JPH07643B2 - Process for producing amorphous cyclic olefin random copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an amorphous cyclic olefin random copolymer. More specifically, an amorphous olefin random copolymer having excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and various mechanical properties, and having a narrow molecular weight distribution and composition distribution. It provides a manufacturing method of.

[Conventional technology]

Polycarbonate, polymethylmethacrylate, polyethylene terephthalate, and the like are known as synthetic resins having excellent transparency. For example, polycarbonate is a resin that is excellent in transparency, heat resistance, heat aging resistance, and impact resistance. However, there is a problem that it is easily attacked by a strong alkali and has poor chemical resistance. Polymethylmethacrylate is easily attacked by ethyl acetate, acetone, toluene, etc., swells in ether, and has a problem of low heat resistance. Further, although polyethylene terephthalate has excellent heat resistance and mechanical properties, it has a problem that it is weak against strong acids and alkalis and is easily hydrolyzed.

On the other hand, polyolefin, which is widely used as a general-purpose resin, has many excellent chemical resistance, solvent resistance, and mechanical properties, but many have poor heat resistance. Inferior in transparency. In general, in order to improve the transparency of polyolefin, a method of adding a nucleating agent to refine the crystal structure or quenching to stop the crystal growth is used, but the effect cannot be said to be sufficient. Rather, the addition of a third component such as a nucleating agent may impair the excellent properties inherent to polyolefin, and the quenching method requires a large amount of equipment and reduces the crystallinity. As a result, heat resistance and rigidity may be reduced.

For a copolymer of ethylene and a bulky comonomer,
For example, in US Pat. No. 2,883,372, ethylene and 2.3-
Copolymers with dihydrodicyclopentadiene are disclosed. However, although this copolymer has an excellent balance of rigidity and transparency, it has a glass transition temperature of around 100 ° C and is poor in heat resistance.

Further, JP-B-48-196 proposes a method for producing a homogeneous copolymer by continuously copolymerizing ethylene and bicycloheptene in the presence of a catalyst composed of a vanadium compound and an organoaluminum compound. . However, the copolymer obtained by this method is a crystalline cyclic olefin random copolymer because the melting point is recognized in any of them, such crystalline cyclic olefin random copolymer is poor in transparency, optical disk, light When it is used for optical materials such as fibers, it cannot be used for applications where these performances are required due to light scattering by the crystal part, light loss or increase in birefringence.

[Problems to be solved by the invention]

In view of the drawbacks of the conventional polyolefin or olefin copolymer as described above, the inventors of the present invention have transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and mechanical properties. As a result of investigating a well-balanced synthetic resin such as ethylene, it was obtained by continuously copolymerizing ethylene and cyclic olefin under specific conditions in the presence of a catalyst formed from a specific vanadium compound and an organoaluminum compound. The inventors have found that an amorphous cyclic olefin random copolymer to be achieved achieves the above-mentioned object, and arrived at the present invention.

[Means for Solving Problems] and [Action] According to the present invention, ethylene and bicycloquerken in a liquid phase composed of a hydrocarbon medium in the presence of a catalyst formed from a vanadium compound and an organoaluminum compound. And at least one selected from the group consisting of tricycloalkenes
In the method for producing an amorphous cyclic olefin random copolymer by copolymerizing with a cyclic olefin of a species, the vanadium compound is represented by the general formula VO (OR) aXb or V (OR) cXd (where R is a hydrocarbon). Base, 0 ≦ a ≦ 3, 0
≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4,
3 ≦ c + d ≦ 4), and a vanadium compound soluble in the hydrocarbon medium is used, and the vanadium compound is supplied to the copolymerization reaction system at a concentration not more than 10 times the concentration in the copolymerization reaction system. Keeping the ratio of aluminum atoms to vanadium atoms (Al / V) in the polymerization reaction system to 2 or more, continuously copolymerizing so that the content of the cyclic olefin component in the copolymer is in the range of 10 to 60 mol%. There is provided a method for producing an amorphous cyclic olefin random copolymer, which comprises carrying out polymerization.

FIG. 1 shows the steps for preparing the catalyst used in the method of the present invention.

In the method of the present invention, the vanadium compound catalyst component used as the catalyst constituent component is a vanadium compound soluble in the hydrocarbon medium of the polymerization reaction system (hereinafter sometimes referred to as a soluble vanadium compound), and specifically, General formula VO (OR) aXb or V (OR) cXd (where R is a hydrocarbon group,
0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦
Representative examples are vanadium compounds represented by 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4), or electron donor adducts thereof. More specifically, VOCl ₃ , VO
(OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (O-isoC ₃ H ₇ ) Cl ₂ , VO (OnC ₄
H ₉ ) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ , VOCl ₂ , VO (OnC ₄ H ₉ ) ₃ , V
Examples include Cl ₃ and 20C ₈ H ₁₇ OH.

