JP2003192716A - Olefin polymerization catalyst and method for polymerizing olefin by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst comprising a transition metal compound and having excellent olefin polymerization activity and a method for polymerizing an olefin by using the catalyst. <P>SOLUTION: The olefin polymerization catalyst is characterized by comprising (A) a transition metal compound represented by general formula YZMX<SB>k</SB>S<SB>n</SB>and, if necessary, (B) (B-1) an organometallic compound, (B-2) an organoaluminumoxy compound, and (B-3) at least one compound selected from compounds that form an ion pair by reacting with the transition metal compound (A). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst comprising a transition metal compound, and an olefin polymerization method using the olefin polymerization catalyst.

[0002]

BACKGROUND OF THE INVENTION As an olefin polymerization catalyst,
So-called Kaminsky catalysts are well known. 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 as such a Kaminsky catalyst include bis (cyclopentadienyl) zirconium dichloride (see JP-A-58-19309) and ethylenebis (4,5,6,7-tetrahydro). Indenyl) zirconium dichloride (see JP-A-61-130314) and the like are known. It is also known that when the transition metal compound used for polymerization is different, the olefin polymerization activity and the properties of the obtained polyolefin are greatly different. More recently, a transition metal compound having a ligand of diimine structure as a new catalyst for olefin polymerization (International Publication No. 96230
No. 10) is proposed.

By the way, polyolefins are generally used in various fields such as for various molded products because they are excellent in mechanical properties and the like. In recent years, the demand for physical properties of polyolefins has been diversified, and polyolefins having various properties are being used. The needs of are increasing. Further, it is known that polyolefins having various properties can be synthesized by copolymerizing different olefins. Further, it is known that the properties of the copolymer are different depending on the transition metal catalyst used for the copolymerization, and a polymerization catalyst which produces a copolymer having a narrow molecular weight distribution and a uniform composition from various olefins is desired. Improving productivity is also an issue. Under these circumstances, the advent of an olefin polymerization catalyst that has excellent olefin polymerization activity and is capable of producing a polyolefin having excellent properties is desired.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an olefin polymerization catalyst comprising a transition metal compound and having excellent olefin polymerization activity, and an olefin polymerization method using the catalyst.

[0005]

The olefin polymerization catalyst according to the present invention comprises:

(A) A transition metal compound represented by the following general formula (I) YZMX _k S _n (I)

(In the formula, Y is a bidentate ligand having a monovalent anionic coordination site and a neutral coordination site, and Z is a monodentate coordination site having an anionic or neutral coordination site. Child, or a polydentate ligand having an anionic and / or neutral coordination site, where Z is a bidentate ligand having a monovalent anionic coordination site and a neutral coordination site. Then the ligand Y
And the ligand Z do not have the same basic skeleton. Also, Y and Z
May be linked to each other, and when Y and Z are linked to each other, the ligand composed of Y and Z is asymmetric. M is a transition metal of Groups 3 to 9 of the Periodic Table, and 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 group selected from the group containing and the tin-containing group, k is a number satisfying the valence of M, and when k is 2 or more, the plurality of groups represented by X may be the same or different from each other. Further, plural groups represented by X may be bonded to each other to form a ring. S represents a monodentate ligand having only a neutral coordination site, and n represents a number from 0 to 4. ) And as required

(B) (B-1) organometallic compound, (B-2) organoaluminum oxy compound, and (B-3) transition metal compound
It is characterized by containing at least one compound selected from compounds which react with (A) to form an ion pair.

In the present invention, as the transition metal compound (A), the monovalent anionic coordination site constituting Y or Z in the above general formula is an aryloxy group, a pyrrolyl group, an indolyl group, an amide group or a silylamide group. It is preferably a hetero atom of a group selected from a sulfonamide group and an arylthio group. Further, in the present invention, as the transition metal compound (A), in the general formula, the neutral coordination site constituting Y or Z is imine, ketone, aldehyde,
It is preferably a hetero atom in a compound selected from amine, ether, phosphine and sulfide. Further, in the present invention, as the (A) transition metal compound, a bidentate ligand Y having a monovalent anionic coordination site and a neutral coordination site in the above general formula is represented by the above general formula (I). ~ (X)
Is more preferable.

Further, the olefin polymerization catalyst according to the present invention comprises the above-mentioned (A) transition metal compound and, if necessary, the above-mentioned (B-1) organometallic compound, (B-2) organoaluminumoxy compound,
In addition to (B-3) at least one compound (B) selected from compounds that react with the transition metal compound (A) to form an ion pair, a carrier (C) may be further included. The olefin polymerization method according to the present invention is characterized in that the olefin is polymerized or copolymerized in the presence of the catalyst as described above.

[0011]

DETAILED DESCRIPTION OF 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” may be used to mean not only homopolymerization but also copolymerization, and the term “polymer” means not only homopolymer but also copolymerization. It may be used in the sense of including coalescence.

The olefin polymerization catalyst according to the present invention is
(A) a transition metal compound represented by the general formula (I) and, if necessary, (B) an organometallic compound (B-1), an organoaluminum oxy compound (B-2), and a transition metal (B-3) Compound (A)
It is formed from at least one compound selected from the compounds that react with to form an ion pair, and further from (C) carrier as required.

First, each catalyst component forming the olefin polymerization catalyst of the present invention will be described.

