JPH062786B2 - Preparation of cyclic olefin random copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a cyclic olefin random copolymer. More specifically, the production of a cyclic 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 method.

[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 is accompanied by a decrease in 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
Copolymers with 2.3-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, a copolymer of ethylene and 5-ethylidene-2-norbornene has the same drawback.

Further, Japanese Patent Publication No. 46-14910 proposes a homopolymer of 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a, -octahydronaphthalene. However, the polymer is inferior in heat resistance and heat aging resistance. Further, JP-A-58-127728 discloses a homopolymer of 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene or a cyclic olefin thereof. Although a copolymer of a norbornene type comonomer has been proposed, it is apparent from the above-mentioned publication that all of the polymers are ring-opening polymers. Since such a ring-opening polymer has an unsaturated bond in the polymer main chain,
It has the drawback of being poor in heat resistance and heat aging resistance.

[Problems to be solved by the invention]

Therefore, the present inventors have earnestly researched a method for obtaining a synthetic resin having a balance of heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and mechanical properties while having transparency. Have found that a copolymer of ethylene and a specific bulky comonomer can achieve the object, and have already proposed Japanese Patent Application No. 59-
16995, Japanese Patent Application No. 59-220550, Japanese Patent Application No. 59-236828,
Proposed in Japanese Patent Application No. 59-236829 and Japanese Patent Application No. 59-242336.
The present inventors have studied a method capable of producing a copolymer having a narrow molecular weight distribution and composition distribution in the cyclic olefin random copolymer, excellent uniformity, and improved transparency, a soluble vanadium compound And, in the presence of a catalyst formed from an organoaluminum compound, it was found that the above objects can be achieved by carrying out continuous copolymerization in a liquid phase composed of a hydrocarbon medium under specific conditions, and the present invention has been achieved. did.

[Action for Solving Problems] and [Action] The present invention provides ethylene and the following general formula in a liquid phase consisting of a hydrocarbon medium in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound. I] and a method of copolymerizing at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by the general formula [II], in the liquid phase of the polymerization reaction system A method for producing a cyclic olefin random copolymer, characterized in that the ratio (Al / V) is kept at 2 or more and the copolymerization is continuously carried out.

General formula [In the formula, n and m are both positive integers, l is a positive number of 3 or more, and R ¹ to R ¹⁰ 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 constituent is a vanadium compound component soluble in a hydrocarbon catalyst of a polymerization reaction system, specifically, the 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 thereof include vanadium compounds represented by 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4) or atom donor adducts thereof. More specifically, VOCl ₃ , V
O (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , VO (O
-nC ₄ H ₉ ) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ , VOCl ₂ , VO (O-
_{nC 4 H 9) 3, VCl} 3 · 20C 8 H 17 OH , etc. can be exemplified.

Examples of the electron donor that may be used for preparing the soluble vanadium catalyst component include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid or inorganic acid esters, ethers, acid amides, and 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, naphthol; acetone; , C3 to C15 ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; acetoaldehyde , Aldehydes having 2 to 15 carbon atoms such as propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, Methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonic acid, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, benzoic acid Cyclohexyl, phenyl benzoate, benzyl benzoate, methyl toluate,
Ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicuate, diisopropyl tetrahydrophthalate, diethyl phthalate, phthalate. Diisobutyl acid salt, di-n-butyl phthalate, di2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate and other carbon atoms 2
To 30 organic acid esters; C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran,
Ethers having 2 to 20 carbon atoms such as anisole and diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, Examples thereof include amines such as pyridine, picoline, and tetramethylenediamine; nitriles such as acetonitrile, benzonitrile, 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 (where R ¹ and R ² are usually 1 to 15 carbon atoms)
Hydrocarbon groups, including one, preferably one to four, 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, and q is 0 ≦ q
<A number of 3 and m + n + p + q = 3)
In an organic aluminum compound represented, (ii) General color M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na, K, and alkyl complex of Group 1 metal and aluminum R ¹ is represented by the same as the And the like.

The organoaluminum compound belonging to (i) above,
The following can be illustrated.

