JP2003082017A - Method for producing cyclic olefinic copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a cyclic olefinic copolymer in the presence of a catalyst simultaneously satisfying characteristics which comprise not producing a gel-like polymer component or a solvent-insoluble polymer component, having excellent polymerization activity, having high cyclic olefin copolymerization efficiency and giving the copolymer having a narrow mol.wt. distribution. SOLUTION: This method for producing the cyclic olefinic copolymer comprises copolymerizing an α-olefin with a cyclic olefin in the presence of a catalyst comprising an aluminoxane and a metallocene compound represented by the general formula [1]: H2 C(R'm Cp)(R"n Cp)MX2 [M is Zr or Hf atom; Cp is a group having a cyclopentadienyl skeleton; R', R" are each a 1 to 10C hydrocarbon group; X is a halogen atom, or the like; (m) and (n) are different from each other, and (m)+(n) is an integer of 3 to 6].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a cyclic olefin copolymer. More specifically, the present invention copolymerizes an α-olefin such as ethylene and a cyclic olefin in the presence of a catalyst system containing a metallocene compound and an aluminoxane to give a high cyclic olefin content and a narrow molecular weight distribution. The present invention relates to a method capable of efficiently producing a cyclic olefin-based copolymer with high polymerization activity.

[0002]

2. Description of the Related Art An olefin-based addition polymer having a ring structure obtained by copolymerizing a cyclic olefin represented by norbornene or a so-called cyclic polyene having two or more double bonds in the molecule with an α-olefin (hereinafter , Which are called cyclic olefin-based copolymers) generally have a higher glass transition temperature and higher transparency than olefin-based polymers that do not contain a ring structure. Is expected to be applied. Various methods are known for producing such a cyclic olefin-based copolymer, and norbornene or its derivative and α
-For copolymers with olefins, see, for example, Japanese Patent Laid-Open No.
A method using a catalyst composed of a vanadium compound and an organoaluminum compound is disclosed in JP-A-0-168708 and JP-A-61-271308. However, these methods have a problem that the catalytic activity is low. As a method for improving this point, Japanese Patent Laid-Open No. 61-221
No. 206, Japanese Unexamined Patent Publication No. 64-106 and Japanese Unexamined Patent Publication No. 2-173112 propose a production method using a catalyst composed of various metallocene compounds and aluminoxane. These methods have relatively high catalytic activity,
Although the copolymerization efficiency of cyclic olefins has been considerably improved, further improvement of polymerization activity and improvement of copolymerization efficiency of cyclic olefins with α-olefins are desired.

By the way, in general, cyclic olefins have poor reactivity and low copolymerization efficiency as compared with α-olefins such as ethylene and propylene. Therefore, in order to produce a copolymer containing a high content of cyclic olefin, it is necessary to allow a large amount of cyclic olefin to be present in the polymerization system.
When a large amount of cyclic olefin is present in the polymerization system, not only the catalytic activity is impaired, but also a gel-like polymer component swelling in a solvent or a polymer component insoluble in the solvent is easily produced. On the other hand, in applications such as optical materials of cyclic olefin-based copolymers, the homogeneity of the materials is important, and when such gel-like polymer components or solvent-insoluble polymer components are produced, cyclic olefin-based copolymer components The homogeneity of the copolymer is reduced and the commercial value is significantly impaired.

The formation of such a gel-like polymer component or a solvent-insoluble polymer component is generally caused by a low catalyst activity, or when the copolymerization efficiency of the catalyst is poor and the amount of cyclic olefin is unavoidably increased, or It tends to occur when the polymerization temperature is raised. This is because the catalyst performance is insufficient, and there is a strong demand for a high-performance catalyst that does not cause such a problem.

[0005]

The object of the present invention relates to a method for producing a cyclic olefin-based copolymer, which does not form a gel-like polymer component or a solvent-insoluble polymer component and has excellent polymerization activity. To provide a method for efficiently producing a cyclic olefin copolymer using a catalyst that simultaneously satisfies the characteristics that the copolymerization efficiency of the cyclic olefin is high and the obtained cycloolefin copolymer has a narrow molecular weight distribution. is there.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies as to a method for producing a cyclic olefin copolymer using a metallocene catalyst, and as a result, a metallocene compound having a specific structure was used. The present invention has been completed by finding that the above object can be sufficiently satisfied and the object of the present invention can be achieved when a catalyst in which is combined with aluminoxane is used.

That is, the present invention relates to a method for producing a cyclic olefin copolymer by copolymerizing an α-olefin and a cyclic olefin, and the following general formula [1] H ₂ C (R ' _m Cp) is used as a catalyst. (R ″ _n Cp) MX ₂ ··· [1] [wherein, M is a zirconium atom or a hafnium atom, Cp is a group having a cyclopentadienyl skeleton, and R ′ and R ″ are carbon numbers. 1 to 10 hydrocarbon groups, and two X's may be the same or different and each is a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, an alkylamino group. , An arylamino group, an alkoxy group, a general formula —O—Ar—Y _p
(Here, Ar represents an aromatic ring, Y is a halogen atom,
It is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, an alkoxy group, an alkylamino group, a cyano group or a nitro group, and p represents an integer of 1 to 5. ) Is an aryloxy group represented by), a thioalkyl group, or a thioaryl group represented by the general formula —S—Ar—Y _p (where Ar, Y and p have the same meanings as described above), Then, m and n are integers of 0 to 4, m and n are not equal, and m + n is an integer of 3 to 6. ] It is related with the manufacturing method of the cyclic olefin type copolymer characterized by using the catalyst containing the metallocene compound (A) and aluminoxane (B) represented by these.