(A) Transition Metal Compound The (A) transition metal compound used in the present invention is represented by the following general formula (I). YZMX _k S _n (I)

In the formula, M represents a transition metal selected from Groups 3 to 9 of the periodic table (including lanthanoids in Group 3), and more preferably selected from Groups 3 to 5 and 9. It is a transition metal atom, and particularly preferably a transition metal atom selected from Group 4 or Group 5. Specifically, scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium and the like, preferably scandium, titanium, zirconium, Hafnium, vanadium, niobium, tantalum, cobalt, rhodium and the like, more preferably titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium, tantalum and the like, particularly preferably titanium, zirconium, hafnium, vanadium, tantalum. Is.

Y is a bidentate ligand having a monovalent anionic coordination site and a neutral coordination site, and preferably the monovalent anionic coordination site is an aryloxy group, a pyrrolyl group or an indolyl group. A hetero atom of a group selected from a group, an amide group, a silylamide group, a sulfonamide group and an arylthio group, and a neutral coordination site of a compound selected from imines, ketones, aldehydes, amines, ethers, phosphines and sulfides. It is a hetero atom. More preferably, it is a bidentate ligand represented by the general formula (II) to (XI). In the formula, A represents an oxygen atom, a sulfur atom, or a nitrogen atom having a substituent R ⁶⁵ , and R ^{1 to} R ⁶⁵ may be the same or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group, or a heterocycle. Formula compound residue, oxygen-containing group,
Represents a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which are linked together to form a ring. May be. More specifically, R ^{1 to} R ⁶⁵ are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group,
Hydrocarbon-substituted siloxy group, alkoxy group, alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, Nitro group, carboxyl group, sulfo group,
It is preferably a mercapto group, an aluminum-containing group or a hydroxy group.

Here, the halogen atom is fluorine,
Examples include chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl and the like having 1 to 10 carbon atoms.
30, preferably 1 to 20 linear or branched alkyl group; vinyl, allyl, isopropenyl and the like having 2 to 30 carbon atoms, preferably 2 to 20 linear or branched alkyl group Alkenyl group: ethynyl, propargyl, etc., having 2 to 30 carbon atoms, preferably 2 to 20 linear or branched alkynyl group; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc., having 3 to 30 carbon atoms , Preferably 3 to 20
A cyclic saturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl, and fluorenyl; a carbon atom number such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl. 6-30, preferably 6-20 aryl groups; alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl, and the like.

In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen, for example, trifluoromethyl, pentafluorophenyl, chlorophenyl and the like having 1 to 30 carbon atoms, preferably 1 to 20 halogenated carbon atoms. A hydrogen group is mentioned. Further, the above hydrocarbon group may have a hydrogen atom substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl and cumyl. Furthermore, the hydrocarbon group is a heterocyclic compound residue; an alkoxy group, an aryloxy group,
Ester group, ether group, acyl group, carboxyl group,
Oxygen-containing groups such as carbonate group, hydroxy group, peroxy group and carboxylic acid anhydride group; amino group, imino group,
Nitrogen-containing groups such as amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and amino groups which have become ammonium salts; Borondiyl group, boranetriyl group, diboranyl group and other boron-containing groups; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group,
Sulfur-containing groups such as thioether groups, thiocyanate ester groups, isothiocyanate ester groups, sulfone ester groups, sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, and sulfenyl groups; phosphido groups, Phosphoryl group,
It may have a phosphorus-containing group such as a thiophosphoryl group or a phosphato group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

Of these, methyl, ethyl, n-
Bropil, isopropyl, n-butyl, isobutyl, sec-
Butyl, t-butyl, neopentyl, n-hexyl, adamantyl and the like having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms
A linear or branched alkyl group having 6 to 30 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl, preferably 6 to
20 aryl groups; a halogen atom, an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an aryl group or aryloxy group having 6 to 30 carbon atoms, in these aryl groups; Substituted aryl groups and the like in which 1 to 5 substituents are substituted are preferable.

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. R ¹ ~ R ⁶⁵
Examples of the oxygen-containing group, nitrogen-containing group, sulfur-containing group, and phosphorus-containing group represented by are the same as those exemplified as the substituents that may be contained in the above hydrocarbon group.

Examples of the boron-containing group are the same as those exemplified as the substituents which may be contained in the above hydrocarbon group, as well as alkyl group-substituted boron, aryl group-substituted boron, boron halide, alkyl group-substituted halogen. Examples thereof include groups such as boron oxide. Examples of the alkyl group-substituted boron include (Et) ₂ B-, (iPr) ₂ B-, (iBu) ₂ B-, and (Et).
_{3 B, (iPr) 3 B} , (iBu) 3 B; the aryl group substituted _{boron, (C 6 H 5) 2} B -, (C 6 H 5) 3 B, (C 6 F 5) 3 B,
The boron _{halide, BCl 2 -, BCl 3;} ; (3,5- (CF 3) 2 C 6 H 3) 3 B The alkyl group substituted boron halides, (Et) BCl -, ( iBu) BCl _{-, (C 6 H 5)} 2
BCl and the like can be mentioned. Of these, tri-substituted boron may be in a state of coordinate bond. here,
Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

