JP2003183316A - Olefin polymerization catalyst and method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst having an excellent activity of polymerizing olefins, and to provide an olefin polymerization method using the same. <P>SOLUTION: The olefin polymerization catalyst comprises (A) a transition metal compound represented by general formula (I) or comprises (A) the transition metal compound represented by the formula (I) and (B) at least one compound selected from among (B-1) an organometallic compound, (B-2) an organoaluminumoxy compound, and (B-3) a compound which reacts with the transition compound (A) to form an ion pair. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel olefin polymerization catalyst and a process for olefin polymerization using the olefin polymerization catalyst.

[0002]

2. Description of the Related Art Generally, polyolefins are used in various fields such as for various molded products because of their excellent mechanical properties. In recent years, however, the demands for physical properties of polyolefins have been diversified, and they have various properties. Polyolefins are desired. In addition, productivity improvement is also desired.

The so-called Kaminsky catalyst is well known as a catalyst for olefin polymerization. This catalyst has a very high polymerization activity and is characterized in that a polymer having a narrow molecular weight distribution can be obtained. Examples of the transition metal compound used in such a Kaminsky catalyst include bis (cyclopentadienyl) zirconium dichloride (JP-A-58-58).
19309) and ethylene bis (4,5,5)
6,7-Tetrahydroindenyl) zirconium dichloride (see JP-A-61-130314) and the like are known. In addition, a transition metal compound having a ligand having a diimine structure (see WO 9623010) has recently been proposed as a new catalyst for olefin polymerization.

More recently, as a new olefin polymerization catalyst, the present applicant has proposed a transition metal compound having a salicylaldimine ligand as WO 01/55231. In this case, it shows a high living polymerizability in olefin polymerization, and various block polymers can be produced, but there is still room for improvement in its polymerization activity.
Further improvements were desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an olefin polymerization catalyst having excellent olefin polymerization activity. Furthermore, it aims at providing the olefin polymerization method using this catalyst for olefin polymerization.

[0006]

The olefin polymerization catalyst according to the present invention is characterized by comprising (A) a transition metal compound represented by the following general formula (I).

[0007]

[Chemical 7]

(In the formula, M represents a titanium atom, and m is 1
To R 2, R ¹ represents a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms, R ⁴ represents a hydrocarbon group having 5 or more carbon atoms, and a primary or secondary hydrocarbon group having 4 or less carbon atoms. A group selected from three groups of a group and a hydrocarbon-substituted silyl group,
R ⁶ represents a t-butyl group, R ² , R ³ and R ⁵ may be the same or different from each other and represent a hydrocarbon group, a hydrogen atom or a hydrocarbon-substituted silyl group, and m is 2 In the case of, two of the groups represented by R ² , R ³ and R ⁵ may be linked, and n is a number satisfying 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, or a silicon-containing group. A group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X are bonded to each other. May form a ring. )

The olefin polymerization catalyst of the present invention comprises
(A) a transition metal compound represented by the following general formula (I),
(B) (B-1) organometallic compound, (B-2) organoaluminum oxy compound, and (B-3) at least one selected from compounds that react with the transition metal compound (A) to form an ion pair It is preferred that the compound of

[0010]

[Chemical 8]

(In the formula, M represents a titanium atom, and m is 1
Indicates an integer of 2 and R¹Is a fluorine-containing compound having 1 to 30 carbon atoms.
Represents a hydrocarbon group, R^FourIs a hydrocarbon having 5 or more carbon atoms
Carbon having 4 or less carbon atoms consisting only of primary, primary or secondary carbon
It is selected from three types of groups: hydrogenated groups and hydrocarbon-substituted silyl groups.
R represents a group exposed⁶Represents a t-butyl group, R², R
³, R^FiveMay be the same or different from each other,
Represents a hydrogen atom or a hydrocarbon-substituted silyl group,
If m is 2, R², R³, R^FiveGroup
2 groups may be linked together, and n is the valence of M.
X is a hydrogen atom, halogen atom, carbonized
Hydrogen group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boro
Element-containing group, aluminum-containing group, phosphorus-containing group, halogen
Containing group, heterocyclic compound residue, silicon-containing group, germanium
Indicates a group containing nickel or a group containing tin, and n is 2 or more.
In this case, the plural groups represented by X are the same or different from each other.
Or a plurality of groups represented by X are bonded to each other.
To form a ring. )

Another embodiment of the olefin polymerization catalyst according to the present invention is characterized by comprising (A) a transition metal compound represented by the following general formula (II).

[0013]

[Chemical 9]

(In the formula, M represents a titanium atom, and m is 1
R2 is an integer of 2 to 4, and R ⁷ is a phenyl group having 4 or less nuclear-bonded fluorine atoms, a fluorine-containing aromatic hydrocarbon group having 7 to 30 carbon atoms and a fluorine-containing aliphatic group having 1 to 30 carbon atoms. R < ¹⁰ >, R < ¹² > represents a t-butyl group, R < ⁸ >, R <^9> , R < ¹¹ >, which may be the same or different, are a hydrocarbon group, a hydrogen atom or a hydrocarbon substitution group. A silyl group, and when m is 2, R ⁸ , R ⁹ ,
Two of the groups represented by R ¹¹ may be linked, n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, Sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, or tin-containing group, n is 2 or more In the case of, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. )

The olefin polymerization catalyst of the present invention comprises:
(A) a transition metal compound represented by the following general formula (II), (B) (B-1) an organometallic compound, (B-2)
It is preferably composed of an organoaluminum oxy compound and (B-3) at least one compound selected from compounds that react with the transition metal compound (A) to form an ion pair.

[0016]

[Chemical 10]

(In the formula, M represents a titanium atom, and m is 1
R2 is an integer of 2 to 4, and R ⁷ is a phenyl group having 4 or less nuclear-bonded fluorine atoms, a fluorine-containing aromatic hydrocarbon group having 7 to 30 carbon atoms and a fluorine-containing aliphatic group having 1 to 30 carbon atoms. R < ¹⁰ >, R < ¹² > represents a t-butyl group, R < ⁸ >, R <^9> , R < ¹¹ >, which may be the same or different, are a hydrocarbon group, a hydrogen atom or a hydrocarbon substitution group. A silyl group, and when m is 2, R ⁸ , R ⁹ ,
Two of the groups represented by R ¹¹ may be linked, n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, Sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, or tin-containing group, n is 2 or more In the case of, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. )

The olefin polymerization method of the present invention is characterized by polymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst.

The olefin polymerization method of the present invention comprises:
(A) an olefin polymerization catalyst comprising a transition metal compound represented by the following general formula (III), or (A) a transition metal compound represented by the following general formula (III); ) (B-1) Organometallic compound, (B-
2) Organoaluminum oxy compound, and (B-
3) Homopolymerization of ethylene and an α-olefin having 4 or more carbon atoms or ethylene and 4 carbon atoms in the presence of at least one compound selected from compounds that react with the transition metal compound (A) to form an ion pair. It is characterized by copolymerizing the above α-olefins.

[0020]

[Chemical 11]

(In the formula, M represents a titanium atom, and m is 1 to
2 is an integer of 2, R ¹³ is a pentafluorophenyl group, R ¹⁶ and R ¹⁸ are t-butyl groups, R ¹⁴ and
R ¹⁵ and R ^{17, which} may be the same or different, each represents a hydrocarbon group, a hydrogen atom or a hydrocarbon-substituted silyl group, and when m is 2, represented by R ¹⁴ , R ¹⁵ and R ¹⁷ . Two groups may be linked together, n is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, or nitrogen. Content group, boron content group, aluminum content group, phosphorus content group,
Represents a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, n
When is 2 or more, the plural groups represented by X may be the same or different from each other, and the plural groups represented by X may be bonded to each other to form a ring. )

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The olefin polymerization catalyst of the present invention and the olefin polymerization method using this catalyst will be specifically described below.

In the present specification, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" refers not only to homopolymers. In some cases, it is used in the sense of including a copolymer.

The olefin polymerization catalyst according to the present invention is
(A) a transition metal compound represented by the following general formula (I), or (A) a transition metal compound represented by the following general formula (I), and (B) (B-1) an organometallic compound, ( B-
2) Organoaluminum oxy compound, and (B-
3) It is formed from at least one compound selected from compounds that react with the transition metal compound (A) or the transition metal compound (B) to form an ion pair.

[(A) Transition Metal Compound] The (A) transition metal compound used in the present invention is a compound represented by the following general formula (I).

