JPH10279630A - Method for producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an amorphous olefin polymer by polymerizing a cyclic olefin with a very small amount of a catalyst at a high conversion. SOLUTION: An olefin for polymerizing a cyclic olefin represented by the formula [II] in the presence of a catalyst comprising a compound (A) and an organoaluminum compound (B) and / or a boron compound (C). And a method for producing an olefin polymer obtained by copolymerizing a cyclic olefin represented by the formula [II] and another monomer having copolymerizability with the cyclic olefin. (A) A transition metal compound represented by the formula [I]. (M is a group 4 or lanthanide series transition metal A, A ′
Is a hydrocarbon group, X and X 'are halogen atoms, etc., Y is a hydrocarbon group P is a group 15 atom, and L is a Lewis base) (R is a hydrogen atom, n such as an organic group is 0 or more)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an olefin polymer, and more particularly to a method for producing a polymer obtained by polymerizing a cyclic olefin using a catalyst containing a specific transition metal compound as a main component. .

[0002]

2. Description of the Related Art In recent years, in the field of polymerization of olefins such as ethylene and propylene, with the advent of transition metal catalysts called metallocene catalysts, polymers having properties different from those of conventional ones can be produced, or very small amounts of catalysts can be produced. Are being made to produce a large amount of polymer by using the above method.

It has been proposed to apply such a metallocene catalyst to a cyclic olefin represented by norbornene. For example, Japanese Patent Application Laid-Open No. 2-173112 discloses isopropylidene (cyclopentadienyl) (fluorenyl).
Japanese Patent Application Laid-Open No. 5-194641 discloses a method for copolymerizing norbornene and ethylene using titanium dichloride as a catalyst component (tert-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dichloride. . Although these methods are excellent in that relatively high catalyst efficiency can be achieved,
It is not a sufficient method in that a cyclic olefin is polymerized at a high conversion to produce a polymer having a sufficiently high content of the cyclic olefin.

On the other hand, examples using a non-metallocene-based transition metal catalyst are disclosed in WO8702370 and
Japanese Patent Publication No. 230133 discloses an olefin polymerization method using a sulfur atom-bridged bisphenoxytitanium complex. The catalyst is cheaper and easier to synthesize than metallocene catalysts. However, the catalyst has low activity for the polymerization of cyclic olefins and cannot be said to be an industrially satisfactory method.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. That is, an object of the present invention is to polymerize a cyclic olefin with a very small amount of a catalyst at a high conversion rate,
An object of the present invention is to provide a method for producing an amorphous olefin polymer.

[0006]

Means for Solving the Problems In order to achieve the above object, the present inventors have intensively studied a catalyst for olefin polymerization, and have completed the present invention. That is, the present invention provides the following compound (A), and the following compound (B) and / or
Alternatively, a method for producing an olefin polymer in which a cyclic olefin represented by the general formula [II] is polymerized in the presence of a catalyst comprising the following compound (C);
The present invention relates to a method for producing an olefin polymer in which a cyclic olefin represented by the formula (1) and another monomer having copolymerizability with the cyclic olefin are copolymerized. (A) A transition metal compound represented by the following general formula [I]. (In the formula, M is a transition metal atom belonging to Group 4 of the periodic table of elements or a lanthanide series. A and A ′ each have 1 to 1 carbon atoms.
50 hydrocarbon groups, halogenated hydrocarbon groups, or hydrocarbon groups or halogenated hydrocarbon groups having an oxygen atom-containing substituent, and A and A ′ may be the same or different.
X and X 'are a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X and X' may be the same or different.
Y represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. O represents an oxygen atom, and P represents an atom belonging to Group 15 of the periodic table of the elements. L is a Lewis base and w is an integer of 0 or more. (B) Any one of the following (B1) to (B3) or a mixture of two or three of them (B1) Organoaluminum compound represented by general formula E ¹ _a AlZ _3-a (B2) General formula Cyclic aluminoxane having a structure represented by Al (E ² ) -O-｝ _b (B3) general formula E ³ ｛-Al (E ³ ) -O-｝ _c AlE ³
_A linear aluminoxane having a structure represented by ₂ , wherein E ^{1 to} E ³ are a hydrocarbon group having 1 to 8 carbon atoms;
All E ¹ , all E ² and all E ³ may be the same or different. Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different.
a represents a number of 0 to 3, b represents an integer of 2 or more, and c represents an integer of 1 or more. (C) any one of the following (C1) to (C3): (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C2) a general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- a boron compound represented by, (C3) the general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - boron compound represented by (wherein, B is a trivalent valence state boron atom And Q
^{1 to} Q ⁴ represent a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, a halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, 1
An alkoxy group containing -20 carbon atoms or an amino group containing 2-20 carbon atoms, which may be the same or different. G ⁺ is an inorganic or organic cation, L is a neutral Lewis base, (LH) ⁺
Is a Bronsted acid. ) (Wherein, R _{9 to} R ₂₀ each independently represent a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an amino group and an organic group having 1 to 20 carbon atoms, and R _{13 to} R ₁₆ represent a ring. May be formed. N represents an integer of 0 or more.)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the transition metal compound represented by the above general formula [I] in the present invention, M is the periodic table of elements (I
It is a transition metal atom belonging to Group 4 of the UPAC inorganic chemical nomenclature revised edition 1989) or a lanthanide series, and specific examples include a titanium atom, a zirconium atom, a hafnium atom and a samarium atom, and preferably a titanium atom , A zirconium atom or a hafnium atom.

A and A 'in the above formula [I] are a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group, a hydrocarbon group having an oxygen atom-containing substituent or a halogenated hydrocarbon group. Yes, specific examples include, for example, a (substituted) alkylene group, a (substituted) vinylene group, a (substituted) phenylene group, a (substituted) naphthylene group represented by the following general formula, and any combination thereof. However, the present invention is not limited to these.

(Substituted) alkylene group

(Substituted) vinylene group

(Substituted) phenylene group

(Substituted) naphthylene group

Here, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ and R ₈ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, a hydrocarbon group having an oxygen-containing substituent, or a halogen atom. Good. n ₁ , n ₂ , n ₃ , and n ₄ are integers of 1 to 5, preferably 1 or 2. l and m are 0
4 and 0 ≦ l + m ≦ 4, and x is 0 to
And y is an integer of 0 to 4.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈
As specific examples of the hydrocarbon group, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, secondary butyl group, tertiary butyl group, normal pentyl group, neopentyl group , Normal hexyl group, normal octyl group, phenyl group, 2-
Methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,
6-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3
Examples thereof include a 6-trimethylphenyl group, a 2,3,4,5-tetramethylphenyl group, a 2,3,4,6-tetramethylphenyl group, and a pentamethylphenyl group.