Examples of the aluminum-containing group include alkyl group-substituted aluminum, aryl group-substituted aluminum, aluminum halide, alkyl group-substituted aluminum halide and the like. Alkyl group-substituted aluminum includes (Et) ₂ Al-, (iPr) ₂ Al-, and (iBu) ₂ Al.
_{-, (Et) 3 Al,} (iPr) 3 Al, (iBu) 3 Al; the aryl group substituted _{aluminum, (C 6 H 5) 2} Al-; The halogenated aluminum, AlCl ₂ -, AlCl _3; Alkyl group-substituted aluminum halides include (Et) AlC
1-, (iBu) AlCl- and the like. Of these, tri-substituted aluminum may be in a state of coordinate bond. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

Examples of the silicon-containing group include silyl group, siloxy group, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group and the like. Specific examples of the hydrocarbon-substituted silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluoro Phenyl) silyl and the like. Of these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly, trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are preferable. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

Examples of the germanium-containing group and the tin-containing group include those in which silicon in the silicon-containing group is replaced with germanium and tin.

Next, the examples of R ^{1 to} R ⁶⁵ described above will be described more specifically. Of the oxygen-containing groups, the alkoxy groups include methoxy, ethoxy, n-propoxy,
Isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like, as the aryloxy group, phenoxy,
2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like, the acyl group, formyl group, acetyl group,
A benzoyl group, a p-chlorobenzoyl group, a p-methoxybenzoyl group and the like are preferable, and an ester group is preferably acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like.

Among the nitrogen-containing groups, amide groups include acetamide, N-methylacetamide, N-methylbenzamide, etc., amino groups include dimethylamino, ethylmethylamino, diphenylamino, etc., and imide groups include: Acetimide, benzimide and the like are preferably exemplified as the imino group such as methylimino, ethylimino, propylimino, butylimino and phenylimino.

Among the sulfur-containing groups, the alkylthio group is methylthio, ethylthio, etc., the arylthio group is phenylthio, methylphenylthio, naphthylthio, etc., and the thioester group is acetylthio, benzoylthio, methylthiocarbonyl, phenylthio. Carbonyl and the like, sulfone ester groups such as methyl sulfonate, ethyl sulfonate, and phenyl sulfonate, and sulfonamide groups such as phenyl sulfonamide, N-methyl sulfonamide, N-methyl-p-toluene sulfonamide. Are preferred.

R ^{1 to} R ⁶⁵ are two or more of these groups, preferably adjacent groups connected to each other to form an alicyclic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. And these rings may further have a substituent.

Z is an anionic or neutral coordination site.
Monodentate ligand, or anionic and / or neutral
Z is a monovalent anion, which is a multidentate ligand composed of coordination sites.
It is a bidentate ligand consisting of a sex coordination site and a neutral coordination site.
Sometimes the same as Y can be used, but at this time
The ligand Y and the ligand Z do not have the same basic skeleton. In the present invention
The ligand Y and the basic skeleton of the ligand Z are bidentate ligands.
The structure of the shortest chemical bond that connects the two coordination sites
Is called the main chain), and any one or more of the main chains
When the bond is part of a cyclic structure, it includes the main chain and its bond.
It is a circular structure. Therefore, in the general formula (II)
For example, when the ligand is given, N = C-C-N^-Is the main chain
And the pyrrole ring and the main chain are contained in the basic skeleton.
To R⁷~ R ¹¹If any one or more of them are different, the basic bone
I do not say that the case is different.

The monovalent anionic coordination site of Z is
Ryloxy group, pyrrolyl group, indolyl group, amide group,
Silylamide group, sulfonamide group and arylthio
Heteroatoms of groups selected from the groups are preferred. Z neutral
Coordination sites include imines, ketones, aldehydes, and amines.
Selected from amines, ethers, phosphines and sulfides
It is preferably a heteroatom of a compound. Also, Y
And Z may be linked to each other. As this linking group
Is oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium
At least one selected from tin, tin, boron, etc.
And a group containing the element of₂-O-
CH₂-, -CH₂-S-CH₂-, -CH₂-Se-CH
₂-A chalcogen atom-containing group such as; -CH₂-NH-CH
₂-, -CH₂-N (CH₃) -CH₂-, -CH₂-PH-
CH₂-, -CH₂-P (CH₃) -CH₂-Such as nitrogen or
Is a phosphorus atom-containing group; -CH₂-, -CH₂-CH₂-,-
C (CH₃) ₂-, -CH₂-C (CH₃)₂-, -CH₂-C
H₂-CH₂-, -CH = CH- and other such carbon atoms having 1 to
20 saturated or unsaturated chain hydrocarbon groups; benzene, na
Carbon sources such as phthalene, anthracene, and cyclohexane
Saturated or unsaturated cyclic unsaturated hydrocarbon having 6 to 20 children
Residues: pyridine, quinoline, thiophene, furan, pyro
Group containing 3 to 20 carbon atoms, including heteroatoms such as
Telocyclic compound residue; -SiH₂-, -Si (CH₃)
₂-, -Si (CH₃)₂-Si (CH₃)₂-Such as silicon source
Child-containing group, -SnH₂-, -Sn (CH₃)₂− Such as tin
Atom-containing group; -BH-, -B (CH₃)-, -BF-, etc.
And a boron atom-containing group. Of these,
Saturated or unsaturated chain hydrocarbon group, saturated or unsaturated ring
Unsaturated hydrocarbon residues are particularly preferred. However, Y and Z
Are linked to each other, the ligand consisting of Y and Z is non-
It is symmetrical. When Y and Z are connected to each other, Y and Z
The asymmetric ligand consisting of consists of the basic skeleton of the ligand.
, The same symmetry as the molecular plane when it is a planar molecule
Face and C₁Indicates that there is no symmetry element other than the symmetry axis.
At this time, the ligand has a thermodynamically stable conformation (conforma).
However, it can have any conformation. For example
The transition metal compound represented by the formula (XII) is shown by a broken line.
Dashed line that is plane-symmetric with respect to the plane perpendicular to the paper and passes through sulfur
C on the axis of₂It is symmetric, not asymmetric. The following formula (XII
The complex represented by I) has the same plane of symmetry as the molecular plane and C₁versus
It is asymmetric because there is no symmetric element other than the nominal axis.

