JPH10204114A - Catalyst for producing olefin polymer and method for producing olefin polymer - Google Patents

Abstract

(57) [Problem] To provide a polymer having good morphology with high polymerization activity. SOLUTION: A polyolefin is produced using an olefin polymerization catalyst comprising a modified clay, a transition metal compound and an organoaluminum compound, in which a clay mineral is treated with an organic compound and the pore volume is less than 0.1 ml / g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for producing an olefin polymer comprising a modified clay, a transition metal compound and an organoaluminum compound, and a method for producing an olefin polymer using the same.

[0002]

2. Description of the Related Art As a method for producing a polyolefin by polymerization of an olefin, the use of a catalyst system comprising a combination of a transition metal compound and an organometallic compound is already known. Kaminski et al. Disclose in JP-A-58-19309 and the like that a catalyst using metallocene and methylaluminoxane exhibits high activity in producing an olefin polymer containing propylene.

However, the catalyst system disclosed herein has excellent polymerization activity, but since the catalyst system is soluble in the reaction system, a solution polymerization system is often employed, and the production process is limited. Alternatively, in order to produce a polymer exhibiting industrially useful physical properties, it is necessary to use a relatively expensive methylaluminoxane in a large amount. Therefore, when these catalyst systems are used, there are problems such as cost and a problem that a large amount of aluminum remains in the polymer.

On the other hand, a catalyst system in which the above-mentioned soluble catalyst system is supported on an inorganic oxide carrier such as silica is disclosed in
No. 5006 discloses this. However, even when olefins were polymerized according to the methods described therein, the polymerization activity per methylaluminoxane was not sufficient.

[0005] As a method for improving these, for example, JP-A-4-8704, JP-A-4-11604 and JP-A-4-213305 disclose a catalyst system preliminarily polymerized with a small amount of methylaluminoxane. It is disclosed that a polymer having excellent polymerization activity and good particle properties can be obtained by performing gas phase polymerization using the polymer. However, although the amount of methylaluminoxane used is small, the polymerization activity is still not satisfactory, and high activation of the catalyst system has been desired.

[0006] JP-A-1-503788 describes a method for producing an ethylene / α-olefin copolymer by a high-pressure high-temperature method using a transition metal compound and methylaluminoxane as catalysts. However, regarding the use of these catalysts on a large industrial scale, it is difficult to synthesize methylaluminoxane in a reproducible form as described above, and despite the fact that methylaluminoxane is expensive, As a problem, in order to obtain sufficient activity, the ratio of methylaluminoxane to the transition metal compound must be significantly increased.

Recently, new cocatalysts which do not use an organoaluminum oxy compound such as methylaluminoxane have been studied. For example, Japanese Patent Application Laid-Open Nos. 1-501950 and 1-5020236 disclose a special co-catalyst. It is disclosed that boron compounds are effective cocatalysts. However, these boron compounds are very complicated compounds and have not solved the problem of cost.

A catalyst system comprising a metallocene, an organoaluminum compound and clay, a clay mineral or an ion-exchange layered compound is disclosed in, for example, JP-A-5-3019.
17 publications. However, with these catalysts, in order to sufficiently increase the polymerization activity per clay, clay mineral, or ion-exchange layered compound, a catalyst having a large pore volume must be used, or a pretreatment for increasing the pore volume must be performed. I had to give it.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and is an inexpensive olefin excellent in polymerization activity and polymerization behavior without using an expensive cocatalyst in olefin polymerization. It is intended to provide a catalyst for producing a polymer. Still another object of the present invention is to provide a catalyst for obtaining a polymer having a good morphology with high polymerization activity while suppressing adhesion of the polymer to a reactor wall in slurry polymerization.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, modified clay (a) obtained by treating a clay mineral with an organic compound, transition metal compound (b) and organic When the modified clay having a pore volume of less than 0.1 ml / g is used as the catalyst for producing an olefin polymer comprising the aluminum compound (c), excellent polymerization activity and polymerization behavior can be obtained. The present inventors have found that a polyolefin having an excellent polymer shape can be produced, and have completed the present invention.

That is, the present invention comprises a modified clay (a) obtained by treating a clay mineral with an organic compound and having a pore volume of less than 0.1 ml / g, a transition metal compound (b) and an organoaluminum compound (c). And a catalyst for producing an olefin polymer. The present invention also relates to a method for producing an olefin polymer using the catalyst or the catalyst and the organoaluminum compound (d). Hereinafter, the present invention will be described in detail.

The clay mineral used for preparing the modified clay (a) of the present invention is a fine particle mainly composed of microcrystalline silicate. Most of the clay minerals have a layered structure as a structural feature, and include various sizes of negative charges in the layer. In this respect, it is significantly different from metal oxides having a three-dimensional structure such as silica and alumina. These clay minerals generally have a layer charge magnitude of pyrophyllite, kaolinite, dickite and talc (negative charge per chemical formula is about 0), smectite group (negative charge is 0.25 to 0.6). , A vermiculite group (having a negative charge of 0.6 to 0.9), a mica group (about 1), and a brittle mica group (about 2). Each group shown here includes various minerals, and examples of clay minerals belonging to smectite include montmorillonite, beidellite, saponite, hectorite, and the like. Also, although these clay minerals exist naturally,
The one with less impurities can be obtained by artificial synthesis. In the present invention, if a modified clay having a pore volume of less than 0.1 ml / g treated with an organic compound can be obtained, all of the natural clay minerals shown here and the clay minerals obtained by artificial synthesis can be used. Can be used, and all those belonging to the definition of clay minerals can be used even if they are not exemplified above. The modified clay used in the present invention has a pore volume of less than 0.1 ml / g, and if it has a pore volume of less than 0.09 ml / g, it is preferable in that high activity can be maintained. Further, it is used for slurry polymerization. And a polymer having an excellent particle shape can be produced.

