JP3362802B2 - Polymerization catalyst and method for producing polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful polymerization catalyst, and a method for producing a polymer using the same. More specifically, it relates to a polymerization catalyst particularly useful as an olefin polymerization catalyst, and a method for producing a polyolefin-based polymer using the same.

[0002]

2. Description of the Related Art Heretofore, a catalyst comprising a combination of a transition metal compound and an aluminoxane has been known as a highly active soluble olefin polymerization catalyst (JP-A-58-1930).
9 and JP-A-60-217209). Further, it has been proposed that cationic species are useful as active species of soluble olefin polymerization catalysts [J. Am. Chem. Soc. 81, 81.
(1959), J.Am.Chem.Soc.82,1953 (1960), J.Am.Chem.So
c.107, 7219 (1985)]. In addition, as an example of isolating this active species and applying it to olefin polymerization, J. Am. Chem. Soc.
(1986), Japanese Patent Publication No. 01-502636, Japanese Patent Laid-Open No. 03-13.
9504, European Patent Publication 468651 and the like, and Japanese Patent Application Laid-Open No. 03-207704, International Patent Publication 92 as an example in which an organoaluminum compound is used in combination with this active species.
Such as -1723, further, and the like European Patent 519,746 as an olefin polymerization catalyst comprising a transition metal compound and an organoaluminum oxy-compound having a ligand containing a -SO ₃ R group.

[0003]

However, in a catalyst system comprising a combination of a transition metal compound and aluminoxane, trimethylaluminum, which is a raw material for synthesizing aluminoxane, is ignitable and explosive, and its handling is dangerous and expensive. In addition, there are drawbacks such that a large amount of aluminoxane must be used with respect to the transition metal compound, so that it cannot be said that it is necessarily efficient in industrial productivity. Further, all of the polymerization examples disclosed in the above publications and documents relating to active species are those using a monocationic species as the active species, and in terms of catalytic activity for olefin polymerization, and molecular weight of the resulting polymer. It was not always satisfactory. The present invention has been made in view of the above problems, is highly active when used as a polymerization catalyst, the obtained polymer, or the composition of the copolymer is uniform, further, the molecular weight and molecular weight distribution It is an object of the present invention to provide a polymerization catalyst capable of controlling the temperature and a method for producing a polymer using the same.

[0004]

In order to achieve the above object, according to the present invention, a polymerization catalyst containing a polycationic complex represented by the following general formula (I) as a catalyst component: Will be provided. [(CUHC) _n MX _m ] ^{j +} · ([Y] ⁻ ) _j (I) [(I) In the formula, M represents a metal of Group 4 of the periodic table. CUH
C represents a cyclic unsaturated hydrocarbon group-containing group. Each CUHC may be the same or different. Two or more CUHCs may be crosslinked. X represents a σ-bonding ligand.
Each X may be the same or different. CUHC and X may be crosslinked. j is an integer of 2 to 4, n is an integer of 0 to 2, m is an integer of 0 to 6, and n + m is [(valence of M)-
j] is shown. [Y] ^- is A plurality of groups are bonded to the boron
Noncoordinating anions are anions [Y ^{1] -,} or, Sankai
The separation constant (pKa) of -10 or less Bronsted acid
The combination of a role base, Bronsted acid and Lewis acid
Non-coordinating anion which is a role base or a conjugate base of superacid
[Y ² ] ⁻ and at least one of [Y] ⁻ is boron.
Non-coordinating anion, which is an anion in which multiple groups are bonded
^[Y 1] ^- is. A Lewis base may be coordinated. ] Further, the polycationic complex is the following compound
A reaction product is obtained by reacting (a) with the compound (b).
In addition, the reaction product and the compound (b)
There is provided a polymerization catalyst obtained by reacting one or different compounds (b) . (A): Transition metal compound (b): Ionic compound which reacts with the transition metal compound (a) to form an ionic complex. Further, the non-coordinating anion [Y] ⁻ constituting the polycationic complex. at least one trifluoromethanesulfonate anion [CF ₃ SO _3] of ^- can be polymerization catalyst.

Also provided is a polymerization catalyst in which at least one of the non-coordinating anions [Y] ⁻ constituting the polycationic complex is an anion in which a plurality of groups are bonded to boron.

Further, there is provided a polymerization catalyst containing the polycationic complex and an organoaluminum compound as a catalyst component.

There is also provided a polymerization catalyst in which at least one of the polycationic complex and the organoaluminum compound as a catalyst component is supported on a carrier.

Further, there is provided a method for producing a polymer, which comprises homopolymerizing or copolymerizing a monomer in the presence of the above-mentioned polymerization catalyst.

The polymerization catalyst according to the present invention is not limited to the one containing a polycationic complex (hereinafter sometimes referred to as the catalyst component (A)) as a catalyst component as described above, but also a polycationic complex ( A) and a Lewis acid (hereinafter sometimes referred to as a catalyst component (C)) may be contained, and as the catalyst component, a polycationic complex (A), an organoaluminum compound (hereinafter referred to as a catalyst). It may be referred to as component (B)) and a Lewis acid (C).

Further, as described above, the catalyst component, (A),
One or more components of (B) and (C) are added to a carrier (hereinafter,
It may be referred to as a catalyst component (D). ). By using such a supported catalyst, the bulk density and particle size distribution of the polymer can be improved.

The catalyst according to the present invention is particularly suitable for the polymerization of olefins, but other unsaturated compounds, for example, chain diolefins such as butadiene, isoprene and 1,5-hexadiene, norbornene, 1, 4,
5,8-Dimethano-1,2,3,4,4a, 5,8,8
cyclic olefins such as a-octahydronaphthalene,
Cyclic diolefins such as norbornadiene and ethylidene norbornene, unsaturated esters such as ethyl acrylate and methyl methacrylate, β-propiolactone, β-
It can also be used for the polymerization of lactones such as butyrolactone and γ-butyrolactone.

