluene solution of 3,4,5-trifluorophenol prepared as a compound (b) at a concentration of 35.6 wt% was added, and the temperature of the reactor contents was changed to 5 ° C. ± The solution was added dropwise in 61 minutes while maintaining at 3 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 0.11 liter of water was added dropwise as the compound (c) in 92 minutes while maintaining the temperature of the reactor contents at 22 ° C. ± 1 ° C. After completion of dropping, the mixture was stirred at 22 ° C for 1.5 hours, at 40 ° C for 2 hours, and at 80 ° C for 2 hours. Then, it left still and the upper layer part which settled the solid component was removed. Then 13 liters of toluene was added. Then, it heated up at 95 degreeC and stirred for 4 hours. Then, it was allowed to stand at 95 ° C. for 4 times with 24 liters of toluene and at room temperature for 3 times with 24 liters of hexane to repeat the washing operation to settle the solid component and remove the upper layer portion. The solid component was dried at 40 ° C. under reduced pressure for 8 hours to obtain 4.16 kg of modified particles (B). As a result of elemental analysis, zinc atom = 1.7 mmol / g, fluorine atom = 3.1 mmol / g.

(3) Preparation of modified particles (B ′) 1 liter of hexane was added as a solvent to a 1-liter four-necked flask purged with nitrogen, and the temperature was raised to 30 ° C. 8.70 g of the modified particles (B) obtained in Example 1 (2) above and 2.19 ml of a triisobutylaluminum hexane solution adjusted to 1 mol / liter were added and stirred at 30 ° C. for 30 minutes. The temperature was raised to 50 ° C. over 30 minutes, and sales were expanded for 3 hours. The supernatant was filtered through a filter and dried at room temperature under reduced pressure. As a result, 7.07 g of modified particles (B ′) having good fluidity were obtained.

(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 0.022 MPa, and 55 g of 1-butene was polymerized as a comonomer. 695 g of butane was charged as a solvent, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was 1.07% for hydrogen and 3.55 mol% for 1-butene. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mol / l as the organoaluminum compound (C). Next, 0.25 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide adjusted to a concentration of 2 μmol / ml was added as the transition metal compound (A), and then the above-described implementation as a solid catalyst component was performed. 5.7 mg of the modified particles (B ′) obtained in Example 1 (3) were charged. Polymerization was carried out at 70 ° C. for 1 hour while feeding an ethylene / hydrogen mixed gas (hydrogen 0.29 mol%) so as to keep the total pressure constant. As a result, 99 g of an olefin polymer was obtained. The polymerization activity per zirconium atom was 2.0 × 10 ⁸ g / molZr, and the polymerization activity per solid catalyst component was 17400 g / g solid catalyst component. In the obtained olefin polymer, SCB = 17.8, MFR = 0.31, MFRR = 98, SR = 1.22. The bulk density of the polymer powder was 0.371 g / ml.

Comparative Example 1 (polymerization)
The modified particles (B ′) used as the solid catalyst component were changed to the modified particles (B) obtained in Example 1 (2) above, and the input amount was changed to 4.5 mg, and the gas As a gas composition in the system by chromatography analysis, hydrogen was 0.97 mol%, 1-butene was 3.71 mol%, and the hydrogen concentration of the mixed gas of ethylene / hydrogen was 0.35 mol%. Except for the above, polymerization was carried out in the same manner as in Example 1 (4).
As a result, 76 g of an olefin polymer was obtained. The polymerization activity per zirconium atom was 1.5 × 10 ⁸ g / molZr, and the polymerization activity per solid catalyst component was 16900 g / g solid catalyst component. Moreover, in the obtained olefin polymer, they were SCB = 17.5, MFR = 0.25, MFRR = 117, SR = 1.19. The bulk density of the polymer powder was 0.299 g / ml.

Example 2
(1) Preparation of modified particles (B ′) The above Example 1 (except that the modified particles (B) were changed to 8.65 g and the amount of triisobutylaluminum solution was changed to 3.28 ml. Adjustment was carried out in the same manner as 3). As a result, 6.99 g of modified particles (B ′) having good fluidity were obtained.
(2) Polymerization The modified particles (B ′) used as the solid catalyst component were changed to the modified particles (B ′) obtained in Example 2 (1) and the input amount was changed to 4.6 mg. Polymerization was conducted in the same manner as in Example 1 (4) except that the gas composition in the system by gas chromatography analysis was 0.92 mol% for hydrogen and 3.57 mol% for 1-butene. Went. As a result, 78 g of an olefin polymer was obtained. The polymerization activity per zirconium atom was 1.6 × 10 ⁸ g / molZr, and the polymerization activity per solid catalyst component was 17000 g / g solid catalyst component. Moreover, in the obtained olefin polymer, they were SCB = 16.6, MFR = 0.16, MFRR = 139, SR = 1.19. The bulk density of the polymer powder was 0.330 g / ml.

