JP2002047295A - Transition metal compound, olefin polymerization catalyst, method for producing olefin polymer and olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new double crosslinked metallocene compound useful as a component of olefin polymerization catalyst and provide an olefin polymerization catalyst containing the compound. SOLUTION: The transition metal compound is expressed by general formula (I) or (II) (R1 to R8 are each H, a 1-20C hydrocarbon group, an Si-containing group or the like; each of R1 to R3 does not form a ring with adjacent group; each of R5 to R8 may form a ring together with adjacent group; A is a group composed of a group 14 element of the periodic table; (p) is an integer of 2-10; X is a σ-bonding ligand; Y is a Lewis base; (q) is an integer of 1-5 and equal to [(the valence of M)-2]; (r) is an integer of 0-3; and M is a metal element of the groups 3-10 of the periodic table or a lanthanoid series metal element). The olefin polymerization catalyst contains the transition metal compound and an activated cocatalyst as main components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel transition metal compound useful as an olefin polymerization catalyst component, an olefin polymerization catalyst containing the same, a method for producing an olefin polymer using the catalyst, and a method for producing the same. It relates to an olefin polymer.

[0002]

2. Description of the Related Art Hitherto, as a highly active soluble olefin polymerization catalyst, a catalyst comprising a combination of a transition metal compound and an aluminoxane has been known (JP-A-58-1930).
No. 9, JP-A-60-217209). It is also reported that a cationic species is effective as an active species of a soluble olefin polymerization catalyst. [J. Am. Che
m. Soc. 81, page 81 (1959)
Year, 82, 1953 (1960), 107, 7219 (1986)]. Also,
An example of isolating this active species and applying it to olefin polymerization is described in [J. Am. Chem. Soc. , Vol. 108,
7410 (1986)], Tokiohei 1-502
636, JP-A-3-139504, and EP-A-468865. Examples of the combination of the active species with an organoaluminum compound include JP-A-3-207704 and International Patent. Publication No. 92-1723 can be cited. By the way, there are few examples of the synthesis of a multi-bridged (double-bridged) metallocene complex.
No. 201113 and "Organometalli"
cs, Vol. 12, p. 1931 (1993) and Organometallics, Vol. 13, 38.
Page 68, Organometallics No. 1
7, page 5528. In addition, its behavior as a polymerization catalyst is described in “Organometalli”.
cs ", Vol. 12, p. 1931 (1993) describes a polymerization example of propylene. However, in order to obtain isotactic polypropylene, it is necessary to resolve a meso- and racemic metallocene complex and obtain it. The molecular weight of the polypropylene was low. On the other hand, recently, some novel double-bridged metallocene complexes have been proposed. (International Patent Publication Nos. 95-9172 and 96-3)
No. 0380, No. 99-67303)

[0003]

The present invention relates to (1) a novel double-bridged metallocene complex useful as a component of an olefin polymerization catalyst; and (2) an olefin polymer having a high molecular weight and high polymerization activity. Giving, olefin polymerization catalyst,
It is another object of the present invention to provide (3) an efficient method for producing an olefin polymer using the polymerization catalyst, and (4) the polymer.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and is directed to a specific transition metal compound, an olefin polymerization catalyst containing the same, a method for producing an olefin polymer using the catalyst, and It has been found that the object can be achieved by the olefin polymer obtained by the production method, and based on this, the present invention has been completed. That is, the present invention provides the following transition metal compound, an olefin polymerization catalyst containing the same, a method for producing an olefin polymer using the catalyst, and an olefin polymer obtained by the production method. [1] A transition metal compound represented by the following general formula (I) or (II).

[0005]

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(Wherein, R ^{1 to} R ⁸ each represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a hetero atom-containing group. R ^{1 to} R ³ each represent an adjacent group and a ring R ^{5 to} R ⁸ may each form a ring with an adjacent group without the formation of A. A represents a group consisting of an element of Group 14 of the periodic table, and when there are a plurality of A, they are P is an integer of 2 to 10. X is σ
It represents a binding ligand, and when there are a plurality of Xs, they may be the same or different. Y represents a Lewis base, and when there are a plurality of Y, they may be the same or different, and may be other Y, cyclopentadienyl group or X
And may be crosslinked. q represents an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3. M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanoid series. [2] The transition metal compound according to the above [1], wherein M in the formula (I) or (II) is a transition metal of Group 4 of the periodic table. [3] A polymerization catalyst for olefins containing (A) the transition metal compound according to [1] or [2] above, and (B) an activation promoter as a main component. [4] A polymerization catalyst for olefins containing (A) the transition metal compound according to [1] or [2], (B) an activation co-catalyst, and (C) organoaluminum as main components. [5] (B) The activating co-catalyst is (B-1) the (A)
(B-2) an aluminoxane, which reacts with a transition metal compound as a component to form an ionic complex;
-3) The above [3], which is any one selected from Lewis acids and (B-4) clays, clay minerals or ion exchange compounds.
Or the olefin polymerization catalyst according to [4]. [6] In the presence of the olefin polymerization catalyst according to any one of the above [3] to [5], olefins are homopolymerized or olefins are copolymerized with other olefins and / or other monomers. A process for producing an olefin polymer. [7] An olefin polymer obtained by the method for producing an olefin polymer according to [6].

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The transition metal compound [I], olefin polymerization catalyst [II], olefin polymer production method [III] and olefin polymer [I] of the present invention are described below.
V] will be described in detail. [I] Transition metal compound The transition metal compound of the present invention is a compound represented by the general formula (I) or (I)
The novel double-bridged metallocene complex represented by I). That is, as shown in the general formula (I) or (II), the ligand is a cyclopentadienyl ring or a substituted cyclopentadienyl ring (provided that R ^{1 to} R ³ represent an adjacent group and a ring, respectively). Is not formed), an indenyl ring or a substituted indenyl ring, and at least one of the two bridging groups is required to have at least two bridging groups consisting of elements of Group 14 of the periodic table. Is a double-bridged metallocene complex. Thereby, an olefin can be produced with a high molecular weight and high polymerization activity. Formula (I)
Or in (II), R ^{1 to} R ⁸ are each a hydrogen atom,
It represents a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a hetero atom-containing group. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group and an octyl group, a vinyl group, a propenyl group, and a cycloalkyl group. Alkenyl group such as hexenyl group; arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group , Methyl naphthyl group,
And aryl groups such as anthracenyl group and phenanthonyl group.

The silicon-containing group is preferably a silicon-containing group having 1 to 20 carbon atoms. Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group; Trihydrocarbon-substituted silyls such as tripropylsilyl, dimethyl (t-butyl) silyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl Group; hydrocarbon-substituted silyl ether group such as trimethylsilyl ether group; silicon-substituted alkyl group such as trimethylsilylmethyl group; silicon-substituted aryl group such as trimethylsilylphenyl group; dimethylhydrosilyl group; methyldihydrosilyl group; Among them, a trimethylsilylmethyl group, a phenyldimethylsilylethyl group and the like are preferable.