The 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).

The general formula R ¹ _m AlX _3-m (wherein R ¹ is as defined above, X is halogen, and m is preferably 0 <m <3).

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

The general formula R ¹ _m Al (OR ² ) _n Xq (wherein R ¹ and R ² are the same as before. X is halogen, 0
<M ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3
And the like can be exemplified.

In the aluminum compound belonging to (), more specifically, trialkyl aluminum such as triethyl aluminum and tributyl aluminum; trialkyl aluminum such as triisopropyl 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 aluminumized alkylaluminum having an average composition represented by R ¹ _0.5 Al (OR ² ) _0.5 ; diethylaluminum chloride ,
Dialkylaluminum dichloride, dialkylaluminum halide such as diethylaluminium bromide;
Partially halogenated such as alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, etc. Alkyl aluminum; 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 butoxycyclolide, ethyl aluminum ethoxy Partially alkoxylated and halogenated alkylaluminum such as Romido can be exemplified. Further, a compound similar to () may be an organoaluminum compound in which two or more aluminum atoms 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 , (C ₄ H ₉ ) ₂ AlOAl (C
₄ H ₉ ) ₂ , (C ₂ H ₅ ) ₂ Al Can be exemplified.

Examples of the compound belonging to (ii) 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 represented by the general formula [I] and the general formula [II] [Wherein, n and m are both positive integers, l is a positive integer of 3 or more, and R ¹ to R ¹⁰ are each a hydrogen atom, a halogen atom or a hydrocarbon group] It is at least one cyclic olefin selected from the group consisting of saturated monomers. The cyclic olefin represented by the general formula [I] can be easily produced by condensing cyclopentadiene and the corresponding olefin by the Diels-Alder reaction, and the cyclic olefin represented by the general formula [II] can also be prepared. Similarly, it can be easily produced by condensing cyclopentadiene and the corresponding cyclic olefin by the Diels-Alder reaction. Specific examples of the cyclic olefin represented by the general formula [I] include, for example, 1,4,5,8-dimethano-1,2,
In addition to 3,4,4a, 5,8,8a-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-1,2,3,4,4a, 5,8,8
a-Octahydronaphthalene, 2-hexyl-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-stearyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-
1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene, 2-bromo-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-
1,4,5,8-Dimethano-1,2,3,4,4a, 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-1,2,3,4,4a, 5,8,8
a-Octahydronaphthalene, 2-isobutyl-1,4,5,8
-Dimethano-1,2,3,4,4a, octahydronaphthalene such as 5,8,8a-octahydronaphthalene, and the compounds shown in Table 1 can be exemplified.

Specific examples of the cyclic olefin represented by the general formula [II] include the compounds shown in Table 2.

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-octadecene, 1-eicocene 2-olefins having 3 to 20 carbon atoms are produced. Cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, 3a, which is less than the equimolar amount of the cyclic olefin component unit in the random copolymer,
5,6,7a-Tetrahydro-4,7-methano-1H-indene (general formula: ) Such as cycloolefin, 1,4-hexadiene, 4-
Methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene,
5-ethylidene-2-norbornene, 5-vinyl-2-
Non-conjugated dienes such as norbornene, norbornene-
2,5-Methylnorbornene-2,5-ethylnorbornene-2,5-isopropylnorbornene-2,5-n
-Butylnorbornene-2,5-i-butylnorbornene-2,5,6-dimethylnorbornene-2,5-chloronorbornene-2,2-fluoronorbornene-2,5,
Examples thereof include norbornenes such as 6-dichloronorbornene-2.

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, aliphatic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, and the above-mentioned polymerizable compounds. An unsaturated monomer and the like can be exemplified, and a mixed medium of two or more kinds of these may be used.

In the method of the present 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. 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 usually diluted with the hydrocarbon medium and supplied. Here, it is desirable to dilute the soluble vanadium compound within the above concentration range, but a 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. To be done. 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 as vanadium atom.
Gram atom /, preferably 0.05 to 3 gram atom /
Is the range.

