JPH10231313A - Catalyst for polymerizing olefin and production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject inexpensive catalyst capable of manifesting excellent polymerization activities and polymerization behaviors and useful for producing a high-molecular weight polymer with a low ash content by compounding a specific modified clay compound with a transition metallic compound and an organoaluminum compound. SOLUTION: This catalyst comprises (A) a transition metallic compound, (B) a modified clay compound which is a reactional product of (B1 ) a clay mineral such as a kaolin mineral, a smectite group or a (brittle)mica group with (B2 ) a protonic acid salt of an amine compound which is a compound represented by the formula I (R<1> is H or a 1-20C hydrocarbon group and at least one is a 6-20C hydrocarbon group) or formula II [R<2> and R<3> are each H or a 1-20C hydrocarbon group; (n) is 4-5] and (C) an organoaluminum compound. The catalyst preferably comprises the component B in a molar mount of 1-10,000 times, based on the component A and expressed in terms of the amount of the cation in the component B and the component C in a molar amount of <=100,000 times (more preferably 1-10,000 times) based on the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transition metal compound,
The present invention relates to an olefin polymerization catalyst comprising a modified clay 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 an aluminoxane as a catalyst. 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.

[0008] JP-A-5-301917 and JP-A-7-309907 disclose catalyst systems using inexpensive clay or clay treated with inorganic salts. However, the olefin polymerization activity of these catalyst systems was not sufficient.

In Japanese Patent Application Laid-Open No. Hei 7-224106, an interlayer cation-modified clay obtained by reacting a clay with an organic cation is used for the purpose of positively utilizing the surface negative charge of the clay mineral as a co-catalyst. Although a highly active catalyst system is obtained by this, considering the actual production, from the viewpoint of ash content or process applicability, even in a solution polymerization process with higher activity, higher temperature, and longer catalyst residence time, etc. There was a need for a catalyst system with improved polymerization behavior that could be used.

[0010]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide an inexpensive olefin polymerization catalyst having excellent polymerization activity and polymerization behavior.

[0011]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, a modified clay compound obtained by modifying a clay mineral with a protonic acid salt of an amine compound having a specific structure. It has been found that polyolefins can be produced with high activity by using a catalyst comprising a transition metal compound and an organoaluminum compound, and the present invention has been completed.

That is, the present invention relates to a catalyst component comprising a transition metal compound (a), a modified clay compound (b) and an organoaluminum compound (c), wherein the modified clay compound (b) is represented by the following (b-1) and (b) The present invention relates to a catalyst for olefin polymerization characterized by being a reaction product of -2) with a protonic acid salt, and a method for producing an olefin polymer using the catalyst.

(B-1) a clay mineral, (b-2) an amine compound represented by the following general formula (1) or (2)

[0014]

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[Wherein R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms.
And 20 hydrocarbon groups such as an alkyl group, an alkenyl group, and an aralkyl group, which may be the same or different, but at least one R ¹ is a hydrocarbon group having 6 or more carbon atoms. R ² and R ³ may be the same or different and each is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. n is 4 or 5. Hereinafter, the present invention will be described in detail.

As the transition metal compound (a), the following general formula (3) or (4)

[0017]

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Wherein M ¹ is a titanium atom, a zirconium atom or a hafnium atom, and X 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 ⁴ and R ⁵ are each independently the following general formulas (5), (6), (7) or
(8)

[0019]

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(Wherein, R ⁹ 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). And the ligand is M
¹ and a sandwich structure is formed, and R ⁶ and R ⁷ are each independently the following general formula (9), (10), (11) or (12)

[0021]

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(Wherein R ¹⁰ 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
Forming a sandwich structure with R ¹ , wherein R ⁸ is represented by the following general formula (13) or (14):

[0023]

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Wherein R ¹¹ is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an arylalkyl group or an alkylaryl group having 6 to 20 carbon atoms, and M ² is Atom, a germanium atom or a tin atom), which acts to bridge R ⁶ and R ⁷ , m is an integer of 1 to 5, and when m is 2 or more, R ⁸ is Each is independent. Or a transition metal compound of Group 4 of the periodic table represented by the following general formula (15), (16), (17) or (18):

[0025]

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Wherein M ³ is independently a titanium atom,
Z is a zirconium atom or a hafnium atom; Z is each independently a hydrogen atom, a halogen 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;
Is a Lewis base, p is 0-3, JR ¹² _q-1 ,
JR ¹² _q-2 is a heteroatom ligand, and J has a coordination number of 3
Wherein R ¹² is an element of Group 15 of the periodic table or an element of Group 16 of the periodic table having a coordination number of 2.
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; R ¹³ is a coordination number of the element J, and R ¹³ is the following general formula (19), (20), (21) or (22)

[0027]

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(Wherein, R ¹⁶ is each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group, an arylalkyl group or an alkyl are group having 6 to 20 carbon atoms). R ¹⁵ is a group represented by the following general formula (23), (24), (25) or (26)

[0029]

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(Wherein, R ¹⁷ 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). And R ¹⁴ is a group represented by the following general formula (27) or (28)

[0031]