The hetero atom-containing group includes a hetero atom-containing hydrocarbon group. Examples of the hetero atom-containing hydrocarbon group include a p-fluorophenyl group, a 3,5-difluorophenyl group, a pentachlorophenyl group, a 3,4,5-
Trifluorophenyl group, pentafluorophenyl group,
A 3,5-bis (trifluoromethyl) phenyl group, a bis (trimethylsilyl) methyl group, and the like.

R ^{1 to} R ³ may not form a ring with an adjacent group, and R ^{5 to} R ⁸ may form a ring with an adjacent group. There is no limitation in particular for a substituent, R ¹ ~
The case where R ³ is a substituent other than a hydrogen atom is preferable because of high activity. When R ³ is a hydrogen atom, the van of R ⁴
The der Waals radius is the van der W of R ^1.
It may be preferable that the diameter be equal to or less than the aals radius. When R ³ is not a hydrogen atom, van der Waa of R ⁴
ls radius may preferably greater than van der Waals radius of R ^1.

A represents a group consisting of elements of Group 14 of the periodic table, and when there are a plurality of A, they may be the same or different. As elements of Group 14 of the periodic table, carbon, silicon, germanium, and tin are preferable. Examples of the group consisting of elements of Group 14 of the periodic table include the following general formula

[0012]

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(E represents carbon, silicon, tin, germanium, and R ⁹ and R ¹⁰ are a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon group having 6 to 20 carbon atoms, respectively.
And a silicon-containing group having 1 to 20 carbon atoms, which may be the same or different from each other, or may be bonded to each other to form a ring. ). Examples of the hydrocarbon group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, the aryloxy group having 6 to 20 carbon atoms and the silicon-containing group having 1 to 20 carbon atoms include those described above in R ^{1 to} R ⁸ . Similar ones can be mentioned. Specific examples include methylene, isopropylidene, dimethylsilylene, diphenylsilylene, diethylsilylene, dimethylgermylene, and dimethylstannylene.

P represents an integer of 2 to 10. X represents a σ-binding ligand, and when there are a plurality of Xs, they may be the same or different. X represents a halogen atom,
A hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, 1 carbon atom
An amide group having 1 to 20 carbon atoms; a silicon-containing group having 1 to 20 carbon atoms; a phosphide group having 1 to 20 carbon atoms; a sulfide group having 1 to 20 carbon atoms; a sulfoxide group having 1 to 20 carbon atoms;
And 20 acyl groups. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. As the hydrocarbon group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group,
Alkyl groups such as hexyl group, cyclohexyl group and octyl group; alkenyl groups such as vinyl group, propenyl group and cyclohexenyl group; arylalkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; phenyl group, tolyl group, Dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group,
And aryl groups such as a biphenyl group, a naphthyl group, a methylnaphthyl group, an anthracenyl group, and a phenanthonyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, a phenylmethoxy group and a phenylethoxy group. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. Examples of the amide group having 1 to 20 carbon atoms include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, a dicyclohexylamide group, an alkylamide group such as a methylethylamide group, a divinylamide group, and a dipropenylamide group. And alkenylamide groups such as dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; and arylamide groups such as diphenylamide group and dinaphthylamide group. Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group; Tripropylsilyl group,
Trihydrocarbyl-substituted silyl groups such as dimethyl (t-butyl) silyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilyl group, and trinaphthylsilyl group; trimethylsilyl ether group A silicon-substituted alkyl group such as a trimethylsilylmethyl group; a silicon-substituted aryl group such as a trimethylsilylphenyl group; a dimethylhydrosilyl group; a methyldihydrosilyl group; Among them, a trimethylsilylmethyl group, a phenyldimethylsilylethyl group and the like are preferable. Examples of the sulfide group having 1 to 20 carbon atoms include a methyl sulfide group, an ethyl sulfide group,
Alkyl sulfide groups such as propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group, and alkenyl sulfide groups such as vinyl sulfide group, propenyl sulfide group, cyclohexenyl sulfide group; benzyl sulfide group, phenylethyl Arylalkyl sulfide groups such as sulfide group and phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group,
Aryl sulfide groups such as dimethyl phenyl sulfide group, trimethyl phenyl sulfide group, ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide group, anthracenyl sulfide group, phenanthyl sulfide group No. Carbon number 1-2
As the sulfoxide group of 0, a methylsulfoxide group,
An alkylsulfoxide group such as an ethylsulfoxide group, a propylsulfoxide group, a butylsulfoxide group, a hexylsulfoxide group, a cyclohexylsulfoxide group, and an octylsulfoxide group; an alkenylsulfoxide group such as a vinylsulfoxide group, a propenylsulfoxide group and a cyclohexenylsulfoxide group; Groups, phenylethylsulfoxide groups, arylalkylsulfoxide groups such as phenylpropylsulfoxide groups; phenylsulfoxide groups, tolylsulfoxide groups, dimethylphenylsulfoxide groups, trimethylphenylsulfoxide groups, ethylphenylsulfoxide groups,
And arylsulfoxide groups such as a propylphenylsulfoxide group, a biphenylsulfoxide group, a naphthylsulfoxide group, a methylnaphthylsulfoxide group, an anthracenylsulfoxide group, and a phenanthenylsulfoxide group. Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, tearoyl group, alkylacyl group such as oleoyl group, benzoyl group, toluoyl group, salicyloyl group, Cinnamoyl group, naphthoyl group,
Examples include an arylacyl group such as a phthaloyl group, an oxalyl group, a malonyl group, and a succinyl group each derived from a dicarboxylic acid such as oxalic acid, malonic acid, and succinic acid. X is preferably an alkyl group such as a methyl group, an ethyl group or a propyl group, or an aryl group such as a phenyl group.

