JPH11286491A - Ionic compound, catalyst for polymerizing olefin, and production of olefin-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as an ingredient in a catalyst for polymerizing olefin and applicable to vapor phase polymerization and slurry polymerization process, capable of making the performance of a metallocene catalyst exhibit at its maximum without decreasing the melting point of the resultant polymer and the activity of the catalyst even in a supported state. SOLUTION: This compound is expressed by the formula [wherein, R<1> to R<3> are each H or the like; R<4> to R<8> are each a halogen or the like; X and Y are each a 1-20C alkylene or the like and one of X and Y is an arylene; (i) and (j) are each 0 or 1, and (i)=1 where X is an arylene and (j)=1 where Y is an arylene; Z is an onium compound], e.g. N,N-dimethylanilinium tris(pentafluorophenyl)4-(4-vinylbenzyl)-2,3,5,6-tetrafluorophenyl borate. For example, the compound of the formula is obtained by treating lithium 2,3,5,6- tetrafluorophenyl tris(pentafluorophenyl) borate with n-butylithium, followed by reacting the resultant product with dimethylanilinium chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel ionic compound having high utility as a component of an olefin polymerization catalyst, an olefin polymerization catalyst containing the ionic compound as one component, and an olefin polymerization catalyst. And a method for producing an olefin polymer having a uniform composition and a narrow molecular weight distribution.

[0002]

2. Description of the Related Art Conventionally, in the production of polypropylene,
A Ziegler-Natta type catalyst is used, and polypropylene obtained by a gas phase method or a slurry method has a good morphology of a product obtained since the catalyst is supported on a carrier such as magnesium chloride or silica gel.

[0003] In recent years, a metallocene catalyst which has been rapidly developed can produce a polyolefin in a homogeneous system.
To actually apply a metallocene catalyst to a gas phase method or a slurry method, the catalyst must be supported on a carrier. Therefore, there is a demand for a supporting technique in which the performance of the metallocene catalyst does not decrease even when the catalyst is supported. As a method for supporting a metallocene catalyst, for example, in JP-A-7-70227 or JP-A-9-188712, a method in which methylalumoxane is reacted with silica gel, and a metallocene catalyst is supported on a reaction product thereof. Proposed.
Meanwhile, these supported catalysts for polymerization have a problem that the melting point, which is an index of the rigidity of the polymer, is lower than that of homogeneous polymerization.

Japanese Patent Laid-Open Publication No. Hei 6-336502 proposes a technique in which dimethylanilinium tetrakis (pentafluorophenyl) borate, which is a highly active cocatalyst, is supported on silica gel or the like. Fixation on the carrier is not sufficient. Therefore, Japanese Patent Application Laid-Open
In Japanese Patent No. 127611 and JP-A-8-143617, a technique in which a borate compound is directly supported on a polymer is proposed. However, in this case, although the loading effect is improved, there is a disadvantage that the catalytic activity is not sufficient.

[0005]

DISCLOSURE OF THE INVENTION The present invention makes it possible to maximize the performance of a metallocene catalyst without lowering the melting point and activity even when supported, and is applicable to gas phase polymerization and slurry polymerization. It is an object of the present invention to provide a supported catalyst and a method for producing an olefin polymer using the same.

[0006]

The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that an ionic compound having a specific chemical structure is supported by using it as one component of a metallocene catalyst. It has been found that an excellent olefin polymerization catalyst without lowering the melting point and the activity can be obtained even in this case, and based on these findings, the present invention has been completed.

That is, the gist of the present invention is as follows. (1) An ionic compound represented by the following general formula [1].

