JP2000191713A - Catalytic component for ethylenic unsaturated monomer polymerization, catalyst for ethylenic unsaturated monomer polymerization and polymerization of ethylenic unsaturated monomer using the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalytic component to be made into a catalyst for polymerizing an ethylenic unsaturated monomer by using the component together with a transition metal compound, and a catalyst composed of the catalytic component and the transition metal compound, and to provide a method for polymerization using the catalyst. SOLUTION: This catalytic component is obtained by reacting in an arbitrary order (i) a compound containing a metal of the group 13 of the periodic table with (ii) a compound which is reacted with the compound (i) to become bondable to two or more metals of the group 13 and, if required, (iv) at least one compound selected from a hydrocarbon compound, a halogenated hydrocarbon compound, a hydroxyhydrocarbon compound, an organic carboxylic acid compound, or the like, and their metal salts, and further, with (iii) a compound capable of forming an ionized ionic compound by a reaction with a compound containing a metal of the group 13 of the periodic table.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst component which, when used in combination with a transition metal compound such as a metallocene compound, can be a highly active catalyst for the polymerization of ethylenically unsaturated monomers. The present invention also relates to a catalyst for polymerizing an ethylenically unsaturated monomer comprising the catalyst component and a catalyst of a transition metal compound such as a metallocene compound, and a method for polymerizing an ethylenically unsaturated monomer using the same.

[0002]

BACKGROUND OF THE INVENTION Conventionally, ethylene such as polyethylene, polypropylene, poly-4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / styrene copolymer, ethylene / propylene / butene terpolymer, etc. As a catalyst for producing the unsaturated unsaturated monomer (co) polymer, a titanium catalyst comprising a titanium compound and an organic aluminum compound and a vanadium catalyst comprising a vanadium compound and an organic aluminum compound are known.

Further, as a catalyst capable of producing an olefin polymer with high polymerization activity, a metallocene compound such as zirconocene and a boron compound such as an organoaluminum oxy compound (aluminoxane) or tris (pentafluorophenyl) borane are used. Ziegler type catalysts are known.

Further, a catalyst comprising a nickel compound or a palladium compound and a co-catalyst such as an aluminoxane or an ionic compound has been proposed (J. Am. Chem. Soc. 19).
95,117,6414-6415).

[0005] Ethylenically unsaturated monomer (co) polymers such as polyolefins are generally used in various fields such as moldings because of their excellent mechanical properties. Demands for physical properties of monomer (co) polymers are increasing, and polymers having various properties are desired.

[0006] Under such circumstances, the emergence of a new cocatalyst component which can produce an ethylenically unsaturated monomer (co) polymer having excellent polymerization activity and excellent properties has been desired.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has been developed in view of the fact that, when used in combination with a transition metal compound such as a metallocene compound, it exhibits an ethylenically unsaturated monomer polymerization activity. It is an object of the present invention to provide a novel catalyst component, a catalyst capable of obtaining a highly active polymer having a high molecular weight containing the catalyst component, and a method for polymerizing an ethylenically unsaturated monomer using the catalyst.

[0008]

The catalyst component for the polymerization of ethylenically unsaturated monomers according to the present invention comprises a compound obtained by reacting the following (i) to (iii) and, if necessary, (iv) in any order. (I) a compound containing an atom belonging to Group 13 of the periodic table; (ii) reacting with a compound (i) containing an atom belonging to Group 13 of the periodic table, and capable of bonding to two or more Group 13 atoms. (Iii) a compound capable of reacting with a compound containing an atom of Group 13 of the periodic table to form an ionized ionic compound; (iv) a hydrocarbon compound, a halogenated hydrocarbon compound, a hydroxyhydrocarbon compound, a silanol compound, Boronic acid compounds, organic carboxylic acid compounds, organic sulfonic acid compounds, hydroxylamine compounds, sulfonamide compounds, ketoimide compounds, amide compounds, oxime compounds, amine compounds , An imide compound, a diimine compound, an imine compound, a diketone compound, and at least one compound selected from these metal salts. The catalyst component for the polymerization of ethylenically unsaturated monomers according to another embodiment of the present invention includes the following (i) and (Ii) a compound obtained by reacting (iv) in an arbitrary order, if necessary, and then further reacting (iii); (i) represented by the following general formula: Compound MR ¹ R ² R ³ (where M represents an atom belonging to Group 13 of the periodic table, and R ¹ , R
² and R ³ may be the same or different from each other;
Represents a halogen atom, a hydrogen atom, a hydroxyl group or an organic group,
Further, ^two groups out of R ¹ , R ² and R ³ may be connected to each other to form a ring. (Ii) a compound capable of reacting with the compound (i) and binding to two or more M. (iii) the above (i) and (ii), if necessary,
a compound capable of forming an ionized ionic compound by reacting with a reaction product obtained by reacting v) in an arbitrary order (iv) a hydrocarbon compound, a halogenated hydrocarbon compound, a hydroxyhydrocarbon compound, a silanol compound , Boronic acid compounds, organic carboxylic acid compounds, organic sulfonic acid compounds, hydroxylamine compounds, sulfonamide compounds, ketoimide compounds, amide compounds, oxime compounds, amine compounds, imide compounds, diimine compounds, imine compounds, diketone compounds and their metals the at least one compound wherein chosen from salts (i), there is an aluminum compound represented by the following general _{^{formula; R a m Al (oR b}} ) n X p ( where, R ^a and R ^b, They may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms. ,
X represents a halogen atom, m is 0 ≦ m ≦ 3, n is 0 ≦ n
≦ 3, p is a number satisfying 0 ≦ p ≦ 3, and m + n + p = 3
It is. As the compound (ii), there is at least one compound selected from the group consisting of H ₂ O, H ₂ S and a compound represented by the following general formula;

[0009]

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Wherein R ⁴ represents a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or an oxygen-containing group, and R ⁵ represents a divalent hydrocarbon group A divalent halogenated hydrocarbon group, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, a divalent boron-containing group or a single bond, wherein R ⁶ and R ⁷ are ^May be the same or different from each other, and represent a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or an oxygen-containing group, and R ⁶ and R ⁷ each form R ⁵ And R ⁸ and R ⁹
May be the same or different, and represent a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group. As the compound (iii), a carbonium cation,
There are compounds that can form an ionized ionic compound with an oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation or ferrocenium cation.

The compound (iv) includes at least one selected from compounds represented by the following general formula;
¹⁰ X, R ¹⁰ H, R ¹⁰ OH, R ¹⁰ R ¹¹ NH, R ¹⁰ COO
H, R ¹⁰ SO ₃ H, R ¹⁰ R ¹¹ CNOH, R ¹⁰ R ¹¹ NO
H, R ¹⁰ CONHR ¹¹ , R ¹⁰ SO ₂ NHR ¹¹ , R ¹⁰ CO
CH ₂ COR ¹¹ , R ¹⁰ C (＝ NH) CH ₂ COR ¹¹ ,
(Wherein, R ¹⁰ represents a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group, or a boron-containing group, and R ¹¹ is the same as or a hydrogen atom, an alkoxy group, or R ¹⁰ It represents a different hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group, or a boron-containing group, and X represents a halogen atom.) The catalyst component for saturated monomer polymerization is characterized by being represented by the following formula.

[0012]

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(Wherein M is the same or different and represents an atom belonging to Group 13 of the periodic table, n is an integer of 0 or more, Y is a divalent linking group, and n is 1 or more.) In some cases, a plurality of Ys may be the same or different from each other, and Z is 1
Or a group capable of bonding to two or more M, m is an integer of 1 or more and n + 1 or less, Q may be the same or different, and is a group selected from the following groups: Indicates that

[0014]

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[However, R ¹⁰ represents a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or a boron-containing group, and R ¹¹ represents a hydrogen atom, an alkoxy group or R ¹⁰ . The same or different hydrocarbon groups, halogenated hydrocarbon groups, silicon-containing groups, germanium-containing groups, tin-containing groups and boron-containing groups are shown. ]
A represents a cation, j is the valence of Z, m is the number of Z, k is k = jm / r, and represents the valence of the A cation. ).

The divalent linking group Y includes one type of linking group selected from the following divalent linking groups and the like;

[0017]

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(Wherein R ⁴ represents a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or an oxygen-containing group, and R ⁵ is a divalent hydrocarbon group. A divalent halogenated hydrocarbon group, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, a divalent boron-containing group or a single bond, wherein R ⁶ and R ⁷ are They may be the same or different from each other, and represent a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or an oxygen-containing group, and R ⁶ and R ⁷ each represent R ⁵ combine with forming carbon atoms may form a ring, R ⁸ and R
⁹ may be the same or different and each represents a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group. 1)
The group Z that can be bonded to one or more Ms includes a halogen anion, hydride, carbanion, alcoholate, aryl alcoholate, alkylcarboxylate, arylcarboxylate, thiolate, carbothiolate, dithiocarbonate, trithiocarbonate, One kind of group selected from carbonate, sulfonate, sulfamate, phosphate and the like can be mentioned.

The A cation is not particularly limited, but may be, for example, a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a dicyclohepsyltrienyl cation, a ferrocenium cation, or a group 1 or 11 group of the periodic table. One type of cation selected from the group consisting of group metal cations and the like.

The catalyst for polymerizing an ethylenically unsaturated monomer according to the present invention comprises (A) a compound of a transition metal selected from Groups 3 to 12 of the periodic table, (B) the catalyst component, and (C) a compound of the periodic table. It is characterized by being composed of an organic compound containing a group 13 atom.

The catalyst for polymerizing ethylenically unsaturated monomers according to the present invention comprises the component (A) alone, or together with the component (A), the component (B) and / or the component (C).
May be supported on the particulate carrier (D).

The method for polymerizing an ethylenically unsaturated monomer according to the present invention is characterized by polymerizing or copolymerizing an ethylenically unsaturated monomer in the presence of the above-mentioned catalyst.

[0023]

DETAILED DESCRIPTION OF THE INVENTION The catalyst component for the polymerization of ethylenically unsaturated monomers, the catalyst for the polymerization of ethylenically unsaturated monomers and the method for polymerizing the ethylenically unsaturated monomers using the catalyst according to the present invention will be specifically described below. I do.

The catalyst component for ethylenically unsaturated monomer polymerization according to the present invention comprises the following (i), (ii) and (iii):
If necessary, (iv) is reacted in any order, or preferably (i) and (ii) described below, and if necessary, (iv) is reacted in any order, and then (iii) is reacted. Obtained. (I) a compound containing an atom belonging to Group 13 of the periodic table, preferably a compound represented by the following general formula: MR ¹ R ² R ³ (where M represents an atom belonging to Group 13 of the periodic table; R ¹ and R
² and R ³ may be the same or different from each other;
Represents a halogen atom, a hydrogen atom, a hydroxyl group or an organic group,
Further, ^two groups out of R ¹ , R ² and R ³ may be connected to each other to form a ring. (Ii) reacting with the compound (i) and capable of bonding to two or more Group 13 atoms. (Iii) reacting with a compound containing an atom of Group 13 of the periodic table to form an ionized ionic compound. And preferably a reaction product obtained by reacting the above (i) and (ii) and, if necessary, the following (iv) in any order to form an ionized ionic compound. Compounds (iv) hydrocarbon compounds, halogenated hydrocarbon compounds, hydroxy hydrocarbon compounds, silanol compounds, boronic acid compounds, organic carboxylic acid compounds, organic sulfonic acid compounds, hydroxylamine compounds, sulfonamide compounds, ketoimide compounds, amide compounds, Oxime compounds, amine compounds, imide compounds, diimine compounds, imine compounds, diketone compounds and these At least one compound selected from Shokushio First, a description will be given of each component used for preparing the ethylenically unsaturated monomer polymerization catalyst component according to the present invention.

(I) A compound containing an atom belonging to Group 13 of the periodic table The compound (i) containing an atom belonging to Group 13 of the periodic table used in the present invention is preferably represented by the general formula MR ¹ R ² R ³ Compound. In the compound represented by the general formula MR ¹ R ² R ³ , M is a Group 13 atom, specifically, boron, aluminum, gallium, indium, etc., and particularly preferably boron or aluminum.

R ¹ , R ² and R ³ may be the same or different and are a halogen atom, a hydrogen atom, a hydroxyl group or an organic group. Further, ^two groups out of R ¹ , R ² and R ³ may be connected to each other to form a ring.

The halogen atom is fluorine, chlorine, bromine or iodine, of which chlorine and bromine are preferred. Examples of the organic group include a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, and the like. Among them, a hydrocarbon group having 1 to 20 carbon atoms,
A hydrocarbon-substituted silyl group substituted with 20 hydrocarbons, an alkoxy group having 1 to 20 carbon atoms, and 6 to 6 carbon atoms
20 aryloxy groups are preferred.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group, an aryl group and the like. More specifically, methyl, ethyl, propyl, Alkyl groups such as butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; vinyl,
Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl, naphthyl, methylnaphthyl, anthryl and phenanthryl An aryl group is mentioned, and as the halogenated hydrocarbon group, a group obtained by halogenating the hydrocarbon group having 1 to 20 carbon atoms is exemplified.

Examples of the hydrocarbon-substituted silyl group substituted with a hydrocarbon having 1 to 20 carbon atoms include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl; Trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tolylsilyl, trinaphthylsilyl and other trihydrocarbon-substituted silyls and the like, and the number of carbon atoms is 1 to 1.
Examples of the 20 alkoxy groups include methoxy, ethoxy, propoxy, butoxy, etc., and have 6 to 6 carbon atoms.
Examples of the aryloxy group of 20 include phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy and the like.

Preferred examples of the compound represented by the general formula MR ¹ R ² R ³ include a compound represented by the following general formula ^: _Ram Al (OR ^b ) _n X _p (wherein ^Ra and R ^b are the same or different. A hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0 ≦
m ≦ 3, n is a number of 0 ≦ n ≦ 3, p is a number of 0 ≦ p ≦ 3,
And m + n + p = 3. )).

More specifically [0031] the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, preferably an 1-4 hydrocarbon group, m is preferably a number 1.5 ≦ m ≦ 3.) aluminum compound represented by the general formula R ^a _m AlX _3-m (wherein, R ^a has 1 to 15 carbon atoms, preferably 1 to
4 represents a hydrocarbon group, X represents a halogen atom, and m is 0 ≦ m ≦ 3. Aluminum compound represented by), the general formula _{^{R a m Al (OR b)}} n X p ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, preferably Represents a hydrocarbon group of 1 to 4, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is a number of 0 ≦ n <3, p is a number of 0 ≦ p <3,
And m + n + p = 3. An aluminum compound represented by the formula:

More specifically, such aluminum compounds include tri-n-alkyl aluminums such as tri-ethyl aluminum, tri-n-butyl aluminum, and tri-n-octyl aluminum;
Triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum,
Tri-branched alkyl aluminum such as tri-2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexylaluminum, tri2-ethylhexylaluminum; tricyclohexyl Tricycloalkylaluminum such as aluminum; triarylaluminum such as triphenylaluminum and tolylaluminum; trialkenylaluminum such as triisoprenylaluminum; alkylaluminum such as isobutylaluminum methoxide, isobutylaluminum ethoxide and isobutylaluminum isopropoxide Alkoxide;
Portion having an average composition represented by like _{^{R a 2.5 Al (OR b)}} 0.5; diethylaluminum ethoxide, dialkylaluminum alkoxides such as dibutyl aluminum butoxide; ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride butoxide Alkylaluminum which has been alkoxylated; diethylaluminum chloride;
Dialkylaluminum halides such as dibutylaluminum chloride and diethylaluminum bromide; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; ethylaluminum dichloride and propylaluminum dichloride;
Partially halogenated alkyl aluminums such as alkyl aluminum dihalides such as butyl aluminum dibromide; partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxycyclolide, butyl aluminum butoxycyclolide, ethyl aluminum ethoxy bromide Aluminum trihalides such as aluminum trichloride and aluminum tribromide; aryl-substituted aluminum halides such as trispentafluorophenylaluminum; alkyl aluminum halides such as tristrifluoromethylaluminum.

Preferred examples of the compound represented by the general formula MR ¹ R ² R ³ include aryl-substituted boron halides such as trispentafluorophenyl boron; and organic borons such as alkyl boron halides such as tristrifluoromethyl boron. Compounds.

Preferred examples of the compound represented by the general formula MR ¹ R ² R ³ include BH ₃ , boronic acid and B (O
H) ₃ , Al (OH) ₃ , and aluminum trichloride such as aluminum trichloride, aluminum tribromide and aluminum triiodide, and boron trihalide such as boron trichloride, boron tribromide and boron triiodide And the like.

The compounds (i) as described above can be used alone or in combination of two or more. (Ii) reacting with the compound (i), and
Reacting with two or more of the compounds (i) capable of bonding to an atom;
The compound (ii) capable of bonding to a group 3 atom preferably reacts with the compound represented by the above general formula MR ¹ R ² R ³ to provide a crosslinked structure bonded to two or more M in the obtained compound. A compound, specifically, at least one compound selected from the group consisting of H ₂ O, H ₂ S, and a compound represented by the following general formula.

[0036]

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In the formula, R ⁴ represents a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or an oxygen-containing group. Specifically, as the hydrocarbon group, methyl, ethyl, propyl, butyl,
Alkyl groups such as hexyl, octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl A hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl, naphthyl, methylnaphthyl, anthryl and phenanthryl. The aryl group may be substituted with one or more alkyl groups.

As the halogenated hydrocarbon group, specifically,
Examples thereof include a group obtained by halogenating a hydrocarbon group having 1 to 20 carbon atoms. Examples of the silicon-containing group include alkylsilyl groups such as trimethylsilyl, triethylsilyl and dimethyltrifluoromethylsilyl; alkylsilyl halide groups; arylalkylsilyl groups such as tribenzylsilyl, dimethylphenylsilyl and trifluoromethyldiphenylsilyl; Arylalkylsilyl groups; arylsilyl groups such as triphenylsilyl and tripentafluorophenylsilyl; halogenated arylsilyl groups; alkylsilyloxy groups such as trimethylsilyloxy, dimethylphenylsilyloxy and triphenylsilyloxy; arylalkylsilyloxy groups An arylsilyloxy group and the like.

Examples of the germanium-containing group include groups in which silicon of the above-mentioned silicon-containing group is substituted with germanium. Examples of the tin-containing group include groups in which silicon of the above-mentioned silicon-containing group is substituted with tin.

Examples of the oxygen-containing group include an alkylalkoxy group such as methoxy, ethoxy, phenoxy, triphenylcarbinoxy, and benzyloxy; an arylalkoxy group; an alkylarylalkoxy group, and some of the above substituents are halogenated. Halogenated alkylalkoxy groups; halogenated arylalkoxy groups; halogenated alkylarylalkoxy groups, and the like.

Among these, an alkyl group, an aryl group, a halogen-substituted alkyl group, a halogen-substituted aryl group and the like are preferable. R ⁵ represents a divalent hydrocarbon group, a divalent halogenated hydrocarbon group, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, a divalent boron-containing group or a single bond. Shown, specifically as preferred examples, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-
Alkylene groups such as 1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene; diphenylmethylene, diphenyl-1,2
-An arylalkylene group such as ethylene; phenylene,
1 to 2 carbon atoms such as an arylene group such as naphthylene
And a divalent hydrocarbon group of 0.

Specific examples of the divalent halogenated hydrocarbon group include those having 1 to 20 carbon atoms such as chloromethylene.
And a group obtained by halogenating a divalent hydrocarbon group. Examples of the divalent silicon-containing group include alkylsilylene groups such as silylene, methylsilylene, dimethylsilylene, diethylsilylene, diphenylsilylene, and methylphenylsilylene; arylsilylene groups; alkylarylsilylene groups; tetramethyl-1,2-disilylene; Alkyldisilylene groups such as tetraphenyl-1,2-disilylene; aryldisilylene groups; alkylaryldisilylene groups;
A halogenated alkylsilylene group in which a part of the substituents is halogenated; a halogenated arylsilylene group;
Halogenated alkylarylsilylene groups; halogenated alkyldisilylene groups; halogenated aryldisilylene groups; halogenated alkylaryldisilylene groups, and the like.

Examples of the divalent germanium-containing group include groups in which silicon of the above-mentioned divalent silicon-containing group is substituted with germanium. Examples of the divalent tin-containing group include a group in which silicon of the divalent silicon-containing group is substituted with tin.

Examples of the divalent boron-containing group include —BR ^{5 ′} —
(However, R ^{5 ′} represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing group similar to R ⁴ ).