[0031]

[Chemical 2]

[0032]

[Chemical 3]

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 group containing a silicon-containing group, a group containing germanium, and a group containing tin.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the hydrocarbon group are the same as ^those exemplified above for R ^{1 to} R ⁶⁵ . Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl;
Cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethyl Phenyl, trimethylphenyl, ethylphenyl,
Examples include aryl groups such as propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, phenanthryl and the like. Further, these hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is replaced with halogen. Of these, those having 1 to 20 carbon atoms are preferable.

Examples of the oxygen-containing group include the same groups as ^those exemplified above for R ^{1 to} R ⁶⁵ .
Hydroxy group; alkoxy group such as methoxy, ethoxy, propoxy, butoxy; aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy; arylalkoxy group such as phenylmethoxy, phenylethoxy; acetoxy group; carbonyl group; oxo group (= O) and the like.

Examples of the sulfur-containing group include the same groups as ^those exemplified above for R ^{1 to} R ^65. Specific examples include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate and benzyl. Sulfonate groups such as sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfonate, phenyls Examples thereof include sulfinate groups such as ruffinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate; alkylthio groups; arylthio groups.

Specific examples of the nitrogen-containing group include R ¹ to
Examples thereof include those similar to those exemplified for R ⁶⁵ , specifically, amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenyl. Examples thereof include arylamino groups such as amino, ditolylamino, dinaphthylamino, and methylphenylamino, and alkylarylamino groups.

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, etc.) and the like.

Specifically as the aluminum-containing group, A
and lR 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 phosphite groups (phosphide groups) such as phenylphosphite; phosphonic acid groups; phosphinic acid groups.

Specific examples of the halogen-containing group include P
Examples thereof include fluorine-containing groups such as F ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl ₆ , iodine-containing groups such as IO ₄ . Examples of the heterocyclic compound residue include R ^{1 to} R ⁶⁵ described above.
Examples of the same as those exemplified above.

Specific examples of the silicon-containing group include R ¹
To R ⁶⁵ are exemplified, and specific examples thereof include phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl and tritolylsilyl. A hydrocarbon-substituted silyl group such as trinaphthylsilyl; a hydrocarbon-substituted silyl ether group such as trimethylsilyl ether; a silicon-substituted alkyl group such as trimethylsilylmethyl; and a silicon-substituted aryl group such as trimethylsilylphenyl.

Specific examples of the germanium-containing group include the same groups as ^those exemplified above for R ^{1 to} R ⁶⁵ ,
Specific examples include groups in which silicon in the silicon-containing group is replaced with germanium.

Specific examples of the tin-containing group include R ¹ to
Examples thereof are the same as those exemplified for R ⁶⁵ , and more specifically, examples thereof include groups in which silicon in the silicon-containing group is substituted with tin.

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

X is preferably a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group or a nitrogen-containing group, more preferably a hydrogen atom, a halogen atom or a hydrocarbon group. k is M
When k is 2 or more, the plural groups represented by X may be the same or different from each other,
Further, a plurality of groups represented by X may combine with each other to form a ring.

S represents a monodentate ligand having a neutral coordination site, specifically, a solvent used during the synthesis of the transition metal compound (A), such as an ether such as tetrahydrofuran or diethyl ether, or Pyridine and the like can be mentioned. n
Indicates a number from 0 to 4.

Specific examples of the transition metal compound (A) are shown below, but the transition metal compound (A) is not limited thereto.

[0050]

[Chemical 4]

[0051]

[Chemical 5]

[0052]

[Chemical 6]

[0053]

[Chemical 7]

[0054]

[Chemical 8]

In the above examples, Me represents a methyl group and Mes represents a mesityl group. In the present invention, a transition metal compound in which zirconium metal is replaced with a metal other than zirconium such as titanium and hafnium in the above compound can also be used. The dashed line does not necessarily mean that a bond is present.

Next, each compound of the component (B) used as needed will be described. (B-1) Organometallic compound As the (B-1) organometallic compound used as necessary in the present invention, specifically, the periodic table groups 1, 2 and 12 as represented by the following general formula: , Group 13 organometallic compounds.

(B-1a) 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 and have 1 to 15 carbon atoms, 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 <3
And m + n + p + q = 3. ) An organoaluminum compound represented by.

