JP2001278909A - Polymerization method of olefin, and olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an olefin polymer by using a specific supported catalyst and to provide a fibrous olefin polymer produced by the method. SOLUTION: The method for producing an olefin polymer includes a polymerization of an olefin compound in the presence of an olefin polymerization catalyst consisting of (A) a transition metal compound having a salicylic aldoimine ligand, (B) a mesoporous solid with a pore size in the range of 1.5-10 nm, and (C) at least one kind of compound selected from an organometalleic compound (C-1), an organoaluminumoxy compound (C-2) or an ionization ionic compound (C-3), as needed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for polymerizing an olefin and an olefin polymer produced by the method.

[0002]

BACKGROUND OF THE INVENTION In general, polyolefins are used in various fields such as for various molded articles because of their excellent mechanical properties. Polyolefins with properties are desired.

[0003] As a method for producing polyolefin, a method of supporting an olefin polymerization catalyst on various supports is generally widely used. In this case, the shape of a polymer formed by the support used and the supporting method is generally used. And morphology can be controlled.

Recently, as a method for producing polyethylene, a method has been proposed in which ethylene is polymerized using a catalyst having titanocene dichloride supported on a mesoporous compound (Scie).
nce, Vol. 285, 1999, 2113). And according to this method,
It is described that a high molecular weight, highly crystalline polymer can be produced in a fibrous form, and that the fiber diameter is very small. However, what is shown here is only ethylene homopolymerization using titanocene dichloride, no other transition metal compound other than titanocene is shown, and a catalyst in which another transition metal compound is supported on a mesoporous compound. No olefin polymer can be obtained by polymerizing olefins other than ethylene using the above method.

[0005] The applicant of the present invention discloses Japanese Patent Application Laid-Open No. H11-31510.
No. 9 proposes a transition metal compound having a salicylaldimine ligand as a new olefin polymerization catalyst. The present inventors have studied under such circumstances, and as a result, the olefin using a catalyst in which the transition metal compound having the salicylaldimine ligand is supported on a porous solid having a pore size in a specific range. The inventors have found that a fibrous polymer can be obtained with high polymerization activity upon polymerization, and have completed the present invention.

[0006]

An object of the present invention is to provide a method for polymerizing olefins using an olefin polymerization catalyst containing a specific carrier. Another object of the present invention is to provide a fibrous olefin polymer produced using this method.

[0007]

SUMMARY OF THE INVENTION An olefin polymerization method according to the present invention comprises:
(A) a transition metal compound represented by the following general formula (I);
(B) a mesoporous solid having a pore diameter in the range of 1.5 to 10 nm, and, if necessary, (C) an (C-1) organometallic compound, (C-2) an organoaluminum oxy compound, and (C-3)
Characterized by polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst comprising at least one compound selected from compounds which form an ion pair by reacting with the transition metal compound (A);

[0008]

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(Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , and R ^{1 to} R ⁶
May be the same or different from each other, and include 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, and a silicon-containing group. A 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, and when m is 2 or more, it is represented by R ^{1 to} R ⁶ May be linked to each other, n is a number satisfying the valence of M, and 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, and a silicon-containing group. , A germanium-containing group or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X are bonded to each other to form a ring. May be formed. ).

The fibrous olefin polymer according to the present invention comprises:
The fiber diameter is 3 obtained by the olefin polymerization method described above.
It is in the range of 0-50 nm.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the olefin polymerization method according to the present invention and the olefin polymer obtained by this method will be specifically described.

In the present specification, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also homopolymer. , May also be used in a meaning including a copolymer.

The olefin polymerization method according to the present invention comprises:
(A) a transition metal compound represented by the following general formula (I);
(B) a mesoporous compound having a pore diameter in the range of 1.5 to 10 nm, and if necessary, (C) a (C-1) organometallic compound,
An olefin in the presence of a polymerization catalyst comprising (C-2) an organic aluminum oxy compound and (C-3) at least one compound selected from compounds which react with the transition metal compound (A) to form an ion pair. Is polymerized.

First, each component forming the olefin polymerization catalyst used in the present invention will be described. (A) Transition gold
Group compound transition metal compound (A) used in the present invention is represented by the following general formula (I).