R ⁶ and R ⁷ may be the same or different from each other, and may be an atom selected from a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group, and an oxygen-containing group. Or a group, and specific examples include the same groups as those described above for R ⁴ . R ⁶ may be bonded to the carbon atom forming R ⁵ to form a ring together with the nitrogen atom to which R ⁶ is bonded, and R ⁷ may be bonded to the carbon atom forming R ⁵ and R ⁷ is bonded. May form a ring with a nitrogen atom. Among these, an alkyl group is preferred.

[0046] R ⁸ and R ⁹ may be the same or different from each other, a hydrogen atom, an atom or a group selected from hydrocarbon and halogenated hydrocarbon radicals, and to specifically not the R ¹ R ³ Similar groups are mentioned. Of these, an alkyl group is preferred.

Among such compounds (ii), H ₂
It is particularly preferred that O or a compound in which R ⁴ or R ⁵ is an alkyl group, an aromatic hydrocarbon group, a silicon-containing group, a boron-containing group or a halogen-containing substituent.

It is presumed that such a compound (ii) reacts with the above-mentioned compound (i) to form, for example, the following crosslinked structure in the obtained compound.

[0049]

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[0050]

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Specific examples of such compound (ii) include:

[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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The compounds (ii) as described above can be used alone or in combination of two or more. (Iii) reacting with a compound containing an atom belonging to Group 13 of the periodic table;
Compounds capable of forming an ionized ionic compound Compounds capable of forming an ionized ionic compound by reacting with a compound containing an atom belonging to Group 13 of the periodic table include compounds represented by the aforementioned general formula MR ¹ R ² R ³ . A compound capable of reacting with the compound to be formed to form an ionized ionic compound, the above (i) and (ii), and if necessary, the following (iv)
Are reacted in any order with a reaction product obtained to form an ionized ionic compound, LiB (C ₆ F ₅ ) ₄ , LiB (Ph) ₄ , LiAl
Compounds that can react with (C ₆ F ₅ ) ₄ or LiAl (Ph) ₄ to form an ionized ionic compound can be used. The compound capable of forming an ionized ionic compound by reacting with a compound containing an atom belonging to Group 13 of the periodic table is preferably a cation capable of providing a proton or a cation capable of not providing a proton. There are compounds that can form an ionized ionic compound having a cation such as a cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation.

Specifically, alkyl metal salts such as methyllithium, alkoxy metal salts such as methoxylithium, and triphenylchloromethane and acetyltriphenylmethane; potassium triethylboron hydride, bis (η-cyclopentadienyl) iron. Sulfate, N, N-dimethylanilinium chloride, triethylammonium chloride and the like can be mentioned.

The compounds (iii) as described above can be used alone or in combination of two or more. Compound (iv) The compound (iv) optionally used in the present invention is a compound which provides a group 13 atom (M) derived from the compound (i) with a substituent effective as a co-catalyst component. Specifically, hydrocarbon compounds, halogenated hydrocarbon compounds, hydroxy hydrocarbon compounds, silanol compounds, boronic acid compounds, organic carboxylic acid compounds, organic sulfonic acid compounds, hydroxylamine compounds, sulfonamide compounds, ketoimide compounds, amide compounds, oximes It is at least one compound selected from a compound, an amine compound, an imide compound, a diimine compound, an imine compound, a diketone compound and a metal salt thereof.

Such compounds include, for example,
Compounds represented by any of the general formulas and their metals
There is salt. R^TenX, R^TenH, R^TenOH, R^TenR¹¹NH, R^TenCOO
H, R^TenSO_ThreeH, R ^TenR¹¹CNOH, R^TenR¹¹NO
H, R^TenCONHR¹¹, R^TenSO_TwoNHR¹¹, R ^TenCO
CH_TwoCOR¹¹, R^TenC (= NH) CH_TwoCOR¹¹ Where R^TenRepresents a hydrocarbon group, a halogenated hydrocarbon group,
Silicon-containing groups, germanium-containing groups, tin-containing groups or borane
An oxygen-containing group;^FourHydrocarbons similar to
Group, halogenated hydrocarbon group, silicon-containing group, germanium
And tin-containing groups.

Examples of the boron-containing group include —BR ^{10 ′} R ^{10 ″}
(However, R ^{10 ′} and R ^{10 ″} may be the same or different from each other, and are the same as R ^{4 in} a hydrocarbon group having 1 to 20 carbon atoms and a halogenated hydrocarbon having 1 to 20 carbon atoms. A group or an oxygen-containing group, and R ^{10 ′} and R ^{10 ″} may be linked to each other to form a ring).

R ¹¹ is a hydrogen atom, an alkoxy group or R ¹⁰
Identical or different hydrocarbon radicals and halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or a boron-containing group, and specifically same alkoxy group as to R ³ not said R ^1, said The same hydrocarbon group, halogenated hydrocarbon, silicon-containing group, germanium-containing group and tin-containing group as those of R ⁴ can be mentioned. The boron-containing group include the same groups as R ^10.

R ¹⁰ and R ¹¹ are linked to each other to form R
^A ring may be formed together with the nitrogen atom or carbon atom to which ¹⁰ and R ¹¹ are bonded, and this ring may have a double bond.

X represents a halogen atom. Examples of such compounds are shown below. Examples of the compound represented by the general formula R ¹⁰ X include, for example,

[0071]

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As the compound represented by the general formula R ¹⁰ H, for example,

[0073]

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As the compound represented by the general formula R ¹⁰ OH, for example,

[0075]

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Examples of the compound represented by the general formula R ¹⁰ R ¹¹ NH include, for example,

[0077]

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As the compound represented by the general formula R ¹⁰ COOH, for example,

[0079]

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As the compound represented by the general formula R ¹⁰ SO ₃ H, for example,

[0081]

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As the compound represented by the general formula R ¹⁰ R ¹¹ NOH, for example,

[0083]

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As the compound represented by the general formula R ¹⁰ R ¹¹ CNOH, for example,

[0085]

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The compound represented by the general formula R ¹⁰ CONHR ¹¹ includes, for example,

[0087]

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Examples of the compound represented by the general formula R ¹⁰ SO ₂ NHR ¹¹ include, for example, Ph-SOO-NH-Ph, P
h-SOO-NH-Me, having the general formula R ¹⁰ COC
Examples of the compound represented by H ₂ COR ¹¹ include, for example,

[0089]

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Formula R ¹⁰ C (＝ NH) CH ₂ COR ¹¹
Examples of the compound represented by

[0091]

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Among such compounds (iv),
R in the general formula^TenIs a substituted aromatic hydrocarbon group or
Is preferably a compound that is a fluorine-containing substituent
K, R ^TenOr R¹¹At least one of has a substituent
Which are aromatic hydrocarbon groups or fluorine-containing substituents
Compounds are also preferred.

Examples of the aromatic hydrocarbon group having a substituent include an aromatic group substituted by at least one substituent selected from an alkyl group, a halogenated alkyl group, an alkoxy group, and halogen (particularly, fluorine is preferable). And hydrocarbon groups.

As the fluorine-containing substituent, a fluorine atom
Substituents containing one or more substituents. these
As the metal salt of the compound of^TenY, R^TenOY, R^TenR
¹¹NY, R^TenCOOY, R^TenSO_ThreeY, R^TenR¹¹CNO
Y, R^TenR¹¹NOY, R^TenCONR¹¹Y, R^TenSO_TwoN
R¹¹Y (however, R^TenAnd R¹¹Is the same as above, and Y
Is an alkali metal such as lithium, sodium or potassium
It is. ). Furthermore, (R^TenSO_Three)_Two
Ba etc. (R ^TenIs the same as above)
Compounds having a genus as a metal salt, for example (C₆F_FiveSO_Three)_TwoBa etc.
Are also mentioned.

The above compounds (iv) can be used alone or in combination of two or more. The catalyst component for polymerizing ethylenically unsaturated monomers according to the present invention reacts (i), (ii) and (iii) or (i), (ii), (iii) and (iv) as described above. Can be prepared.

In preparing the catalyst component for the polymerization of ethylenically unsaturated monomers, compound (i) is used in an amount of 1 to 5 mol, preferably 2 to 3 mol, per 1 mol of compound (ii).
i) is 0.1 to 2 mol, preferably 0.5 to 1 mol, per 1 mol of the compound (i), and the compound (iv) optionally used is 1 to 1 mol per 1 mol of the compound (i). It can be used in a proportion of 6 mol, preferably 2 to 3 mol.

In the present invention, in particular, compound (i) is about 2 mol per 1 mol of compound (ii), and compound (iii) is about 0.5 mol per 1 mol of compound (i), if necessary. The compound (iv) used is preferably used in a ratio of about 2 or 3 mol per 1 mol of the compound (i).

Solvents used in the reaction include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane and dodecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; , Toluene, xylene and other aromatic hydrocarbons; ethylene chloride, chlorobenzene,
Halogenated hydrocarbons such as dichloromethane and chloroform; ether-containing aliphatic hydrocarbons such as diethyl ether and tetrahydrofuran; ether-containing alicyclic hydrocarbons; and mixtures thereof.

[0099] At least one compound selected from (i), at least one compound selected from (ii) and at least one compound selected from (iii) are used for the polymerization of the ethylenically unsaturated monomer according to the present invention. As a method for preparing the catalyst component, (i) and (ii) are reacted in a nonpolar solvent such as toluene at, for example, -10 to + 10 ° C, and then stirred at room temperature or under heating, Further, there is a method in which (iii) is added, and the reaction product of (i) and (ii) is reacted with (iii) at -78 ° C to room temperature.

Preferred combinations of (i), (ii) and (iii) used for preparing such a catalyst component for the polymerization of ethylenically unsaturated monomers include, for example, those shown in Table 1 below.

[0101]

[Table 1]

At least one compound selected from (i), at least one compound selected from (ii),
The method for preparing the catalyst component for the polymerization of ethylenically unsaturated monomers according to the present invention from at least one compound selected from (iii) and at least one compound selected from (iv) includes, for example, a solvent such as toluene. ,
(I) in a non-polar solvent, for example at -10 to + 10 ° C
After reacting (ii) and (ii), (iv)
Is added, and the reaction product of (i) and (ii) is reacted with (iv), and then (iii) is further added and reacted.

As another method, after reacting (i) and (iv) at -100 to -50 ° C in a nonpolar solvent such as toluene, (ii) is added at -10 to + 10 ° C. ,
After the reaction product of (i) and (iv) is reacted with (ii), there is a method of further adding (iii) and reacting.

(I), (ii) and (ii) used for preparing such a catalyst component for the polymerization of ethylenically unsaturated monomers.
Preferred combinations of i) and (iv) include, for example, those shown in Table 2 below.

[0105]

[Table 2]

The catalyst component for the polymerization of ethylenically unsaturated monomers according to the present invention will be described more specifically. Aluminum (tribromide) is used as compound (i), water is used as compound (ii), and Using phenylchloromethane, lithium pentafluorobenzene as compound (iv), and (i) as (ii)
When 2 moles per mole, (iii) at 0.5 moles per 1 mole of (i), and (iv) at 3 moles per 1 mole of (i), the following reaction is obtained. It is assumed that the product is obtained.

[0107]

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As still another method, ethyl aluminum dichloride is used as compound (i) and compound (ii)
Is used, triphenylchloromethane is used as the compound (iii), lithium pentafluorobenzene is used as the compound (iv), (i) is 2 mol per 1 mol of (ii), and (iii) is ( i) 0.5 to 1 mole
It is presumed that the same reaction product as described above can be obtained by using 4 mol per mol of (iv) per 2 mol of (i).

[0109]

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The catalyst component for the polymerization of ethylenically unsaturated monomers according to another embodiment of the present invention is a compound represented by the following formula.

[0111]

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In the formula, M represents an atom belonging to Group 13 of the periodic table which may be the same or different from each other, and specific examples thereof include boron, aluminum, gallium and indium.
Particularly, boron and aluminum are preferable.

N is an integer of 0 or more, preferably 0 to
5, more preferably 0 to 3, and n = 0 is one of the most preferred embodiments. Y represents a divalent linking group, and when n is 1 or more, a plurality of Ys may be the same or different. Specific examples of the divalent linking group represented by Y include the following linking groups.

[0114]

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In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ represent R ⁴ , R ⁵ , R ⁶ ,
It is synonymous with R ⁷ , R ⁸ and R ⁹ . More specifically, as such a linking group,

[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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As Y, —O— or R ⁴ and R ⁵ in the above linking group is an alkyl group, a silicon-containing group, a boron-containing group,
A linking group that is an aromatic hydrocarbon group or a halogen-containing substituent is more preferred. Z is one or more M
A group capable of bonding to, specifically, halogen; hydrogen; an alkyl group having 1 to 20, preferably 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, and dodecyl; Methoxy, ethoxy,
It is one group selected from an alkoxy group having 1 to 20, preferably 1 to 10 carbon atoms, such as propoxy and butoxy, an acetyl group, a sulfate anion and the like. As Z,
Particularly, halogen is preferable.

J represents the valence of Z, and j = 1 is one of preferred embodiments. m represents the number of Z and is 1 or more and n +
It is an integer of 1 or less, preferably 1 to 6, preferably 1
-4.

Q may be the same or different,
One type selected from the following groups is shown.

[0130]

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In the formula, R ¹⁰ and R ¹¹ are the same as those of the aforementioned compound (iv)
Has the same meanings as R ¹⁰ and R ¹¹ . Specific examples of such a group represented by Q are shown below. Examples of the group represented by the general formula R ¹⁰ − include, for example,

[0132]

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Examples of the group represented by the general formula R ¹⁰ O— include, for example,

[0134]

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Examples of the group represented by the general formula R ¹⁰ R ¹¹ N- include, for example,

[0136]

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The group represented by the general formula R ¹⁰ COO— includes, for example,

[0138]

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Examples of the group represented by the general formula R ¹⁰ SO ₃ − include, for example,

[0140]

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Examples of the group represented by the general formula R ¹⁰ SO ₂ — include, for example,

[0142]

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Examples of the group represented by the general formula R ¹⁰ CO— include MeCO—, EtCO— and PhCO—.
And a group represented by the general formula R ¹⁰ R ¹¹ NO—

[0144]

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Examples of the group represented by the general formula R ¹⁰ R ¹¹ CNO— include, for example,

[0146]

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[0147]

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[0148]

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Examples of the group represented by the general formula R ¹⁰ COCH ₂ CO— include, for example,

[0150]

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[0151]

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It is preferable that at least one group represented by Q as described above is an aromatic hydrocarbon group having a substituent or a group containing fluorine in which R ¹⁰ in the above general formula is a substituent. , R ¹⁰ or R ¹¹ is also preferably a substituent which is a substituted aromatic hydrocarbon group or a fluorine-containing substituent.

Examples of the aromatic hydrocarbon group having a substituent include an aromatic group substituted by at least one substituent selected from an alkyl group, a halogenated alkyl group, an alkoxy group, and halogen (especially fluorine). And hydrocarbon groups.

Examples of the fluorine-containing substituent include substituents containing one or more fluorine atoms. Below, an example of the anion part represented by the following formula of the catalyst component for ethylenically unsaturated monomer polymerization according to the present invention represented by the above formula is shown.

[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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In the above examples, C ₆ F ₅ represents a pentafluorophenyl group, n-Oct represents an n-octyl group,
Ph represents a phenyl group, and Me represents a methyl group. A represents a cation, and the cation is not particularly limited. Examples thereof include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, a ferrocenium cation, and a group 1 or group 11 of the periodic table. One type of cation selected from the group consisting of metal cations is exemplified.

Examples of the cation represented by A include the following cations. [Li ⁺ ], [N
a ⁺ ], [K ⁺ ], [Ag ⁺ ], [Li (Et ₂ O) ₂ ⁺ ],
[Ph ₃ C ⁺ ], [KBEt ₃ ⁺ ], [NaAlH (OCH
^{_{2 CH 2 OCH 3) 2 +}} ], [H 3 O +], [Ph 4 P +],
[PhNMe ₂ H ⁺ ], [Et ₃ NH ⁺ ], [Me ₃ N
H ⁺ ], [(n-Bu) ₃ NH ⁺ ], [MePh ₂ NH ⁺ ],
[Cp ₂ Fe ⁺ ],

[0167]

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K represents the valence of the A cation, and k = jm /
r. Hereinafter, an example of the catalyst component for ethylenically unsaturated monomer polymerization according to the present invention represented by the above formula will be shown.

[0169]

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The catalyst component for ethylenically unsaturated monomer polymerization according to the present invention represented by the above formula includes, for example, the compound (i) and the compound (ii), and if necessary, the compound (iv).
And further reacted with the above compound (iii).

The catalyst component for the polymerization of ethylenically unsaturated monomers according to the present invention can be used as a catalyst for the polymerization of ethylenically unsaturated monomers having excellent polymerization activity when used in combination with a transition metal compound described below. The catalyst component for the polymerization of ethylenically unsaturated monomers according to the present invention becomes a catalyst for the polymerization of ethylenically unsaturated monomers having excellent polymerization activity even when used in combination with any of the transition metal compounds described below.

The catalyst component for the polymerization of ethylenically unsaturated monomers according to the present invention has a high polymerization activity even when added in a small amount. Further, it is easily dissolved in a solvent, is easy to handle, and easily exhibits activity. From the catalyst component of the present invention, a high molecular weight polymer can be easily obtained.

Catalyst for Polymerization The catalyst for polymerizing an ethylenically unsaturated monomer of the present invention comprises: (A) a compound selected from transition metals of Groups 3 to 12; (B) the catalyst component described above; It consists of an organic compound containing a group atom.

(A) Selected from Group 3 to Group 12
The transition metal compound (A) used in the present invention is, for example, a transition metal compound represented by any of the following general formulas (I) to (VIII). Is mentioned.

First, the compound represented by formula (I) will be described. M ¹ L ¹ _x (I) In the formula, M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, and preferably zirconium.

X is a transition metal atom M¹The valence of
Transfer metal atom M¹L coordinated to ¹Indicates the number of L
¹Represents a ligand coordinated to a transition metal atom, and at least
One L¹Is a ligand having a cyclopentadienyl skeleton
Other than a ligand having a cyclopentadienyl skeleton
L¹Is a hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group having 1 to 20 atoms, an oxygen-containing group,
Ow-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups,
It is a halogen atom or a hydrogen atom.

Examples of the ligand having a cyclopentadienyl skeleton include, for example, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a (halogenated) hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom, or the like.

When the compound represented by the above general formula (I) contains two or more ligands having a cyclopentadienyl skeleton, two of the ligands having a cyclopentadienyl skeleton are connected to each other. , (Substituted) alkylene group, (substituted) silylene group and the like. Such a transition metal compound in which a ligand having a cyclopentadienyl skeleton is bonded via a divalent bonding group is represented by the following general formula (II) or (IIa). Transition metal compounds.

Specific examples of the ligand L ¹ other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group,
An arylalkyl group, an aryl group, and the like; more specifically, an alkyl group such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; a cycloalkyl such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl Alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl,
And aryl groups such as anthryl and phenanthryl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. A hydroxy group as the oxygen-containing group; methoxy, ethoxy, propoxy,
Alkoxy groups such as butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and arylalkoxy groups such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing group include a substituent in which oxygen of the above-mentioned oxygen-containing group is substituted by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, and p-toluene sulfonate. , Trimethylbenzenesulfonate,
Sulfonate groups such as triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzene Sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

Examples of the nitrogen-containing group include an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; phenylamino, diphenylamino,
Examples thereof include an arylamino group such as ditolylamino, dinaphthylamino, and methylphenylamino, or an alkylarylamino group.

Examples of the phosphorus-containing group include phosphino groups such as dimethylphosphino and diphenylphosphino. Examples of the silicon-containing group include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, and dimethylphenylsilyl , Methyldiphenylsilyl, tritolylsilyl, trinaphthylsilyl and other trihydrocarbon-substituted silyls; hydrocarbon-substituted silyl silyl ethers such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylphenyl Is mentioned.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Such transition metal compounds are, for example, those having a transition metal valence of 4
Is more specifically represented by the following general formula (I ′).

R ¹² R ¹³ R ¹⁴ R ¹⁵ M ¹ (I ′) In the formula, M ¹ represents a transition metal atom selected from Group 4 of the periodic table as described above, and is preferably a zirconium atom.