Examples of the electron donor that may be used in the preparation of the vanadium compound catalyst component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides. , Oxygen-containing electron donors such as alkoxysilane, nitrogen-containing electron donors such as ammonia, amine, nitrile and isocyanate can be used. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc. C1-C18 alcohols; C6-C20 phenols which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol; acetone , Methyl ethyl ketone, methyl isobutyl ketone,
Acetonephenone, benzophenone, benzoquinone and other ketones having 3 to 15 carbon atoms; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and other aldehydes having 2 to 15 carbon atoms; methyl formate, methyl 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, benzoic acid ethyl,
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 nadicuate, diisopropyne tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, phthalate Acid di-n-butyl phthalate di2-ethylhexyl, γ-
Organic acid esters having 2 to 30 carbon atoms such as butyrolactone, δ-valerolactone, coumarin, phthalide and ethylene carbonate; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride. Ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acid amides such as acetamide, benzoic acid amide, toluic acid amide; methylamine, Ethylamine, diethylamine,
Tributylamine, piperidine, tribenzylamine,
Amines such as aniline, pyridine, picoline, and tetramethylenediamine; acetonitrile, benzonitrile,
Examples thereof include nitriles such as tolunitrile; and alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane. Two or more kinds of these electron donors can be used.

As the organoaluminum compound catalyst component used in the present invention, a compound having at least one Al-carbon bond in the molecule can be used. For example, (i) the general formula ▲ R ¹ _m ▼ Al (OR ² ) _n H _p X _q Here, R ¹ and R ² are hydrocarbon groups having usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other. X is halogen, m is 0 <m ≦ 3,
n is 0 ≦ n <3, p is 0 ≦ n <3, q is a number ≦ q <3, and m + n + p + q = 3), (ii) the general formula M ¹ Al Examples thereof include complex alkylated products of a Group 1 metal and aluminum represented by R ¹ ₄ (where M ¹ is Li, Na and K, and R ¹ is the same as above).

Examples of the organoaluminum compound belonging to (i) above include the following.

General formula ▲ R ¹ _m ▼ Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably 1.5
≦ m ≦ 3).

General formula ▲ R ¹ _m ▼ AlX _3-m (wherein R ¹ is the same as above, X is halogen, and m is preferably 0 <m <3).

General formula ▲ R ¹ _m ▼ AlH _3-m (where R ¹ is the same as above. M is preferably 2 ≦ m <3
Is).

General formula ▲ R ¹ _m ▼ Al (OR ² ) _n Xq (wherein R ¹ and R ² are the same as above. X is halogen, 0 <
m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

In the aluminum compound belonging to (i), more specifically, trialkyl aluminum such as triethyl aluminum and tributyl aluminum; trialkyl aluminum such as triisoprenyl aluminum; dialkyl aluminum alkoxide such as diethyl aluminum ethoxide and dibutyl aluminum butoxide;
In addition to alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, partially alkoxylated alkylaluminum having an average composition represented by ▲ R ¹ _0.5 ▼ Al (OR ² ) _0.5 ; diethyl Dialkyl aluminum halides such as aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide; ethyl aluminum sesquichloride, butyl aluminum sesquichloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide, ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dichloride Partially halogenated alkyl ethers such as alkyl aluminum dihalides such as bromide Minium; Dialkyl aluminum hydride such as diethyl aluminum hydride and dibutyl aluminum hydride; Partially hydrogenated alkyl aluminum such as alkyl aluminum dihydride such as ethyl aluminum dihydride and propyl aluminum dihydride; Ethyl aluminum ethoxy chloride, Butyl aluminum butoxy Partially alkoxylated and halogenated alkyl aluminums such as chloride and ethyl aluminum ethoxy bromide can be exemplified. Further, the compound similar to (i) may be an organoaluminum compound in which two or more aluminums are bound via an oxygen atom or a nitrogen atom. Examples of such compounds include (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ and (C ₄ H ₉ ) ₂ AlOAl.
(C ₄ H ₉ ) ₂ , Can be exemplified.

Examples of the compound belonging to (ii) above include LiAl (C ₂ H ₅ ) ₄ and LiAl
(C ₇ H _{15) 4} etc. can be exemplified. Among these, it is particularly preferable to use an alkylaluminum halide, an alkylaluminum dihalide or a mixture thereof.