Examples of the halogenated hydrocarbon group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a 1,1-difluoroethyl group,
1,2-difluoroethyl group, 1,1,2-trifluoroethyl group, perfluoroethyl group, chloromethyl group,
Dichloromethyl group, chloroethyl group, 1,1-dichloroethyl group, 1,2-dichloroethyl group, 1,1,2-trichloroethyl group, 1,1,2,2-tetrachloroethyl group, bromomethyl group, dibromomethyl Group, bromoethyl group, 1,1-dibromoethyl group, 1,2-dibromoethyl group, 1,1,2-tribromoethyl group, 1,1,
2,2-tetrabromoethyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group , 2,6
-Difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,
3,6-trifluorophenyl group, 2,3,4,5-tetrafluorophenyl group, 2,3,4,6-tetrafluorophenyl group, perfluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 2,3,4-trichlorophenyl group, 2,3,5-tri Chlorophenyl group, 2,3,6-
Trichlorophenyl group, 2,3,4,5-tetrachlorophenyl group, 2,3,4,6-tetrachlorophenyl group, pentachlorophenyl group, 2-bromophenyl group,
3-bromophenyl group, 4-bromophenyl group, 2,3
-Dibromophenyl group, 2,4-dibromophenyl group,
2,5-dibromophenyl group, 2,6-dibromophenyl group, 2,3,4-tribromophenyl group, 2,3,5
-A tribromophenyl group, a 2,3,6-tribromophenyl group, a 2,3,4,5-tetrabromophenyl group,
Examples thereof include a 2,3,4,6-tetrabromophenyl group and a pentabromophenyl group.

Examples of the hydrocarbon group having an oxygen-containing substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a primary butoxy group, a secondary butoxy group, a tertiary butoxy group, an isobutoxy group and a phenoxy group. Group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Of these, A and A 'are preferably
A (substituted) phenylene group, wherein R _Five, R₆As a
Tyl group, ethyl group, normal propyl group, isopropyl
Group, normal butyl group, secondary butyl group, tertiary butyl group
Group, phenyl group, methoxy group, ethoxy group, chlorine atom,
A bromine atom, and more preferably A and A ′
1,2-phenylene, 1,2- (6-methylphenylene
), 1,2- (6-tert-butylphenylene), 1,
2- (4,6-dimethylphenylene), 1,2- (4
6-di-tert-butylphenylene), 1,2- (6-
Tertiary butyl-4-methylphenylene), 1,2- (6-
Tert-butyl-4-methoxyphenylene), 1,2-
(6-tert-butyl-4-bromophenylene).

X and X 'in the transition metal compound represented by the above general formula [I] are a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a hydrocarbon group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a phenyl group, and a benzyl group. Can be Among these, a chlorine atom, a methyl group and a benzyl group are preferred.

P in the transition metal compound represented by the above general formula [I] represents an atom belonging to Group 15 of the periodic table of elements, and is, for example, a nitrogen atom or a phosphorus atom. Preferably P is a phosphorus atom.

In the transition metal compound represented by the general formula [I], Y represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group.

As specific examples, hydrocarbon groups include methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, normal pentyl, neopentyl Group, normal hexyl group, normal octyl group, phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, propylphenyl group, isopropylphenyl group, primary Examples include a butylphenyl group, a secondary butylphenyl group, a tertiary butylphenyl group, a naphthyl group, and the like.

Examples of the halogenated hydrocarbon group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a 1,1-difluoroethyl group,
1,2-difluoroethyl group, 1,1,2-trifluoroethyl group, perfluoroethyl group, chloromethyl group,
Dichloromethyl group, chloroethyl group, 1,1-dichloroethyl group, 1,2-dichloroethyl group, 1,1,2-trichloroethyl group, 1,1,2,2-tetrachloroethyl group, bromomethyl group, dibromomethyl Group, bromoethyl group, 1,1-dibromoethyl group, 1,2-dibromoethyl group, 1,1,2-tribromoethyl group, 1,1,
2,2-tetrabromoethyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group , 2,6
-Difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,
3,6-trifluorophenyl group, 2,3,4,5-tetrafluorophenyl group, 2,3,4,6-tetrafluorophenyl group, perfluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 2,3,4-trichlorophenyl group, 2,3,5-tri Chlorophenyl group, 2,3,6-
Trichlorophenyl group, 2,3,4,5-tetrachlorophenyl group, 2,3,4,6-tetrachlorophenyl group, pentachlorophenyl group, 2-bromophenyl group,
3-bromophenyl group, 4-bromophenyl group, 2,3
-Dibromophenyl group, 2,4-dibromophenyl group,
2,5-dibromophenyl group, 2,6-dibromophenyl group, 2,3,4-tribromophenyl group, 2,3,5
-A tribromophenyl group, a 2,3,6-tribromophenyl group, a 2,3,4,5-tetrabromophenyl group,
Examples thereof include a 2,3,4,6-tetrabromophenyl group and a pentabromophenyl group. Among them, Y is preferably a (substituted) phenyl group.

L in the transition metal compound represented by the above general formula [I] is a Lewis base. w is an integer of 0 or more, preferably 0 or 1. Specific examples of Lewis bases include, for example, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, tertiary butyl methyl ether, furan, tetrahydrofuran, methyltetrahydrofuran, dimethylthioether, diethylthioether, dipropylthioether, dibutylthioether, thiophene , Tetrahydrothiophene, methyltetrahydrothiophene, trimethylamine, triethylamine, trinormalpropylamine, triisopropylamine, trinormalbutylamine, trinormalhexylamine, dimethylamine,
Diethylamine, dinormalpropylamine, diisopropylamine, dinormalbutylamine, dinormalhexylamine, methylamine, ethylamine, normalpropylamine, isopropylamine, normalbutylamine, normalhexylamine, pyridine, methylpyridine, dimethylpyridine, trimethylpyridine, tetra Examples include methylpyridine, pentamethylpyridine, piperidine, methylpiperidine, dimethylpiperidine, trimethylpiperidine, tetramethylpiperidine, pentamethylpiperidine, acetonitrile, propiononitrile, butanonitrile, hexanonitrile, benzonitrile and the like.