[0026]

[Chemical 12]

(Note that N ... M generally indicates coordination, but in the present invention, it may or may not coordinate.) In the general formula (I), M is a titanium atom.

M is 2. R ¹ represents a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms, R ⁴ represents a hydrocarbon group having 5 or more carbon atoms, a hydrocarbon group having 4 or less carbon atoms and a hydrocarbon group having only primary or secondary carbon, and a hydrocarbon. A group selected from three types of substituted silyl groups, R ⁶ represents a t-butyl group,
R ² , R ³ and R ^{5, which} may be the same or different, each represents a hydrocarbon group, a hydrogen atom or a hydrocarbon-substituted silyl group, two or more of which are linked to each other to form a ring. May be.

Specific examples of the fluorine-containing hydrocarbon group of R ¹ having 1 to 30 carbon atoms include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl and monofluorophenyl. , Difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, (trifluoromethyl) fluorophenyl,
Trifluoromethylphenyl, bis (trifluoromethyl) phenyl, tris (trifluoromethyl) phenyl, tetrakis (trifluoromethyl) phenyl, pentakis (trifluoromethyl) phenyl, perfluoroethylphenyl, bis (perfluoroethyl) phenyl, Perfluoropropylphenyl, perfluorobutylphenyl, perfluoropentylphenyl, perfluorohexylphenyl, bis (perfluorohexyl)
Examples include phenyl, perfluoronaphthyl, perfluorophenanthrenyl, perfluoroanthracenyl, and the like.

Preferably, R ¹ is an aromatic hydrocarbon group having 6 to 30 carbon atoms and having a fluorine substituent or a fluorine-containing hydrocarbon substituent, specifically, monofluorophenyl, difluorophenyl, trifluorophenyl, Tetrafluorophenyl, pentafluorophenyl, (trifluoromethyl) fluorophenyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, tris (trifluoromethyl) phenyl, tetrakis (trifluoromethyl) phenyl, pentakis (trifluoromethyl) ) Phenyl, perfluoroethylphenyl, bis (perfluoroethyl) phenyl, perfluoropropylphenyl, perfluorobutylphenyl, perfluoropentylphenyl, perfluorohexylphenyl, bis (perfluoro) Hexyl) phenyl, perfluoronaphthyl, perfluoro phenanthrenyl, perfluoro anthracenyl, and the like.

More preferably, R ¹ is an aromatic hydrocarbon group having 6 to 30 carbon atoms and having two or more substituents selected from the group consisting of a fluorine substituent and a fluorine-containing hydrocarbon substituent, and specifically, Is difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, (trifluoromethyl) fluorophenyl,
Bis (trifluoromethyl) phenyl, tris (trifluoromethyl) phenyl, tetrakis (trifluoromethyl) phenyl, pentakis (trifluoromethyl) phenyl, bis (perfluoroethyl) phenyl, bis (perfluorohexyl) phenyl, etc. Can be mentioned.

Particularly preferably, R ¹ is a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group or a pentafluorophenyl group. In this case, a 2,6-difluorophenyl group, 2,
Specific examples include a 4,6-trifluorophenyl group and a pentafluorophenyl group.

Examples of the hydrocarbon group represented by R ² , R ³ and R ⁵ include those having 1 to 30 carbon atoms. In particular,
Methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, neopentyl, n-hexyl and the like have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Chain or branched alkyl group; vinyl, allyl, i-propenyl and the like having 2 to 2 carbon atoms
30, preferably 2 to 20 straight or branched alkenyl groups; ethynyl, propargyl, etc., having 2 carbon atoms
-30, preferably 2-20, linear or branched alkynyl group; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc., having 3 to 30 carbon atoms, preferably 3 to 20 cyclic saturated carbon atoms. A hydrogen group; a cyclounsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl, fluorenyl; a carbon atom number of 6 to 30, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, Preferably, an aryl group having 6 to 20; an alkyl-substituted aryl group such as tolyl, i-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl, and the like.

The above hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl and cumyl.

Examples of the hydrocarbon-substituted silyl group for R ² , R ³ and R ⁵ include groups having 1 to 30 carbon atoms in total. Specific examples thereof include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl and dimethyl (pentafluorophenyl) silyl. Of these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly, trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are preferable.

Examples of the hydrocarbon group having 5 or more carbon atoms for R ⁴ include those having 5 to 30 carbon atoms. Specifically, a linear or branched alkyl group having 5 to 30, preferably 5 to 20 carbon atoms such as n-pentyl, neopentyl, and n-hexyl; the number of carbon atoms such as cyclopentyl, cyclohexyl, and adamantyl. Is a hydrocarbon group having a monocyclic or polycyclic alicyclic skeleton of 5 to 30, preferably 5 to 20; phenyl, benzyl, naphthyl, biphenylyl, triphenylyl, fluorenyl, anthranyl, phenanthryl and the like having 6 carbon atoms. To 30 and preferably 6 to 20 aryl groups; and these groups having 1 to 30 and preferably 1 to 20 carbon atoms, and aryl groups having 6 to 30 and preferably 6 to 20 carbon atoms. A group in which a substituent such as a group is further substituted is preferred.

[0037] The primary or secondary only hydrocarbon group having 4 or less carbon atoms consisting of carbon of R ^4, a hydrocarbon carbon directly bonded to the benzene skeleton in the carbon of R ⁴ is a primary or secondary carbon A group, and examples thereof include those having 1 to 4 carbon atoms. Specifically, methyl, ethyl, n-propyl,
Examples thereof include alkyl groups having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms such as i-propyl, n-butyl, i-butyl and s-butyl.

R ⁶ is a t-butyl group.

N is a number satisfying the valence of M, specifically, an integer of 2 to 4, and preferably 2. X is
Hydrogen atom, halogen atom, hydrocarbon group, oxygen containing group, sulfur containing group, nitrogen containing group, boron containing group, aluminum containing group, phosphorus containing group, halogen containing group, heterocyclic compound residue, silicon containing group, germanium A containing group or a tin containing group is shown. When n is 2 or more, the groups represented by X may be the same as or different from each other, and the groups represented by X are bonded to each other to form a ring. Good.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. As the hydrocarbon group, the above R
^The same as those exemplified for ² , R ³ and R ⁵ can be mentioned. Specifically, methyl, ethyl, propyl, butyl,
Alkyl groups such as hexyl, octyl, nonyl, dodecyl, and eicosyl; carbon atoms such as cyclopentyl, cyclohexyl, norbornyl and adamantyl having 3 to 30 carbon atoms.
Cycloalkyl group; alkenyl group such as vinyl, propenyl, cyclohexenyl; arylalkyl group such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl,
Examples thereof include aryl groups such as naphthyl, methylnaphthyl, anthryl, and phenanthryl, but are not limited thereto. In addition, these hydrocarbon groups include
A halogenated hydrocarbon, specifically, a group in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is replaced with halogen is also included.

Examples of the heterocyclic compound residue include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran,
Residues such as sulfur-containing compounds such as thiophene, and groups obtained by further substituting these heterocyclic compound residues with a substituent such as an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Is mentioned.

Specific examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy;
Examples thereof include arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; carbonyl groups and the like, but are not limited thereto.

Specific examples of the sulfur-containing group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate and tri i. -Sulfonate groups such as butylbenzene sulfonate, p-chlorobenzene sulfonate and pentafluorobenzene sulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzene Examples thereof include, but are not limited to, sulfinate groups such as sulfinate and pentafluorobenzenesulfinate; alkylthio groups; arylthio groups.

Specific examples of the nitrogen-containing group include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; phenylamino, diphenylamino and 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; triarylphosphine groups such as triphenylphosphine and tritolylphosphine; methylphosphite, ethylphosphite, Examples thereof include, but are not limited to, phosphite groups (phosphide groups) such as phenylphosphite; phosphonic acid groups; phosphinic acid groups.

Specific examples of the silicon-containing group include hydrocarbons such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl. Substituted silyl groups; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylsilylphenyl.

Specific examples of the germanium-containing group include groups in which silicon in the silicon-containing group is replaced with germanium. Specific examples of the tin-containing group include groups in which silicon in the silicon-containing group is replaced with tin.

Specific examples of the halogen-containing group include P
F₆, BF_FourFluorine-containing groups such as ClO _Four, SBCl₆Na
Which chlorine-containing group, IO_FourIodine-containing groups such as
However, the present invention is not limited to these.

Specifically as the aluminum-containing group, A
1R ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom or the like).
It is not limited to these.