R ¹² represents a group (ligand) having a cyclopentadienyl skeleton. R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different from each other, and represent a group having a cyclopentadienyl skeleton. (Ligand) represents a (halogenated) hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a halogen atom or a hydrogen atom.

In the present invention, in the transition metal compound represented by the general formula (I ′), at least one of R ¹³ , R ¹⁴ and R ¹⁵ is a group (ligand) having a cyclopentadienyl skeleton. Compounds, for example, compounds in which R ¹² and R ¹³ are groups (ligands) having a cyclopentadienyl skeleton are preferably used. When R ¹² and R ¹³ are a group (ligand) having a cyclopentadienyl skeleton, R ¹⁴ and R ¹⁵ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an alkenyl group,
It is preferably an arylalkyl group, an aryl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a sulfonate group, a halogen atom or a hydrogen atom.

Hereinafter, M ¹ is represented by the general formula (I).
Specific examples of the transition metal compound in which is zirconium are shown. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentane Dienyl) zirconium phenoxymonochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium Dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (octylcyclopentadienyl)
Zirconium dichloride, bis (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadi (Enyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxychloride, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p -Toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate) Nato), bis (ethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (propylcyclopentadienyl)
Zirconium bis (trifluoromethanesulfonate),
Bis (butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (hexylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate) , Bis (methylethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylpropylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylbutylcyclopentadienyl) zirconium bis (trifluoro Methanesulfonato), bis (dimethylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (methyl Tylcyclopentadienyl) zirconium dichloride, bis (methylhexylcyclopentadienyl) zirconium dichloride, bis (ethylbutylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopenta Dienyl)
Zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylbenzylcyclopentadienyl) zirconium dichloride, bis (ethylhexylcyclopentadienyl) zirconium dichloride, bis (methylcyclohexylcyclopentadienyl) zirconium dichloride, Bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl)
Phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl zirconium monochloride, bis (cyclopentadienyl) methyl zirconium monohydride, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) dibenzyl zirconium, Bis (indenyl) zirconium bis (p-toluenesulfonato), bis (dimethylcyclopentadienyl) zirconium ethoxychloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (Methylbutylcyclopentadienyl) zirconium bis (methanesulfonate), bis (trimethylsilylcyclopentadienyl) zirconium dichloride, etc.

In the above examples, disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituted, and tri-substituted is 1,2,3- and 1,2,4 -Including substitutions. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert
-Including isomers.

Further, in the above-mentioned zirconium compounds, compounds in which zirconium is replaced by titanium or hafnium can also be mentioned. Examples of the transition metal compound in which a ligand having two cyclopentadienyl skeletons are bonded via a divalent bonding group include a compound represented by the following general formula (II).

[0191]

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In the formula, M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, preferably zirconium.
R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different from each other, and include a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, and silicon-containing. Group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, phosphorus-containing group, hydrogen atom or halogen atom. R ¹⁶ ,
Among the groups represented by R ¹⁷ , R ¹⁸ and R ¹⁹ , some of the groups adjacent to each other may be bonded to form a ring together with the carbon atom to which those groups are bonded. Note that R ¹⁶ , R ¹⁷ ,
Although R ¹⁸ and R ¹⁹ are respectively shown at two places, for example, R ¹⁶ and R ¹⁶ may be the same group or different groups. Of the groups represented by R, those having the same suffix represent a preferred combination when forming a ring by inheriting them.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include the same groups as L in the above formula (I).
As a ring formed by combining these hydrocarbon groups, a benzene ring, a naphthalene ring, an acenaphthene ring, a condensed ring such as an indene ring, and a hydrogen atom on the condensed ring is methyl,
Examples include groups substituted with an alkyl group such as ethyl, propyl, and butyl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Silicon-containing groups,
Examples of the oxygen-containing group, the nitrogen-containing group, and the phosphorus-containing group include the same groups as L in the general formula (I).

Examples of the sulfur-containing group include substituents in which oxygen of the above-mentioned oxygen-containing group has been replaced by sulfur. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Of these, a hydrocarbon group having 1 to 20 carbon atoms is preferable, and in particular, a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl, and a hydrocarbon group are bonded. A hydrogen atom on the benzene ring formed by bonding a benzene ring and a hydrocarbon group formed by methyl, ethyl, n-propyl, iso-propyl, n-butyl, is
It is preferably a group substituted with an alkyl group such as o-butyl and tert-butyl.

X ¹ and X ² may be the same or different from each other and include a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group,
It represents a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom, and specific examples include the same groups or atoms as L in the aforementioned general formula (I).

Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferable.

Y¹Is a divalent carbon having 1 to 20 carbon atoms
Hydrogenated group, divalent halogenated carbon having 1 to 20 carbon atoms
Hydride group, divalent silicon-containing group, divalent germanium-containing
Group, divalent tin-containing group, -O-, -CO-, -S-,
-SO-, -SO_Two-, -Ge-, -Sn-, -NR²⁰
-, -P (R²⁰)-, -P (O) (R²⁰)-, -BR ²⁰
-Or -AlR²⁰-[However, R²⁰Are identical to each other
May also be different, and hydrocarbons having 1 to 20 carbon atoms
Elemental group, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
A hydrogen atom or a halogen atom].

As the divalent hydrocarbon group having 1 to 20 carbon atoms, specifically, methylene, dimethylmethylene, 1,2-
Ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-
Alkylene groups such as cyclohexylene; arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene;

Specific examples of the divalent halogenated hydrocarbon group having 1 to 20 carbon atoms include groups obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene. Is mentioned.

Examples of the divalent silicon-containing group include silylene,
Methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p- Alkylsilylene groups such as chlorophenyl) silylene; alkylarylsilylene groups; arylsilylene groups; alkyldisilylene groups such as tetramethyl-1,2-disilylene and tetraphenyl-1,2-disilylene; alkylaryldisilylene groups; And a silylene group.

Examples of the divalent germanium-containing group include groups in which silicon of the above-mentioned divalent silicon-containing group is substituted with germanium. Examples of the divalent tin-containing group include a group in which silicon of the divalent silicon-containing group is substituted with tin.

Of these, substituted silylene groups such as dimethylsilylene, diphenylsilylene and methylphenylsilylene are particularly preferred. Further, R ²⁰ has the same halogen atom and carbon number as 1 to L in the general formula (I).
And 20 halogenated hydrocarbon groups having 1 to 20 carbon atoms.

The following are specific examples of the transition metal compound represented by the general formula (II). Ethylene-bis (indenyl) dimethyl zirconium, ethylene-bis (indenyl) zirconium dichloride, ethylene-bis (indenyl) zirconium bis (trifluoromethanesulfonate), ethylene-bis (indenyl) zirconium bis (methanesulfonate), ethylene
-Bis (indenyl) zirconium bis (p-toluenesulfonate), ethylene-bis (indenyl) zirconium bis (p-chlorobenzenesulfonato), ethylene-bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride , Isopropylidene (cyclopentadienyl)
(Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene
-Bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene-bis (trimethylcyclopentadienyl) Zirconium dichloride, dimethylsilylene-bis (indenyl) zirconium dichloride, dimethylsilylene-bis (indenyl) zirconiumbis (trifluoromethanesulfonato), dimethylsilylene
-Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilylene-bis (indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) Zirconium dichloride, rac-dimethylsilylene-bis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethylcyclopentadienyl) zirconium dichloride, rac-dimethyl Silylene-bis (2-methyl-4-tert-butylcyclopentadienyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (3-
tert-butylcyclopentadienyl) (indenyl) zirconium dichloride, isopropylidene (4-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene (4-tert-butylcyclopentadienyl) (3 -Methylindenyl) zirconium dichloride, isopropylidene (4-tert-butylcyclopentadienyl) (3-tert-butylindenyl) zirconium dichloride, dimethylsilylene (4-methylcyclopentadienyl) (3-methylindenyl ) Zirconium dichloride, dimethylsilylene (4-tert-butylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, dimethylsilylene (4-tert-butylcyclopentadienyl) (3-tert-butylindenyl) zirconium Dichloride, dimethylsilylene (3-ter t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride; isopropylidene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride;

Further, there may be mentioned compounds in which zirconium in the above compounds is replaced with titanium or hafnium. Other specific examples of the transition metal compound represented by the general formula (II) include the following general formula (I
There is a transition metal compound represented by I ′) or (II ″).

[0207]

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In the formula, M ¹ represents a transition metal atom belonging to Group 4 of the periodic table, specifically, titanium, zirconium or hafnium, and preferably zirconium. R
²¹ may be the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms, and specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl Alkyl groups such as tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl;
And alkenyl groups such as vinyl and propenyl.

Among these, a primary alkyl group having carbon atoms bonded to the indenyl group is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are particularly preferable.

R ²² , R ²⁴ , R ²⁵ and R ²⁶ may be the same or different and represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms similar to R ²¹ . R ²³ may be the same or different, and represent a hydrogen atom or an aryl group having 6 to 16 carbon atoms;
Specifically, phenyl, α-naphthyl, β-naphthyl, anthryl, phenanthryl, pyrenyl, acenaphthyl,
Examples include phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Of these, phenyl, naphthyl, anthryl and phenanthryl are preferred.

These aryl groups include a halogen atom such as fluorine, chlorine, bromine and iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl,
Alkyl groups such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl and ethylphenyl , Propylphenyl, biphenyl,
α- or β-naphthyl, methylnaphthyl, anthryl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and other hydrocarbon groups having 1 to 20 carbon atoms. It may be substituted by an organic silyl group such as trimethylsilyl, triethylsilyl and triphenylsilyl.

[0212] X ¹ and X ² may be the same or different from each other, X ¹ and X in the general formula (II)
Same as ² . Among these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable.

[0213] Y ¹ is in the formula (II), Y ¹
Is the same as Of these, divalent silicon-containing groups, 2
It is preferably a divalent germanium-containing group, more preferably a divalent silicon-containing group, and more preferably an alkylsilylene, an alkylarylsilylene or an arylsilylene.

Specific examples of the transition metal compound represented by the above general formula (II ') are shown below. rac-dimethylsilylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2
-Methyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛ 1- (2-methyl-
4- (1-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (2
-Anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (9-
Anthryl) indenyl)｝ zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (pentafluorophenyl) indenyl) )｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-
4- (p-chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-
4- (m-chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-
4- (o-chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-
4- (o, p-dichlorophenyl) phenylindenyl) zirconium dichloride, rac-dimethylsilylene-bis
-(2-methyl-4- (p-bromophenyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-methyl-4- (p-tolyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (m-tolyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene -Bis ｛1- (2-methyl-4- (o
-Tolyl) indenyl) zirconium dichloride, rac
-Dimethylsilylene-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p -
Ethylphenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (pi
-Propylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4-
(p-benzylphenyl) indenyl) ニ ル zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-
4- (p-biphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (m
-Biphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (p-
Trimethylsilylenephenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
Methyl-4- (m-trimethylsilylenephenyl) indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-phenyl-4-phenylindenyl)} zirconium dichloride, rac-diethylsilylene-bis ｛1-
(2-methyl-4-phenylindenyl) zirconium dichloride, rac-di- (i-propyl) silylene-bis ｛1- (2
-Methyl-4-phenylindenyl) zirconium dichloride, rac-di- (n-butyl) silylene-bis {1- (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dicyclohexylsilylene-bis} 1- (2-methyl-4-phenylindenyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-methyl-
4-phenylindenyl) zirconium dichloride, ra
c-diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} Zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-methyl-4-phenylindenyl) )｝ Zirconium dichloride, rac-ethylene-bis ｛1- (2-methyl-4-
Phenylindenyl) zirconium dichloride, rac-
Dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylstannylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac- Dimethylsilylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dibromide, rac-dimethylsilylene-bis {1- (2
-Methyl-4-phenylindenyl) zirconium dimethyl, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium methyl chloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ Me,

Rac-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride O
SO ₂ Me, rac-dimethylsilylene-bis {1- (2-ethyl)
-4-phenylindenyl)｝ zirconium dichloride, r
ac-dimethylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (β-naphthyl) indenyl) ｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (2-methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-ethyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (9-anthryl) indenyl)} zirconium Dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (o-methylphenyl) ) Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (m-methylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4) -(P-methylphenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-ethyl-4- (2,4-dimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,5-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,
4,6-trimethylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (o-chlorophenyl) indenyl) デ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (m-chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (p-chlorophenyl) indenyl) デ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (2,3-dichlorophenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,6-dichlorophenyl) indenyl)} zirconium dichloride,

Rac-Dimethylsilylene-bis {1- (2-ethyl)
-4- (3,5-dichlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (2-bromophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (3-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-biphenylyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-trimethylsilylphenyl) indenyl) )｝
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-
Propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
n-propyl-4- (5-acenaphthyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis
(2-n-propyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-n-propyl-4- (9-phenanthryl) indenyl)｝
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-
Propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4- (8-methyl-9-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
i-propyl-4- (5-acenaphthyl) indenyl) デ zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-i-propyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-i-propyl-4- (9-phenanthryl) indenyl)｝
Zirconium dichloride,

Rac-Dimethylsilylene-bis {1- (2-s-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4-)
(Α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4-
(Β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4- (2
-Methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4)
-(5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4)
-(9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4-
(9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-pentyl)
-4-phenylindenyl)｝ zirconium dichloride, r
ac-dimethylsilylene-bis ｛1- (2-n-pentyl-4- (α-
Naphthyl) indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-n-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (α-naphthyl) indenyl) )｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-butyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (5- Acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-butyl-4- (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n -Butyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4-phenylindenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis
-(2-i-butyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-
i-butyl-4- (2-methyl-1-naphthyl) indenyl) zirconium dichloride,

Rac-Dimethylsilylene-bis {1- (2-i-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4-) (9-anthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-butyl
-4- (9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-neopentyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2- Neopentyl
-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-hexyl-4
-Phenylindenyl) zirconium dichloride, rac
-Dimethylsilylene-bis {1- (2-n-hexyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-
Methylphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride , Rac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-anthryl) indenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) ) Indenyl) zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride , Rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-anthryl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl )｝ Zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2-ethyl-4- (4-biphenylyl) indenyl)｝ zirconium dichloride, rac-methylene-
Bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4-)
(Α-naphthyl) indenyl)｝ zirconium dichloride, rac-ethylene-bis ｛1- (2-ethyl-4-phenylindenyl)｝ zirconium dichloride, rac-ethylene-bis ｛1- (2-ethyl-4- ( α-naphthyl) indenyl)｝ zirconium dichloride, rac-ethylene-bis ｛1- (2-n-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylgermyl-bis ｛1- (2 -ethyl
-4-phenylindenyl)｝ zirconium dichloride, r
ac-dimethylgermyl-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (2-n-propyl-4-phenylindenyl) )｝ Zirconium dichloride and the like.

Further, there may be mentioned compounds in which zirconium in the above compounds is replaced with titanium or hafnium. Next, the transition metal compound represented by the general formula (II ″) will be described.

[0220]

Embedded image

In the formula, M ¹ represents a transition metal atom of Group 4 of the periodic table, specifically, titanium, zirconium or hafnium, and preferably zirconium. R
³¹ and R ³² may be the same or different from each other,
Hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms
20 represents a halogenated hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a hydrogen atom or a halogen atom, and specifically, L in the general formula (I) And the same atoms or groups as mentioned above.

Among these, R ³¹ has 1 to 2 carbon atoms.
It is preferably a hydrocarbon group of 0, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms of methyl, ethyl and propyl.

R ³² has a hydrogen atom or a carbon atom number of 1 to
The hydrocarbon group is preferably 20 hydrocarbon groups, and particularly preferably a hydrogen atom or methyl, ethyl or propyl having 1 carbon atom.
It is preferably from 3 to 3 hydrocarbon groups.

R ³³ and R ³⁴ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms, and specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl and the like.

Among them, R ³³ is preferably a secondary or tertiary alkyl group. X ¹ and X ² may be the same or different from each other, are the same as X ¹ and X ² in the general formula (II).

[0226] Y ¹ is in the formula (II), Y ¹
Is the same as Hereinafter, specific examples of the transition metal compound represented by the general formula (II ″) will be shown. rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1
-(2,7-dimethyl-4-n-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7
-Dimethyl-4-i-propylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-butylindenyl) zirconium dichloride, rac-dimethylsilylene-bis} 1- (2,7-dimethyl-4-
sec-butylindenyl) zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-pentylindene) Nil)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-n-hexylindenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl) )｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-) Trimethylsiloxymethylindenyl) zirconium dichloride, ra
c-Diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl) silylene-bis {1- (2,7-dimethyl-4) -i-
Propylindenyl) zirconium dichloride, rac-
Di (n-butyl) silylene-bis {1- (2,7-dimethyl-4-i-
Propylindenyl) zirconium dichloride, rac-
Di (cyclohexyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-i- Propylindenyl) zirconium dichloride,

Rac-Methylphenylsilylene-bis ｛1-
(2,7-dimethyl-4-t-butylindenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2,7
-Dimethyl-4-t-butylindenyl) zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl) zirconium dichloride, rac-diphenylsilylene-bis} 1- (2,7-dimethyl-4-ethylindenyl) zirconium dichloride, r
ac-di (p-tolyl) silylene-bis {1- (2,7-dimethyl-4)
-i-propylindenyl) zirconium dichloride, r
ac-di (p-chlorophenyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-)
i-propyl-7-ethylindenyl) zirconium dibromide, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-ethylindenyl) zirconium dichloride, rac-dimethylsilylene-bis} 1- (2,3,7-trimethyl-4-n-propylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl -4-sec-butylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-t-butylindenyl) zirconium dichloride, rac-dimethylsilylene-bis} 1- (2,3,7-trimethyl-4-n-pentylindenyl) Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl 4-cyclohexylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-methylcyclohexylindenyl) zirconium dichloride, rac-dimethylsilylene-bis
(2,3,7-trimethyl-4-trimethylsilylmethylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,3,7-trimethyl-4-trimethylsiloxymethylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-phenylethylindenyl)} zirconium dichloride,

Rac-Dimethylsilylene-bis {1- (2,3,7-
Trimethyl-4-phenyldichloromethylindenyl)｝
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-diethylsilylene
-Bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl)
Silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (n-butyl) silylene-bis {1- (2,3,7-trimethyl- 4-i-propylindenyl)｝ zirconium dichloride, rac-di (cyclohexyl) silylene-bis ｛1- (2,3,7-trimethyl-
4-i-propylindenyl) zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl) zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl) zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-i-propylindenyl) zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7)
-Trimethyl-4-ethylindenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis ｛1- (2,3,7
-Trimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis ｛1- (2,3,7-trimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl, rac-dimethylsilylene-
Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium methyl chloride, rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindene) Nil) zirconium-bis (methanesulfonato), r
ac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium-bis (p-phenylsulfinato), rac-dimethylsilylene-bis {1-
(2-methyl-3-methyl-4-i-propyl-7-methylindenyl) zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4,6-di-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-phenyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methylindenyl)} zirconium dichloride, rac-ethylene- Bis {1- (2,4,7-trimethylindenyl)} zirconium dichloride, rac-isopropylidene-bis {1- (2,4,7-trimethylindenyl)}
Zirconium dichloride and the like.

Further, there may be mentioned compounds in which zirconium in the above compounds is replaced with titanium or hafnium. Another example of a transition metal compound in which a ligand having two cyclopentadienyl skeletons is bonded via a divalent bonding group is, for example, the following general formula (IIa):
The compound represented by these is mentioned.

[0230]

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In the formula, M Represents a transition metal atom selected from Groups 3 to 6 of the periodic table. Y ² represents a carbon atom, a silicon atom or a germanium atom. R ¹ and R ² are
May be the same or different from each other, a hydrogen atom, a group having 1 to 40 carbon atoms, an OH group, a halogen atom, or
NR ¹⁵ ₂ group (wherein, R ¹⁵ is a halogen atom, carbon atoms alkyl group or a number of carbon atoms of 1 to 10 is an aryl group having 6 to 10.) Or a, or, R ¹ and R
² together with the atoms connecting them form a ring. Examples of the group having 1 to 40 carbon atoms include an alkyl group having 1 to 10 carbon atoms and 1 to 1 carbon atoms.
0 alkoxy group, aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 25 carbon atoms, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms or An arylalkenyl group having 7 to 40 carbon atoms is exemplified.