In the method of the present invention, the cyclic olefin used as a polymerization raw material is at least one cyclic olefin selected from the group consisting of bicycloalkenes and tricycloalkenes, and usually has 7 to 20 carbon atoms. Is. Specific examples of cyclic olefins are shown in Table 1.
And the bicycloalkenes and tricycloalkenes listed in Table 2 can be exemplified.

Further, in the method of the present invention, the ethylene and the cyclic olefin are copolymerized, but in addition to the essential two components, other copolymers may be copolymerized as necessary within the range not impairing the object of the present invention. It is also possible to copolymerize unsaturated monomer components.
Specific examples of the copolymerizable unsaturated monomer include, for example, propylene, 1-butene, 4-methyl-1-pentene in the range of less than equimolar to the ethylene component unit in the produced random copolymer, -Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. α-olefins having 3 to 20 carbon atoms, random copolymer produced Cycloolefins such as cyclopentene, cyclohexene, 3-methylcyclohexene, and cyclooctene, which are less than equimolar to the cyclic olefin component unit in
1,4-hexadiene, 4-methyl-1,4-hexadiene,
5-methyl-1,4-hexadiene, 1,7-octadiene,
Non-conjugated dienes such as dicyclopentadiene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene, tetracyclo such as tetracyclododecene, 2-methyltetracyclododecene and 2-ethyltetracyclododecene Examples thereof include dodecenes.

The copolymerization reaction according to the method of the present invention is carried out in a hydrocarbon medium. Examples of the hydrocarbon medium include aliphatic hydrocarbons such as hexane, heptane, octane and kerosene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, and the above-mentioned polymerization. Examples thereof include a polyunsaturated monomer, and a mixed medium of two or more of these may be used.

In the method of the present invention, the copolymerization reaction is carried out in a continuous manner. At that time, the concentration of the soluble vanadium compound supplied to the polymerization reaction system is 10 times or less, preferably 7 to 1 times, more preferably 5 to 1 times the concentration of the soluble vanadium compound in the polymerization reaction system, 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 3 to 20. When the concentration of the soluble vanadium compound supplied to the copolymerization reaction system is higher than 10 times the concentration in the copolymerization reaction system, a copolymer having a uniform molecular weight distribution and a narrow composition distribution as the object of the present invention can be obtained. Absent. Further, when the ratio of aluminum atoms to vanadium atoms (Al / V) in the copolymerization reaction system is smaller than 2, the polymerization activity is low and the copolymer aimed at by the present invention cannot be obtained. The soluble vanadium compound and the organoaluminum compound are usually supplied after being diluted with the hydrocarbon medium. here,
The soluble vanadium compound needs to be diluted to the above concentration range, but the method of adjusting the organoaluminum compound to an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization reaction system and supplying it to the polymerization reaction system is adopted. It In the method of the present invention, the concentration of the soluble vanadium compound in the copolymerization reaction system is usually 0.01 to 5 gram atom / l as vanadium atom, preferably 0.05 to 3 gram atom / l.

In the method of the present invention, the copolymerization reaction is -50 to
It is carried out at a temperature of 100 ° C, preferably -30 to 80 ° C, more preferably -20 to 60 ° C. In the method of the present invention, the copolymerization reaction is carried out in a continuous manner. Polymerization raw material ethylene, cyclic olefin, a copolymerizable component to be copolymerized as necessary, a soluble vanadium compound component of the catalyst component, an organoaluminum compound component and a hydrocarbon medium are continuously supplied to the polymerization reaction system, The polymerization reaction mixture is continuously discharged from the polymerization reaction system. When the continuous polymerization method is not adopted, that is, when the batch copolymerization method is adopted, a copolymer having a wide molecular weight distribution and poor transparency is obtained, and the above-described effects of the present invention cannot be sufficiently achieved. The average distillation time in the copolymerization reaction varies depending on the kind of the polymerization raw material, the concentration of the catalyst component and the temperature, but it is usually 5 minutes to 5 minutes.
The time is preferably in the range of 10 minutes to 3 hours. The pressure during the copolymerization reaction is usually maintained at more than 0 and 50 kg / cm ² , preferably more than 0 and 20 kg / cm ² , depending on the case, in the presence of an inert gas such as nitrogen or argon. Good. Further, in order to adjust the molecular weight of the copolymer, a molecular weight modifier such as hydrogen can be appropriately present. An amorphous cyclic olefin random copolymer is obtained by treating the polymerization reaction mixture after completion of the copolymerization reaction according to a conventional method.