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Wherein R ¹⁸ 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 ¹⁵ and JR ¹² _q-2 , and r is an integer of 1 to 5,
When r is 2 or more, R ¹⁴ is each independently. ]
Is preferably a transition metal compound of Group 4 of the periodic table represented by

Examples of the compound represented by the general formula (3) or (4) include bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride, 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-1-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 (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (3-methylcyclo Pentadienyl) zirconium dichloride,
Dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride,
Dimethylsilanediylbis (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (indenyl) zirconium dichloride,
Dimethylsilanediylbis (2-methyl-1-indenyl) 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 (2,4-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-methyl-1-indenyl) 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, diethylsilanediylbis (3-methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (4-t-butyl-2-) Methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (indenyl) titanium dichloride, diethylsilanediylbis (2-methyl-1-indenyl) titanium dichloride, Diethylsilanediylbis (tetrahydroindenyl) titanium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) titanium dichloride Ride, 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 Chloride,
Diethylsilanediylbis (indenyl) zirconium dichloride, diethylsilanediylbis (2-methyl-1-indenyl) zirconium dichloride, diethylsilanediylbis (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-methyl-1-indenyl) 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-methylcyclopentane) Dienyl) titanium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (indenyl) titanium dichloride, diphenylsilanediylbis (2-methyl-1-indenyl) titanium dichloride, diphenylsilanediyl Bis (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-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (3 -Methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (4-t
-Butyl-2-methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (indenyl) zirconium dichloride, diphenylsilanediylbis (2-methyl-1- Indenyl) 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-methylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (4-t-butyl- 2-methylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) hafnium dichloride, diphenylsilanediylbis (indenyl) hafnium dichloride, diphenylsilanediylbis (2-methyl-1-indenyl) hafnium Dichloride, diphenylsilanediylbis (tetrahydroindenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl-9-phenyl) Oreniru) hafnium dichloride, diphenyl silane diyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) hafnium dichloride, diphenyl silane diyl (cyclopentadienyl-2,7-di -t- butyl -9
Examples thereof include dichloro-forms such as (-fluorenyl) hafnium dichloride and the like, and dimethyl-, diethyl-, dihydro-, diphenyl- and dibenzyl-forms of the above Group 4 transition metal compounds.

The general formulas (15), (16) and (17)
Or a compound represented by (18), 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, dimethylsilanediyltrimethylsilylcyclopentadienyl-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, etc. It can be exemplified.

The modified clay compound (b) used in the present invention
Is a reaction product of the following (b-1) and (b-2) protonic acid salt.

(B-1) a clay mineral, (b-2) an amine compound represented by the following general formula (1) or (2)

[0037]

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[Wherein, R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms.
And 20 hydrocarbon groups such as an alkyl group, an alkenyl group, and an aralkyl group, which may be the same or different, but at least one R ¹ is a hydrocarbon group having 6 or more carbon atoms. R ² and R ³ may be the same or different and each is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. n is 4 or 5. The clay mineral is generally composed of a tetrahedron formed by coordinating oxygen ions to silicon ions and an octahedron formed by coordinating ions of oxygen or hydroxide to ions of aluminum, magnesium or iron. Many clay minerals are not electrically neutral and have a positive or negative charge on the surface. Cations are provided between the layers to compensate for this negative charge, and the interlayer cations can be ion-exchanged with other cations. For this reason, the amount of interlayer cations depends on the cation exchange capacity (CE
C), and the number of milliequivalents per 100 g of clay (me)
q). The CEC varies depending on the clay, but according to the second edition of the Clay Handbook (edited by The Clay Society of Japan, published by Gihodo Shuppan Co., Ltd.), kaolinite: 3 to 15
meq / 100g, halloysite: 5-40 meq / 1
00 g, montmorillonite: 80 to 150 meq / 10
0 g, illite: 10 to 40 meq / 100 g, vermiculite: 100 to 150 meq / 100 g, chlorite: 10 to 40 meq / 100 g, sepiolite attapulgite: 20 to 30 meq / 100 g.

The clay mineral used in the present invention (b-
1) is a clay mineral having a negative charge on the surface of the clay mineral and having a cation exchange ability. Specifically, kaolin minerals such as kaolinite, dickite and halloysite; montmorillonite, hectorite, beidellite,
Smectites such as saponite, teniolite and sauconite; mica such as muscovite, paragonite and illite;
Vermiculite group; brittle mica group such as margarite and clintonite; chlorite group such as dombasite, cocoaite, clinochlore; sepiolite palygorskite; and the like, but are not limited thereto. These clay minerals exist naturally, but can be obtained with less impurities by artificial synthesis. In the present invention, the natural clay minerals shown here and the clay minerals obtained by artificial synthesis can be used.

The modified clay compound (b), which is a component of the catalyst for olefin polymerization of the present invention, comprises a clay mineral (b-
1) Modified with a protonic acid salt of an amine compound (b-2) represented by the following general formula (1) or (2).