The polymerization catalyst of the present invention will be described in detail below. 1. Polycationic Complex Catalyst Component (A) The catalyst component (A) used in the present invention is represented by the following general formula. [(CUHC) _n MX _m ] ^{j +} · ([Y] ⁻ ) _j (I) [(I) In the formula, M represents a metal of Group 4 of the periodic table. CUH
C represents a cyclic unsaturated hydrocarbon group-containing group. Each CUHC may be the same or different. Two or more CUHCs may be crosslinked. X represents a σ-bonding ligand.
Each X may be the same or different. CUHC and X may be crosslinked. j is an integer of 2 to 4, n is an integer of 0 to 2, m is an integer of 0 to 6, and n + m is [(valence of M)-
j] is shown. [Y] ^- is A plurality of groups are bonded to the boron
Noncoordinating anions are anions [Y ^{1] -,} or, Sankai
The separation constant (pKa) of -10 or less Bronsted acid
The combination of a role base, Bronsted acid and Lewis acid
Non-coordinating anion which is a role base or a conjugate base of superacid
[Y ² ] ⁻ and at least one of [Y] ⁻ is boron.
Non-coordinating anion, which is an anion in which multiple groups are bonded
^[Y 1] ^- is. A Lewis base may be coordinated. ]

Here, specific examples of M include titanium and di
Examples include ruconium and hafnium . CUH
Specific examples of C include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an isopropylcyclopentadienyl group, a 1,2-methylcyclopentadienyl group, and a 1,3-dimethylcyclo group. Examples thereof include a pentadienyl group, a 1,2,3-trimethylcyclopentadienyl group, a 1,2,4-trimethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, and a trimethylsilylcyclopentadienyl group. . Examples of the crosslinked bisCUHC include ethylenebisindenyl group, ethylenebis (tetrahydroindenyl group), isopropylidene (cyclopentadienyl-9-
Fluorenyl) group, cyclohexylidene (cyclopentadienyl-9-fluorenyl) group, dimethylsilylene (tetrahydroindenyl) group, dimethylsilylenebis (indenyl) group, racemic dimethylsilylenebis (3
-Methylcyclopentadienyl) group and racemic-dimethylsilylenebis (1,2,4-trimethylcyclopentadienyl) group. Specific examples of X include hydrogen atom, halogen atom: fluorine, chlorine, bromine, iodine, hydrocarbon group having 1 to 20 carbon atoms: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
1 to 20 carbon atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, tolyl group and benzyl group
Oxygen-containing group: methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, n-octyloxy group, phenoxy group, benzyloxy group, acetoxy group, etc. Group: trimethylsilyl group, trimethylsilylmethyl group and the like, chelating ligand: acetylacetonate group and the like.

[0014] anion in which a plurality of groups are bonded to an element [Y ^{1] -,} i.e. specific examples of ^{[M 1 Z 1 Z 2 ···} Z n] is, B as ^{M 1, Al, Si, P} , As , Sb can be mentioned, among which B and Al are preferable, and Z ¹ ~
Z ⁿ is a dialkylamino group: a dimethylamino group,
Diethylamino group, C1-C20 oxygen-containing group: methoxy group, ethoxy group, n-butoxy group, phenoxy group,
2,6-di-t-butyl-4-methylphenoxy group, hydrocarbon group having 1 to 20 carbon atoms: methyl group, ethyl group, n-
Propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group, 3,5-dimethylphenyl group , Halogen atom: fluorine, chlorine, bromine, iodine, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms: p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,
4,5-Trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, organic metalloid group: pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group , Diphenylboron group.

The non-coordinating anion [Y ² ] ^- , that is, a conjugate base of Bronsted acid having an acid dissociation constant (pKa) of -10 or less, a conjugate base of a combination of Bronsted acid and Lewis acid, or generally specific examples of the conjugate base of what is defined as super acid, trifluoromethanesulfonic acid anion (CF ₃ SO ₃₎ ^- [hereinafter (OTf) ^- may be abbreviated as, 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 ) ^- , fluorosulfonate anion (FSO _3). ) ^- , Chlorosulfonate anion (Cl
SO ₃₎ ^-, fluorosulfonic acid anion / antimony pentafluoride (FSO ₃ -SbF ₅₎ ^-, fluorosulfonic acid anion / 5- fluoride arsenic (FSO ₃ -AsF ₅₎ -, trifluoromethyl meth acid / 5 -Antimony fluoride (C
_{F 3 -SO 3 / SbF 5)} - can be cited, among others,
The trifluoromethanesulfonic acid anion (triflate) [OTf] ⁻ is preferred.

The catalyst component (A) is a transition metal compound (a).
And a reaction product of an ionic compound (b) that reacts with the transition metal compound (a) to form an ionic complex, and a compound formed of the compound (b). Here, examples of the transition metal compound (a) include those represented by the following general formula. (CUHC) _n MX _{m + j} (II) In the formula (II), M, CUHC, X, n, m and j are the same as those described in the formula (I).

Specific examples of such a transition metal compound (a) include the following, and these zirconium compounds:
The compound substituted by titanium and hafnium can be mentioned. (Pentamethylcyclopentadienyl) zirconium trimethyl, (pentamethylcyclopentadienyl) zirconium triphenyl, (pentamethylcyclopentadienyl) zirconium tribenzyl, (pentamethylcyclopentadienyl) zirconium trichloride, (pentamethyl (Cyclopentadienyl) zirconium trimethoxide, (cyclopentadienyl) zirconium trimethyl, (cyclopentadienyl) zirconium triphenyl, (cyclopentadienyl) zirconium tribenzyl, (cyclopentadienyl) zirconium trichloride, ( Cyclopentadienyl) zirconium trimethoxide, (cyclopentadienyl) zirconium dimethylmethoxide, (methylcyclopentadienyl) zirconium trimethyl , (Methylcyclopentadienyl) zirconium triphenyl, (methylcyclopentadienyl) zirconium tribenzyl, (methylcyclopentadienyl) zirconium trichloride, (methylcyclopentadienyl) zirconium trimethoxide, (methylcyclopenta (Dienyl) zirconium dimethylmethoxide, (dimethylcyclopentadienyl) zirconium trichloride, (trimethylcyclopentadienyl) zirconium trichloride, (trimethylsilylcyclopentadienyl) zirconium trichloride,
(Tetramethylcyclopentadienyl) zirconium trichloride, indenyl zirconium trichloride, fluorenyl zirconium trichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadiene (Enyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dimethoxide, bis (cyclopentadienyl) zirconium diethyl, bis (cyclopentadienyl) zirconium methoxy chloride, bis ( Cyclopentadienyl) zirconium dihydride, bis (cyclopentadienyl) zirconium dichloride hydride, bis (methylcyclopentadienyl)
Zirconium dimethyl, bis (methylcyclopentadienyl) zirconium diphenyl, bis (methylcyclopentadienyl) zirconium dibenzyl, bis (methylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (Pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dibenzyl, bis (pentamethylcyclopentadienyl) zirconium methyl chloride, bis (pentamethylcyclopentadienyl) zirconium methyl hydride, Ethylenebis (indenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dichloride, ethylenebis (tetrahydroindenyl) zirconi Dimethyl, ethylenebis (tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dimethyl, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium Dimethyl, phenylmethylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dimethyl, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dimethyl, ethylene (cyclopentadienyl) (9-fluorenyl)) zirconium dimethyl , Cyclohexylidene (cyclopentadienyl)
(9-Fluorenyl) zirconium dimethyl, cyclopentylidene (cyclopentadienyl) (9-fluorenyl) zirconium dimethyl, cyclobutylidene (cyclopentadienyl) (9-fluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl)
(9-fluorenyl) zirconium dimethyl, dimethylsilylene bis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (2,3,5-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene bis ( Indenyl) zirconium dichloride, zirconium tetramethyl, zirconium tetrabenzyl, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrabutoxide, zirconium tetrachloride, zirconium tetrabromide, zirconium butoxytrichloride, zirconium dibutoxydichloride, bis (2, 5-di-t-butylphenoxy) zirconium dimethyl, bis (2,5-di-t-butylphenoxy) zirconium dichloride Zirconium bis (acetylacetonate) dichloride,