(B-1b) M ² AlR ^a ₄ (In the formula, M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. .) A complex alkylated product of a Group 1 metal 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). And M ³ is Mg, Zn or Cd.)
A dialkyl compound of a Group 2 or Group 12 metal represented by:

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

[0061] In _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b are optionally carbon atoms may be the same or different 1 to 15 together, preferably 1-4 hydrocarbon group And m is preferably a number of 1.5 ≦ m ≦ 3.),

[0062] R ^a _m AlX _3-m (wherein, R ^a is the number of carbon atoms 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

[0063] 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

R ^a _m Al (OR ^b ) _n X _q (wherein R ^a and R ^b may be the same or different from each other and have 1 to 15, preferably 1 to 4 carbon atoms). , 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.

As the organoaluminum compound belonging to (B-1a), more specifically, trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum,
Tri-n-alkyl aluminum such as tridecyl aluminum; triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert.
-Butyl aluminum, tri 2-methylbutyl aluminum, tri 3-methylbutyl aluminum, tri 2-methylpentyl aluminum, tri 3-methylpentyl aluminum, tri 4-methylpentyl aluminum, tri 2-methylhexyl aluminum, tri 3-methyl Tri-branched alkyl aluminum such as hexyl aluminum and tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; diethyl aluminum hydride and diisobutyl aluminum dialkylaluminum hydride such as _{hydride; (i-C 4 H 9} ) x Al y (C 5 H 10) z ( wherein, x, y, z are positive numbers And z ≧ 2x) and the like, trialkenylaluminum such as triisoprenylaluminum; alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide; dimethylaluminum methoxide, Dialkyl aluminum alkoxides such as diethyl aluminum ethoxide and dibutyl aluminum butoxide; alkyl aluminum sesqui alkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide; portions having an average composition represented by R ^a _2.5 Al (OR ^b ) _0.5 Alkyloxylated aluminum; diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl -4-methylphenoxide), ethyl aluminum bis (2,6-di-t
-Butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide),
Dialkyl aluminum aryloxides such as isobutyl aluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethyl aluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride,
Dialkyl aluminum halides such as diethyl aluminum bromide and diisobutyl aluminum chloride;
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; partially halogenated alkyl aluminums such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide ; Diethylaluminum hydride,
Dialkylaluminum hydrides such as dibutylaluminum hydride; Other partially hydrogenated alkylaluminums such as ethylaluminum dihydride, alkylaluminium dihydrides such as propylaluminium dihydride; Ethylaluminum ethoxy chloride, Butylaluminum butoxycyclolide, Ethylaluminum ethoxy Partially alkoxylated and halogenated alkyl aluminum such as bromide and the like can be mentioned.

Compounds similar to (B-1a) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H
₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like.

Compounds belonging to the above (B-1b) include Li
Al (C₂H_Five)_Four, LiAl (C₇H₁₅) _FourEtc.
It

In addition, (B-1) organometallic compounds include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride and propylmagnesium bromide. It is also possible to use propyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like. 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. Among the organometallic compounds (B-1), organoaluminum compounds are preferable. The above (B-1) organometallic compounds may be used alone or in combination of two or more.

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

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, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. The method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of, and reacting the adsorbed water or crystal water with the organoaluminum 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 an 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 when preparing the aluminoxane include the above-mentioned (B-1a)
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to 1) can be mentioned. Among these, trialkyl aluminum and tricycloalkyl aluminum are preferable, and trimethyl aluminum is particularly preferable. The organoaluminum compound as described above 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 in terms of Al atom,
It is preferably 5% or less, particularly preferably 2% or less, that is, insoluble or hardly soluble in benzene.

Examples of the organoaluminum oxy compound used in the present invention include organoaluminum oxy compounds containing boron represented by the following general formula (XIV).

[0076]

[Chemical 9]

In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different from each other. The organoaluminum oxy compound containing boron represented by the general formula (XIV) is an alkylboronic acid represented by the following general formula (XV),

R ^c -B- (OH) ₂ (XV) (In the formula, R ^c represents the same group as above.) An organoaluminum compound and an organic aluminum compound in an inert solvent in an inert gas atmosphere,
It can be produced by reacting at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

Specific examples of the alkylboronic acid represented by the general formula (XIV) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylpyrronic acid, n-butylboronic acid, isobutylboronic acid, n- Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl)
Phenylboronic acid and the like can be mentioned. Of these, methylboronic acid, n-butylboronic acid, isobutylboronic 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-1a)
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to 1) can be mentioned. Among these, trialkyl aluminum and tricycloalkyl aluminum are preferable, and trimethyl aluminum, triethyl aluminum and triisobutyl aluminum are particularly preferable. These may be used alone or in combination of two or more. The above-mentioned (B-2) organoaluminum oxy compound is used alone or in combination of two or more kinds.

(B-3) Ionized Ionic Compound A transition metal compound (A) optionally used in the present invention.
As the compound (B-3) which reacts with and forms an ion pair,
Japanese Patent Application Laid-Open Nos. 1-501950 and 1-50203
No. 6, JP-A-3-179005, and JP-A-3-17905.
179006, JP-A-3-207703,
JP-A-3-207704, USP-532110
Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in No. 6 and the like. Furthermore, a heteropoly compound and an isopoly compound can also be mentioned.

Specifically, as the Lewis acid, BR is
₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group and a trifluoromethyl group or fluorine. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron , Tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3, 5-dimethylphenyl)
Examples include boron. Examples of the ionic compound include compounds represented by the following general formula (XVI).

[0083]

[Chemical 10]

In the formula, examples of R ^e include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^{f to} R ⁱ are organic groups which may be the same or different from each other, preferably an aryl group or a substituted aryl group.