[0041]

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In the formula, R ¹ is a hydrogen atom or methyl, ethyl, propyl, isopropyl, isobutyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, 1 carbon atoms such as octadecyl and cyclohexyl
-20 alkyl groups; vinyl, propenyl, oleyl,
Alkenyl group having 2 to 20 carbon atoms, such as cyclohexenyl; benzyl, a hydrocarbon group such as an aralkyl group having 7 to 20 carbon atoms, such as phenylethyl, or may be the same as or different from each other, but at least one of R ¹ Is hexyl, cyclohexyl, cyclohexenyl, heptyl, benzyl, octyl, phenylethyl, nonyl, decyl,
It is a hydrocarbon group having 6 to 20 carbon atoms such as dodecyl, hexadecyl, octadecyl, oleyl and the like. R ² and R ³ may be the same or different and each represents a hydrogen atom or a carbon atom
A 20 hydrocarbon groups are the same hydrocarbon groups as above R ^1. n is 4 or 5.

As the amine compound represented by the general formula (1), specifically, hexylamine, 2-aminoheptane,
3-aminoheptane, heptylamine, 1,5-dimethylhexylamine, 1-methylheptylamine, octylamine, t-octylamine, nonylamine, decylamine, undecylamine, dodecylamine, trisylamine, 1-tetradecylamine, penta Decylamine, 1-hexadecylamine, octadecylamine, oleylamine, cyclohexylamine, cycloheptylamine, cyclohexanemethylamine, 2-methylcyclohexylamine, 4-methylcyclohexylamine,
Aliphatic primary amines such as 2,3-dimethylcyclohexylamine, cyclododecylamine, 2- (1-cyclohexenyl) ethylamine and geranylamine; N-methylhexylamine, dihexylamine, bis (2-ethylhexyl) amine; Dioctylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, dioleylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-isopropylcyclohexylamine, Nt-butylcyclohexyl Amines, aliphatic secondary amines such as N-allylcyclohexylamine;
N-dimethyloctylamine, N, N-dimethylundecylamine, N, N-dimethyldodecylamine, N, N
-Dimethyltetradecylamine, N, N-dimethylhexadecylamine, N, N-dimethyloctadecylamine, N, N-dioctylmethylamine, N, N-diundecylmethylamine, N, N-didodecylmethylamine, N , N-ditetradecylmethylamine, N, N-dihexadecylmethylamine, N, N-dioctadecylmethylamine, N, N-dioleylmethylamine, trihexylamine, triisooctylamine, trioctylamine, Triisodecylamine, tridodecylamine,
N-methyl-N-octadecyl-1-octadecaneamine, N, N-dimethylcyclohexylamine, N, N-
Examples thereof include, but are not limited to, aliphatic tertiary amines such as dimethylcyclohexanemethylamine and N, N-diethylcyclohexylamine.

Specific examples of the amine compound represented by the general formula (2) include pyrrolidine, piperidine, 2,5-dimethylpyrrolidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 2,6- Dimethylpiperidine, 3,3-dimethylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, 2,2,6
6-tetramethylpiperidine, 1-methylpyrrolidine,
Examples include, but are not limited to, aliphatic heterocyclic compounds such as 1-methylpiperidine, 1-ethylpiperidine, 1-butylpyrrolidine, 1,2,2,6,6-pentamethylpiperidine.

The amine compound (b-2) is reacted with the clay mineral (b-1) as a proton acid salt of an amine reacted with a protonic acid. Examples thereof include, but are not limited to, hydrogen chloride, hydrogen fluoride, hydrogen bromide, hydrogen iodide, sulfuric acid, and the like.