[0008]

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[In the formula [1], R¹~ R^Three Are each independently
Hydrogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 to 2 carbon atoms
0 represents a halogenated hydrocarbon group or a silicon-containing group;
^Four~ R ⁸Are each independently a halogen atom, having 1 to 20 carbon atoms
A hydrocarbon group or a halogenated hydrocarbon having 1 to 20 carbon atoms
X and Y each independently represent 1-20 carbon atoms
Alkylene, arylene, phenylene, silyl
Group, germylene group, -O-, -CO-, -S-, -S
O2-, -NR⁹-(However, R⁹Is hydrogen atom, carbon number
An alkyl group having 1 to 20 or an aryl having 6 to 12 carbon atoms
And X or Y is aryl.
And i and j are 0 or 1, and X
Is an arylene group, i is 1, and Y is an arylene group.
In the case of a zirconium group, j is 1 and Z is an onium compound.
(2) (a) transition metal compound and (b) organic aluminum
And (c) ionization according to (1) above.
An olefin polymerization catalyst comprising a compound. (3) (a) transition metal compound and (b) organic aluminum
And (c) ionization according to (1) above.
Polymer of the compound, or ionization according to (1) above
Consisting of a copolymer of a compound and a compound having a double bond.
Refin polymerization catalyst. (4) Olefin polymerization according to the above (2) or (3)
Polymerize or copolymerize olefins using catalysts
A method for producing an olefin-based polymer, comprising:

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The ionic compound of the present invention is a compound represented by the aforementioned general formula [1], wherein the carbonized compound having ¹ to 20 carbon atoms represented by R ^{1 to} R ³ in the general formula [1] is used. As the hydrogen group, specifically, a methyl group, an ethyl group,
Preferred are an alkyl group such as a propyl group and an aryl group such as a phenyl group. Preferred examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include a trifluoromethyl group and a trichloromethyl group. Further, as the silicon-containing group, a trimethylsilyl group, a phenethyldimethyl group and the like are preferable.

The halogen atom represented by R ^{4 to} R ⁸ includes a chlorine atom, a fluorine atom and a bromine atom.
And a C1-C20 hydrocarbon group or C1-C1
Examples of the halogenated hydrocarbon group of 20 include the above R ^{1 to} R ³
Is the same as Next, carbon number 1 represented by X and Y
As the alkylene group of 20, a methylene group, an ethylene group and a propylene group are preferable, and as an arylene group, a phenylene group is preferable. The silylene group is preferably a dimethylsilylene group, a methylphenylsilylene group, or a diphenylsilylene group, and the germylene group is preferably a dimethylgermylene group, a methylphenylgermylene group, or a diphenylgermylene group. In addition, -NR ⁹ -
The group represented by is preferably a group in which R ⁹ is a methyl group.

The onium compounds represented by Z include dimethylanilinium, dimethylammonium, methylphenylammonium, trimethylammonium,
Examples include methylanilinium, triphenylcarbonium, ferrocenium, phosphonicum, potassium, sodium, lithium and the like, and particularly preferred are dimethylanilinium and triphenylcarbonium.

Specific examples of the ionic compound represented by the general formula [1] include N, N-dimethylanilinium tris (pentafluorophenyl) -4- (4-vinylbenzyl) -2,3 5,6-tetrafluorobiphenyl borate, N, N-dimethylanilinium tris (pentafluorophenyl) -4- (3-vinylbenzyl)-
2,3,5,6-tetrafluorobiphenyl borate,
N, N-dimethylanilinium tris (pentafluorophenyl) -4- (2-vinylbenzyl) -2,3,5,
6-tetrafluorobiphenyl borate, methyldiphenylammonium tris (pentafluorophenyl)-
4- (4-vinylbenzyl) -2,3,5,6-tetrafluorobiphenyl borate, methyldiphenylammonium tris (pentafluorophenyl) -4- (3-
Vinylbenzyl) -2,3,5,6-tetrafluorobiphenyl borate, methyldiphenylammonium tris (pentafluorophenyl) -4- (2-vinylbenzyl) -2,3,5,6-tetrafluorobiphenyl borate, trimethyl Ammonium tris (pentafluorophenyl) -4- (4-vinylbenzyl) -2,3,
5,6-tetrafluorobiphenyl borate, trimethylammonium tris (pentafluorophenyl) -4
-(3-vinylbenzyl) -2,3,5,6-tetrafluorobiphenyl borate, trimethylammonium tris (pentafluorophenyl) -4- (3-vinylbenzyl) -2,3,5,6-tetrafluorobiphenyl Borate, triphenylcarbonium tris (pentafluorophenyl) -4- (2-vinylbenzyl) -2,
3,5,6-tetrafluorobiphenyl borate, triphenylcarbonium tris (pentafluorophenyl) -4- (4-vinylbenzyl) -2,3,5,6-
Tetrafluorobiphenyl borate, triphenylcarbonium tris (pentafluorophenyl) -4- (3
-Vinylbenzyl) -2,3,5,6-tetrafluorobiphenyl borate, ferrocenium tris (pentafluorophenyl) -4- (4-vinylbenzyl) -2,
3,5,6-tetrafluorobiphenyl borate, ferrocenium tris (pentafluorophenyl) -4-
(3-vinylbenzyl) -2,3,5,6-tetrafluorobiphenyl borate, ferrocenium tris (pentafluorophenyl) -4- (2-vinylbenzyl)-
2,3,5,6-tetrafluorobiphenyl borate,
Preferred is N, N-dimethylanilinium tris (pentafluorophenyl) -4- (4-vinylbenzyl)
-2,3,5,6-tetrafluorobiphenyl borate and N, N-dimethylanilinium tris (pentafluorophenyl) -4- (4-vinylbenzyl) -2,
3,5,6-tetrafluorobiphenyl borate.