Specific examples of the carbonium cation include triphenylcarbonium cation, tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and other trisubstituted carbonium cations. Specifically as the ammonium cation, trimethyl ammonium cation,
Trialkylammonium cations such as triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- 2,4,
Examples include N, N-dialkylanilinium cations such as 6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) 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.

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

Further, examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, triarylphosphonium salts and the like. Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl). Boron, 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 (3,5-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, Examples include 4,6-pentamethylanilinium tetra (phenyl) boron. 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 pentaphenylcyclopentadienyl complex represented by the following formula (XVII) or (XVII
The boron compound represented by I) may also be mentioned.

[0091]

[Chemical 11] (In the formula, Et represents an ethyl group.)

[0092]

[Chemical 12]

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, bis [tri (n-
Butyl) ammonium] dodecachloro dodecaborate and other anion salts; tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecarate) Examples thereof include salts of metal borane anions such as borate) nickelate (III).

Specific examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14) and dodecahydride-1-phenyl- 1,3-Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaun Decaborane (13),
2,7-dicarbaundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundodecaborane, 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 (1)
2), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-)
Butyl) ammonium undeca hydride-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 -Salts of anions such as carbaundecaborate; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undeca) Hydride-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate Cobalt) (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undeca) Hydride-7,8-dicarbaundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-
Dicarbaundecaborate) aurate (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 (II
I), 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 metal carborane anion salts, etc. Is mentioned.

The heteropoly compound is composed of an atom composed of silicon, phosphorus, titanium, germanium, arsenic or tin, and one or more kinds of 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, 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, With barium etc. And organic salts such as triphenylethyl salts, and an isopoly compound may be used, not limited thereto. As the heteropoly compound and the isopoly compound, not only one kind of the above compounds but also two or more kinds can be used.

The above-mentioned (B-3) ionized ionic compound is used alone or in combination of two or more kinds.

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

(C) Carrier The carrier (C) optionally 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 an oxide, an inorganic chloride, clay, a clay mineral, or an ion-exchange layered compound.

As the oxide, specifically, SiO₂, Al₂
O₃, MgO, ZrO, TiO₂, B ₂O₃, CaO, Zn
O, BaO, ThO₂Or a composite containing these
Or using mixtures such as natural or synthetic Zeoli
G, SiO₂-MgO, SiO₂-Al₂O₃, SiO₂−
TiO₂, SiO₂-V₂O_Five, SiO₂-Cr₂O₃, Si
O ₂-TiO₂-MgO etc. can be used. This
Of these, SiO₂And / or Al₂O₃The main component
Is preferred. In addition, the inorganic oxide is a small amount
Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na
₂SO_Four, Al₂(SO_Four)₃, BaSO_Four, KNO₃, Mg
(NO₃)₂, Al (NO₃)₃, Na₂O, K₂O, Li₂
Contains carbonates, sulfates, nitrates, oxides such as O
It doesn't matter if you do. Such porous oxides are
Although its properties vary depending on the production method, it is preferred for the present invention.
The carrier used often has a particle size of 10 to 300 μm and is preferably
20 to 200 μm and specific surface area of 50 to 10
00m²/ G, preferably 100-700m²/ G range
And the pore volume is 0.3-3.0 cm³In the range of / g
Is desirable. Such a carrier may be used as needed.
Baked at 100-1000 ° C, preferably 150-700 ° C
Used.

As inorganic chlorides, 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.

The clay used as a carrier in the present invention is usually
Consists mainly of clay minerals. Also in the present invention
The ion-exchangeable layered compound used as a carrier is an
The surfaces formed by bond
A compound having a crystal structure that is stacked in parallel and contains
The ions that it has are exchangeable. Most clay ores
The substance is an ion-exchange layered compound. Also, these stickiness
Soil, clay minerals, ion-exchangeable layered compounds are natural
It is not limited to products produced locally, and artificial compounds can also be used.
It Also, clay, clay minerals or ion-exchangeable layered compounds
As materials, clay, clay minerals, and hexagonal close packing
Type, antimony type, CdCl₂ Mold, CdI ₂Layers such as mold
Examples of ionic crystalline compounds with a crystalline structure
You can As such clay and clay minerals,
Kaolin, bentonite, kibushi clay, gyrome clay, a
Lophen, hissingelite, pyrophyllite, ummo
Group, montmorillonite group, vermiculite, ryokde
Stone group, Palygorskite, Kaolinite, Nakrai
, Dickite, halloysite, etc.
As the ion-exchangeable layered compound, α-Zr (HAsO_Four)₂
・ H₂O, α-Zr (HPO_Four)₂, Α-Zr (KPO_Four)
₂・ 3H₂O, α-Ti (HPO_Four)₂, Α-Ti (HAs
O_Four)₂・ H₂O, α-Sn (HPO_Four)₂・ H₂O, γ-Z
r (HPO_Four)₂, Γ-Ti (HPO_Four)₂, Γ-Ti (N
H_FourPO_Four)₂・ H₂Crystalline acidic salts of polyvalent metals such as O
Is mentioned. Such clay, clay minerals or ions
The exchangeable layered compound had a radius of 20 o measured by mercury porosimetry.
Pore volume of ngstrom or more is 0.1 cc / g or more
Those having 0.3 to 5 cc / g are particularly preferable.
Good Here, for the pore volume, a mercury porosimeter is used.
By the mercury injection method, the pore radius is 20 to 3 × 10^FourOng
Measured over the strom range. Radius 20 ang
Pore volume above strom is less than 0.1 cc / g
When used as a carrier, high polymerization activity is not obtained.
It tends to be difficult to get rid of.