R^Three, R^Four, R^Five, R⁶, R⁷, R⁸And
And R⁹May be the same or different from each other,
, A halogen atom, a group having 1 to 40 carbon atoms, -Si
R¹⁵ _ThreeGroup, -NR¹⁵ _TwoGroup or -PR¹⁵ _TwoGroup (however, R
¹⁵May be the same or different from each other,
, An alkyl group having 1 to 10 carbon atoms or carbon atom
Is an aryl group having 6 to 10 atoms or forms a ring
are doing. ) Or R^Three, R^Four, R^Five, R
⁶, R⁷, R⁸And R⁹Two or more adjacent to each other
The above groups together with the atoms connecting them, preferably 4
Contains from 40 to 40, particularly preferably from 6 to 20, carbon atoms
To form a ring. A group having 1 to 40 carbon atoms
Is, for example, an optionally halogenated carbon source
An alkyl group having 1 to 10 children, even if halogenated
Aryl group having good carbon number of 6 to 30, carbon number is good
6-20 aryloxy groups, having 2-12 carbon atoms
Alkenyl group, arylalkyl having 7 to 40 carbon atoms
Group, an alkylaryl group having 7 to 40 carbon atoms or
Is an arylalkenyl group having 8 to 40 carbon atoms.
It is.

R ¹⁰ has a hydrogen atom or a carbon atom number of 1 to 1.
Or R ¹⁰ is a group of R ³ , R ⁴ , R
⁵ and to one or more of R ⁶ . Examples of the group having 1 to 40 carbon atoms include a group having 1 to 2 carbon atoms.
An alkyl group having 0, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an arylalkyl group having a carbon number of 7 to 40, an alkylaryl group or the number of carbon atoms of carbon atoms 7-40 can be mentioned arylalkenyl group of 8 to 40, these groups, -NR ¹⁵ ₂ group, -SiR ¹⁵ ₃ groups,
-SR ¹⁵ ₂ group, -OSiR ¹⁵ ₃ group (wherein, R ¹⁵ is a halogen atom, an alkyl group or a number of carbon atoms of the carbon atoms 1 to 10 an aryl group having 6 to 10.) Substituents such as May be provided.

R ¹¹ and R ¹² may be the same or different and represent a hydrogen atom or a group having 1 to 40 carbon atoms. Examples of the group having 1 to 40 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon atom. An alkenyl group having 2 to 12 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms or 8 to
It includes arylalkenyl groups 40, these groups, a halogen atom, -NR ¹⁵ ₂ group, -SiR ¹⁵ ₃ group, -
A substituent such as an SR ¹⁵ group or an —OSiR ¹⁵ ₃ group (where R ¹⁵ is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms); May be.

R ¹³ and R ¹⁴ may be the same or different and represent a hydrogen atom or a group having 1 to 40 carbon atoms. Examples of the group having 1 to 40 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon atom number. Is an alkenyl group having 2 to 12 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and 7 carbon atoms.
-40 alkylaryl groups or 8-4 carbon atoms
And an arylalkenyl group of 0. These groups include, for example, a halogen _{^{atom, -NR 15 2, -SR 15,}} -S
¹⁵ _3, -OSiR ¹⁵ ₃ (wherein, R ¹⁵ is a halogen atom, an alkyl group or a number of carbon atoms of the carbon atoms 1 to 10 is an aryl group of 6 to 10.) iR have a substituent such as May be.

Note that Y ² is a carbon atom and R ¹⁰ and R ¹³
And when R ¹⁴ is a methyl group, R ³ , R ⁵ , R
^6, unlike at least one hydrogen atom of R ⁷ and R ^9, and / or, R ⁸ is a hydrogen atom.

In the transition metal compound represented by the general formula (IIa), M is a metal atom of Group 4 of the periodic table, for example, titanium, zirconium or hafnium, preferably zirconium, and R ¹ and R ² are identical to each other, the number of carbon atoms is from 1 to 4 alkyl group or a halogen atom (e.g., fluorine, chlorine, bromine or iodine, preferably chlorine) ^{there, R 3, R 4, R} 5, R 6, R ⁷ , R
⁸ and R ⁹ may be the same or different from each other,
A hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 24 carbon atoms, or R
³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹
Two or more groups adjacent to each other, together with the atoms connecting them, form an aromatic or aliphatic ring having 4 to 20 carbon atoms, wherein R ¹⁰ is hydrogen, 6 carbon atoms.
An aryl group having from 24 to 24 or an alkyl group having from 1 to 10 carbon atoms (preferably an alkyl group having from 1 to 4 carbon atoms), Y ² is a carbon atom, and R ¹¹ and R ¹²
May be the same or different from each other, and R ¹¹ represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 4 carbon atoms or 6 to R ¹² is a hydrogen atom, R ¹³ and R ¹⁴ may be the same or different from each other, and represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably , the number of carbon atoms is an alkyl group or number of carbon atoms of 1 to 4 aryl group 6 to 10), R ^3, R
Preferably, a transition metal compound in which at least one of ⁵ , R ⁶ , R ⁷ and R ⁹ is different from hydrogen and / or R ⁸ is hydrogen, M is zirconium, R ¹
And R ² are the same as each other and are a halogen atom, preferably chlorine, and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁹ may be the same or different from each other, and represent a hydrogen atom or An alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl or isobutyl), an aryl group having 6 to 14 carbon atoms (for example, phenyl or naphthyl), or
R ³ and R ⁴ and / or R ⁵ and R ⁶ are
Together with the atoms connecting them, they form an aromatic hydrocarbon ring having 4 to 20 carbon atoms, preferably a 6-membered ring which may be substituted, wherein R ⁸ is hydrogen and Y ²
Is a carbon atom, R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (particularly, methyl) or an aryl group having 6 to 10 carbon atoms (particularly, phenyl);
¹¹ and R ¹² are the same as each other, are a hydrogen atom,
R ¹³ and R ¹⁴ may be the same or different from each other, and a transition metal compound which is a methyl or phenyl group is particularly preferred.

Specific examples of the transition metal compound represented by the formula (IIa) are shown below. {Four-
(Η ⁵ -cyclopentadienyl) (η ⁵ -4,5-tetrahydropentalene)｝ dichlorotitanium, {4- (η ⁵ -cyclopentadienyl) (η ⁵ -4,5-tetrahydropentalene)｝ dichlorozirconium, {4- (η ⁵ - cyclopentadienyl) (eta ^{5-4,5-tetrahydropentalene)}} dichloro hafnium, {4- (η ⁵ - cyclopentadienyl) -4-methyl - (eta ⁵ -4,5-tetrahydropentalene)} dichlorozirconium, {4- (eta ⁵ - cyclopentadienyl) -4-ethyl - (eta ^{5-4,5-tetrahydropentalene)}} dichlorozirconium, {4- (Η ⁵ -cyclopentadienyl) -4-
Phenyl- (η ⁵ -4,5-tetrahydropentalene) dichlorozirconium and the like.

In the present invention, a compound represented by the following general formula (III) can be used as the transition metal compound (A).

[0240] L in _{^{2 M 2 X 3 2 ... (}} III) formula, M ² represents a periodic table group IV transition metal atom. L ²
Is a derivative of a delocalized π-bonded group, imparts a constrained geometry to the metal M ² active site, and X ³ may be the same or different from each other, and represent a hydrogen atom, a halogen atom,
A hydrocarbon group containing not more than 20 carbon atoms, a silyl group containing not more than 20 silicon atoms, or a germyl group containing not more than 20 germanium atoms.

Among the compounds represented by the general formula (III), a compound represented by the following general formula (III ′) is preferable.

[0242]

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In the formula, M ² represents a transition metal atom of Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, and preferably zirconium. Cp is
A cyclopentadienyl group bonded to M ² by a π bond or a derivative thereof is shown.

[0244] Z represents an oxygen atom, a ligand containing a sulfur atom, a boron atom or the periodic table Group 14 atoms, for example, _{^{-Si (R 35 2) -,}} - C (R 35 2) -, - Si (R
^{_{35 2) Si (R 35 2}} ) -, - C (R 35 2) C (R 35 2) -,
_{^{-C (R 35 2) C (}} R 35 2) C (R 35 2) -, - C
^{(R 35) = C (R} 35) -, - C (R 35 2) Si (R 35 2)
_{^{-, - Ge (R 35 2}} ) - , and the like.

Y ² represents a ligand containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, for example, —N (R
³⁶ )-, -O-, ^-S- , -P ( ^R36 )-and the like.
Z and Y ² may form a condensed ring.

R ³⁵ is a group selected from a hydrogen atom or an alkyl group having up to 20 non-hydrogen atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group and combinations thereof. ³⁶ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, or one or more R ³⁵ and 30 And condensed ring systems of up to non-hydrogen atoms.

Specific examples of the transition metal compound represented by the general formula (III) are shown below.

(Tert-butylamide) (tetramethyl-η
^Five-Cyclopentadienyl) -1,2-ethanediylzirconi
Um dichloride, (tert-butylamide) (tetramethyl
Le-η ^Five-Cyclopentadienyl) -1,2-ethanediyl tita
Dichloride, (methylamide) (tetramethyl-η^Five-
Cyclopentadienyl) -1,2-ethanediylzirconium
Mudichloride, (methylamide) (tetramethyl-η^Five-
Cyclopentadienyl) -1,2-ethanediyl titanium
Loride, (ethylamide) (tetramethyl-η^Five-Cyclo
Pentadienyl) -methylene titanium dichloride, (tert-
Butylamido) dimethyl (tetramethyl-η^Five-Cyclope
(Antadenyl) silane titanium dichloride, (tert-butyl)
Lumido) dimethyl (tetramethyl-η^Five-Cyclopenta
Dienyl) silane zirconium dichloride, (benzyl
Amido) dimethyl- (tetramethyl-η^Five-Cyclopentadi
(Enyl) silane titanium dichloride, (phenylphosphine)
Do) dimethyl (tetramethyl-η^Five-Cyclopentadieni
Le) silane zirconium dibenzyl and the like.

Next, the compound represented by formula (IV) will be described. Compounds of the general formula (IV) are listed in the Periodic Tables 8 to 1
It is a Group 0 transition metal compound.

[0250]

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In the formula, M ³ represents a transition metal atom belonging to Groups 8 to 10 of the periodic table, and is preferably nickel, palladium or platinum. X ⁴ and X ⁵ may be the same or different and represent a nitrogen atom or a phosphorus atom.

R ⁴¹ and R ⁴² may be the same or different and each represents a hydrogen atom or a hydrocarbon group. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
a linear or branched alkyl group having 1 to 20 carbon atoms such as a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group; an aryl group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group A group having 1 to 5 substituents such as an alkyl group having 1 to 20 carbon atoms.
And a monosubstituted substituted aryl group.

M and n may be the same or different from each other, and are 1 or 2 and satisfy the valences of X ⁴ and X ⁵ respectively. R ⁴³ is

[0254]

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FIG. However, R ⁵⁰ , R ⁵⁵ , R ⁵¹ ,
R ⁵² , R ⁵⁶ and R ⁵⁷ may be the same or different from each other, and represent a hydrogen atom or the same hydrocarbon group as R ⁴¹ and R ⁴² .

The aforementioned R ⁴¹ , R ⁴² , R ⁵⁰ (or R ⁵¹ ,
R ⁵² ) and R ⁵⁵ (or R ⁵⁶ , R ⁵⁷ ) may form a ring by linking two or more of them, preferably adjacent groups, to each other.

R ⁴⁴ and R ⁴⁵ may be the same or different and represent a hydrogen atom, a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

Specific examples of the hydrocarbon group include those having the same number of carbon atoms as the aforementioned R ⁴¹ and R ^{42, such} as an alkyl group having 1 to 20 carbon atoms and an aryl group and a benzyl group having 6 to 20 carbon atoms. And 7 to 20 aralkyl groups. One or more substituents such as the alkyl group having 1 to 20 carbon atoms may be substituted on the aryl group and the aralkyl group.

Further, as R ⁴⁴ and R ⁴⁵ , —OR ⁴⁶ ,
-SR ^47, a group represented by -N (R ⁴⁸⁾ ₂ or -P (R ⁴⁹⁾ ₂ is also shown. R ^{46 to} R ⁴⁹ are the same as those of R ⁴¹ and R ⁴²
Cycloalkyl groups having 6 to 20 carbon atoms such as alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and cyclohexyl groups; and 7 to 20 carbon atoms such as benzyl groups. 20 aralkyl group; represents an organic silyl group such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, and a triethylsilyl group. The aryl group and the aralkyl group may be substituted with one or more substituents such as the alkyl group having 1 to 20 carbon atoms. And R
^{48 and} R ⁴⁹ may be connected to each other to form a ring.

R ⁴⁴ and R ⁴⁵ may be linked to each other to form a ring. As the transition metal compound represented by the general formula (IV), a compound represented by the following general formula (IV ′) is preferable.

[0261]

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(Wherein, M ³ , X ⁴ , X ⁵ , R ⁴¹ , R ⁴² ,
R ⁴⁴ , R ⁴⁵ , R ⁵⁰ and R ⁵⁵ are the same as in the above formula (IV). Specific examples of the transition metal compound represented by the general formula (IV ′) include the following compounds.
In the following formula, iPr represents an isopropyl group.

[0263]

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[0264]

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[0265]

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[0266]

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[0267]

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[0268]

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[0269]

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[0270]

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[0271]

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[0272]

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Other than the above, examples of the transition metal compound represented by the general formula (IV ′) include compounds in which palladium or nickel in the above compounds is replaced by platinum.

The compounds represented by the above general formula (IV) include the following compounds in addition to the above. In the following formula, iPr represents an isopropyl group.

[0275]

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[0276]

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Other than the above, examples of the transition metal compound represented by the general formula (IV) include compounds in which palladium or nickel in the above compounds is replaced by platinum.

Next, the transition metal compound represented by the general formula (V) will be described. The compound represented by the general formula (V) is a transition metal amide compound belonging to Groups 3 to 6 of the periodic table.

[0279]

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In the formula, M ⁴ represents a transition metal atom belonging to Groups 3 to 6 of the periodic table, and is preferably a transition metal atom belonging to Group 4 of the periodic table such as titanium, zirconium and hafnium.
R ′ and R ″ may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an organic silyl group, or at least selected from nitrogen, oxygen, phosphorus, sulfur, and silicon. A hydrocarbon group substituted with a substituent containing one kind of element is shown.

Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl,
Octyl, decyl, octadecyl, etc. have 1 carbon atom
A straight-chain or branched alkyl group having from 20 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms such as phenyl and naphthyl; and a substituent such as the alkyl group having 1 to 20 carbon atoms being 1 to these aryl groups. A substituted or substituted aryl group having from 5 to 5 cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; vinyl, propenyl,
Alkenyl groups such as cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl;

Examples of the halogenated hydrocarbon group include groups in which the above hydrocarbon group is substituted with halogen. Specific examples of the organic silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, triphenylsilyl and the like.

Nitrogen, oxygen, phosphorus, sulfur and silicon
Substituted with a substituent containing at least one element selected from the group consisting of
As the hydrocarbon group obtained, -COOC is used as the hydrocarbon group.
H_Three, -N (CH_Three) C (O) CH_Three , -OC (O) CH_Three
 , -CN, -N (C_TwoH_Five)_Two , -N (CH_Three) S (O_Two) C
H_Three , -P (C₆H_Five)_TwoSuch as substituted groups
You.

M is an integer of 0 to 2. n is 1 to 5
Is an integer. A represents an atom belonging to Groups 13 to 16 of the periodic table, and specifically includes a boron atom, a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, a germanium atom, a selenium atom, a tin atom, and the like. And preferably a carbon atom or a silicon atom. When n is 2 or more, a plurality of A may be the same or different from each other.

E is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. When m is 2, two E's may be the same or different, and two E's may be connected to each other to form a ring.

Specific examples of such a bonding group for bonding two nitrogen atoms represented by-((E _m ) A) _n -include the following groups. _{-CH 2 -, - C (Me} ) 2 -, - C (Ph) 2 -, - Si
(Me) _2- , -Si (Ph) _2- , -Si (Me) (Ph)-,
_{-CH 2 CH 2 -, - CH} 2 Si (Me) 2 -, - CH 2 CH 2
CH ₂ —, —CH ₂ C (Me) ₂ CH ₂ —, —CH ₂ C (E
t) ₂ CH ₂ —, —CH ₂ C (n-Pr) ₂ CH ₂ —, —CH _{2
C (i-Pr) 2 CH} 2 -, - CH 2 C (n-Bu) 2 CH 2 -,
—CH ₂ C (i-Bu) ₂ CH ₂ —, —CH ₂ C (s-Bu) ₂ C
_{H 2 -, - CH 2 C} (c-Pen) 2 CH 2 -, - CH 2 C (c-
Hex) ₂ CH ₂ —, —CH ₂ C (Ph) ₂ CH ₂ —, —CH ₂
C (Me) (Et) CH 2 -, - CH 2 C (Me) (i-Pr)
CH ₂ —, —CH ₂ C (Me) (i-Bu) CH ₂ —, —CH ₂
C (Me) (t-Bu ) CH 2 -, - CH 2 C (Me) (i-Pe
_{n) CH 2 -, - CH} 2 C (Me) (Ph) CH 2 -, - C
_{H 2 C (Et) (i} -Pr) CH 2 -, - CH 2 C (Et) (i-
_{Bu) CH 2 -, - CH} 2 C (Et) (i-Pen) CH
_{2 -, - CH 2 C (} i-Pr) (i-Bu) CH 2 -, - CH 2 C
(I-Pr) (i- Pen) CH 2 -, - CH 2 Si (Me) 2 CH
_{2 -, - CH 2 Si (} Et) 2 CH 2 -, - CH 2 Si (n-Bu)
_{2 CH 2 -, - CH 2} Si (Ph) 2 CH 2 -, - CH (M
_{e) CH 2 CH (Me)} -, - CH (Ph) CH 2 CH
(Ph) -, - Si ( Me) 2 OSi (Me) 2 -, - CH 2 C
_{H 2 CH 2 CH 2 -,} - Si (Me) 2 CH 2 CH 2 Si (Me) 2
−,

[0287]

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[0288]

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[0289]

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[0290]

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[0291]

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In the above examples, Me represents a methyl group, Et represents an ethyl group, n-Pr represents an n-propyl group, i-Pr represents an isopropyl group, and n-Bu represents n-butyl. I-Bu represents an isobutyl group, s-Bu represents sec-
Represents a butyl group, t-Bu represents a tert-butyl group, i-P
en represents an isopentyl group, c-Pen represents a cyclopentyl group, c-Hex represents a cyclohexyl group, Ph
Represents a phenyl group.

P is an integer from 0 to 4.

X ⁶ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a silicon-containing group. Specifically, it is the same as L ¹ in the general formula (I). When p is 2 or more, X ⁶
May be the same or different from each other.

Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferable. Hereinafter, specific examples of the transition metal amide compound represented by the general formula (V) will be shown, but the invention is not limited thereto.

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[0298]

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[0299]

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[0300]

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In the above examples, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, and tBu represents a tert-butyl group. In the present invention, a transition metal amide compound in which titanium is replaced with zirconium or hafnium in the above-described compounds can also be used.

In the present invention, in the transition metal amide compound represented by the general formula (V), R ′ and R ″ are substituted aryl groups in which 1 to 5 substituents such as an alkyl group are substituted. It is desirable to use a transition metal amide compound represented by the following general formula (V ′).

[0303]

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In the formula, M ⁴ is the same as M ⁴ in the general formula (V), and is preferably a transition metal atom of Group 4 of the periodic table such as titanium, zirconium and hafnium, and titanium is particularly preferable. .

R ^{61 to} R ⁷⁰ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an organic silyl group, an alkoxy group, an aryloxy group, —COOR ⁷¹ , N (R ⁷² ) C (O)
^{R 73, -OC (O) R} 74, -CN, -NR 75 2 , or -
N (R ⁷⁶ ) S (O ₂ ) R ⁷⁷ (where R ^{71 to} R ⁷⁷ represent an alkyl group having 1 to 5 carbon atoms). However, at least one of R ^{61 to} R ⁶⁵ is a group other than hydrogen, and at least one of R ^{66 to} R ⁷⁰ is a group other than hydrogen.

The halogen atom is represented by the general formula (V)
In it is the same as X ^6, a hydrocarbon group, a halogenated hydrocarbon group and an organic silyl group, the same as R 'and R''in the formula (V).

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like. Specifically as the aryloxy group, phenoxy, 2,
6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like.