Transition metal compound (A) used in the present invention
As a preferred structure of the above general formula (I) M is a titanium atom, m is 2, and R ¹ is an aromatic hydrocarbon group having 6 to 30 carbon atoms and having at least 3 or more fluorine substituents. Preferably there is. Further, it is particularly preferable that R ¹ is a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group or a pentafluorophenyl group.

Specific examples of the transition metal compound represented by the above general formula (I) are shown below, but the invention is not limited thereto.

[0053]

[Chemical 13]

In the above example, Me represents a methyl group and E represents
t is an ethyl group, Pr is a propyl group, Bu is a butyl group, Ph is a phenyl group, and Bn is a benzyl group.

Another form of the olefin polymerization catalyst according to the present invention is (A) a transition metal compound represented by the following general formula (II), or (A) a transition metal compound represented by the following general formula (II). Ions by reacting with a metal compound, (B) (B-1) organometallic compound, (B-2) organoaluminum oxy compound, and (B-3) transition metal compound (A) or transition metal compound (B) It is formed from at least one compound selected from pair-forming compounds.

[(A) Transition Metal Compound] The (A) transition metal compound used in the present invention has the following general formula (II).
Is a compound represented by.

[0057]

[Chemical 14]

(Note that N ... M generally indicates coordination, but in the present invention, it may or may not coordinate.) In the general formula (II), M is a titanium atom.

M, n and X are the same as in the general formula (I). R ⁸ , R ⁹ , R ¹¹ and R ¹² are respectively the same as R ² , R ³ , R ⁵ and R ^{6 in} formula (I).

Specific examples of R ⁷ include a phenyl group having 4 or less nuclear-bonded fluorine atoms, a fluorine-containing aromatic hydrocarbon group having 7 to 30 carbon atoms or a fluorine-containing aliphatic group having 1 to 30 carbon atoms. Is trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, (trifluoromethyl) fluorophenyl, trifluoro Methylphenyl,
Bis (trifluoromethyl) phenyl, tris (trifluoromethyl) phenyl, tetrakis (trifluoromethyl) phenyl, pentakis (trifluoromethyl) phenyl, perfluoroethylphenyl, bis (perfluoroethyl) phenyl, perfluoropropylphenyl, Examples include perfluorobutylphenyl, perfluoropentylphenyl, perfluorohexylphenyl, bis (perfluorohexyl) phenyl, perfluoronaphthyl, perfluorophenanthrenyl, perfluoroanthracenyl and the like.

R ⁷ is preferably a phenyl group having 4 or less nuclear-bonded fluorine atoms, a fluorine substituent or an aromatic hydrocarbon group having 7 to 30 carbon atoms and having a fluorine-containing hydrocarbon substituent. Includes monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, (trifluoromethyl) fluorophenyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, tris (trifluoromethyl) phenyl, tetrakis (trifluoro). Methyl) phenyl, pentakis (trifluoromethyl) phenyl, perfluoroethylphenyl, bis (perfluoroethyl) phenyl, perfluoropropylphenyl, perfluorobutylphenyl, perfluoropentylphenyl, perfluorohexyl Eniru, bis (perfluorohexyl) phenyl, perfluoronaphthyl, perfluoro phenanthrenyl, perfluoro anthracenyl, and the like.

More preferably, R ⁷ is a phenyl group having 4 or less nuclear-bonded fluorine atoms, a fluorine substituent or an aromatic hydrocarbon group having 7 to 30 carbon atoms and having a fluorine-containing hydrocarbon substituent. Difluorophenyl, trifluorophenyl, tetrafluorophenyl,
(Trifluoromethyl) fluorophenyl, bis (trifluoromethyl) phenyl, tris (trifluoromethyl) phenyl, tetrakis (trifluoromethyl) phenyl, pentakis (trifluoromethyl) phenyl, bis (perfluoroethyl) phenyl, bis ( Perfluorohexyl) phenyl, and the like.

Particularly preferably, R ⁷ is a difluorophenyl group, a trifluorophenyl group or a tetrafluorophenyl group. In this case, a 2,6-difluorophenyl group, a 2,4,6-trifluorophenyl group and the like can be specifically exemplified.

R ¹⁰ is a t-butyl group. R ¹² is a t-butyl group.

Transition metal compound (A) used in the present invention
As the preferred structure of, the general formula (II) M is a titanium atom, m is 2, and R ⁷ is an aromatic hydrocarbon group containing 4 or less directly bonded fluorine atoms. . Further, it is particularly preferable that R ⁷ is a difluorophenyl group, a trifluorophenyl group or a tetrafluorophenyl group.

Specific examples of the transition metal compound represented by the general formula (II) are shown below, but the invention is not limited thereto.

[0067]

[Chemical 15]

In the above example, Bu represents a butyl group.

The method for producing such a transition metal compound (A) is not particularly limited and can be produced, for example, as follows.

First, as a ligand constituting the transition metal compound (A), a salicylaldehyde compound is represented by the formula R ¹ -NH ₂
Alternatively, it can be obtained by reacting with a primary amine compound of R ⁷ —NH ₂ (R ¹ or R ⁷ has the same meaning as described above), for example, an aniline compound or an alkylamine compound. Specifically, both starting compounds are dissolved in a solvent. As the solvent, those commonly used in such reactions can be used, but among them, alcohol solvents such as methanol and ethanol, or hydrocarbon solvents such as toluene are preferable. Then, the obtained solution is stirred at room temperature to reflux conditions for about 1 to 48 hours to obtain the corresponding ligand in good yield. As a catalyst when synthesizing a ligand compound,
An acid catalyst such as formic acid, acetic acid or toluenesulfonic acid may be used. In addition, when molecular sieves, magnesium sulfate or sodium sulfate is used as a dehydrating agent or dehydration is performed by Dean Stark, it is effective for the reaction progress.

Then, the ligand thus obtained is reacted with a transition metal M-containing compound to synthesize a corresponding transition metal compound. Specifically, the synthesized ligand is dissolved in a solvent and, if necessary, brought into contact with a base to prepare a phenoxide salt, and then mixed with a metal compound such as a metal halide or a metal alkylated compound at a low temperature. , -78
Stir for about 1 to 48 hours under the conditions of ℃ to room temperature or reflux. As the solvent, those commonly used in such a reaction can be used, but among them, polar solvents such as ether and tetrahydrofuran (THF), hydrocarbon solvents such as toluene and the like are preferably used. The base used when preparing the phenoxide salt is preferably a lithium salt such as n-butyllithium, a metal salt such as sodium salt such as sodium hydride, or an organic base such as triethylamine or pyridine. Not as long.

Depending on the nature of the compound, the corresponding transition metal compound can be synthesized by directly reacting the ligand with the metal compound without going through the phenoxide salt preparation. Further, the metal M in the synthesized transition metal compound can be exchanged with another transition metal by a conventional method. Further, for example, when any one of R ^{1 to} R ⁶ or R ^{7 to} R ¹² is H, H at any stage of the synthesis.
Substituents other than can be introduced.

It is also possible to use the reaction solution of the ligand and the metal compound as it is for the polymerization without isolating the transition metal compound.

The transition metal compound (A) as described above is 1
They may be used alone or in combination of two or more.

[(B-1) Organometallic Compound] As the (B-1) organometallic compound used in the present invention, specifically, the following periodic table groups 1, 2 and 12, 13 are given.
Group organometallic compounds are used.

[0076] (B-1a) In the 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 is a halogen atom, and m is 0 <m.
≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦ q <
It is a number of 3 and m + n + p + q = 3. ) An organoaluminum compound represented by.

(B-1b) General formula M ² AlR ^a ₄ (In the formula, M ² represents Li, Na or K, and R ^a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. A complex alkylated product of a metal of Group 1 of the periodic table and aluminum.

(B-1c) R ^a R ^b M ³ (wherein R ^a and R ^b may be the same or different from each other, and 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, and M ³ is Mg, Zn or Cd.

Examples of the organoaluminum compound belonging to the above (B-1a) include the following compounds.

[0080] In 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 1 to 4 An organic aluminum compound represented by a hydrocarbon group, and m is preferably a number of 1.5 ≦ m ≦ 3.

[0081] formula R ^a _m AlX _3-m (wherein, R ^a is the number of carbon atoms is 1 to 15, preferably 1 to
4 is a hydrocarbon group, X is a halogen atom, and m is preferably 0 <m <3. ) An organoaluminum compound represented by

[0082] formula R ^a _m AlH _3-m (wherein, R ^a is the number of carbon atoms 1 to 15, preferably 1 to
4 is shown, and m is preferably 2 ≦ m <3. ) An organoaluminum compound represented by

[0083] In 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, preferably 1 to 4 Represents a hydrocarbon group, X represents a halogen atom, and m is 0 <m
≦ 3, n is 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3. ) An organoaluminum compound represented by.