The organic compound used for preparing the modified clay (a) of the present invention can be represented by the following general formula (29) [C] ⁺ [A] ^- (29). However, in the formula, [C] ⁺ is a cation, and an organic cation or an organometallic cation which is a cation containing at least one carbon atom as a constituent component is exemplified.

Among the organic cations, those containing active protons include onium compounds in which a proton is coordinated to a lone pair of an element represented by the following general formula (30).

[R ¹⁹ _s Z ² H] ⁺ (30) wherein Z ² is an element selected from Group 15 or 16 of the periodic table, and specifically, Z ² is a nitrogen atom An ammonium compound, a phosphonium compound as a phosphorus atom, an oxonium compound as an oxygen atom or a sulfonium compound as a sulfur atom. R ¹⁹ may be the same or different and is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Specific hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl,
C1-C20 alkyl groups such as heptyl, octyl, nonyl, decyl, dodecyl, isopropyl, isobutyl, s-butyl, t-butyl and cyclohexyl; C1-2 such as vinyl, propenyl and cyclohexenyl
0 alkenyl group; C6-C20 such as phenyl, methylphenyl, ethylphenyl, biphenyl and naphthyl
And arylalkyl groups having 7 to 20 carbon atoms such as benzyl and phenylethyl. At least one R ¹⁹ is a hydrocarbon group having 1 to 20 carbon atoms, and each R ¹⁹ may be bonded to each other. S = 3 when Z ² belongs to Group 15, and s when Z ² belongs to Group 16.
= 2. Among the organic cation, does not contain an active proton, which does not have a ring structure of the general formula _{^{(31) [R 20 3 Z}} 3] + (31) [ wherein, Z ³ is the group 14 of the periodic table R ²⁰ is a hydrocarbon group having 1 to ²⁰ carbon atoms. ]. When Z ³ is carbon (carbonium cation), specific examples thereof include an ethane cation and a triphenylcarbenium cation.

Examples of the cation having no active proton and having a ring structure include aromatic cations such as benzenium cation and tropylium cation.

Specific examples of the organic metal cation include a ferrocenium cation.

Meanwhile, [A] ^- is a counter anion, as fluorine ion, chlorine ion, a bromine ion, an inorganic anion of halide ion or sulfate ion such as iodide ion is exemplified, which is limited to is not.

Among the above organic compounds, those in which [C] ⁺ has an active proton, Z ² is a nitrogen element, and [A] ⁻ is a chloride ion, specifically, methylamine hydrochloride, ethylamine hydrochloride, Hydrochloric acid of aliphatic primary amines such as propylamine hydrochloride, isopropylamine hydrochloride, butylamine hydrochloride, hexylamine hydrochloride, decylamine hydrochloride, dodecylamine hydrochloride, allylamine hydrochloride, cyclopentylamine hydrochloride, cyclohexylamine hydrochloride Salts; hydrochlorides of aliphatic secondary amines such as dimethylamine hydrochloride, diethylamine hydrochloride, diamylamine hydrochloride, didecylamine hydrochloride, diallylamine hydrochloride; trimethylamine hydrochloride, tributylamine hydrochloride, triamylamine hydrochloride, triallylamine Hydrochloride, N, N-dimethyldecylamine hydrochloride Salts, hydrochlorides of aliphatic tertiary amines such as N, N-dimethylundecylamine hydrochloride; aniline hydrochloride, N-methylaniline hydrochloride, N, N-dimethylaniline hydrochloride, N-ethylaniline hydrochloride, N, N-
Diethylaniline hydrochloride, N-allylaniline hydrochloride,
o-toluidine hydrochloride, m-toluidine hydrochloride, p-toluidine hydrochloride, N-methyl-o-toluidine hydrochloride,
N-methyl-m-toluidine hydrochloride, N-methyl-p-
Toluidine hydrochloride, N, N-dimethyl-o-toluidine hydrochloride, N, N-dimethyl-m-toluidine hydrochloride,
N, N-dimethyl-p-toluidine hydrochloride, benzylamine hydrochloride, dibenzylamine hydrochloride, tribenzylamine hydrochloride, N-benzyl-N-ethylaniline hydrochloride, diphenylamine hydrochloride, α-naphthylamine hydrochloride, β-naphthylamine hydrochloride, N, N-dimethyl-α
-Naphthylamine hydrochloride, N, N-dimethyl-β-naphthylamine hydrochloride, o-anisidine hydrochloride, m-anisidine hydrochloride, p-anisidine hydrochloride, N, N-2,6-
Tetramethylaniline hydrochloride, N, N-3,5-tetramethylaniline hydrochloride, N, N-2,4,6-pentamethylaniline hydrochloride, 2,3,4,5,6-pentafluoroaniline hydrochloride Hydrochloride of an aromatic amine such as a salt, or hydrofluoride of an amine compound in which [A] ⁻ of the above ammonium compound is represented by fluorine ion, bromide ion, iodine ion or sulfate ion instead of chloride ion,
Examples include, but are not limited to, hydrobromide, hydroiodide or sulfate. Z ² is a phosphorus element and [A] ⁻ is a bromide ion, specifically, triphenylphosphine hydrobromide, tri (o-
Examples thereof include phosphonium compounds such as tolyl) phosphine hydrobromide, tri (p-tolyl) phosphine hydrobromide, and tri (mesityl) phosphine hydrobromide, but are not limited thereto. With respect to those in which Z ² is an oxygen element and [A] ⁻ is a chlorine ion, specific examples thereof include oxonium compounds such as hydrochloride of methyl ether, hydrochloride of ethyl ether, and hydrochloride of phenyl ether. It is not limited. In addition, a sulfonium compound in which Z ² is represented by a sulfur element is exemplified.