The compound (a) has the following general formula (II '):

[0019]

[Chemical 1]

[In the formula, CUHC, M and X are the same as those described in the formula (I). Z is SiR ¹ ₂ , C
R ¹ ₂ , SiR ¹ ₂ SiR ¹ ₂ , CR ¹ ₂ CR ¹ ₂ , CR ¹ ₂ CR ¹ ₂
Is _{^{CR 1 2, CR 1 = CR}} 1, CR 1 2 SiR 1 2 or GeR ¹ _2, Y is the formula ^{-N (R 2) -, -} O -, - S- or -
P (R ² )-, wherein R ¹ is hydrogen or a moiety having up to 20 non-hydrogen atoms selected from alkyl, aryl, silyl, alkyl halide, halogenated aryl groups and combinations thereof. And R ² has 1 carbon atom
10 alkyl or may form a condensed ring system non-hydrogen atoms of an aryl having 6 to 10 carbon atoms or one or more of R ¹ and up to thirty. n is 1 or 2
Is an integer. ] The compound shown by these is also included. The following can be illustrated as specific examples of these compounds. Dimethylsilylene (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) zirconium dichloride, dimethylsilylene (methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) zirconium dichloride,

Specific examples of the transition metal compound (a) include, in addition to these, compounds composed of a metal of group 3 to 10 of the periodic table such as vanadium or a lantinoid series metal.

The compound (b) which reacts with the transition metal compound (a) to form an ionic complex is not particularly limited, but compounds of the following general formulas (III) and (IV) can be preferably used. ^{([L 1 -R 1] k} +) p ([Y] -) q ... (III) ([L 2] k +) p ([Y] -) q ... (IV) ( provided that, L ² is M ^2, R ² R ³ M ³ , R ⁴ ₃ C or R ⁵ M ³ ) [[III], (IV) In the formula, the non-coordinating anion [Y] ⁻ is the same as the above formula (I). It is the same. L ¹ represents a Lewis base, R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and R ² and R ³ represent a cyclopentadienyl group (Cp) or a substituted cyclopentadienyl group (each Cp Can be the same or different, and two or more C
p may have a crosslinked structure. ) Is shown. R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing group having 1 to 20 carbon atoms. k is an ionic valence number of [L ¹ -R ¹ ] and [L ² ] from 1 to 3, p is an integer of 1 or more, and q = p × k. M ² includes elements of groups ¹ to 11, 11 to 13 and 17 and M ³ represents elements of group 7 to 12. R ⁵ represents porphines, phthalocyanines, allyl group derivatives and the like. ]

Specific examples of the Lewis base (L ¹ ) include amines: ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline,
Trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N
-Dimethylaniline, bis (triphenylphosphorus)
-Μ-Nitrido, phosphines: triethylphosphine, triphenylphosphine, diphenylphosphine,
Ethers: dimethyl ether, diethyl ether, dioxane, tetrahydrofuran, thioethers: tetrahydrothiophene, esters: ethyl benzoate, nitriles: acetonitrile, benzonitrile, chain unsaturated hydrocarbons: ethylene, butadiene, 1-pentene, isoprene and These derivatives and cyclic unsaturated hydrocarbons: benzene, toluene, xylene, cyclooctadiene, cyclooctatetraene can be mentioned.

Specific examples of R ¹ include hydrogen, methyl group, ethyl group, benzyl group and trityl group. Specific examples of R ² and R ³ include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R ⁴ include phenyl,
Examples thereof include p-tolyl and p-methoxyphenyl. Specific examples of R ⁵ include tetraphenylporphyrin, phthalocyanine, allyl and methallyl. Specific examples of M ² include Li, Na, K, A
Examples thereof include g, Cu, Br, I and I ₃ .
Specific examples of M ³ include Mn, Fe, Co, Ni and Zn.

Specific examples of the ionic compound (b) which reacts with the transition metal compound (a) to form an ionic complex include triethylammonium tetraphenylborate and tri (n-butyl) ammonium tetraphenylborate. Trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyltetraborate Phenyl (methyl) ammonium, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-sia Pyridinium), triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-tetrakis (pentafluorophenyl) borate Butylammonium, tetraethylammonium tetrakis (pentafluorophenyl) borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, trikis (pentafluorophenyl) borate tri Phenyl (methyl) ammonium, tetrakis (pentafluorophenyl) methylanilinium borate, tetrakis (penta Ruorofeniru)
Dimethylanilinium borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate,
Benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4 -Cyanopyridinium), trikis (pentafluorophenyl) borate triphenylphosphonium, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, Tetraphenylborate Tetraphenylporphyrin Manganese, Tetrakis (pentafluorophenyl) ferrocenium borate, Tetrakis (pentafluorophenyl) Acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) tetraphenylporphyrin manganese borate,
Tetrafluoroboric acid, silver tetrafluoroborate, hexafluorophosphoric acid, silver hexafluorophosphate, hexafluoroarsenic acid, silver hexafluoroarsenate, perchloric acid, silver perchlorate, trifluoroacetic acid, silver trifluoroacetate, trifluoro Rhomethanesulfonic acid, silver trifluoromethanesulfonate, silver-bis (trifluoromethylsulfonyl) methyl, silver-bis (trifluoromethylsulfonyl) benzyl, silver-bis (trifluoromethylsulfonyl) amide, bis (trifluoromethylsulfonyl) Methane, bis (trifluoromethylsulfonyl) phenylmethane,
Bis (trifluoromethylsulfonyl) amine can be mentioned.

As a method for synthesizing the polycation complex (A) represented by the general formula (I), for example, in the case of a dication, 2 equivalents of ([) to (b) the transition metal compound (a). L ¹ −R ¹ ] ^{k +} ) _p ([Y ² ] ⁻ ) _q <(III) formula> or ([L ² ] ^{k +} ) _p ([Y ² ] ⁻ ) _q <(IV) formula> was used. In this case, a dicationic complex corresponding to the formula (I) can be obtained. The dicationic complex [(CU
HC) _n MX _m ] ^{2 +} · ([Y ² ] ^- ) ₂ with 1 equivalent of ([L ¹ -R ¹ ] ^{k +} ) _p ([Y ¹ ] ^- ) _q <(III) formula>, or By reacting ([L ² ] ^{k +} ) _p ([Y ¹ ] ^- ) _q <(IV) formula>, a dicationic complex [(CUHC) _n MX _m ] ²⁺ · ([Y
² ] ⁻ ) ([Y ¹ ] ⁻ ), or by reacting 2 equivalents thereof, a dicationic complex [(CUHC) _n MX _m ] 2 ^+. ([Y
¹ ] ^- ) ₂ can be obtained.