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.

These compounds may be used alone or in combination of two or more. In addition, when intercalating these compounds, Si (OR) ₄ , Al (O
Polymers obtained by hydrolyzing metal alkoxides such as R) ₃ and Ge (OR) ₄ (R is a hydrocarbon group etc.), SiO
A colloidal inorganic compound such as ₂ can also be present together. Examples of the pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then heating and dehydrating them.

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, hectorite, 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-
Number of carbon atoms such as butene and 4-methyl-1-pentene is 2
Produced mainly from 14 α-olefins (co)
Examples thereof include polymers or vinylcyclohexane, (co) polymers produced by using styrene as a main component, and modified products thereof.

The olefin polymerization catalyst according to the present invention comprises the above-mentioned transition metal compounds (A), (B-1) organometallic compounds and (B
-2) at least one compound (B) selected from an organoaluminum oxy compound and (B-3) an ionizable ionic compound, and optionally a carrier (C), and optionally a specific compound as described below. An organic compound component (D) can also be included.

(D) Organic Compound Component The (D) organic compound component optionally used in the present invention 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, phenolic compounds,
Examples thereof include carboxylic acids, phosphorus compounds and sulfonates.

As alcohols and phenolic compounds, those represented by R ^j --OH are usually used,
Here, R ^j represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms. As the alcohols, halogenated hydrocarbons having R ^j 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 R ^k --COOH.
What is represented by is used. R ^k has 1 to 5 carbon atoms
A hydrocarbon group having 0 or a halogenated hydrocarbon group having 1 to 50 carbon atoms is shown, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

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 (XI
What is represented by X) is used.

[0113]

[Chemical 13]

In the formula, M is an atom selected from Groups 1 to 14 of the periodic table. R ¹ 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, or 1 carbon atom
To 20 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms. m is an integer of 1 to 7, and n is 1
≦ n ≦ 7.

FIG. 1 shows the steps for preparing the olefin polymerization catalyst according to the present invention. At the time of polymerization, the usage of each component,
The order of addition is arbitrarily selected, but the following method is exemplified. (1) A method of adding the component (A) and the component (B) to the polymerization vessel in any order. (2) A method in which the catalyst component in which the component (A) is supported on the carrier (C) and the component (B) are added to the polymerization vessel in any order. (3) A method in which the catalyst component in which the component (B) is supported on the carrier (C) and the component (A) are added to the polymerization vessel in any order. (4) A method of adding the catalyst component in which the component (A) is supported on the carrier (C) and the catalyst component in which the component (B) is supported on the carrier (C) 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 (1) to (5), at least two or more catalyst components may be contacted in advance. Further, the solid catalyst component in which the component (A) and the component (B) are supported on the above component (C) may be prepolymerized with an olefin, and the prepolymerized solid catalyst component may further have a catalyst The component may be supported.

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 is polymerized using the above olefin polymerization catalyst, the component (A) is
Usually 10 ^-12 to 10 ^-2 mol per liter of polymerization 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 [(B-1) of the component (B-1) to all transition metal atoms (M) in the component (A).
/ M] is usually used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000. The component (B-2) is a molar ratio of the aluminum atom in the component (B-2) and the transition metal atom (M) in the component (A) [(B-2)
/ M] is usually 10 to 500,000, preferably 20 to
It is used in an amount to be 100,000. Ingredient (B-
3), the molar ratio [(B-3) / M] of the component (B-3) to the transition metal atom (M) in the component (A) is usually 1 to 10,
It is preferably used in an amount of 1 to 5.

In the component (D), the component (B) is the component (B-1).
In the case of, the molar ratio [(D) / (B-1)] is usually 0.0
When the component (B) is the component (B-2) in an amount of 1 to 10, preferably 0.1 to 5, the molar ratio [(D) /
(B-2)] is usually 0.001 to 2, preferably 0.00
When the component (B) is the component (B-3), the molar ratio [(D) / (B-3)] is usually 0.01 to
It is optionally used in an amount of 10, preferably 0.1 to 5.

The olefin polymerization temperature using such an olefin polymerization catalyst is usually from -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-eicosene; cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene , 2-methyl 1,4,5,8-dimethano-1,2,
3,4,4a, 5,8,8a-octahydronaphthalene; polar monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo
Α, β-unsaturated carboxylic acids such as (2,2,1) -5-heptene-2,3-dicarboxylic acid anhydride, and their sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts, calcium Α, β-Unsaturated carboxylic acid metal salts such as salts; methyl acrylate, ethyl acrylate, acrylic acid
n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, methacrylic acid α, β-Unsaturated carboxylic acid esters such as n-butyl and isobutyl methacrylate; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc. Examples thereof include unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate and monoglycidyl itaconic acid, and halogen-containing olefins such as vinyl chloride and vinyl fluoride.

It is also possible to use vinylcyclohexane, dienes or polyenes. The diene or polyene has 4 to 30 carbon atoms, preferably 4 carbon atoms.
A cyclic or chain compound having 20 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,
An example is 9-dimethyl-1,4,8-decatriene.