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 present invention, the copolymerization reaction is carried out in a continuous manner.
Polymerization raw material ethylene, a cyclic olefin, a copolymerizable component to be copolymerized as required, 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 to perform polymerization. The reaction mixture is continuously withdrawn 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 during the copolymerization reaction depends on the type of polymerization raw material,
Although it depends on the concentration and temperature of the catalyst component, it is usually 5
It is in the range of minutes to 5 hours, preferably 10 minutes to 3 hours. The pressure during the copolymerization reaction usually exceeds 0 and is 50
kg / cm ^2, preferably maintained beyond the 0 to 20 kg / cm ^2, by the case connexion nitrogen, may be present with an inert gas such as argon. Further, in order to adjust the molecular weight of the copolymer, a molecular weight modifier such as hydrogen can be appropriately present. A 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 present invention is usually 99/1 to 1 /
The range is 99, preferably 98/2 to 2/98.

Further, the cyclic olefin random copolymer obtained by the method of the present invention is amorphous or crystalline, but among the cyclic olefin random copolymers, it does not have a DSC melting point and the measurement result by X-ray diffraction shows that Also, a non-crystalline copolymer is suitable. Furthermore, the cyclic olefin random copolymer obtained by the method of the present invention usually has an ethylene / cyclic olefin molar ratio of 99/1 to 1/99,
It is preferably in the range of 98/2 to 2/98. The glass transition point (Tg) of the cyclic olefin random copolymer is usually 10 to 240 ° C., preferably 20.
To 200 ° 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 is narrow and excellent in uniformity, for example, its low-molecular weight product is used as a synthetic wax for candle applications, pine wood shaft impregnating agent, paper processing agent, sizing agent, rubber anti-aging agent, corrugated cardboard waterproofing agent, chemical fertilizer retarding agent, Heat storage agents, ceramic binders, paper capacitors, electrical insulation materials such as electric wires and cables, neutron moderators, fiber processing aids,
Building material water repellent, coating protector, polish, thixotropy agent, pencil / crayon core hardness agent, carbon ink base material, electrostatic copying toner, synthetic resin molding lubricant, release agent, resin colorant, It can be used in the fields of hot melt adhesives, lubricating greases, pigment dispersants, inks for laser printers, coating primers, paints and viscosity index improvers. The high molecular weight materials are optical lenses, magneto-optical disks, optical cards, optical disks, optical fibers, glass windows, Fresnel lenses, laser array lenses, optical fiber connectors, holographic recording sheets and films, and refractive index distribution. Mold plane lens (grated lens), surface hardness, modified optical material (glass with the same refractive index,
Dispersed ceramics, polarization filter, optical wavelength selection filter, photosensitive film, LED and semiconductor laser covers and sealants, mirrors, prisms, beam splitters, optical substrates such as EL substrates, water for electric irons. Tanks, microwave oven products, liquid crystal 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 devices, electrical equipment housings, electrical fields such as protective film for lithography, syringes, pipettes, animal cages, thermometers, beakers, sheares, graduated cylinders, bottles, artificial joints, chromatography Medical fields such as carriers for graphs, chemical fields, gas separation membranes, ultrafiltration membranes, reverse osmosis membranes, separation membrane fields such as gas-liquid separation membranes, camera bodies, various instrument housings, films, helmets, toys, stationery It can be used in various fields such as classes.

On the other hand, when the cyclic olefin content is about 20 mol% or less, it can be used as 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 body (soundproofing material), medical tube, wrap film, protect film (metal plate, pipe, etc.), heat sealable film and the like.