[0015]

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(Note that N ... M generally indicates coordination, but in the present invention, it may or may not be coordinated.) In the general formula (I), 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), more preferably Is 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 and the like, preferably scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, and 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 is an integer of 1 to 6, preferably 1 to 4,
Particularly preferably, 2 or 3 is shown. 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. Specifically, the hydrocarbon group has 1 to 1 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, tert-amyl, and n-hexyl. 30, preferably 1 to 20 linear or branched alkyl groups; linear or branched alkenyl groups having 2 to 30, preferably 2 to 20 carbon atoms, such as vinyl, allyl and isopropenyl; A straight-chain or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms such as ethynyl and propargyl; and 3 to 30 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl, preferably 3-20 cyclic saturated hydrocarbon groups; alkyls such as 2-methylcyclopentyl, 2-methylcyclohexyl and 2,5-dimethylcyclohexyl; Cyclic substituted hydrocarbon groups having 5 to 30 carbon atoms, such as cyclopentadienyl, indenyl and fluorenyl; phenyl, benzyl, naphthyl, biphenylyl, terphenylyl, phenanthryl,
6-30 carbon atoms such as anthryl, preferably 6
To 20 aryl groups; tolyl, iso-propylphenyl,
Examples thereof include alkyl-substituted aryl groups such as t-butylphenyl, dimethylphenyl, and di-t-butylphenyl.

In the above-mentioned hydrocarbon group, a hydrogen atom may be substituted by halogen, for example, trifluoromethyl,
Examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as pentafluorophenyl and chlorophenyl.

The hydrocarbon group may be substituted with another hydrocarbon group, for example, a cycloalkyl-substituted alkyl group such as cyclopropylmethyl, cyclohexylmethyl and cyclopentylmethyl; an aryl group such as benzyl and cumyl. And a substituted alkyl group.

Further, the hydrocarbon group may be a heterocyclic compound residue; an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, and a carboxylic anhydride. Oxygen-containing groups such as groups; amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, amino groups A boron-containing group such as a boranediyl group, a borantoriyl group, a diboranyl group, etc .; a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group;
A sulfur-containing group such as a thioether group, a thiocyanate ester group, an isothiocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group; It may have a phosphorus-containing group such as a phosphoryl group, a thiophosphoryl group, or a phosphato group, or a silicon-containing group, a germanium-containing group, or a tin-containing group as described later.

Of these, methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobutyl, sec-
Butyl, tert-butyl, neopentyl, tert-amyl, n-
C1-C30, preferably 1-2, carbon atoms such as hexyl
0 linear or branched alkyl group; 6 to 30, preferably 6 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl.
A halogen atom, an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an aryl group or an aryloxy having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. A substituted aryl group in which 1 to 5 substituents such as a group are substituted is preferable.

Oxygen-containing groups, nitrogen-containing groups, boron-containing groups,
Examples of the sulfur-containing group and the phosphorus-containing group include the same as those exemplified above. Heterocyclic compound residues include pyrrole, pyridine, pyrimidine, quinoline, nitrogen-containing compounds such as triazines, 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. Note that when referring to an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, and a phosphorus-containing group, they do not include a heterocyclic compound.

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 obtained by substituting silicon in the silicon-containing group with germanium and tin. Next, the examples of R ^{1 to} R ⁶ described above will be described more specifically.

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 and 2,6-dimethylphenoxy. , 2,4,6-trimethylphenoxy, etc .; acyl groups include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, p-methoxybenzoyl group, etc., and ester groups include acetyloxy, benzoyl Preferred examples include oxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like.

Among the nitrogen-containing groups, amide groups include acetamido, N-methylacetamido, N-methylbenzamide, etc., amino groups include dimethylamino, ethylmethylamino, diphenylamino, etc., 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, ethylthio, etc., arylthio groups include phenylthio, methylphenylthio, naltylthio, etc., and thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthio groups. Carbonyl and the like, as a sulfone ester group,
Preferable examples include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Examples of the sulfonamide group include phenyl sulfonamide, N-methyl sulfonamide, and N-methyl-p-toluene sulfonamide.

Preferably, R ⁶ is a substituent other than hydrogen. That is, R ⁶ is preferably a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a boron-containing group, a sulfur-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. In particular, R ⁶ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester. Group, an amide group, an amino group, an imide group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group or a hydroxy group. Preferably, there is.

Preferred hydrocarbon groups for R ⁶ include:
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl, neopentyl, n-hexyl, etc.
A linear or branched alkyl group having 30, preferably 1 to 20; a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl;
Phenyl, benzyl, naphthyl, biphenylyl, triphenylyl and the like having 6 to 30 carbon atoms, preferably 6 to 30 carbon atoms.
20 aryl groups; and these groups have 1 to 30 carbon atoms, preferably 1 to 20 alkyl groups or alkoxy groups, and 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
And a group further substituted with a substituent such as an aryl group having 6 to 30, preferably 6 to 20 carbon atoms, an aryloxy group, a halogen, a cyano group, a nitro group or 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, isophenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like.