The above-mentioned characteristic of the catalyst used in the present invention is that the metallocene compound (A) is different in two cyclopentadiene rings bonded to the transition metal atom (asymmetric structure), and It has a structure in which two cyclopentadiene rings are linked by a methylene group. Further, the use of the metallocene compound (A) having such a specific structure in the catalyst of the present invention shows particularly good results in the production of the cyclic olefin-based copolymer, and achieves the above-mentioned object of the present invention. Was found to contribute to.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The α-olefin used in the present invention is
Specific examples thereof include ethylene, propylene, and 1
-Butene, 1-hexene, 4-methyl-1-pentene,
Examples of the α-olefin having 2 to 20 carbon atoms include 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Of these, ethylene is particularly preferable.

The cyclic olefin copolymerized with the α-olefin in the present invention is a monocyclic olefin such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, 5-methylcyclohexene, cyclooctene, or the following general formula [2].

[Chemical 2] (In the formula, R ^{1 to} R ¹² represent a substituent selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 20 carbon atoms, provided that R ⁵ and R ⁷ are bonded to each other. And a carbon atom present therein may form a ring, and q is an integer of 0 to 3).

Specific examples of the polycyclic olefin represented by the general formula (2) include norbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octa. Hydronaphthalene, 5-methyl-2-norbornene, 7-
Methyl-2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5-isobutyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2-norbornene, 5-ethylidene- 2-norbornene, 5-vinyl-2-norbornene,
5-chloro-2-norbornene, 5-fluoro-2-norbornene, 5-chloromethyl-2-norbornene, 5
-Methoxy-2-norbornene, 5,6-dimethyl-2
-Norbornene, 5,5-dichloro-2-norbornene, 5,5,6-trimethyl-2-norbornene, 5,
5,6-trifluoro-6-trifluoromethyl-2-
Norbornene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene etc. can be mentioned. Among the monocyclic olefins and polycyclic olefins listed above, particularly preferred cyclic olefins are norbornene and 1,4,5,8.
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

One component of the catalyst used in the method of the present invention is the metallocene compound (A), which is represented by the general formula [1]. H ₂ C (R ′ _m Cp) (R ″ _n Cp) MX ₂ ... [1] In the formula, M is a zirconium atom or a hafnium atom, and Cp is a group having a cyclopentadienyl skeleton, R ′ and R ″ are hydrocarbon groups having 1 to 10 carbon atoms, and two Xs may be the same or different and each is a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 20 carbons, or a halogen. Hydrocarbon group, alkylamino group, arylamino group, alkoxy group, general formula —O—Ar—Y _p
(Here, Ar represents an aromatic ring, Y is a halogen atom,
It is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, an alkoxy group, an alkylamino group, a cyano group or a nitro group, and p represents an integer of 1 to 5. ) Is an aryloxy group represented by), a thioalkyl group, or a thioaryl group represented by the general formula —S—Ar—Y _p (where Ar, Y and p have the same meanings as described above), And m and n are integers of 0-4, m and n are not equal, and m + n is an integer of 3-6.

In the above general formula [1], R'and R "are hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6. Specific examples thereof include methyl group, ethyl group, propyl group, Examples thereof include isopropyl group, butyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, etc. Preferably, methyl group, ethyl group,
A propyl group, an isopropyl group, a butyl group, and a hexyl group.

In the above general formula [1], when the substituent X and the substituent Y are halogen atoms, they may be the same or different, but specific examples thereof are fluorine, chlorine, bromine and iodine. can do.

The substituent X and the substituent Y have 1 to 2 carbon atoms.
In the case of 0, preferably 1 to 10 hydrocarbon groups, specific examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group; cyclohexyl group. , Cycloalkyl groups such as cyclooctyl group; aryl groups such as phenyl group and naphthyl group; alkenyl groups such as vinyl group and propenyl group; alkynyl groups such as ethynyl group and propynyl group; arylalkyl groups such as benzyl group and phenethyl group An arylalkenyl group such as a styryl group and a cinnamyl group; and an alkylaryl group such as a tolyl group, a xylyl group and a mesyl group.

When the substituent X and the substituent Y are halogenated hydrocarbon groups, specific examples thereof include chloromethyl group, fluoromethyl group, bromomethyl group, iodomethyl group, dichloromethyl group, difluoromethyl group, trichloromethyl group. Group, trifluoromethyl group, chlorophenyl group and the like.

When the substituent X and the substituent Y are an alkylamino group or an arylamino group, specific examples thereof include N-methylamino group, N, N-dimethylamino group, N, N-diethylamino group; anilino. Group, N, N-
A diphenylamino group etc. can be mentioned.