-COOR ⁷¹ , -N (R ⁷² ) C (O)
^{R 73, -OC (O) R} 74, -CN, -NR 75 2 , or -
Examples of the group represented by N (R ⁷⁶ ) S (O ₂ ) R ⁷⁷ (where R ^{71 to} R ⁷⁷ represent an alkyl group having 1 to 5 carbon atoms) include —COOCH ₃ and —N (CH ₃ ) C (O) CH
_{3, -OC (O) CH 3} , -CN, -N (C
_{2 H 5) 2, -N (} CH 3) S (O 2) such as CH ₃ and the like.

In addition, two or more of the groups represented by R ^{61 to} R ⁶⁵ , preferably, adjacent groups are bonded to each other to form a ring such as an aromatic ring or an aliphatic ring together with the carbon atom to which they are bonded. Two or more of the groups represented by R ^{66 to} R ⁷⁰ , preferably an aromatic ring, an aliphatic ring, etc. May form a ring.

M is an integer of 0 to 2. n is 1 to 5
Is an integer. A is the same as A in the general formula (V), and is preferably a carbon atom or a silicon atom. When n is 2 or more, a plurality of A may be the same or different from each other.

E is the same as E in formula (V), and is preferably a substituent containing at least one element selected from carbon, hydrogen, nitrogen and silicon. When m is 2, two E's may be the same or different, and two E's may be connected to each other to form a ring.

Specific examples of such a bonding group for bonding two nitrogen atoms represented by-((E _m ) A) _n- include the same groups as described above. p is an integer of 0 to 4.

X ⁶ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a silicon-containing group. And specifically, the general formula (I)
Is the same as L ¹ in.

Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferable. When p is 2 or more, a plurality of groups represented by X ⁶ may be the same or different from each other.

Specific examples of the transition metal amide compound represented by the above general formula (V ') are shown below, but it should not be construed that the invention is limited thereto.

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[0317]

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[0319]

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[0320]

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[0321]

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In the above examples, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, nPr represents an n-propyl group, nBu represents an n-butyl group, and sBu represents an butyl group. sec-butyl group, t Bu is tert-butyl group,
nOct represents an n-octyl group.

In the present invention, a transition metal amide compound in which titanium is replaced with zirconium or hafnium in the above compounds may be used. Next, the transition metal compound represented by the general formula (VI) will be described.

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(Note that, here, N... M generally indicates coordination, but in the present invention, coordination may or may not be performed.) In the formula (VI) , M represents a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 also includes lanthanoids), preferably a metal atom of Groups 3 to 9 (Group 3 also includes lanthanoids), It is preferably a metal atom of groups 3 to 5 and 9 and particularly preferably a metal atom of group 4 or 5. Specifically, scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, etc., preferably scandium, titanium, zirconium, Hafnium, vanadium, niobium, tantalum, cobalt, rhodium, etc., more preferably,
Titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium, tantalum and the like are particularly preferable, and titanium, zirconium and hafnium are particularly preferable.

M represents an integer of 1 to 6, preferably 1 to 4. R ^{1 to} R ⁶ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group,
A sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be connected to each other to form a ring;

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl having 1 to 30 carbon atoms, preferably A linear or branched alkyl group having 1 to 20 carbon atoms, such as vinyl, allyl, and isopropenyl;
30, preferably 2 to 20 linear or branched alkenyl groups; ethynyl, propargyl and the like having 2 carbon atoms
A linear or branched alkynyl group having a carbon number of 3 to 30, preferably 2 to 20; a cyclic saturated hydrocarbon group having a carbon number of 3 to 30, preferably 3 to 20, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl. A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl and fluorenyl; and a carbon unsaturated group having 6 to 30 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl; 20 aryl groups; tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t
And alkyl-substituted aryl groups such as -butylphenyl.

In the above-mentioned hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated hydrocarbon having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl and chlorophenyl. And a hydrogen group.

The hydrocarbon group may be substituted with another hydrocarbon group, such as an aryl-substituted alkyl group such as benzyl and cumyl. Furthermore, the hydrocarbon group is a heterocyclic compound residue;
Alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, oxygen-containing groups such as carboxylic anhydride groups; amino groups, imino groups, amide groups, imide groups,
Hydrazino group, hydrazono group, nitro group, nitroso group,
Nitrogen-containing groups such as cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group, and ammonium salts thereof; boron-containing groups such as borandiyl group, borantriyl group, diboranyl group; mercapto group , Thioester, dithioester, alkylthio, arylthio, thioacyl, thioether, thiocyanate, isothiocyanate, sulfoneester, sulfonamide, thiocarboxyl, dithiocarboxyl, sulfo, sulfonyl Groups, sulfinyl groups, sulfur-containing groups such as sulfenyl groups; phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphorus-containing groups such as phosphato groups, silicon-containing groups,
It may have a germanium-containing group or a tin-containing group.

Of these, methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobutyl, sec-
Butyl, t-butyl, neopentyl, n-hexyl and other linear or branched alkyl groups having 1 to 30, preferably 1 to 20 carbon atoms; phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl and the like. Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms; halogen atoms, alkyl or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, 6 to 30 carbon atoms, Preferably, 6 to 20 substituents such as an aryl group or an aryloxy group have 1 to 5 substituents.
A monosubstituted substituted aryl group is preferred.

Examples of the oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group and phosphorus-containing group represented by R ^{1 to} R ⁶ include the same as those exemplified above. Heterocyclic compound residues include pyrrole, pyridine, pyrimidine, quinoline, nitrogen-containing compounds such as triazine, furans, oxygen-containing compounds such as pyran, residues such as sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. Examples include groups in which the compound residue is further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Specific examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, and diphenylmethyl. Silyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like. Among them, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly, trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are preferred. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

Examples of the germanium-containing group and the tin-containing group include those in which silicon of the silicon-containing group is replaced with germanium and tin. Next, the examples of R ^{1 to} R ⁶ described above will be described more specifically.

Of the oxygen-containing groups preferred as R ^{1 to} R ⁶ , alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like, and aryloxy groups include
Phenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like, as an acyl group, a formyl group,
Acetyl group, benzoyl group, p-chlorobenzoyl group, p-
A methoxybenzoyl group and the like and an ester group are preferably exemplified by acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl and p-chlorophenoxycarbonyl.

Among the nitrogen-containing groups preferred as R ^{1 to} R ⁶ , the amino group includes dimethylamino, ethylmethylamino, diphenylamino and the like, and the amide group includes
Acetamide, N-methylacetamide, N-methylbenzamide and the like are preferable, and the imide group is preferably acetimide and benzimide. The imino group is preferably methylimino, ethylimino, propylimino, butylimino and phenylimino.

Of the sulfur-containing groups preferred as R ^{1 to} R ⁶ , alkylthio groups include methylthio and ethylthio, arylthio groups include phenylthio, methylphenylthio and naphthylthio, and thioester groups include acetylthio and benzoyl. Thio, methylthiocarbonyl, phenylthiocarbonyl and the like; sulfonate groups such as methyl sulfonate, ethyl sulfonate and phenyl sulfonate; and sulfonamide groups such as phenylsulfonamide, N-methylsulfonamide, N-methyl Preferred is -p-toluenesulfonamide.

Preferably, R ⁶ is a substituent other than hydrogen. That is, R ⁶ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group,
It is preferably a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group.

Preferred hydrocarbon groups for R ⁶ include:
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, etc. having 1 to 30, preferably 1 to 20 linear or branched carbon atoms A cyclic alkyl group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl; and a carbon atom such as phenyl, naphthyl, biphenylyl and triphenylyl. 6 to 30, preferably 6 to 20 aryl groups; 7 to 30 carbon atoms such as benzyl, preferably 7 to 20
And an alkyl or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms.
20 halogenated alkyl groups having 6 to 30 carbon atoms,
Preferable examples include groups further substituted with 6 to 20 substituents such as an aryl group or an aryloxy group, a halogen, a cyano group, a nitro group and a hydroxy group.

Preferred hydrocarbon-substituted silyl groups for R ⁶ include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl,
Dimethylphenylsilyl, dimethyl-t-butylsilyl,
Dimethyl (pentafluorophenyl) silyl and the like. Particularly preferred are trimethylsilyl, triethylphenyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like.

In the present invention, R ⁶ has, in particular, 3 to 30 carbon atoms, preferably 3 to 2 carbon atoms, such as isopropyl, isobutyl, sec-butyl, tert-butyl and neopentyl.
A branched alkyl group of 0, a group in which a hydrogen atom of these groups is substituted with an aryl group having 6 to 30, preferably 6 to 20 carbon atoms (such as a cumyl group), adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, Cyclohexyl or the like having 3 to 30, preferably 3 to 2 carbon atoms.
0 is preferably a group selected from cyclic saturated hydrocarbon groups, or phenyl, naphthyl, fluorenyl,
6 to 3 carbon atoms such as anthranil and phenanthryl
It is also preferably 0, preferably 6 to 20 aryl groups or hydrocarbon-substituted silyl groups.

R ^{1 to} R ⁶ represent two or more of these groups, preferably adjacent groups, being linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. And these rings may further have a substituent.

When m is 2 or more, R ^{1 to} R ⁶
And two groups may be linked to each other.
However, R ¹ is not bonded to each other. Furthermore, m
Is 2 or more, R ¹ and R ² , R ³ and R ^3
4 together, R ⁵ each other, R ⁶ to each other may be the same or different from each other.

N is a number that satisfies the valency of M, and is specifically 0 to 5, preferably 1 to 4, more preferably 1 to 3.
Is an integer. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, or a silicon-containing residue. Group, germanium-containing group, or tin-containing group. When n is 2 or more, they may be the same or different.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. As the hydrocarbon group, the aforementioned R
^{The same} ones as exemplified for ^{1 to} R ⁶ can be mentioned. Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl; vinyl, Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl,
Examples include, but are not limited to, aryl groups such as methylnaphthyl, anthryl, and phenanthryl. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms has been replaced with halogen.

Of these, those having 1 to 20 carbon atoms are preferred. As the heterocyclic compound residue, the aforementioned R
^{The same} ones as exemplified for ^{1 to} R ⁶ can be mentioned.

Examples of the oxygen-containing group include the same ones as those described above for R ^{1 to} R ^6. Specific examples include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; a phenoxy group and a methyl group. Aryloxy groups such as phenoxy, dimethylphenoxy and naphthoxy;
Arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; carbonyl groups, and the like, but are not limited thereto.

Examples of the sulfur-containing group include the same as those exemplified above for R ^{1 to} R ⁶ , and specific examples include methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, and benzylsulfonate. Sulfonate groups such as phonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfate Sulfonate groups such as carboxylate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate; alkylthio; arylthio; and the like, but are not limited thereto. .

Specific examples of the nitrogen-containing group include the aforementioned R ¹ to
The same ones as those exemplified for R ⁶ can be mentioned, and specifically, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino , Ditolylamino, dinaphthylamino, an arylamino group such as methylphenylamino or an alkylarylamino group.
It is not limited to these.

Specific examples of the boron-containing group include BR
₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like). Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triphenylphosphine;
Triarylphosphine groups such as tolylphosphine; phosphite groups (phosphide groups) such as methyl phosphite, ethyl phosphite and phenyl phosphite; phosphonic acid groups; phosphinic acid groups, and the like, but are not limited thereto. is not.

As the silicon-containing group, specifically, the aforementioned R ¹
It includes the same ones as exemplified to R ^6, specifically, phenyl silyl, diphenyl silyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl silyl, triphenyl silyl, methyl diphenyl silyl, tritolylsilyl A hydrocarbon-substituted silyl group such as trinaphthylsilyl; a hydrocarbon-substituted silyl ether group such as trimethylsilyl ether; a silicon-substituted alkyl group such as trimethylsilylmethyl; a silicon-substituted aryl group such as trimethylsilylphenyl.

Specific examples of the germanium-containing group include the same groups as those exemplified in the above R ^{1 to} R ⁶ , and specific examples include a group in which silicon of the silicon-containing group is replaced with germanium. .

Specific examples of the tin-containing group include the aforementioned R ¹ to
The same groups as those exemplified for R ⁶ can be mentioned, and more specifically, a group in which silicon of the silicon-containing group is substituted with tin is mentioned.

Specific examples of the halogen-containing group include P
Examples include, but are not limited to, fluorine-containing groups such as F ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl _6, and iodine-containing groups such as IO ₄ .

Specific examples of the aluminum-containing group include A
lR ₄ (R represents a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like), but is not limited thereto.

When n is 2 or more, a plurality of groups represented by X may be the same or different from each other.
May be bonded to each other to form a ring.

Specific examples of the transition metal compound represented by the above general formula (VI) are shown below, but it should not be construed that the invention is limited thereto. In the following specific examples, M is a transition metal element, and is individually Sc (III), Ti (III), Ti (III).
(IV), Zr (III), Zr (IV), Hf (IV), V (IV), Nb
(V), Ta (V), Co (II), Co (III), Rh (II), R
h (III) and Rh (IV) are shown, but not limited thereto. Among these, Ti (IV), Zr (I
V) and Hf (IV) are preferred.

X represents a halogen such as Cl or Br, or an alkyl group such as methyl, but is not limited thereto. When there are a plurality of Xs, they may be the same or different.

N is determined by the valence of the metal M. For example, if two monoanion species are bound to a metal,
N = 0 for a divalent metal, n = 1 for a trivalent metal, n = 2 for a tetravalent metal, and n = 3 for a pentavalent metal. For example, when the metal is Ti (IV), n = 2, when Zr (IV), n = 2, and when Hf (IV), n = 2.

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[0367]

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[0368]

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[0370]

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[0372]

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[0373]

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[0374]

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[0375]

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[0377]

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[0378]

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[0379]

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[0384]

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More specific examples of such transition metal compounds include the following compounds.

[0386]

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[0387]

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[0388]

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In the above examples, Me is a methyl group, Et
Represents an ethyl group, iPr represents an i-propyl group, tBu represents a tert-butyl group, and Ph represents a phenyl group. Next, the general formula (VII)
The transition metal compound represented by is described.

[0390]

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In the formula, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, and R ^{1 to} R ¹⁰ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic group. A formula compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, two or more of which are linked to each other May form a ring,
n is a number that satisfies the valence of M; X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group,
A nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group; May be the same or different from each other, and a plurality of groups represented by X may combine with each other to form a ring, and Y represents oxygen, sulfur, carbon, nitrogen, phosphorus, It represents a divalent linking group containing at least one element selected from the group consisting of silicon, selenium, tin and boron. In the case of a hydrocarbon group, it is a group having three or more carbon atoms.

In the general formula (VII), at least one of R ^{6 and} R ¹⁰ , especially both, are a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group,
It is preferably a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

In formula (VII), M, R ^{1 to} R ¹⁰ and X can be the same groups as M, R ^{1 to} R ⁶ and X described for the compound of formula (VI).
Specific examples of Y will be described later.

The transition metal compound represented by the general formula (VII) is preferably a transition metal compound represented by the following general formula (VII-a).

[0395]

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In the formula, M represents a transition metal atom of Groups 3 to 11 of the periodic table, preferably Group 4 or Group 5, more preferably Group 4 such as titanium, zirconium and hafnium. It is titanium.

R ^{1 to} R ¹⁰ may be the same or different from each other and include a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, It represents a sulfonamide group, a nitrile group or a nitro group, and two or more of them, preferably adjacent groups, may be connected to each other to form a ring.

N is a number satisfying the valency of M, and is generally an integer of 0 to 4, preferably 1 to 4, more preferably 1 to 3. X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a silicon-containing group; In the above case, the groups represented by X may be the same or different from each other, and 2
Two or more Xs may be connected to each other to form a ring.

Y represents oxygen, sulfur, carbon, nitrogen, phosphorus,
Silicon, selenium, a divalent bonding group containing at least one element selected from the group consisting of tin and boron,
When it is a hydrocarbon group, it is a group having three or more carbon atoms.

These linking groups preferably have a structure in which the main chain is composed of 3 or more atoms, more preferably 4 or more and 20 or less, particularly preferably 4 or more and 10 or less. In addition, these bonding groups may have a substituent.

In the general formula (VII-a), R ⁶ or R ¹⁰
It is preferable that at least one, particularly both, are a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an alkoxy group, an aryloxy group, an ester group, an amide group, an amino group, a sulfonamide group, a nitrile group, or a nitro group. .

In the general formula (VII-a), X and R ¹ to
Specific examples of R ¹⁰ include the same groups as X and R ^{1 to} R ⁶ described in formula (VI). X is particularly preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group. When n is 2 or more, the ring formed by linking two or more Xs to each other may be an aromatic ring or an aliphatic ring.

As the divalent linking group (Y), specifically,-
A chalcogen atom such as O-, -S-, -Se-; -NH
-, -N (CH ₃ )-, -PH-, -P (CH ₃ )-and other nitrogen or phosphorus atom-containing groups; -SiH _2- , -Si (C
A silicon atom-containing group such as H ₃ ) _2- ; -SnH _2- , -Sn
(CH _{3) 2} - tin atom-containing groups such as; -BH -, - B
And a boron atom-containing group such as (CH ₃ ) — and —BF—. The hydrocarbon group _{- (CH 2) 4 -,} - (C
_{H 2) 5 -, - (} CH 2) 6 - saturated hydrocarbon group having 3 to 20 carbon atoms such as, cyclohexylidene group, a cyclic saturated hydrocarbon group such as cyclohexylene group, these saturated hydrocarbon groups A part of 1 to 10 hydrocarbon groups, fluorine, chlorine,
A group substituted with a hetero atom such as halogen such as bromine, oxygen, sulfur, nitrogen, phosphorus, silicon, selenium, tin or boron, and a cyclic hydrocarbon having 6 to 20 carbon atoms such as benzene, naphthalene or anthracene. Group, pyridine, quinoline, thiophene, furan and the like, and a residue of a cyclic compound having 3 to 20 carbon atoms including a hetero atom.

Specific examples of the transition metal compound represented by the above general formula (VII) are shown below, but it should not be construed that the invention is limited thereto.

[0405]

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[0406]

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In the above examples, Me represents a methyl group, Ph represents a phenyl group, and tBu represents a tert-butyl group. In the present invention, a transition metal compound in which titanium metal is replaced with a metal other than titanium, such as zirconium or hafnium, in the compounds described above can also be used.

The production method of the transition metal compound represented by the general formula (VI) or (VII) is not particularly limited.
For example, it can be manufactured as follows.

First, a ligand constituting the transition metal compound according to the present invention is a compound represented by the formula R ¹
By reacting with a primary amine compound of —NH ₂ (R ¹ has the same meaning as R ¹ in the general formulas (VI) and (VII)), for example, an aniline compound or an alkylamine compound; can get. Specifically, both starting compounds are dissolved in a solvent. As the solvent, those which are commonly used in such reactions can be used, and among them, alcohol solvents such as methanol and ethanol, and hydrocarbon solvents such as toluene are preferable. Then, the obtained solution is stirred under a reflux condition from room temperature for about 1 to 48 hours to obtain a corresponding ligand in a good yield.

In synthesizing the ligand compound, the catalyst
An acid catalyst such as formic acid, acetic acid, and toluenesulfonic acid may be used. Further, when molecular sieves, magnesium sulfate or sodium sulfate is used as a dehydrating agent, or when dehydration is performed by Dean Stark, it is effective for the progress of the reaction.

Next, by reacting the ligand thus obtained with a compound containing a transition metal M, a corresponding transition metal compound can be synthesized. Specifically, the synthesized ligand is dissolved in a solvent, and if necessary, contacted with a base to prepare a phenoxide salt, and then mixed with a metal compound such as a metal halide or a metal alkylate at a low temperature. , -78
The mixture is stirred for about 1 to 48 hours at a temperature from C to room temperature or under reflux. As the solvent, those which are commonly used in such reactions can be used, and among them, polar solvents such as ether and tetrahydrofuran (THF), and hydrocarbon solvents such as toluene are preferably used. Further, as a base used when preparing a phenoxide salt, a lithium salt such as n-butyllithium, a metal salt such as a sodium salt such as sodium hydride, and an organic base such as triethylamine and pyridine are preferable. Not as long.

Further, depending on the properties of the compound, the corresponding transition metal compound can be synthesized by directly reacting the ligand with the metal compound without going through the preparation of the phenoxide salt.

Further, the metal M in the synthesized transition metal compound can be exchanged for another transition metal by a conventional method. Further, for example, when any of R ^{1 to} R ⁶ is H, a substituent other than H can be introduced at any stage of the synthesis.