Of the above organic compounds, those in which [C] ⁺ does not contain an active proton include, but are not limited to, bromotriphenylmethane, chlorotriphenylmethane, tropylium bromide and the like. Not something.

Examples of the organometallic compound include, but are not limited to, ferrocenium sulfate, ferrocenium hexafluorophosphate, ferrocenium tetraphenylborate, and the like.

As the transition metal compound (b), the following general formula (1) or (2)

[0023]

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[0024]

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Wherein M ¹ is a titanium atom, a zirconium atom or a hafnium atom, and Y is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
Or an aryl group, an arylalkyl group or an alkylaryl group having 6 to 20 carbon atoms, wherein R ¹ and R ² are each independently the following general formulas (3), (4), (5) or
(6)

[0026]

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(Wherein, R ⁶ is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, an arylalkyl group or an alkylaryl group having 6 to 20 carbon atoms). And the ligand is M
The sandwich structure was formed with ^1, R ^3, R ⁴ are each independently represented by the following general formula (7), (8), (9) or (1
0)

[0028]

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(Wherein, R ⁷ is each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, arylalkyl group or alkylaryl group having 6 to 20 carbon atoms). And the ligand is M
Forming a sandwich structure with R ^1, and R ⁵ is represented by the following general formula (11) or (12):

[0030]

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Wherein R ⁸ is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, an arylalkyl group or an alkylaryl group having 6 to 20 carbon atoms, and M ² is Atom, germanium atom or tin atom), and acts so as to bridge R ³ and R ⁴ , and m is an integer of 1 to 5. Or a transition metal compound of Group 4 of the periodic table represented by the following general formula (13), (14), (15) or (16):

[0032]

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[Wherein, M ³ is each independently a titanium atom,
A zirconium atom or a hafnium atom, and Z ^{1 s} are each independently a hydrogen atom, a halogen atom,
Or an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group,
L ¹ is a Lewis base; q is 0-3;
R ⁹ _p-1 and JR ⁹ _p-2 are heteroatom ligands, and J is a group 15 element of the periodic table having a coordination number of 3 or a group 16 element of the periodic table having a coordination number of 2; R ⁹ is each independently a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, or an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an alkyl group having 6 to 20 carbon atoms. An aryl group or an alkylaryloxy group, p is the coordination number of the element J, and R
¹⁰ is the following general formula (17), (18), (19) or (20)

[0034]

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(Wherein, R ¹³ is each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, an arylalkyl group or an alkylaryl group having 6 to 20 carbon atoms). R ¹² is a ligand represented by the following general formula (21), (22), (23) or (24)

[0036]

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(In the formula, R ¹⁴ is each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, an arylalkyl group or an alkylaryl group having 6 to 20 carbon atoms.) R ¹¹ is represented by the following general formula (25) or (26)

[0038]

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Wherein R ¹⁵ is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, an arylalkyl group or an alkylaryl group having 6 to 20 carbon atoms, and M ⁴ is Atom, a germanium atom or a tin atom), which acts to bridge R ¹² and JR ⁹ _p-2 , and r is an integer of 1 to 5. ]
Is preferably a transition metal compound of Group 4 of the periodic table represented by