Further, aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-
Mono or polyalkyl styrene such as ethyl styrene, p-ethyl styrene; methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, o-chloro styrene, p-chloro styrene, divinyl benzene, etc. Functional group-containing styrene derivatives; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like. These olefins may be used alone or in combination of two or more.

[0127]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. The structures of the compounds and polymers obtained in the examples are 270 MHz ¹ H-NMR (JEOL GSH-27
Type 0, FT-IR (SHIMAZUFTIR-820
OD type), FD-mass spectrometry (JEOL SX-102A
Type) and the like.

Complex Synthesis Example 1 Previous report (Chemistry Letters 1990,
2167. 2.6-dimethylphenoxyzirconium trichloride 0.38 g (0.81 mm)
sol) in tetrahydrofuran (10 ml) was charged into a 30 ml glass reactor sufficiently purged with nitrogen, then -7
Cooled to 8 ° C. While stirring this solution, N- (3-t
-Butylsalicylidene) aniline lithium salt 0.20
g (0.76 mmol) of tetrahydrofuran (5 m
l) The solution is slowly added dropwise, and then the temperature of the reactor is set to -7.
The temperature was slowly raised from 8 ° C to room temperature over 17 hours.
After completion of the reaction, the solvent was distilled off under reduced pressure, and the reaction product was extracted with methylene chloride. Methylene chloride in the extract was distilled off under reduced pressure to obtain 0.40 g of a yellow powdery zirconium compound represented by the following formula (XX).

[0129]

[Chemical 14]

Example 1 250 ml of toluene was charged into a glass reactor having an inner 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, and subsequently, the zirconium compound (XX) 2. synthesized in Complex Synthesis Example 1.
7 mg (0.005 mmol) was added to initiate polymerization.
Under normal pressure ethylene gas atmosphere (gas flow rate 100L /
h) After reacting at 25 ° C. for 5 minutes, the supply of ethylene was stopped and the polymerization was stopped by adding a small amount of methanol / hydrochloric acid. After termination of the polymerization, the reaction product was put into 500 ml of methanol to precipitate the whole amount of the polymer, and the polymer was recovered by filtration. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 2.88 g of polyethylene was obtained. Polymerization activity of 6.92 kg per 1 mmol of zirconium
Met.

Example 2 In Example 1, ethylene gas was mixed with ethylene / propylene mixed gas (gas flow rate: 100 L / h, 10:
0L / h), and added zirconium compound (X
The amount of X) was 1.1 mg (0.002 mmol), and the polymerization time was 10 minutes. Polymerization was performed in the same manner to obtain 3.48 g of an ethylene-propylene copolymer. The polymerization activity per 1 mmol of zirconium was 8.36 kg, and the propylene content in the obtained polymer was 3.37 m.
It was ol%.

[0132]

The olefin polymerization catalyst according to the present invention has a high polymerization activity for olefins.

[Brief description of drawings]

FIG. 1 shows a process for preparing an olefin polymerization catalyst according to the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J028 AA01A AB01A AC00A AC01A                       AC31A AC41A AC44A AC45A                       BA01B BB01B BC01B BC05B                       BC06B BC12B BC15B BC16B                       BC20B BC25B BC28B BC29B                       CA17B CB94B EB02 EB04                       EC01 EC03

Claims (6)

[Claims] 1. (A) a transition metal compound represented by the following general formula (I): YZMX _k S _n (I) (wherein Y is a monovalent anionic coordination site or a neutral coordination site) And Z is a monodentate ligand having an anionic or neutral coordination site, or a multidentate ligand having an anionic and / or neutral coordination site. , Z is a bidentate ligand having a monovalent anionic coordination site and a neutral coordination site, the ligand Y and the ligand Z do not have the same basic skeleton. And Z may be connected to each other, and when Y and Z are connected to each other, Y
The ligand consisting of and Z is asymmetric. M is a transition metal of Group 3 to Group 9 of the periodic table, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group,
Represents a group selected from 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, and a tin-containing group, and k is M Is a number that satisfies the valence, and k
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. S represents a monodentate ligand having only a neutral coordination site, and n represents a number from 0 to 4. ) And, if necessary, (B) (B-1) 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, olefin polymerization characterized by containing Catalyst. 2. The monovalent anionic coordination site constituting Y or Z is a hetero atom of a group selected from aryloxy group, pyrrolyl group, indolyl group, amide group, silylamide group, sulfonamide group and arylthio group. The catalyst for olefin polymerization according to claim 1, which is present. 3. The neutral coordination site constituting Y or Z is
The olefin polymerization catalyst according to claim 1, which is a hetero atom of a compound selected from imines, ketones, aldehydes, amines, ethers, phosphines and sulfides. 4. A bidentate ligand (Y and Z) having a monovalent anionic coordination site and a neutral coordination site is represented by the following general formulas (II) to (XI). The olefin polymerization catalyst according to claim 1. [Chemical 1] (In the formula, A is an oxygen atom, a sulfur atom, or a substituent R ⁶⁵
Wherein R ^{1 to} R ⁶⁵ are the same or different from each other, hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group , Aluminum-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups,
Alternatively, it represents a tin-containing group, and two or more of these may be linked to each other to form a ring. ) 5. An olefin polymerization catalyst, which further comprises a carrier (C) in addition to the olefin polymerization catalyst according to any one of claims 1 to 4. 6. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1.