These ionic compounds can be synthesized by various methods.
It can be obtained by treating 3,5,6-tetrafluorophenyltris (pentafluorophenyl) borate with n-butyllithium and then reacting with diethylanilinium chloride. This ionic compound is
Although this can be used as it is as a catalyst component for olefin polymerization, a polymer of this ionic compound may be used as the catalyst component. Further, a copolymer of the ionic compound with a compound having a double bond capable of forming a copolymer, or a polymer obtained by crosslinking the copolymer with a crosslinking agent may be used as the catalyst component. Good.

As described above, compounds having a double bond capable of forming a copolymer with the ionic compound include, for example, α-olefins such as ethylene, propylene, 1-butene, 1-pentene and 1-hexene. , Styrene, α
-Methylstyrene, pt-butylstyrene, p-chlorostyrene, m-chlorostyrene, halogenated styrenes such as o-chlorostyrene, acrylates such as divinylbenzene, methyl methacrylate and methacrylate, acrylonitrile, butadiene, 5-hexadiene and vinyl acetate. Among these, divinylbenzene and styrene are particularly preferred.

Next, among the catalyst components of the present invention, (a)
The transition metal compound is not limited to the transition metal compound that gives isotactic polypropylene, but specifically, rac-ethylenebis (indenyl) zirconium dichloride, rac-ethylenebis (indenyl) hafnium dichloride, rac -Dimethylsilylenebis (indenyl) zirconium dichloride, rac-dimethylsilylenebis (indenyl) hafnium dichloride, rac-ethylenebis (tetrahydroindenyl) zirconium dichloride, rac-ethylenebis (tetrahydroindenyl) hafnium dichloride, rac-dimethylsilylenebis (Tetrahydroindenyl) zirconium dichloride, rac-dimethylsilylenebis (tetrahydroindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4,5-benzoin Nil) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,5-benzoindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-phenylindenyl)
Hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4,7-dimethylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,7
-Dimethylindenyl) hafnium dichloride, rac-
Dimethylsilylenebis (2-methyl-4,5,6,7-tetramethylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,5,6,7-tetramethylindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-5,6-dimethylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-5,6-dimethylindenyl) hafnium dichloride,
rac-dimethylsilylenebis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4- (1-naphthyl) indenyl) hafnium dichloride, rac-dimethylsilylenebis ( 2-methyl-4- (2-naphthyl) indenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4- (2-naphthyl) indenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4- i-propylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-i-propylindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-ethyl-4-phenylindenyl) zirconium dichloride, rac -Dimethylsilylenebis (2-ethyl-4-phenylindenyl) hafnium dichloride, rac-dimethylsi Rylene bis (2-methyl-4-toluylindenyl)
Zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-toluylindenyl) hafnium dichloride, rac-ethylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, rac-ethylenebis (2-methyl -4,5-benzoindenyl) hafnium dichloride, rac-ethylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-ethylenebis (2-methyl-4-phenylindenyl) hafnium dichloride, rac- Ethylenebis (2-methyl-4,7-dimethylindenyl) zirconium dichloride, rac-ethylenebis (2-methyl-4,7-dimethylindenyl) hafnium dichloride, rac-ethylenebis (2-methyl-4,5 , 6,7-tetramethylindenyl) zirconium dichloride, rac
-Ethylenebis (2-methyl-4,5,6,7-tetramethylindenyl) hafnium dichloride, rac-ethylenebis (2-methyl-5,6-dimethylindenyl) zirconium dichloride, rac-ethylenebis (2 -Methyl-5,6-dimethylindenyl) hafnium dichloride, rac-ethylenebis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride, rac-ethylenebis (2-methyl-4-
(1-naphthyl) indenyl) hafnium dichloride, r
ac-ethylenebis (2-methyl-4- (2-naphthyl) indenyl) zirconium dichloride, rac-ethylenebis (2-methyl-4- (2-naphthyl) indenyl) hafnium dichloride, rac-ethylenebis (2-methyl) -4-i-propylindenyl) zirconium dichloride, rac-ethylenebis (2-methyl-4-i-propylindenyl) hafnium dichloride, rac-ethylenebis (2-ethyl-4-phenylindenyl) zirconium dichloride, rac-ethylenebis (2-ethyl-4-phenylindenyl) hafnium dichloride, rac-ethylenebis (2-methyl-4-toluylindenyl) zirconium dichloride, rac-ethylenebis (2-methyl-4-toluylindenyl) ) Hafnium dichloride, 1,2-ethanediyl (1- (4,7-diisopropylindenyl)) (2- (4,7-diisopropylindenyl))
Hafnium dichloride, 1,2-ethanediyl (1- (4,7-diisopropylindenyl)) (2- (4,7-diisopropylindenyl)) zirconium dichloride, 1,2-ethanediyl (9
-Fluorenyl) (2- (4,7-diisopropylindenyl))
Hafnium dichloride, 1,2-ethanediyl (9-fluorenyl) (2- (4,7-diisopropylindenyl)) zirconium dichloride, isopropylidene (1- (4,7-diisopropylindenyl)) (2- (4, 7-diisopropylindenyl)) hafnium dichloride, isopropylidene (1- (4,7-
(Diisopropylindenyl)) (2- (4,7-diisopropylindenyl)) zirconium dichloride, 1,2-ethanediyl (1- (4,7-dimethylindenyl)) (2- (4,7-diisopropylindenyl) )) Hafnium dichloride, 1,2-ethanediyl (1- (4,7-dimethylindenyl)) (2- (4,7-diisopropylindenyl)) zirconium dichloride, 1,2-ethanediyl (9-fluorenyl) ( 2- (4,7-dimethylindenyl)) hafnium dichloride, 1,2-ethanediyl (9-fluorenyl) (2- (4,7-dimethylindenyl)) zirconium dichloride, isopropylidene (1- (4,7 -Dimethylindenyl)) (2- (4,7-diisopropylindenyl)) hafnium dichloride, isopropylidene (1- (4,7-dimethylindenyl)) (2- (4,7-diisopropylindenyl)) Zirconium dichloride, bis (1,2-ethylene) bis (1,
2-indenyl) zirconium dichloride, bis (1,2-ethylene) bis (1,2-indenyl) hafnium dichloride, bis (1,2-ethylene) bis (1,2- (3-methylindenyl)) zirconium dichloride , Bis (1,2-ethylene) bis (1,2- (3-methylindenyl)) hafnium dichloride, bis (1,2- (4,7-dimethylindenyl)) zirconium dichloride, bis (1,2 -Ethylene) bis (1,
2- (4,7-dimethylindenyl)) hafnium dichlorideisopropylidene (4-methyl-cyclopentadienyl)
(3-t-butylindenyl) zirconium dichloride, isopropylidene (4-methyl-cyclopentadienyl)
(3-t-butylindenyl) hafnium dichloride, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) hafnium dichloride, Dimethylsilylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilylenebis (3-t-butylcyclopentadienyl) zirconium dichloride ,
Compounds such as dimethylsilylenebis (3-t-butylcyclopentadienyl) hafnium dichloride, dimethylsilylenebis (3-methylcyclopentadienyl) zirconium dichloride, and dimethylsilylenebis (3-methylcyclopentadienyl) hafnium dichloride It is mentioned as a suitable thing.