Y represents a Lewis base, and when there are a plurality of Y, they may be the same or different, and may be cross-linked to another Y, cyclopentadienyl group or X. Examples of Y include amines, ethers, esters, phosphines, thioethers, and nitriles. Examples of the amines include amines having 1 to 20 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, Dicyclohexylamine, methylethylamine, trimethylamine, triethylamine, alkyl amines such as tri-n-butylamine, vinylamine, propenylamine,
Alkenylamines such as cyclohexenylamine, divinylamine, dipropenylamine and dicyclohexenylamine; arylalkylamines such as phenylamine, phenylethylamine and phenylpropylamine; arylamines such as diphenylamine and dinaphthylamine; or ammonia, aniline, N- Examples include methylaniline diphenylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline and the like. As ethers,
Methyl ether, ethyl ether, propyl ether,
Aliphatic single ether compounds such as isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether;
Aliphatic hybrid ether compounds such as methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl Aliphatic unsaturated ether compounds such as vinyl ether, methyl allyl ether, ethyl vinyl ether and ethyl allyl ether; anisole;
Phenetole, phenyl ether, benzyl ether,
Phenylbenzyl ether, α-naphthyl ether, β
-Aromatic ether compounds such as naphthyl ether; and cyclic ether compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, and dioxane. Examples of the esters include ethyl benzoate. As phosphines,
C1-20 phosphine is mentioned. Specifically, monohydrocarbon-substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, and octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine,
Alkenyl substituted two hydrogen atoms of alkyl phosphine such as trihydrocarbon-substituted phosphine such as trihexyl phosphine, tricyclohexyl phosphine, and trioctyl phosphine; monoalkenyl phosphine such as vinyl phosphine, propenyl phosphine and cyclohexenyl phosphine; and phosphine. Dialkenylphosphine; trialkenylphosphine in which phosphine is substituted with three alkenyl hydrogen atoms; arylalkylphosphine such as benzylphosphine, phenylethylphosphine, phenylpropylphosphine; diarylalkyl in which phosphine is substituted with three aryl or alkenyl hydrogen atoms. Phosphine or aryldialkylphosphine; phenylphosphine, tolylphosphine, dimethylphenylphosphine , Trimethylphenyl phosphine, ethylphenyl phosphine, propylphenyl phosphine, biphenyl phosphine, naphthyl phosphine,
Methylnaphthylphosphine, anthracenylphosphine, phenanthylphosphine; di (alkylaryl) phosphine in which two alkylaryls are substituted for phosphine hydrogen atoms; tri (alkylaryl) in which three alkylaryls are substituted for phosphine hydrogen atoms Aryl phosphines such as phosphine; Examples of the thioethers include the above-mentioned sulfides. Nitriles include acetonitrile, benzonitrile and the like.

Q is an integer of 1 to 5 [(valence of M)-
2], and r represents an integer of 0 to 3. M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanoid series, and specifically includes titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid-based metals. Among them, titanium, zirconium and hafnium, which are Group 4 elements, are suitable for use as an olefin polymerization catalyst.

Specific examples of such a transition metal compound include (1,1′-dimethylsilylene) (2,2′-tetramethyldisilylene) (indenyl) (cyclopentadienyl) zirconium dichloride, 1'-dimethylsilylene) (2,2'-tetramethyldisilylene)
(Indenyl) (3'-methylcyclopentadienyl)
Zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-tetramethyldisilylene) (indenyl) (4′-methylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2 ,
2'-tetramethyldisilylene) (indenyl) (5 '
-Methylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-tetramethyldisilylene) (indenyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride,
(1,1′-dimethylsilylene) (2,2′-tetramethyldisilylene) (indenyl) (4 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride,
(1,1′-dimethylsilylene) (2,2′-tetramethyldisilylene) (3-methylindenyl) (4′-methylcyclopentadienyl) zirconium dichloride,
(1,1′-dimethylsilylene) (2,2′-tetramethyldisilylene) (3-isopropylindenyl)
(4′-isopropylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene)
(2,2′-tetramethyldisilylene) (3-methylindenyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-ethylene ) (Indenyl) (cyclopentadienyl) zirconium dichloride,
1′-dimethylsilylene) (2,2′-ethylene) (indenyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene)
(2,2′-ethylene) (indenyl) (4′-methylcyclopentadienyl) zirconium dichloride,
(1,1′-dimethylsilylene) (2,2′-ethylene) (indenyl) (5′-methylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-ethylene) (Indenyl)
(3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene)
(2,2′-ethylene) (indenyl) (4 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-ethylene) (3-methylindenyl ) (3′-methylcyclopentadienyl) zirconium dichloride, (1,1 ′)
-Dimethylsilylene) (2,2′-ethylene) (3-isopropylindenyl) (3′-isopropylcyclopentadienyl) zirconium dichloride, (1,1′-
Dimethylsilylene) (2,2′-ethylene) (3-methylindenyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-tetramethyldisilylene) (2,2 ′ -Dimethylsilylene) (indenyl) (cyclopentadienyl) zirconium dichloride, (1,1′-tetramethyldisilylene) (2
2′-dimethylsilylene) (indenyl) (3′-methylcyclopentadienyl) zirconium dichloride,
(1,1′-tetramethyldisilylene) (2,2′-dimethylsilylene) (indenyl) (4′-methylcyclopentadienyl) zirconium dichloride, (1,1 ′
-Tetramethyldisilylene) (2,2′-dimethylsilylene) (indenyl) (5′-methylcyclopentadienyl) zirconium dichloride, (1,1′-tetramethyldisilylene) (2,2′-dimethylsilylene ) (Indenyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-tetramethyldisilylene) (2,2′-dimethylsilylene) (indenyl) (4 ′, 5′-) Dimethylcyclopentadienyl)
Zirconium dichloride, (1,1'-tetramethyldisilylene) (2,2'-dimethylsilylene) (3-methylindenyl) (3'-methylcyclopentadienyl)
Zirconium dichloride, (1,1′-tetramethyldisilylene) (2,2′-dimethylsilylene) (3-isopropylindenyl) (3′-isopropylcyclopentadienyl) zirconium dichloride, (1,1′-tetra Methyldisilylene) (2,2′-dimethylsilylene) (3-methylindenyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride;
1′-ethylene) (2,2′-dimethylsilylene) (indenyl) (cyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-dimethylsilylene) (indenyl) (3′- Methylcyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-dimethylsilylene) (indenyl)
(4′-methylcyclopentadienyl) zirconium dichloride, (1,1′-ethylene) (2,2′-dimethylsilylene) (indenyl) (5′-methylcyclopentadienyl) zirconium dichloride, (1,1 '-Ethylene) (2,2'-dimethylsilylene) (indenyl)
(3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene)
(2,2′-ethylene) (indenyl) (4 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-ethylene) (3-methylindenyl ) (3′-methylcyclopentadienyl) zirconium dichloride, (1,1 ′)
-Dimethylsilylene) (2,2′-ethylene) (3-isopropylindenyl) (3′-isopropylcyclopentadienyl) zirconium dichloride, (1,1′-
Dimethylsilylene) (2,2′-ethylene) (3-methylindenyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium. They can be mentioned, but are not limited to them. Further, a transition metal compound similar to the above, wherein zirconium is replaced by a transition metal of another group, or
A compound similar to the above, in which zirconium is replaced with a lanthanoid-based metal element, may be used. [II] Catalyst for Olefin Polymerization The catalyst for olefin polymerization of the present invention comprises (A) a transition metal compound represented by the above general formula (I) or (II);
It contains an activation co-catalyst and, if necessary, (C) an organoaluminum compound.

The component (B) is not particularly limited as long as it is an activating co-catalyst. However, the component (B-1) is an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex. The compound, (B-2) aluminoxane, (B-3) Lewis acid or (B-4) clay, clay mineral or ion-exchange compound can be preferably cited from the viewpoint of high polymerization activity and reduction of catalyst cost. .