The ethylene / cyclic olefin molar ratio fed to the copolymerization reaction in the process of the invention is usually in the range of 99/1 to 1/99, preferably 92/2 to 2/98.

In addition, the amorphous cyclic olefin random copolymer obtained by the method of the present invention has no DSC melting point and is an amorphous copolymer from the measurement results by X-ray diffraction. Furthermore, the molar ratio of ethylene component / cycloolefin component of the amorphous cyclic olefin random copolymer obtained by the method of the present invention is usually 99/1 to 1/99, preferably 98/2 to 2/98. , More preferably in the range of 90/10 to 10/90, the content of the cyclic olefin component in the copolymer is usually
10 to 60 mol%. The glass transition point (Tg) of the amorphous cyclic olefin random copolymer is usually -10.
To 150 ° C, preferably 10 to 130 ° C.

The cyclic olefin random copolymer obtained by the method of the present invention is excellent in transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and various mechanical properties, and has a molecular weight distribution and a composition distribution. Since it has a characteristic of being narrow and excellent in uniformity, for example, its low molecular weight product can be used as a synthetic wax for candle applications, pine wood shaft impregnating agents, paper processing agents, sizing agents, rubber anti-aging agents, corrugated cardboard waterproofing agents, chemical conversion agents. Fertilizer slow-acting agent, heat storage agent, ceramic binder, electrical insulation material for paper capacitors, electric wires, cables, neutron moderator,
Textile processing aids, water repellents for building materials, paint protectors, polishes,
Thixotropic agent, pencil crayon core hardness agent,
Carbon ink base material, electrostatic copying toner, synthetic resin molding lubricant, release agent, resin colorant, hot melt adhesive, lubricating grease, pigment dispersant, laser printer ink, painting primer, paint, viscosity index It can be used in fields such as improvers. Also, the high molecular weight substance is an optical lens,
Magneto-optical disk, optical card, optical disk, optical fiber, glass window, Fresnel lens, array lens for laser, optical fiber connector, recording sheet / film for holographic, flat lens with gradient index distribution (grated lens), surface Hardness, modified optical materials (glass with the same refractive index, dispersed ceramics), polarization filters, optical wavelength selection filters, photosensitizing films, LED and semiconductor laser covers and sealants, mirrors, prisms,
Optical fields such as beam splitters and EL substrates, water tanks for electric irons, microwave oven products, substrates for liquid crystal displays,
Flexible printed circuit boards, high-frequency circuit boards, transparent conductive sheets and films, film capacitors, insulating coatings, materials for certification devices, window materials for display devices, housings for electrical equipment, electrical fields such as protect films for lithography, syringes , Pipette, animal cage, thermometer,
Medical fields such as beakers, sheares, graduated cylinders, bottles, artificial joints, carriers for chromatographs, chemical fields, gas separation membranes, ultrafiltration membranes, reverse osmosis membranes, separation membrane fields such as gas-liquid separation membranes, cameras It can be used in various fields such as bodies, various instrument housings, films, helmets, toys and stationery.

On the other hand, when the cyclic olefin content is about 20 mol% or less, it can be used in a field utilizing shape memory, a vibration damping material, or a tube. Specifically, vibration damping as a laminate with joints for deformed pipes, laminated materials inside and outside pipes and rods, optical fiber connectors, tightening pins, casts, containers, automobile bumpers, various gap prevention materials, and metal surface materials. It can be used in various fields such as materials (soundproofing materials), medical tubes, wrap films, protect films (metal plates, pipes, etc.) and heat-sealable films.

〔The invention's effect〕

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

〔Example〕

 Next, the method of the present invention will be specifically described with reference to examples.

