JPS61272216A - Production of cyclic olefin random copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having transparency and improved heat and chemical resistance, etc., by continuously copolymerizing ethylene with a cyclic olefin in a hydrocarbon based solvent containing a catalyst consisting of a soluble V compound and organoaluminum compound kept under specific conditions. CONSTITUTION:Ethylene is continuously copolymerized with a cyclic olefin expressed by formula I or II (n and m are positive numbers; l is >=3; R<1>-R<10> are H, halogen or hydrocarbon) in the presence of a catalyst consisting of a soluble vanadium compound, e.g. VO(OC2H5)Cl2 and an organoaluminum compound, e.g. ethylaluminum sesquichloride, existing to keep >=2, preferably 3-20 ratio (Al/V) of the vanadium atom to the aluminum atom in a hydrocarbon based solvent, e.g. toluene, in the polymerization system preferably at -20-+60 deg.C to afford the aimed copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a cyclic olefin random copolymer. More specifically, the production of a cyclic olefin random copolymer that has excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties, and has a narrow molecular weight distribution and composition distribution. The present invention provides a method.

[Conventional technology]

Polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and the like are known as synthetic resins with excellent transparency. For example, polycarbonate is a resin that has excellent heat resistance, heat aging resistance, and impact resistance as well as transparency. However, there is a problem that it is easily attacked by strong alkalis and has poor chemical resistance. Polymethyl methacrylate is Kfl such as ethyl acetate, acetone, and toluene.
There are problems in that it easily erodes, swells in ether, and has low heat resistance. Furthermore, although polyethylene terephthalate has excellent heat resistance and mechanical properties, it is susceptible to strong acids and alkalis and is susceptible to hydrolysis.

On the other hand, polyolefins, which are widely used as general-purpose resins, have excellent chemical resistance, solvent resistance, and mechanical properties, but many have poor heat resistance, and because they are crystalline resins, less transparent. Generally, to improve the transparency of polyolefins, methods are used to refine the crystal structure by adding a nucleating agent, or to stop crystal growth by rapid cooling, but these methods cannot be said to be sufficiently effective. On the contrary, adding a third component such as a nucleating agent may impair the excellent properties originally possessed by polyolefins, and the rapid cooling method not only requires large-scale equipment, but also reduces the degree of crystallinity. Therefore, there is a possibility that heat resistance and rigidity may also be reduced.

For copolymers of ethylene and bulky comonomers,
For example, U.S. Pat. No. 2,883,372 discloses a copolymer of ethylene with 2,3-dihydrodicyclopentadiene. However, although this copolymer has an excellent balance of rigidity and transparency, it has a glass transition temperature of 100%.
It has poor heat resistance, around ℃. Also, copolymers of ethylene and 5-ethylidene-2-norbornene have similar drawbacks.

Also, in Japanese Patent Publication No. 46-14910, 1.4.5
゜8-dimethano-1,2,3,4,,4a% 5.8
．． A homopolymer of 8"s-octahydronaphthalene has been proposed, but this polymer has poor heat resistance and heat aging resistance.
Furthermore, in Japanese Patent Application Laid-Open No. 58-127728,
．． 5.8-dimethano-1,2,3,4,4as 5,8
．． A homopolymer of 8a-, t-tahito-of-y talene or a copolymer of the cyclic olefin and a norbornene type comonomer has been proposed, but the above-mentioned publication states that both of these polymers are ring-opening polymers. It is clear from the description.

Since such ring-opened polymers have unsaturated bonds in the polymer main chain, they have the disadvantage of poor heat resistance and heat aging resistance.

[Problem that the invention seeks to solve]

Therefore, the present inventors conducted extensive research into a method for obtaining a synthetic resin that is transparent and has a good balance of heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and mechanical properties. discovered that a copolymer of ethylene and a specific bulky comonomer could achieve the purpose, and had already filed a patent application in 1982.
-16995, Japanese Patent Application No. 59-220550, Japanese Patent Application No. 59-236828, Japanese Patent Application No. 59-236829,
This was proposed in Japanese Patent Application No. 59-242336. The present inventors investigated a method for producing a cyclic olefin random copolymer having narrow molecular weight distribution and composition distribution, excellent uniformity, and improved transparency.Soluble vanadium compound We have discovered that the above object can be achieved by carrying out continuous copolymerization under specific conditions in a liquid phase consisting of a hydrocarbon medium in the presence of a catalyst formed from an organic aluminum compound and an organoaluminum compound, and have thus arrived at the present invention. did.