More specifically, the organoaluminum compound belonging to (B-1a) is trimethylaluminum, triethylaluminum, tri-n-butylaluminum,
Tri-n-alkylaluminums such as tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tri-i-propylaluminum, trii
-Butylaluminum, trisec-butylaluminum, tri-t-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum,
Tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri2-methylhexylaluminum, tri3
-Tri-branched alkyl aluminum such as methylhexyl aluminum and tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; di-butyl aluminum dialkyl aluminum hydride such as _{hydride; (i-C 4 H 9} ) x Al y (C 5 H 10) z (. wherein, x, y, z are each a positive number, and z ≧ 2x), such as Trialkenylaluminum such as tri-i-prenylaluminum represented by the formula; alkylaluminum alkoxide such as i-butylaluminum methoxide, i-butylaluminum ethoxide, i-butylaluminum i-propoxide. Sid; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide and dibutyl aluminum butoxide; Alkyl aluminum sesqui alkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide; R ^a _2.5 Al (OR ^b ) _0.5 Partially alkoxylated alkylaluminum having an average composition; diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t) -Butyl-4-methylphenoxide), di-i-butylaluminum (2,6-di-t-butyl-4-methylphenoxide), i-butylaluminum bis (2,6-di-t-butyl) 4-Methylphenoxide) and other dialkyl aluminum aryloxides; dimethyl aluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, dialkyl aluminum halides such as di-butyl aluminum chloride; ethyl aluminum sesquichloride, butyl aluminum sesquichloride Alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide; Partially halogenated alkyl aluminums such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; diethyl aluminum hydride, dibutyl aluminum hydride etc. Dialkyl aluminum Dorido; other partially hydrogenated alkyl aluminum such as alkyl aluminum dihydride such as ethyl aluminum dihydride, propyl aluminum dihydride; partially alkoxy such as ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide, ethyl aluminum ethoxy bromide Alkylated aluminum and the like can be mentioned.

A compound similar to (B-1a) is also used.
Can be, for example, two or more alkyls through the nitrogen atom.
Examples of organoaluminum compounds to which a minium compound is bound are listed.
You can get it. Specifically as such a compound
Is (C₂H_Five)₂AlN (C₂H _Five) Al (C₂H_Five)₂Such
Can be mentioned.

Examples of the compounds belonging to the above (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

In addition, as the (B-1) organometallic compound, methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide. , Propylmagnesium chloride,
Butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium,
Dibutyl magnesium, butyl ethyl magnesium, etc. can also be used.

It is also possible to use a compound capable of forming the organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium.

Of the organometallic compounds (B-1), organoaluminum compounds are preferred. As described above (B-
1) The organometallic compounds may be used alone or in combination of two or more.

[(B-2) Organoaluminum Oxy Compound] The (B-2) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, and is exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound as described above.

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, such as magnesium chloride hydrate, copper sulfate hydrate,
An organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension such as aluminum sulfate hydrate, nickel sulfate hydrate, and ceric chloride hydrate to obtain adsorbed water or crystal water and organoaluminum. A method of reacting with a compound. (2) A method in which water, ice or water vapor 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 organometallic component. Further, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the 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 (B-
The same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to 1a) can be mentioned.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

The above-mentioned organoaluminum compound is
They may be used alone or in combination of two or more.

As the solvent used for preparing the aluminoxane, 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 light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

In the benzene-insoluble organoaluminum oxy compound used in the present invention, the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Some are preferred, that is, those that are insoluble or sparingly soluble in benzene.

The organoaluminum oxy compound used in the present invention may also include an organoaluminum oxy compound containing boron represented by the following general formula (IV).

[0099]

[Chemical 16]

In the formula, R ¹⁹ represents a hydrocarbon group having 1 to 10 carbon atoms. R ^{20 s} may be the same as or different from each other, and each has a hydrogen atom, a halogen atom, and a carbon atom number of 1 to 10.
Shows a hydrocarbon group of.

The organoaluminum oxy compound containing boron represented by the general formula (IV) is the same as the alkylboronic acid represented by the following general formula (V).

R ¹⁹ -B (OH) ₂ (V) (In the formula, R ¹⁹ represents the same group as described above.) An organoaluminum compound and -80 in an inert solvent in an inert gas atmosphere. It can be produced by reacting at a temperature of ℃ to room temperature for 1 minute to 24 hours.

Specific examples of the alkylboronic acid represented by the general formula (V) include methylboronic acid, ethylboronic acid, i-propylboronic acid, n-propylboronic acid, n-butylboronic acid and i-butylboron. Acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like can be mentioned. Of these, methylboronic acid, n-butylboronic acid, i-butylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferable. These may be used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with such an alkylboronic acid include (B-
The same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to 1a) can be mentioned.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and tri-i-butylaluminum are particularly preferable. These may be used alone or in combination of two or more.

The organoaluminum oxy compound (B-2) as described above may be used alone or in combination of two or more.

[(B-3) Compound which reacts with the transition metal compound (A) to form an ion pair] Compound (B- which reacts with the transition metal compound (A) used in the present invention to form an ion pair 3) (hereinafter, "ionized ionic compound")
Say. ), Japanese Patent Laid-Open No. 1-501950,
JP-A-1-502036, JP-A-3-17900
No. 5, JP-A-3-179006, JP-A-3-
207703, JP-A-3-207704,
Lewis acids described in USP-5321106 and the like,
An ionic compound, a borane compound, a carborane compound, etc. can be mentioned. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

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

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

[0110]

[Chemical 17]

In the formula, R ²¹ includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{22 to} R ^{25, which} may be the same or different, are organic groups, preferably aryl groups or substituted aryl groups.

Specific examples of the carbonium cations include triphenylcarbonium cations, tri (methylphenyl) carbonium cations, tri (dimethylphenyl) carbonium cations and like trisubstituted carbonium cations.

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; N, N-dimethylaniline. Cation, N, N-diethylanilinium cation, N, N-
Examples include N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as di (i-propyl) ammonium cation and dicyclohexylammonium cation.

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

R ²¹ is preferably a carbonium cation, an ammonium cation or the like, particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

As the ionic compound, trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, triarylphosphonium salts and the like can 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 and trimethylammonium tetra (p). -Tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (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 (3,3
5-ditrifluoromethylphenyl) 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 can be mentioned.

Specific examples of the dialkyl ammonium 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 pentaphenylcyclo Pentadienyl complex, the following formula (VII) or (V
Examples thereof include boron compounds represented by III).

[0122]

[Chemical 18]

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

[0124]

[Chemical 19]

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. ] Undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-
Butyl) ammonium] decachlorodecaborate, anion salts such as bis [tri (n-butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride dodecaborate)
Examples thereof include salts of metal borane anions such as cobalt salt (III) and bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III).

Specific examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), and 6,9-dicarbadecaborane (1).
4), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-
1,3-Dicarbano Naborane, Undeca Hydride-
1,3-dimethyl-1,3-dicarbanonaborane, 7,
8-dicarbaundecaborane (13), 2,7-dicarbaundecaborane (13), undeca hydride-
7,8-dimethyl-7,8-dicarbaundecaborane,
Dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri (n-butyl) ammonium 1-
Carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, 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 (12),
Tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,
8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarbaundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundeca Borate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, Tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate
, Tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate, etc. Anion salt of

Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaun) Decaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undeca) Hydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n) -Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) gold Salt (III), tri (n- butyl)
Ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (II
I), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride) -7,8-Dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri] (N-Butyl) ammonium] bis (undecahydride-7
-Carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ) Ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV) and other salts of metal carborane anions.

The heteropoly compound includes an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin.
It is composed of one or more atoms selected from vanadium, niobium, molybdenum and tungsten.
Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorous Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdo Tungstic acid, phosphomolybdo niobate, and salts of these acids, such as metals of Group 1 or 2 of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium. ,barium Salts with organic salts of triphenyl ethyl salts, and the like can be used but not limited thereto.

The above-mentioned (B-3) ionized ionic compounds may be used alone or in combination of two or more.

