JPH0718021A - Method for polymerizing cycloolefin - Google Patents

Abstract

PURPOSE:To obtain a cycloolefin polymer with a mol.wt. suitable for its application by polymerizing a cycloolefin using a specific catalyst in the presence of a specific alpha-olefin in a controlled concn. CONSTITUTION:A cycloolefin is polymerized using a catalyst comprising a compd. of a metal of group VIII [e g. bis(acetylacetonato)metal] and an organometallic compd. [e.g. an organoaluminum compd. of formula I or II (wherein R is a 1-3C hydrocarbon group; and n is 1-50)] in the presence of a 3-20C alpha-olefin (e.g. propylene or heptadecene) in a controlled concn. The mol.wt. of the resultant cycyloolefin polymer is controlled as desired by controlling the concn. of the alpha-olefin. A cycloolefin polymer formerly obtd. by using the above catalyst has too high a mol.wt., and a method for obtaining the polymer with a desired mol.wt., i.e., desired physical properties, moldability, etc., has been wanted.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for polymerizing cyclic olefins. Specifically, it relates to a method for controlling the molecular weight of a cyclic olefin polymer when polymerizing a cyclic olefin using a catalyst composed of a specific metal compound and an organometallic compound.

[0002]

The first method for polymerizing a cyclic olefin to produce an addition polymerization type heat-resistant resin is a method using a catalyst composed of a metallocene compound and an aluminoxane by W. Kaminsky et al. (Catalytic Olefin Polymeri).
zation edited T. Keii and K. Soga Kodansha 1990).
Moreover, some of the present inventors have already reported that cyclic olefins can be polymerized with relatively high activity by using a metallocene catalyst having an asymmetric ligand (Japanese Patent Laid-Open No. 3-1395).
No. 06 bulletin). It has also been reported that a cyclic olefin polymer with high activity can be obtained by using a catalyst composed of a metal compound of Group VIII of the Periodic Table and an organometallic compound (JP-A-4-63807).

[0003]

The method using a catalyst composed of a metal compound of Group VIII of the Periodic Table and an organometallic compound can give a cyclic olefin copolymer with high activity with a relatively inexpensive catalyst. Although it is an excellent method, the molecular weight of the obtained polymer is large, and it is necessary to develop a method of giving a polymer having a desired molecular weight according to the purpose such as making desired physical properties and moldability.

[0004]

[Means for Solving the Problems] The present inventors have conducted intensive studies on a method for producing a cyclic olefin polymer having a controlled molecular weight by solving the above problems, and completed the present invention.

That is, the present invention is a method for polymerizing a cyclic olefin using a catalyst comprising a metal compound of Group VIII of the Periodic Table and an organometallic compound, wherein the cyclic olefin is polymerized by an α-olefin having 3 to 20 carbon atoms. And the molecular weight of the resulting cyclic olefin polymer is 3 to 20 carbon atoms.
The method for polymerizing cyclic olefins is characterized in that it is controlled by the concentration of α-olefin. In the present invention, the α-olefin having 3 to 20 carbon atoms is a compound represented by the following general formula (Formula 1).

[0006]

Embedded image H ₂ C═CH—R (wherein R is an alkyl residue having 1 to 18 carbon atoms) can be exemplified, and specifically, propylene, butene, pentene, hexene, heptene, octene, nonene, decene. , Heptadecene, octadecene, and the like. Examples of the cyclic olefin in the present invention include cyclopentene, cyclohexene, norbornene, and those in which a part of hydrogen is substituted with an alkyl group having 1 to 20 carbon atoms.

In the present invention, compounds of Group VIII metal of the periodic table include iron, ruthenium, osmium, cobalt, iridium, nickel, palladium, platinum, cyclopentadienyl group, substituted cyclopentadienyl group and indenyl group. , A fluorenyl group, a π-allyl group, a substituted allyl group, an acetylacetonate group, a substituted acetylacetonate group, a cyclic unsaturated hydrocarbon group, a halogen atom, a carbonyl group and the like. Specifically, biscyclopentadienyl metal, bis (substituted cyclopentadienyl) metal, bisindenyl metal, virfluorenyl metal, bisallyl metal, allyl (cyclopentadienyl) metal, tricarbonyl (allyl) Examples include metal, bis (acetylacetonate) metal, and tris (acetylacetonate) metal. Furthermore, a triphenylphosphine complex such as tetrakis (triphenylphosphine) nickel can be exemplified.