[Operations for solving the problems] and [Operations] The present invention provides the following method for reacting ethylene with the following general formula ( r) and general formula (ff
), the ratio of aluminum atoms to vanadium atoms in the liquid phase of the polymerization reaction system (, Jl/V) This is a method for producing a cyclic olefin random copolymer, which is characterized in that the copolymerization is carried out continuously while maintaining 2 or more.

In formula C, both n and m are positive integers, and! is a positive number of 3 or more, and R1 to RIG each represent a hydrogen atom, a halogen atom, or a hydrocarbon group].

In the method of the present invention, the soluble vanadium compound component used as a catalyst component is a vanadium compound component soluble in the hydrocarbon medium of the polymerization reaction system, and specifically has the general formula VO(OR)aXb or ■(OR). cXd (However, L
R is a hydrocarbon group, 0≦a≦6.0≦b≦6.2≦a-)
-b≦3, Q≦C≦4.0≦d≦4.6≦c+d≦4)
Typical examples include vanadium compounds represented by or electron donor adducts thereof. More specifically, 1dVo(J, , VO(QC2H,)(J
2. VC(○CtH+)t C6, VO(0-iso
-C,H? ) C11t, ■○ (0-n-G< HQ
) C1t, ■○(OCt R5)s, VOBr
2.VC:1. , VOC12, VO(0-n -C4H
Examples include a)s, V C1, 20'C, H, OH, and the like.

Electron donors that may be used in the preparation of the soluble vanadium catalyst component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides. , an oxygen-containing electron donor such as alkoxysilane, a nitrogen-containing electron donor such as ammonia, amine, nitrile, iso-7anate, and the like. More specifically, methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, inglobil alcohol, cumyl alcohol, isopropylbenzyl Alcohols having 1 to 18 carbon atoms such as alcohol; phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, flobylphenol, nonylphenol, cumylphenol, and naphthol; ; Acetone, methyl ethyl ketone, methyl in butyl ketone,
Ketones having 3 to 15 carbon atoms such as acetophenone, benzophenone, and benzoquinone; Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde; methyl formate, methyl acetate, and ethyl acetate. , vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, benzoate ethyl acid, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate,
Methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diimpropyl tetrahydrophthalate, diethyl heptathalate, shitubunal phthalate, di-n-butyl phthalate, phthalate 2-60 carbon atoms such as di2-ethylhexyl acid, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc.
organic acid esters; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride; methyl ether;
Ethers with 2 to 20 carbon atoms such as ethyl ether, inpropyl ether, butyl ether, amyl ether, tetrahydrofuran, phenol, and diphenyl ether; Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; Methylamine, ethylamine, diethylamine , tributylamine, viveridine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine, and other nitrites; acetonitrile, benzonitrile, tolnitrile, and other nitriles; ethyl silicate, diphenyldimethoxysilane, and other alkoxysilanes. be able to. Two or more types of these electron donors can be used.

As the organoaluminum compound catalyst component used in the present invention, compounds having at least one kl-carbon bond in the molecule can be used. For example, (1) general formula R+m
AA (OR”)nHpX.

(Here, R1 and Rt are carbon atoms usually from 5 to 15.
, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. X is halogen, m is 0≦
m≦6, n is 0≦n(3, p is 0≦n(3, q is 0≦q
<3, and m+n-)-p+q=3), (11) General color M'AIR' (Kokote M' has Ll, Na, and R' is the same as above), and complex alkylated products of Group 1 metals and aluminum can be mentioned.

Examples of the organoaluminum compounds belonging to the above (1) include the following.

General formula R'mA! (OR”)s−m (where R1 and R2 are the same as above; m is preferably a number of 1.5≦m≦3).

General formula R'mAIX, -1 (Here R1 is the same as above. Same as above. m is preferably 2≦m(3
).

General formula R'TnAl(OR2)nXQ (where R' and R2 are the same as before.
≦n (3,0≦q<3, and m-)-n+q=3)
Examples include those expressed as .