When the transition metal compound according to the present invention is used as a catalyst, when it is used in combination with an organoaluminum oxy compound (B-2) such as methylaluminoxane as a co-catalyst component, a very high polymerization activity for an olefin compound is obtained. Show. When an ionizable ionic compound (B-3) such as triphenylcarbonium tetrakis (pentafluorophenyl) borate is used as a co-catalyst component, an olefin polymer having good activity and a very high molecular weight can be obtained.

The olefin polymerization catalyst according to the present invention is (A)
The transition metal compound represented by the above (I) or (II) may be used alone, or (A) the transition metal compound represented by the above (I), and (B) (B-1) organometal The compound (B-2) may be formed from an organoaluminum oxy compound and (B-3) at least one compound selected from compounds that react with the transition metal compound (A) to form an ion pair. , These compounds are

[0132]

[Chemical 20]

(In the formula, R ^{1 to} R ⁶ , M, m, n and X are the same as in (I), and Y represents a so-called weakly coordinating anion.) Or

[0134]

[Chemical 21]

(Wherein R ^{7 to} R ¹² , M, m, n and X are the same as in (II) and Y represents a so-called weakly coordinating anion). .

In this formula, the bond between the metals M and Y may be a covalent bond or an ionic bond. R ¹ in the formula
Specific examples of ^{~R 6, M, m, n} , X are the same as (I), specific examples of ^{R 7 ~R 12, M, m} , n, X are the same as (II), the Y As an example, Chemical Re
view, 88, 1405 (1988), Ch.
vol.93, Electronic Review 93 pages 927 (19
1993), the weakly coordinating anion described in WO98 / 306126 page 6, specifically,

[0137] AlR ₄ ^- (R may be two or more in one, an oxygen atom, a nitrogen atom, phosphorus atom, a hydrogen atom, a halogen atom or a substituent containing them, and aliphatic hydrocarbon group, an aromatic hydrocarbon Group, an alicyclic hydrocarbon group, which may have a substituent containing an oxygen atom, a nitrogen atom, a phosphorus atom, a hydrogen atom, or a halogen atom)

[0138] BR ₄ ^- (R may be two or more in one, an oxygen atom, a nitrogen atom, phosphorus atom, a hydrogen atom, a halogen atom or a substituent containing them, and aliphatic hydrocarbon group, an aromatic hydrocarbon Group, an alicyclic hydrocarbon group, which may have a substituent containing an oxygen atom, a nitrogen atom, a phosphorus atom, a hydrogen atom, or a halogen atom)

Further, PF ₆ ⁻ , SBF ₅ ⁻ , trifluoromethanesulfonate, p-toluenesulfonate and the like can be mentioned.

Further, the olefin polymerization catalyst according to the present invention comprises the above transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminumoxy compound, and (B-3) an ionized compound. A carrier (C) as described below can be used, if necessary, together with at least one compound (B) selected from ionic compounds.

[(C) Carrier] The carrier (C) used in the present invention is an inorganic or organic compound, and is a granular or fine particle solid.

Of these, the inorganic compound is preferably a porous oxide, an inorganic chloride, clay, clay mineral or an ion-exchange layered compound.

As the porous oxide, specifically, Si
O ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , C
AO, ZnO, BAO, ThO _2, etc., or a mixture or mixture containing them is used, for example, natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , S
_{iO 2 -TiO 2, SiO 2 -V} 2 O 5, SiO 2 -Cr
And the like may be used _{2 O 3, SiO 2 -TiO 2} -MgO. Of these, SiO ₂ and / or Al ₂ O
Those containing ₃ as a main component are preferable.

The above inorganic oxide is a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ )
₂ , carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O, sulfates, nitrates and oxides may be contained.

The properties of such a porous oxide differ depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20.
˜200 μm and specific surface area of 50˜1000 m ²
/ G, preferably 100 to 700 m ² / g, and the pore volume is preferably 0.3 to 3.0 cm ³ / g. Such a carrier may be used as needed.
It is used by firing at 0 to 1000 ° C, preferably 150 to 700 ° C.

As the inorganic chloride, MgCl ₂ , MgB
r ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic chloride may be used as it is, or may be used after being crushed by a ball mill or a vibration mill. Alternatively, the inorganic chloride may be dissolved in a solvent such as alcohol and then precipitated in the form of fine particles with a precipitant.

The clay used in the present invention is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak bonding forces, and the ions contained therein are exchangeable. . Most clay minerals are ion-exchangeable layered compounds. Further, these clays, clay minerals, and ion-exchange layered compounds are not limited to naturally occurring compounds, and artificial synthetic products can also be used.

Further, as the clay, clay mineral or ion-exchange layered compound, clay, clay mineral, or ionic crystallinity having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. A compound etc. can be illustrated.

Examples of such clays and clay minerals include kao.
Phosphorus, bentonite, kibushi clay, gyrome clay, alov
En, Hisingelite, Pyrophyllite, Unmo group, Mo
Nmorillonite group, vermiculite, ryokdei stone
Flock, palygorskite, kaolinite, nakrite, de
Ickite, halloysite, etc.
The layered compound is α-Zr (HAsO_Four)₂・ H₂
O, α-Zr (HPO_Four) ₂, Α-Zr (KPO_Four)₂・ 3
H₂O, α-Ti (HPO_Four)₂, Α-Ti (HAsO_Four)
₂・ H₂O, α-Sn (HPO_Four)₂・ H₂O, γ-Zr
(HPO_Four)₂, Γ-Ti (HPO_Four)₂, Γ-Ti (NH
_FourPO_Four)₂・ H₂Crystalline acid salts of polyvalent metals such as O
Can be mentioned.

Such clay, clay mineral or ion-exchangeable layered compound preferably has a pore volume of 0.1 cc / g or more with a radius of 20 Å or more measured by mercury porosimetry.
Those of 0.3 to 5 cc / g are particularly preferable. Here, the pore volume is measured by a mercury intrusion method using a mercury porosimeter in the range of a pore radius of 20 to 3 × 10 4 Å. When a carrier having a pore volume with a radius of 20 Å or more and smaller than 0.1 cc / g is used as the carrier, it tends to be difficult to obtain high polymerization activity.

The clay and clay mineral used in the present invention include:
It is also preferable to carry out a chemical treatment. As the chemical treatment, any of surface treatment for removing impurities adhering to the surface and treatment for affecting the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment not only removes impurities on the surface, but also Al, Fe, Mg in the crystal structure.
Surface area is increased by eluting cations such as. Alkali treatment destroys the crystal structure of clay,
It causes a change in the structure of clay. Further, in the salt treatment and the organic substance treatment, an ionic complex, a molecular complex, an organic derivative and the like can be formed to change the surface area and the interlayer distance.

Ion-exchangeable layered compounds used in the present invention
The ion exchange property is used to separate exchangeable ions between layers.
By exchanging with bulky ions with large
It may be a layered compound in a large state. Such a bulk
High ions play a pillar-like role supporting the layered structure
It is usually called a pillar. Also layered like this
Intercalating the introduction of another substance between the layers of the compound
Solution. Guest compound to be intercalated
As the product, TiCl_Four, ZrCl_FourNo cationic properties such as
Organic compound, Ti (OR)_Four, Zr (OR)_Four, PO (O
R)₃, B (OR)₃Such as metal alkoxide (R is carbonized
Hydrogen group, etc.), [Al₁₃O_Four(OH)_{twenty four}] ⁷⁺, [Zr
_Four(OH)₁₄]²⁺, [Fe₃O (OCOCH₃)₆]⁺Such
The metal hydroxide ion and the like can be mentioned. A combination of these
The products may be used alone or in combination of two or more. Well
Also, when intercalating these compounds,
Si (OR)_Four, Al (OR)₃, Ge (OR)_FourSuch as
Hydrolyzes metal alkoxides (R is a hydrocarbon group etc.)
Dissolved polymer, SiO₂Colloidal inorganic compounds such as
Things can coexist. Also as a pillar
Intercalates the metal hydroxide ion between the layers.
Oxide produced by heating and dehydration after
Which can be mentioned.

The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as they are, or may be used after treatments such as ball milling and sieving. Further, it may be used after newly adsorbing water or adsorbing water, or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more.

Among these, preferred are clays and clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

The organic compound has a particle size of 10 to 300.
A granular or fine particle solid in the range of μm can be mentioned. Specifically, ethylene, propylene, 1
(Butene, 4-methyl-1-pentene, etc.) A (olefin) olefin having 2 to 14 carbon atoms as a main component (co) polymer or vinylcyclohexane, styrene (mainly) produced (co) Examples thereof include polymers and their modified products.