Further, for the transition metal compound (a),
As (b), 1 equivalent of ([L ¹ -R ¹ ] ^{k +} ) _p ([Y ² ] ^- )
_q <(III) expression> or ([L ² ] ^{k +} ) _p ([Y ² ] ^- ) _q <(I
V) formula> is reacted, and [(CUHC) _n MX _{m + 1} ] ⁺ ·
([Y ² ] ^- ) is synthesized and then 1 equivalent of ([L ¹ -R ¹ ]
^{1k +} ) _p ([Y ¹ ] ^- ) _q <(III) formula> or ([L ² ] ^{k +} )
_{Even if p} ([Y ¹ ] ^- ) _q <(IV) formula> is reacted, the dicationic complex [(CUHC) _n MX _m ] ²⁺ · ([Y ¹ ] ^- )
([Y ² ] ^- ) can be synthesized. In addition, as a synthesis example of a dicationic complex, Inorg.Chem.1987,26,383,
Anorg.Chem., Org.Chem.1983,38B (11), 1501, J.Organ
It is reported in omet.Chem.1978,150,59 etc.

Dication complex [(CUHC) _n MX _m ] ^{j +
· ([Y] -) j} ] in [Y] ^- of [Y ^{1] -} and [Y ^2]
- ratio of can be arbitrarily adjusted. Further, the dicationic complex may be formed in the polymerization system, or may be prepared in advance. In this case, as the solvent species, halogenated hydrocarbons such as dichloromethane, aromatic solvents such as toluene, benzene, and xylene, and aliphatic solvents such as hexane and heptane are preferably used. In addition, a trication complex, a tetracation complex, etc. can also be used as a catalyst component. The ratio of the reaction product of the compound (a) and the compound (b) to the compound (b) used in the present invention is not particularly limited, but usually the reaction product: (b) = 1: 0.2 to. 1: 2
0, preferably 1: 0.5 to 1: 5 (molar ratio).

Specific examples of the polycation complex thus obtained include those shown below. [(Pentamethylcyclopentadienyl) zirconium methyl] [tetrakis (pentafluorophenyl) borate] [trifluoromethanesulfonate],
[(Pentamethylcyclopentadienyl) zirconium methyl] [tetrakis (pentafluorophenyl) borate] [tetraphenylborate], [(pentamethylcyclopentadienyl) zirconiummethyl] [tetrakis (pentafluorophenyl) borate] ₂ , [(Pentamethylcyclopentadienyl) zirconium chloride] [Tetrakis (pentafluorophenyl) borate] [Trifluoromethanesulfonate], [(Pentamethylcyclopentadienyl) zirconium chloride]
[Tetrakis (pentafluorophenyl) borate]
[Tetraphenylborate], [(Pentamethylcyclopentadienyl) zirconium chloride] [Tetrakis (pentafluorophenyl) borate] ₂ , [(Cyclopentadienyl) zirconiummethyl] [Tetrakis (pentafluorophenyl) borate] [Trifluoro Chloromethanesulfonate], [(cyclopentadienyl) zirconium methyl] [tetrakis (pentafluorophenyl) borate] [tetraphenylborate], [(cyclopentadienyl) zirconiummethyl] [tetrakis (pentafluorophenyl) borate] ₂ , [(Cyclopentadienyl) zirconium chloride] [Tetrakis (pentafluorophenyl) borate] [Trifluoromethanesulfonate], [(Cyclopentadienyl)
Zirconium chloride] [tetrakis (pentafluorophenyl) borate] [tetraphenylborate],
[(Cyclopentadienyl) zirconium chloride]
[Tetrakis (pentafluorophenyl) borate] ₂ , [Bis (cyclopentadienyl) zirconium] [Tetrakis (pentafluorophenyl) borate] [Trifluoromethanesulfonate], [Bis (cyclopentadienyl) zirconium] [Tetrakis (penta Fluorophenyl) borate] [tetraphenylborate], [bis (cyclopentadienyl) zirconium] [tetrakis (pentafluorophenyl) borate] ₂ , [ethylenebis (indenyl) zirconium]
[Tetrakis (pentafluorophenyl) borate]
[Trifluoromethanesulfonate], [Ethylenebis (indenyl) zirconium] [Tetrakis (pentafluorophenyl) borate] [Tetraphenylborate], [Ethylenebis (indenyl) zirconium]
[Tetrakis (pentafluorophenyl) borate] ₂ , [Ethylenebis (tetrahydroindenyl) zirconium] [Tetrakis (pentafluorophenyl)]
Borate] [trifluoromethanesulfonate], [ethylenebis (tetrahydroindenyl) zirconium]
[Tetrakis (pentafluorophenyl) borate]
[Tetraphenylborate], [Ethylenebis (tetrahydroindenyl) zirconium] [Tetrakis (pentafluorophenyl) borate] ₂ , [Dimethylsilylenebis (cyclopentadienyl) zirconium] [Tetrakis (pentafluorophenyl) borate] [Trifluor Rhomethanesulfonate], [isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium] [tetrakis (pentafluorophenyl) borate] [trifluoromethanesulfonate], [dimethylsilylenebis (2,3,5-trimethylcyclopentadiene] (Enyl) zirconium] [tetrakis (pentafluorophenyl) borate] [trifluoromethanesulfonate], [zirconium dimethyl] [tetrakis (pentafluorophenyl)] Rate] [trifluoromethanesulfonate], [zirconium dibenzyl] [tetrakis (pentafluorophenyl) borate] [trifluoromethanesulfonate], [zirconium dimethoxide] [tetrakis (pentafluorophenyl) borate] [trifluoromethanesulfonate], [zirconium Diethoxide] [tetrakis (pentafluorophenyl) borate] [trifluoromethanesulfonate], [zirconium dibutoxide] [tetrakis (pentafluorophenyl) borate] [trifluoromethanesulfonate], [zirconium dichloride] [tetrakis (pentafluorophenyl) Borate] [trifluoromethanesulfonate], [zirconium dibromide] [tetrakis (pentafluorophenyl)] Rate [trifluoromethanesulfonate], [bis (2,5-di -t- butyl phenoxy) zirconium]
[Tetrakis (pentafluorophenyl) borate]
[Trifluoromethanesulfonate], [Zirconium (acetylacetonate)] [Tetrakis (pentafluorophenyl) borate] [Trifluoromethanesulfonate]

2. Catalyst component (B) The polymerization catalyst of the present invention may contain an organoaluminum compound (B) as a catalyst component together with the catalyst component (A). Polymerization or copolymerization using this catalyst can improve the polymerization activity.