In the present invention, R ⁶ is particularly a branched alkyl group having 3 to 30, preferably 3 to 20 carbon atoms, such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, tert-amyl and the like. And the hydrogen atoms of these groups have 6 to 30 carbon atoms, preferably 6 to 30 carbon atoms.
A group selected from a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as a group substituted with an aryl group of 20 (such as a cumyl group), adamantyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Preferably, or phenyl, naphthyl,
An aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as fluorenyl, anthryl and phenanthryl, or a hydrocarbon-substituted silyl group is also preferable.

R ^{1 to} R ⁶ are two or more of these groups, preferably, adjacent groups are 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 s} , R ^{2 s} , R ^{3 s} , R ^{4 s} , R ^{5 s} , and R ^{6 s} may be the same or different from each other. R ¹ to R ^6, the belonging at least one group of the groups represented by R ¹ to R ⁶ belonging to one of the ligands, the other ligands case of more
May be linked to at least one of the groups represented by

N is a number that satisfies the valence of M, and is specifically 0 to 5, preferably 1 to 4, more preferably 1 to 3.
Is an integer. A represents -O-, -S-, -N (R ⁷ )-or-
It represents Se-, and is preferably -O-. Examples of R ⁷ include the same groups and atoms as those described above for R ^{1 to} R ⁶ .

X represents a hydrogen atom, a halogen atom, a hydrocarbon group, a residue of a heterocyclic compound, an oxygen-containing group, a nitrogen-containing group,
It indicates a boron-containing group, a sulfur-containing group, a phosphorus-containing group, an aluminum-containing group, a halogen-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group. When n is 2 or more, they may be the same or different.

The halogen atom includes 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, methyl, ethyl, propyl,
Alkyl groups such as butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; Arylalkyl groups such as phenylethyl and phenylpropyl; and aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl, but are not limited thereto. It is not something to be done. Further, these hydrocarbon groups include halogenated hydrocarbons, specifically, having 1 to 1 carbon atoms.
A group in which at least one hydrogen of the 20 hydrocarbon groups has been replaced by halogen is also included. Of these, the number of carbon atoms is 1
~ 20 are preferred.

As the heterocyclic compound residue, R ¹
It includes the same as those exemplified in to R ^6. 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; phenoxy, methylphenoxy, and dimethyl. Examples include, but are not limited to, aryloxy groups such as phenoxy and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; and carbonyl groups.

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.). Examples of the sulfur-containing group include the same ones as those exemplified above in R ^{1 to} R ⁶ , and specifically, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, sulfonate groups such as p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzyl Examples include, but are not limited to, sulfinate groups such as sulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate; alkylthio groups; arylthio groups.

Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methylphosphite, ethylphosphite and the like. Examples include, but are not limited to, phosphite groups such as phenyl phosphite (phosphide groups); phosphonic acid groups; and phosphinic acid groups.

Specific examples of the halogen-containing group include P
F₆, BF_FourFluorine-containing groups such as ClO _Four, SbCl₆What
Which chlorine-containing groups, IO_FourAnd iodine-containing groups such as
However, the present invention is not limited to these.

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.

Specific examples of the silicon-containing group include the aforementioned R ¹
To R ⁶ , and specifically include phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, and tolylsilyl. 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.

When n is 2 or more, Xs may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring. Hereinafter, specific examples of the transition metal compound represented by the general formula (I) are shown, but the invention is not limited thereto.

In the following specific examples, M is a transition metal element, and is individually Sc (III), Ti (III), Ti (I
V), Zr (III), Zr (IV), Hf (IV), V (IV), Nb
(V), Ta (V), Co (II), Co (III), Rh (II), Rh
(III) and Rh (IV), but are not limited thereto. Among them, Ti (IV), Zr (IV), Hf (I
V) is 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, if the metal is T
In the case of i (IV), n = 2, and in the case of Zr (IV), n = 2
In the case of Hf (IV), n = 2.

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[0059]

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More specifically, the following can be mentioned.

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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. In addition, the general formula (I)
As the transition metal compound (B) represented by the following, there is a transition metal compound represented by the following general formula (Ib).

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In the formula, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, and specific examples thereof include the same transition metal atoms as M in the general formula (I). 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 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, and specifically the same as R ^{1 to} R ⁶ in the above general formula (I) Atoms or groups. Further, two or more of R ^{1 to} R ¹⁰ may be connected to each other to form a ring.

At least one of R ^{6 and} R ¹⁰ , particularly both, is 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.