The protic acid salt of the amine compound (b-2) to be reacted with the clay mineral (b-1) may be one obtained by previously reacting the amine compound (b-2) with a protonic acid. Alternatively, it may be produced in a reaction solvent when reacting with the clay mineral (b-1). Specific examples of the protonic acid salt of the amine compound (b-2) to be used by isolation include hexylamine hydrochloride, 2-aminoheptane hydrochloride, 3-aminoheptane hydrochloride, heptylamine hydrochloride, 1,5- Dimethylhexylamine hydrochloride, 1-methylheptylamine hydrochloride, octylamine hydrochloride, t-
Octylamine hydrochloride, nonylamine hydrochloride, decylamine hydrochloride, undecylamine hydrochloride, dodecylamine hydrochloride, trisylamine hydrochloride, 1-tetradecylamine hydrochloride, pentadecylamine hydrochloride, 1-hexadecylamine hydrochloride, Octadecylamine hydrochloride, oleylamine hydrochloride, cyclohexylamine hydrochloride, cycloheptylamine hydrochloride, cyclohexanemethylamine hydrochloride, 2-methylcyclohexylamine hydrochloride, 4-methylcyclohexylamine hydrochloride, 2,3-dimethylcyclohexylamine hydrochloride Salt, cyclododecylamine hydrochloride, 2- (1-cyclohexenyl) ethylamine hydrochloride, geranylamine hydrochloride, N-methylhexylamine hydrochloride, dihexylamine hydrochloride, bis (2-ethylhexyl) amine hydrochloride Dioctylamine hydrochloride, didecylamine hydrochloride, didodecyl hydrochloride, di tetradecyl amine hydrochloride, dihexadecylamine hydrochloride, dioctadecyl amine hydrochloride, dioleylamine hydrochloride,
N-methylcyclohexylamine hydrochloride, N-ethylcyclohexylamine hydrochloride, N-isopropylcyclohexylamine hydrochloride, Nt-butylcyclohexylamine hydrochloride, N-allylcyclohexylamine hydrochloride,
N, N-dimethyloctylamine hydrochloride, N, N-dimethylundecylamine hydrochloride, N, N-dimethyldodecylamine hydrochloride, N, N-dimethyltetradecylamine hydrochloride, N, N-dimethylhexadecylamine Hydrochloride,
N, N-dimethyloctadecylamine hydrochloride, N, N-
Dioctylmethylamine hydrochloride, N, N-diundecylmethylamine hydrochloride, N, N-didodecylmethylamine hydrochloride, N, N-ditetradecylmethylamine hydrochloride,
N, N-dihexadecylmethylamine hydrochloride, N, N-
Dioctadecylmethylamine hydrochloride, N, N-dioleylmethylamine hydrochloride, trihexylamine hydrochloride, triisooctylamine hydrochloride, trioctylamine hydrochloride, triisodecylamine hydrochloride, tridodecylamine hydrochloride, N-methyl-N-octadecyl-1-octadecaneamine hydrochloride, N, N-dimethylcyclohexylamine hydrochloride, N, N-dimethylcyclohexanemethylamine hydrochloride, N, N-diethylcyclohexylamine hydrochloride, pyrrolidine hydrochloride, Piperidine hydrochloride, 2,5-
Dimethylpyrrolidine hydrochloride, 2-methylpiperidine hydrochloride, 3-methylpiperidine hydrochloride, 4-methylpiperidine hydrochloride, 2,6-dimethylpiperidine hydrochloride, 3,3
-Dimethylpiperidine hydrochloride, 3,5-dimethylpiperidine hydrochloride, 2-ethylpiperidine hydrochloride, 2,2,
6,6-tetramethylpiperidine hydrochloride, 1-methylpyrrolidine hydrochloride, 1-methylpiperidine hydrochloride, 1-ethylpiperidine hydrochloride, 1-butylpyrrolidine hydrochloride,
Amine hydrochloride, such as 1,2,2,6,6-pentamethylpiperidine hydrochloride, or this hydrochloride is used as another hydrofluoride, hydrobromide, hydroiodide, acetate or Examples thereof include protonic salts such as sulfates, but are not limited thereto.

The olefin polymerization catalyst of the present invention comprises:
A modified clay compound (b) obtained by modifying the above clay mineral (b-1) with a protonic acid salt of an amine compound (b-2) having a specific structure is used as a component. Here, the modification means that the exchangeable cation of the metal ion present in the clay mineral (b-1) is exchanged for the ammonium cation component of the proton of the amine compound (b-2). Means the resulting clay mineral-organic ion complex. (B-1) and (b-
The reaction conditions of 2) with the protonic acid salt are not particularly limited, and the reaction amount ratio of (b-1) and (b-2) is not particularly limited. It is preferable to react with a protonic acid salt of (b-2) in an amount of 0.5 equivalent or more based on the cation present in the catalyst, and more preferably an equivalent or more for high activation of the catalyst. One of the above-mentioned clay minerals (b-1) may be used alone, or a plurality of them may be used in combination. The protonic acid salt of the amine compound (b-2) may be used alone. They may be used, or a plurality of types may be mixed and used. The reaction solvent used at this time is water or an organic solvent having polarity, specifically, alcohols such as methyl alcohol and ethyl alcohol, acetone, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide, methylene chloride and the like. For example, these solvents can be used alone or as a mixed solvent. Of these, water or alcohol is particularly preferably used.

The organoaluminum compound (c) used in the present invention is represented by the following general formula (29).

[0049]

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[Wherein, R ¹⁹ is each independently a hydrogen atom, a halogen atom, an amino group, an alkyl group, an alkoxy group or an aryl group, and at least one of R ¹⁹ is an alkyl group. Specific examples of these include trimethylaluminum, triethylaluminum, tri (normalpropyl) aluminum, tri (isopropyl) aluminum, tri (normalbutyl) aluminum, tri (isobutyl) aluminum, tri (t-butyl) aluminum, Trialkylaluminums such as triamylaluminum; dialkylaluminum hydrides such as diisobutylaluminum hydride; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, di (t-butyl) aluminum chloride and diamylaluminum chloride; Methyl aluminum dichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride Examples thereof include, but are not limited to, alkyl aluminum dihalides such as chloride, t-butyl aluminum dichloride, and amyl aluminum dichloride; and dialkyl aluminum alkoxides such as diethyl aluminum ethoxide. Of these, trialkyl aluminum is preferred.

The transition metal compound (a), modified clay compound (b) and organoaluminum compound (c) shown above
The three components are brought into contact with each other to form an olefin polymerization catalyst,
The method or order of adding the catalyst components at this time is not particularly limited. For example, the order of addition is shown as follows.

(1) After bringing the transition metal compound (a) into contact with the modified clay compound (b), the organoaluminum compound (c) is added.

(2) After bringing the modified clay compound (b) into contact with the organoaluminum compound (c), the transition metal compound (a) is added.

(3) After bringing the modified clay compound (b) into contact with the organoaluminum compound (c), a contact mixture of the transition metal compound (a) and the organoaluminum compound (c) is added.