Next, the transition metal compound represented by the general formula (VIII) will be described.

[0415]

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In the formula, M represents a transition metal atom belonging to Groups 8 to 11 of the periodic table, and includes iron, ruthenium, osnium, cobalt,
It is preferably a transition metal atom of Groups 8 and 9 of the periodic table such as rhodium and iridium, and particularly preferably iron and cobalt.

R ^{1 to} R ⁴ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group,
It indicates a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a tin-containing group, or the like.

The halogen atom includes fluorine, chlorine, bromine, and iodine. As the hydrocarbon group, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and other straight or branched carbon atoms having 1 to 20 carbon atoms. Alkyl groups; aryl groups having 6 to 20 carbon atoms such as phenyl, naphthyl and anthryl; and 1 to 5 substituents such as the alkyl groups having 1 to 20 carbon atoms are substituted on these aryl groups. A substituted aryl group; a cycloalkyl group such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl; an alkenyl group such as vinyl, propenyl and cyclohexenyl; an arylalkyl group such as benzyl, phenylethyl, and phenylpropyl. Not something.

Examples of the halogenated hydrocarbon group include, but are not limited to, the above-mentioned hydrocarbon groups substituted with halogen. Examples of the heterocyclic compound include, but are not limited to, nitrogen-containing heterocyclic compounds, oxygen-containing heterocyclic compounds, and sulfur-containing heterocyclic compounds.

An oxygen-containing group, a nitrogen-containing group, a boron-containing group,
As the sulfur-containing group and the phosphorus-containing group, those represented by the general formula (VI)
Examples include the same groups as R ^{1 to} R ⁶ in the following, but are not limited thereto.

Examples of the silicon-containing group include a hydrocarbon-substituted silyl group, a silyl ether group of a hydrocarbon-substituted silyl, a silicon-substituted alkyl group, a silicon-substituted aryl group, and the like, but are not limited thereto.

Examples of the germanium-containing group include a hydrocarbon-substituted germyl group, a germanium ether group of a hydrocarbon-substituted germyl, a germanium-substituted alkyl group, a germanium-substituted aryl group, and the like, but are not limited thereto.

Examples of the tin-containing group include a hydrocarbon-substituted stannyl group, a hydrocarbon-substituted tin stannyl ether group, a tin-substituted alkyl group, and a tin-substituted aryl group.
It is not limited to this.

Among the oxygen-containing groups, alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like, and aryloxy groups include phenoxy, 2,6-dimethylphenoxy. , 2,4,6-trimethylphenoxy and the like; acyl groups include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group and p-methoxybenzoyl group; and ester groups such as acetyloxy and benzoyloxy. , Methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like.

Among the nitrogen-containing groups, amino groups include dimethylamino, ethylmethylamino and diphenylamino, amide groups include acetamido, N-methylacetamido and N-methylbenzamide, and imide groups include Preferred examples of the imino group include methylimino, ethylimino, propylimino, butylimino, and phenylimino.

Among the sulfur-containing groups, alkylthio groups include methylthio and ethylthio, arylthio groups include phenylthio, methylphenylthio, and naphthylthio, and thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthio. Carbonyl and the like, as a sulfone ester group,
Methyl sulfonate, ethyl sulfonate, phenyl sulfonate and the like, and preferred sulfonamide groups include phenylsulfonamide, N-methylsulfonamide, N-methyl-p-toluenesulfonamide and the like.

R ¹ and R ⁵ , R ² and R ⁶ , R ¹ and R ³ , R ² and R ⁴ , and R ³ and R ⁴ are mutually connected to form an aromatic ring, an aliphatic ring, a nitrogen atom, A hydrocarbon ring containing a hetero atom such as a sulfur atom or an oxygen atom may be formed, and these rings may further have a substituent.

N is a number that satisfies the valency of M, and specifically 1 to 8, preferably 1 to 5, more preferably 1 to 3.
Is an integer.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, or a silicon-containing group; Specific examples include the same groups or atoms as L in the general formula (I). When n is 2 or more, a plurality of groups represented by X may be the same or different.

Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferred. Y represents an atom of Group 15 or 16 of the periodic table, and specifically includes a nitrogen atom, a phosphorus atom, an arsenic atom, an antimony atom, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, and preferably a nitrogen atom , An oxygen atom or a sulfur atom.

In the present invention, the imine compound represented by the general formula (VIII) is preferably a transition metal imine compound represented by the following general formula (VIII-a).

[0432]

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In the formula, M represents a transition metal atom belonging to Groups 8 to 11 of the periodic table, and includes iron, ruthenium, osnium, cobalt,
It is preferably a transition metal atom of Groups 8 and 9 of the periodic table such as rhodium and iridium, and particularly preferably iron and cobalt.

[0434] R⁷~ R^TenAre the same or different
May be a hydrogen atom, a halogen atom, a hydrocarbon group, a halo
Genated hydrocarbon group, heterocyclic compound residue, oxygen-containing
Group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group
Group containing, silicon containing group, germanium containing group or tin containing
Shows organic groups. Specifically, R in the general formula (VIII)
¹~ R^FourAnd the same groups as mentioned above.

R ¹¹ represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, or a silicon-containing group. , A germanium-containing group or a tin-containing group. Specifically, R in the general formula (VIII)
It includes the same groups as ¹ to R ^4.

[0436] R ⁷ and R ^9, R ⁸ and R ^10, R ⁸ and R ^11, R
⁹ and R ¹⁰ may be connected to each other to form an aromatic ring, an aliphatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom, a sulfur atom, or an oxygen atom, and these rings are Further, it may have a substituent.

[0437] R¹²~ R¹⁶Are the same or different
May be a hydrogen atom, a halogen atom, a hydrocarbon group, a halo
Genated hydrocarbon group, heterocyclic compound residue, oxygen-containing
Group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group
Group containing, silicon containing group, germanium containing group or tin containing
Shows organic groups. Specifically, R in the general formula (VIII)
¹~ R^FourAnd the same groups as mentioned above.

At least one of R ^{12 to} R ¹⁶ is a group other than a hydrogen atom, and two or more of the groups represented by R ^{12 to} R ¹⁶ are connected to each other to form a ring. And preferably, an adjacent group is linked to each other to form an aliphatic ring,
An aromatic ring or a hydrocarbon ring containing a hetero atom such as a nitrogen atom may be formed, and these rings may further have a substituent.

N is a number that satisfies the valency of M, and specifically 1 to 8, preferably 1 to 5, more preferably 1 to 3.
Is an integer. X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, or a silicon-containing group; In the above case, the groups represented by X may be the same or different from each other. Specific examples include the same groups or atoms as described above.

Y represents an atom belonging to Group 15 or 16 of the periodic table, and specific examples thereof include a nitrogen atom, a phosphorus atom, an arsenic atom, an antimony atom, an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. Is a nitrogen atom, an oxygen atom or a sulfur atom.

In the present invention, the imine compound represented by the general formula (VIII) is more preferably a transition metal imine compound represented by the following general formula (VIII-b).

[0442]

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In the formula, M represents a transition metal atom belonging to Groups 8 to 11 of the periodic table, and includes iron, ruthenium, osnium, cobalt,
It is preferably a transition metal atom of Groups 8 and 9 of the periodic table such as rhodium and iridium, and particularly preferably iron and cobalt.

[0444] R¹⁷~ R²⁰Are the same or different
May be a hydrogen atom, a halogen atom, a hydrocarbon group, a halo
Genated hydrocarbon group, heterocyclic compound residue, oxygen-containing
Group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group
Group containing, silicon containing group, germanium containing group or tin containing
Shows organic groups. Specifically, R in the general formula (VIII)
¹~ R^FourAnd the same groups as mentioned above.

R ¹⁷ and R ¹⁹ , R ¹⁸ and R ²⁰ , R ¹⁹ and R ²⁰ are
Each may be connected to each other to form an aromatic ring, an aliphatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom, a sulfur atom, or an oxygen atom, and these rings further have a substituent. May be.

R ^{21 to} R ³⁰ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, It indicates a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a tin-containing group, or the like.

At least one of R ^{21 to} R ²⁵ is a group other than a hydrogen atom, and at least one of R ^{26 to} R ³⁰
One is a group other than a hydrogen atom, and two or more of the groups represented by R ^{21 to} R ²⁵ may be connected to each other to form a ring, and are represented by R ^{26 to} R ³⁰ Two or more of the groups may be connected to each other to form a ring, and preferably, adjacent groups are connected to each other to contain an aliphatic ring, an aromatic ring, or a heteroatom such as a nitrogen atom. They may form a hydrocarbon ring, and these rings may further have a substituent.

N is a number that satisfies the valence of M, and is specifically 1 to 8, preferably 1 to 5, more preferably 1 to 3.
Is an integer. X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, or a silicon-containing group; In the above case, the groups represented by X may be the same or different from each other. Specifically, X is the same as described above.

Y represents an atom belonging to Group 15 or 16 of the periodic table, and specific examples thereof include a nitrogen atom, a phosphorus atom, an arsenic atom, an antimony atom, an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. Is a nitrogen atom, an oxygen atom or a sulfur atom.

The following formulas (VIII) and (VIII-
Specific examples of the transition metal imine compounds represented by a) and (VIII-b) are shown below, but are not limited thereto.

[0451]

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[0452]

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[0453]

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[0454]

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[0455]

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[0456]

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[0457]

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[0458]

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[0459]

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[0460]

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[0461]

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In the above examples, Me represents a methyl group,
Et represents an ethyl group, nPr represents an n-propyl group,
iPr represents an i-propyl group, sBu represents a sec-butyl group, tBu represents a tert-butyl group, nOc represents an n-octyl group, and Ph represents a phenyl group.

In the present invention, a compound in which iron is replaced with cobalt in the above transition metal compounds can also be exemplified. The transition metal compounds as described above can be used alone or in combination of two or more.

Further, in the present invention, a transition metal compound represented by the following formula can be used in addition to the transition metal compound represented by any of the above formulas (I) to (VIII).

[0465]

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[0466]

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[0467]

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(C) Organic Compound Containing Group 13 Atom As the organic compound (C) containing a Group 13 atom used in the present invention, an organic aluminum compound represented by the following general formula is specifically mentioned. Can be

[0469] In _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms is 1 to 15, preferably 1 to 4 X represents a hydrocarbon group, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q
<3 and m + n + p + q = 3. Examples of such organoaluminum compounds include the following compounds.

[0470] formula R ^a _m Al (OR ^b) in _3-m (wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms is 1 to 15, preferably 1 to 4 a hydrocarbon group, m is preferably a number 1.5 ≦ m ≦ 3. the organic aluminum compound represented by), the general formula R ^a _m AlX _3-m (wherein, R ^a is the number of carbon atoms Is 1 to 15, preferably 1 to
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organic aluminum compound represented by the formula: R ^a _m AlH _3-m (where R ^a has 1 to 15 carbon atoms, preferably 1 to
4 represents a hydrocarbon group, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by), the general formula _{^{R a m Al (OR b)}} n X q ( wherein, R ^a and R ^b may be the same or different, are carbon atoms 1 to 15, It preferably represents 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is a number of 0 ≦ n <3, q is a number of 0 ≦ q <3,
And m + n + q = 3. The organoaluminum compound represented by).

More specifically, as the organoaluminum compound, tri-n-alkylaluminums such as triethylaluminum and tri-n-butylaluminum; triisopropylaluminum, triisobutylaluminum, trise
c-butylaluminum, tri-tert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methyl Tri-branched alkyl aluminum such as hexyl aluminum, tri-3-methylhexyl aluminum and tri 2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; diisobutyl aluminum hydride and the like Dialkylaluminum hydride; trialkenylaluminum such as triisoprenylaluminum; isobutylaluminum methoxy , Isobutyl ethoxide, alkyl aluminum alkoxides such as isobutyl aluminum isopropoxide; diethylaluminum ethoxide, dibutyl aluminum blanking dialkylaluminum alkoxides such as butoxide; ethylaluminum sesquichloride ethoxide, butyl aluminum sesqui Bed alkylaluminum sesqui alkoxides such butoxide; R ^a _2.5 Al (OR ^b ) _0.5 Partially alkoxylated alkylaluminum having an average composition represented by _0.5 ; dialkylaluminum halide such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum Sesquichloride, ethyl aluminum sesquibromide, etc. Alkyl aluminum sesquihalides; partially aluminum halides such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; ethyl Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as aluminum dihydride and propylaluminum dihydride; partially alkoxylated and halogenated such as ethylaluminum ethoxychloride, butylaluminum butoxycyclolide and ethylaluminum ethoxybromide Alkyl aluminum and the like.

Also, a compound similar to the above-mentioned organoaluminum compound can be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

In addition, as the organic compound (C),
Formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y and z are each a positive number, and z ≧ 2x.) Isoprenylaluminum represented by Can also be used.

The catalyst for the polymerization of ethylenically unsaturated monomers according to the present invention comprises the components (A), (B) and (C). In the present invention, the component (A) alone or together with the component (A) is used. Component (B) and / or component (C)
May be supported on the particulate carrier (D).

The particulate carrier (D) is an inorganic or organic compound having a particle size of 10 to 300 μm.
m, preferably a solid in the form of granules or fine particles in the range of 20 to 200 μm. Among them, a porous oxide is preferable as the inorganic carrier, and specifically, Si
O ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O
_{3, CaO, ZnO, BaO,} ThO 2 and the like or mixtures containing these, for example, SiO ₂ -MgO, SiO ₂ -A
l ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO
₂ -Cr ₂ O _3, etc. SiO ₂ -TiO ₂ -MgO can be exemplified. Among them, SiO ₂ and Al ₂ O ₃
Those having at least one component selected from the group consisting of:

[0476] A small amount of Na is added to the inorganic oxide._TwoC
O_Three, K_TwoCO_Three, CaCO_Three, MgCO_Three, Na_TwoSO
_Four, Al_Two(SO_Four)_Three, BaSO_Four, KNO_Three, Mg (N
O_Three)_Two , Al (NO_Three)_Three, Na_TwoO, K_TwoO, Li_TwoO etc.
Contains carbonate, sulfate, nitrate and oxide components of
I don't mind.

The properties of the particulate carrier (D) vary depending on the kind and production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. And the pore volume is desirably 0.3 to 2.5 cm ³ / g. The particulate carrier is used by firing at 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.

Further, as the particulate carrier, a particle size of 10
Granular or particulate solids of the organic compound having a size in the range of from 300 to 300 μm can be mentioned. These organic compounds include ethylene, propylene, 1-butene, 4-methyl
Examples thereof include (co) polymers formed mainly of α-olefins having 2 to 14 carbon atoms, such as 1-pentene, and polymers or copolymers formed mainly of vinylcyclohexane and styrene. be able to.

The catalyst for polymerizing an ethylenically unsaturated monomer according to the present invention includes (A) a compound selected from the group 3 to 12 transition metals described above, and (B) the (i), (i)
i) and (iii) or the above (i), (ii), (ii)
a compound obtained by reacting i) and (iv), (C)
Organic compounds containing Group 13 atoms, if necessary (D)
Consists of a particulate carrier. FIG. 1 shows a process for preparing the catalyst for polymerizing an ethylenically unsaturated monomer according to the present invention.

In the polymerization, the method of using each component and the order of addition are arbitrarily selected, but the following methods are exemplified. (1) A method in which the component (A), the component (B), and the component (C) are added to a polymerization vessel in an arbitrary order. (2) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance and the component (C) are added to the polymerization reactor in an arbitrary order. (3) A method in which the catalyst component in which the component (A) and the component (C) are brought into contact in advance and the component (B) are added to the polymerization reactor in an arbitrary order. (4) A method in which the catalyst component in which the component (A) is supported on the particulate carrier (D), the component (B) and the component (C) are added to the polymerization reactor in an arbitrary order. (5) A method in which the catalyst component in which the component (A) and the component (B) are supported on the particulate carrier (D) and the component (C) are added to the polymerization reactor in an arbitrary order. (6) A method in which the catalyst component in which the component (A) and the component (C) are supported on the particulate carrier (D) and the component (B) are added to the polymerization reactor in an arbitrary order. (7) A method in which a catalyst in which the component (A), the component (B), and the component (C) are supported on a particulate carrier (D) is added to a polymerization reactor.

The above-mentioned particulate carrier (D) is added to component (A)
The solid catalyst component carrying component (B) may have an ethylenically unsaturated monomer preliminarily polymerized. In the method for polymerizing an ethylenically unsaturated monomer according to the present invention, a polymer is obtained by polymerizing or copolymerizing an ethylenically unsaturated monomer in the presence of a polymerization catalyst as described above.

In the present invention, the polymerization can be carried out by any of liquid phase polymerization such as solution polymerization and suspension polymerization or gas phase polymerization. Specifically as the inert hydrocarbon medium used in the liquid phase polymerization method, propane, butane, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, and xylene; ethylene chloride and chlorin Examples thereof include halogenated hydrocarbons such as benzene and dichloromethane, and mixtures thereof, and the ethylenically unsaturated monomers used for polymerization can be used as a medium.

In carrying out the (co) polymerization of the ethylenically unsaturated monomer using the above-mentioned polymerization catalyst, the component (A) is usually used in an amount of 10 ^-12 to 1 per liter of the reaction volume.
It is used in an amount of 0 ^-2 mol, preferably 10 ^-10 to 10 ^-2 mol.

The component (B) has a molar ratio [M _B / M _A ] of the group 13 atom (M _B ) in the component ( _B ) to the transition metal atom (M _A ) in the component (A) which is usually It is used in an amount of 0.01 to 10000, preferably 0.05 to 2000. Component (C) has a molar ratio [(C) / M] of component (C) to transition metal atom (M) in component (A) of usually 1 to 5.
0000, preferably 1 to 20,000.

The polymerization temperature of the ethylenically unsaturated monomer using such a polymerization catalyst is usually from -50 to -20.
0 ° C., preferably in the range of 0-170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to
Under a condition of 50 kg / cm ² , the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.

The molecular weight of the resulting (co) polymer of the ethylenically unsaturated monomer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature.

The ethylenically unsaturated monomers for which the polymerization catalyst of the present invention is used include ethylene, propylene, 1-
Butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-olefins such as 1-hexadecene, 1-octadecene, and 1-eicosene; styrene, aryl-substituted ethylenically unsaturated monomers such as α-methylstyrene; acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, Unsaturated fatty acids such as itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-acrylate -Butyl, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate Methacrylate n- butyl, unsaturated carboxylic acid esters such as isobutyl methacrylate; dienes, trienes, etc. tetraene are exemplified.

The (co) polymer of the obtained ethylenically unsaturated monomer includes, for example, polyethylene, polypropylene, polybutene, polypentene, polyhexene,
Poly-4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-pentene copolymer, ethylene-hexene copolymer, ethylene-4-
Methyl-1-pentene copolymer, ethylene / octene copolymer, ethylene / propylene / butene / terpolymer,
Ethylene / butene / hexene / terpolymer, ethylene / butene / octene / terpolymer, propylene / butene copolymer, propylene / pentene copolymer, propylene / hexene copolymer, propylene / octene copolymer Copolymer, ethylene / styrene copolymer, propylene / styrene copolymer, ethylene / propylene / styrene terpolymer, ethylene / octene / styrene terpolymer, ethylene / α-olefin / diene terpolymer (Examples of dienes include butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 7-methyl-1,6-octadiene.), Ethylene / α-olefin / triene Terpolymers (trienes include 6,10-dimethyl-1,5,9-undecatriene and 5,9-dimethyl-1,4,8-decatriene A chain or cyclic triene such as ethylene).
α-olefin / tetraene terpolymer (tetraene is 6,10,14-trimethyl-1,5,9,13-pentadecatriene, 5,9,13-trimethyl-1,4,8,12 -Tetradecatriene, etc.). In addition, 3
As the α-olefin of the base copolymer, propylene,
n-butene, pentene, n-hexene, n-octene, decene and the like.

[0489]

The catalyst component for the polymerization of ethylenically unsaturated monomers according to the present invention can be a highly active catalyst for the polymerization of ethylenically unsaturated monomers when used in combination with a transition metal compound such as a metallocene compound.

According to the catalyst for polymerization of ethylenically unsaturated monomer and the polymerization method of the present invention, an ethylenically unsaturated monomer (co) polymer having excellent polymerization activity and excellent properties can be obtained.

[0490]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In the present invention, the intrinsic viscosity [η] is 1
It was measured in decalin at 35 ° C. and expressed in dl / g.