Examples of the compound represented by the general formula (1) or (2) include bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride, and bis (cyclopentadienyl) Hafnium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) hafnium dichloride, bis (butylcyclopentadienyl) titanium dichloride, bis (butyl) Cyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) hafnium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (pentamethyl Cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) hafnium dichloride, bis (indenyl) titanium dichloride, bis (indenyl) zirconium dichloride, bis (indenyl) hafnium dichloride, methylenebis (cyclopentadienyl)
Titanium dichloride, methylenebis (cyclopentadienyl) zirconium dichloride, methylenebis (cyclopentadienyl) hafnium dichloride, methylenebis (methylcyclopentadienyl) titanium dichloride, methylenebis (methylcyclopentadienyl) zirconium dichloride, methylenebis (methylcyclopenta Dienyl) hafnium dichloride, methylenebis (butylcyclopentadienyl) titanium dichloride, methylenebis (butylcyclopentadienyl) zirconium dichloride, methylenebis (butylcyclopentadienyl) hafnium dichloride, methylenebis (tetramethylcyclopentadienyl) titanium dichloride , Methylenebis (tetramethylcyclopentadienyl) Ruconium dichloride, methylenebis (tetramethylcyclopentadienyl) hafnium dichloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) hafnium dichloride, ethylenebis (tetrahydroindenyl) titanium dichloride, Ethylenebis (tetrahydroindenyl) zirconium dichloride, ethylenebis (tetrahydroindenyl) hafnium dichloride, ethylenebis (2-methyl-1-indenyl) titanium dichloride, ethylenebis (2-methyl-1)
-Indenyl) zirconium dichloride, ethylenebis (2-methyl-1-indenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-9-)
Fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-2,7)
-Dimethyl-9-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-2,7)
-Dimethyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,
7-dimethyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-2,
7-di-t-butyl-9-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2, 7-di-t-butyl-9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentane) Dienyl-9-fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadiene) 2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-2,7-dimethyl -9
-Fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl-2,7-di-t-butyl-9) -Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-
2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, dimethylsilanediylbis (cyclopentadienyl) titanium dichloride, dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (cyclopentane Dienyl) hafnium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) hafnium dichloride, dimethylsilane Diylbis (butylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (butylcyclopentadienyl) zirconiumdichloride Chloride, dimethylsilanediylbis (butylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) ) Titanium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl)
Titanium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl)
Titanium dichloride, dimethylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilanediylbis (indenyl) titanium dichloride, dimethylsilanediylbis (2
-Methyl-indenyl) titanium dichloride, dimethylsilanediylbis (tetrahydroindenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-)
2,7-dimethyl-9-fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) titanium dichloride, dimethylsilanediylbis (2,7
4,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4-
Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediyl Bis (tetramethylcyclopentadienyl)
Zirconium dichloride, dimethylsilanediylbis (indenyl) zirconium dichloride, dimethylsilanediylbis (2-methylindenyl) zirconium dichloride, dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-9- Fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) Zirconium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis ( , 4-dimethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (3-methylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) hafnium dichloride, Dimethylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (indenyl) hafnium dichloride, dimethylsilanediylbis (2-methylindenyl) hafnium dichloride, dimethylsilanediylbis (tetrahydroindenyl) hafnium dichloride , Dimethylsilanediyl (cyclopentadienyl-9)
-Fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl-2,7-di-
t-butyl-9-fluorenyl) hafnium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diethyl Silanediylbis (3-methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (4-t
-Butyl-2-methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride,
Diethylsilanediylbis (indenyl) titanium dichloride, diethylsilanediylbis (2-methylindenyl) titanium dichloride, diethylsilanediylbis (tetrahydroindenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium Dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-)
Di-t-butyl-9-fluorenyl) titanium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride , Diethylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) ) Zirconium dichloride, diethylsilanediylbis (indenyl) zirconium dichloride, diethylsilanediylbis (2-methylindenyl) zirconium dichloride, diethylsilane Ilbis (tetrahydroindenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (Cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (3- Methylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis Tetramethylcyclopentadienyl) hafnium dichloride, diethylsilanediylbis (indenyl) hafnium dichloride, diethylsilanediylbis (2-methylindenyl) hafnium dichloride, diethylsilanediylbis (tetrahydroindenyl) hafnium dichloride, diethylsilanediyl ( Cyclopentadienyl-9
-Fluorenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-di-
t-butyl-9-fluorenyl) hafnium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride,
Diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (3-methylcyclopentadienyl)
Titanium dichloride, diphenylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl)
Titanium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (indenyl)
Titanium dichloride, diphenylsilanediylbis (2-methylindenyl) titanium dichloride, diphenylsilanediylbis (tetrahydroindenyl)
Titanium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl-) 2,7-di-t-butyl-9-fluorenyl) titanium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadiene) (Enyl) zirconium dichloride, diphenylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (4-t-butyl-2-methylcyclo) Ntajieniru) zirconium dichloride, diphenyl silane diyl bis (tetramethylcyclopentadienyl) zirconium dichloride,
Diphenylsilanediylbis (indenyl) zirconium dichloride, diphenylsilanediylbis (2-methylindenyl) zirconium dichloride, diphenylsilanediylbis (tetrahydroindenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium Dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, Diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (3-methyl (Clopentadienyl) hafnium dichloride, diphenylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis ( Indenyl) hafnium dichloride, diphenylsilanediylbis (2-methylindenyl) hafnium dichloride, diphenylsilanediylbis (tetrahydroindenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) hafnium dichloride,
Diphenylsilanediyl (cyclopentadienyl-2,
Dichlorides such as 7-dimethyl-9-fluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) hafnium dichloride, and the above-mentioned Group 4 transition metal compounds Dimethyl form, diethyl form, dihydro form,
Examples thereof include a diphenyl form and a dibenzyl form.