The organoaluminum compound (b) as the catalyst component of the present invention includes trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride , Dimethylaluminum fluoride, diethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, diethylaluminum sesquichloride and the like. Further, various alumoxanes such as methylalumoxane, isobutylalumoxane, and ethylalumoxane can be used. The alumoxane may have a chain structure or a cyclic structure,
Those having a degree of polymerization of 3 to 50, preferably 7 to 40 are used.

Of these various organoaluminum compounds, those having an alkyl group having 3 or more carbon atoms, an alkylaluminum compound having at least one branched alkyl group or an alumoxane having a polymerization degree of 7 or more are particularly preferably used. Can be These organoaluminum compounds may be used alone or in combination of two or more.

Next, in the olefin polymerization catalyst of the present invention, the mixing ratio of the component (a) and the component (b) is as follows:
The organoaluminum compound of the component (b) is generally added to the transition metal compound of the component (a) in an amount of 1 to 2 mol per mol.
000 mol, preferably 5 to 1000 mol, particularly preferably 10 to 500 mol. If the compounding ratio of the component (b) is less than 1 mol with respect to the component (a), the effect of improving the polymerization activity is not sufficient, and even if the compounding amount exceeds 2,000 mol, no further effect can be expected. .

The compounding ratio of the ionic compound of the component (c) is 0.1 to 20 mol per 1 mol of the component (a).
Preferably it is 1 to 5 mol. Next, the polymerization method of the olefin of the present invention, there is no restriction on the polymerization method, employ any method of slurry polymerization method, gas phase polymerization method, bulk polymerization method, solution polymerization method, suspension polymerization method. Is also good. The olefin used for polymerization or the unsaturated compound used for copolymerization is not particularly limited, but has 2 to 2 carbon atoms.
Twenty α-olefins are preferably used.

Such olefins include, for example,
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, styrene, p-methylstyrene,
p-chlorostyrene, pt-butylstyrene, p-phenylstyrene, p-methylsilylstyrene, p-trimethylsilylstyrene and the like. These are 1
Species may be used alone or in combination of two or more.

Further, unsaturated compounds suitable for forming a copolymer with these olefins and styrenes include, for example, chain diolefins such as butadiene, isoprene, 1,5-hexadiene, norbornene and octaene. Cyclic olefins such as hydronaphthalene, cyclic diolefins such as norbornadiene and ethylidene norbornene, unsaturated esters such as ethyl acrylate and methyl methacrylate, lactones such as β-propiolactone, β-butyrolactone and γ-butyrolactone Can be used.

The olefin polymerization conditions in the present invention are such that the polymerization temperature is usually -100 to 250 ° C, preferably -50 to 200 ° C, particularly preferably 0 to 130 ° C. The use ratio of the catalyst to the reaction raw material is such that the molar ratio of the raw material monomer / the component (a) or the raw material monomer / the component (b) is 1 to 10 ⁸ , preferably 100 to 10 ⁵ . And the polymerization time is from 5 minutes to
10 hours, reaction pressure is from normal pressure to 100 kg / c
m ² , preferably normal pressure to 30 kg / cm ² .

Further, at the time of polymerization of the olefin in the present invention, preliminary polymerization can be carried out 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 from 1 to 10,000.
It is preferable to adjust the conditions so as to be 0 g, preferably 10 to 1,000 g.