N is a number satisfying the valence of M. A and A ′ may be the same or different from each other, and —O—,
-S-, -N (R ⁷ )-or -Se-, both of which are -O-
It is preferred that As R ⁷ , the above R ^{1 to} R ⁶
And the same groups or atoms as mentioned above.

X represents 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, an aluminum-containing group, a halogen-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and specifically the same as X in the above general formula (I) Atoms or groups.

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

Y is 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.
These bonding groups Y preferably have a main chain of 3 or more atoms,
More preferably 4 or more and 20 or less, particularly preferably 4
It has a structure composed of not less than 10 pieces and not more than 10 pieces. In addition, these bonding groups may have a substituent.

Specific examples of the divalent linking group (Y) include:
Chalcogen atoms such as O-, -S-, -Se-; -NH-,-
_{, - - N (CH 3)} PH -, - P (CH 3) - nitrogen or phosphorus atom-containing groups such _{as; -SiH 2 -, - Si (} CH 3) 2 - silicon atom-containing groups such as; -SnH ₂ -, -Sn (CH ₃ ) _2- and the like; and a boron atom-containing group such as -BH-, -B (CH ₃ )-and -BF-. The hydrocarbon group is not particularly limited, but is-(CH ₂ ) ₄ -,-(CH ₂ ) ₅ -,-(CH ₂ ) ₆
Cyclic saturated hydrocarbon groups such as a saturated hydrocarbon group having 3 to 20 carbon atoms, cyclohexylidene group, cyclohexylene group, etc .;
Hydrocarbon groups, fluorine, chlorine, bromine and other halogens,
Groups substituted with heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, silicon, selenium, tin, and boron; residues of cyclic hydrocarbons having 6 to 20 carbon atoms such as benzene, naphthalene, and anthracene; pyridine and quinoline , Thiophene,
Examples thereof include a residue of a cyclic compound having 3 to 20 carbon atoms including a hetero atom such as furan.

The following are specific examples of the transition metal compound represented by the above general formula (Ib), but the invention is not limited thereto.

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

(B) Mesoporous Solid The mesoporous solid used in the present invention has a pore size of 1.5.
-10 nm, preferably 1.5-7 nm,
And a porous solid (compound,
Mixtures, composites, etc.). As a mesoporous solid,
It is preferable to use a porous solid in which the openings of the pores are regularly arranged in the same direction, for example, a solid having a honeycomb structure.

As the mesoporous solid, conventionally known ones can be used. For example, as the mesoporous solid containing silica as a main component, Bretane of Chemical Society of Japan (Bull. Chem. Soc. Jpn.), 63
Vol. 988, 1990, FSM-16 produced by inserting a quaternary ammonium salt between layers of a layered silicate was reported. Nature, 359, 710, 1992 Reports MCM-41 produced from the polymerization of silicic acid using a quaternary ammonium salt as an organic auxiliary. Also, Advanced Materials (Adv. Mater.), 9
Vol. 974, 1997, a filamentous mesoporous silica compound (MSF) produced at a water-oil interface using a quaternary ammonium salt as an organic auxiliary is reported.

Examples of the mesoporous solid having pores of 1.5 to 10 nm other than silica include, for example, a quaternary ammonium salt in Advanced Materials (Adv. Mater.), Vol. A zirconium phosphate salt produced by using as a template was reported, and Chemical Communication (Chem. Commun.), P. 1009, in 1997, an aluminum phosphate salt produced by using an alkylamine as an organic auxiliary was reported. I have.

The mesoporous solid produced by the above-described method may have some of the structure-forming elements replaced with other metal elements, as long as the structure is maintained. More specifically, as a method for producing a mesoporous solid, for example, a metal alkoxide such as tetraethoxysilane is hydrolyzed by using an alkylamine as an organic auxiliary agent, and is used in an amount of 500 to 800.
C., a quaternary ammonium salt is inserted between layers of a layered compound such as kanemite, and hydrothermally synthesized.
A method of calcining at ~ 800 ° C, a method of hydrothermally synthesizing colloidal silica such as colloidal silica or water glass using a quaternary ammonium salt as a template, and calcining at 500 to 800 ° C. Note that the present invention is not limited to these production methods as long as the object of the present invention is met.

When a mesoporous solid is produced by the above method, the pore size of the mesoporous solid is determined by the molecular size of the alkylamine or quaternary ammonium salt used in the production. In order to produce a mesoporous solid having a pore diameter of 1.5 to 10 nm, the number of carbon atoms is 6 to 2
It is preferable to use an alkylamine having a linear alkyl group of 4 or a quaternary ammonium salt, particularly 8 to 20.
It is preferable to use an alkylamine having a linear alkyl group or a quaternary ammonium salt.