[0493]

Example 1 Preparation of Solution A of Catalyst Component A solution of 7.41 g (30.0 mmol) of bromopentafluorobenzene in 70 ml of a dehydrated toluene solution in a flask sufficiently purged with nitrogen was charged with hexane of n-BuLi at −78 ° C. Add 19 ml (30.6 mmol) of the solution,
The mixture was stirred at -78 ° C for 4 hours. To this was added 300 ml of a dehydrated toluene solution in which 2.67 g (10.0 mmol) of aluminum tribromide was dissolved. After the temperature was raised naturally, the mixture was stirred at room temperature for 12 hours. This slurry was filtered with a glass filter, and the filtrate was separated. While stirring the mixture at 0 ° C., wet nitrogen containing 0.09 ml of distilled water in dry nitrogen was introduced into the system while bubbling. After the introduction, the mixture was stirred at room temperature for 3 hours and then at 60 ° C. for 3 hours. This solution is
After cooling to 40 ° C., 40 ml of a dehydrated toluene solution in which 1.39 g (5.0 mmol) of triphenylchloromethane was dissolved was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 12 hours to prepare a solution A of a catalyst component.

[0494]

Example 2 Preparation of Catalyst Component Solution B A 20 ml dehydrated toluene solution in which 5 mmol of triisobutylaluminum was dissolved in a flask sufficiently purged with nitrogen.
while stirring at 0 ° C. while adding 0.045 distilled water to dry nitrogen.
Hydrous nitrogen containing ml was introduced into the system while bubbling. After the introduction, the mixture was stirred at room temperature for 3 hours. Add this solution to 0
Cooled to 1.8 ° C., 1.84 g of pentafluorophenol
(10.0 mmol) of a dehydrated toluene solution (10 ml) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 12 hours, and then at 60 ° C.
For 2 hours. The solution was cooled to 0 ° C., and 0.69 g (2.5 mmol) of triphenylchloromethane was added thereto.
10 ml of a dehydrated toluene solution in which 1) was dissolved was added dropwise.
After the dropwise addition, the mixture was stirred at room temperature for 12 hours to prepare a solution B of a catalyst component.

[0495]

Example 3 Preparation of Solution C of Catalyst Component 20 m of a dehydrated toluene solution in which 5 mmol of triisobutylaluminum was dissolved in a flask sufficiently purged with nitrogen.
while stirring at 0 ° C. while adding 0.045 distilled water to dry nitrogen.
Hydrous nitrogen containing ml was introduced into the system while bubbling. After the introduction, the mixture was stirred at room temperature for 3 hours. Add this solution to 0
℃, cooled to 2.12 g of pentafluorobenzoic acid
(10.0 mmol) of a dehydrated toluene solution (10 ml) was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 12 hours, and then at 60 ° C.
For 5 hours. The solution was cooled to 0 ° C., and 0.69 g (2.5 mmol) of triphenylchloromethane was added thereto.
10 ml of a dehydrated toluene solution in which 1) was dissolved was added dropwise.
After the dropwise addition, the mixture was stirred at room temperature for 12 hours to prepare a solution C of a catalyst component.

[0496]

Example 4 Preparation of Catalyst Component Solution D 40 m of dehydrated o-xylene solution in which 17 mmol of triethylaluminum was dissolved in a flask sufficiently purged with nitrogen.
While stirring at room temperature, a solution of 1.56 g (8.5 mmol) of 2,3,4,5,6-pentafluoroaniline in 30 ml of dehydrated o-xylene was slowly added dropwise. After the dropwise addition, the mixture was heated and stirred at 130 ° C. for 35 hours. After removing the solvent of this solution, 50 ml of dehydrated toluene was added. The solution was cooled to 0 ° C., and 12.52 g of pentafluorophenol (6
70 mmol of a dehydrated toluene solution of 8 mmol) was added dropwise.
After the addition, the mixture was stirred at room temperature for 12 hours. This was stirred at 60 ° C. for 2 hours. The solution was cooled to 0 ° C., and 50 ml of a dehydrated toluene solution in which 2.37 g (8.5 mmol) of triphenylchloromethane was dissolved was added dropwise. After dripping,
By stirring at room temperature for 12 hours, a solution D of the catalyst component is obtained.
Was prepared.

[0497]

Example 5 Preparation of Solution E of Catalyst Component In a flask sufficiently purged with nitrogen, 20 ml of a dehydrated toluene solution in which 5 mmol of trinormal octyl aluminum was dissolved was stirred at 0 ° C. while adding distilled water to dry nitrogen.
Hydrous nitrogen containing 045 ml was introduced into the system while bubbling. After the introduction, the mixture was stirred at room temperature for 5 hours. The solution was cooled to 0 ° C., and thereto was added dropwise 10 ml of a dehydrated toluene solution of 0.69 g (2.5 mmol) of triphenylchloromethane. After the dropwise addition, the mixture was stirred at room temperature for 12 hours to prepare a solution E of a catalyst component.

[0498]

Example 6 Ethylene Polymerization 400 ml of toluene was charged into a 500 ml-volume glass autoclave which was sufficiently purged with nitrogen, and ethylene was added to 1 ml of ethylene.
It was flowed at a rate of 00 liters / hour and kept at 75 ° C. for 10 minutes. To this, 0.28 mmol of triisobutylaluminum was added, then 0.0008 mmol of rac-dimethylsilylene-bis (2-methyl-4-phenylindenyl) zirconium dichloride was added. 0.0032 mmol of solution A of the catalyst component was added to initiate polymerization. Ethylene gas is supplied continuously at a rate of 100 liters / hour,
After the polymerization was performed for a minute, a small amount of methanol was added to terminate the polymerization. Add the polymer solution to a large excess of methanol,
The polymer was precipitated and dried under reduced pressure at 80 ° C. for 12 hours to obtain 8.00 g of a polymer. Polymerization activity was 100 kg-PE / mmol-Zr · hr, and [η] of the obtained polymer was 6.10 dl / g.

[0499]

Example 7 Ethylene Polymerization Example 2 was repeated in place of the catalyst component solution A in Example 6.
The polymerization of ethylene was carried out in the same manner as in Example 6 except that the catalyst component solution B prepared in 1. was used.
44 g were obtained. Polymerization activity is 18 kg-PE / mmo
l-Zr · hr, and [η] of the obtained polymer was 3.50 dl / g.

[0500]

Example 8 Ethylene Polymerization Example 4 was repeated in place of the catalyst component solution A in Example 6.
Using the catalyst component solution D prepared in the above, a catalyst component solution of 0.0032 mmol in terms of Al atoms was added, except that 0.016 mmol of catalyst component solution D in terms of Al atoms was added. Was subjected to ethylene polymerization in the same manner as in Example 6, and as a result, 0.50 g of a polymer was obtained. The polymerization activity was 6.25 kg-PE / mmol-Zr · hr, and [η] of the obtained polymer was 3.48 dl / g.

[0501]

Example 9 Ethylene Polymerization 400 ml of toluene was charged into a 500 ml-volume glass autoclave which was sufficiently purged with nitrogen, and ethylene was added to the autoclave.
It was flowed at a rate of 00 liters / hour and kept at 75 ° C. for 10 minutes. To this, 0.28 mmol of triisobutylaluminum was added, then 0.0008 mmol of ethylenebis (indenyl) zirconium dichloride was added, and finally 0.0032 mmol of a solution A of a catalyst component in terms of Al atom was added to carry out polymerization. Started. Ethylene gas was continuously supplied at a rate of 100 liter / hour, polymerization was carried out at 75 ° C. under normal pressure for 6 minutes, and then a small amount of methanol was added to terminate the polymerization. The polymer solution was added to a large excess of methanol to precipitate a polymer, which was dried under reduced pressure at 80 ° C. for 12 hours. As a result, 5.80 g of the polymer was obtained.
was gotten. Polymerization activity is 72.5 kg-PE / mmol
-Zr · hr, and the obtained polymer has [η] of 1.
It was 8 dl / g.

[0502]

Example 10 Ethylene Polymerization Example 2 was repeated in place of the catalyst component solution A in Example 9.
Polymerization of ethylene was carried out in the same manner as in Example 9 except that the polymerization time was set to 10 minutes using the solution B of the catalyst component prepared in the above. As a result, 1.44 g of a polymer was obtained. The polymerization activity is 10.8 kg-PE / mmol-Zr · hr,
[Η] of the obtained polymer was 1.43 dl / g.

[0503]

Example 11 Ethylene Polymerization As a result of polymerizing ethylene in the same manner as in Example 10 except that the catalyst component solution B prepared in Example 3 was used instead of the catalyst component solution B in Example 10, 0.80 g of polymer was obtained. The polymerization activity is 6.0 kg-PE /
mmol-Zr · hr, and [η] of the obtained polymer was 1.58 dl / g.

[0504]

Example 12 Polymerization of Propylene 400 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen, and propylene was flowed at a rate of 100 liter / hour and kept at 50 ° C. for 20 minutes. To this was added 0.28 mmol of triisobutylaluminum, then 0.0008 mmol of rac-dimethylsilylene-bis (2-methyl-4-phenylindenyl) zirconium dichloride, and finally
0.0032 mmol of catalyst component solution A in terms of Al atom
Was added to initiate polymerization. Propylene gas is supplied continuously at a rate of 100 liters / hour, and at normal pressure, 50 ° C. and 30
After the polymerization was performed for a minute, a small amount of methanol was added to terminate the polymerization. Add the polymer solution to a large excess of methanol,
The polymer was precipitated and dried under reduced pressure at 80 ° C. for 12 hours to obtain 2.40 g of the polymer. Polymerization activity was 6.00 kg-PP / mmol-Zr · hr, and [η] of the obtained polymer was 3.60 dl / g.

[0505]

Example 13 Propylene Polymerization The procedure of Example 12 was repeated except that the catalyst was changed from rac-dimethylsilylene-bis (2-methyl-4-phenylindenyl) zirconium dichloride to ethylenebis (indenyl) zirconium dichloride. As a result of propylene polymerization in the same manner, 0.24 g of a polymer was obtained. The polymerization activity is 0.60 kg-PP / mmol-Zr · hr
And [η] of the obtained polymer was 0.45 dl / g.
Met.

[0506]

EXAMPLE 14 Ethylene / propylene copolymer 400 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen, and ethylene 40
A mixed gas of 1 liter / hour and 60 liter / hour of propylene was circulated and kept at 50 ° C. for 20 minutes.
To this was added 0.28 mmol of triisobutylaluminum and then rac-dimethylsilylene-bis (2-methyl-
4-phenylindenyl) zirconium dichloride 0.0
008 mmol, and finally, 0.0
032 mmol of the solution A of the catalyst component was added to initiate polymerization. A mixed gas of 40 liters / hour of ethylene and 60 liters / hour of propylene is continuously supplied.
After polymerization at 30 ° C. for 30 minutes, a small amount of methanol was added to terminate the polymerization. The polymer solution is washed with an aqueous hydrochloric acid solution, and the polymer is precipitated by concentrating the solution.
After drying under reduced pressure at 30 ° C. for 12 hours, 2.80 g of a polymer was obtained. The polymerization activity was 7.00 kg-polymer / mmol-Zr · hr, the [η] of the obtained polymer was 0.67 dl / g, and the density was 0.864 g.
/ Cm ³ .

[0507]

Example 15 Ethylene-octene Copolymerization Toluene (380 ml) was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen, and 20 ml of 1-octene was added thereto. And kept at 50 ° C. for 20 minutes. To this was added 0.28 mmol of triisobutylaluminum, then 0.0008 mmol of rac-dimethylsilylene-bis (2-methyl-4-phenylindenyl) zirconium dichloride, and finally 0.0032 mmol of Al atoms. Polymerization was initiated by adding mmol of catalyst component solution A. Ethylene gas was continuously supplied at a rate of 100 liter / hour, polymerization was performed at 50 ° C. for 30 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization.

The polymer solution was washed with an aqueous hydrochloric acid solution, and the solution was concentrated to precipitate a polymer. The polymer was dried under reduced pressure at 130 ° C. for 12 hours. As a result, 0.36 g of the polymer was obtained.
was gotten. Polymerization activity is 0.90 kg-polymer / mm
ol-Zr · hr, [η] of the obtained polymer was 0.89 dl / g, and the density was 0.858 g / cm ^3.
Met.

[0509]

EXAMPLE 16 Ethylene Polymerization A 250 ml-volume glass autoclave, which was sufficiently purged with nitrogen, was charged with 250 ml of toluene, and ethylene was added to 1 ml of ethylene.
It was flowed at a rate of 00 liters / hour and kept at 25 ° C. for 10 minutes. To this, 0.0625 mmol of triisobutylaluminum was added, then 0.0025 mmol of the following Ni catalyst was added, and finally 0.005 mmol of a solution A of a catalyst component in terms of Al atom was added to initiate polymerization. Ethylene gas was continuously supplied at a rate of 100 liter / hour, polymerization was performed at 25 ° C. for 15 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate a polymer, which was dried at 80 ° C. for 12 hours under reduced pressure. As a result, 0.20 g of a polymer was obtained. The polymerization activity is 0.32 kg-
PE / mmol-Zr · hr.

[0510]

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[0511]

Example 17 Ethylene Polymerization 250 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen, and ethylene was added to the autoclave.
It was flowed at a rate of 00 liters / hour and kept at 25 ° C. for 10 minutes. To this, 0.833 mmol of triisobutylaluminum was added, then 0.0105 mmol of 2,2'-thiobis (4-methyl-6-t-butylphenoxy) titanium dichloride was added. 0.021 mmol of solution A of the catalyst component was added to initiate polymerization. Ethylene gas was continuously supplied at a rate of 100 liter / hour, polymerization was performed at 25 ° C. for 60 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization.
As a result of adding the polymer solution to a large excess of methanol to precipitate the polymer, and drying at 80 ° C. for 12 hours under reduced pressure,
4.50 g of polymer were obtained. The polymerization activity is 0.43k
g-PE / mmol-Zr · hr.

Table 3 shows the above results. In the table, Zr concentration and Al concentration are respectively expressed as Zr atom conversion, Al concentration.
It is an atom conversion.

[0513]

[Table 3]

[0514]

Example 18 Preparation of Solution F of Catalyst Component In a flask sufficiently purged with nitrogen, 20 ml of a dehydrated o-xylene solution in which 20 mmol of diethylaluminum chloride was dissolved was stirred at room temperature while 2,3,4,5,6- Dehydration of 1.83 g (10.0 mmol) of pentafluoroaniline
30 ml of a xylene solution was slowly added dropwise. After dripping, 1
The mixture was heated and stirred at 25 ° C. for 40 hours. Subsequently, after removing the solvent in this solution, 50 ml of hexane was added and stirred. Only this solution part was removed by decantation, and 100 ml of dehydrated toluene was added to the insoluble part to obtain a toluene solution (solution f-1).

Next, 0.57 ml (4.56 mmol) of pentafluorobenzene was placed in another flask which was sufficiently purged with nitrogen.
While stirring 20 ml of the dehydrated toluene solution of l) at -78 ° C, 2.95 ml (4.6 ml) of a hexane solution of n-BuLi was used.
9 mmol) and stirred at -78 ° C for 7 hours to obtain a solution (solution f-2).

The solution f-1 was converted to 2.2 in terms of Al atoms.
After fractionating the 8 mmol solution, the whole amount of the solution f-2 was slowly added dropwise while stirring the solution at -78 ° C. After the temperature of the resulting mixture was raised naturally, the mixture was stirred at room temperature for 12 hours.
The slurry was filtered with a glass filter, and the filtrate was separated to obtain a solution (solution f-3).

In a flask sufficiently purged with nitrogen, a solution of 0.852 mmol in terms of Al atoms was fractionated from the solution f-3, and 0.24 g of triphenylchloromethane was stirred at -78 ° C. (0.86 mmol) of a dehydrated toluene solution (10 ml) was added dropwise. After the resulting mixture was naturally heated, it was stirred at room temperature for 12 hours to prepare a solution F of a catalyst component.

[0518]

Example 19 Preparation of Solution G of Catalyst Component 1.00 g (4.62 mmol) of diphenylsilanediol and dehydrated toluene 5 in a flask sufficiently purged with nitrogen.
After stirring 0 ml at room temperature, it was cooled to -78 ° C with stirring, followed by diethyl aluminum chloride 9.24.
30 ml of a dehydrated toluene solution in which mmol was dissolved was slowly added dropwise. After the dropwise addition, the obtained mixture was naturally heated to room temperature and stirred for 12 hours, and then heated and stirred at 100 ° C. for 6 hours. After removing the solvent in the resulting solution,
Hexane (50 ml) was added and stirred. Only this solution part was removed by decantation, and 100 ml of dehydrated toluene was added to the insoluble part to obtain a toluene solution (solution g-1).

Next, 2.30 ml (18.50 mm) of pentafluorobenzene in another flask which was sufficiently purged with nitrogen.
ol) in 20 ml of a dehydrated toluene solution while stirring at −78 ° C. in 11.50 ml of a hexane solution of n-BuLi (1 ml).
8.50 mmol) and stirred at -78 ° C for 7 hours to obtain a solution (solution g-2).

While stirring the solution g-1 at -78 ° C,
Solution g-2 was slowly added dropwise. After the temperature of the resulting mixture was raised naturally, the mixture was stirred at room temperature for 12 hours. This slurry was filtered through a glass filter, and the filtrate was separated and the solution (solution g)
-3) was obtained.

[0521] While stirring this solution g-3 at -78 ° C,
1.28 g of triphenylchloromethane (4.60 mmol
30 ml of a dehydrated toluene solution of 1) was added dropwise. After the temperature of the resulting mixture of the gills was raised naturally, the mixture was stirred at room temperature for 12 hours to prepare a solution G of a catalyst component.

[0522]

Example 20 Ethylene Polymerization 400 ml of toluene was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen, and ethylene was added to the autoclave.
It was passed at a rate of 00 liter / hour and kept at 75 ° C. for 10 minutes. To this, triisobutylaluminum was added in 0.1 ml.
28 mmol, then 0.0008 mmol of rac-dimethylsilylene-bis (2-methyl-4-phenylindenyl) zirconium dichloride were added, and finally 0.0032 mmol of a catalyst component solution F in terms of Al atom was added. In addition, polymerization was started. Ethylene gas was continuously supplied at a rate of 100 liter / hour, polymerization was carried out at 75 ° C. under normal pressure for 6 minutes, and then a small amount of methanol was added to terminate the polymerization. The polymer solution was added to a large excess of methanol to precipitate a polymer, which was dried at 80 ° C. for 12 hours under reduced pressure. As a result, 5.90 g of a polymer was obtained. The polymerization activity is 73.
It was 75 kg-PE / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained polymer was 5.63 dl / g.

[0523]

Example 21 Ethylene Polymerization In Example 20, rac-dimethylsilylene-bis (2-
Ethylene polymerization was carried out in the same manner except that ethylene-bis (indenyl) zirconium dichloride was used in place of methyl-4-phenylindenyl) zirconium dichloride. As a result, 7.20 g of a polymer was obtained. The polymerization activity was 90.00 kg-PE / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained polymer was 1.75 d.
1 / g.

[0524]

Example 22 Ethylene Polymerization Ethylene polymerization was carried out in the same manner as in Example 20 except that the catalyst component solution F was used instead of the catalyst component solution F. As a result, 4.57 g of a polymer was obtained. The polymerization activity was 57.13 kg-PE / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained polymer was 6.91 dl.
/ G.

[0525]

Example 23 Ethylene Polymerization In Example 20, rac-dimethylsilylene-bis (2-
Methyl-4-phenylindenyl) zirconium dichloride was replaced with ethylene-bis (indenyl) zirconium dichloride, and the catalyst component solution G was used in place of the catalyst component solution F. As a result of the polymerization, 10.64 g of a polymer was obtained. The polymerization activity is 133.00 kg-PE / mmol-Zr
Hr, and the intrinsic viscosity [η] of the obtained polymer was 1.48 dl / g.

[0526]

Example 24 Ethylene Polymerization A 250 ml-volume glass autoclave sufficiently purged with nitrogen was charged with 250 ml of toluene, and ethylene was added to 1 ml of ethylene.
It was flowed at a rate of 00 liters / hour and kept at 25 ° C. for 10 minutes. To this, 0.25 mmol of triisobutylaluminum was added, then 0.005 mmol of a zirconium compound represented by the following formula was added, and finally 0.012 mmol of a solution G of a catalyst component in terms of Al atom was added to carry out polymerization. Started. Ethylene gas was continuously supplied at a rate of 100 liter / hour, polymerization was carried out at 25 ° C. for 5 minutes under normal pressure, and then a small amount of methanol was added to terminate the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer, and the polymer was dried at 80 ° C. for 12 hours under reduced pressure. As a result, 2.10 g of a polymer was obtained. The polymerization activity was 5.04 kg-PE / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained polymer was 0.15 dl / g.