When the catalyst of the present invention is supported on a carrier, it is preferable that the catalyst is supported on a polymer. Such a carrier polymer has a particle size of 1 to 300 μm.
m, preferably 10 to 200 μm, more preferably 20
１００100 μm. When the particle size is smaller than 1 μm, fine particles in the polymer increase, and when the particle size exceeds 300 μm, coarse particles in the polymer increase, resulting in a decrease in bulk density and clogging of the hopper in the production process. Becomes In this case, the specific surface area of the support is 1 to 1,000 m ² / g, preferably 50 to 500 m ² / g, and the pore volume is 0.1 to 5 m ² / g.
³ / g, preferably 0.3 to ³ m3 / g.

[0026]

The present invention will be described in more detail with reference to the following examples. Example 1 2.0 g (8.8 mmol) of 1-bromo-2,3,5,6-tetrafluorobenzene and 50 ml of dehydrated diethyl ether were added to 300 ml of Schlenk under a nitrogen stream. Then, 6.0 ml of a hexane solution of n-butyllithium (1.47 molar concentration) was slowly added thereto at -78 ° C. One hour later, into Schlenk, a solution in which 4.5 g (8.8 mmol) of tris (pentafluorophenyl) borane was dissolved in 150 mmol of hexane was slowly added. Thereafter, the temperature was raised to room temperature and stirred for 2 hours.
After completion of the reaction, the solution was filtered off using a cannula, and the residue was washed twice with 100 ml of dehydrated hexane to give lithium-2,3,5,6-tetrafluorophenyltris (pentafluorophenyl) borate 5 .8
g (yield 99%).

Next, 0.1 ml of p-chloromethylstyrene was added to 100 ml of Schlenk under a nitrogen stream.
4 g (0.75 mmol) and 5 ml of dehydrated tetrahydrofuran were charged. Separately, in a 100 ml Schlenk, under a nitrogen stream, lithium-2,
0.50 g (0.75 mmol) of 3,5,6-tetrafluorophenyltris (pentafluorophenyl) borate and 15 ml of dehydrated tetrahydrofuran were added, and a hexane solution of n-butyllithium (1.55 mol concentration) was added. .48 ml at -78 ° C
Was added slowly, and the solution obtained by stirring for 1 hour was poured into the above p-chloromethylstyrene solution at -78 ° C using a cannula. After 1.5 hours, the reaction vessel was returned to room temperature, and the solvent was distilled off under reduced pressure.

The residue obtained contains 10 parts of dehydrated methylene chloride.
Milliliter and dimethylanilinium chloride
118 g (0.75 mmol) was added, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off, and the residue was washed twice with 20 ml of degassed water and once with 50 ml of dehydrated hexane, and the obtained solid was dried at room temperature under reduced pressure to obtain 0.1% of the product. 65 g (96% yield) were obtained.

The product obtained here is the result of elemental analysis,
To the absorption peak based on the aromatic ring of 7.7 to 7.1 ppm observed in the molecular weight measurement result and ¹ H-NMR analysis, the absorption peak based on the vinyl group of 5.9 to 5.1 ppm, and the methylene group of 4.5 ppm Absorption peak based on
From an absorption peak based on a methyl group at 3.1 ppm, N, N-dimethylanilinium tris (pentafluorophenyl)-represented by the following (Me in the formula represents a methyl group):
4- (4-vinylbenzyl) -2,3,5,6-tetrafluorophenyl borate.

[0030]

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Example 2 A 20 ml three-necked flask equipped with a magnetic stirrer was placed under a nitrogen stream.
5 ml of toluene, 0.025 g of azobisisobutyronitrile, 0.234 g (2.25 mmol) of styrene, N, N-dimethylanilinium tris (pentafluorophenyl) -4- (4-vinylbenzyl)-
0.65 g (0.72 mmol) of 2,3,5,6-tetrafluorobiphenyl borate and 0.03 ml of a toluene solution of divinylbenzene (concentration: 70% by weight) were charged. Then, the reaction was carried out under a nitrogen atmosphere at 80 ° C. for 2 hours with stirring. After the completion of the reaction, the reaction product was washed three times with 10 ml of toluene. The residue was dried at 80 ° C. under reduced pressure, crushed in a glove box using a mortar, and powdered product 0.6.
g was obtained. The product obtained here is styrene, N,
N-dimethylanilinium tris (pentafluorophenyl) -4- (4-vinylbenzyl) -2,3,5,6
-Copolymerized crosslinked product with tetrafluorophenylborate.