The mesoporous solid used in the present invention has different properties depending on the kind and the production method, but the mesoporous solid preferably used has a particle size of 10 to 300 μm, preferably 20 to 200 μm. , Specific surface area is 50 ~
1000 m ² / g, preferably in the range of 100~700m ² / g, it is desirable that the pore volume is in the range of 0.3~3.0cm ³ / g.

(C-1) Organometallic Compound As the (C-1) organometallic compound used as necessary in the present invention, specifically, the following Periodic Table Groups 1 and 2 and Groups 12 and 13 Group organometallic compounds are used.

[0087] (C-1a) of the general formula _{^{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 from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, 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. The organoaluminum compound represented by).

[0088] (C-1b) In the general formula M ² AlR ^a ₄ (wherein, M ² represents a Li, Na or K, R ^a is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups A complex alkylated product of a metal belonging to Group 1 of the periodic table and aluminum.

(C-1c) Formula R ^a R ^b M ³ (wherein R ^a and R ^b may be the same or different and each have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) A dialkyl compound of a metal of Group 2 or 12 of the periodic table represented by a hydrocarbon group, wherein M ³ is Mg, Zn or Cd.

As the organoaluminum compound belonging to (C-1a), the following compounds can be exemplified. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, 1 to 15, preferably 1 to 4 hydrocarbon group having carbon atoms are shown, m is preferably a number 1.5 ≦ m ≦ 3.) an organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms 15, preferably 1
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 from each other, the number of 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, the organoaluminum compounds belonging to (C-1a) include trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum. Tri-n-alkyl aluminum such as triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-
Butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexyl Aluminum, tribranched alkyl aluminum such as tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum such as diisobutyl aluminum hydride Hydride; (i-C ₄ H ₉ ) _x
Trialkenyl aluminum such as triisoprenyl aluminum represented by Al _y (C ₅ H ₁₀ ) _z (where x, y and z are positive numbers and z ≧ 2x); isobutylaluminum methoxy Aluminum alkoxides such as dimethyl, isobutylaluminum ethoxide and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkyls such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide Aluminum sesquialkoxide; ^Ra
_2.5 Al (OR ^b ) _0.5 A partially alkoxylated alkyl aluminum having an average composition such as _0.5 ; diethyl aluminum phenoxide, diethyl aluminum (2,6-di-t-butyl-4-methylphenoxide), ethyl Aluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-
Dialkyl aluminum aryloxides such as 4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutyl Dialkylaluminum halides such as aluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; parts such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide Alkyl aluminum halides; diethyl aluminum hydride Dialkylaluminum hydrides such as dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as ethylaluminum dihydride, alkylaluminum dihydrides such as propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum Partially alkoxylated and halogenated alkyl aluminums such as ethoxy bromide and the like.

Also, a compound similar to (C-1a) is used.
For example, two or more aluminum
Organoaluminum compounds to which an aluminum compound is bound
It is. As such a compound, specifically, (C_TwoH_Five)_Two
AlN (C_TwoH_Five) Al (C_TwoH_Five) _TwoAnd the like.

Compounds belonging to the above (C-1b) include L
iAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . In addition, as the (C-1) organometallic compound, methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium Chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium and the like can also be used.

Further, a compound which forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium can also be used.

Among the organometallic compounds (C-1), organoaluminum compounds are preferred. The above-mentioned (C-1) organometallic compounds are used alone or in combination of two or more.

(C-2) Organoaluminum oxy compound The organoaluminum oxy compound (C-2) used as necessary in the present invention may be a conventionally known aluminoxane, and JP-A-2-78687. And a benzene-insoluble organoaluminum oxy compound as exemplified in (1).

The conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate,
An organic aluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension such as aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, and adsorbed water or water of crystallization is added to the organic aluminum. A method of reacting with a compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. The solvent or unreacted organoaluminum compound may be removed from the recovered solution of the aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of the organoaluminum compound used in preparing the aluminoxane include the above-mentioned (C-1)
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to a) can be mentioned.

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene and gas oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons (E.g., chlorinated products, brominated products, etc.). Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component soluble in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Certain, ie, those that are insoluble or poorly soluble in benzene, are preferred.

The above-mentioned (C-2) organoaluminum oxy compounds are used alone or in combination of two or more. (C-3) Reaction with transition metal compounds to form ion pairs
Transition metal compound is optionally used in the compound (A) of the invention
Compounds which form an ion pair by reacting with (hereinafter referred to as "ionized ionic compounds") (C-3) are described in JP-A-1-501950, JP-A-1-502036, and JP-A-3-503. No. 179005, JP-A-3-1790
06, JP-A-3-207703, JP-A-3-207703
Examples include Lewis acids, ionic compounds, borane compounds and carborane compounds described in US Pat. No. 207704 and US Pat. No. 5,321,106.