(4) Simultaneously contact the three components.

In particular, in order to reduce the influence of impurities and the like in the clay mineral, the modified clay compound (b) is brought into contact with part or all of the organoaluminum compound (c) in advance (2) or The method (3) is preferable from the viewpoint of improving reproducibility.

The above three components are contacted in an inert gas atmosphere in a solvent inert to each component. Specifically, butane, pentane, hexane, heptane, octane, nonane, decane, tetradecane, cyclopentane,
Examples thereof include aliphatic hydrocarbon compounds such as cyclohexane and aromatic hydrocarbon compounds such as benzene, toluene and xylene. In addition to the above organic solvents, it is also possible to use halogen-containing compounds such as chloroform, methylene chloride and chlorobenzene. The temperature at the time of the contact can be in the range of −50 ° C. to the boiling point of the solvent. Preferably it is above room temperature.

The amount of the modified clay compound (b) relative to the transition metal compound (a) in the catalyst system may be an amount of the modified clay compound (b) sufficient to cause the reaction of the transition metal compound (a). Although there is no particular limitation, the amount of the cation in the modified clay compound (b) relative to the transition metal compound (a) is preferably 1 to 10,000 times the molar amount. If the amount is less than 1 time, sufficient activity cannot be obtained. If the amount exceeds 10,000 times, the activity per catalyst component becomes low, and it becomes necessary to remove ash from the polymer. Further, an organoaluminum compound (c)
The amount is not particularly limited, but is preferably 100,000 times or less the molar amount of the transition metal compound (a). If the amount exceeds this, it is necessary to consider the step of demineralization. Considering the viewpoints of catalyst stabilization and elimination of catalyst poisons, it is preferable to use the organoaluminum compound (c) in a range of 1 to 10000 times mol.

When the transition metal compound (a) of the present invention is used as a catalyst component, it is possible to carry out polymerization using two or more transition metal compounds.

The catalyst for olefin polymerization in the present invention comprises:
Ordinary olefin polymerization method, namely slurry polymerization,
It can be used for any of gas phase polymerization, high pressure polymerization, solution polymerization and bulk polymerization. At the time of polymerization, when a solvent is used, any organic solvent may be used as long as it is a commonly used organic solvent.Specifically, benzene, toluene, xylene, butane, pentane,
Hexane, heptane, cyclohexane, methylene chloride and the like can be mentioned, and olefin itself provided at the time of polymerization such as propylene, 1-butene, 1-octene and 1-hexene can also be used as a solvent.

In the present invention, examples of the olefin used for the polymerization include α-olefins having 2 to 20 carbon atoms, diene compounds, cyclic olefins, etc., and homopolymerization using one of these, and furthermore, The copolymerization used can be carried out.

As the α-olefin having 2 to 20 carbon atoms, for example, ethylene, propylene, 1-butene, 1-
Pentene, 4-methyl-1-pentene, 1-hexene,
1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1- Examples include, but are not limited to, eicosene and styrene.

The diene compounds include 1,4
-Hexadiene, 1,5-hexadiene, 3-methyl-
1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3- Dimethyl-1,4-hexadiene, 5
-Methyl-1,4-heptadiene, 5-ethyl-1,4
Heptadiene, 5-methyl-1,5-heptadiene,
6-methyl-1,5-heptadiene, 5-ethyl-1,
5-heptadiene, 1,6-octadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-
Methyl-1,6-octadiene, 6-ethyl-1,6-
Octadiene, 6-propyl-1,6-octadiene,
6-butyl-1,6-octadiene, 4-methyl-1,
4-nonadiene, 5-methyl-1,4-nonadiene, 4
-Ethyl-1,4-nonadiene, 5-ethyl-1,4-
Nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6- Nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-
1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-
1,7-nonadiene, 1,9-decadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-
1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-
1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-
1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-
1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-
Aliphatic non-conjugated polyenes such as 1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl-1,8-undecadiene;
Conjugated dienes such as butadiene and isoprene; dicyclopentadiene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylenyl-2-norbornene, 2,3-diisopropylidene Examples thereof include, but are not limited to, alicyclic polyenes such as -5-norbornene and 2-ethylidene-3-isopropylidene-5-norbornene.

Examples of the cyclic olefin include monocyclic olefins such as cyclobutene, cyclopentene, cyclohexene, cycloheptene and cyclooctene; substituted monocyclic olefins such as 3-methylcyclopentene and 3-methylcyclohexene; norbornene, 1,2-dihydro Dicyclopentadiene, 1,4,5,8-dimethano-
Polycyclic olefins such as 1,2,3,4,4a, 5,8,8a-octahydronaphthalene; 1-methylnorbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5-phenylnorbornene; 5-benzylnorbornene, 7-methylnorbornene, 5,6-dimethylnorbornene, 2-methyl-
1,4,5,8-dimethano-1,2,3,4,4a,
Examples include, but are not limited to, substituted polycyclic olefins such as 5,8,8a-octahydronaphthalene.