Examples of the organoaluminum compound (B) include those represented by the following general formula (V), (VI) or (VII). ^{_{R 6 r AlQ 3-r ...}} (V) (R 6 is from 1 to 20 carbon atoms, preferably 1 to 12 alkyl group, Q is a hydrogen atom, a halogen atom, an alkoxy group or C 6 to C20 20 represents an aryl group and Q may be the same or different. R is an integer of 0 to 3.) Specific examples of the compound of the formula (V) include trimethylaluminum, triethylaluminum, triisopropylaluminum, Triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride,
Diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like can be mentioned.

[0032]

[Chemical 2] (R ⁷ represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and a halogen atom, which may be the same or different. Further, s represents the degree of polymerization, and the number of repeating units is preferably 3 to 50, and more preferably 7 to 40.) A chain aluminoxane.

[0033]

[Chemical 3] (R ⁷ is the same as in formula (VI), s is the degree of polymerization, and the number of repeating units is preferably 3 to 50, more preferably 7 to 40.) Alkylaluminoxane.

Among the compounds of the formulas (V) to (VII), preferred are alkyl groups having 3 or more carbon atoms, and particularly alkyl group-containing aluminum compounds or aluminoxane having at least one branched alkyl group. Particularly preferred is triisobutylaluminum or aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, an aluminoxane having a degree of polymerization of 7 or more, or a mixture thereof is used, high activity can be obtained.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum (one or more kinds) and a condensing agent such as water are brought into contact with each other, but the method is not particularly limited, and a known method can be used. All you have to do is react. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization, and water is added later, water of crystallization contained in a metal salt, etc. , A method of reacting water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water. The aluminoxane may be insoluble in toluene.

When the component (B) is used, the amount used is usually 1 to 2,000 mol per 1 mol of the component (A),
Preferably 5 to 1,000 moles, particularly preferably 10 to
It is 500 mol. If the component (B) is used, the polymerization activity can be improved, but if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable. Even when aluminoxane is used, it can be used in a small amount. In addition,
The component (B) may be used in contact with the catalyst of the present invention. The contact may be made in advance or in the polymerization system.

3. Catalyst Component (C) The polymerization catalyst of the present invention may contain a Lewis acid (C) as the catalyst component together with the catalyst component (A). There is no particular limitation on this Lewis acid,
It may be an organic substance or a solid inorganic substance. As organic matter,
As the boron compound, the aluminum compound, and the inorganic material, a magnesium compound is preferably used.

As the aluminum compound, bis (2,2
6-di-t-butyl-4-methyl) aluminum methyl, (1,1′-bis-2-naphthoxy) aluminum methyl, magnesium compounds such as magnesium chloride and diethoxymagnesium, and boron compounds such as triphenylboron. , Tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron, tri (n)
-Butyl) boron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris (3,5, -difluoro) Phenyl) boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron, di (n-butyl) fluoroboron, (pentafluorophenyl) difluoroboron , Phenyldifluoroboron, (pentafluorophenyl) difluoroboron, phenyldifluoroboron, (pentafluorophenyl) dichloroboron, methyldifluoroboron, ethyldifluoroboron, (n-butyl) difluoroboron. Of these, tris (pentafluorophenyl) boron is particularly preferable.

4. Catalyst component (D) The catalyst for polymerization of the present invention comprises the catalyst components (A), (B),
The carrier may carry at least one of (C) and (C). The type of carrier [catalyst component (D)] is not limited, and any of an inorganic carrier, an inorganic oxide carrier or an organic carrier can be used, but an inorganic carrier or an inorganic oxide carrier is particularly preferable.

Specifically, as the inorganic carrier, MgC
Examples thereof include magnesium compounds such as l ₂ , MgCl (OEt), and Mg (OEt) ₂ and complex salts thereof, and organomagnesium compounds represented by MgR ¹³ _X X ¹ _Y. Here, R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2 and y is 0 to 2.

As the inorganic oxide carrier, SiO ₂ , Al ₂
O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ ,
CaO, ZnO, BaO, ThO ₂ and mixtures thereof such as silica alumina, zeolite, ferrite,
Glass fiber etc. can be illustrated. Among these,
SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate or the like.

As the organic carrier, polystyrene,
Styrene-divirbenzene copolymer, polyethylene, linear low-density polyethylene, polypropylene, poly-4-
Examples thereof include polymers such as methyl-1-pentene, substituted polystyrene and polyarylate, and starch and carbon.

The properties of the carrier [catalyst component (D)] used in the present invention vary depending on the type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm. . When the particle size is small, fine powder in the polymer increases, and when the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper.

The specific surface area of the carrier [catalyst component (D)] is usually 1 to 1,000 m ² / g, preferably 50 to 5
00 m ² / g, the pore volume is usually 0.1 to ⁵ cm ³ / g,
It is preferably 0.3 to ³ cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be obtained, for example, from the volume of nitrogen gas adsorbed according to the BET method [“Journal of American Chemical Society (J.Am.Chem.Soc.)”]. 6
0, p. 309 (1983)].

Further, the carrier [catalyst component (D)] is
Usually 150 to 1000 ° C, preferably 200 to 800 ° C
It is desirable to use it after firing.

The polymerization catalyst of the present invention comprises the compound (a)
And a compound (b) as a main component, and at least one of the compound (a) or the reaction product and the compound (b), preferably the compound (a).
Alternatively, both the reaction product and the compound (b) are supported on the carrier [catalyst component (D)].

The method for supporting at least one of the compound (a) or the reaction product and the compound (b) on the carrier [catalyst component (D)] is not particularly limited, but the following methods (1) to (4) are exemplified. be able to. A method of mixing at least one of the compound (a) or the reaction product and (b) with a carrier [catalyst component (D)]. A method in which a carrier [catalyst component (D)] is treated with an organoaluminum compound or a halogen-containing silicon compound and then mixed with at least one of the compound (a) or a reaction product and (b) in an inert solvent. A method of reacting a carrier [catalyst component (D)] with a compound (a) or a reaction product, and / or (b) with an organoaluminum compound or a halogen-containing silicon compound. A method in which the compound (a) or the reaction product or (b) is supported on a carrier [catalyst component (D)], and then the compound (b) or (a) or the reaction product is mixed. A method of mixing the compound (a) or a reaction product of the reaction product and the compound (b) with a carrier [catalyst component (D)].
A method of allowing a carrier [catalyst component (D)] to coexist during the catalytic reaction of the compound (a) or the reaction product with the compound (b).
The organoaluminum compound (B) may be added in the above reactions.

The catalyst thus obtained may be used for the polymerization after the solvent is distilled off to take it out as a solid, or it may be used for the polymerization as it is. Further, in the present invention, the loading operation on at least one carrier [catalyst component (D)] of the compound (a), the reaction product of the compound (a) and the compound (b), and the compound (b) is carried out. The catalyst can also be produced by carrying out in a polymerization system. In addition, olefin such as ethylene is at atmospheric pressure to 20 Kg.
/ Cm ² and prepolymerization at −20 to 100 ° C. for 1 minute to 2 hours to produce catalyst particles.