Specific examples of the compound represented as the transition metal compound represented by the general formula [I] include, for example, 2,
2 ′-(phenylphosphido) bisphenoxytitanium dichloride, 2,2 ′-(phenylphosphido) bis (6-methylphenoxy) titanium dichloride,
2,2 ′-(phenylphosphido) bis (6-tert-butylphenoxy) titanium dichloride, 2,2′-
(Phenylphosphido) bis (6-phenylphenoxy) titanium dichloride, 2,2 ′-(phenylphosphido) bis (4,6-dimethylphenoxy) titanium dichloride, 2,2 ′-(phenylphosphido) bis (4 , 6-Di-tert-butylphenoxy) titanium dichloride, 2,2 '-(phenylphosphido) bis (6-tert-butyl-4-methylphenoxy)
Titanium dichloride, 2,2 '-(phenylphosphido) bis (6-methyl-4-tert-butylphenoxy) titanium dichloride, 2,2'-(phenylphosphido) bis (3-tert-butyl-4) , 6-Dimethylphenoxy) titanium dichloride, 2,2 '-(phenylphosphido) bis (4,6-di-tert-butyl-
3-methylphenoxy) titanium dichloride, 2,
2 ′-(phenylphosphido) bis (6-tert-butyl-4-fluorophenoxy) titanium dichloride,
2,2 '-(phenylphosphido) bis (6-tert-butyl-4-chlorophenoxy) titanium dichloride, 2,2'-(phenylphosphido) bis (6-tert-butyl-4-bromophenoxy) ) Titanium dichloride, 2,2 '-(phenylphosphido) bis (6-tert-butyl-4-methoxyphenoxy) titanium dichloride, 2,2'-(phenylphosphido) bis (6
-Tert-butyl-4-ethoxyphenoxy) titanium dichloride, 2,2 '-(phenylphosphido) bis (6-tert-butyl-4-normalpropoxyphenoxy) titanium dichloride, 2,2'-(phenylphospho) Fido) bis (6-tert-butyl-4-isopropoxyphenoxy) titanium dichloride,

2,2 '-(4-methylphenylphosphido) bisphenoxytitanium dichloride, 2,2'
-(4-methylphenylphosphide) bis (6-methylphenoxy) titanium dichloride, 2,2 '-(4
-Methylphenylphosphide) bis (6-tert-butylphenoxy) titanium dichloride, 2,2 '-(4
-Methylphenylphosphide) bis (6-phenylphenoxy) titanium dichloride, 2,2 ′-(4-methylphenylphosphide) bis (4,6-dimethylphenoxy) titanium dichloride, 2,2 ′-(4-methyl Phenylphosphido) bis (4,6-di-tert-butylphenoxy) titanium dichloride, 2,2′-
(4-methylphenylphosphide) bis (6-tert-butyl-4-methylphenoxy) titanium dichloride, 2,2 ′-(4-methylphenylphosphido) bis (6-methyl-4-tert-butyl) Phenoxy) titanium dichloride, 2,2 ′-(4-methylphenylphosphide) bis (3-tert-butyl-4,6-dimethylphenoxy) titanium dichloride, 2,2 ′-(4-
Methylphenylphosphido) bis (4,6-di-tert-butyl-3-methylphenoxy) titanium dichloride, 2,2 ′-(4-methylphenylphosphido) bis (6-tert-butyl-4-) Fluorophenoxy) titanium dichloride, 2,2 ′-(4-methylphenylphosphide) bis (6-tert-butyl-4-chlorophenoxy) titanium dichloride, 2,2 ′-(4-methylphenylphosphide) bis (6-tert-butyl-4-
Bromophenoxy) titanium dichloride, 2,2 '
-(4-methylphenylphosphido) bis (6-tert-butyl-4-methoxyphenoxy) titanium dichloride, 2,2 '-(4-methylphenylphosphido) bis (6-tert-butyl-4-ethoxy) Phenoxy) titanium dichloride, 2,2 ′-(4-methylphenylphosphide) bis (6-tert-butyl-4-n-propoxyphenoxy) titanium dichloride, 2,2 ′
-(4-methylphenylphosphido) bis (6-tert-butyl-4-isopropoxyphenoxy) titanium dichloride,

2,2 ′-(4-tert-butylphenylphosphide) bisphenoxytitanium dichloride,
2,2 ′-(4-tert-butylphenylphosphide) bis (6-methylphenoxy) titanium dichloride,
2,2 '-(4-tert-butylphenylphosphido) bis (6-tert-butylphenoxy) titanium dichloride, 2,2'-(4-tert-butylphenylphosphido) bis (6-phenyl) Phenoxy) titanium dichloride, 2,2 ′-(4-tert-butylphenylphosphide) bis (4,6-dimethylphenoxy) titanium dichloride, 2,2 ′-(4-tert-butylphenylphosphido) bis (4,6-di-tert-butylphenoxy) titanium dichloride, 2,2 ′-(4-tert-butylphenylphosphide) bis (6-tert-butyl-
4-methylphenoxy) titanium dichloride, 2,
2 '-(4-tert-butylphenylphosphido) bis (6-methyl-4-tert-butylphenoxy) titanium dichloride, 2,2'-(4-tert-butylphenylphosphido) bis (3 -Tert-butyl-4,6-dimethylphenoxy) titanium dichloride, 2,2'-
(4-tert-butylphenylphosphide) bis (4,6
-Di-tert-butyl-3-methylphenoxy) titanium dichloride, 2,2 '-(4-tert-butylphenylphosphide) bis (6-tert-butyl-4-fluorophenoxy) titanium dichloride, , 2 '-(4
-Tert-butylphenyl phosphide) bis (6-tert-butyl-4-chlorophenoxy) titanium dichloride, 2,2 '-(4-tert-butylphenylphosphido) bis (6-tert-butyl) -4-bromophenoxy)
Titanium dichloride, 2,2 ′-(4-tert-butylphenylphosphide) bis (6-tert-butyl-4-
Methoxyphenoxy) titanium dichloride, 2,
2 '-(4-tert-butylphenylphosphido) bis (6-tert-butyl-4-ethoxyphenoxy) titanium dichloride, 2,2'-(4-tert-butylphenylphenylphosphido) bis (6 -Tert-butyl-4-n-propoxyphenoxy) titanium dichloride,
2,2 '-(4-tert-butylphenylphosphido) bis (6-tert-butyl-4-isopropoxyphenoxy) titanium dichloride, 2,2'-(phenylphosphido) bisphenoxy (tetrahydrofuran) titanium Dichloride, 2,2 ′-(phenylphosphide) bis (6-methylphenoxy) (tetrahydrofuran) titanium dichloride, 2,2 ′-(phenylphosphide) bis (6-tert-butylphenoxy) (tetrahydrofuran) titanium dichloride , 2, 2'-
(Phenylphosphido) bis (6-phenylphenoxy) (tetrahydrofuran) titanium dichloride,
2,2 '-(phenylphosphido) bis (4,6-dimethylphenoxy) (tetrahydrofuran) titanium dichloride, 2,2'-(phenylphosphido) bis (4,6-di-tert-butylphenoxy) ( Tetrahydrofuran) titanium dichloride, 2,2 '-(phenylphosphido) bis (6-tert-butyl-4-methylphenoxy) (tetrahydrofuran) titanium dichloride, 2,2'-(phenylphosphido) bis (6-
Methyl-4-tert-butylphenoxy) (tetrahydrofuran) titanium dichloride, 2,2 ′-(phenylphosphido) bis (3-tert-butyl-4,6-dimethylphenoxy) (tetrahydrofuran) titanium dichloride, 2, 2 '-(phenylphosphido) bis (4,6-di-tert-butyl-3-methylphenoxy)
(Tetrahydrofuran) titanium dichloride, 2,
2 '-(phenylphosphido) bis (6-tert-butyl-4-fluorophenoxy) (tetrahydrofuran) titanium dichloride, 2,2'-(phenylphosphido) bis (6-tert-butyl-4-chloro) Phenoxy)
(Tetrahydrofuran) titanium dichloride, 2,
2 '-(phenylphosphido) bis (6-tert-butyl-4-bromophenoxy) (tetrahydrofuran) titanium dichloride, 2,2'-(phenylphosphido) bis (6-tert-butyl-4-methoxy) Phenoxy) (tetrahydrofuran) titanium dichloride,
2,2 ′-(phenylphosphido) bis (6-tert-butyl-4-ethoxyphenoxy) (tetrahydrofuran) titanium dichloride, 2,2 ′-(phenylphosphido) bis (6-tert-butyl-4) -Normalpropoxyphenoxy) (tetrahydrofuran) titanium dichloride, 2,2 '-(phenylphosphido) bis (6-tert-butyl-4-isopropoxyphenoxy)
(Tetrahydrofuran) titanium dichloride and the like.