When the substituent X and the substituent Y are alkoxy groups, specific examples thereof include a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

When the substituent X is an alkylthio group, specific examples thereof include a methylthio group, an ethylthio group, a propylthio group and a butylthio group.

Further, when the substituent X in the general formula [1] is a —O—Ar—Y _p group, specific examples thereof include
2-fluorophenoxy, 3-fluorophenoxy, 4
-Fluorophenoxy, 2-chlorophenoxy, 3-chlorophenoxy, 4-chlorophenoxy, 2-bromophenoxy, 3-bromophenoxy, 4-bromophenoxy, 2-iodophenoxy, 3-iodophenoxy, 4
-Iodophenoxy, 2,3-difluorophenoxy,
2,4-difluorophenoxy, 2,5-difluorophenoxy, 2,6-difluorophenoxy, 3,4-difluorophenoxy, 3,5-difluorophenoxy,
2,3-dichlorophenoxy, 2,4-dichlorophenoxy, 2,5-dichlorophenoxy, 2,6-dichlorophenoxy, 3,4-dichlorophenoxy, 3,5-dichlorophenoxy, 2,3,4-trifluoro Phenoxy, 2,3,5-trifluorophenoxy, 2,3,6
-Trifluorophenoxy, 2,4,5-trifluorophenoxy, 2,4,6-trifluorophenoxy,
3,4,5-trifluorophenoxy, 2,3,5,6
-Tetrafluorophenoxy, pentafluorophenoxy, 2-fluoromethylphenoxy, 3-fluoromethylphenoxy, 4-fluoromethylphenoxy, 2-chloromethylphenoxy, 3-chloromethylphenoxy,
4-chloromethylphenoxy, 2-trifluoromethylphenoxy, 3-trifluoromethylphenoxy, 4-
Trifluoromethylphenoxy, 3,5-bis (trifluoromethyl) phenoxy, 2- (2,2,2-trifluoroethyl) phenoxy, 3- (2,2,2-trifluoroethyl) phenoxy, 4- ( 2,2,2-Trifluoroethyl) phenoxy, 2-trichloromethylphenoxy, 3-trichloromethylphenoxy, 4-trichloromethylphenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethyl Phenoxy, 2,4-dimethylphenoxy, 2,5
-Dimethylphenoxy, 2,6-dimethylphenoxy,
3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5
-Trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4
6-trimethylphenoxy, 3,4,5-trimethylphenoxy, pentamethylphenoxy, 2-methyl-4-
Fluorophenoxy, 2-chloro-4-fluorophenoxy, 2-chloro-4-trifluoromethylphenoxy, 2-fluoro-4-trifluoromethylphenoxy, 2-trifluoromethyl-4-fluorophenoxy, 2-ethylphenoxy, 3-ethylphenoxy, 4
-Ethylphenoxy, 2-isopropylphenoxy, 3
-Isopropylphenoxy, 4-isopropylphenoxy, 2-tert-butylphenoxy, 3-tert-butylphenoxy, 4-tert-butylphenoxy, 3,5-di-tert-butylphenoxy, 2-cyclohexylphenoxy, 3-cyclohexylphenoxy, 4-cyclohexylphenoxy, 1-naphthoxy, 2-naphthoxy, 8-trifluoromethyl-1-naphthoxy, 2,8-dimethyl-1-naphthoxy, 1-tert-butyl-2-naphthoxy, 8-bromo-2-naphthoxy , 2-phenylphenoxy, 3-phenylphenoxy, 4-phenylphenoxy, 2-benzylphenoxy, 3-benzylphenoxy, 4-benzylphenoxy, 2-tolylphenoxy, 3-tolylphenoxy, 4-tolylphenoxy, 2-vinylphenoxy , 3-vinylfe Carboxymethyl, 4-vinyl-phenoxy, 2
-(2-propenyl) phenoxy, 3- (2-propenyl) phenoxy, 4- (2-propenyl) phenoxy,
2-methyl-6- (2-propenyl) phenoxy, 2-
Ethynylphenoxy, 3-ethynylphenoxy, 4-ethynylphenoxy, 2-methoxyphenoxy, 3-methoxyphenoxy, 4-methoxyphenoxy, 2-tertiary butoxyphenoxy, 3-tertiary butoxyphenoxy, 4-
Tertiary butoxyphenoxy, 2-phenoxyphenoxy,
3-phenoxyphenoxy, 4-phenoxyphenoxy, 2-formylphenoxy, 3-formylphenoxy, 4-formylphenoxy, 2-acetylphenoxy, 3-acetylphenoxy, 4-acetylphenoxy, 2-benzoylphenoxy, 3-benzoylphenoxy, 4-benzoylphenoxy, 2-cyanophenoxy, 3-cyanophenoxy, 4-cyanophenoxy, 2
-Nitrophenoxy, 3-nitrophenoxy, 4-nitrophenoxy, 2-anilinophenoxy, 3-anilinophenoxy, 4-anilinophenoxy, 2-dimethylaminophenoxy, 3-dimethylaminophenoxy, 4-
Dimethylaminophenoxy, 2-dimethylaminomethylphenoxy, 3-dimethylaminomethylphenoxy, 4
-Dimethylaminomethylphenoxy and the like can be mentioned.