In producing a polyolefin using the method of the present invention, polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure and monomer concentration are not particularly limited, but the polymerization temperature is -100 to 300 ° C. The polymerization is preferably performed for 10 seconds to 20 hours at a polymerization pressure of normal pressure to 3500 kg / cm ² . It is also possible to adjust the molecular weight using hydrogen or the like during polymerization. The polymerization is batch type,
It can be carried out by any of a semi-continuous method and a continuous method, and can be carried out in two or more stages by changing the polymerization conditions. The polyolefin obtained after the polymerization is separated and recovered from the polymerization solvent by a conventionally known method,
The polyolefin can be obtained by drying.

[0066]

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 were carried out in the following manner.
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 MI of the olefin polymer obtained in the present invention
(Melt index) was measured by a method according to ASTM D1238 condition E.

The measurement of the melting point of the olefin polymer is carried out by DSC
(DSI200 manufactured by SEIKO) at 200 ° C.
After cooling the sample held for 5 minutes to 0 ° C.,
It was calculated by measuring the crystal melting peak when the temperature was raised at 0 ° C./min.

The deactivation rate constant is shown as an index of the polymerization behavior during solution polymerization. The polymerization reaction gradually deactivates after showing the maximum flow rate of the monomer in the early stage of the polymerization. The change with time of the deactivation at this time is approximately a straight line when the ethylene flow rate (Nl / min) is plotted against the polymerization time (min) on a logarithmic scale of a semilogarithmic graph. This regression line is represented by the following exponential function.

F (t) = Ae ^(−kt) (where, f (t) is an ethylene flow rate (Nl / min), k is a deactivation rate constant, t is a polymerization time (min), and A is this deactivation. It can be said that the smaller the deactivation rate constant k, the less the catalyst deteriorates with time.

The time-dependent degradation was determined by plotting the deactivation rate constant by plotting within a certain polymerization time range or from the point of the maximum flow rate until deactivation to 1/4 flow rate.
Under these conditions, the correlation coefficient of the regression line obtained from the plot was 0.97 or more.

Example 1 [Preparation of Modified Clay Compound] Dodecylamine (4.17 g, 22.5 mmol) was suspended in 150 ml of sufficiently degassed water in a 300 ml flask, and hydrochloric acid (12N) was added.
1.8 ml was added, and the mixture was stirred at room temperature for 2 hours to obtain a homogeneous solution. This was stirred in a 2 liter flask with a suspension prepared by dispersing 9.5 g of high-purity montmorillonite (trade name: Kunipia, manufactured by Kunimine Industries, ion exchange capacity: 115.0 meq / 100 g) in 1 liter of sufficiently degassed water. Was added and then stirred for 24 hours. This was filtered, washed with water and ethanol, and dried under reduced pressure at room temperature to obtain a modified clay compound.

[Preparation of Catalyst Suspension] After suspending 1.0 g of the modified clay compound obtained above in 56 ml of toluene in 300 ml of Schlenk, triethylaluminum (1.44 mol / l, toluene solvent) was used. 8 ml was added and the mixture was stirred for 1 hour. Separately, 22.3 mg of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride (40.
0 μmol), toluene 24 ml, triethylaluminum (1.44 mol / l, toluene solvent) 5.6 ml
Was prepared, and this solution was added to the suspension of the modified clay compound and stirred for 12 hours to obtain a catalyst suspension.

[Solution 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 Petrochemical)) and 20 ml of 1-hexene were added, and the autoclave was purged with ethylene. The internal pressure was adjusted to 21 kgf / cm ² , and the temperature of the autoclave was set to 170 ° C. Next, 1.1 ml of the catalyst suspension synthesized by the above method (0.5 μmo in terms of Zr)
12 ml of decane containing l) is added to the autoclave and 1
Polymerization was performed for 0 minutes. After the completion of the polymerization reaction, unreacted ethylene was removed, and ethanol was added to the reaction solution to obtain 48.0.
g of polymer were obtained. The properties of the obtained polymer are shown in Table 1. The deactivation rate constant k in this polymerization is 0.1.
It was 20 min ^-1 .

Example 2 In preparing a modified clay compound, 2.26 g (22.8 mmol) of N-methylpiperidine was used instead of dodecylamine.
The modified clay compound was prepared in the same manner as in Example 1 except that

A catalyst suspension was prepared and polymerized in the same manner as in Example 1 except that the modified clay compound thus obtained was used. The results are shown in Table 1.

Example 3 In preparing a modified clay compound, 3.18 g of 2,2,6,6-tetramethylpiperidine was used instead of dodecylamine.
A modified clay compound was prepared in the same manner as in Example 1 except that (22.5 mmol) was used.

A catalyst suspension was prepared and polymerized in the same manner as in Example 1 except that the thus obtained modified clay compound was used. The results are shown in Table 1.

Example 4 [Preparation of Modified Clay Compound] In a 300 ml flask, 6.06 g (22.5 mmol) of octadecylamine was suspended in 150 ml of sufficiently degassed ethanol, and 1.8 ml of hydrochloric acid (12N) was added. In addition, the mixture was stirred at room temperature for 2 hours to obtain a homogeneous solution. Then, under stirring, synthetic hectorite 9.
After adding 5 g (trade name: Laponite, manufactured by Nippon Silica Industry Co., Ltd.), the mixture was stirred for 24 hours. This was filtered, washed with water and ethanol, and dried under reduced pressure at room temperature to obtain a modified clay compound.