The catalyst of the present invention comprises the compound represented by the above general formula [I] and the following compound (B) and / or the following compound (C). (B) Any of the following (B1) to (B3) or a mixture of two or three of them (B1) Organoaluminum compound represented by general formula E ¹ _a AlZ _3-a (B2) General formula ｛-Al A cyclic aluminoxane having a structure represented by (E ² ) -O-｝ _b (B3) a general formula E ³ ｛-Al (E ³ ) -O-｝ _c AlE ³
_A linear aluminoxane having a structure represented by ₂ , wherein E ^{1 to} E ³ are a hydrocarbon group having 1 to 8 carbon atoms;
All E ¹ , all E ² and all E ³ may be the same or different. Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different.
a represents a number of 0 to 3, b represents an integer of 2 or more, and c represents an integer of 1 or more. (C) any one of the following (C1) to (C3): (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C2) a general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- a boron compound represented by, (C3) the general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - boron compound represented by (wherein, B is a trivalent valence state boron atom And Q
^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, a halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, 1
An alkoxy group containing -20 carbon atoms or an amino group containing 2-20 carbon atoms, which may be the same or different. G ⁺ is an inorganic or organic cation, L is a neutral Lewis base, (LH) ⁺
Is a Bronsted acid. )

[0028] As specific examples of the general formula E ¹ _a AlZ organoaluminum compound represented by the _3-a (B1), trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as tri-hexyl aluminum; Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride; alkylaluminums such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride Dichloride; dimethyla Examples thereof include dialkylaluminum hydrides such as luminium hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride. Preferably, it is a trialkylaluminum, and more preferably, triethylaluminum and triisobutylaluminum.

[0029] In the general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having the structure represented by _b (B2), the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3 2 In a linear aluminoxane (B3) having the structure shown,
Specific examples of E ² and E ³ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group,
Examples thereof include an alkyl group such as an isobutyl group, a normal pentyl group, and a neopentyl group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ²
And E ³ are a methyl group and an isobutyl group, and b is 2 to 4
0 and c is 1 to 40.

The above aluminoxane is made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution prepared by dissolving a trialkylaluminum (for example, trimethylaluminum) in a suitable organic solvent (benzene, aliphatic hydrocarbon, or the like) is brought into contact with water. In addition, a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt (for example, copper sulfate hydrate or the like) containing water of crystallization can be exemplified.

Specific examples of the boron compound (C1) represented by the above general formula BQ ¹ Q ² Q ³ include tris (pentafluorophenyl) borane and tris (2,3,5,6-
Tetrafluorophenyl) borane, tris (2,3,
4,5-tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, and the like. Is most preferably tris (pentafluorophenyl) borane.

As specific examples of the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ which is an inorganic cation includes a ferrocenium cation and an alkyl-substituted cation. G ⁺ , which is an organic cation including a ferrocenium cation and a silver cation, includes a triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - , the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistriborate) Fluoromethylphenyl) borate and the like.

Specific examples of these combinations include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

General formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^-
As a specific example of the boron compound (C3) represented by the formula, (LH) ⁺ which is a Bronsted acid includes trialkyl-substituted ammonium, N, N-dialkylanilinium,
Examples thereof include dialkylammonium and triarylphosphonium. Examples of (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include the same as described above.

Specific combinations of these include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal) Butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N- 2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5
-Bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl)
Examples thereof include borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate. Most preferably, tri (normal butyl) ammonium tetrakis (pentane) Fluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

The catalyst in the present invention is preferably one comprising the transition metal compound (A), compound (B) and compound (C) represented by the above general formula [I].

In the present invention, the transition metal compound (A) represented by the general formula [I] and the compound (B) and / or the compound (C) are charged and used in an arbitrary order during polymerization. Alternatively, a reaction product obtained by previously contacting any combination of these compounds may be used.

The amount of each catalyst component used is such that the molar ratio of compound (B) or compound (C) / transition metal compound (A) is usually 0.01 to 10000, preferably 0.5 to 2000.
It is desirable to use each component so as to fall within the range. Regarding the concentration when each catalyst component is used in a solution state, the transition metal compound (A) is usually 0.0001 to 5 mmol / mol.
It is desirable to use it in liters, preferably in the range of 0.001 to 1 mmol / l. Usually 0.00001 based on the sum of all monomers used
To 1 mol%, preferably 0.0001 to 0.1 mol%.