When the substituent X is a -S-Ar-Y _p group, specific examples thereof include 2-methylthiophenoxy, 3-methylthiophenoxy, 4-methylthiophenoxy, 2-tert-butylthiophenoxy, 3-tert-butylthiophenoxy, 4-tert-butylthiophenoxy, 2-
Fluorothiophenoxy, 3-fluorothiophenoxy, 4-fluorothiophenoxy, 2-chlorothiophenoxy, 3-chlorothiophenoxy, 4-chlorothiophenoxy, 2-trifluoromethylthiophenoxy, 3
-Trifluoromethylthiophenoxy, 4-trifluoromethylthiophenoxy, 2-methoxythiophenoxy, 3-methoxythiophenoxy, 4-methoxythiophenoxy, 2-cyanothiophenoxy, 3-cyanothiophenoxy, 4-cyanothiophenoxy, 2 -Nitrothiophenoxy, 3-nitrothiophenoxy, 4-nitrothiophenoxy, 2-anilinothiophenoxy, 3-anilinothiophenoxy, 4-anilinothiophenoxy,
Examples thereof include 2-dimethylaminothiophenoxy, 3-dimethylaminothiophenoxy, 4-dimethylaminothiophenoxy, 2-dimethylaminomethylthiophenoxy, 3-dimethylaminomethylthiophenoxy and 4-dimethylaminomethylthiophenoxy.

Specific examples of the metallocene compound (A) represented by the general formula [1] include methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride and methylene (2-methylcyclopentadienyl). ) (Tetramethylcyclopentadienyl) zirconium dichloride, methylene (3-methylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (2,3,5-trimethylcyclopenta (Dienyl)
Zirconium dichloride, methylene (cyclopentadienyl) (2,3,4-trimethylcyclopentadienyl) zirconium dichloride, methylene (2-methylcyclopentadienyl) (2,3,4-trimethylcyclopentadienyl) zirconium Dichloride, methylene (3-methylcyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, methylene (2-methylcyclopentadienyl)
(2,3-Dimethylcyclopentadienyl) zirconium dichloride, methylene (3-methylcyclopentadienyl) (2,4-dimethylcyclopentadienyl) zirconium dichloride, methylene (2-methylcyclopentadienyl) (2 , 5-Dimethylcyclopentadienyl) zirconium dichloride, methylene (2-methylcyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, methylene (3-methylcyclopentadienyl) (2 , 3,4-Trimethylcyclopentadienyl) zirconium dichloride, methylene (2-methylcyclopentadienyl)
(2,4-Dimethylcyclopentadienyl) zirconium dichloride, methylene (2-methylcyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, methylene (3-methylcyclopentadienyl) (2 , 3-Dimethylcyclopentadienyl) zirconium dichloride, methylene (3-methylcyclopentadienyl) (2,5-dimethylcyclopentadienyl) zirconium dichloride, methylene (3-methylcyclopentadienyl) (3,4 -Dimethylcyclopentadienyl) zirconium dichloride, methylene (2,3-dimethylcyclopentadienyl) (2,3,3
5-trimethylcyclopentadienyl) zirconium dichloride, methylene (2,4-dimethylcyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, methylene (2,3-dimethylcyclopentadienyl) ) (2,3,4-Trimethylcyclopentadienyl) zirconium dichloride, methylene (2,3-dimethylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, methylene (2,4-dimethylcyclopentadiene) (Phenyl) (tetramethylcyclopentadienyl) zirconium dichloride, methylene (2,5-dimethylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, methylene (3,4-dimethylcyclopentadienyl) (Tetramethylcyclopentadienyl) zirconium dichloride, methylene (2,4-dimethylcyclopentadienyl) (2,3,4-trimethylcyclopentadienyl) zirconium dichloride, methylene (2,5-dimethylcyclopentadienyl) )
(2,3,4-Trimethylcyclopentadienyl) zirconium dichloride, methylene (2,5-dimethylcyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, methylene (3,4- Dimethylcyclopentadienyl) (2,3,
4-trimethylcyclopentadienyl) zirconium dichloride, methylene (3,4-dimethylcyclopentadienyl) (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, methylene (3-ethylcyclopentadienyl) ( Tetramethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) bis (2-fluorophenoxy) zirconium, methylene (3-methylcyclopentadienyl) (tetramethylcyclopentadienyl) Enyl) bis (2-fluorophenoxy)
Zirconium, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dimethyl, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium diphenyl, methylene (cyclopentadienyl) (tetramethylcyclopenta Dienyl) bis (2-trifluoromethylphenoxy) zirconium, methylene (cyclopentadienyl)
(Tetramethylcyclopentadienyl) bis (2-methyl-4-fluorophenoxy) zirconium, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dimethoxide, methylene (cyclopentadienyl) (tetramethyl Cyclopentadienyl) zirconium diphenoxide, methylene (3-methylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dithiophenoxide, methylene (3-methylcyclopentadienyl) (tetramethylcyclopentadienyl) bis Examples thereof include (4-cyanophenoxy) zirconium, methylene (2-n-butylcyclopentadienyl) (tetramethylcyclopentadienyl) bis (2-trifluoromethylphenoxy) zirconium and the like. . Further, in the zirconium compound shown above, a hafnium compound corresponding to each zirconium compound in which a zirconium atom which is a transition metal atom thereof is replaced with a hafnium atom can be similarly used.