Example 1 Ethylene and 6-ethylbicyclo [2,2,1] hept-2-ene ((A) in Table 3: hereinafter referred to as MBH are abbreviated as abbreviated as MBH using a 2 l glass polymerization vessel equipped with a stirring blade. ) Was carried out. That is, the toluene solution of MBH from the upper part of the polymerization vessel was 0.9 l / h so that the MBH concentration in the polymerization vessel was 60 g / l, and the toluene solution of VO (OC ₂ H ₅ ) Cl ₂ was used as a catalyst in the polymerization vessel. 0.7 l / h so that the vanadium concentration is 1 mmol / l (the supplied vanadium concentration is 2.86 times the concentration in the polymerization vessel), ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) ₁₅
Cl ₁₅ ) toluene solution was continuously fed into each of the polymerization vessels at a rate of 0.4 l per hour so that the aluminum concentration in the polymerization vessel was 4 mmol / l, while the lower part of the polymerization vessel was fed into the polymerization vessel. The polymerization liquid of is continuously withdrawn so that it is always 1. Further, from the upper part of the polymerization vessel, ethylene is supplied at a rate of 40 l / hour and nitrogen is supplied at a rate of 80 l / hour. The copolymerization reaction was carried out at 10 ° C by circulating a refrigerant through a jacket attached outside the polymerization vessel. When the copolymerization reaction is performed under the above conditions,
A polymerization reaction mixture containing an ethylene / MBH random copolymer is obtained. A small amount of methanol was added to the polymerization liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction, and the mixture was poured into a large amount of acetone / methanol to precipitate the produced copolymer. The copolymer was thoroughly washed with acetone and then dried under reduced pressure at 80 ° C for 24 hours. Through the above operation, an ethylene / MBH random copolymer was obtained at a rate of 25 g / h. The ethylene composition of the copolymer measured by ¹³ C-NMR analysis was 62 mol%, and the intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.7.
9 The iodine value was 0.9.

The crystallinity by X-ray diffraction is 0%. Transparency is ASTM
It was 3.4% when measured on a 1 mm sheet with a haze meter according to D1003-52.

The glass transition temperature Tg was 100 ° C. when the loss elastic modulus E ″ was measured at a temperature rising rate of 5 ° C./min by Dynamic Mechanical Analyser (DMA) manufactured by Dupont Co. and calculated from the peak temperature. Tm was measured by a DSC 990 type manufactured by Dyupon Co. at a temperature rising rate of 10 ° C / min in the range of -120 ° C to 400 ° C, and no melting curve (peak) was observed.

Examples 2 to 8 and Comparative Examples 1 to 3 Continuous copolymerization was performed in the same manner as in Example 1 except that the copolymerization conditions were as shown in Table 4. Table 4 shows the physical properties of the obtained copolymer.

Comparative Example 4 A sufficiently dry 500 ml separable flask was equipped with a stirring blade,
A gas blowing tube, a thermometer and a dropping funnel were attached and the atmosphere was sufficiently replaced with nitrogen. 250 ml of toluene dehydrated and dried with a molecular sieve was placed in this flask. In a flask under nitrogen flow, 7.5 g of (a) in Table 3 as a cyclic olefin, 1 mol of ethylaluminum sesquichloride (Al (C ₂ H ₅ ) ₁₅ Cl ₁₅ ) and VO (OC ₂ H ₅ ) Cl in the dropping funnel. 0.25 mmol of ₂ was added.

Dry ethylene through gas blow pipe 10l / hr Nitrogen 40l / hr
The mixed gas of was passed through a flask controlled at 10 ° C for 10 minutes.
Ethyl aluminum sesquichloride was added dropwise from the dropping funnel to start the copolymerization reaction, and the batchwise copolymerization reaction was carried out at 10 ° C. for 30 minutes while passing the mixed gas. The copolymerization reaction was stopped by adding 5 ml of methanol to the polymerization solution. The polymer solution after termination of the reaction was poured into a large amount of methanol and acetone to precipitate a copolymer, which was further washed with acetone and vacuum dried at 80 ° C. for 24 hours to obtain 5.4 g of a copolymer.

The physical properties of the obtained copolymer were measured by the same methods as in Example 1. The results are shown in Table 5.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a preparation process of a catalyst used in the method of the present invention.

Claims (1)

[Claims] 1. At least one selected from the group consisting of ethylene and bicycloalkenes and tricycloalkenes in the liquid phase consisting of a hydrocarbon medium in the presence of a catalyst formed from a vanadium compound and an organoaluminum compound. In the method for producing an amorphous cyclic olefin random copolymer by copolymerizing with a cyclic olefin of, a vanadium compound represented by the general formula VO (OR) _a X _b or V (OR) _c X _d (provided that R Is a hydrocarbon group, 0 ≦ a ≦ 3, 0
≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4,
3 ≦ c + d ≦ 4), and a vanadium compound soluble in the hydrocarbon medium is used, and the vanadium compound is supplied to the copolymerization reaction system at a concentration not more than 10 times the concentration in the copolymerization reaction system. Keep the ratio of aluminum atom to vanadium atom (Al / V) in the polymerization reaction system to 2 or more, and continuously copolymerize so that the content of cyclic olefin component in the copolymer is in the range of 10 to 60 mol%. A process for producing an amorphous cyclic olefin random copolymer, characterized by carrying out polymerization.