In the present invention, the mixing ratio (weight ratio) of the compound (b) to the carrier [catalyst component (D)] is 1: 5.
It is preferably 1: 10000, particularly preferably 1:10 to 1: 500. The mixing ratio (weight ratio) of the compound (a) or the reaction product and the carrier [catalyst component (D)] is 1: 5.
It is preferable that the ratio is ˜1: 10000, particularly 1:10 to 1: 500. Compound (b) and carrier [catalyst component (D)]
If the mixing ratio of the compound (a) or the mixing ratio of the compound (a) and the carrier [catalyst component (D)] is out of the above range, the activity may decrease.

The average particle size of the polymerization catalyst of the present invention prepared as described above is usually 2 to 200 μm, preferably 10 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably from 50 to 500 m ² / g. Average particle size is 2 μm
If it is less than 2, the fine powder in the polymer may increase.
If it exceeds 00 μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. In the catalyst of the present invention, the amount of transition metal in 100 g of the carrier is usually 0.05.
It is preferably 10 to 10 g, particularly 0.1 to 2 g. If the amount of the transition metal is out of the range, the activity may decrease. By thus supporting the catalyst on the carrier [catalyst component (D)], a polymer having industrially advantageous high bulk density and excellent particle size distribution can be obtained.

5. Method for producing polymer In the method for producing a polymer of the present invention, for example, homopolymerization of olefin or copolymerization of olefin is carried out using the above-mentioned polymerization catalyst. In this case, the type of olefin is not particularly limited, but α-olefin having 2 to 20 carbon atoms is preferable. Specifically, ethylene, propylene, 1
-Butene, 3-methyl-1-butene, 1-pentene, 1
-Hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1
-Hexadecene, 1-octadecene, 1-eicosene, etc., styrene, p-methylstyrene, p-chlorostyrene, pt-butylstyrene, p-phenylstyrene,
Styrenes such as p-methylsilylstyrene and p-trimethylsilylmethylstyrene can be preferably used.

In the present invention, when the copolymerization of two or more kinds of olefins is carried out, the above-mentioned monomers can be arbitrarily combined. For example, when propylene and ethylene or ethylene and an α-olefin having 3 to 10 carbon atoms are copolymerized, the copolymerization ratio of propylene and ethylene or ethylene and the α-olefin having 3 to 10 carbon atoms is:
Usually, the molar ratio is 99.9: 0.1-60.0: 40.0.
It is preferably 99.5: 0.5 to 75.0: 25.0.

The method for producing a polymer of the present invention is particularly suitable for the polymerization of olefins, but other unsaturated compounds such as butadiene, isoprene, and chain diolefins such as 1,5-hexadiene. , Norbornene,
1,4,5,8-dimethano-1,2,3,4,4a,
Cyclic olefins such as 5,8,8a-octahydronaphthalene, cyclic diolefins such as norbornadiene and ethylidene norbornene, unsaturated esters such as ethyl acrylate and methyl methacrylate, β-propiolactone, β-butyrolactone, It can also be used for the polymerization of lactones such as γ-butyrolactone or the copolymerization of these unsaturated compounds with the above olefins. Usually, the amount of the other unsaturated compound is 20 mol% or less based on the olefin. In this case, one or more olefins can be preferably used.

In the present invention, the polymerization method is not particularly limited, and any method such as slurry polymerization method, gas phase polymerization method, bulk polymerization method, solution polymerization method and suspension polymerization method may be used. The legal method and the gas phase polymerization method are particularly preferable. Regarding the polymerization conditions, the polymerization temperature is usually -100 to 250 ° C, preferably -50 to 200 ° C, more preferably 0 to 130 ° C.
Is. The ratio of the catalyst used to the reaction raw material is such that the raw material monomer / the above-mentioned component (a) (molar ratio) or the raw material monomer / the above-mentioned (b) component (molar ratio) is 1 to 10 ⁸ , and particularly 100 to 10 ^5. Is preferred. Further, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is atmospheric pressure to 100 Kg.
/ Cm ² G, preferably atmospheric pressure to 30 Kg / cm ² G.

The method of controlling the molecular weight of the polymer includes the selection of the type and amount of each catalyst component, the polymerization temperature, and further the polymerization in the presence of hydrogen. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, aliphatic hydrocarbons such as pentane, hexane, heptane and octane. , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Further, a monomer such as α-olefin may be used as a solvent. The polymerization may be performed without a solvent.

In the method for producing a polymer of the present invention, prepolymerization can be carried out using the polymerization catalyst of the present invention. The prepolymerization can be carried out by contacting the solid catalyst component with, for example, a small amount of olefin.
The method is not particularly limited, and a known method can be used. The olefin used in the prepolymerization is not limited, and examples thereof include the same ones as described above, for example, ethylene, C _{3 to} C ₂₀ α-olefins, or a mixture thereof. It is preferable to use. The prepolymerization temperature is usually −
20-100 degreeC, Preferably it is -10-70 degreeC, More preferably, it is 0-50 degreeC.

In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferable. Further, the prepolymerization may be carried out without a solvent. In the prepolymerization, the intrinsic viscosity [η] of the prepolymerized product (measured in decalin at 135 ° C.) was 0.2.
dl / g or more, particularly 0.5 dl / g or more, and the conditions are adjusted so that the amount of the prepolymerized product per mmol of the transition metal component in the catalyst is 1 to 10,000 g, particularly 10 to 1,000 g. It is preferable.

[0058]

EXAMPLES The present invention will be specifically described below based on Examples and Comparative Examples, but the present invention is not limited by the following Examples and Comparative Examples. In the following examples and comparative examples, physical properties were measured as follows. The results are shown in Table 2 or 4. Intrinsic viscosity [η] : Measured in decalin at 135 ° C. GPC measurement condition device : Waters ALC / GPC 150C column : Tosoh Corp. TSK HM + GMH6 × 2 solvent : 1,2,4-trichlorobenzene temperature : 135 ° C. polyethylene conversion DSC (differential scanning calorimeter) fast heating: from room temperature 190 ℃, 10 ℃ /
Hold for 3 mins, fast cooling: 190 ℃ to room temperature, 10 ℃ / mi
Second heating for n, 3min: Room temperature to 190 ℃, 10 ℃ / mi
n

1. Preparation of Polymerization Catalyst (1) Preparation of [Cp ₂ Zr] [OTf] ₂ Cp ₂ ZrCl ₂ [bis (cyclopentadienyl) zirconium dichloride] 0.05 in 10 ml of dry toluene.
85 g (solution A, 0.02 mol / l) and 0.103 g (solution B, 0.04 mol / l) of AgOTf [silver trifluoromethanesulfonate] in 10 ml of dry toluene.
l) were prepared respectively. Solution B was gradually added dropwise to solution A at room temperature. The produced silver chloride (solid) was filtered off, and [C
A 0.01 mol / l solution of p ₂ Zr] [OTf] ₂ was prepared.