The olefin polymerization catalyst according to the present invention comprises the above transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound. At least one compound (B) selected from the compounds and, if necessary, the carrier (C), and if necessary, a specific organic compound component (D) as described later may be contained.

[(D) Organic Compound Component] In the present invention, the (D) organic compound component is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Such organic compounds include alcohols,
Examples thereof include, but are not limited to, phenolic compounds, carboxylic acids, phosphorus compounds and sulfonates.

As the alcohols and the phenolic compounds, those represented by R ²⁶ --OH are usually used,
Here, R ²⁶ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms.

As alcohols, those in which R ²⁶ is a halogenated hydrocarbon are preferable. Further, the phenolic compound is preferably one in which the α, α′-position of the hydroxyl group is substituted with a hydrocarbon having 1 to 20 carbon atoms.

The carboxylic acid is usually R²⁷-COO
What is represented by H is used. R ²⁷Is 1 to 1 carbon atoms
50 hydrocarbon groups or halogens having 1 to 50 carbon atoms
A hydrocarbon group, especially halo having 1 to 50 carbon atoms.
A genated hydrocarbon group is preferred.

As the phosphorus compound, phosphoric acids having a P—O—H bond, P—OR, a phosphate having a P═O bond, and a phosphine oxide compound are preferably used.

As the sulfonate, the following general formula (I
What is represented by X) is used.

[0163]

[Chemical formula 22]

In the formula, M is an element of Groups 1 to 14 of the periodic table. R ²⁸ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. m is an integer of 1 to 7, and n is 1 ≦ n ≦ 7.
Is.

1 to 4 show the steps for preparing the olefin polymerization catalyst according to the present invention.

At the time of polymerization, the method of using each component and the order of addition are arbitrarily selected, but the following methods are exemplified. (1) A method of adding the component (A) alone to a polymerization vessel. (2) A method of adding the component (A) and the component (B) to the polymerization vessel in any order. (3) A catalyst component in which the component (A) is supported on the carrier (C),
A method of adding the component (B) to the polymerization vessel in any order. (4) A catalyst component in which the component (B) is supported on the carrier (C),
A method of adding the component (A) to the polymerization vessel in any order. (5) A method of adding a catalyst component in which a component (A) and a component (B) are supported on a carrier (C) to a polymerization vessel.

In each of the above methods (2) to (5),
At least two or more of each catalyst component may be contacted in advance.

The above (4) in which the component (B) is supported.
In each method of (5), the unsupported component (B) may be added in any order, if necessary. In this case, the components (B) may be the same or different.

Further, the solid catalyst component in which the component (A) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) are preliminarily olefins. It may be polymerized, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

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 above olefin polymerization catalyst.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. 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, and other aromatic hydrocarbons; ethylene chloride, chlorobenzene, dichloromethane, and other halogenated hydrocarbons, or mixtures thereof. The olefin itself is used as a solvent. You can also

When the olefin polymerization is carried out using the above olefin polymerization catalyst, the component (A) is
Usually 10 ^-12 to 10 ^-2 mol per liter of reaction volume,
It is preferably used in an amount so as to be 10 ⁻¹⁰ to 10 ⁻³ mol.

The component (B-1) is a molar ratio of the component (B-1) to all transition metal atoms (M) in the component (A) [(B-
1) / M] is usually used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000.
In the component (B-2), the molar ratio [(B-2) / M] of the aluminum atom in the component (B-2) and the transition metal atom (M) in the component (A) is usually 10 to 10. It is used in an amount of 500,000, preferably 20 to 100,000. The component (B-3) is a molar ratio [(B-3) / M] of the component (B-3) and the component (transition metal atom (M) in A).
Is usually used in an amount of 1 to 10, preferably 1 to 5.

In the component (D), the component (B) is the component (B-
In the case of 1), the component (B) is a component (B) in an amount such that the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 to 5. In the case of -2), the component (B) is a component (B) in an amount such that the molar ratio [(D) / (B-2)] is usually 0.001 to 2, preferably 0.005 to 1. In the case of B-3), the molar ratio [(D) / (B-
3)] is usually used in an amount of 0.01 to 10, preferably 0.1 to 5.

The olefin polymerization temperature using such an olefin polymerization catalyst is usually -50 to +200.
C., preferably in the range of 0 to 170.degree. The polymerization pressure is usually normal pressure to 100 kg / cm ² , preferably normal pressure to
It is under the condition of 50 kg / cm ² , and the polymerization reaction can be carried out by any of batch method, semi-continuous method and continuous method. It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. Further, it can be adjusted depending on the difference in the component (B) used.

As the olefin which can be polymerized by such an olefin polymerization catalyst, a linear or branched α-olefin having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, for example, 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-icosene, particularly preferably ethylene, propylene, 1-butene, 1-hexene; cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms,
For example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,2.
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-2,3-dicarboxylic acid anhydride, etc. Α, β-unsaturated carboxylic acid of, and their sodium salts, potassium salts,
Metal salts such as lithium salt, zinc salt, magnesium salt, calcium salt; methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, acrylic acid t-butyl, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-methacrylate
Α, β-unsaturated carboxylic acid esters such as butyl and i-butyl methacrylate; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate and vinyl trifluoroacetate. Unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate and monoglycidyl itaconic acid; halogenated olefins such as vinyl fluoride, vinyl chloride, vinyl bromide and vinyl iodide.

As the olefin, vinylcyclohexane, diene, polyene or the like can be used. The diene or polyene has 4 to 4 carbon atoms.
A cyclic or chain compound having a number of 30, preferably 4 to 20 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, as an olefin, an aromatic vinyl compound such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p.
-Mono- or poly-alkyl styrene such as ethyl styrene; methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, o-chloro styrene, p-
Functional group-containing styrene derivatives such as chlorostyrene and divinylbenzene; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like. These olefins may be used alone or in combination of two or more.

As a combination of olefins used for copolymerization with such an olefin polymerization catalyst, for example, ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene and the like are preferable.

In another olefin polymerization method according to the present invention, (A) an olefin polymerization catalyst comprising a transition metal compound represented by the following general formula (III), or (A) Reaction of the transition metal compound represented by the general formula (III) with (B), (B-1) organometallic compound, (B-2) organoaluminumoxy compound, and (B-3) transition metal compound (A). In the presence of at least one compound selected from the group of compounds forming an ion pair, ethylene and α-olefin having 4 or more carbon atoms are homopolymerized or ethylene and α-olefin having 4 or more carbon atoms are used.
An olefin polymer is obtained by copolymerizing an olefin.

[0183]

[Chemical formula 23]

(Note that N ... M generally indicates coordination, but in the present invention, it may or may not coordinate.) In the general formula (III), M is a titanium atom.

M, n and X are the same as in the general formula (I). R ¹⁴ , R ¹⁵ , R ¹⁷ , and R ¹⁸ are the same as R ² , R ³ , R ⁵ , and R ^{6 in} formula (I), respectively.

R ¹³ is a pentafluorophenyl group.
R ¹⁶ is a t-butyl group. R ¹⁸ is a t-butyl group.

Specific examples of the transition metal compound represented by the general formula (III) are shown below, but the invention is not limited thereto.

[0188]

[Chemical formula 24]

In the above example, Bu represents a butyl group.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. 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, and other aromatic hydrocarbons; ethylene chloride, chlorobenzene, dichloromethane, and other halogenated hydrocarbons, or mixtures thereof. The olefin itself is used as a solvent. You can also

When the olefin polymerization is carried out using the above olefin polymerization catalyst, the component (A) is
Usually 10 ^-12 to 10 ^-2 mol per liter of reaction volume,
It is preferably used in an amount so as to be 10 ⁻¹⁰ to 10 ⁻³ mol.

The component (B-1) is a molar ratio of the component (B-1) and all transition metal atoms (M) in the component (A) [(B-
1) / M] is usually used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000.
In the component (B-2), the molar ratio [(B-2) / M] of the aluminum atom in the component (B-2) and the transition metal atom (M) in the component (A) is usually 10 to 10. It is used in an amount of 500,000, preferably 20 to 100,000. The component (B-3) is a molar ratio [(B-3) / M] of the component (B-3) and the component (transition metal atom (M) in A).
Is usually used in an amount of 1 to 10, preferably 1 to 5.

In the component (D), the component (B) is the component (B-
In the case of 1), the component (B) is a component (B) in an amount such that the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 to 5. In the case of -2), the component (B) is a component (B) in an amount such that the molar ratio [(D) / (B-2)] is usually 0.001 to 2, preferably 0.005 to 1. In the case of B-3), the molar ratio [(D) / (B-
3)] is usually used in an amount of 0.01 to 10, preferably 0.1 to 5.