Example 3
(1) Preparation of modified particles (B ′) The above Example 1 (except that the modified particles (B) were changed to 8.73 g and the amount of triisobutylaluminum solution was changed to 4.38 ml. Adjustment was carried out in the same manner as 3). As a result, 7.00 g of modified particles (B ′) having good fluidity was obtained.
(2) Polymerization The modified particles (B ′) used as the solid catalyst component were changed to the modified particles (B ′) obtained in Example 3 (1), and the input amount was changed to 4.9 mg. Polymerization was performed in the same manner as in Example 1 (4) except that the gas composition in the system by gas chromatography analysis was 0.96 mol% for hydrogen and 3.66 mol% for 1-butene. Went. As a result, 70 g of an olefin polymer was obtained. The polymerization activity per zirconium atom was 1.4 × 10 ⁸ g / mol Zr, and the polymerization activity per solid catalyst component was 14300 g / g solid catalyst component. Moreover, in the obtained olefin polymer, they were SCB = 16.3, MFR = 0.20, MFRR = 128, SR = 1.22. The bulk density of the polymer powder was 0.360 g / ml.

Example 4
(1) Preparation of modified particles (B ′) To a hexane solution of diethyl zinc adjusted to 8.75 g of modified particles (B) and 2.0 mol / liter of triisobutylaluminum solution and the amount thereof The adjustment was carried out in the same manner as in Example 1 (3) except that was changed to 1.64 ml. As a result, 7.65 g of modified particles (B ′) having good fluidity were obtained.
(2) Polymerization The modified particles (B ′) used as the solid catalyst component were changed to the modified particles (B ′) obtained in Example 4 (1) and the input amount was changed to 4.0 mg. Polymerization was conducted in the same manner as in Example 1 (4) except that the gas composition in the system by gas chromatography analysis was 0.97 mol% for hydrogen and 3.32 mol% for 1-butene. Went. As a result, 63 g of an olefin polymer was obtained. The polymerization activity per zirconium atom was 1.3 × 10 ⁸ g / molZr, and the polymerization activity per solid catalyst component was 15800 g / g solid catalyst component. Moreover, in the obtained olefin polymer, they were SCB = 17.5, MFR = 0.82, MFRR = 70, SR = 1.36. The bulk density of the polymer powder was 0.311 g / ml.

  As described in detail above, according to the present invention, a catalyst that can be applied to polymerization accompanied by the formation of addition polymer particles, which is a modified particle capable of producing an addition polymer with high bulk density that is preferably used, There are provided an addition polymerization catalyst component, an addition polymerization catalyst, and a method for producing an addition polymer having a high bulk density using the addition polymerization catalyst.

Claims (8)

