JP2953530B2 - Method for producing cyclic olefin random copolymer - Google Patents

Description

Description TECHNICAL FIELD [0001] The present invention relates to a method for producing a cyclic olefin-based random copolymer. More specifically, the present invention relates to a method for producing a cyclic olefin-based random copolymer that does not require a step of depositing the generated cyclic olefin-based random copolymer.

TECHNICAL BACKGROUND OF THE INVENTION A cyclic olefin random copolymer composed of ethylene and a specific bulky cyclic olefin is a synthetic resin in which optical properties, mechanical properties, thermal properties, and the like are balanced. Used in the field of optical materials such as disks and optical fibers.

Such a cyclic olefin-based random copolymer, ethylene and cyclic olefin, in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound, toluene, a hydrocarbon such as cyclohexane or the above cyclic olefin as a solvent It is produced by copolymerization using

However, for example, it is a good solvent for the produced ethylene / cyclic olefin copolymer and has a solubility parameter (δ
Olefin random copolymer obtained by copolymerizing ethylene and a cyclic olefin using a hydrocarbon solvent such as toluene or cyclohexane or a cyclic olefin having a value of 7.7 [(cal / cm ³ ) ^1/2 ] or more. With high concentration (=
(80 g / min.), It is necessary to add a large amount of a poor solvent to the resulting cyclic olefin-based random copolymer solution to precipitate the copolymer. Was desired.

Therefore, when producing a cyclic olefin random copolymer by copolymerizing ethylene and a cyclic olefin, an efficient cyclic olefin random copolymer which does not require a step of precipitating the obtained copolymer from the polymerization system. The emergence of a method for producing a polymer has been desired.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technology, and has been made in consideration of the above-described conventional technique, and does not require a step of precipitating a generated cyclic olefin-based random copolymer from a polymerization system. It is an object of the present invention to provide a method for producing a polymer.

SUMMARY OF THE INVENTION A method for producing a cyclic olefin random copolymer according to the present invention comprises: (a) ethylene; and (b) the following formula [I] or [II]. (In the formula, n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, A halogen atom or a hydrocarbon group, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond. R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group).

[Wherein, is an integer of 0 or 1 or more, and m and n
Is 0, 1 or 2, and R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R ⁵ (or R ⁶ )
R ⁹ (or R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group. And at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by the following formulas in a hydrocarbon solvent in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound: In producing a cyclic olefin random copolymer by copolymerization, the solubility parameter (δ value) of the hydrocarbon solvent is 7.7 [(cal / c
m ³ ) ^1/2 ] or more and a hydrocarbon solvent (A) having a δ value of 7.5 [(cal / cm ³ ) ^1/2 ] or less. In addition, a mixed solvent in the range of (A) / (B) = 45/55 to 0/100 (volume ratio) or the hydrocarbon solvent (B) is used.

According to the present invention, at the time of copolymerizing ethylene and a cyclic olefin, since at least two kinds of hydrocarbon mixed solvents or specific hydrocarbon solvents having specific solubility parameters are used as a solvent, the produced copolymer is used. The step of coalescing is unnecessary, and the cyclic olefin-based random copolymer can be efficiently produced.

Specific description of the invention The method for producing the cyclic olefin-based random copolymer according to the present invention is specifically described above.

In the present invention, the above-mentioned cyclic olefin represented by the general [I] or the general formula [II] and ethylene are mixed with at least two or more kinds of specified hydrocarbon mixed solvents or in a specified solvent. Copolymerization is carried out in the presence of a catalyst comprising a vanadium compound and an organoaluminum compound which are soluble in a solvent to produce a cyclic olefin random copolymer.

As the cyclic olefin represented by the above formula [I] used in the present invention, specifically, Specific examples of such compounds are shown below.

Bicyclo [2.2.1] hept-2-ene derivatives such as; Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene derivatives such as; Hekisashikuron such as [6.6.1.1 ^3,6 .1 ^10,13 .0.1 ^2,7 .0
^9,14] -4-heptadecene derivatives; Octacyclo such as ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16.
0 ^3,8 .0 ^12,17] -5-docosene derivatives; Pentacyclo such as ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4-
Hexadecene derivatives; Heptacyclo-5-eicosene derivatives or heptacyclo-5-heneicosene derivatives; Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives such as; Tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivatives; Pentacyclo such as ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4-
Pentadecene derivatives; Diene compounds such as; Pentacyclo such ^{[7.4.0.1 2,5 .1 9,12 .0 8,13]} -3-
Pentadecene derivatives; Heptacyclo such as ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7.
0 ^11,16 ] -4-eicosene derivatives; Nonashikuro such as ^{[10.9.1.1 4,7 .1 13,20 .1 15,18 .0} 3,8 .0
^2,10 .0 ^12,21 .0 ^14,19] -5-pentacosene derivatives; Heptacyclo such ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3-
Hexadecene derivatives; Heptacyclo such as ^{[8.8.0.1 4,7 .1 11,18 .1 13,16 .0} 3,8.
0 ^12,17 ] -5- ^heneicosene derivatives; Nonashikuro such as [10.10.1.1 ^5,8 .1 ^14,21 .1 ^16,19.
0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^15,20] -5-hexacosenoic derivatives; and further, Can be mentioned.