The component (B-1) includes the component (A)
Any ionic compound capable of reacting with the transition metal compound of the component to form an ionic complex can be used, but from the viewpoint that a polymerization active site can be formed particularly efficiently, the following general compounds can be used. Those represented by the formulas (II) and (III) are preferred.

([L¹-R¹¹]^{h +})_a([Z]^-)_b ... (III) ([L^Two]^{h +})_a([Z]^-)_b ... (IV) (where L^TwoIs M¹, R¹²R¹³M^Two, R¹⁴ _ThreeC or R^FifteenM
^TwoIt is. [In the formulas (III) and (IV), L¹Is a Lewis base,
[Z]^-Is a non-coordinating anion [Z¹]^-Or [Z^Two]^-,
Here [Z¹]^-Is an anion in which multiple groups are bonded to an element
In other words, [M^ThreeG¹G^Two... G^f(Where M^ThreeIs periodic
Group 5-15 elements, preferably Periodic Tables 13-15
Indicates a group element. G¹~ G^fAre hydrogen and halogen, respectively
Atom, alkyl group having 1 to 20 carbon atoms, 2 to 40 carbon atoms
A dialkylamino group, an alkoxy group having 1 to 20 carbon atoms,
Aryl group having 6 to 20 carbon atoms, aryl having 6 to 20 carbon atoms
Roxy group, C7-C40 alkylaryl group, charcoal
An arylalkyl group having a prime number of 7 to 40 and a carbon number of 1 to 20;
Halogen-substituted hydrocarbon group, acyloxy having 1 to 20 carbon atoms
Si group, organic metalloid group, or hetero group having 2 to 20 carbon atoms
Shows an atom-containing hydrocarbon group. G¹~ G^fTwo or more of
It may form a ring. f is [(center metal M^ThreeAtom of
+1). ), [Z^Two]^-Is the acid dissociation constant
With the logarithm (pKa) of the reciprocal of -10 or less
Acid alone or a combination of Bronsted and Lewis acids
Conjugated bases or conjugate salts generally defined as superacids
Represents a group. Further, a Lewis base may be coordinated. Ma
R¹¹Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
An aryl group, alkylaryl group or a
A reel alkyl group;¹⁴And R¹³Is Shik
Lopentadienyl group, substituted cyclopentadienyl group, i
Ndenyl group, substituted indenyl group, fluorenyl group or
A substituted fluorenyl group, R¹⁴Is alkyl having 1 to 20 carbon atoms
Group, aryl group, alkylaryl group or arylal
Represents a kill group. R^FifteenIs tetraphenylporphyrin,
Shows macrocyclic ligands such as tarocyanines. h is [L ¹−
R¹¹], [L^TwoAn integer of 1 to 3 and a is 1
The above integer, b = (h × a). M¹Is the periodic table
Containing the first to third, eleventh, thirteenth, and thirteenth group elements;
M^TwoRepresents an element in Groups 7 to 12 of the periodic table. ]
Can be suitably used.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹¹ include hydrogen, methyl group, ethyl group, benzyl group and trityl group. Specific examples of R ¹² and R ¹³ include cyclopentadienyl group, methylcyclopentane Examples thereof include a dienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R ¹⁴ include a phenyl group, a p-tolyl group, a p-methoxyphenyl group and the like, and specific examples of R ¹⁵ include a tetraphenylporphine, phthalocyanine, allyl, methallyl and the like. . Specific examples of M ¹ include Li, Na, K, Ag, Cu, Br, I, I _{3, and the} like. Specific examples of M ² include Mn, F
e, Co, Ni, Zn and the like.

[Z ¹ ] ⁻ , that is, [M ³ G ¹ G ^2.
··· G ^f ], examples of M ³ include B, Al, S
i, P, As, Sb and the like, preferably B or Al. Specific examples of G ¹ , G ^{2 to} G ^f include dimethylamino and diethylamino as dialkylamino groups, methoxy, ethoxy, n-butoxy, phenoxy and the like as alkoxy or aryloxy groups. Methyl group, ethyl group, n-
Propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t-butylphenyl, 3,5-dimethylphenyl For example, fluorine, chlorine, bromine, iodine as a halogen atom, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,4 as a hetero atom-containing hydrocarbon group.
5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group,
Organic metalloid groups such as bis (trimethylsilyl) methyl group, pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group,
Examples include a dicyclohexylantimony group and diphenylboron.

Further, a non-coordinating anion, ie, pKa
Specific examples of the conjugated base [Z ² ] ⁻ , which is a Brönsted acid alone or a combination of a Brönsted acid and a Lewis acid having a trifluoromethanesulfonic acid anion (C
F ₃ SO ₃ ) ^- , bis (trifluoromethanesulfonyl)
Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ⁻ , trifluoroacetate anion (CF ₃ CO ₂ ) ⁻ , hexafluoroantimony anion (SbF ₆ ) ^-, fluorosulfonic acid anion (FSO ₃₎ ^-, chlorosulfonic acid anion (ClSO ₃₎ ^-, fluorosulfonic acid anion / antimony pentafluoride ^{_{(FSO 3 / SbF 5) -}} , fluorosulfonic acid anion / 5- fluoride Arsenic (FSO ₃ / AsF ₅ )
^-, trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of such an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, ie, the compound of the component (B-1), include:
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (tri-n-butyl) Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium) , Triethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ) Tri-n-butylammonium borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Dimethylanilinium fluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis Methylpyridinium pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, benzyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, tetrakis ( Methyl (pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [3
5-di (trifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Fluorophenyl) borate (1,1′-dimethylferrocenium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate,
Trityl tetrakis (pentafluorophenyl) borate,
Lithium tetrakis (pentafluorophenyl) borate,
Sodium tetrakis (pentafluorophenyl) borate, tetraphenylporphyrin manganese tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

As the component (B-1), an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex may be used alone or in combination of two or more. May be used.

On the other hand, examples of the aluminoxane as the component (B-2) include a chain aluminoxane represented by the following general formula (V) and a cyclic aluminoxane represented by the following general formula (VI).

[0028]

Embedded image

(Wherein, R ¹⁶ is a group having 1 to 2 carbon atoms.
It represents 0, preferably 1 to 8 alkyl groups, which may be the same or different. Also, m is 2 <m ≦
40 and n are integers of 1 <n ≦ 50. Specific examples include aluminoxanes such as methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The means is not particularly limited, and the reaction may be carried out according to a known method. For example, a method of dissolving an organoaluminum compound in an organic solvent and bringing it into contact with water, a method of adding an organoaluminum compound at the beginning during polymerization and adding water later, water of crystallization contained in a metal salt or the like, There are a method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water. In addition,
The aluminoxane may be toluene-insoluble.