〔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 Using a 2-glass polymerization vessel equipped with a stirring blade, ethylene and 2-methyl-1,4,5,8-dimethano-1,2, were continuously added.
3,4,4a, 5,8,8a-octahydronaphthalene ((A) in Table 5:
Hereinafter, a copolymerization reaction of M-DMON) was performed. That is, a toluene solution of M-DMON was added from the upper part of the polymerization vessel at 0 / hr so that the concentration of M-DMON in the polymerization vessel was 60 g / hour.
9. Toluene solution of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst was used to adjust the vanadium concentration in the polymerization vessel to 0.5 mmol / h, 0.7 per hour, ethyl aluminum sesquichloride (Al (C ₂ H ₅ )
_1.5 Cl _1.5 ) toluene solution was continuously fed into each of the polymerization reactors at a rate of 0.4 per hour so that the aluminum concentration in the polymerization reactor was 2 mmol / min. The polymerization liquid is continuously withdrawn so that it is always 1. In addition, from the top of the polymerization vessel, ethylene is
, Nitrogen is supplied at a rate of 80 per hour. The copolymerization reaction was carried out at 10 ° C. by circulating a refrigerant in a jacket attached outside the polymerization vessel. When the copolymerization reaction is performed under the above conditions, a polymerization reaction mixture containing an ethylene / M-DMON random copolymer is obtained. To the polymerization liquid extracted from the lower part of the polymerization vessel, a small amount of notanol was added to stop the polymerization reaction, and the mixture was poured into a large amount of acetone / methanol.
The produced copolymer was precipitated. The copolymer was thoroughly washed with acetone and then dried under reduced pressure at 80 ° C. for 24 hours. With the above operation, ethylene / M-DMON random copolymer 30 g / h
Obtained at the speed of. The ethylene composition of the copolymer measured by ¹³ C-NMR analysis was 63 mol%, and the intrinsic viscosity [η] measured in 135 ° C. decalin 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 mm sheet with a haze meter according to ASTM D 1003-52.

The glass transition temperature Tg is the Dynamic Mechanical manufactured by Deupon.
The loss modulus E ″ was measured with an Analyser (DMA) at a heating rate of 5 ° C./min, and the peak temperature was calculated to be 1
The temperature was 27 ° C. Further, the melting point Tm is 990 manufactured by Deu Pont.
-12 at a temperature rising rate of 10 ° C / min with a DSC of the type
When measured in the range of 0 ° C to 400 ° C, no melting curve (peak) was observed.

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 as shown in Table 3. Table 3 shows the physical properties of the obtained copolymer. In addition, in Example 8, a 1: 1 mixed solvent of toluene / cyclohexane was used as a polymerization solvent.

Comparative Example 2 A well-dried 500 ml separable flask was equipped with a stirring blade, a gas blowing tube, a thermometer and a dropping funnel, and 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 5 and ethylaluminum sesquichloride Al (C ₂ H ₅ ) _1.5 Cl _1.5 ) were added as cyclic olefins.
0.5 mmol, and 0.125 mmol of VO (OC ₂ H ₅ ) Cl ₂ was added to the dropping funnel. Ethylene dried through a gas injection tube 10
/ Hr, nitrogen 40 / hr mixed gas was passed through the flask controlled at 10 ° C for 10 minutes. Ethyl aluminum sesquichloride was added dropwise from the dropping funnel to start the copolymerization reaction,
A batch type copolymerization reaction was carried out at 10 ° C. for 30 minutes while passing the mixed gas. After 5 ml of methanol was added to the polymerization solution to terminate the copolymerization reaction, the polymerization solution was poured into a large amount of methanol and acetone to precipitate the copolymer, which was further washed with acetone and vacuum dried at 80 ° C. for one day. 2.0 g of a copolymer was obtained. The physical properties of the obtained copolymer were measured by the same methods as in Example 1. The results are shown in Table 4.

Claims (1)

[Claims] 1. Unsaturation represented by the following general formula [I] and general formula [II] in a liquid phase consisting of a hydrocarbon medium in the presence of a catalyst formed of a soluble vanadium compound and an organoaluminum compound. In the method of copolymerizing at least one cyclic olefin selected from the group consisting of monomers, the ratio of aluminum atom to vanadium atom (Al / V) in the liquid phase of the polymerization reaction system is kept at 2 or more, and continuous. A process for producing a cyclic olefin random copolymer, characterized in that the copolymerization is carried out dynamically. [In the formula, n and m are both positive integers, l is an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom, or a hydrocarbon group].