[0527]

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[0528]

Example 25 Ethylene Polymerization Ethylene polymerization was carried out in the same manner as in Example 24 except that a titanium compound represented by the following formula was used in place of the zirconium compound represented by the above formula. 40 g were obtained. The polymerization activity is 0.48kg-
PE / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polymer was 6.32 dl / g.

[0529]

Embedded image

[0530]

Example 26 Ethylene Polymerization Ethylene polymerization was carried out in the same manner as in Example 24, except that the zirconium compound represented by the above formula was used instead of the zirconium compound represented by the above formula. 15 g were obtained. Polymerization activity is 5.1
6 kg-PE / mmol-Zr · hr, and the intrinsic viscosity [η] of the obtained polymer was 1.17 dl / g.

[0531]

Embedded image

[0532]

Example 27 Ethylene Polymerization Ethylene polymerization was carried out in the same manner as in Example 24 except that a titanium compound represented by the following formula was used instead of the zirconium compound represented by the above formula. 15 g were obtained. The polymerization activity is 0.18kg-
PE / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polymer was 6.31 dl / g.

[0533]

Embedded image

[0534]

Example 28 Ethylene Polymerization To a 500 ml glass autoclave sufficiently purged with nitrogen, 250 ml of toluene was charged, and ethylene was added to 1 ml of ethylene.
It was flowed at a rate of 00 liters / hour and kept at 25 ° C. for 10 minutes. To this, 0.100 mmol of triisobutylaluminum was added, then 0.005 mmol of an iron compound represented by the following formula was added, and finally 0.010 mmol of a solution G of a catalyst component in terms of Al atom was added to carry out polymerization. Started. Ethylene gas was continuously supplied at a rate of 100 liter / hour, polymerization was carried out at 25 ° C. for 5 minutes under normal pressure, and then a small amount of methanol was added to terminate the polymerization.
As a result of adding the polymer solution to a large excess of methanol to precipitate the polymer, and drying at 80 ° C. for 12 hours under reduced pressure,
0.45 g of polymer was obtained. Polymerization activity is 10.80
kg-PE / mmol-Fe · hr, and the intrinsic viscosity [η] of the obtained polymer was 3.01 dl / g.

[0535]

Embedded image

Table 4 shows the results of Examples 20 to 28. In the table, the term “concentration” refers to the atomic conversion of the corresponding metal.

[0537]

[Table 4]

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a preparation process of a catalyst containing a catalyst component for polymerizing an ethylenically unsaturated monomer according to the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Terunori Fujita 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Toshiyuki Tsutsui Waki-cho, Kuga-gun, Yamaguchi Prefecture 6-1-2 Waki F-term in Mitsui Chemicals Co., Ltd. F-term (reference) 4J028 AA01A AB01A AC01A AC08A AC09A AC10A AC26A AC27A AC28A AC31A AC41A AC45A BA01A BA01B BB01A BB01B BC12A BC15A BC15B BC16A BC16BCA19 BC18 BC18ABC BC CA25B CA26B CA27B CA28B CA29B CB22A CB24A CB25A CB54A CB61A CB62A CB63A CB64A CB81A CB84A DB05A EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB11 EB21 EB25 EC01 EC02 EC04 FA01 FA02 FA03 FA04 FA07 FA09 GA04 GA08 GB02 4J100 AA02P AA03P AA03Q AA04P AA04Q AA04R AA07P AA07Q AA15P AA16P AA16Q AA16R AA17P AA17Q AA18P AA19P AA19Q AA19R AA21P AA21Q AB02P AB02Q AB02R AB03P AJ02P AJ08P AJ09P AK31P AK32P AL03P AL04P AR16R AR22R AS02R AS03R AS11R AU21R CA01 CA04 FA10

Claims (15)

[Claims] (1) The following (i) to (iii), if necessary, (i)
(i) a compound containing an atom belonging to Group 13 of the periodic table; and (ii) a compound containing an atom belonging to Group 13 of the periodic table. A compound capable of reacting with a compound (i) containing an atom and capable of bonding to two or more Group 13 atoms; and (iii) reacting with a compound containing a Group 13 atom of the periodic table to form an ionized ionic compound. Compounds (iv) hydrocarbon compounds, halogenated hydrocarbon compounds, hydroxy hydrocarbon compounds, silanol compounds, boronic acid compounds, organic carboxylic acid compounds, organic sulfonic acid compounds, hydroxylamine compounds, sulfonamide compounds, ketoimide compounds, amide compounds, Oxime compounds, amine compounds, imide compounds, diimine compounds, imine compounds, diketone compounds and metal salts thereof Al least one compound selected. 2. An ethylene comprising a compound obtained by reacting the following (i) and (ii), if necessary, (iv) in an arbitrary order, and further reacting (iii). (I) a compound represented by the following general formula MR ¹ R ² R ³ (where M represents an atom belonging to Group 13 of the periodic table, and R ¹ , R
² and R ³ may be the same or different from each other;
Represents a halogen atom, a hydrogen atom, a hydroxyl group or an organic group,
Further, ^two groups out of R ¹ , R ² and R ³ may be connected to each other to form a ring. (Ii) a compound capable of reacting with the compound (i) and binding to two or more M. (iii) the above (i) and (ii), if necessary,
a compound capable of forming an ionized ionic compound by reacting with a reaction product obtained by reacting v) in an arbitrary order (iv) a hydrocarbon compound, a halogenated hydrocarbon compound, a hydroxyhydrocarbon compound, a silanol compound , Boronic acid compounds, organic carboxylic acid compounds, organic sulfonic acid compounds, hydroxylamine compounds, sulfonamide compounds, ketoimide compounds, amide compounds, oxime compounds, amine compounds, imide compounds, diimine compounds, imine compounds, diketone compounds and their metals At least one compound selected from salts. Wherein the compound (i) is an ethylenically unsaturated monomer polymerization catalyst component according to claim 1 or 2 is an aluminum compound represented by the following general _{^{formula; R a m Al (OR b}} ) n X _p (wherein, R ^a and R ^b may be the same or different from each other and represent a hydrocarbon group having 1 to 15 carbon atoms;
X represents a halogen atom, m is 0 ≦ m ≦ 3, n is 0 ≦ n
≦ 3, p is a number satisfying 0 ≦ p ≦ 3, and m + n + p = 3
It is. ) 4. The compound according to claim 1, wherein the compound (ii) is at least one compound selected from the group consisting of H ₂ O, H ₂ S and a compound represented by the following general formula. The catalyst component for the polymerization of ethylenically unsaturated monomers as described above; (Wherein, R ⁴ represents a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group, or an oxygen-containing group; R ⁵ represents a divalent hydrocarbon group;
Divalent halogenated hydrocarbon group, divalent silicon-containing group, 2
A divalent germanium-containing group, a divalent tin-containing group, a divalent boron-containing group or a single bond, and R ⁶ and R ⁷ may be the same or different from each other, and represent a hydrogen atom, a hydrocarbon group, a halogenated group; hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or an oxygen-containing group, may each R ⁶ and R ⁷ are bound to the carbon atoms forming the R ⁵ to form a ring, R ⁸ And R ⁹ may be the same or different and represent a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group. ) 5. The compound (iii) which is capable of forming an ionized ionic compound having a carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation or ferrocenium cation. The catalyst component for the polymerization of ethylenically unsaturated monomers according to any one of claims 1 to 4. 6. The catalyst component for ethylenically unsaturated monomer polymerization according to claim 1, wherein the compound (iv) is at least one compound selected from compounds represented by the following general formula. ^{; R 10 X, R 10 H} , R 10 OH, R 10 R 11 NH, R 10 COOH, R 10 SO 3 H, R 10 R 11 CNOH, R 10 R 11 NOH, R 10 CONHR 11, R 10 SO 2 NHR ¹¹ , R ¹⁰ COCH ₂ COR ¹¹ , R ¹⁰ C (＝ NH) CH ₂ COR ¹¹ , wherein R ¹⁰ is a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or shows a boron-containing group, R ¹¹ is a hydrogen atom, an alkoxy group, or, R ¹⁰ the same or different hydrocarbon group, halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or a boron-containing group Shows, X is a halogen atom.) 7. A catalyst component for the polymerization of ethylenically unsaturated monomers, which is represented by the following formula: (Wherein, M may be the same or different and each represents an atom of Group 13 of the periodic table, n is an integer of 0 or more, Y is a divalent linking group, and when n is 1 or more, A plurality of Ys may be the same or different from each other, Z is a group capable of bonding to one or more Ms, m is 1 or more and n + 1
Wherein Q is the same or different, and Q represents one group selected from the following groups; [However, R ¹⁰ represents a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group, or a boron-containing group, and R ¹¹ is the same as or a hydrogen atom, an alkoxy group, or R ^10. Shows different hydrocarbon groups, halogenated hydrocarbon groups, silicon containing groups, germanium containing groups, tin containing groups or boron containing groups. A represents a cation, j is the valence of Z, m is the number of Z, k is k = jm / r, and represents the valence of the A cation. ). 8. The catalyst component for the polymerization of ethylenically unsaturated monomers according to claim 7, wherein the divalent linking group Y is one kind of linking group selected from the following divalent linking groups: ] (Wherein, R ⁴ represents a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group, or an oxygen-containing group; R ⁵ represents a divalent hydrocarbon group;
Divalent halogenated hydrocarbon group, divalent silicon-containing group, 2
A divalent germanium-containing group, a divalent tin-containing group, a divalent boron-containing group or a single bond, and R ⁶ and R ⁷ may be the same or different from each other, and represent a hydrogen atom, a hydrocarbon group, a halogenated group; hydrocarbon group, a silicon-containing group, a germanium-containing group, a tin-containing group or an oxygen-containing group, may each R ⁶ and R ⁷ are bound to the carbon atoms forming the R ⁵ to form a ring, R ⁸ And R ⁹ may be the same or different and represent a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group. ) 9. The method according to claim 9, wherein the group Z capable of binding to one or more M is a halogen anion, hydride, carbanion, alcoholate, aryl alcoholate, alkylcarboxylate, arylcarboxylate, thiolate, carbothiolate, The catalyst component for the polymerization of ethylenically unsaturated monomers according to claim 7 or 8, which is one kind of group selected from dithiocarbonate, trithiocarbonate, sulfonate, sulfamate, and phosphate. 10. The A cation is a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a diclohepsyltrienyl cation, a ferrocenium cation, and a group 1 of the periodic table.
The catalyst component for the polymerization of ethylenically unsaturated monomers according to any one of claims 7 to 9, which is one kind of cation selected from the group consisting of group 1 metal cations. 11. A compound of a transition metal selected from (A) a group 3 to group 12 of the periodic table, (B) a catalyst component according to any one of claims 1 to 10, and (C) a group 13 of the periodic table. A catalyst for the polymerization of ethylenically unsaturated monomers, comprising an organic compound containing the following atoms: 12. The component (A) is represented by the following general formula (I):
A transition metal compound represented by any of the following:
The ethylenically unsaturated monomer polymerization according to claim 11,
Catalyst; M¹L¹ _x ... (I) (where M¹Represents a transition metal atom of Group 4 of the periodic table, and x
Is the transition metal atom M¹Is a number that satisfies the valence of¹Is
Indicates a ligand coordinated to a transition metal atom, and at least one ligand
L¹Is a ligand having a cyclopentadienyl skeleton
L other than a ligand having a cyclopentadienyl skeleton
¹Is a hydrocarbon group having 1 to 20 carbon atoms,
1 to 20 halogenated hydrocarbon groups, oxygen-containing groups, sulfur
Containing group, nitrogen containing group, phosphorus containing group, silicon containing group, halo
A gen atom or a hydrogen atom, and cyclopentadienyl
When two or more ligands having a skeleton are included,
Ligand having two cyclopentadienyl skeletons
Represents a (substituted) alkylene group or a (substituted) silylene group.
May be connected via )(Where M¹Represents a transition metal atom of Group 4 of the periodic table;
R¹⁶, R¹⁷, R¹⁸And R¹⁹Are the same or different
A hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group having 1 to 20 atoms, including silicon
Organic, oxygen-containing, sulfur-containing, nitrogen-containing, phosphorus-containing
Represents a group, a hydrogen atom or a halogen atom;¹⁶,
R¹⁷, R¹⁸And R¹⁹Are adjacent to each other
Carbon atoms to which some of the groups are bonded
And may form a ring together with¹And X^TwoIs
They may be the same or different from each other, and have 1 to 2 carbon atoms.
0 hydrocarbon group, halogenated carbon having 1 to 20 carbon atoms
Hydrogen group, oxygen-containing group, sulfur-containing group, silicon-containing group, water
Y represents an elementary atom or a halogen atom;¹Is the number of carbon atoms
Is a divalent hydrocarbon group having 1 to 20, and has 1 to 20 carbon atoms.
A divalent halogenated hydrocarbon group, a divalent silicon-containing group,
Divalent germanium containing group, divalent tin containing group, -O
-, -CO-, -S-, -SO-, -SO_Two-, -Ge
-, -Sn-, -NR^{Two 0}-, -P (R²⁰)-, -P
(O) (R²⁰)-, -BR²⁰-Or -AlR²⁰−
But R²⁰May be the same or different from each other,
A hydrocarbon group having 1 to 20 elementary atoms, 1 to 2 carbon atoms
0 halogenated hydrocarbon group, hydrogen atom or halogen atom
Is a child]. ) L^TwoM^TwoX^Three _Two ... (III) (where M^TwoRepresents a transition metal atom of Group 4 of the periodic table;
^TwoIs a derivative of a delocalized π-bonded group,^TwoActivity
The site has a constrained geometric shape, and X^ThreeAre mutually
Hydrogen atom, halogen atom,
, A hydrocarbon group containing up to 20 carbon atoms,
Silyl groups containing not more than 20 silicon atoms or not more than 20
Shown below are germanyl atoms containing germanyl groups. )(Where M^ThreeIndicates a transition metal atom belonging to Groups 8 to 10 of the periodic table.
Then X^FourAnd X^FiveAre the same or different
Often represents a nitrogen atom or a phosphorus atom;⁴¹And R⁴²
May be the same or different from each other, and may be a hydrogen atom or
Represents a hydrocarbon group, and m and n are the same or different
May be 1 or 2 and each represents X
^FourAnd X^FiveIs a number that satisfies the valence of R⁴³Is[Where R⁵⁰, R⁵⁵, R⁵¹, R⁵², R⁵⁶And R
⁵⁷May be the same or different from each other,
Or the R⁴¹And R⁴²Shows the same hydrocarbon group],
Note R⁴¹, R⁴², R⁵⁰[Or R⁵¹, R⁵²] And R
⁵⁵[Or R⁵⁶, R⁵⁷] Is two or more of these,
Preferably, adjacent groups are linked to each other to form a ring
May be R⁴⁴And R⁴⁵Are the same or different
May be a hydrogen atom, a halogen atom, a hydrocarbon group,-
OR⁴⁶, -SR⁴⁷, -N (R⁴⁸)_TwoOr -P (R⁴⁹)
_Two[However, R⁴⁶~ R⁴⁹Is an alkyl having 1 to 20 carbon atoms.
Kill group, aryl group having 6 to 20 carbon atoms, carbon atom
A cycloalkyl group having 6 to 20 carbon atoms, 7 to 2 carbon atoms
0 represents an aralkyl group or an organic silyl group;⁴⁸Each other
Or R⁴⁹May be connected to each other to form a ring
No. And R⁴⁴And R⁴⁵Are connected to each other to form a ring
It may be formed. )(Where M^FourRepresents a transition metal atom of Groups 3 to 6 of the periodic table.
And R ′ and R ″ may be the same or different from each other.
Well, hydrogen atom, hydrocarbon group, halogenated hydrocarbon group,
Organic silyl group or nitrogen, oxygen, phosphorus,
C) a device containing at least one element selected from silicon
Represents a hydrocarbon group substituted with a substituent, and m is an integer of 0 to 2.
Is a number, n is an integer of 1 to 5, and A is
A group 13-16 atom, and when n is 2 or more,
The numbers A may be the same or different from each other and E is
Carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, borane
Contains at least one element selected from silicon and silicon
And when m is 2, two Es are
They may be the same or different, and two E
P may be an integer of 0 to 4;
Yes, X⁶Is a hydrogen atom, a halogen atom, a carbon atom 1
To 20 hydrocarbon groups, halogenation of 1 to 20 carbon atoms
Hydrocarbon, oxygen-containing, sulfur-containing or silicon-containing
When p is 2 or more, a plurality of X⁶Is
They may be the same or different. )(Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table)
M represents an integer of 1 to 3;¹~ R⁶Are mutually
Hydrogen atom, halogen atom,
, A hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group,
Nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing
Group, silicon-containing group, germanium-containing group or tin-containing
And two or more of these are linked together to form a ring
May be formed, and when m is 2 or more, R¹
~ R⁶Even when two of the groups represented by
Well (however, R¹Are not joined together), n
Is a number satisfying the valence of M, and X is a hydrogen atom, halo
Gen atoms, hydrocarbon groups, oxygen-containing groups, sulfur-containing groups, nitrogen
Element containing group, boron containing group, aluminum containing group, phosphorus containing
Organic group, halogen-containing group, heterocyclic compound residue, silicon
Indicates a containing group, a germanium containing group or a tin containing group,
When n is 2 or more, a plurality of groups represented by X are the same as each other.
Two or more groups represented by X
May combine with each other to form a ring. )(Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table)
Then R¹ ~ R^TenMay be the same or different from each other
, Hydrogen atom, halogen atom, hydrocarbon group, heterocyclic
Compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group,
Sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium
Or tin-containing groups, two of which
The above may be linked to each other to form a ring, and n is
X represents a number satisfying the valence of M, and X represents a hydrogen atom, a halogen
Atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing
Carboxy, boron-containing, aluminum-containing, phosphorus-containing
Group, halogen-containing group, heterocyclic compound residue, silicon-containing
Indicates a group having a group, a germanium-containing group or a tin-containing group, and
Is 2 or more, the plurality of groups represented by X are the same as each other
Two or more groups represented by X
May be linked to each other to form a ring, and Y is oxygen, i
Au, carbon, nitrogen, phosphorus, silicon, selenium, tin and
At least one element selected from the group consisting of boron
A divalent linking group containing
It is a bonding group consisting of three or more elementary atoms. )(In the formula, M represents a transition metal atom of Groups 8 to 11 of the periodic table.
Then R¹~ R^FourMay be the same or different from each other
Hydrogen atom, halogen atom, halogenated hydrocarbon group,
Hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen
Group, boron-containing group, sulfur-containing group, phosphorus-containing group,
Indicates an i-containing group, germanium-containing group or tin-containing group
Then R^FiveAnd R⁶Are the same or different
Well, halogen atom, halogenated hydrocarbon group, hydrocarbon
Group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group,
Boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing
Group, germanium-containing group or tin-containing group;
R¹And R^Five, R^TwoAnd R⁶, R¹And R ^Three, R^TwoAnd R^Four, R
^ThreeAnd R^FourMay be linked to each other to form a ring, and n
Is a number satisfying the valence of M, and X is a hydrogen atom, halo
Gen atom, hydrocarbon group having 1 to 20 carbon atoms, carbon atom
Halogenated hydrocarbon groups of formulas 1 to 20, oxygen-containing groups,
C indicates a silicon-containing group or a silicon-containing group, and when n is 2 or more,
Is that a plurality of groups represented by X are the same or different
And Y represents an atom belonging to Group 15 or 16 of the periodic table.
You. ) 13. The catalyst for polymerizing an ethylenically unsaturated monomer according to claim 11, wherein the component (C) is an organoaluminum compound. 14. The method according to claim 1, wherein the component (A) alone or the component (B) and / or the component (C) is carried on the particulate carrier (D) together with the component (A). The catalyst for polymerizing an ethylenically unsaturated monomer according to claim 11. 15. A method for polymerizing an ethylenically unsaturated monomer, comprising polymerizing or copolymerizing an ethylenically unsaturated monomer in the presence of the catalyst according to any one of claims 11 to 14.