Example 3 A pressure-resistant autoclave made of styrene with a stirrer having a capacity of 1.4 liters was heated to 55 ° C.
After drying under reduced pressure sufficiently, the pressure was returned to the atmospheric pressure with dry nitrogen and cooled to room temperature. Then, 400 ml of dry deoxygenated toluene and 1.0 ml of a toluene solution of triisobutylaluminum (1.0 molar concentration) were added thereto under a stream of dry nitrogen.

Next, this was stirred for 15 minutes, and then cross-linked poly [styrene-co-N, N-dimethylanilinium tris (pentafluorophenyl) -4- (4-vinylbenzyl) -2,3,5 , 6-tetrafluorophenylborate-methylstyrene] in 0.4 mL of a heptane suspension (converted to borane: 10 mmol / L) and rac-dimethylsilylenebis (2-methyl-
4,5-Henzoindenyl) zirconium dichloride in toluene solution (concentration; 10 mmol / L) 0.1
Milliliters were charged into the autoclave.

Then, the solution was stirred at 500 rpm, propylene was continuously supplied thereto at a gauge pressure of 7.0 kg / cm ² , the temperature was raised to 60 ° C., and polymerization was carried out for 10 minutes. After the reaction, unreacted propylene was removed by depressurization. The reaction mixture was poured into a large amount of methanol to precipitate polypropylene, followed by filtration and drying to obtain 69 g of polypropylene. The catalytic activity in this case is
It was 3,800 kg / g-zirconium. There were no deposits inside the autoclave. Table 1 shows the evaluation results on the properties of the obtained polypropylene.

[Comparative Example 1] 27.1 g of SiO ₂ (manufactured by Fuji Silysia; P-10) was charged at 200 ° C for 2.0 hours.
It was dried under reduced pressure to obtain 25.9 g of dried silica. The dried silica was put into 400 ml of toluene cooled to -78 with a dry ice / methanol bath and stirred. Then, 145.5 ml of a methylaluminoxane / toluene solution (concentration: 1.5 mol / l) was added dropwise to the stirred suspension in 1 hour. After leaving for 4 hours in this state, the temperature is changed from -78 ° C to 20 ° C.
Until 6 hours, and then left in this state for 4 hours. Thereafter, the temperature was raised from 20 ° C. to 80 ° C. in one hour, and 8
It was left at 0 ° C. for 4 hours to complete the reaction between silica and methylaluminoxane.

The suspension obtained by filtering the suspension at 60 ° C. was washed twice with 400 ml of toluene at 60 ° C.
Washing was performed twice with 400 ml of n-hexane at 60 ° C. The washed solid was dried under reduced pressure at 60 ° C. for 4 hours to obtain 33.69 g of silica-supported methylaluminoxane. The loading ratio of methylaluminoxane was 23.12% by weight. N-Heptane was added to the total amount of the obtained silica-supported methylaluminoxane to make the total volume 500 ml, thereby obtaining a suspension having a methylaluminoxane concentration of 0.27 mol / liter.

Next, 7.41 milliliters (2.0 millimoles) of the above-obtained silica-supported methylaluminoxane was collected in a dry nitrogen purged vessel, and 20 milliliters of n-heptane was added and stirred. To this suspension was added a solution of rac-dimethylsilylenebis (2-methyl-4,5-henzoindenyl) zirconium dichloride in toluene. 0
Micromolar was added and stirring continued at room temperature for 0.5 hour. Thereafter, the stirring was stopped to settle the solid catalyst component,
It was confirmed that the precipitated solid catalyst component was red and the solution was colorless and transparent. The obtained solid catalyst component was used as a silica-supported metallocene catalyst in the next step.