More specifically, aluminum compounds belonging to (1) include trialkylaluminum such as triethylaluminum and tributylaluminium; trialkylaluminum such as triisopropylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and diptylaluminium butoxide. ; In addition to alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, R' Al0R2)
Partially alkoxylated alkyl aluminum having an average composition of 0.5 to 0.5; dialkylaluminum halides such as diethylaluminum chloride, diptylaluminum chloride, diethylaluminium bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride, alkylaluminum sesquihalides such as ethylaluminum sesquipromide, ethylaluminum dichloride, propylaluminum dichloride,
Partially halogenated alkylaluminiums such as alkylaluminum cybarides such as butylaluminum dipromide; dialkylaluminum hydrides such as diethylaluminum hydride, diptylaluminum hydride, ethylaluminum dicdride, propylaluminum dihydride, etc. Partially hydrogenated alkyl aluminums such as alkylaluminum haladride; partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxy chloride, ethylaluminum ethoxybromide, etc. may be exemplified.

Further, as a compound similar to (1), an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. Examples of such compounds include (c, H,)2 AAOA/ (c, R5
)2゜(C4Ha)t AIOAg (04H1+
)2, (C2Hs)2 AAN Al(C2R5)2
Examples include:

C,H.

As a compound belonging to the above (11), LiAJl!
(Crt Hs)42, LIAjl (C, lH1!
) 4 etc. can be exemplified. Among these, it is particularly preferable to use alkylaluminum halides, alkylaluminum cibarides, or mixtures thereof.

In the method of the present invention, the cyclic olefin used as a polymerization raw material has the general formula (1) and the general formula [where n and m are both positive integers, β is a positive integer of 6 or more, , R' to RIG each represent a hydrogen atom, a halogen atom, or a hydrocarbon group.

The cyclic olefin represented by the general formula (I) can be easily produced by condensing cyclopentadiene and the corresponding olefin by Diels-Alder reaction, and the cyclic olefin represented by the general formula [II] Olefins can also be easily produced by condensing cyclopentadiene and the corresponding cyclic olefin by Diels-Alder reaction. General formula (1)
Specifically, the cyclic olefin represented by is, for example, 1,4.5.8-dimethano-1,2,3,4,4a
+ 5.8.8a-In addition to octahydronaphthalene,
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-propyl-1,4,5,8-dimethano-1,2,3
゜4,4as s, s, 8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethanol-1,
2,3,4,4as 5.8゜8a-octahydronaphthalene, 2-stearyl-1,4,5,8-dimethano-
1,2,3,4,4am 5.8.8a-octahydronaphthalene, 2.3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4ax 5.8.8a- Octahydronaphthalene, 2-methyl-3-ethyl-1,4,
5,8-dimethano-1,2,3,4,4a15.8.8
a-octahydronaphthalene, 2-chloro-1,4,5
,8-dimethano-1,2,3,4,4a+ 5.8.8
a+ -octahydronaphthalene, 2-promo 1.4
．． 5.8-dimethano-1,2,3,4,4a%5,8.
8a-octahydronaphthalene, 2-fluoro-1,4
,5,8,-dimethano-1,2,3,4,4at s,
a, 8a-octahydronaphthalene, 2,3-dichloro-1,4,5°8-dimethano-1,2,3,4,4
a, 5.8.8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3
, 4,4a, 5.8.8a-octahydronaphthalene, 2-n-butyl-1,4,5,8-dimethano-i,
2.3.4.4a+, 5.8.8a-octahydronaphthalene, 2-inbutyl-1,4,5,8-dimethano-1,2,3,4°4a+ 5.8.8a-octahydronaphthalene Examples include octahydronaphthalenes such as and the compounds listed in Table 1.

In addition, in the method of the present invention, the ethylene and the cyclic olefin are copolymerized, but in addition to the two essential components, other copolymerizable components may be used as necessary within the scope of not impairing the purpose of the present invention. It is also possible to copolymerize unsaturated monomer components.

Specifically, the copolymerizable unsaturated monomers include propylene, 1-butene, 4-methyl-1-pentene, - 2-olefins having 3 to 20 carbon atoms, such as hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-octadecene, 1-eicosene, etc. cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene t3 in an amount less than equimolar to the cyclic olefin component unit in the random copolymer.
a, s.