The cyclic olefin represented by the above formula [I] or [II] can be easily produced by subjecting a cyclopentadiene and a corresponding olefin to a Diels-Alder reaction.

In the present invention, the cyclic olefins and ethylene as described above have a solubility parameter (δ value) of 7.7 [(cal / cm ³ )
^1/2 ] or more, preferably 8.0 [(cal / cm ³ ) ^1/2 ] or more, and a solubility parameter (δ value) with a hydrocarbon solvent (A).
7.5 [(cal / cm ³ ) ^1/2 ] or less, preferably 7.4 (cal / cm ³ )
^The copolymerization is carried out in a mixed solvent with the hydrocarbon solvent (B) which is ^1/2 or less or in the hydrocarbon solvent (B).

When a mixed solution of the hydrocarbon solvent (A) and the hydrocarbon solvent (B) as described above is used, the mixing ratio ((A) / (B)) (volume ratio) depends on the cyclic olefin used. Slightly, depending on the type of copolymer and the composition of the copolymer,
0/100, preferably 35/65 to 0/100.

The above solubility parameter (δ value) is 7.7 [(cal
/ cm ³ ) ^1/2 ] or more, specifically, the following compounds are used.

The solubility parameter (δ value) is 7.5 [(c
al / cm ³ ) ^1/2 ] or less, specifically, the following compounds and isomers thereof are used.

Such a hydrocarbon solvent (A) may be used alone, or may be used as a mixture. The hydrocarbon solvent (B) may be used alone, or may be used as a mixture.

As a combination in the case where the above-mentioned hydrocarbon-based solvent (A) and the hydrocarbon-based solvent (B) are used in combination, the following combinations are particularly preferable.

Cyclohexane-hexane Cyclohexane-heptane Cyclohexane-pentane Cyclohexane-hexane isomer mixture Toluene-hexane Toreen-heptane Toluene-pentane Toluene-hexane isomer mixture In the present invention, the copolymerization reaction between cyclic olefin and ethylene is carried out as described above. By performing the slurry polymerization in the presence of a mixed solvent of the hydrogen-based solvent (A) and the hydrocarbon-based solvent (B) or the above-mentioned hydrocarbon-based solvent (B), the resulting cyclic olefin-based random copolymer is polymerized. This eliminates the need for a step of precipitating the copolymer using a poor solvent for the copolymer, so that a cyclic olefin-based random copolymer can be produced more efficiently.

In the present invention, when ethylene and a cyclic olefin are copolymerized, a catalyst formed from a soluble vanadium compound and an organoaluminum compound is used.

As the vanadium compound, specifically, the general formula VO
(OR) _a X _b or V (OR) _c X _d (where 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) or an electron donor adduct thereof. More specifically, VOCl ₃ , VO (OC ₂ H ₅ ) C
_{2, VO (OC 2 H 5} ) 2 C, VO (O-iso-C 3 H 7) C 2,
VO (On-C ₄ H ₉ ) C ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VC
_{4, VOC 2, VO (O} -n-C 4 H 9) 3, VC 3 · 2OC 8 H
A vanadium compound such as ₁₇ OH is used.

Further, as the electron donor that may be used when preparing the soluble vanadium catalyst component, alcohol,
Oxygen-containing electron donors such as phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates Body and the like. More specifically, it has 1 carbon atom such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecic alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol, and the like. Alcohols having 18 to 18 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol;
20 phenols; ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; 2 to 2 carbon atoms such as acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde and naphthaldehyde 15 aldehydes; 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 dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, Ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, maleic acid N-butyl acid, diisobutyl methylmalonate, di-n-hexyl cyclohexanecarboxylate, diethyl nadicate, diisosopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-phthalate Organic acid esters having 2 to 30 carbon atoms such as tyl, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride C2-C15 acid halides such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; C2-C20 ethers; acetate amide, benzoic amide, toluyl Acid amides such as acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine; acetonitrile, benzo Tolyl, nitriles such as trinitriles; ethyl silicate, and the like alkoxysilanes such as diphenyldimethoxysilane. Two or more of these electron donors can be used.