The above general formulas (13), (14) and (15)
Or the compound represented by (16), for example, pentamethylcyclopentadienyl-di-t-butylphosphinotitanium dichloride, pentamethylcyclopentadienyl-di-t-butylamidotitanium dichloride, pentamethylcyclo Pentadienyl-n-butoxidetitanium dichloride, pentamethylcyclopentadienyl-di-t-butylphosphinozirconium dichloride, pentamethylcyclopentadienyl-di-t-butylamido zirconium dichloride, pentamethylcyclopentadienyl- n-butoxide zirconium dichloride, pentamethylcyclopentadienyl-di-t-butylphosphinohafnium dichloride,
Pentamethylcyclopentadienyl-di-t-butylamidohafnium dichloride, pentamethylcyclopentadienyl-n-butoxide hafnium dichloride,
Dimethylsilanediyltetramethylcyclopentadienyl-t-butylamidotitanium dichloride, dimethylsilanediyl-t-butyl-cyclopentadienyl-
t-butylamidotitanium dichloride, dimethylsilanediyltrimethylsilylcyclopentadienyl-t
-Butylamidotitanium dichloride, dimethylsilanediyltetramethylcyclopentadienylphenylamidotitanium dichloride, methylphenylsilanediyltetramethylcyclopentadienyl-t-butylamidotitanium dichloride, dimethylsilanediyltetramethylcyclopentadienyl-p- n-butylphenylamidotitanium dichloride, dimethylsilanediyltetramethylcyclopentadienyl-p-methoxyphenylamidotitanium dichloride, dimethylsilanediyl-t-butylcyclopentadienyl-2,5-
Di-t-butyl-phenylamidotitanium dichloride, dimethylsilanediylindenyl-t-butylamidotitanium dichloride, dimethylsilanediyltetramethylcyclopentadienylcyclohexylamidotitanium dichloride, dimethylsilanediylfluorenylcyclohexylamidotitanium dichloride, dimethyl Silanediyltetramethylcyclopentadienylcyclododecylamidotitanium dichloride, dimethylsilanediyltetramethylcyclopentadienyl-t
-Butylamidozirconium dichloride, dimethylsilanediyl-t-butyl-cyclopentadienyl-t-
Butylamidozirconium dichloride, dimethylsilyltrimethylsilanediylcyclopentadienyl-t-
Butylamidozirconium dichloride, dimethylsilanediyltetramethylcyclopentadienylphenylamidozirconium dichloride, methylphenylsilanediyltetramethylcyclopentadienyl-t-butylamidozirconium dichloride, dimethylsilanediyltetramethylcyclopentadienyl-pn -Butylphenylamidozirconium dichloride, dimethylsilanediyltetramethylcyclopentadienyl-p-methoxyphenylamidozirconium dichloride, dimethylsilanediyl-t-butylcyclopentadienyl-
2,5-di-t-butyl-phenylamidozirconium dichloride, dimethylsilanediylindenyl-t-
Butylamidozirconium dichloride, dimethylsilanediyltetramethylcyclopentadienylcyclohexylamidozirconium dichloride, dimethylsilanediylfluorenylcyclohexylamidozirconium dichloride, dimethylsilanediyltetramethylcyclopentadienylcyclododecylamidozirconium dichloride, dimethylsilanediyltetramethyl Cyclopentadienyl-t-butylamidohafnium dichloride, dimethylsilanediyl-t-butyl-cyclopentadienyl-t-butylamidohafnium dichloride, dimethylsilanediyltrimethylsilylcyclopentadienyl-t-butylamidohafnium dichloride, dimethylsilane Diyltetramethylcyclopentadienylphenylamide Off pyridinium dichloride, methylphenyl silane diyl tetramethylcyclopentadienyl -t- butyl amide hafnium dichloride, dimethylsilanediyl tetramethylcyclopentadienyl -p
-N-butylphenylamido hafnium dichloride,
Dimethylsilanediyltetramethylcyclopentadienyl-p-methoxyphenylamidohafnium dichloride, dimethylsilanediyl-t-butylcyclopentadienyl-2,5-di-t-butyl-phenylamidohafnium dichloride, dimethylsilanediylindenyl Dichlor such as t-butylamidohafnium dichloride, dimethylsilanediyltetramethylcyclopentadienylcyclohexylamidohafnium dichloride, dimethylsilanediylfluorenylcyclohexylamidohafnium dichloride, dimethylsilanediyltetramethylcyclopentadienylcyclododecylamidohafnium dichloride , Diethyl, dihydro, diphenyl, dibenzyl, dibenzyl, dibenzyl It can be exemplified, and the like.

[0042] Further, as the organoaluminum compound used in the present invention (c) and (d), the following general formula _{^{(27) AlR 16 3 (27}} ) [ wherein, R ¹⁶ are each independently hydrogen atom, a carbon Numbers 1-20
Alkyl group or alkoxy group, or 6 to
20 aryl groups, aryloxy groups, arylalkyl groups, arylalkoxy groups, alkylaryl groups or alkylaryloxy groups. ] Is an organoaluminum compound represented by the formula:

As the compound represented by the general formula (27), for example, trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n
-Propyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, triamyl aluminum, dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum ethoxide, di-n-propyl aluminum ethoxide, diisobutyl aluminum ethoxide, di-
n-butylaluminum ethoxide, dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, di-n
-Propyl aluminum hydride, diisobutyl aluminum hydride, di-n-butyl aluminum hydride and the like.

The catalyst for producing an olefin polymer of the present invention comprises:
The modified clay (a) obtained by treating the above-mentioned clay mineral with an organic compound is used as a constituent. The reaction conditions of the clay mineral and the organic compound at this time are not particularly limited, and the reaction amount of the clay mineral and the organic compound is not limited. There is no particular limitation on the ratio. One of the above-mentioned clay minerals may be used alone, or a plurality of them may be used as a mixture. Even if one kind of the organic compound represented by the general formula (29) is used alone, You may mix and use types. As the reaction solvent used at this time, water and commonly used organic solvents, specifically, ethyl alcohol, methyl alcohol, acetone, benzene, toluene, xylene, pentane, hexane, methylene chloride and the like can be used. When alcohols such as ethyl alcohol and methyl alcohol are used alone or as a component of the solvent, aggregation of particles can be suppressed, and the denaturation reaction can efficiently proceed, which is preferable.

The method or order of contacting the modified clay (a), transition metal compound (b) and organoaluminum compound (c) synthesized above is not particularly limited, but the influence of impurities and the like in the clay mineral is reduced. In order to do so, it is preferable that the modified clay (a) and some or all of the organoaluminum compound (c) are brought into contact in advance. Further, in synthesizing the catalyst of the present invention, the amounts of the modified clay (a), the transition metal compound (b) and the organoaluminum compound (c) used and the ratio of the amounts used are not particularly limited, but the transition metal compound (b) It is preferable to add a sufficient amount of the modified clay to react with the clay.