These aluminoxanes may be used alone or in combination of two or more. There is no particular limitation on the Lewis acid of the component (B-3).
It may be an organic compound or a solid inorganic compound. As the organic compound, a boron compound, an aluminum compound, or the like is preferably used, and as the inorganic compound, a magnesium compound, an aluminum compound, or the like is preferably used because an active site can be efficiently formed. Examples of the aluminum compound include bis (2,6-di-t-butyl-4-methylphenoxy) aluminum methyl and (1,1-bi-2-naphthoxy) aluminum methyl. Examples of the magnesium compound include magnesium chloride, Diethoxymagnesium and the like; aluminum compounds such as aluminum oxide and aluminum chloride; and boron compounds such as triphenylboron, tris (pentafluorophenyl) boron and tris [3,5-bis (trifluoromethyl) phenyl] boron , Tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron, tri-n
-Butylboron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris (3,5-difluoro) boron , Tris [3,5-bis (trifluoromethyl) phenyl] boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron, di-n -Butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron,
Examples include pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboron, and n-butyldifluoroboron. One of these Lewis acids may be used, or two or more thereof may be used in combination.

Clay or clay mineral is used as one of the components (B-4). Clay is an aggregate of fine hydrated silicate minerals, a material that produces plasticity when mixed with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures. Clay minerals are hydrated silicates that are the main component of clay. For the preparation of the olefin polymerization catalyst component, any of clay and clay mineral may be used, and these may be naturally occurring or artificially synthesized.

As the component (B-4), an ion-exchange layered compound can be used. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces constituted by ionic bonds and the like are stacked in parallel with weak bonding force to each other, and ions contained therein can be exchanged. Some clay minerals are ion-exchangeable layered compounds.

Specific examples of the component (B-4) include, for example, phyllosilicic acids as clay minerals. The phyllosilicic acids include phyllosilicic acid and phyllosilicates. The phyllosilicates include, as natural products, montmorillonite belonging to smectite group, saponite, hectorite, illite belonging to mica group, sericite, and mixed layer minerals of smectite group and mica group or mica group and vermiculite group. Can be.
Also, as synthetic products, tetrasilicon mica, laponite,
Smecton and the like can be mentioned. In addition, α-Zr
(HPO ₄ ) ₂ , γ-Zr (HPO ₄ ) ₂ , α-Ti (HP
An ionic crystalline compound having a layered crystal structure that is not a clay mineral such as O ₄ ) ₂ and γ-Ti (HPO ₄ ) ₂ can be used.

Clays and clay minerals which do not belong to the ion-exchangeable layered compound include clays called bentonite due to low montmorillonite content, Kibushi clay, montmorillonite which contains many other components in montmorillonite,
Sepiolite, palygorskite, showing fibrous form,
In addition, there are amorphous or low-crystalline allophane, imogolite, and the like.

Further, as the component (B-4), particles having a volume average particle diameter of 10 μm or less are preferable, and particles having a volume average particle diameter of 3 μm or less are more preferable. Generally, the particle shape of the particles has a particle size distribution, but (B
-4) The component preferably has a particle size distribution in which the volume average particle diameter is 10 μm or less, and the content ratio of the volume average particle diameter of 3.0 μm or less is 10% by mass or more, and the volume average particle diameter is Is more preferably 10 μm or less, and more preferably has a particle size distribution in which the content ratio of the volume average particle diameter of 1.5 μm or less is 10% by mass or more. As a method of measuring the volume average particle diameter and the content ratio, for example, a device (GALA) for measuring the particle diameter by light transmittance by laser light is used.
I Production Ltd. CIS-1)
Is used. Further, the component (B-4) may be an acid-treated, alkali-treated, salt-treated, or organic matter-treated one. Among them, those pretreated with an organosilicon compound or an organoaluminum compound are preferable because of their improved polymerization activity.

Among these (B-4) components, quaternary ammonium salts (without particular limitation, quaternary alkyl ammonium salts, quaternary aryl ammonium salts, quaternary aryl alkyl ammonium salts, quaternary benzyl salts) Ammonium salts,
Those having high ability to adsorb or react with a clay or the like to form an interlayer compound (also referred to as intercalation) are preferred. For example, clay or clay mineral is preferable, specifically, phyllosilicic acids are preferable, smectite is more preferable, and montmorillonite is particularly preferable. Further, as the synthetic product, tetrasilicic mica is preferable.

In the polymerization catalyst of the present invention, the use ratio of the catalyst component (A) to the catalyst component (B) is preferably a molar ratio when the compound (B-1) is used as the catalyst component (B). Is from 10: 1 to 1: 100, more preferably from 2: 1 to
If the ratio is outside the above range, the catalyst cost per unit mass polymer becomes high,
Not practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1,000,000.
0, more preferably in the range of 1:10 to 1: 10,000. If the ratio is outside this range, the cost of the catalyst per unit mass of the polymer increases, which is not practical. The use ratio of the (A) catalyst component and the (B-3) catalyst component is as follows:
The molar ratio is preferably in the range of 10: 1 to 1: 2,000, more preferably in the range of 5: 1 to 1: 1,000, and still more preferably in the range of 2: 1 to 1: 500. Is not practical because the catalyst cost per unit mass polymer increases. The ratio of the component (A) to the component (B-4) is such that the transition metal complex of the component (A) is 0.1 to 1,000 μm per unit mass [g] of the clay or the like of the component (B-4). Moles, preferably in the range of 1 to 100 micromolar.

As the catalyst component (B), (B-
1), (B-2) and (B-3) can be used alone or in combination of two or more. The polymerization catalyst of the present invention may contain the above components (A) and (B) as main components,
It may contain the component (B) and the organoaluminum compound (C) as main components.

Here, the organoaluminum compound as the component (C) is represented by the following general formula (VII): R ¹⁷ _v AlP _3-v (VII) (wherein, R ¹⁷ is an alkyl group having 1 to 10 carbon atoms) , P is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms.
And v is a real number of 1 to 3).

Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride and dimethylaluminum. Aluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.

These organoaluminum compounds may be used alone or in combination of two or more. The molar ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10,000, more preferably 1: 5 to 1: 2,000, and still more preferably 1: 1. : 1
A range of 0 to 1: 1,000 is desirable. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, when the amount is too large, especially when it is out of the above range, the organoaluminum compound is wasted and the polymer is not contained. If the amount is large and the amount is small, sufficient catalytic activity cannot be obtained, which may be undesirable.

Further, in the present invention, when each component is contacted,
Or after contact, polyethylene, polypropylene, etc.
Inorganic oxides such as polymers, silica and alumina (so-called
Body) may coexist or be in contact. To be supported on a carrier
In this case, it is preferable to support the polymer on a polymer.
For such a carrier polymer, the particle size is 1 to 300 μm.
m, preferably 10 to 200 μm, more preferably 20
１００100 μm. If this particle size is smaller than 1 μm
Fine powder in the polymer increases and exceeds 300 μm
This increases the size of coarse particles in the polymer, lowering the bulk density and
It causes hopper clogging in the process. in this case
The specific surface area of the carrier is 1 to 1,000 m ^Two/ G, preferred
Ku is 50-500m^Two/ G, and the pore volume is 0.1 to
5m^Three/ G, preferably 0.3-3 m^Three/ G.