As the organoaluminum compound catalyst component, a compound having at least one A-carbon bond in the molecule is used. For example, (i) the general formula R ¹ _mA (OR ² _{) n} H _p Χ _q (where R ¹ and R ²
Are hydrocarbon groups containing 1 to 15, preferably 1 to 4 carbon atoms, which may be the same or different. Χ
Is halogen, m is 0 ≦ m ≦ 3, n is 0 ≦ n <3, and p is 0
≦ n <3, q is a number satisfying 0 ≦ q <3, and m + n
Organoaluminum compounds represented by + p + q = a 3), (ii) the general formula M ¹ AR ¹ ₄ (M ¹ is here Li, Na, K, and the first group of R ¹ is represented by the same) and the Examples thereof include a complex alkylated product of a metal and aluminum.

The following can be exemplified as the organoaluminum compound belonging to the above (i).

General formula R ¹ _mA (OR ² ) _3-m (where R ¹ and R ² are the same as above. M is preferably 1.5
≦ m3 <).

General formula R ¹ _m AΧ _3-m (where R ¹ is the same as above, Χ is halogen, and m is preferably 0 <m <3).

General formula R ¹ _m AH _3-m (where R ¹ is the same as above, m is preferably 2 ≦ m <3).

Formula _{^{R 1 m A (OR 2)}} n Χ q ( wherein R ¹ and R ² are as .Χ said halogen, 0 <
m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

More specifically, the aluminum compounds belonging to (i) include trialkylaluminums such as triethylaminium and tributylaluminum; trialkenylaluminums such as triisopropenylaluminum; and dialkylaluminums such as diethylaluminum ethoxide and dibutylaluminum butoxide. Aluminium alkoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; and partially alkoxylated alkyl having an average composition represented by R ¹ _2.5 A (OR ² ) _0.5 aluminum,
Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, isobutylaluminum sesquichloride and ethylaluminum sesquibromide; ethylaluminum dichloride, propyl Alkylaluminum dihalides such as aluminum dichloride, butylaluminum dibromide and the like; partially halogenated alkylaluminums such as
Partially alkylated aluminum, such as diethylaluminum hydride such as diethylaluminum hydride and dibutylaluminum hydride; alkylaluminum dihydride such as ethylaluminum dihydride and propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide Partially alkoxylated and halogenated alkyl aluminum, such as ethylaluminum ethoxy bromide. Further, a compound similar to (i), for example, an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. As such compounds, specifically, (C ₂ H ₅ ) ₂ AOA (C ₂ H ₅ ) ₂ , (C ₄ H ₅ ) ₂ AOA (C
₄ H _{9) 2,} And the like.

As a compound belonging to the above (ii), LiA (C
_{2 H 5) 4, LiA (} C 7 H 15) 4 etc. can be exemplified. Among these, it is particularly preferable to use an alkyl aluminum halide, an alkyl alnium dihalide or a mixture thereof.

In the present invention, ethylene and one or more of the above-mentioned cyclic olefins (general formula [I] or [II]) are copolymerized. If necessary, α-olefins having 3 or more carbon atoms are copolymerized. And α having 3 or more carbon atoms
Examples of the olefin include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, Α-olefins having 3 to 20 carbon atoms such as eicosene can be mentioned.

In addition, another copolymerizable unsaturated monomer component can be copolymerized as needed within a range not to impair the object of the present invention. Specific examples of such copolymerizable unsaturated monomers include cyclopentene, cyclohexene, 3-methylcyclohexene, and cyclooctene such as cyclooctene having less than an equimolar amount to the cyclic olefin component unit in the generated random copolymer. Olefin, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5
Non-conjugated dienes such as -ethylidene-2-norbornene and 5-vinyl-2-norbornene.

In producing the cyclic olefin-based random copolymer, the copolymerization reaction between ethylene and the above-mentioned cyclic olefin (general formula [I] or general formula [II]) is preferably performed by a continuous method. At that time, the concentration of the soluble vanadium compound supplied to the polymerization reaction system is usually 10 times or less, preferably 1 to 7 times, more preferably 1 to 5 times the concentration of the soluble vanadium compound in the polymerization reaction system. It is desirable to be within the range.

In the present invention, the ratio (A / V) of aluminum atoms to vanadium atoms in the polymerization reaction system is desirably 2 or more, preferably 2 to 50, particularly preferably 3 to 20.

The soluble vanadium compound and the organoaluminum compound are usually supplied after being diluted with the hydrocarbon solvent or the cyclic olefin, respectively. Here, it is desirable to dilute the soluble vanadium compound within the above concentration range, but the method of preparing the organoaluminum compound at an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization reaction system and supplying the same to the polymerization reaction system. Is adopted.