As the reaction solvent used at this time, an aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, an ether compound, a halogen-containing compound, or the like can be used as a generally used organic solvent. Among them, the use of an aromatic hydrocarbon compound or a halogen-containing compound is particularly preferred because the polymerization activity per catalyst is improved.
Specific examples of the aliphatic hydrocarbon compound include butane, pentane, hexane, heptane, octane, nonane, decane,
Tetradecane, cyclopentane, cyclohexane and the like can be exemplified.Specific examples of the aromatic hydrocarbon compound include benzene, toluene, xylene and the like, and specific examples of the ether compound include diethyl ether, tetrahydrofuran and the like. Examples can be given. Examples of the halogen-containing compound include chloroform, methylene chloride, 1,2-dichloroethane, and chlorobenzene.

The olefin used in the polymerization reaction of the present invention is ethylene, propylene, 1-butene, 4-methyl-1-
Α-olefins such as pentene and 1-hexene; conjugated and non-conjugated dienes such as butadiene and 1,4-hexadiene; and cyclic olefins such as styrene and cyclobutene. Two or more of these components are mixed to polymerize. You can also.

The olefin polymerization of the present invention can be carried out in a liquid phase or a gas phase. Among these, as the solvent when the polymerization is carried out in the liquid phase, any organic solvent that is generally used may be used, and specifically, benzene, toluene,
Xylene, pentane, hexane, methylene chloride and the like, or the olefin itself can be used as the solvent. Further, the polymerization temperature is not particularly limited, -100 ~
It is preferable to carry out in the range of 300 ° C.

[0049]

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

The polymerization operation, reaction and solvent purification
All were performed under an inert gas atmosphere. The solvents used for the reaction were all purified, dried and deoxygenated by a known method in advance. Furthermore, the compound used for the reaction was synthesized and identified by a known method.

The specific surface area and pore volume described in the examples were measured by a nitrogen adsorption method using ASAP2400 manufactured by Shimadzu Corporation. In addition, the melting index (MI) is ASTM
The measurement was performed by a method according to D1238 condition E.

Example 1 [Preparation of modified clay] Dimethylanilinium hydrochloride (Me
111 g of ₂ PhNHCl) was added to montmorillonite (trade name Kunipia F, manufactured by Kunimine Industries, specific surface area 8.6 m ² /
g, pore volume 0.06 ml / g) water 1 containing 270 g
0 l. After removing the supernatant, it was washed with methanol. Thereafter, drying under reduced pressure was performed to obtain a modified clay. (Specific surface area: 7.0 m ² / g, pore volume: 0.04 ml / g) [Preparation of catalyst] To a 10 l flask, 500 g of the modified clay synthesized above and 2 l of toluene were added, and then 2.6 mol of triisobutylaluminum was added. 30 mmol of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was added, and the mixture was stirred at room temperature for 21 hours. After removing the supernatant, it was washed with hexane. A part of the obtained catalyst slurry was collected, dried, and analyzed for Zr in the catalyst. The specific surface area of the catalyst was 10 m ² / g, and the pore volume was 0.08 ml / g.

[Polymerization] After replacing 2 L of a stainless steel autoclave with nitrogen, 1 L of hexane was added, and then a slurry of the catalyst synthesized above (corresponding to 50 mg of catalyst) and 2.2 mmol of triisobutylaluminum were added. Ethylene was introduced therein while maintaining the pressure at 6 kgf / cm ² , and polymerization was carried out at a temperature of 80 ° C. for 1.5 hours. After adding ethanol and terminating the polymerization, unreacted ethylene was removed to obtain 66 g of a particulate polymer. The MI of the obtained polymer was 0.013 g / 10 minutes.

Example 2 [Preparation of catalyst] Example 1 was placed in a 300 ml glass container.
5 g of modified clay synthesized according to [Preparation of Modified Clay],
Hexane (40 ml) was added, and then triisobutylaluminum (20 mmol) and bis (indenyl) zirconium dichloride (200 μmol) were added, followed by stirring at room temperature for 24 hours. After removing the supernatant, it was washed with hexane. Thereafter, the catalyst was dried under reduced pressure to obtain a catalyst. When Zr in the catalyst was analyzed, it was 0.10% by weight.

[Polymerization] After replacing 2 L of a stainless steel autoclave with nitrogen, 1 L of hexane was added, and then 118 mg of the catalyst synthesized above and 2.2 mmol of triisobutylaluminum were added. 6 kgf ethylene
/ Cm ² while maintaining the pressure, and polymerized at a temperature of 80 ° C. for 1.5 hours. After adding ethanol and terminating the polymerization, unreacted ethylene was removed to obtain 102 g of a particulate polymer. MI of the obtained polymer is 0.1
It was 2 g / 10 minutes.

Example 3 [Preparation of modified clay] Montmorillonite (trade name Kunipia F, manufactured by Kunimine Kogyo Co., Ltd., specific surface area: 8.6 m ² /) dispersed in 8 l of ethanol (trade name: Echinen F-3, manufactured by Nippon Kaseihin Co., Ltd.) g, pore volume 0.06 ml / g) and 1 kg of dimethylanilinium hydrochloride (Me ₂ PhNHCl) 3
Treated twice with 00g. After washing with ethanol, the residue was dried under reduced pressure to obtain a denatured clay. (Specific surface area 10 m ² / g, pore volume 0.05 ml / g) [Preparation of catalyst] To a 10 l flask, 500 g of the modified clay synthesized above and 3 l of toluene were added, and then 3 mol of triisobutylaluminum and bis (indenyl) were added. Add 30 mmol of zirconium dichloride and add 14 mmol at room temperature.
Stirred for hours. After removing the supernatant, it was washed with hexane. A part of the obtained catalyst slurry is collected and dried,
When Zr in the catalyst was analyzed, it was 0.19 wt%.