The contact may be carried out in an inert gas such as nitrogen or a hydrocarbon such as pentane, hexane, heptane, toluene or xylene. Addition or contact of each component,
The reaction can be carried out at a polymerization temperature of -30.
C. to the boiling point of each solvent, particularly from room temperature to the boiling point of the solvent. [III] Method for Producing Olefin Polymer The method for producing an olefin polymer of the present invention is a method for producing a polymer, which comprises homopolymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst. .

As the organoaluminum compound (C), a compound represented by the general formula (VII) is used, and a trialkylaluminum compound is preferable. Among them, trimethylaluminum and triisobutylaluminum are preferable. In the method for producing an olefin polymer of the present invention, the organoaluminum compound (C) may be used in contact with the component (A) and / or the component (B) in advance, or the component (C) may be placed in a reactor. It may be charged and brought into contact with the components (A) and (B) before use.
The amount of the component (C) is the same as in the olefin polymerization catalyst. According to the method for producing an olefin polymer of the present invention, homopolymerization of olefins or copolymerization of olefins with other olefins and / or other monomers (that is, heterogeneous Copolymerization of olefins with each other, copolymerization of olefins with other monomers, or copolymerization of different olefins with other monomers).

The olefin is not particularly limited, but ethylene or an α-olefin having 3 to 20 carbon atoms is preferable. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene,
Heptene, 1-octene, 1-nonene, 1-decene, 4
-Phenyl-1-butene, 6-phenyl-1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-hexene, 5-methyl -1-hexene, 3,3-dimethyl-
1-pentene, 3,4-dimethyl-1-pentene, 4,
Α-olefins such as 4-dimethyl-1-pentene and vinylcyclohexane, dienes such as 1,3-butadiene, 1,4-pentadiene and 1,5-hexadiene, hexafluoropropene, tetrafluoroethylene and 2-fluoro Halogen-substituted α-olefins such as propene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene, 3,4-dichloro-1-butene, cyclopentene, cyclohexene, norbornene, 5-methylnorbornene, Cyclic olefins such as -ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene and 5-benzylnorbornene; and styrenes such as styrene, p-methylstyrene, p-ethylstyrene, p-propylstyrene and p- Isopropyl Styrene, p-butylstyrene,
p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene, m-butyl Styrene, mesityl styrene, 2,
4-dimethylstyrene, 2,5-dimethylstyrene,
Alkylstyrenes such as 3,5-dimethylstyrene, p
-Methoxystyrene, o-methoxystyrene, alkoxystyrenes such as m-methoxystyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p
Halogenated styrenes such as -bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene, furthermore, trimethylsilylstyrene, vinylbenzoate Acid esters, divinylbenzene and the like. The other olefins described above may be appropriately selected from the olefins.

In the present invention, the above olefins may be used alone or in combination of two or more. When copolymerizing two or more olefins, the above olefins can be arbitrarily combined.

In the present invention, the above-mentioned olefins and other monomers may be copolymerized. Examples of other monomers used in this case include butadiene, isoprene and 1,4-pentadiene. , 1,5-hexadiene and other chain diolefins, norbornene, 1,4,5,8
Polycyclic olefins such as dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and 2-norbornene, norbornadiene, 5-ethylidene norbornene, 5-vinylnorbornene and dicyclopentadiene; Examples include cyclic diolefins, unsaturated esters such as ethyl acrylate and methyl methacrylate.

The method for polymerizing olefins in the present invention is not particularly limited, and any polymerization method such as a slurry polymerization method, a solution polymerization method, a gas phase polymerization method, a bulk polymerization method, and a suspension polymerization method may be employed. Can be.

When a polymerization solvent is used, the solvent may be benzene, toluene, xylene, n-hexane,
Examples thereof include hydrocarbons such as n-heptane, cyclohexane, methylene chloride, chloroform, 1,2-dichloroethane, and chlorobenzene, and halogenated hydrocarbons.
These may be used alone or in combination of two or more. Further, the monomers used for the polymerization may be used depending on the type.

The amount of the catalyst used in the polymerization reaction is as follows:
The component [A] is usually 0.5 to 1 per liter of the solvent.
It is advantageous from the viewpoints of polymerization activity and reactor efficiency to select from 00 micromol, preferably from 2 to 25 micromol.

As for the polymerization conditions, the pressure is usually selected from the range of normal pressure to 200 MPa (gauge). The reaction temperature is usually in the range of -50C to 250C. Examples of the method for adjusting the molecular weight of the polymer include the type and amount of each catalyst component, the selection of the polymerization temperature, and the introduction of hydrogen. Further, at the time of polymerization of the olefin in the present invention, preliminary polymerization can be performed using the above catalyst. This prepolymerization can be carried out by bringing a small amount of olefin into contact with the solid catalyst component.
The temperature is -20 to 100C, preferably -10 to 70C, particularly preferably 0 to 50C. As a solvent used in the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, or a monomer is used, and an aliphatic hydrocarbon is particularly preferable. This prepolymerization can also be performed without a solvent. The prepolymerized product is preferably subjected to an intrinsic viscosity [η] (measured at 135 ° C. in decalin) of 0.2 deciliter / g, preferably 0.5 deciliter / g or more. The amount of the prepolymerized product per 1 mmol of the transition metal component in the catalyst is 1 to 10,000.
g, preferably 10 to 1,000 g. According to this production method, in particular, a copolymer of polypropylene, polyethylene or propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms has a high molecular weight and a high polymerization activity. [IV] Olefin-based polymer The olefin-based polymer of the present invention is obtained by the above-mentioned method for producing an olefin-based polymer. Specific examples include polypropylene, polyethylene or a copolymer of propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms. Regarding the stereoregularity of the olefin polymer, the pentad meso fraction [mmmm] determined by ¹³ C-NMR is usually 0.01 to 0.8, preferably 0.05 to 0.8. They have a uniform composition and a narrow molecular weight distribution. The molecular weight distribution is usually 5 or less, preferably 4 or less.