The aluminoxane (B), another component of the catalyst used in the process of the present invention, is
It is represented by the following general formula [3].

[Chemical 3] In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and r represents a number of 4 to 100, preferably 8 to 20. Specific examples of R ¹ include a methyl group, an ethyl group,
Examples thereof include a propyl group and an isobutyl group. In addition,
R ¹ in the aluminoxane (B) may contain different alkyl groups. A preferred aluminoxane is an aluminoxane in which all or most of R ^{1 in} the general formula [3] is a methyl group, that is, methylaluminoxane. Such an aluminoxane (B) generally has a molecular weight of 200 to 10,000, and its structure may be a linear structure or a compound in which both ends are bonded to form a ring.

Various known methods can be used to synthesize the aluminoxane (B). For example, a method of dissolving a trialkylaluminum in a hydrocarbon solvent and gradually adding an equivalent amount of water to the trialkylaluminum for hydrolysis, and suspending copper sulfate hydrate or aluminum sulfate hydrate in the hydrocarbon solvent. Then, 1 to 3 times equivalent amount of trialkylaluminum is brought into contact with the hydrated water of crystallization in the suspension to slowly hydrolyze the trialkylaluminum, or unsuspended in a hydrocarbon solvent. It can be synthesized by a method of bringing trialkylaluminum in an amount equivalent to 1 to 3 times the adsorbed water of dehydrated silica gel and slowly hydrolyzing the trialkylaluminum.

The above catalyst components (A) and (B) may be used as they are, but in some cases, they may be supported on a carrier before use. Examples of the carrier include inorganic compounds such as silica, alumina and magnesium chloride, and organic polymer compounds such as polyethylene and polypropylene.

The copolymerization of ethylene and cyclic olefin in the method of the present invention is caused by a catalyst composed of the above metallocene compound (A) and aluminoxane (B), and this catalyst is usually produced by bringing both components into contact with each other. . As a method for bringing the above two components into contact with each other, any method can be adopted. That is, the metallocene compound (A) and the aluminoxane (B) may be supplied to the polymerization system as a solution in which the metallocene compound (A) and the aluminoxane (B) are mixed in advance in an appropriate solvent, or the metallocene compound (A) and the aluminoxane (B), or those may be added to the polymerization system. The monomer or a solution in a suitable solvent may be supplied simultaneously or separately and brought into contact with each other in the polymerization system.

In the catalyst used in the process of the invention,
The amount of the metallocene compound (A) used is preferably 10 ⁻⁶ to 1 gram atom / as the transition metal concentration in the polymerization reaction system.
Liter, particularly preferably 10 ^-5 to 10 ^-1 gram atom /
It is in the liter range. The amount of the aluminoxane (B) used is preferably in the range of 10 ⁻⁴ to 10 gram atom / liter, particularly preferably 10 ⁻³ to 1 gram atom / liter, as the concentration of aluminum atom in the polymerization reaction system. . Further, in the catalyst used in the method of the present invention,
The ratio of the aluminoxane (B) to the metallocene compound (A) in the polymerization reaction system is usually 1 to 10 ⁷ , preferably 10 to 10 as the ratio of the aluminum atom in the aluminoxane (B) to 1 mol of the metallocene compound (A). It is in the range of ⁵ .

For the polymerization in the present invention, any of batch-type or continuous-type gas phase polymerization method, bulk polymerization method, solution polymerization method using a suitable solvent, slurry polymerization method and the like can be adopted. You can When using a solvent,
Generally, an inert hydrocarbon solvent is used, but a cyclic olefin itself which is a monomer used for polymerization may be used as a solvent. Examples of the inert hydrocarbon solvent include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane and decalin; cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane,
Alicyclic hydrocarbons such as dimethylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene; naphtha
Petroleum fractions such as kerosene and light oil can be used.

The polymerization conditions of the present invention are such that the temperature is generally -10.
0 to 250 ° C, preferably -50 to 200 ° C, and the pressure is generally 10 MPa or less, preferably atmospheric pressure to 5M.
Pa.

The cyclic olefin copolymer obtained by the method of the present invention contains 5 to 99 mol% of repeating units derived from α-olefin, preferably 15 to 95 mol%,
It is particularly preferably in the range of 30 to 90 mol%, and the repeating unit derived from a cyclic olefin is in the range of 1 to 95 mol%, preferably 5 to 85 mol%, particularly preferably 10 to 70 mol%. The repeating units derived from the α-olefin and the repeating units derived from the cyclic olefin form a substantially linear olefin-based random copolymer in which they are randomly arranged. According to the method of the present invention, a cyclic olefin-based copolymer which is substantially linear and does not have a gel-like cross-linking structure can be produced. The fact is that the obtained cyclic olefin-based copolymer has a decalin temperature of 135 ° C. It can be confirmed by completely dissolving in.