[Polymerization] After replacing 2 L of a stainless steel autoclave with nitrogen, 1 L of hexane was added, and then a slurry of the catalyst synthesized above (corresponding to 60 mg of catalyst) and 2.2 mmol of triisobutylaluminum were added. Ethylene was introduced therein while maintaining the pressure at 6 kgf / cm ² , and polymerization was carried out at a temperature of 80 ° C. for 1 hour. After adding ethanol and terminating the polymerization, unreacted ethylene was removed to obtain 160 g of a particulate polymer. The MI of the obtained polymer was 0.24 g / 10 min, and the bulk density was 0.2.
It was 29 g / cm ³ .

Example 4 [Preparation of catalyst] Example 3 was placed in a 300 ml glass container.
5 g of modified clay synthesized according to [Preparation of Modified Clay],
20 ml of toluene was added, and then 100 ml of a toluene solution containing 11 mmol of triisobutylaluminum and 200 μmol of bis (indenyl) zirconium dichloride.
Was added and stirred at room temperature for 18 hours. After removing the supernatant, it was washed with hexane. A part of the obtained catalyst slurry was collected, dried, and analyzed for Zr in the catalyst.

[Polymerization] After replacing 2 L of stainless steel autoclave with nitrogen, 1 L of hexane was added, and then the catalyst slurry synthesized above (corresponding to 50 mg of catalyst),
2.2 mmol of triisobutylaluminum were added.
Ethylene was introduced therein while maintaining the pressure at 6 kgf / cm ² , and polymerization was carried out at a temperature of 80 ° C. for 45 minutes. After adding ethanol and terminating the polymerization, unreacted ethylene was removed, MI was 0.17 g / 10 min, and bulk density was 0.25 g / c.
114 g of m ³ polymer were obtained. At this time, no adhesion of the polymer was observed on the reactor wall and the stirring blade.

Comparative Example 1 [Preparation of catalyst] In Example 4, montmorillonite (trade name: Kunipia F, manufactured by Kunimine Industries, specific surface area: 8.6 m ² / g, pore volume: 0) was vacuum-dried at 60 ° C. for 3 hours as a clay. (0.06 ml / g) except that 5 g was used. A part of the obtained catalyst slurry was collected, dried, and analyzed for Zr in the catalyst.

[Polymerization] Polymerization was carried out for 90 minutes in the same manner as in Example 4, except that the catalyst slurry synthesized above (corresponding to 500 mg of the catalyst) was used. MI is 0.09 g / 1
In 0 minutes, 15 g of a polymer having a bulk density of 0.20 g / cm ³ was obtained.

Example 5 [Preparation of modified clay] 2.5 g of synthetic mica (trade name: ME-100, manufactured by Corp Chemical) dispersed in 50 ml of water / 50 ml of methanol was mixed with dimethylanilinium hydrochloride (Me).
₍₂ PhNHCl). After washing with methanol, the residue was dried under reduced pressure to obtain a modified clay. (Specific surface area 10m
² / g, pore volume 0.05 ml / g) [Preparation of catalyst] 19.9 mg of the modified clay synthesized above,
0.22 mg of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride and 0.14 mmol of triisobutylaluminum were stirred in 12 ml of hexane for 10 minutes.

[Polymerization] After replacing 1 liter of autoclave with nitrogen, 600 ml of C ₉ -C ₁₃ saturated hydrocarbon solvent (IP Solvent 1620 (manufactured by Idemitsu Petrochemicals)) and 20 ml of 1-hexene were added, and the internal pressure of the autoclave was adjusted with ethylene. Was adjusted to 21 kgf / cm ² , and the temperature of the autoclave was set to 150 ° C. Next, the slurry of the catalyst synthesized above was added to an autoclave, and polymerization was performed for 20 minutes. The temperature of the autoclave reached 172 ° C. After the completion of the polymerization reaction, 25 g of a polymer was obtained. The MI of the obtained polymer was 9.2 g / 10 minutes, and the melting point was 107 ° C.

Example 6 [Preparation of catalyst] 100 mg of modified clay synthesized according to [Preparation of modified clay] in Example 3, 0.83 mg of ethylenebis (indenyl) zirconium dichloride and 0.2 mmol of triisobutylaluminum were added to toluene 20
Stirred in ml for 10 minutes.

[Polymerization] After replacing 2 L of a stainless steel autoclave with nitrogen, 500 ml of toluene was added, and then the catalyst slurry (equivalent to 100 mg of catalyst) synthesized above and 2.2 mmol of triisobutylaluminum were added.
Was added. 500 ml of propylene was introduced into this, and 60
Polymerization was carried out at a temperature of 1 ° C. for 1 hour. After completion of the reaction, unreacted propylene was removed to obtain 60 g of a polymer. The melting point of the obtained polymer was 133 ° C.

Example 7 [Preparation of catalyst] 25 mg of modified clay synthesized according to [Preparation of modified clay] in Example 3, 0.56 mg of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride and 0.1 mg of triisobutylaluminum. 2 mmol was stirred in 20 ml of toluene for 15 hours.