[0053]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Example 1 (1,1′-SiMe ₂ ) (2,2′-M
Synthesis of e ₂ SiSiMe ₂ ) (indenyl) (4′-methylcyclopentadienyl) zirconium dichloride (1) Under a nitrogen stream, 50 mL of tetrahydrofuran (THF) and 1.3 g (53 mmol) of Mg were added to a 1 L three-necked flask. Here, 0.1 mL of 1,2-dibromoethane is added and stirred to activate Mg. After stirring for 30 minutes, the solvent is drawn off, and 50 mL of THF is newly added. Here, 2.6 g (13.3 mmol) of 2-bromoindene in THF
(200 mL) solution is added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, cooled to -78 ° C, and dichlorotetramethyldisilane (2.3 mL, 13.3 mmol)
A solution of l) in THF (50 mL) is added dropwise over 1 hour. 1
After stirring for 5 hours, the solvent is distilled off. The residue is hexane 200
After extraction with mL, the solvent was distilled off to obtain 3.12 g of 1-chloro-2-indenyltetramethyldisilane.
(13.1 mmol) obtained (98% yield) Under a nitrogen stream, 200 mL of hexane and 1.0 g (12.5 mmol) of methylcyclopentadiene were placed in a three-necked flask.
And n-butyllithium (n-BuL) at -78 ° C.
A hexane solution of i) (1.53 M, 8.2 mL) is added dropwise. After stirring at room temperature for 2 hours, the solid was filtered off and dried under reduced pressure to obtain a white solid. This solid is dissolved in ether 3
0 mL, and a solution of 3.12 g of 1-chloro-2-indenyltetramethyldisilane in THF (20 m
L) is added dropwise at room temperature. After further stirring at room temperature for 10 hours, the solvent is distilled off. After the residue was extracted with 100 mL of hexane, the solvent was distilled off to give 1-indenyl-2-.
3.58 g (11.5 mmol) of (3-methylcyclopentadienyl) -tetramethyldisilane was obtained. (Yield 92%) 1-indenyl-2- (3'-methylcyclopentadienyl) -tetramethyldisilane 3.58 was placed in a Schlenk bottle.
g (11.5 mmol) and 50 mL of ether and -7
At 8 ° C., a hexane solution of n-BuLi (1.53 M, 1
5.1 mL) is added dropwise. After raising the temperature to room temperature and stirring for 3 hours, the ether is distilled off. The obtained solid is washed with 30 mL of hexane and then dried under reduced pressure. This white solid is treated with THF 50m
L and dissolved at room temperature in 1.4 mL of dimethyldichlorosilane
(10.6 mmol) is added dropwise. After stirring at room temperature for 12 hours, the solvent is distilled off, and the residue is extracted with 50 mL of hexane.
Evaporation of the hexane from the filtrate gives a tan oil.
This was dissolved in 80 mL of ether, and n-BuL was added at -78 ° C.
A solution of i in hexane (1.53 M, 15.8 mL) is added dropwise. After stirring at room temperature for 12 hours, the solvent was distilled off, and the residue was washed with 50 mL of hexane to obtain a dilithium salt as an ocher solid. 50 mL of this solid in dichloromethane
And ZrCl4 (1.5 g) suspended in 20 mL of dichloromethane in a separate container is added dropwise. The orange suspension is stirred at room temperature for 12 hours. After evaporating the solvent, the residue is washed with 50 mL of hexane. The obtained solid was recrystallized from 30 mL of dichloromethane to obtain 0.78 g of a yellow powder. (23% yield) ¹ H NMR (90 MHz, CDCl ₃ ): δ 0.46,
0.50, 0.54, 0.59 (s, -Me ₂ SiSi
_{Me 2 -, 12H); 0.97,1.05} (s, -Si
_{Me 2, 6H); 2.21 (} s, -CH 3, 3H); 5.
90, 6.58 (d, CH, 2H); 7.0-7.8.
(M, CH and ArH, 5H ) Example 2 (1,1'-Me ₂ SiSiMe ₂₎
Synthesis of (2,2′-SiMe ₂ ) (indenyl) (4′-t-butylcyclopentadienyl) zirconium dichloride (2) In a nitrogen stream, 50 mL of THF and M were placed in a 1 L three-necked flask.
2.6 g (107 mmol) are added. Where 1,2
-Add 0.1 mL of dibromoethane and stir to activate Mg. After stirring for 30 minutes, the solvent was extracted, and THF 5
Add 0 mL. Here, 5.2 g of 2-bromoindene
(26.7 mmol) in THF (250 mL)
Drip over time. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, cooled to −78 ° C., and dimethyldichlorosilane 3.2 was added.
A solution of mL (26.7 mmol) in THF (70 mL) is added dropwise over 1 hour. After stirring for 15 hours, the solvent is distilled off.
After extracting the residue with 200 mL of hexane, the solvent is distilled off to obtain 4.33 g (20.7 mmol) of 1-chloro-2-indenyldimethylsilane (yield 78).
%) In a nitrogen stream, 100 mL of ether and 2.5 mL of 6,6-dimethylfulvene (20.7 mmol
l) was added, and a MeLi ether solution (1.
14M, 18.2 mL) is added dropwise. After stirring at room temperature for 2 hours, ether was distilled off, and the obtained solid was distilled off with 50 ml of hexane.
After washing with L and drying under reduced pressure, a white solid was obtained. This solid was dissolved in 50 mL of THF, and 1-chloro-
A solution of 4.33 g of 2-indenyldimethylsilane in THF (50 mL) is added dropwise at room temperature. After further stirring at room temperature for 10 hours, the solvent is distilled off. After extracting the residue with 100 mL of hexane, the solvent was distilled off to obtain indenyl- (3
5.34 g (18.1 mmol) of -t-butylcyclopentadienyl) -dimethylsilane were obtained. (Yield 87
%) In a Schlenk bottle, 5.34 g (18.1) of indenyl- (3-t-butylcyclopentadienyl) -dimethylsilane was added.
mmol) and 50 mL of ether and n-B at -78 ° C.
A hexane solution of uLi (1.54 M, 23.5 mL) is added dropwise. After raising the temperature to room temperature and stirring for 3 hours, the ether is distilled off. The obtained solid was washed with 30 mL of hexane and dried under reduced pressure to obtain 4.82 g (12.7 mmol). This yellow-white solid is dissolved in 50 mL of THF, and 2.5 mL (12.7 mmol) of dichlorotetramethyldisilane is added dropwise at room temperature. After stirring at room temperature for 12 hours, the solvent is distilled off, and the residue is extracted with 50 mL of hexane. The hexane of the filtrate was distilled off to obtain 5.21 g of a yellow-brown oil. This is ether 8
After dissolving in 0 mL, a hexane solution of n-BuLi (1.54 M, 16.5 mL) is added dropwise at -78 ° C. 12 at room temperature
After stirring for an hour, the precipitate was collected by filtration and washed with 30 mL of hexane to convert the dilithium salt to a yellow solid at 1.28.
g (2.6 mmol) were obtained. This solid is 30m in toluene
And 0.61 g (2.6 mmol) of ZrCl ₄ suspended in 20 mL of toluene in a separate container.
The orange suspension is stirred at room temperature for 12 hours. After distilling off the solvent, the residue is extracted with 60 mL of hexane. The solvent of the extract was concentrated to about half the volume and refrigerated at -20 ° C to obtain 0.47 g of a yellow-orange powder. (Yield 32%) ¹ H-NMR (CDCl ₃ ): δ (s, -Me ₂ SiSi)
_{Me 2 -, 12H); (} s, -SiMe 2, 6H);
(S, -t-Bu, 9H); (d, CH, 2H);
(M, CH and ArH, 5H) Example 3 Polymerization of Propylene To a heated and dried 1 liter autoclave, 400 mL of toluene and 1.5 mmol of triisobutylaluminum were added at room temperature under a nitrogen atmosphere. After the temperature was raised to 50 ° C. with stirring, 3 mmol of methylaluminoxane and (1,1′-SiMe ₂ ) (2,2′-) obtained in Example 1 were obtained.
₃ μmol of Me ₂ SiSiMe ₂ ) (indenyl) (4′-methylcyclopentadienyl) zirconium dichloride was added. Subsequently, the pressure is increased to 0.7 M with propylene.
Polymerization was carried out for 1 hour while maintaining Pa · G. After the completion of the polymerization reaction, the reaction product was poured into a methanol-hydrochloric acid solution, and after sufficiently stirring, separated, and further thoroughly washed with methanol,
After drying, 82.2 g of polypropylene was obtained. The intrinsic viscosity measured by the method described below is 1.03 dl /
g, weight average molecular weight Mw is 109,000, molecular weight distribution Mw
/ Mn was 1.8 and the pentad meso fraction [mmmm] was 0.093. Upon DSC measurement, no melting point was observed. (Method of evaluating resin properties) Pentad meso fraction [mmm
m] is 19 to 22 p of ¹³ C-NMR of the polymer.
The ratio of the area occupied by a 21.8 ppm signal attributed to pentad meso in the total area of the nine signals appearing in pm was measured using the following apparatus and conditions. Apparatus: JNM-EX400 type NMR apparatus manufactured by JEOL Ltd. Observation nucleus: ¹³ C (100.4 MHz) Method: ¹ H complete decoupling method Concentration: about 200 mg / 3 mL (6.7 × 10 kg /
m ³ ) (10φ sample tube) Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds Integration: 1000 times The melting point was measured under the conditions of an apparatus: DSC7 manufactured by PerkinElmer Inc. Temperature rising rate: 10 ° C./min Temperature range: −50 ° C. to 150 ° C. The intrinsic viscosity [η] was determined by VM manufactured by Rigo Co.
The molecular weight and the molecular weight distribution were measured at 135 ° C. in decalin using an R-053 type automatic viscometer. Apparatus: Waters ALC / GPC 150C Column: Tosoh, GMHHR + H (S) HT × 2 Temperature: 145 ° C. Solvent: 1,2,4-trichlorobenzene Flow rate: 1 mL / min. Under the conditions described above, the measurement was carried out in terms of polyethylene by gel permeation chromatography (GPC). Example 4 Polymerization of Propylene (1,1′-SiMe ₂ ) (2,2′-Me ₂ SiSiMe)
₂₎ (indenyl) (obtained in 4'-methyl cyclopentadienyl) zirconium dichloride embodiment in place of the chloride Example _{2 (1,1'-Me 2 SiSiMe 2} ) (2,2'-SiM
e ₂ ) An experiment was conducted in the same manner as in Example 4 except that (indenyl) (4′-t-butylcyclopentadienyl) zirconium dichloride was used. As a result, 28.0 g of polypropylene was obtained. Has a melting point of 135
° C, intrinsic viscosity 0.32 dl / g, weight average molecular weight Mw
Was 35,900, the molecular weight distribution Mw / Mn was 2.29, and the pentad meso fraction [mmmm] was 0.701. Comparative Example 1 (1,1′-SiMe ₂ ) (2,2′-Me ₂ )
Instead of (SiSiMe ₂ ) (indenyl) (4′-methylcyclopentadienyl) zirconium dichloride, (1,2′-SiMe ₂ ) (2,1′-SiMe ₂ ) (tetrahydroindenyl) ₂ zirconium dichloride was used. Except for the above, the procedure of Example 4 was repeated to obtain 15.6 g of isotactic polypropylene. The obtained polymer had a melting point of 116.0 ° C. and an intrinsic viscosity of 0.15 dl /.
g, weight average molecular weight Mw is 15,000, molecular weight distribution Mw /
Mn is 1.7 and pentad meso fraction [mmmm] is 0.7.
757.