Specifically, examples of the Lewis acid include BR
₃ (R is a phenyl group or a fluorine atom which may have a substituent such as fluorine, a methyl group and a trifluoromethyl group.), For example, trifluoroboron, triphenylboron, Tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o- Tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include compounds represented by the following general formula (II).

[0106]

Embedded image

In the formula, R ¹⁹ includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{20 to} R ²³ may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; Nium cation, N,
N, N-dialkylanilinium cations such as N-diethylanilinium cation and N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation No.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

As R ¹⁹ , a carbonium cation, an ammonium cation and the like are preferable, and a triphenylcarbonium cation, an N, N-dimethylanilinium cation and an N, N-diethylanilinium cation are particularly preferable.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts,
Dialkylammonium salts, triarylphosphonium salts and the like can also be mentioned.

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p -Tolyl) boron, trimethylammoniumtetra (o-tolyl) boron, tri (n-butyl) ammoniumtetra (pentafluorophenyl) boron, tripropylammoniumtetra (o, p-dimethylphenyl) boron,
Tri (n-butyl) ammonium tetra (m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditri Fluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron and the like.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like.

Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (III) or (IV) can also be mentioned.

[0117]

Embedded image

(In the formula, Et represents an ethyl group.)

[0119]

Embedded image

Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and bis [tri (n-butyl) ammonium Anions such as undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, and bis [tri (n-butyl) ammonium] dodecachlorododecaborate Metals such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III) And borane anion salts.

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl- 1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane,
Undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane (13), 2,7-dicarboundecaborane (13), undecahydride
-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane,
Tri (n-butyl) ammonium 1-carbadecaborate,
Tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) Ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarboundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarboundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-
Methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaune decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaune Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salts of anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III) (N-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarboundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Metal carborane anions such as (carboundecaborate) nickelate (IV).

The above-mentioned (C-3) ionized ionic compounds are used alone or in combination of two or more. In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components.

In the olefin polymerization method according to the present invention, the transition metal compound (A) and the mesoporous solid (B)
And, if necessary, at least one compound (C) selected from the above-mentioned organometallic compounds (C-1), organoaluminum oxy compounds (C-2) and ionized ionic compounds (C-3). An olefin polymerization catalyst (solid catalyst) is used.

In the olefin polymerization catalyst used in the present invention, the transition metal compound (A) and, if necessary, the compound (C) are supported in the pores of the mesoporous solid (B).
This olefin polymerization catalyst can be prepared by mixing and contacting the transition metal compound (A) and the mesoporous solid (B) in an inert hydrocarbon solvent. When the components are mixed and contacted, the compound (C) can be further added.

In order to collect acidic substances generated when the transition metal compound (A) and the mesoporous solid (B) are brought into contact with each other, a basic substance such as triethylamine or tributylamine may be used during catalyst preparation. Alkylamines can also be added.

When the compound (C) is used, the order of mixing is arbitrarily selected. Preferably, the compound (C) is added after the transition metal compound (A) and the mesoporous solid (B) are brought into contact in advance. Or mixing the mesoporous solid (B) with the compound (C) in advance and then adding and mixing the transition metal compound (A).

After the mixed contact, the amount of the transition metal compound (A) supported on the mesoporous solid (B) was determined per 1 g of the mesoporous solid (B) per transition metal in the transition metal compound (A). 10 ^-8 to 10 ^-3 mol, preferably 10 ^-6 , in terms of the amount of atoms
It is prepared to 〜１０10 ^-4 mol.

The inert hydrocarbon solvent used in the preparation of the olefin polymerization catalyst in the present invention includes, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene;
Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

As the compound (C), an organometallic compound (C-1)
Is used, the molar ratio of the organometallic compound (C-1) to the transition metal atom (M) in the transition metal compound (A) [(C
-1) / M] is usually used in an amount of 0.1 to 100,000, preferably 0.5 to 50,000. When the organic aluminum oxy compound (C-2) is used as the compound (C), the organic aluminum oxy compound (C-
The molar ratio [(C-2) / M] between the aluminum atom in 2) and the transition metal atom (M) in the transition metal compound (A) is usually 10 to 50,000, preferably 20 to 10,000. Used in appropriate amounts. When the ionized ionic compound (C-3) is used as the compound (C), the molar ratio of the ionized ionic compound (C-3) to the transition metal atom (M) in the transition metal compound (A) [ (C-3) / M] is usually 1-2.
It is used in an amount such that it becomes 0, preferably 1 to 10.