The cyclic olefin used in the present invention is different from the cyclic olefin in that four or more carbon atoms which may have various substituents form a ring, and one carbon-carbon double bond is contained in the ring. Is a compound containing. Such cyclic olefins include monocyclic olefins such as cyclobutene, cyclopentene and cyclohexene; 3-methylcyclopentene;
Substituted monocyclic olefins such as 3-methylcyclohexene;
Polycyclic olefins such as norbornene and 1,2-dihydrodicyclopentadiene; 1-methylnorbornene and 5-
Examples include substituted polycyclic olefins such as methyl norbornene.

The cyclic olefin is preferably a compound represented by the following general formula [II]. (Wherein, R _{9 to} R ₂₀ each independently represent a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an amino group and an organic group having 1 to 20 carbon atoms, and R _{13 to} R _{16 each} represent a ring. May be formed. N represents an integer of 0 or more.)

Here, the substituent has 1 to 20 carbon atoms.
Specific examples of the organic group of are alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group and dodecyl group; aryl groups such as phenyl group, tolyl group and naphthyl group; benzyl group and phenethyl group Aralkyl groups such as groups; alkylidene groups such as methylidene and ethylidene groups; alkenyl groups such as vinyl and allyl groups; alkoxy groups such as methoxy and ethoxy groups; aryloxy groups such as phenoxy groups; methoxycarbonyl groups and ethoxycarbonyl groups Acyloxy group such as acetyl group; acyloxy group such as acetyloxy group; silyl group such as trimethylsilyl group; alkylamino group such as dimethylamino group, diethylamino group; carboxyl group; cyano group; Atoms of, aryl and aralkyl groups Part is a halogen atom, a hydroxyl group,
Examples include groups substituted with an amino group, a carboxyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a silyl group, an alkylamino group, or a cyano group. A preferred substituent is a hydrogen atom;
Alkyl group, aryl group having 1 to 20 carbon atoms, 1 carbon atom
An aralkyl group having 1 to 20 carbon atoms, an alkylidene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, and a cyano group having 1 to 20 carbon atoms. A substituent selected from the group consisting of groups. n is an integer of 0 or more, preferably 0 ≦
It is an integer satisfying n ≦ 3, and more preferably n is 0 or 1.

Specific examples of preferred cyclic olefins represented by the general formula [II] include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene and tetrabenzylnorbornene. Cyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, ethylidene norbornene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxy Norbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5
-Methyl-5-methoxycarbonylnorbornene, 5-
Cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-cyanotetracyclododecene and the like can be mentioned.

In the polymerization, these cyclic olefins are used alone or in combination. In addition, the copolymer has copolymerizability with the cyclic olefin in a range that does not impair the excellent properties of the cyclic olefin polymer, that is, in a range where the proportion of the cyclic olefin in all the monomers is generally less than 10% by weight. Can be used together with cyclic olefins. Examples of such other monomers include α-olefins such as ethylene, propylene, 1-butene, 4-methylpentene-1, 1-hexene and 1-octene; alkenyl aromatic hydrocarbons such as styrene; methyl vinyl ether; Alkyl vinyl ethers such as ethyl vinyl ether; unsaturated halogenated hydrocarbons such as vinyl chloride; α, β-unsaturated carboxylic esters such as methyl acrylate, ethyl acrylate and methyl methacrylate; unsaturated nitriles such as acrylonitrile; Vinyl acid and the like can be mentioned. It is preferably an α-olefin, and more preferably ethylene.

In the present invention, the polymerization method is not particularly limited, but examples thereof include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; Halogenated hydrocarbons such as methylene dichloride and ethylene dichloride; alcohols such as methanol, ethanol, propanol and butanol; ethers such as diethyl ether and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, or a mixture of two or more Solvent polymerization using a solvent as a liquid, slurry polymerization, gas-phase polymerization in a gaseous monomer, high-pressure ionic polymerization, or the like is possible, and continuous polymerization or batch polymerization is also possible.

In the solvent polymerization or slurry polymerization, the polymerization temperature can be in the range of -50 to 200 ° C.
The temperature is preferably in the range of 0 to 100 ° C, and the polymerization pressure is from normal pressure to 6 ° C.
0 kg / cm ² G is preferred. In the gas phase polymerization, the polymerization temperature is 60 to 120 ° C., and the polymerization pressure is 1 to 30 kg / c.
m ² G is preferred. In high pressure ionic polymerization, the polymerization temperature is 1
50-300 ° C, polymerization pressure 300-2,500 kg / c
m ² G is preferred. In general, the polymerization time is appropriately determined depending on the kind of a target polymer and a reaction apparatus.
It can range from minutes to 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.

[0046]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the Examples.

The ligands and complexes in the examples were identified by ¹ H-NMR measurement (EX-270 manufactured by JEOL Ltd.). [Η] refers to the intrinsic viscosity measured at 135 ° C. using tetralin as a solvent using an Ubbelohde viscometer.

Reference Example 1 (1) Bis (2-hydroxy-3-tert-butyl-5-
Synthesis of methylphenyl) phenylphosphine In a nitrogen atmosphere, 10.41 g of 2-tert-butyl-4-methylphenylmethoxymethyl ether was dissolved in 100 ml of tetrahydrofuran, and 31.3 ml of n-butyllithium (-1.6 M at -78 ° C) was dissolved. (n-hexane solution) was added dropwise, and then the temperature was raised to room temperature and stirring was continued for 12 hours. Hexamethylphosphoric amide 10m
After cooling to -78 ° C, 4.71 g of dichlorophenylphosphine was added, and the temperature was raised to room temperature.
The mixture was refluxed for another 30 minutes. After cooling, water was added to stop the reaction, and the mixture was extracted with toluene. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and the solvent was distilled off. 200 ml of ethanol and 15 ml of 10% hydrochloric acid aqueous solution are added to the obtained residue.
Was added and refluxed for 2 hours. After cooling, water was added to stop the reaction, followed by extraction with toluene. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and the solvent was distilled off. The residue was isolated and purified by silica gel column chromatography to obtain 4.3 g of bis (2-hydroxy-3-tert-butyl-5-methylphenyl) phenylphosphine as colorless crystals.
Melting point, 117-118 ° C ¹ H-NMR (CDCl ₃ , 270 MHz) δ 1.39 (s, 18H), 2.18 (s, 6H),
6.26 (d, 2H, J = 8.3 Hz), 6.73 (d
d, 2H, J = 6.3, 2.0 Hz), 7.14 (d,
2H, J = 2.0 Hz), 7.23-7.36 (m, 5
H)