A catalyst suspension was prepared and polymerized in the same manner as in Example 1 except that the thus obtained modified clay compound was used. The results are shown in Table 1. No deactivation of the catalyst was observed within a polymerization time of 10 minutes in this system.

Comparative Example 1 [Preparation of Modified Clay Compound]
3.6 g of N-dimethylaniline hydrochloride (22.8 mm
ol) was dissolved in 150 ml of sufficiently degassed water. Under stirring, 9.5 g of high-purity montmorillonite (trade name Kunipia, manufactured by Kunimine Industries, ion exchange capacity: 115.0 m)
eq / 100g) and stirred for 24 hours. This was filtered, washed with water and ethanol, and dried under reduced pressure at room temperature to obtain a modified clay compound.

A catalyst suspension was prepared and polymerized in the same manner as in Example 1 except that the thus obtained modified clay compound was used. The results are shown in Table 1.

Comparative Example 2 A comparative example was conducted except that 3.3 g (22.8 mmol) of 2,6-dimethylpyridine hydrochloride was used instead of N, N-dimethylaniline hydrochloride in preparing the modified clay compound. Example 1
A modified clay compound was prepared in the same manner as described above.

A catalyst suspension was prepared and polymerized in the same manner as in Example 1 except that the thus obtained modified clay compound was used. The results are shown in Table 1.

Comparative Example 3 In preparing a modified clay compound, 2.6 g of pyridine hydrochloride (22.2 g) was used in place of N, N-dimethylaniline hydrochloride.
8 mmol), and a modified clay compound was prepared in the same manner as in Comparative Example 1 except that synthetic hectorite (trade name: Laponite, manufactured by Nippon Silica Industry Co., Ltd.) was used instead of high-purity montmorillonite.

A catalyst suspension was prepared and polymerized in the same manner as in Example 1 except that the thus obtained modified clay compound was used. The results are shown in Table 1.

Comparative Example 4 In the preparation of a modified clay compound, 5.1 g (22.8 mmol) of tri-n-butylamine hydrochloride was used instead of N, N-dimethylaniline hydrochloride to obtain a high-purity montmorillonite. A modified clay compound was prepared in the same manner as in Comparative Example 1 except that synthetic hectorite (trade name: Laponite, manufactured by Nippon Silica Industry Co., Ltd.) was used instead.

A catalyst suspension was prepared and polymerized in the same manner as in Example 1 except that the modified clay compound thus obtained was used. The results are shown in Table 1.

The examples and comparative examples exemplified above show the specificity of the present invention. That is, by using an olefin polymerization catalyst comprising a transition metal compound (a), an organoaluminum compound (c) and a modified clay compound (b) modified with a protonic acid salt of an amine compound having a specific structure, an olefin polymer is obtained. Can be manufactured with high productivity. Further, as shown in the above results, the catalyst has excellent activity persistence even at a high temperature, and thus can be said to be a catalyst suitable for a solution polymerization process at a high temperature and a long residence time of the catalyst.

[0091]

[Table 1]

Example 5 [Preparation of modified clay compound] In a 300 ml flask, N,
N-dimethyloctadecylamine (7.14 g, 24.
0 mmol) was dissolved in 100 ml of sufficiently degassed ethanol, 2.0 ml of hydrochloric acid (12N) was added, and the mixture was stirred at room temperature for 0.5 hour. After adding 100 ml of water, 20 g of high-purity montmorillonite (trade name Kunipia, manufactured by Kunimine Industries, ion exchange capacity: 115.0 meq / 100)
g) was added and stirred for 12 hours. This was filtered, washed with water and ethanol, and dried under reduced pressure at room temperature to obtain a modified clay compound.

[Preparation of Catalyst Suspension] After suspending 1.0 g of the modified clay compound obtained above in 56 ml of toluene in 300 ml of Schlenk, triisobutylaluminum (1.44 mol / l, toluene solvent) 2 0.8 ml was added and stirred for 1 hour. Separately, for 50ml Schlenk,
Diphenylmethylene (cyclopentadienyl) (2,7
-Di-t-butyl-fluorenyl) zirconium dichloride 26.7 mg (40.0 μmol), toluene 2
4 ml, triisobutylaluminum (1.44 mol
/ L, toluene solvent) 5.6 ml was prepared, and this solution was added to the above-mentioned suspension of the modified clay compound.
The mixture was stirred for 2 hours to obtain a catalyst suspension.

[Polymerization] After replacing 5 l of the autoclave with nitrogen, 2250 ml of toluene and 1-hexene 2
50 ml was added, and the temperature of the autoclave was raised to 80 ° C. Further, ethylene is introduced and the internal pressure is set to 4 kgf / cm.
^{And 2} . Next, 11 ml of the catalyst suspension prepared above
(5.0 μmol in terms of Zr) was added to the autoclave, and polymerization was performed for 10 minutes. After the completion of the polymerization reaction, unreacted ethylene is removed, and the reaction solution is poured into ethanol, and 9
5.6 g of polymer were obtained. The results are shown in Table 2.