The olefin polymerization temperature using such an olefin polymerization catalyst is usually -50 to +200.
C., preferably in the range of 0 to 170.degree. The polymerization pressure is usually normal pressure to 100 kg / cm ² , preferably normal pressure to
It is under the condition of 50 kg / cm ² , and the polymerization reaction can be carried out by any of batch method, semi-continuous method and continuous method. It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. Further, it can be adjusted depending on the difference in the component (B) used.

The olefin used for homopolymerization with such an olefin polymerization catalyst is ethylene and an olefin having 4 or more carbon atoms, preferably ethylene and an olefin having 4 to 30 carbon atoms, more preferably ethylene and 4 to 20 carbon atoms. Linear or branched α-olefins such as ethylene, 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-icosene, preferably ethylene, 1-butene, 1-hexene; having 4 to 30 carbon atoms, preferably 4 20 cyclic olefins 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 methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-
Α, β-unsaturated carboxylic acid such as dicarboxylic acid anhydride,
And metal salts thereof such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt; methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-acrylic acid
-Butyl, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate,
I-propyl methacrylate, n-butyl methacrylate,
Α, β-unsaturated carboxylic acid esters such as i-butyl methacrylate; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate and vinyl trifluoroacetate; Unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconic acid; halogenated olefins such as vinyl fluoride, vinyl chloride, vinyl bromide, and vinyl iodide.

As the olefin, vinylcyclohexane, diene, polyene or the like can be used. The diene or polyene has 4 to 4 carbon atoms.
A cyclic or chain compound having a number of 30, preferably 4 to 20 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, as an olefin, an aromatic vinyl compound such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p.
-Mono- or poly-alkyl styrene such as ethyl styrene; methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, o-chloro styrene, p-
Functional group-containing styrene derivatives such as chlorostyrene and divinylbenzene; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like. Examples of the olefin used for copolymerizing ethylene and α-olefin with such an olefin polymerization catalyst include the above-mentioned olefins having 4 or more carbon atoms,
Preferred are 1-butene and 1-hexene.

The olefin polymerization catalyst according to the present invention has a high polymerization activity, and a high molecular weight polymer can be obtained. Also,
In the copolymerization of ethylene and α-olefin, α-
A copolymer having a high olefin content is obtained. The olefin polymerization method according to the present invention has a high polymerization activity,
A high molecular weight polymer is obtained, and in the copolymerization of ethylene and α-olefin, a copolymer having a high α-olefin content can be produced.

[0201]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

The structures of the compounds obtained in the synthesis examples are
It was determined using FD-mass spectrometry (JEOL SX-102A) and the like.

In this Example, the weight average molecular weight (Mw) of the obtained polymer was measured by GPC (gel permeation chromatography) in an orthodichlorobenzene solvent at 140 ° C.

Synthesis Example 1 35.0 ml of ethylmagnesium bromide (ether solution, 3M, was added to a 500 ml reactor sufficiently replaced with nitrogen.
105 mmol) and anhydrous tetrahydrofuran 40 m
I was charged. Under ice-cooling, a solution of 20.63 g (100 mmol) of 2,4-di-t-butylphenol in 40 ml of anhydrous tetrahydrofuran was added dropwise over 10 minutes. After completion of dropping, the mixture was stirred at room temperature, 250 ml of toluene was added, and the mixture was heated with stirring, and tetrahydrofuran and diethyl ether were distilled off. The mixture was cooled to room temperature, 7.73 g (94%, 242 mmol) of paraformaldehyde and 19.9 ml (143 mmol) of triethylamine were added, and the mixture was heated and stirred at 75 ° C for 40 minutes. While cooling to room temperature and further cooling with ice, 170 ml of 10% hydrochloric acid was added for liquid separation,
The organic layer was washed with 100 ml of an aqueous sodium hydrogen carbonate solution and subsequently with 100 ml of an aqueous sodium chloride solution. After drying over anhydrous sodium sulfate, the crystals obtained by drying under reduced pressure were dried under reduced pressure, and the yellow compound represented by the following formula (a) was added to 18.
6 g (yield 77%) was obtained.

[0205]

[Chemical 25]

40 ml of toluene and 2.01 g of pentafluoroaniline were placed in a 100 ml reactor which had been sufficiently replaced with nitrogen.
(11.0 mmol), compound (a) obtained above
2.42 g (purity = 96.9%, 10.0 mmol) and a small amount of p-toluenesulfonic acid as a catalyst were charged, and stirring was continued for 6 hours while refluxing. The reaction solution was concentrated under reduced pressure to obtain 2.99 g (yield 74.2%) of a yellow solid compound represented by the following formula (a ′).

[0207]

[Chemical formula 26]

Place in a 50 ml reactor fully nitrogen purged.
1.21 g of compound (a ') obtained above (purity = 99.
0%, 3.00 mmol) and anhydrous diethyl ether 25
ml was charged, cooled to −78 ° C., and stirred. To this
-Butyllithium 1.92 ml (n-hexane solution,
1.56N, 3.00mmol) was added dropwise over 5 minutes,
Then, the temperature was slowly raised to room temperature. Stir at room temperature for 3 hours
Then, 3.00 ml of titanium tetrachloride cooled to -78 ° C
(1.50 mmol) gradually added to ether slurry
did. After the addition, the temperature was slowly raised to room temperature. Got
The dark red slurry is filtered, and the solid precipitated from the filtrate is collected.
Therefore, it was washed with hexane. The solid obtained is dried under reduced pressure.
To give a brown compound represented by the following formula (1)
Was obtained (0.536 g, yield 37%). Note that the compound
The result of FD-mass spectrometry of (1) was 914 (M ⁺)
It was.

[0209]

[Chemical 27]

Example 1 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml which had been sufficiently replaced with nitrogen, and the liquid phase and the gas phase were saturated with ethylene. Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom was added, and subsequently 0.0005 mmol of titanium compound (1) was added to start polymerization. 25 ℃ under normal pressure ethylene gas atmosphere
After 1 minute of reaction, the polymerization was stopped by adding a small amount of i-butanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer, hydrochloric acid was added, and the mixture was filtered through a glass filter. 80 polymer
After drying under reduced pressure at ℃ for 10 hours, polyethylene (PE)
0.351 g was obtained. The polymerization activity per 1 mmol of titanium was 42.1 kg / hr. The weight average molecular weight (Mw) of the obtained PE was 447,000. The polymerization conditions and results are shown in (Table 1).

Example 2 Except that the polymerization temperature was changed as described in (Table 1).
Polymerization was performed in the same manner. The polymerization activity and the molecular weight of the obtained polymer are shown in (Table 1). Comparative Example 1 Polymerization was performed in the same manner as in Example 1 except that the titanium compound (1) was changed to 0.0005 mmol of the following titanium compound (2) to obtain 0.280 g of polyethylene (PE). Polymerization activity of 34.0 kg per 1 mmol of titanium
It was / hr. The weight average molecular weight of the obtained PE (M
w) was 333,000. The polymerization conditions and results are shown in (Table 1).

[0212]

[Chemical 28]

Comparative Example 2 Except that the polymerization temperature was changed as described in (Table 1),
Polymerization was performed in the same manner. The polymerization activity and the weight average molecular weight (Mw) of the obtained polymer are shown in (Table 1).

[0214]

[Table 1]

Example 3 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml, which had been sufficiently replaced with nitrogen, and 250 ml of a mixed gas of ethylene and 1-butene (70 l / h and 3 was added under stirring).
0 l / h) for 20 minutes. After that, methylaluminoxane was converted into aluminum atoms by 1.25 mmo.
1, then 0.001 mmo of titanium compound (1)
1 was added to initiate polymerization. 25 while blowing mixed gas
After reacting at 5 ° C for 5 minutes, the polymerization was stopped by adding a small amount of methanol. After the polymerization was completed, the reaction product was added to methanol in which a small amount of hydrochloric acid was dissolved to precipitate the polymer, and the polymer was filtered through a glass filter. 130 polymer
It was dried under reduced pressure at 10 ° C. for 10 hours to obtain 0.248 g of an ethylene / 1-butene copolymer. The polymerization activity per 1 mmol of titanium was 2.98 kg / hr. 1 measured by IR
-Butene content was 3.9 mol% and weight average molecular weight (Mw) was 204,000. The polymerization conditions and results are shown in (Table 2).