Cycloolefins such as 6.7a-tetrahydro-4,7-methano-1H-indene (general formula: aOl), 1
．． 4-hexadiene 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-
Norbornene, non-conjugated dienes such as 5-vinyl-2-norbornene, norbornene-2,5-methylnorbornene-2,5-ethylnorbornene-2,5-impropylnorbornene-2,5-n-butylnorbornene-
2,5-1-butylnorbornene-2,5,6-dimethylnorbornene-2,5-chloronorbornene-2,2
-Fluoronorbornene-2+ 5.6- All examples include norbornenes such as dichloronorbornene-2.

The copolymerization reaction according to the method of the invention is carried out in a hydrocarbon medium. Hydrocarbon media include, for example, aliphatic hydrocarbons such as hexane, heptane, octane, and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; Examples include sexually unsaturated monomers, and even mixtures of two or more of these monomers may be used.

In the method of the invention, the copolymerization reaction is carried out in a continuous manner. The concentration of the soluble vanadium compound supplied to the polymerization reaction system at that time is usually 10 times or less, preferably 7 to 1 times the concentration of the soluble vanadium compound in the polymerization reaction system,
More preferably, it is in the range of 5 to 1 times. Further, the ratio of aluminum atoms to vanadium atoms (Al/V) in the polymerization reaction system is 2 or more, preferably 2 to 50,
Particularly preferably, it is in the range of 3 to 20. The soluble vanadium compound and the organoaluminum compound are each normally supplied diluted with the hydrocarbon medium. Here, it is desirable to dilute the soluble vanadium compound to the above concentration range, but a method is adopted in which the organoaluminum compound is prepared to an arbitrary concentration, for example, 50 times or less of the concentration in the polymerization reaction system, and then supplied to the polymerization reaction system. be done. In the method of the present invention, the amount of soluble vanadium compound in the copolymerization reaction system is usually 0.01 to 5 gram atoms/1. A preferred range is 0.05 to 3 gram atoms/l.

Further, in the method of the present invention, the copolymerization reaction is carried out at a temperature of -50 to 100°C, preferably -30 to 80°C, more preferably -20 to 60°C. In the method of the invention, the copolymerization reaction is carried out in a continuous manner.

Ethylene and cyclic olefin as polymerization raw materials, a copolymerizable component to be copolymerized as necessary, a soluble vanadium compound component as a catalyst component, an organoaluminum compound component, and a hydrocarbon medium are continuously supplied to the polymerization reaction system, and the polymerization is carried out. A reaction mixture is continuously withdrawn from the polymerization reaction system. If a continuous polymerization method is not used, that is, if a batch copolymerization method is used, only a copolymer with a wide molecular weight distribution and poor transparency will be obtained, and the effects of the present invention described above will not be fully achieved. The average residence time for the copolymerization reaction varies depending on the type of polymerization raw material, the concentration of the catalyst component, and the temperature, but is usually in the range of 5 minutes to 5 hours, preferably 10 minutes to 6 hours. The pressure during the copolymerization reaction is usually over 0 and 5C.
Lk19/d, preferably maintained at more than 0 and 20 kg/l, and optionally an inert gas such as nitrogen or argon may be present. In addition, in order to adjust the molecular weight of the copolymer, a molecular weight regulator such as hydrogen may be present as appropriate.The cyclic olefin random copolymer can be prepared by treating the polymerization reaction mixture after the copolymerization reaction according to a conventional method. A polymer is obtained.

In the method of the present invention, the molar ratio of ethylene/cyclic olefin fed to the copolymerization reaction is usually 99/1 to 1/
99. Preferably it is in the range of 98/2 to 2/98.

Further, the cyclic olefin random copolymer obtained by the method of the present invention is non-quality or crystalline, but among the cyclic olefin random copolymers, it has a DSC melting point and an X-ray diffraction measurement result. Amorphous copolymers are preferred.

Further, the ethylene/cyclic olefin molar ratio of the cyclic olefin random copolymer obtained by the method of the present invention is usually 99/1 to 1/99, preferably 98/2.
The range is from 2/98 to 2/98. Further, the glass transition point (Tg) of the cyclic olefin random copolymer is usually 10
The temperature range is from 20 to 240°C, preferably from 20 to 200°C.