(2) Preparation of [CpZrCl] [OTf] ₂ 0.058 g of CpZrCl ₃ [cyclopentadienylzirconium trichloride] in 10 ml of dry toluene.
(Solution A, 0.02 mol / l), and dry toluene 1
0.103 g (Solution B, 0.04 mol / l) of AgOTf [silver trifluoromethanesulfonate] was prepared in 0 ml. Solution B was gradually added dropwise to solution A at room temperature. The produced silver chloride (solid) was filtered off, and [CpZrC
l] [OTf] ₂ of 0.01 mol / l solution was prepared.

(3) [Et (Ind) ₂ Zr] [OT
f] ₂ Preparation of Et (Ind) ₂ ZrCl in 10 ml of dry toluene
₂ [ethylene bis (indenyl) zirconium dichloride] 0.0836 g (solution A, 0.02 mol / l),
Further, in 10 ml of dry toluene, 0.103 g of AgOTf [silver trifluoromethanesulfonate] (solution B, 0.0
4 mol / l) was prepared. Solution B was gradually added dropwise to solution A at room temperature. The produced silver chloride (solid) was filtered off, and [Et (Ind) ₂ Zr] [OTf] ₂ 0.01
A mol / l solution was prepared.

(4) [IPr (Cp-Flu) Zr]
Preparation of [OTf] ₂ IPr (Cp-Flu) Zr in 10 ml of dry toluene
Cl ₂ [isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride] 0.0865 g
(Solution A, 0.02 mol / l), and dry toluene 1
0.103 g (Solution B, 0.04 mol / l) of AgOTf [silver trifluoromethanesulfonate] was prepared in 0 ml. Solution B was gradually added dropwise to solution A at room temperature. The produced silver chloride (solid) was filtered off, and [IPr (C
0.01 mol / l of p-Flu) Zr] [OTf] ₂
A solution was prepared.

(5) [{C ₅ (Me) ₄ } SiMe ₂ N
Preparation of (tBu) Ti] [OTf] ₂ {C ₅ (Me) ₄ } SiMe _{2 in} 10 ml of dry toluene.
N (tBu) TiCl ₂ [(tertiary butylamido) dimethyl (tetramethyl η ⁵ -cyclopentadienyl) silanetitanium dichloride] 0.0737 g (solution A,
0.02 mol / l) in 10 ml of dry toluene,
AgOTf [silver trifluoromethanesulfonate] 0.1
03 g (solution B, 0.04 mol / l) was prepared. Solution B was gradually added dropwise to solution A at room temperature. The generated silver chloride (solid) was filtered off, and [{C ₅ (Me) ₄ } Si
0.01 of Me ₂ N (tBu) Ti] [OTf] ₂ ((tertiary butylamido) dimethyl (tetramethyl η ⁵ -cyclopentadienyl) silanetitanium ditriflate)
A mol / l solution was prepared.

(6) Preparation of [ZrCl ₂ ] [OTf] _{2 In} 10 ml of dry toluene, 0.0466 g of ZrCl ₄ [zirconium tetrachloride] (solution A, 0.02 mol /
l), or 0.103 g of AgOTf [silver trifluoromethanesulfonate] in 10 ml of dry toluene (solution B,
0.04 mol / l) was prepared. Solution B was gradually added dropwise to solution A at room temperature. The produced silver chloride (solid) was separated by filtration to prepare a 0.01 mol / l solution of [ZrCl ₂ ] [OTf] ₂ (zirconium dichloride ditriflate).

(7) Preparation of [Cp ₂ Ti] [OTf] ₂ Cp ₂ TiCl ₂ [bis (cyclopentadienyl) titanium dichloride] 0.049 in 10 ml of dry toluene.
8 g (solution A, 0.02 mol / l), or 0.103 g (solution B, 0.04 mol / l) of AgOTf [silver trifluoromethanesulfonate] in 10 ml of dry toluene.
Were prepared respectively. Solution B was gradually added dropwise to solution A at room temperature. The generated silver chloride (solid) was filtered off, and [Cp ₂
A 0.01 mol / l solution of Ti] [OTf] ₂ (bis (cyclopentadienyl) titanium ditriflate) was prepared.

(8) Preparation of [Cp ₂ Hf] [OTf] ₂ Cp ₂ HfCl ₂ [bis (cyclopentadienyl) hafnium dichloride] 0.058 in 10 ml of dry toluene.
5 g (solution A, 0.02 mol / l), or 0.103 g (solution B, 0.04 mol / l) AgOTf [silver trifluoromethanesulfonate] in 10 ml of dry toluene.
Were prepared respectively. Solution B was gradually added dropwise to solution A at room temperature. The generated silver chloride (solid) was filtered off, and [Cp ₂
A 0.01 mol / l solution of Hf] [OTf] ₂ (bis (cyclopentadienyl) hafnium ditriflate) was prepared.

(9) Preparation of [Cp ₂ Zr] [BPh ₄ ] ₂ Cp ₂ ZrCl ₂ [bis (cyclopentadienyl) zirconium dichloride] 0.05 in 10 ml of dry toluene.
85 g (solution A, 0.02 mol / l) and 0.175 g (solution B, 0.04 mol / l) of AgBPh ₄ [silver tetraphenylborate] were prepared in 10 ml of dry toluene. Solution B was gradually added dropwise to solution A at room temperature. The generated silver chloride (solid) was filtered off, and [Cp ₂ Z
0.01 mol of r] [BPh ₄ ] ₂ (dicyclopentadienylzirconium bis (tetraphenylborate))
/ L solution was prepared.

2. Polymerization of olefins (1)Example 1 1.4 liter autoclave, nitrogen flow, room temperature
Under the solvent, 400 ml of dry toluene, TIBA
Liisobutylaluminum) 1 mmol (0.05mo
1 / l-toluene solution) was added and stirred sufficiently. 60 ° C
Then, the temperature was raised to 1 [1] to prepare [Cp₂Zr]
[OTf]₂1 μmol and [PhNMe₂H] [B
(C₆F_Five)_Four] Tetrakis (pentafluorophenyl)
Dimethylanilinium borate) 1 μmol (0.01mo
1 / l-toluene solution) was added and stirred sufficiently. That
Then, while introducing ethylene, raise the temperature to 80 ° C and
8kg / cm²Polymerization is carried out for 1 hour while keeping it constant.
became. After completion of the reaction, demineralize methanol, wash and dry
As a result, 59 g of polyethylene was obtained. The obtained po
Melting point of polyethylene, intrinsic viscosity, molecular weight measurement by GPC
The results of the determination are shown in Table 2.