Example 6 [Preparation of modified clay compound] In a 300 ml flask, N,
N-dimethyloctadecylamine (4.58 g, 15.
4 mmol) was dissolved in 100 ml of sufficiently degassed ethanol, 1.3 ml of hydrochloric acid (12N) was added, and the mixture was stirred at room temperature for 0.5 hour. Then, add 100 ml of water,
Furthermore, synthetic saponite 20g (trade name Smecton SA,
Manufactured by Kunimine Industries, ion exchange capacity; 70 meq / 10
0g) was added and stirred for 12 hours. This was filtered, washed with water and ethanol, and dried under reduced pressure at room temperature to obtain a clay compound.

A catalyst suspension was prepared and polymerized in the same manner as in Example 5, except that the modified clay compound thus obtained was used. The results are shown in Table 2.

Example 7 After replacing 5 l of the autoclave with nitrogen, toluene 22
50 ml, 1-hexene 250 ml and 5-ethylidene-2-norbornene 20 ml were added, and the temperature of the autoclave was raised to 80 ° C. Further, ethylene was introduced to adjust the internal pressure to 4 kgf / cm ² . Next, 11 ml of the catalyst suspension prepared in Example 5 (5.0 μm
l) was added to the autoclave and polymerization was carried out for 15 minutes.
After the completion of the polymerization reaction, unreacted ethylene was removed, and the reaction solution was poured into ethanol to obtain 99.8 g of a polymer.
The results are shown in Table 2.

Comparative Example 5 Unmodified high-purity montmorillonite (trade name Kunipia, manufactured by Kunimine Industries, Ltd., ion exchange capacity: 1) as a clay compound
A catalyst suspension was prepared and polymerized in the same manner as in Example 5 except that 15.0 meq / 100 g) was used. As a result, no copolymer was obtained.

Comparative Example 6 Using the modified clay compound obtained in Comparative Example 1, a catalyst suspension was prepared in the same manner as in Example 5, and polymerization was carried out. Table 2 shows the results.

Comparative Example 7 [Preparation of Modified Clay Compound]
After suspending 3.3 g (27.2 mmol) of N-dimethylaniline in 200 ml of sufficiently degassed water, hydrochloric acid (1
2N) (2.3 ml) was added and the mixture was stirred at room temperature for 0.5 hour to obtain a homogeneous solution. Further, 20 g of synthetic saponite (trade name: Smecton SA, manufactured by Kunimine Industries, ion exchange capacity;
After adding 70 meq / 100 g), the mixture was stirred for 12 hours. After filtering this, it is washed with water and ethanol,
Drying under reduced pressure at room temperature gave a modified clay compound.

A catalyst suspension was prepared and polymerized in the same manner as in Example 5 except that the modified clay compound thus obtained was used. The results are shown in Table 2.

[0102]

[Table 2]

Example 8 After replacing 5 l of the autoclave with nitrogen, toluene 10 l
00 ml and 1000 ml of liquid propylene were added, and the temperature of the autoclave was raised to 40 ° C. Next, 11 ml of the catalyst suspension prepared in Example 5 (5.0 μm
l) was added to the autoclave and polymerization was carried out for 60 minutes.
After the completion of the polymerization reaction, unreacted propylene was removed, and the reaction solution was poured into ethanol to obtain 28.2 g of polypropylene. Racemic pentad of the obtained polypropylene is 8
The MI measured at 0% and 230 ° C. was 0.6 g / 10 min.

Comparative Example 8 Using the modified clay compound obtained in Comparative Example 1, a catalyst suspension was prepared in the same manner as in Example 5, and propylene was polymerized in the same manner as in Example 8. As a result, 12.0 g of polypropylene was obtained. Racemic pentad of the obtained polypropylene was 55%, and the MI measured at 230 ° C. was 3.5 g.
/ 10 minutes.

The examples and comparative examples exemplified above show the specificity of the present invention. That is, by using an olefin polymerization catalyst comprising a transition metal compound (a), an organoaluminum compound (c), and a modified clay compound (b) modified with a protonic acid salt of an amine compound having a specific structure, a high molecular weight olefin is obtained. It can be seen that the polymer can be produced with high productivity. Further, as shown in the above results, the catalyst has excellent activity persistence even at a high temperature, and thus can be said to be a catalyst suitable for a solution polymerization process at a high temperature and a long residence time of the catalyst.

[0106]

As described above, the catalyst described in the present patent application shows high activity for olefin polymerization and enables production of a polymer having a high molecular weight. Furthermore, the polymerization behavior under high-temperature conditions can be improved, and an olefin polymer having low ash content can be obtained with high productivity.

Claims (2)

[Claims] 1. A catalyst component comprising a transition metal compound (a), a modified clay compound (b) and an organoaluminum compound (c), wherein the modified clay compound (b) is represented by the following (b-1) and (b-2): An olefin polymerization catalyst, which is a reaction product of the above with a protonic acid salt. (B-1) a clay mineral, (b-2) an amine compound represented by the following general formula (1) or (2) Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a hydrocarbon group, an aralkyl group, may be the same as or different from each other, at least one R ¹ is the number of carbon atoms Is a hydrocarbon group of 6 or more.
R ² and R ³ may be the same or different and each is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. n is 4 or 5. ] 2. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 1.