In the present invention, the organometallic compound is
Organoaluminum compounds, particularly alumoxane, are preferable, and as alumoxane, two kinds of structures represented by the following general formulas (Formula 2) and (Formula 3) (in the formula, R is a hydrocarbon residue having 1 to 3 carbon atoms, and n is 1 to An integer of 50.) is known,
Any of these can be used, and in particular, a methylaluminoxane in which R is a methyl group and n is 5 or more, preferably 10 or more is used.

[0009]

[Chemical 2]

[0010]

[Chemical 3] The use ratio of the aluminoxane to the Group VIII metal compound is 10 to 100,000 mole times, and usually 50 to 5000 mole times.

In addition to alumoxane, a compound capable of forming a stable anion under the reaction conditions may be used in combination with alkylaluminum.
20 alkylaluminum, specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum, and other trialkylaluminums, and some of their alkyl residues are replaced with halogen atoms. Examples of the compound include The amount of alkylaluminum to be used is generally 1 to 1000 times the molar amount of the compound of Group VIII of the Periodic Table. In addition to tetraphenylborane anion, tetrakis (substituted phenyl) borane anion, tetraphenylaluminum anion, tetrakis (substituted phenyl) aluminum anion, various compounds are already known as compounds that form stable anions under the reaction conditions. Many compounds are exemplified in, for example, JP-A-1-501950 and 1-502036, and the amount of these compounds used is 0.1 to 100 mol times that of the Group VIII compound in the periodic table. Generally there is.

The polymerization conditions are not particularly limited, and a solvent polymerization method using an inert medium, a bulk polymerization method in which substantially no inert medium exists, or a gas phase polymerization method can be used.
Generally, the polymerization temperature is −100 to 200 ° C., and the polymerization pressure is normal pressure to 100 kg / cm ² . The pressure is preferably -100 to 100 ° C and normal pressure to 50 kg / cm ² . The present invention is also applicable to copolymerization of cyclic olefin and ethylene. The amount of α-olefin having 3 to 20 carbon atoms cannot be specified because it depends on what range the molecular weight of the cyclic olefin polymer is controlled. However, the intrinsic viscosity is about 1/10000 to 1/10 of the cyclic olefin. It is possible to reduce the molecular weight to about 1/10, and it is possible to achieve a good balance between physical properties and moldability in this range.

[0013]

EXAMPLES The present invention will be further described with reference to the following examples. Example 1 0.5 g of aluminoxane manufactured by Tosoh Akzo and 1 ml of toluene were placed in a 50 ml flask under a nitrogen stream and 5 mg of bis (acetylacetonato) nickel was added while stirring, 2 ml of norbornene was added, and the mixture was stirred at 20 ° C. for 5 hours. . Reaction solution
The polymer was taken out by throwing it in 50 ml of methanol, filtering and drying. The obtained polymer was 0.90 g, and the intrinsic viscosity measured with a tetralin solution at 135 ° C. was 2.75 dl / g.
On the other hand, 1-hexene is 1/200 with respect to norbornene,
When added in a 1/100 and 1/50 molar ratio, the intrinsic viscosities were
1.20, 0.70, 0.43dl / g, the yields are 0.85,
0.88 and 0.89 g, which is not much different from the glass transition temperature.
238, 242, 237 and 245 ° C.

Example 2 When 1 / octene was used in 1/100 instead of hexene-1, the yield was 0.91 g, the glass transition temperature was 243 ° C., and the intrinsic viscosity was 0.78.

[0015]

The molecular weight of the cyclic olefin polymer can be controlled by carrying out the method of the present invention, which is industrially valuable.

Claims (1)

[Claims] 1. A method for polymerizing a cyclic olefin using a catalyst comprising a metal compound of Group VIII of the Periodic Table and an organometallic compound, wherein the polymerization of the cyclic olefin is carried out with 3 to 2 carbon atoms.
A method for polymerizing a cyclic olefin, which comprises controlling the molecular weight of the resulting cyclic olefin polymer in the presence of 0 α-olefin by controlling the concentration of the α-olefin having 3 to 20 carbon atoms.