The cyclic olefin random copolymer obtained by the method of the present invention has excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties, and has a low molecular weight distribution and composition distribution. Because it is narrow and has excellent uniformity, its low molecular weight product is used as a synthetic wax for waxing, for example.
Pine shaft impregnation agent, paper processing agent, sizing agent, rubber anti-aging agent, cardboard waterproofing agent, chemical fertilizer slowing agent, heat storage agent, ceramic binder, paper capacitor, electric wire, cable, etc.! Air insulation materials, neutron moderators, textile processing aids, water repellents for building materials, paint protection agents, polishing agents, thixotropy agents, pencil/crayon lead hardening agents, carbon ink base materials, electrostatic toners, It can be used in fields such as synthetic resin molding lubricants, mold release agents, resin colorants, hot melt adhesives, and lubricating greases. In addition, the polymer can be used in optical lenses, optical discs, and optical fibers. Optical fields such as glass window applications, electric iron water tanks, microwave oven supplies, LCD display substrates, printed circuit boards, high frequency circuit boards, transparent conductive sheets and films, and electrical fields such as syringes, pipettes, animal gauges, etc. It can be used in a variety of fields such as medicine, chemistry, camera bodies, various instruments, film, helmets, etc.

On the other hand, when the cyclic olefin content is about 20 mol % or less, it can be used in fields utilizing shape memory, as an allocation material or as a tube.

Specifically, we use fittings for odd-shaped pipes, laminate materials for the inside and outside of pipes and rods, and bins for tightening optical fiber connectors.
It can be used in various fields such as casts, containers, rotating bumpers, various gap prevention materials, soundproofing materials as laminates with metal surface materials, and medical tubes.

〔Effect of the invention〕

The cyclic olefin random copolymer obtained by the method of the present invention has excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties, and has a low molecular weight distribution and composition distribution. It has the characteristics of being narrow and having excellent uniformity.

〔Example〕

Next, the method of the present invention will be specifically explained with reference to Examples.

Example 1 Using a 2E glass polymerization vessel equipped with stirring blades, ethylene and 2-methyl-1,4,5,8-dimethano-
A copolymerization reaction of 1,2,3,4,4a, 5.8.8a-octahydronaphthalene ((7) in Table 5: hereinafter abbreviated as M-DMON) was carried out. That is, from the top of the polymerization vessel, M
- A toluene solution of DMON is converted into M-DMO in a polymerization vessel.
N thick & is 60#/A,! −? eru! sea urchin 0.91 per hour,
A toluene solution of VO (00, H,) Czz was used as a catalyst, and the vanadium concentration in the polymerization vessel was 0.5 mm01/β.
0.71 per hour. Ethylaluminum sesquichloride (AI ((It Hs) +, a C right, 5
) were continuously fed into the polymerization vessel at a rate of 0.46 per hour so that the aluminum concentration in the polymerization vessel was 2 mmol/l. The polymerization solution is continuously drawn out so that the amount of polymerization solution is always 14. Also, from the top of the polymerization vessel, ethylene is added every +13!
M, nitrogen is supplied at a rate of 80 A per hour.

The copolymerization reaction was carried out at 10° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel. When the copolymerization reaction is carried out under the above conditions, a polymerization reaction mixture containing an ethylene/M-DMON random copolymer is obtained. Polymerization solution K extracted from the lower part of the polymerization vessel and a small amount of tutanol were added to stop the polymerization reaction, and then poured into a large amount of acetone/methanol to precipitate the produced copolymer. After thoroughly washing the copolymer with acetone, it was dried under reduced pressure at 80° C. all day and night. Through the above operations, an ethylene/M-DMON random copolymer was obtained at a rate of 30 g/hour.

The ethylene composition of the copolymer measured by +30-NMR analysis was 63 mol %, the intrinsic viscosity [η] measured in decalin at 135° C. was 0.92, and the iodine value was 1.0.

The crystallinity by X-ray diffraction was 0%, and the transparency was 3.1% when measured on a 1-hour sheet using a haze meter based on ASTM D 1003-52.

The glass transition temperature Tg is Dynamic Mechanical Anal manufactured by DuPont.
The loss modulus E" was measured using a yser (DMA) at a heating rate of 5°C/Ran, and was found to be 127°C from the peak temperature.Furthermore, the melting point Tm was 127°C.
No melting curve (peak) was observed when the temperature was measured in the range from -120°C to 400°C using a 90 type DSC at a heating rate of 10°C/acid.