[Polymerization] After replacing 5 l of a stainless steel autoclave with nitrogen, 1000 ml of toluene was added, and then the catalyst slurry synthesized above (corresponding to 25 mg of catalyst) and 2.2 mmol of triisobutylaluminum were added. To this, 1000 ml of propylene was introduced, and 40
Polymerization was carried out at a temperature of 1 ° C. for 1 hour. After the completion of the reaction, unreacted propylene was removed to obtain 5 g of a polymer. The melting point of the obtained polymer was 104 ° C.

[0068]

As described above, olefins can be polymerized with high activity by using the catalyst of the present invention without using expensive organoaluminum oxy compounds or special boron compounds. In addition, a polymer having a good morphology can be produced in slurry polymerization.

Claims (7)

[Claims] 1. A clay mineral comprising a modified clay (a) having a pore volume of less than 0.1 ml / g, a transition metal compound (b) and an organoaluminum compound (c) having a pore volume of less than 0.1 ml / g. For producing olefin polymers. 2. The transition metal compound (b) is represented by the following general formula (1): Or the following general formula (2): [In the formula, M ¹ is a titanium atom, a zirconium atom or a hafnium atom, and Y is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, aryl, An alkyl group or an alkylaryl group, wherein R ¹ and R ² are each independently represented by the following general formula (3), (4), (5) or (6): (Wherein, R ⁶ each independently represent a hydrogen atom, a carbon number of 1-20.
Or an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. ), Which form a sandwich structure together with M ¹ , wherein R ³ and R ⁴ are each independently represented by the following general formulas (7), (8), (9) ) Or (10) (Wherein, R ⁷ each independently represent a hydrogen atom, a carbon number of 1 to 20)
Or an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. ) Is a ligand represented by the ligand forms a sandwich structure together with M ^1, R ⁵ is represented by the following general formula (1
1) or (12) (Wherein, R ⁸ is each independently a hydrogen atom, having 1 to 20 carbon atoms)
Or an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group,
M ² is a silicon atom, a germanium atom or a tin atom. ) And acts to crosslink R ³ and R ⁴ , and m is an integer of 1 to 5. The catalyst for producing an olefin polymer according to claim 1, wherein the catalyst is a transition metal compound belonging to Group 4 of the periodic table. 3. The transition metal compound (b) has the following general formula (1)
3), (14), (15) or (16) Wherein M ³ is independently a titanium atom, a zirconium atom or a hafnium atom, and Z ¹ is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. And L ¹ is a Lewis base, q is 0 to 3, and JR ⁹ _p-1 and JR ⁹ _p-2
Is a heteroatom ligand, J is a Group 15 element of the periodic table having a coordination number of 3 or a Group 16 element of the periodic table having a coordination number of 2, and R ⁹ is each independently a hydrogen atom A halogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms, or an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an alkylaryl group or an alkylaryloxy group having 6 to 20 carbon atoms; Is the coordination number of the element J, and R ¹⁰ is the following general formula (17), (18), (19) or (20) (Wherein, R ¹³ is each independently a hydrogen atom, carbon number 1-20
Or an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. ), Wherein R ¹² is a ligand represented by the following general formula (2)
1), (22), (23) or (24) (Wherein, R ¹⁴ is each independently a hydrogen atom, a carbon number of 1-20.
Or an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group. ), And R ¹¹ is represented by the following general formula (2)
5) or (26) (Wherein, R ¹⁵ is each independently a hydrogen atom, a carbon number of 1-20.
Or an aryl group having 6 to 20 carbon atoms, an arylalkyl group or an alkylaryl group,
M ⁴ is a silicon atom, a germanium atom or a tin atom. ) And acts to crosslink R ¹² and JR ⁹ _p-2 , and r is an integer of 1 to 5. The catalyst for producing an olefin polymer according to claim 1, wherein the catalyst is a transition metal compound belonging to Group 4 of the periodic table. Wherein the organoaluminum compound (c) is represented by the following general formula _{^{(27) AlR 16 3 (27}} ) [ wherein, R ¹⁶ are each independently hydrogen atom, C1-20
Alkyl group or alkoxy group, or 6 to
20 aryl groups, aryloxy groups, arylalkyl groups, arylalkoxy groups, alkylaryl groups or alkylaryloxy groups. 2. An organoaluminum compound represented by the formula:
The catalyst for producing an olefin polymer according to the above. 5. A catalyst for producing an olefin polymer, comprising the catalyst for producing an olefin polymer according to claim 1 and an organoaluminum compound (d). 6. An organoaluminum compound (d) represented by the following general formula (27): AlR ¹⁶ ₃ (27) wherein R ¹⁶ is each independently a hydrogen atom or a carbon atom having 1 to 20 carbon atoms.
Alkyl group or alkoxy group, or 6 to
20 aryl groups, aryloxy groups, arylalkyl groups, arylalkoxy groups, alkylaryl groups or alkylaryloxy groups. 5. An organoaluminum compound represented by the formula:
The catalyst for producing an olefin polymer according to the above. 7. A compound represented by the general formula (28) in the presence of the catalyst for producing an olefin polymer according to claim 1. Wherein R ¹⁷ and R ¹⁸ are each independently a hydrogen atom or an alkyl group having 1 to 14 carbon atoms, or an olefin represented by the following formula:
A method for producing an olefin polymer, comprising polymerizing or copolymerizing at a temperature of 100 to 300 ° C. in a solution state, a slurry state, or a gaseous state.