Then, a pressure-resistant autoclave made of styrene with a stirrer having a capacity of 1.4 liters was heated to 55 ° C., dried sufficiently under reduced pressure, returned to atmospheric pressure with dry nitrogen, and cooled to room temperature. Next, 400 ml of dry deoxygenated heptane and 1 ml of a heptane solution of triisobutylaluminum (1.0 molar concentration) were added thereto under a stream of dry nitrogen. After stirring this solution for 15 minutes, the above-mentioned silica-supported metallocene catalyst was charged. After that, 500r
Stirring was started at pm, and propylene was added thereto at a gauge pressure of 7.
0 kg / cm ² continuously, and heated to 60 ° C.
Time polymerization was carried out. After the reaction, unreacted propylene was removed by depressurization. The reaction mixture was poured into a large amount of methanol to precipitate polypropylene, followed by filtration and drying to obtain 25.3 g of polypropylene. The catalytic activity in this case was 46 kg / g-zirconium. The evaluation results on the properties of the obtained polypropylene
It is shown in the table.

Comparative Example 2 A pressure-resistant autoclave made of styrene with a stirrer having a capacity of 1.4 liters was heated to 55 ° C., sufficiently dried under reduced pressure, returned to atmospheric pressure with dry nitrogen, and cooled to room temperature. Then, under a dry nitrogen stream,
400 ml of dry deoxygenated heptane and 0.9 ml of a heptane solution of triisobutylaluminum (1.0 molar concentration) were charged.

Then, the mixture was stirred for 15 minutes, and then 10 ml of heptane and 0.1 ml of a heptane solution of triisobutylaluminum (0.9 molar concentration) were prepared according to the examples described in JP-A-8-143617. 0.4 ml of a prepared heptane suspension (10 mmol / l in terms of borane) of the prepared poly (trimethylammonium tris (pentafluorophenyl) -4-vinylborate-co-styrene) (10:90 mol%), And 0.1 ml of a toluene solution of rac-dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride (10 mmol / l) was stirred in a 20 ml Schlenk for 10 minutes under a nitrogen atmosphere. The suspension was charged into the autoclave. Thereafter, stirring was started at 500 rpm, propylene was continuously supplied at a gauge pressure of 7.0 kg / cm ² , and the temperature was raised to 60 ° C. to perform polymerization for 2 hours.

After completion of the reaction, unreacted propylene was removed by depressurization. The reaction mixture was poured into a large amount of methanol to precipitate polypropylene, followed by filtration and drying to obtain 3.1 g of polypropylene. The catalytic activity in this case is
67 kg / g-zirconium. Table 1 shows the evaluation results of the properties of the obtained polypropylene.

[0042]

[Table 1]

Claims (4)

[Claims] 1. Ionization represented by the following general formula [1]
Compound. Embedded image[In the formula [1], R¹~ R^Three Are each independently a hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms and a halogen having 1 to 20 carbon atoms
A hydrogenated hydrocarbon group or a silicon-containing group;^Four~ R ⁸Is
Each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms
Or a halogenated hydrocarbon group having 1 to 20 carbon atoms,
X and Y are each independently an alkylene having 1 to 20 carbon atoms
Group, arylene group, phenylene group, silylene group, germ
Len group, -O-, -CO-, -S-, -SO_Two-, -N
R⁹-(However, R⁹Is a hydrogen atom, an atom having 1 to 20 carbon atoms.
Alkyl group or an aryl group having 6 to 12 carbon atoms)
And one of X and Y is an arylene group
I and j are 0 or 1 and X is aryl
I is 1 in the case of an arylene group, and i is an arylene group
Represents j and 1 represents an onium compound.] 2. An olefin polymerization catalyst comprising (a) a transition metal compound, (b) an organoaluminum compound, and (c) the ionic compound according to claim 1. 3. A polymer of (a) a transition metal compound, (b) an organoaluminum compound, and (c) a polymer of the ionic compound of claim 1, or a double bond with the ionic compound of claim 1 An olefin polymerization catalyst comprising a copolymer with a compound having the same. 4. A process for producing an olefin polymer, comprising polymerizing or copolymerizing olefins using the catalyst for olefin polymerization according to claim 2 or 3.