(2) 2,2 '-(phenyl phosphide)
Synthesis of bis (6-tert-butyl-4-methylphenoxy) titanium dichloride Under an argon atmosphere, bis (2-hydroxy-3-tert-butyl-5-methylphenyl) phenylphosphine 0.1.
A solution of 435 g and 20 ml of toluene was kept at 20 ° C.
0.11 ml of titanium tetrachloride was added dropwise to this solution. The solution was stirred for 12 hours, the insolubles were filtered off, the filtrate was concentrated, recrystallized from hexane, and 2,2 '-(phenylphosphido) bis (6-tert-butyl-4-methylphenoxy). ) 0.30 g of titanium dichloride solid was obtained. ¹ H-NMR (CD ₂ Cl ₂ , 270 MHz) δ 1.39 (s, 18H), 2.13 (s, 6H),
6.92-7.80 (m, 9H)

Example 1 8 ml of dehydrated toluene, 6 ml of a 5 mol / l toluene solution of norbornene (30 mmol as norbornene) and a toluene solution of methylalumoxane [Tosoh Corporation] were placed in a 300 ml round bottom separable flask substituted with ethylene. Akzo Co., Ltd .: MMAO, type 3A,
Al 6.0 wt%] and 0.62 ml (1.2 mmol as Al) were charged and heated to form a homogeneous solution at 30 ° C. Here, 0.3 μmol of 2,2 ′-(phenylphosphido) bis (3-tert-butyl-5-methylphenoxy) titanium dichloride was added to 1.2 m of dehydrated toluene.
The solution dissolved in 1 was added, and stirring was continued at 30 ° C. for 10 minutes under an ethylene atmosphere. Thereafter, the reaction solution was poured into a mixture of 5 ml of hydrochloric acid and 300 ml of methanol, and the precipitated white solid was filtered off. The solid was washed with methanol and dried under reduced pressure to obtain 655 mg of a polymer. This value corresponds to 13100 kg / mol-Ti · hr as the catalytic activity. The polymer was a high molecular weight polymer insoluble in tetralin at 135 ° C. and was a high-concentration norbornene-containing copolymer having a melting point of 230 ° C. or higher.

Example 2 8 ml of dehydrated toluene, 6 ml of a toluene solution of norbornene having a concentration of 5 mol / l (30 mmol as norbornene), and a toluene solution of triisobutylaluminum (Tosoh Corporation) were placed in a 300 ml round bottom separable flask substituted with ethylene. 75 μl (manufactured by Akzo) (7 as Al)
5 μmol) and 0.3 μmol of 2,2 ′-(phenylphosphido) bis (3-tert-butyl-5-methylphenoxy) titanium dichloride were added to dehydrated toluene 1.2
The solution dissolved in ml was charged and heated to obtain a homogeneous solution at 30 ° C. 1.8 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added thereto, and stirring was continued at 30 ° C. for 10 minutes in an ethylene atmosphere. Thereafter, the reaction solution was diluted with 5 ml of hydrochloric acid and 300 ml of methanol.
And the precipitated white solid was collected by filtration. The solid was washed with methanol and dried under reduced pressure to give polymer 638.
mg was obtained. This value is 12760 kg / catalyst activity.
Equivalent to mol-Ti · hr. [Η] of the polymer is 2.6.
It was 9 dl / g.

Example 3 The same operation as in Example 1 was performed except that the ethylene atmosphere in Example 1 was changed to a nitrogen atmosphere.
72 mg were obtained. This value is 11440 k as the catalytic activity.
g / mol-Ti · hr.

Comparative Example 1 2,2 '-(phenylphosphido) bis (3-tert-butyl-5-methylphenoxy) titanium dichloride in Example 1 was synthesized by the method described in JP-A-3-16388. The same operation as in Example 1 was carried out except for using the obtained (tert-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dichloride, to obtain 376 mg of a polymer. The catalytic activity per mole of titanium per hour was 7520 kg / mol-Ti · hr. [Η] of the polymer is 0.89 d
1 / g.

Comparative Example 2 The 2,2 '-(phenylphosphido) bis (3-tert-butyl-5-methylphenoxy) titanium dichloride in Example 3 was replaced with the (tert-butylamido) dimethyl The same operation as in Example 3 was carried out except that the stirring time was changed from 10 minutes to 1 hour to tetramethylcyclopentadienyl) silanetitanium dichloride, to obtain 4 mg of a polymer. The catalyst activity per mole of titanium and per hour was 13 kg / mol-Ti · hr.

Reference Example 2 (1) Synthesis of 2,2 '-(phenylphosphido) bis (3-tert-butyl-5-methylphenoxy) (tetrahydrofuran) titanium dichloride Under argon atmosphere, 50 ml equipped with a stirrer Bis (2-hydroxy-3-tert-butyl-5-
Methylphenyl) phenylphosphine 0.435 g of T
After adding 10 ml of HF solution and cooling to −78 ° C., 1.6M
1.25 ml of n-BuLi hexane solution was added dropwise.
After heating to room temperature, the mixture was stirred for 12 hours to obtain a white slurry. In another reaction vessel, 0.5 ml of a 1 M toluene solution of titanium tetrachloride was frozen in 10 ml (-196 ° C).
Added to THF. The mixture was heated to -78 ° C to obtain a yellow solution. The above-mentioned white slurry liquid was dropped into this solution, and 12
The solution was warmed to room temperature while stirring for hours. The solvent was removed from the resulting dark red solution, and the residue was extracted with toluene. The mother liquor was concentrated, n-hexane was added, the precipitate was filtered off and washed with n-hexane, and 2,2 ′-(phenylphosphido) bis (6-tert-butyl-4-methylphenoxy) (tetrahydrofuran ) 0.30 g of brown powder of titanium dichloride was obtained. ¹ H-NMR (C ₆ D
₆ , 270 MHz) δ 1.09 (M, 4H), 1.63 (s, 18H),
1.98 (s, 6H), 4.06 (m, 4H), 6.9
6-7.18 (m, 7H), 7.79 (m, 2H)

Example 4 The 2,2 '-(phenylphosphide) bis (3-tert-butyl-5-methylphenoxy) titanium dichloride of Example 1 was replaced with 2,2'-(phenylphosphide).
The same operation as in Example 1 was carried out except that bis (3-tert-butyl-5-methylphenoxy) (tetrahydrofuran) titanium dichloride was used, and a polymer 581 m was obtained.
g was obtained. The catalyst activity per mole of titanium and per hour was 11620 kg / mol-Ti · hr.