The mixing temperature when the above components are mixed is usually -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time is 0.01 to 120 hours, preferably 0.1 to 120 hours.
05-72 hours. Further, the mixing temperature may be changed during the mixing contact.

The olefin polymerization catalyst according to the present invention may be a prepolymerized catalyst obtained by prepolymerizing an olefin. In the olefin polymerization method according to the present invention, an olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the olefin 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. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane Alicyclic hydrocarbons such as benzene, toluene, xylene, etc .; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and mixtures thereof. Can also be used.

When olefin polymerization or copolymerization is carried out using the olefin polymerization catalyst as described above, the amount of the transition metal atom in the transition metal compound (A) contained in the olefin polymerization catalyst is determined by the reaction amount. Volume 100
It is usually used in an amount of 10 ^-10 to 1 mol, preferably 10 ^-8 to 10 ^-2 mol per milliliter. At this time, if necessary, the organic aluminum oxy compound (component
(C-2)) can be used. In this case, the amount of the organic aluminum oxy compound is desirably 20 to 50,000, preferably 50 to 10,000 mol per mol of the transition metal atom in the transition metal compound (A).

The polymerization temperature is usually in the range of −50 to 100 ° C., preferably 0 to 90 ° C. when performing the slurry polymerization method, and is usually in the range of 0 to 90 ° C. when performing the liquid phase polymerization method. The temperature is desirably in the range of 0 to 250C, preferably 20 to 200C. When carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to 120 ° C, preferably 20 ° C.
It is desirable that the temperature be in the range of -100 ° C. The polymerization pressure is
Usually, normal pressure to 9.8 MPa, preferably normal pressure to 4.9 M
Under the conditions of Pa, the polymerization reaction is a batch type, a semi-continuous type,
It can be carried out in any of the continuous methods. Further, the polymerization can be performed in two or more stages having different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by adding hydrogen to the polymerization system or changing the polymerization temperature. Furthermore, it can be adjusted by the difference of the component (C) used.

The olefin that can be polymerized with such an olefin polymerization catalyst has 2 carbon atoms.
-30, preferably 2-20 linear or branched α
Olefins, such as ethylene, propylene, 1-butene, 2-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-hexadecene, 1-octadecene, 1-eicosene; a cyclic olefin having 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2 -Methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; polar monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, Itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene
Α, β-unsaturated carboxylic acids such as -2,3-dicarboxylic anhydride and α, β-unsaturated carboxylic acids such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt and calcium salt thereof Metal salts: methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate Α, such as n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate
β-unsaturated carboxylic esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, and itacone Unsaturated glycidyl such as acid monoglycidyl ester; and halogen-containing olefins such as vinyl chloride and chloroprene. Further, vinylcyclohexane, diene, polyene, or the like can be used.

As the diene or polyene, a cyclic or chain compound having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds is used. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,
5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl Norbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-
8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene; further aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-
Mono- or poly-alkyl styrene such as ethyl styrene and p-ethyl styrene; methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene, etc. And 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like.

These olefins can be used alone or
It can be used in combination of more than one kind. As described above, the transition metal compound (A) and, if necessary, the organometallic compound (C-1), the organoaluminum oxy compound (C-2) and the ionized ionic compound (B) are added to the mesoporous solid (B). When an olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst carrying at least one compound (C) selected from C-3), a fibrous olefin polymer is obtained in a cocoon shape.

The fiber diameter of the fibrous olefin polymer obtained by the polymerization method of the present invention is usually in the range of 30 to 50 nm. The fibrous olefin polymer is 135
C., intrinsic viscosity [η] measured in decalin is 0.1 to 5
It is in the range of 0 dl / g, preferably 1 to 40 dl / g, and the degree of crystallinity determined by the X-ray diffraction method is 70% or more, preferably 75% or more.

[0140]

According to the olefin polymerization method of the present invention, a highly crystalline and highly oriented fibrous olefin polymer can be produced with high activity.

The fibrous olefin polymer obtained by the method of the present invention has various physical properties such as high strength as compared with polyolefin fibers produced by a conventional method, so that it can be developed for various uses. Be expected.

[0142]

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

In this example, the intrinsic viscosity ([η]) was measured at 135 ° C. in decalin.