[0216]

[Table 2]

[0217]

The olefin polymerization catalyst according to the present invention makes it possible to obtain a high molecular weight polymer having high polymerization activity. Further, in the copolymerization of ethylene and α-olefin, a copolymer having a high α-olefin content can be obtained.
Further, the olefin polymerization method according to the present invention provides a polymer having a high polymerization activity and a high molecular weight, and in the copolymerization of ethylene and α-olefin, a copolymer having a high α-olefin content. Can be manufactured.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

FIG. 2 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

FIG. 3 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

FIG. 4 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazutaka Tsuru             Mitsui 6-1-2 Waki, Waki Town, Kuga District, Yamaguchi Prefecture             Inside Chemical Co., Ltd. (72) Inventor Seiichi Ishii             Mitsui Chemicals Co., Ltd. 580-32 Nagaura, Sodegaura City, Chiba Prefecture             Inside the company (72) Inventor Makoto Mitani             Mitsui Chemicals Co., Ltd. 580-32 Nagaura, Sodegaura City, Chiba Prefecture             Inside the company (72) Inventor Terunori Fujita             Mitsui Chemicals Co., Ltd. 580-32 Nagaura, Sodegaura City, Chiba Prefecture             Inside the company F-term (reference) 4J028 AA01 AB01 AC09 BA01 BB01                       BC12 BC14 BC15 BC20 BC25                       BC29 CA24 CA25 CA27 CA28                       CA29 CA30 EB01 EB02 EB03                       EB04 EB05 EB06 EB08 EB09                       GA12 GB02

Claims (7)

[Claims] 1. A transition represented by the following general formula (I):
For olefin polymerization characterized by consisting of metal compounds
catalyst. [Chemical 1] (In the formula, M represents a titanium atom, and m is an integer of 1 to 2.
Show, R¹Is a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms
Indicates R^FourIs a hydrocarbon group having 5 or more carbon atoms, primary or
Is a hydrocarbon group containing only secondary carbon atoms and having 4 or less carbon atoms and
And a group selected from three types of hydrocarbon-substituted silyl groups.
And R⁶Represents a t-butyl group, R², R ³, R^FiveAre mutual
May be the same or different and may be a hydrocarbon group or hydrogen source.
Or a hydrocarbon-substituted silyl group, and m is 2
In some cases R², R³, R^FiveTwo of the groups represented by
It may be linked, and n is a number satisfying the valence of M.
X is a hydrogen atom, a halogen atom, a hydrocarbon group, oxygen
Containing group, sulfur containing group, nitrogen containing group, boron containing group,
Luminium-containing group, phosphorus-containing group, halogen-containing group,
B Cyclic compound residue, silicon-containing group, germanium-containing
A group or a tin-containing group, and when n is 2 or more, X
The plural groups represented by 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 done. ) 2. A transition represented by the following general formula (I):
A metal compound, (B) (B-1) an organometallic compound,
(B-2) Organoaluminum oxy compound, and
(B-3) Ion pair reacting with the transition metal compound (A)
At least one compound selected from the compounds forming
A catalyst for olefin polymerization, characterized by comprising
Medium. [Chemical 2] (In the formula, M represents a titanium atom, and m is an integer of 1 to 2.
Show, R¹Is a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms
Indicates R^FourIs a hydrocarbon group having 5 or more carbon atoms, primary or
Is a hydrocarbon group containing only secondary carbon atoms and having 4 or less carbon atoms and
And a group selected from three types of hydrocarbon-substituted silyl groups.
And R⁶Represents a t-butyl group, R², R ³, R^FiveAre mutual
May be the same or different and may be a hydrocarbon group or hydrogen source.
Or a hydrocarbon-substituted silyl group, and m is 2
In some cases R², R³, R^FiveTwo of the groups represented by
It may be linked, and n is a number satisfying the valence of M.
X is a hydrogen atom, a halogen atom, a hydrocarbon group, oxygen
Containing group, sulfur containing group, nitrogen containing group, boron containing group,
Luminium-containing group, phosphorus-containing group, halogen-containing group,
B Cyclic compound residue, silicon-containing group, germanium-containing
A group or a tin-containing group, and when n is 2 or more, X
The plural groups represented by 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 done. ) 3. A catalyst for olefin polymerization, which comprises (A) a transition metal compound represented by the following general formula (II). [Chemical 3] (In the formula, M represents a titanium atom, m represents an integer of 1 to 2, R ⁷ represents a phenyl group having 4 or less nuclear-bonded fluorine atoms, and a fluorine-containing aromatic group having 7 to 30 carbon atoms in total. Represents a group selected from a hydrocarbon group and a fluorine-containing aliphatic group having 1 to 30 carbon atoms, R ¹⁰ and R ¹² represent a t-butyl group,
R ⁸ , R ⁹ and R ^{11, which} may be the same or different, each represents a hydrocarbon group, a hydrogen atom or a hydrocarbon-substituted silyl group, and when m is 2, R ⁸ , R ⁹ and R 11 are Two of the groups represented by ¹¹ may be linked, and n is
It is a number satisfying the valence of M, and 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,
When n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. ) 4. (A) a transition metal compound represented by the following general formula (II); and (B) (B-1) an organometallic compound,
(B-2) an organoaluminum oxy compound, and (B-3) at least one compound selected from the compounds that react with the transition metal compound (A) to form an ion pair, and an olefin. Polymerization catalyst. [Chemical 4] (In the formula, M represents a titanium atom, m represents an integer of 1 to 2, R ⁷ represents a phenyl group having 4 or less nuclear-bonded fluorine atoms, and a fluorine-containing aromatic group having 7 to 30 carbon atoms in total. Represents a group selected from a hydrocarbon group and a fluorine-containing aliphatic group having 1 to 30 carbon atoms, R ¹⁰ and R ¹² represent a t-butyl group,
R ⁸ , R ⁹ and R ^{11, which} may be the same or different, each represents a hydrocarbon group, a hydrogen atom or a hydrocarbon-substituted silyl group, and when m is 2, R ⁸ , R ⁹ and R 11 are Two of the groups represented by ¹¹ may be linked, and n is
It is a number satisfying the valence of M, and 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,
When n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. ) 5. A method for polymerizing an olefin, which comprises polymerizing an olefin in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 4. 6. (A) Ethylene and α having 4 or more carbon atoms in the presence of an olefin polymerization catalyst comprising a transition metal compound represented by the following general formula (III):
-A polymerization method characterized by homopolymerizing an olefin or copolymerizing ethylene and an α-olefin having 4 or more carbon atoms. [Chemical 5] (In the formula, M represents a titanium atom, m represents an integer of 1 to 2, R ¹³ represents a pentafluorophenyl group, and R ¹⁶ ,
R ¹⁸ represents a t-butyl group, R ¹⁴ , R ¹⁵ and R ^{17, which} may be the same or different, each represents a hydrocarbon group, a hydrogen atom or a hydrocarbon-substituted silyl group, and m is 2 In the case of, two of the groups represented by R ¹⁴ , R ¹⁵ and R ¹⁷ may be linked, n is a number satisfying the valence of M, X is a hydrogen atom or a halogen atom. , Hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, or tin When it contains a group and n is 2 or more, X
The plural groups represented by may be the same or different from each other, and the plural groups represented by X may be bonded to each other to form a ring. ) 7. (A) a transition metal compound represented by the following general formula (III), (B) (B-1) an organometallic compound, (B-2) an organoaluminumoxy compound, and (B-3) ) Ethylene and α having 4 or more carbon atoms are present in the presence of an olefin polymerization catalyst, which comprises at least one compound selected from compounds that form an ion pair by reacting with the transition metal compound (A). -A polymerization method characterized by homopolymerizing an olefin or copolymerizing ethylene and an α-olefin having 4 or more carbon atoms. [Chemical 6] (In the formula, M represents a titanium atom, m represents an integer of 1 to 2, R ¹³ represents a pentafluorophenyl group, and R ¹⁶ ,
R ¹⁸ represents a t-butyl group, R ¹⁴ , R ¹⁵ and R ^{17, which} may be the same or different, each represents a hydrocarbon group, a hydrogen atom or a hydrocarbon-substituted silyl group, and m is 2 In the case of, two of the groups represented by R ¹⁴ , R ¹⁵ and R ¹⁷ may be linked, n is a number satisfying the valence of M, X is a hydrogen atom or a halogen atom. , Hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, or tin When it contains a group and n is 2 or more, X
The plural groups represented by may be the same or different from each other, and the plural groups represented by X may be bonded to each other to form a ring. )