Example 5 The 2,2 '-(phenylphosphide) bis (3-tert-butyl-5-methylphenoxy) titanium dichloride of Example 3 was replaced with 2,2'-(phenylphosphide).
The same operation as in Example 3 was carried out except that bis (3-tert-butyl-5-methylphenoxy) (tetrahydrofuran) titanium dichloride was used.
g was obtained. The catalytic activity per hour per mole of titanium was 10340 kg / mol-Ti · hr.

Reference Example 3 (1) Synthesis of 2-bromo-4-methoxy-6-tert-butylphenol 2-tert-butyl-4-methoxyphenol 18.03
g of dimethylformamide in 100 ml of solution under stirring.
A solution of 17.80 g of -bromosuccinimide in 100 ml of dimethylformamide was added dropwise at 0 ° C, the temperature was raised to room temperature, and stirring was continued for 5 hours. The solvent was removed under reduced pressure, water was added to the residue, and the mixture was extracted with ethyl acetate. The combined organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and then the solvent was removed. The residue was purified by silica gel column chromatography to obtain 12.31 g of oily 2-bromo-4-methoxy-6-tert-butylphenol. ¹ H-NMR
(CDCl ₃ , 270 MHz) δ 1.38 (s, 9H), 3.74 (s, 3H),
5.42 (s, 1H), 6.85 (d, 1H, J = 3.
0 Hz), 6.88 (d, 1H, J = 3.0 Hz)

(2) Synthesis of 1-bromo-2-methoxymethyloxy-3-tertiary butyl-5-methoxybenzene 2.40 g of sodium hydride (60%) in 50 ml of TH
2-Bromo-4-methoxy- at 0 ° C under stirring.
5-Tertiary butylphenol 12.31 g of THF 50
ml solution was added dropwise. Two hours later, a THF solution of 6.04 g of methoxymethyl chloride (80%) was added dropwise. After the temperature was raised to room temperature, stirring was continued for 10 hours. The reaction solution was cooled to 0 ° C., water was added, and the aqueous layer was extracted with toluene. The combined organic layers were washed with saturated saline, dried over anhydrous sodium sulfate, and then the solvent was removed. The residue was purified by silica gel column chromatography to obtain 8.72 g of 1-bromo-2-methoxymethyloxy-3-tert-butyl-5-methoxybenzene as a colorless oil. ¹ H-NMR (CDCl ₃ , 27
0 MHz) δ 1.41 (s, 9H), 3.68 (s, 3H),
3.75 (s, 3H), 5.17 (s, 2H), 6.8
7 (d, 1H, J = 3.0 Hz), 6.94 (d, 1
H, J = 3.0 Hz)

(3) Synthesis of bis (2-hydroxy-3-tert-butyl-5-methoxyphenyl) phenylphosphine 2-tert-butyl-4-methoxy-6 in a nitrogen atmosphere
A tetrahydrofuran solution of 8.72 g of bromophenylmethoxymethyl ether was added dropwise to a slurry of 1.05 g of magnesium and a catalytic amount of iodine in tetrahydrofuran,
After the completion of the dropwise addition, the mixture was refluxed for 1 hour. The resulting homogeneous solution is -7
After cooling to 8 ° C., dichlorophenylphosphine 2.6
8 g of tetrahydrofuran solution was added, and the temperature was raised to room temperature.
Stirring was continued for another 12 hours. Water was added to stop the reaction, and the mixture was extracted with toluene. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and the solvent was distilled off. Ethanol and a 10% aqueous hydrochloric acid solution were added to the obtained residue, and the mixture was refluxed for 2 hours. After cooling, water was added to stop the reaction, and toluene (20
0 ml × 2). The organic layer was washed with brine, dried over anhydrous sodium sulfate, and the solvent was distilled off. The residue was isolated and purified by silica gel column chromatography to obtain 3.83 g of colorless crystals of bis (2-hydroxy-3-tert-butyl-5-methoxyphenyl) phenylphosphine. Melting point, 111-112 ° C ¹ H-NMR (CDC
l ₃ , 270 MHz) δ 1.39 (s, 18H), 3.59 (s, 6H),
5.96 (d, 2H, J = 7.9 Hz), 6.49 (d
d, 2H, J = 6.0, 2.0 Hz), 7.05 (d,
2H, 2.0Hz), 7.26-7.49 (m, 5H)

(4) 2,2 ′-(phenyl phosphide)
Bis (6-tert-butyl-4-methoxyphenoxy)
Synthesis of (tetrahydrofuran) titanium dichloride Under an argon atmosphere, bis (2-hydroxy-3-tert-butyl-5-methoxyphenyl) phenylphosphine 0.1.
1.6 M at −78 ° C. in a solution of 233 g of THF 10 ml
0.63 ml of an n-BuLi hexane solution was added dropwise, and the mixture was heated to room temperature and stirred for 12 hours to obtain a white slurry. In another reaction vessel, 1.0 ml of a 1M toluene solution of titanium tetrachloride was added to 10 ml of frozen (-196 ° C.) THF
Added. The mixture was heated to -78 ° C to obtain a yellow solution.
The above-mentioned white slurry liquid was dropped into this solution, and the solution was heated to room temperature while stirring for 12 hours. The formed dark red solution was removed, and the residue was extracted with toluene. The mother liquor was concentrated, n-hexane was added, the precipitate was filtered off and washed with n-hexane, and 2,2 ′-(phenylphosphido) bis (6-tert-butyl-4-methoxyphenoxy) (tetrahydrofuran ) Titanium dichloride powder 0.1
5 g were obtained. ¹ H-NMR (CDCl ₃ , 270 MH
z) δ 1.15 (m, 4H), 1.60 (s, 18H),
3.22 (s, 3H), 4.04 (m, 4H), 6.7
7 (dd, 2H, J = 7.0, 3.0 Hz), 7.01
(D, 2H, J = 3.0 Hz), 7.08 (m, 3
H), 7.74 (m, 2H)

Example 6 The 2,2 '-(phenylphosphide) bis (3-tert-butyl-5-methylphenoxy) titanium dichloride of Example 1 was replaced with 2,2'-(phenylphosphide).
Bis (6-tert-butyl-4-methoxyphenoxy)
The same operation as in Example 1 was carried out, except that (tetrahydrofuran) titanium dichloride was used.
3 mg were obtained. The catalytic activity per hour per mole of titanium was 10260 kg / mol-Ti · hr.