The cyclic olefin copolymer produced by the method of the present invention generally has a weight average molecular weight Mw of 500 to 2,000,000 measured by gel permeation chromatography (GPC).
In particular, it is in the range of 1,000 to 1,000,000, and the number average molecular weight Mn is 300 to 1,000,000, particularly 5
The range is from 00 to 500,000. The cyclic olefin-based copolymer produced by the method of the present invention has an Mw / Mn value of 1.5 to 4.5, particularly 1.8 to 3.5, which is an index of the molecular weight distribution. It has certain characteristics. When the Mw / Mn value becomes 5 or more, for example, when the cyclic olefin copolymer is used for optical materials, the mechanical strength may be lowered, and a uniform molded product may not be obtained. . Thus, the cyclic olefin-based copolymer of the present invention has a narrow molecular weight distribution and a uniform monomer composition distribution, and is therefore excellent in heat resistance and mechanical properties.

In the present invention, when a cyclic olefin copolymer is produced by copolymerizing an α-olefin and a cyclic olefin, the α-olefin and the cyclic olefin may be copolymerized singly or on the other hand. Alternatively, a plurality of both may be used. Furthermore, if necessary, in addition to the α-olefin and the cyclic olefin, another monomer other than the above can be added and copolymerized.

The cyclic olefin-based copolymer produced by the method of the present invention has excellent heat resistance and mechanical properties, and thus can be used for various purposes. Specifically, low molecular weight materials are used in fields such as electrostatic copying toner, hot melt adhesives, ceramic binders, and photoresist base materials, and high molecular weight materials are used in optical fields such as optical lenses, optical disks, and optical fibers, and electronic fields. Range products, liquid crystal display substrates, printed substrates, electrical fields such as transparent conductive films, syringes,
It can be used in various fields such as medical fields such as pipettes and animal gauges, and chemical fields.

[0034]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples shown below. In the examples, the copolymer composition (mol%) was determined by ¹³ C-NMR (400 MHz, temperature: room temperature, solvent: deuterated benzene), weight average molecular weight (Mw), number average molecular weight (Mn). , And the molecular weight distribution (Mw / Mn) were measured by a high temperature gel permeation chromatography (GPC) method at a temperature of 135 ° C., solvent 1,
It was measured and determined under the condition of 2,4-trichlorobenzene. Further, all the metallocene compound synthesis reactions shown in Reference Examples were carried out under an inert gas atmosphere, and the reaction solvent used was previously dried.

Reference Example 1 Synthesis of methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride 1,2,3,4, in a 300 ml glass reaction vessel.
After dissolving 1.09 g of 5-pentamethylcyclopentadiene in 100 ml of hexane, 8 ml of 1.0 mol / l diethyl ether solution of tert-butyllithium was added to -78.
The solution was added dropwise at 0 ° C over 1 hour. Then, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 12 hours. To this, 100 ml of 1,2-dimethoxyethane was added, and -15 ° C
After cooling to 3, 3.8 g of triphenylcarbenium hexafluorophosphate was added. The reaction solution is warmed to room temperature,
After reacting for 2.5 hours at room temperature, water was added to stop the reaction. Subsequently, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily component, which was then purified by column chromatography (neutral alumina / hexane).
0.75 g of 2,3,4-tetramethylfulvene was obtained as an orange oil. Then, 0.5 g of cyclopentadiene obtained by thermally decomposing dicyclopentadiene was dissolved in 100 ml of tetrahydrofuran in a 200 ml glass flask, and 5 ml of 1.6 ml / l hexane solution of n-butyllithium was kept at -78 ° C for 1 hour. It dripped over. Then
The temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 3 hours. This solution was cooled again to -78 ° C, and 0.75 g of 1,2,3,4-tetramethylfulvene obtained above was-
It was added dropwise at 78 ° C. The temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 12 hours. After water was added to this solution to stop the reaction, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily component, which was then purified by column chromatography (neutral alumina / hexane). Then, 0.84 g of cyclopentadienyl (2,3,4,5-tetramethylcyclopentadienyl) methane was obtained.
0.84 g of this cyclopentadienyl (2,3,4,5-tetramethylcyclopentadienyl) methane was added to 10
50 ml of diethyl ether in a 0 ml glass reactor
1.6 mol / l of n-butyllithium after being dissolved in
2.7 ml of a hexane solution was added dropwise at -78 ° C over 1 hour. Then, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 12 hours. 0.97 g of zirconium tetrachloride suspended in 20 ml of hexane was added to this solution at -78 ° C.
Was added to the mixture, the temperature was raised to room temperature over 1 hour, and the mixture was stirred at room temperature for 12 hours. Subsequently, the formed precipitate (LiCl)
Was removed by filtration, the solvent was distilled off from the filtrate under reduced pressure, and the solid content obtained was extracted with hexane. The solvent was distilled off under reduced pressure, and the obtained crude product was recrystallized from the solvent to give the desired product, methylene (cyclopentadienyl).
1.2 g of (tetramethylcyclopentadienyl) zirconium dichloride was obtained as yellow-green crystals.