Examples 2 to 10 and Comparative Example 1 Continuous copolymerization was carried out in the same manner as in Example 1 except that the copolymerization conditions were changed as shown in Table 3. Table 3 shows the physical properties of the obtained copolymer. In Example 8, a 1:1 mixed solvent of toluene/cyclohexane was used as the polymerization solvent.

Comparative Example 2 A stirring blade, a gas blowing tube, a thermometer, and a dropping funnel were attached to a sufficiently dried SOML separable flask, and the flask was sufficiently purged with nitrogen. 250 ml of toluene dehydrated and dried with a molecular sheep was placed in this flask. In a flask under nitrogen flow, 7. (a) in Table 5 was added as a cyclic olefin.
5. ! i', ethylaluminum sesquichloride (Al
(Ct H5)1.5 Cl11. C1,5+)
%/I/, drip o -) VO(OC, Hs)
(A total of 0.125 mmol of Jt was added. Ethylene 10β/hr, nitrogen 40411/hr, dried through a gas blowing pipe.
hr of mixed gas was passed through the flask controlled at 10° C. for 10 minutes. The copolymerization reaction was started by dropping ethylaluminum sesquichloride from the dropping funnel, and the batchwise copolymerization reaction was carried out at 10° C. for 30 minutes while passing the mixed gas. After stopping the copolymerization reaction by adding 5 methanol to the polymerization solution, the polymerization solution was poured into a large amount of methanol and acetone to precipitate a copolymer, and after further washing with acetone, it was vacuum dried at 80°C overnight. , 2.0 g of copolymer was obtained. The physical properties of the obtained copolymer were measured in the same manner as in Example 1.

The results are shown in Table 4.

Procedural amendment (voluntary) August 2, 1985 Michibe Uga, Commissioner of the Patent Office■, Case description 1985 Patent Application No. 113074 2, Title of invention Process for producing cyclic olefin random copolymer 3, Amendment Patent applicant (588) Mitsui Petrochemical Industries Co., Ltd. Representative: Shogo Takebayashi 4, Agent: 3-2-5-5 Kasumigaseki, Chiyoda-ku, Tokyo 100, No date of amendment order 7, Contents of the amendment The statement "Tomelt adhesive, which can be used in the field of..." on page 27, line 17 to page 28, line 15 of the original specification is corrected as follows.

It can be used in fields such as melt adhesives, lubricating greases, pigment dispersants, laser printer inks, painting primers, paints, and viscosity index improvers.In addition, its high molecular weight products can be used in optical lenses, magneto-optical disks, Optical cards, optical disks, optical fibers, glass windows, Fresnel lenses, array lenses for lasers, optical fiber connectors, recording sheets and films for holography, gradient index flat lenses (gray rad lenses), surface hardness, modified optical materials ( (dispersed glass or ceramics with the same refractive index), polarizing filters, optical wavelength selection filters, photosensitive films, covers and encapsulants for LEDs and semiconductor lasers, mirrors, prisms, substrates for beam splitters-1EL, etc. fields, electric iron water tanks, microwave oven supplies, LCD display substrates, flexible printed circuit boards,
High-frequency circuit boards, transparent conductive sheets and films, film capacitors, insulating coatings, lighting equipment materials, window materials for display elements, housings for electrical equipment, protective films for lithography, etc. in the electrical field, syringes, pipettes, animals Separation membranes in the medical and chemical fields such as cages, thermometers, beakers, petri dishes, graduated cylinders, bottles, artificial indirects, chromatographic carriers, gas separation membranes, ultrafiltration membranes, reverse osmosis membranes, gas-liquid separation membranes, etc. It can be used in various fields such as camera bodies, various instrument housings, films, helmets, toys, and stationery.

Claims (1)

[Claims] (1) In the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound, ethylene and unsaturated monomers represented by the following general formulas [I] and [II] are mixed in a liquid phase consisting of a hydrocarbon medium. In a method of copolymerizing at least one cyclic olefin selected from the group consisting of A method for producing a cyclic olefin random copolymer, which comprises copolymerization. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, n and m are both positive integers, and l is an integer of 3 or more. , R^1 to R^1^0 each represent a hydrogen atom, a halogen atom, or a hydrocarbon group].