Example 7 2,2 ′-(Phenylphosphido) bis (3-tert-butyl-5-methylphenoxy) titanium dichloride in Example 3 was replaced with 2,2 ′-(phenylphospho) described in Example 6. Fido) bis (6-tert-butyl-4-methoxyphenoxy) (tetrahydrofuran) titanium dichloride was replaced with the same operation as in Example 3 to obtain 496 mg of a polymer. The catalytic activity per mole of titanium per hour is 9920 kg / mol-Ti
Hr.

[0064]

As described above in detail, according to the present invention, an olefin polymer such as a cyclic olefin polymer can be extremely efficiently used by using a catalyst containing a specific transition metal compound as a main component. It can be produced, and its industrial value is very large.

Claims (7)

[Claims] 1. A method for polymerizing a cyclic olefin represented by the general formula [II] in the presence of a catalyst comprising the following compound (A) and the following compound (B) and / or the following compound (C): A process for producing an olefin polymer, characterized by the following. (A) A transition metal compound represented by the following general formula [I]. (In the formula, M is a transition metal atom belonging to Group 4 of the periodic table of elements or a lanthanide series. A and A ′ each have 1 to 1 carbon atoms.
50 hydrocarbon groups, halogenated hydrocarbon groups, or hydrocarbon groups or halogenated hydrocarbon groups having an oxygen atom-containing substituent, and A and A ′ may be the same or different.
X and X 'are a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X and X' may be the same or different.
Y represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. O represents an oxygen atom, and P represents an atom belonging to Group 15 of the periodic table of the elements. L is a Lewis base and w is an integer of 0 or more. (B) Any one of the following (B1) to (B3) or a mixture of two or three of them (B1) Organoaluminum compound represented by general formula E ¹ _a AlZ _3-a (B2) General formula Cyclic aluminoxane having a structure represented by Al (E ² ) -O-｝ _b (B3) general formula E ³ ｛-Al (E ³ ) -O-｝ _c AlE ³
_A linear aluminoxane having a structure represented by ₂ , wherein E ^{1 to} E ³ are a hydrocarbon group having 1 to 8 carbon atoms;
All E ¹ , all E ² and all E ³ may be the same or different. Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different.
a represents a number of 0 to 3, b represents an integer of 2 or more, and c represents an integer of 1 or more. (C) any one of the following (C1) to (C3): (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C2) a general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- a boron compound represented by, (C3) the general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - boron compound represented by (wherein, B is a trivalent valence state boron atom And Q
^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, a halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, 1
An alkoxy group containing -20 carbon atoms or an amino group containing 2-20 carbon atoms, which may be the same or different. G ⁺ is an inorganic or organic cation, L is a neutral Lewis base, (LH) ⁺
Is a Bronsted acid. ) (Wherein, R _{9 to} R ₂₀ each independently represent a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an amino group and an organic group having 1 to 20 carbon atoms, and R _{13 to} R _{16 each} represent a ring. May be formed. N represents an integer of 0 or more.) 2. A cyclic olefin represented by the general formula [II] and a cyclic olefin represented by the general formula [II] in the presence of a catalyst comprising the following compound (A) and the following compound (B) and / or the following compound (C): A method for producing an olefin polymer, comprising copolymerizing another monomer having copolymerizability with the olefin polymer. (A) A transition metal compound represented by the following general formula [I]. (In the formula, M is a transition metal atom belonging to Group 4 of the periodic table of elements or a lanthanide series. A and A ′ each have 1 to 1 carbon atoms.
50 hydrocarbon groups, halogenated hydrocarbon groups, or hydrocarbon groups or halogenated hydrocarbon groups having an oxygen atom-containing substituent, and A and A ′ may be the same or different.
X and X 'are a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X and X' may be the same or different.
Y represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group. O represents an oxygen atom, and P represents an atom belonging to Group 15 of the periodic table of the elements. L is a Lewis base and w is an integer of 0 or more. (B) Any one of the following (B1) to (B3) or a mixture of two or three of them (B1) Organoaluminum compound represented by general formula E ¹ _a AlZ _3-a (B2) General formula Cyclic aluminoxane having a structure represented by Al (E ² ) -O-｝ _b (B3) general formula E ³ ｛-Al (E ³ ) -O-｝ _c AlE ³
_A linear aluminoxane having a structure represented by ₂ , wherein E ^{1 to} E ³ are a hydrocarbon group having 1 to 8 carbon atoms;
All E ¹ , all E ² and all E ³ may be the same or different. Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different.
a represents a number of 0 to 3, b represents an integer of 2 or more, and c represents an integer of 1 or more. (C) any one of the following (C1) to (C3): (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C2) a general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- a boron compound represented by, (C3) the general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - boron compound represented by (wherein, B is a trivalent valence state boron atom And Q
^{1 to} Q ⁴ represent a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, a halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, 1
An alkoxy group containing -20 carbon atoms or an amino group containing 2-20 carbon atoms, which may be the same or different. G ⁺ is an inorganic or organic cation, L is a neutral Lewis base, (LH) ⁺
Is a Bronsted acid. ) (Wherein, R _{9 to} R ₂₀ each independently represent a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an amino group and an organic group having 1 to 20 carbon atoms, and R _{13 to} R ₁₆ represent a ring. May be formed. N represents an integer of 0 or more.) 3. Other monomers copolymerizable with cyclic olefins include α-olefins, alkenyl aromatic hydrocarbons, alkyl vinyl ethers, unsaturated halogenated hydrocarbons, and α, β-unsaturated carboxylic acid esters. 3. The method for producing an olefin polymer according to claim 2, wherein the compound is selected from the group consisting of: an unsaturated nitrile and vinyl carboxylate. 4. In the general formula [I], A and / or A ′ are a (substituted) alkylene group, a (substituted) vinylene group,
The method for producing an olefin-based polymer according to any one of claims 1 to 3, wherein the method is a (substituted) phenylene group, a (substituted) naphthalene group, or any combination thereof. 5. The method for producing an olefin polymer according to claim 1, wherein in the general formula [1], P is a phosphorus atom. 6. The olefin system according to claim 1, wherein in the general formula [1], X and / or X ′ is a chlorine atom, a bromine atom, a methyl group or a benzyl group. A method for producing a polymer. 7. The method for producing an olefin polymer according to claim 1, wherein in the general formula [1], Y is a (substituted) phenyl group.