Reference Example 2 Synthesis of methylene (3-methylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride 1,2,3,4,5
After dissolving 0.95 g of pentamethylcyclopentadiene in 100 ml of hexane, 1.
7 ml of a 0 mol / l diethyl ether solution was added dropwise at -78 ° C over 1 hour. Then, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 12 hours. 1,2-
After adding 100 ml of dimethoxyethane and cooling to -15 ° C, 3.3 g of triphenylcarbenium hexafluorophosphate was added. The reaction solution was heated to room temperature and reacted at room temperature for 2.5 hours, and then water was added to stop the reaction. Subsequently, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the oily component obtained was purified by column chromatography (neutral alumina / hexane).
0.61 g of 3,4-tetramethylfulvene was obtained as an orange oil. Next, 0.44 g of methylcyclopentadiene obtained by thermally decomposing methylcyclopentadiene dimer was added to tetrahydrofuran 1 in a 200 ml glass flask.
Dissolve in 00 ml, 1.6 ml of n-butyllithium /
3.5 ml of 1-hexane solution was added dropwise at −78 ° C. over 1 hour. Then, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 3 hours. This solution was cooled to −78 ° C. again, and 0.61 g of 1,2,3,4-tetramethylfulvene obtained above was added dropwise at −78 ° C. The temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 12 hours. After water was added to this solution to stop the reaction, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily component, which was then purified by column chromatography (neutral alumina / hexane). Then, 0.83 g of 3-methylcyclopentadienyl (2,3,4,5-tetramethylcyclopentadienyl) methane was obtained. 0.83 g of this 3-methylcyclopentadienyl (2,3,4,5-tetramethylcyclopentadienyl) methane was dissolved in 50 ml of diethyl ether in a 100 ml glass reactor, and then n-butyllithium was added. 2.5 ml of a 1.6 mol / l hexane solution of was added dropwise at -78 ° C over 1 hour. Then, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 12 hours. 0.9 g of zirconium tetrachloride suspended in 20 ml of hexane was added to this solution at -78 ° C, the temperature was raised to room temperature over 1 hour, and the mixture was further stirred at room temperature for 12 hours. Subsequently, the generated precipitate (LiCl) was removed by filtration, the solvent was distilled off from the filtrate under reduced pressure, and the obtained solid content was extracted with hexane. The solvent was distilled off under reduced pressure, and the obtained crude product was further recrystallized from the solvent to give methylene (3-methylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride 1.1 g as a target product. Was obtained as yellow-green crystals.

Example 1 80 ml of dehydrated and purified toluene, 200 ml of 1,4,5,8-dimethano-in a 200 ml autoclave substituted with nitrogen.
1,2,3,4,4a, 5,8,8a-octahydronaphthalene (hereinafter abbreviated as DMON) 24.0 g
(150 mmol) and 3.2 ml of a toluene solution of methylalumoxane (MMAO manufactured by Tosoh Akzo Co., concentration 1.87 mol / l based on Al) were charged, and heated and stirred to obtain a uniform solution at 60 ° C. Then, a toluene solution of methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride obtained in Reference Example 1 was added in an amount of 1.0 μmol in terms of Zr, and the pressure in the system was maintained at 0.294 MPa with ethylene. 30 at 60 ° C
Minor stirring was continued. After completion of the polymerization, the reaction mixture was put into hydrochloric acid-methanol, and the white solid deposited was separated by filtration. The obtained white solid was washed with acetone and then dried under reduced pressure to obtain 4.39 g of an ethylene-DMON copolymer. Catalytic activity is 4
8.1 kg polymer / gZr, D in the copolymer
The content of the MON component was as high as 43.3 mol%. The Mw and Mw / Mn measured by GPC were 132,000 and 2.8, respectively.

Example 2 The same procedure as in Example 1 was repeated except that methylene (3-methylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride obtained in Reference Example 2 was used as the metallocene compound (A). Polymerization reaction is carried out and ethylene
3.85 g of DMON copolymer was obtained. The catalyst activity is 42.
It was 2 kg polymer / gZr, and the content of the dicyclopentadiene component in the copolymer was a high value of 37.7 mol%. In addition, Mw and Mw / Mn measured by GPC
Were 166,000 and 3.1, respectively.

Comparative Example 1 The copolymerization reaction was carried out in the same manner as in Example 1 except that the metallocene compound was changed to ethylenebisindenyl zirconium dichloride, to obtain 1.82 g of an ethylene-DMON copolymer. The catalyst activity was 20.0 kg polymer / gZr, which was lower than that in the above-mentioned Examples. An attempt was made to dissolve the copolymer in ortho-dichlorobenzene in order to determine the content of the DMON component in the copolymer, but the copolymer was not completely dissolved, but a partially swollen polymer was observed.

Comparative Example 2 An ethylene-DMON copolymer was obtained by the same copolymerization reaction as in Example 1 except that the metallocene compound was changed to isopropylidene (fluorenyl) (cyclopentadienyl) zirconium dichloride. 0.33 g was obtained. Most of the copolymer was attached to the stirring blade in a thread form. The catalytic activity was 3.7 kg polymer / gZr, which was extremely low. The copolymer is insoluble in ortho-dichlorobenzene and trichlorobenzene,
The content and GPC could not be measured.