[0054]

The transition metal compound of the present invention is useful as a catalyst component for olefin polymerization. If an olefin polymerization catalyst containing the same is used, a high-molecular-weight polyolefin can be obtained with high activity.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4H049 VN01 VN06 VP04 VQ12 VQ76 VR23 VU14 VW01 4H050 AA01 AB40 4J028 AA01A AB01A AC01A AC09A AC10A AC27A AC28A BA00A BA02B BB00A BB02B BC12 EB19 EB02 BC19 EB02 BC19B02 EB10 EB12 EB13 EB18 EB21 EB22 EC01 EC02 FA01 FA02 FA03 FA04

Claims (7)

[Claims] 1. A transition metal compound represented by the following general formula (I) or (II). Embedded image (Wherein, R ^{1 to} R ⁸ each represent a hydrogen atom and a carbon number of 1 to 20)
Represents a hydrocarbon group, a silicon-containing group or a hetero atom-containing group. R ^{1 to} R ³ each do not form a ring with an adjacent group;
^{5 to} R ⁸ may each form a ring with an adjacent group. A
Represents a group consisting of an element of Group 14 of the periodic table, and when there are a plurality of A, they may be the same or different. p shows the integer of 2-10. X represents a σ-binding ligand, and when there are a plurality of Xs, they may be the same or different. Y represents a Lewis base, and when there are a plurality of Y, they may be the same or different, and may be crosslinked with another Y, cyclopentadienyl group or X. q represents an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3. M is the 3rd to 1st of the periodic table
It represents a Group 0 or lanthanoid metal element. ) 2. The transition metal compound according to claim 1, wherein M in the formula (I) or (II) is a transition metal of Group 4 of the periodic table. 3. An olefin polymerization catalyst comprising (A) the transition metal compound according to claim 1 or (2) and an activation co-catalyst as a main component. 4. A polymerization catalyst for olefins comprising (A) the transition metal compound according to claim 1 or 2; (B) an activation co-catalyst; and (C) an organoaluminum as a main component. 5. An activated cocatalyst comprising: (B-1) an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex; (B-2) an aluminoxane; The olefin polymerization catalyst according to claim 3 or 4, which is any one selected from (B-3) a Lewis acid and (B-4) a clay, a clay mineral, or an ion-exchange compound. 6. An olefin is homopolymerized or an olefin is copolymerized with another olefin and / or another monomer in the presence of the olefin polymerization catalyst according to any one of claims 3 to 5. A method for producing an olefin-based polymer, comprising: 7. An olefin polymer obtained by the method for producing an olefin polymer according to claim 6.