(2)Example 2 In a nitrogen stream at room temperature, use 10 ml Schlenk, 1
[Cp prepared in (1)₂Zr] [OTf]₂1 ml
(0.01 mol / l-toluene solution), [PhNMe
₂H] [B (C₆F_Five)_Four] 1 ml (0.01 mol / l
-Toluene solution) and stirred for 6 hours. The resulting solution
From 2 ml, 0.2 ml (1 μmol-Zr equivalent amount)
[Cp in Example 1₂Zr] [OTf]₂And [Ph
NMe₂H] [B (C₆F_Five)_Four] Instead of
Polymerization was carried out in the same manner as in Example 1 for 1 hour. End of reaction
After that, by demineralizing methanol, washing and drying,
g of polyethylene was obtained. Melting of the obtained polyethylene
Table 2 shows the measurement results of points, intrinsic viscosity, and molecular weight by GPC.
Show.

(3)Examples 3-19 and Comparative Examples 1-1
1 The catalyst species used, the olefin, Table 1 for the polymerization conditions, and
Example 1 was repeated except that the polymerization was carried out under the conditions shown in Table 3.
Polymerization was carried out in the same manner. The results are shown in Tables 2 and 4.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

[Table 4]

(4)Example 20 In Example 1, instead of TIBA, triphenyl
Aluminum (Ph₃Al) 1 mmol (1 mol / l
-Toluene solution) was added, and other conditions were the same as in Example 1.
Then, polymerization was carried out. After completion of the reaction, methanol deashing and washing
14g polyethylene was obtained by cleaning and drying.
It was Table 5 shows the results of the intrinsic viscosity of the obtained polyethylene.
You

(5)Examples 21, 22 Table 5 shows the catalyst species, olefins and polymerization conditions used.
In accordance with Example 20, except that the polymerization was carried out under
It was done. The results are shown in Table 5.

[0077]

[Table 5]

(6)Example 23 In Example 1, before introducing ethylene, B (C₆
F_Five)₃[Tris (pentafluorophenyl) boric acid] 1μ
mol (0.01 mol / l-toluene solution) was added,
Polymerization was conducted for 1 hour in the same manner as in Example 1 except that the mixture was sufficiently stirred.
Was done. After reaction, demineralize methanol, wash, and dry
By doing so, 51 g of polyethylene was obtained. Got
The intrinsic viscosity of polyethylene was 3.21.

(7)Example 24 Silica (average particle size)
Diameter 70μm, specific surface area 260m²/ G, pore volume 260
cc / g) baked at 300 ° C. for 4 hours 2.3 g,
1 [1] [Cp₂Ti] [OTf]₂Torue
(0.01 mol / l) 100 ml, triisobutyl
Aluminum (TIBA) 5 mmol, tetrakis
N-fluorophenyl) dimethylanilinium borate 2m
mol was added and reacted for 1 hour at room temperature with stirring.
After that, toluene was distilled off under reduced pressure to obtain a solid catalyst. Next
Then, 400 ml of toluene in a 1.4 l autoclave,
The solid catalyst obtained above with 1 mmol of TIBA,
Add 3 μmol of titanium, and further at 80 ° C,
Pressure of 8 kg / cm²Autoclave continuously
And polymerized for 1 hour, 30.1 g of
A polymer was obtained. The obtained polymer has uniform granules.
And showed excellent fluidity. Intrinsic viscosity of the obtained polymer
[Η] was 3.78.

(8)Example 25 In Example 1, [Cp₂Zr] [OTf]₂instead of
Prepared in 1 (9) [Cp₂Zr] [BPh_Four]₂To
Polymerization was carried out in the same manner as in Example 1 except that it was used.
It was After completion of the reaction, demineralize methanol, wash and dry
Thus, 57 g of polyethylene was obtained. Obtained polier
The intrinsic viscosity of thylene is 2.36 and the molecular weight Mw is 1.
The molecular weight distribution was 41,000 and was 2.1.

[0081]

EFFECT OF THE INVENTION By the polymerization catalyst and the method for producing a polymer according to the present invention, the activity of the obtained polymer or copolymer is uniform, and its molecular weight and molecular weight distribution are controlled. It is possible to provide a polymerization catalyst capable of producing a polymer or a copolymer having excellent properties without using a large amount of an organometallic compound.

─────────────────────────────────────────────────── --Continued from the front page (56) References JP-A-5-51407 (JP, A) JP-A-5-339315 (JP, A) JP-A-5-65308 (JP, A) JP-A-5- 186521 (JP, A) Special Table 7-505912 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/64-4/658

Claims (6)

(57) [Claims] 1. A polymerization catalyst comprising a polycationic complex represented by the following general formula (I) as a catalyst component. [(CUHC) _n MX _m ] ^{j +} · ([Y] ⁻ ) _j (I) [(I) In the formula, M represents a metal of Group 4 of the periodic table. CUH
C represents a cyclic unsaturated hydrocarbon group-containing group. Each CUHC may be the same or different. Two or more CUHCs may be crosslinked. X represents a σ-bonding ligand.
Each X may be the same or different. CUHC and X may be crosslinked. j is an integer of 2 to 4, n is an integer of 0 to 2, m is an integer of 0 to 6, and n + m is [(valence of M)-
j] is shown. [Y] ^- is A plurality of groups are bonded to the boron
Noncoordinating anions are anions [Y ^{1] -,} or, Sankai
The separation constant (pKa) of -10 or less Bronsted acid
The combination of a role base, Bronsted acid and Lewis acid
Non-coordinating anion which is a role base or a conjugate base of superacid
[Y ² ] ⁻ and at least one of [Y] ⁻ is boron.
Non-coordinating anion, which is an anion in which multiple groups are bonded
^[Y 1] ^- is. A Lewis base may be coordinated. ] 2. The polycationic complex is a compound described below.
A reaction product is obtained by reacting (a) with the compound (b).
In addition, the reaction product and the compound (b)
The polymerization catalyst according to claim 1, which is obtained by reacting one or a different compound (b) . (A): Transition metal compound (b): Ionic compound that reacts with the transition metal compound (a) to form an ionic complex 3. The polymerization catalyst according to claim 1, wherein at least one of the non-coordinating anions [Y] ⁻ constituting the polycationic complex is a trifluoromethanesulfonic acid anion [CF ₃ SO ₃ ] ^−. . Wherein as the catalyst component, the polycationic complexes and polymerization catalyst of any one of claims 1 to 3, characterized in that it contains an organic aluminum compound. 5. At least one of them comprising supported on a carrier according to claim 4 for the polymerization catalyst according to the polycationic complexes and the organoaluminum compound as a catalyst component. 6. A method for producing a polymer, which comprises homopolymerizing or copolymerizing a monomer in the presence of the polymerization catalyst according to claim 1 .