[0144]

Example 1 (Synthesis of mesoporous solid) A mesoporous compound was synthesized according to the method described in Adv. Mater. 9, 974 (1997). That is, in a 500 ml glass reactor, 14
Cetyltrimethylammonium bromide dissolved in 0 g of water and 47 g of 6N HCl were added and stirred.
To the resulting solution, 1.11 g of tetraethoxysilane dissolved in 45 g of hexane was added over 1 hour without stirring. The reaction mixture separated into two layers was allowed to stand for 3 days without stirring. The solid formed in the aqueous phase was filtered and dried at room temperature. Subsequently, in order to remove organic substances contained in the solid, the temperature was raised from room temperature to 500 ° C. over 10 hours in a stream of air, and then calcined at 500 ° C. for 8 hours. As a result, mesoporous zeolite having a pore size of 2.7 nm was obtained.

(Preparation of solid catalyst component)
In a 0 ml glass reactor, 0.3 g of mesoporous zeolite synthesized as described above and 14.5 mg (0.0 g) of the following compound 1 dissolved in 40 ml of methylene chloride were used.
23 mmol) and 0.2 g of triethylamine were mixed at room temperature and stirred for 2 hours. Thereafter, the solution was filtered, and the solid was washed with 20 ml of methylene chloride three times, and then dried under reduced pressure to obtain a light brown powder (solid catalyst component). This solid catalyst component contains 1 g of mesoporous zeolite,
0.05 mmol of Ti atoms were supported.

[0146]

Embedded image

(Polymerization) After sufficiently replacing the stainless autoclave having a capacity of 100 ml with a glass cylinder having a diameter of 2.5 cm and a stirrer chip inserted with nitrogen, 50 mg of the solid catalyst component obtained as described above (Ti atom 0.0025
mmol), 17.5 ml of toluene, and 2.5 ml of a toluene solution of methylaluminoxane (3 mmol of Al atom).
l) and stirred at 20 ° C. for 1 hour. Next, the inside of the system was pressurized with 8 kg / cm ² G of ethylene, and the mixture was stirred for 4 hours while continuously maintaining the pressure and temperature by continuously supplying ethylene. The cocoon-shaped polymer obtained after the reaction was immersed in 200 ml of benzene, stirred for 48 hours, and then freeze-dried to obtain 1.4 g of a polymer. The obtained polyethylene had a [η] of 22 dl / g, and its structure was observed with a scanning electron microscope. As a result, it was found that the fiber had a fiber diameter of 30 to 50 nm.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a process for preparing an olefin polymerization catalyst used in the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Makoto Mitani 580-32, Takuji Nagaura, Sodegaura City, Chiba Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Terunori Fujita Takuji Nagaura, Sodegaura City, Chiba Prefecture No. 580 No. 32 Mitsui Chemicals Co., Ltd. F-term (reference) 4J015 EA00 4J028 AA01A AB00A AB01A AC01A AC08A AC09A AC10A AC18A AC19A AC20A AC26A AC27A AC28A AC29A AC31A AC37A AC38A AC39A AC41A AC42A AC44A AC45BA01B BB00B BB01B BB02B BC12B BC13B BC15B BC16B BC19B BC24B BC25B BC27B BC29B BC30B CA02C CA28C CA54C CB63C EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB11 EB12 EB13 EB14 EB17 FA02 EB17 FA24 EB17 FA04

Claims (3)

[Claims] An olefin polymerization catalyst comprising: (A) a transition metal compound represented by the following general formula (I); and (B) a mesoporous solid having a pore diameter in a range of 1.5 to 10 nm. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing the olefin in the presence of the olefin; (Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , R ^{1 to} R ⁶ may be the same or different, and may be a 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-containing group or tin-containing group, Two or more of them may be connected to each other to form a ring, and when m is 2 or more, two or more of the groups represented by R ^{1 to} R ⁶ may be connected to each other. 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, and a phosphorus-containing group. Group, halogen-containing group, heterocyclic compound residue, silicon-containing group, When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring. May be formed). (A) a transition metal compound represented by the following general formula (I); (B) a mesoporous solid having a pore diameter in the range of 1.5 to 10 nm; -1) an organic metal compound, (C-2) an organic aluminum oxy compound, and (C-3) at least one compound selected from compounds which react with the transition metal compound (A) to form an ion pair. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of an olefin polymerization catalyst; (Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , R ^{1 to} R ⁶ may be the same or different, and may be a 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-containing group or tin-containing group, Two or more of them may be connected to each other to form a ring, and when m is 2 or more, two or more of the groups represented by R ^{1 to} R ⁶ may be connected to each other. 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, and a phosphorus-containing group. Group, halogen-containing group, heterocyclic compound residue, silicon-containing group, When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring. May be formed). 3. A fiber having a fiber diameter of 30 obtained by the olefin polymerization method according to claim 1 or 2.
~ 50 nm fibrous olefin polymer.