A catalyst for olefin polymerization obtained by contacting a transition metal compound (A) belonging to Group 4 of the periodic table of elements , an organoaluminum compound (C), and modified particles (B ′), Quality particles (B ')
Compound (a) represented by the following formula [1],
M ¹ L ¹ ₂ [1]
(In the formula, M ¹ represents a typical metal atom of Group 12 of the periodic table of elements. L ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and a plurality of L ¹ may be the same or different from each other. May be.)
Compound (b) represented by the following formula [2], and
R ¹ OH [2]
Compound (c) represented by the following formula [3],
H ₂ O [3]
(Oite the above formula [2], ^{R 1} represents a halogenated hydrocarbon group.)
In addition, the modified particles (B) obtained by bringing the particles (d) made of a substance different from any of the compounds (a), (b), and (c) into contact with the following formula [4] Compound (f) represented by
M ² L ² ₃ [4]
(In the formula, M ² represents a typical metal atom of Group 13 of the periodic table of elements. L ² represents a hydrogen atom, a halogen atom or a hydrocarbon group, and a plurality of L ² may be the same or different from each other. May be.)
A catalyst for olefin polymerization, which is a modified particle obtained by contacting the catalyst. The compound (f) is an organoaluminum compound, olefin polymerization catalyst according to claim 1. The catalyst for olefin polymerization according to claim 1 or 2 , wherein the transition metal compound (A) is a transition metal compound having at least one cyclopentadiene-type anion skeleton. An olefin polymer using a catalyst for olefin polymerization obtained by bringing a transition metal compound (A) of Group 4 of the periodic table of elements into contact with an organoaluminum compound (C) and modified particles (B ′) A manufacturing method comprising:
Compound (a) represented by the following formula [1],
M ¹ L ¹ ₂ [1]
(In the formula, M ¹ represents a typical metal atom of Group 12 of the periodic table of elements. L ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and a plurality of L ¹ may be the same or different from each other. May be.)
Compound (b) represented by the following formula [2], and
R ¹ OH [2]
Compound (c) represented by the following formula [3],
H ₂ O [3]
(Oite the above formula [2], ^{R 1} represents a halogenated hydrocarbon group.)
In addition, the modified particles (B) obtained by bringing the particles (d) made of a substance different from any of the compounds (a), (b), and (c) into contact with the following formula [4] Compound (f) represented by
M ² L ² ₃ [4]
(In the formula, M ² represents a typical metal atom of Group 13 of the periodic table of elements. L ² represents a hydrogen atom, a halogen atom or a hydrocarbon group, and a plurality of L ² may be the same or different from each other. May be.)
And the contact is not obtained was該改reformed particles (B '), characterized by using the olefin polymerization catalyst obtained by contacting said transition metal compound (A), olefin polymer Manufacturing method. The method for producing an olefin polymer according to claim 4, wherein the olefin polymer is a copolymer of ethylene and an α-olefin. Compound (a) represented by the following formula [1],
M ¹ L ¹ ₂ [1]
(In the formula, M ¹ represents a typical metal atom of Group 12 of the periodic table of elements. L ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and a plurality of L ¹ may be the same or different from each other. May be.)
Compound (b) represented by the following formula [2], and
R ¹ OH [2]
Compound (c) represented by the following formula [3],
H ₂ O [3]
(Oite the above formula [2], ^{R 1} represents a halogenated hydrocarbon group.)
In addition, the modified particles (B) obtained by bringing the particles (d) made of a substance different from any of the compounds (a), (b), and (c) into contact with the following formula [4] Compound (f) represented by
M ² L ² ₃ [4]
(In the formula, M ² represents a typical metal atom of Group 13 of the periodic table of elements. L ² represents a hydrogen atom, a halogen atom or a hydrocarbon group, and a plurality of L ² may be the same or different from each other. May be.)
Modified particles obtained by contacting with. Compound (a) represented by the following formula [1],
M ¹ L ¹ ₂ [1]
(In the formula, M ¹ represents a typical metal atom of Group 12 of the periodic table of elements. L ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and a plurality of L ¹ may be the same or different from each other. May be good.)
Compound (b) represented by the following formula [2], and
R ¹ OH [2]
Compound (c) represented by the following formula [3],
H ₂ O [3]
(Oite the above formula [2], ^{R 1} represents a halogenated hydrocarbon group.)
And a step of contacting particles (d) comprising a substance different from any of the compound (a), compound (b) or compound (c) to obtain modified particles (B), and the following formula [4 ] Compound (f) represented by
M ² L ² ₃ [4]
(In the formula, M ² represents a typical metal atom of Group 13 of the periodic table of elements. L ² represents a hydrogen atom, a halogen atom or a hydrocarbon group, and a plurality of L ² may be the same or different from each other. May be.)
A method for producing modified particles, comprising the step of bringing the modified particles into contact with the resulting modified particles (B). Compound (a) represented by the following formula [1],
M ¹ L ¹ ₂ [1]
(In the formula, M ¹ represents a typical metal atom of Group 12 of the periodic table of elements. L ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and a plurality of L ¹ may be the same or different from each other. May be.)
Compound (b) represented by the following formula [2], and
R ¹ OH [2]
Compound (c) represented by the following formula [3],
H ₂ O [3]
(Oite the above formula [2], ^{R 1} represents a halogenated hydrocarbon group.)
In addition, the modified particles (B) obtained by bringing the particles (d) made of a substance different from any of the compounds (a), (b), and (c) into contact with the following formula [4] Compound (f) represented by
M ² L ² ₃ [4]
(In the formula, M ² represents a typical metal atom of Group 13 of the periodic table of elements. L ² represents a hydrogen atom, a halogen atom or a hydrocarbon group, and a plurality of L ² may be the same or different from each other. May be good.)
A catalyst component for olefin polymerization consisting of modified particles [B ′] obtained by contacting with.