Comparative Example 3 Example 1 was repeated except that the metallocene compound was changed to isopropylidene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride.
A copolymerization reaction was performed in the same manner as in, to obtain 0.91 g of an ethylene-DMON copolymer. The catalyst activity was 10.0 kg polymer / gZr, and the content of DMON component in the copolymer was 3
It was 5.2 mol%. Compared to Example 1, the value of DMON content was as high as that of Example 1, but the catalytic activity was extremely low.

Example 3 An ethylene-norbornene copolymer was prepared by the same copolymerization reaction as in Example 1 except that the cyclic olefin compound and its addition amount were changed to norbornene and 2.8 g (30 mmol). 3.06 g was obtained. The catalyst activity was 33.6 kg polymer / gZr, and the content of the norbornene component in the copolymer was as high as 32.4 mol%. In addition, Mw and Mw / M measured by GPC
The n was 171,000 and 3.4, respectively.

Comparative Example 4 An ethylene-norbornene copolymer was prepared in the same manner as in Example 3 except that the metallocene compound was changed to isopropylidene (fluorenyl) (cyclopentadienyl) zirconium dichloride. 0.99
However, most of the polymer adhered to the stirring blade in a swollen state. Catalytic activity is 10.8 kg polymer / g
It was Zr and had a lower catalytic activity than that of Example 3. In order to determine the content of the norbornene component in the copolymer, an attempt was made to dissolve it in orthodichlorobenzene, but the copolymer was not completely dissolved, but a partially swollen polymer was observed. Therefore, ¹³ C-NMR and GPC
Could not be measured.

[0044]

EFFECTS OF THE INVENTION According to the present invention, a gelled polymer component and a solvent-insoluble polymer component are not formed, the polymerization activity is excellent, the copolymerization efficiency of cyclic olefin is high, and the molecular weight distribution is narrow. Provided is a method for producing a cyclic olefin-based copolymer using a catalyst that simultaneously satisfies the characteristics.

[Brief description of drawings]

FIG. 1 is a flow chart showing a manufacturing method of the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoko Furuyama             2456-2 Goi, Ichihara City, Chiba Prefecture (72) Inventor Masao Kawahara             1907-51 Noman, Ichihara City, Chiba Prefecture (72) Inventor Hiroshi Yamazaki             2-41-10, Matsugaoka, Tokorozawa, Saitama Prefecture F-term (reference) 4J028 AA01A AB00A AC01A AC09A                       AC10A BA00A BA01B BB00A                       BB01B BC25B EA01 EB01                       EB02 EB17 EB18 EC02                 4J100 AA02P AA03P AA04P AP02Q                       AR03Q AR05Q AR11Q CA04                       FA10

Claims (5)

[Claims] 1. A method for producing a cyclic olefin copolymer by copolymerizing an α-olefin and a cyclic olefin, wherein a catalyst represented by the following general formula [1] H ₂ C (R ′ _m Cp) (R ″ _n ) is used. Cp) MX ₂ ... [1] [In the formula, M is a zirconium atom or a hafnium atom, Cp is a group having a cyclopentadienyl skeleton, and R ′ and R ″ have 1 to 10 carbon atoms. It is a hydrocarbon group, and two X's may be the same or different and each is a halogen atom, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, an alkylamino group or an arylamino group. , An alkoxy group, a general formula —O—Ar—Y _p
(Here, Ar represents an aromatic ring, Y is a halogen atom,
It is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, an alkoxy group, an alkylamino group, a cyano group or a nitro group, and p represents an integer of 1 to 5. ) Is an aryloxy group represented by), a thioalkyl group, or a thioaryl group represented by the general formula —S—Ar—Y _p (where Ar, Y and p have the same meanings as described above), And m and n are integers of 0-4, m and n are not equal, and m + n is an integer of 3-6. ] The manufacturing method of the cyclic olefin type copolymer characterized by using the catalyst containing the metallocene compound (A) and aluminoxane (B) represented by these. 2. The cyclic olefin is represented by the general formula [2]: (In the formula, R ^{1 to} R ¹² represent a substituent selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 20 carbon atoms, provided that R ⁵ and R ⁷ are bonded to each other. A cyclic olefin-based copolymer according to claim 1, which is a compound represented by the formula (1) to form a ring together with a carbon atom present therein, and q represents an integer of 0 or more. Manufacturing method. 3. The cyclic olefin-based copolymer is α-
5 to 99 mol% of repeating units derived from olefin,
The repeating unit derived from a cyclic olefin is in the range of 1 to 95 mol%, and the weight average molecular weight (Mw) / number average molecular weight (Mn) is 1.5 to 4.5. Alternatively, the method for producing the cyclic olefin-based copolymer according to item 2. 4. The ratio of the aluminoxane (B) to the metallocene compound (A) in the catalyst is such that the ratio of the aluminum atom in the aluminoxane (B) to 1 mol of the metallocene compound (A) in the polymerization reaction system is 1. producing a cycloolefin copolymer according to any one of claim 1-4, characterized in that in the 10 ⁷ range. 5. The method for producing a cyclic olefin-based copolymer according to any one of claims 1 to 4, wherein the α-olefin is ethylene.