When producing a cyclic olefin-based random copolymer, the concentration of the soluble vanadium compound in the copolymerization reaction system is, as vanadium atom, usually in the range of 0.01 to 5 gram atom /, preferably 0.05 to 3 gram atom /. It is.

Such a copolymerization reaction between ethylene and olefins is carried out at a temperature of -50 to 100C, preferably -30 to 80C, more preferably -20 to 60C.

The reaction time (in the case of a continuous polymerization reaction, the average residence time of the polymerization reaction mixture) for performing the above copolymerization reaction varies depending on the type of the polymerization raw material, the concentration of the catalyst component, and the temperature, but is usually 5 minutes to 5 hours, preferably
The range is from 10 minutes to 3 hours. The pressure at which the copolymerization reaction is carried out is usually more than 0 and 5 kg / cm ² , preferably 0
Over 20 kg / cm ² . In the copolymerization, a molecular weight modifier such as hydrogen may be present in order to adjust the molecular weight of the obtained copolymer.

In producing the cyclic olefin-based random copolymer, the molar ratio of ethylene / cyclic olefin supplied to the copolymer reaction is 99/1 to 1/99, preferably 99/10 to 10/90, and more preferably 40/90. It is desirable to be in the range of / 60 to 85/15.

When a copolymerization reaction of ethylene and a cyclic olefin is performed as described above, a solution of a cyclic olefin-based random copolymer is obtained. The concentration of the cyclic olefin-based random copolymer contained in such a copolymer solution is usually in the range of 10 to 500 g /, preferably 10 to 300 g /, but the copolymerization using the mixed solvent of the present invention is preferred. The reaction is characterized in that the upper limit of the concentration is increased.

The cyclic olefin-based random copolymer thus obtained is amorphous or crystalline, but among the cyclic olefin-based random copolymers, it does not have a DSC melting point, and the results of measurement by X-ray diffraction indicate Amorphous copolymers are preferred. Furthermore, the molar ratio of ethylene / cyclic olefin of the cyclic olefin-based random copolymer obtained by the method of the present invention is usually 95/5 to 30/70, preferably 90/10 to 40.
/ 60 range. The glass transition point (Tg) of the cyclic olefin-based random copolymer is usually in the range of 10 to 280 ° C, preferably 20 to 240 ° C.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Using a mixed solvent composed of the polymerization vessel and cyclohexane / n-hexane of volume 1 with Example 1 stirring blade (20 / 80vol%), continuously ethylene and tetracyclo [4.4.0.1 ^{2, 5} .1
^7.10 ] -3-Dodecene (hereinafter abbreviated as TCD-3). That is, a solution obtained by diluting TCD-3 with the mixed solvent from the upper part of the polymerization vessel was used in an amount of 0.4 per hour so that the TCD-3 concentration in the polymerization vessel was 60 g / vol.
(OC ₂ H ₅ ) The mixed solvent solution of C ₂ was converted to 0.7 per hour so that the vanadium concentration in the polymerization vessel was 0.5 mmol / (the vanadium concentration supplied at this time is 2.86 times the concentration in the polymerization vessel). The mixed solvent solution of ethylaluminum sesquichloride (A (C ₂ H ₅ ) _1.5 C _1.5 ) was added per hour so that the aluminum concentration in the polymerization vessel was 4.0 mmol /.
0.4, and the mixed solvent is continuously fed into the polymerization reactor at a rate of 0.5 / hour, while the polymerization liquid in the polymerization reactor is always 1 from the top of the polymerization reactor (that is, the average residence time). It was continuously withdrawn (so that the time was 0.5 hours). In addition, ethylene was supplied at a rate of 20 / hour, nitrogen was supplied at a rate of 10 / hour, and hydrogen was supplied at a rate of 0.5 / hour using a bubbling tube in the polymerization system.

The copolymerization reaction was carried out at 10 ° C. by circulating a refrigerant through a jacket provided outside the polymerization vessel. When the copolymerization reaction was performed under the above conditions, a polymerization slurry liquid containing an ethylene / TCD-3 random copolymer was obtained.

The polymerization reaction was stopped by adding a cyclohexane / isopropyl alcohol (1/1) mixed solution to the polymerization slurry liquid extracted from the upper part of the polymerization vessel. Thereafter, an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to water 1 and the polymerization slurry liquid were in a one-to-one correspondence.
, And the catalyst residue was transferred to a water tank by using a homomixer under strong stirring. The polymerization slurry was allowed to stand, and after removing the aqueous phase and the oil layer, the polymer slurry was further washed twice with methanol, and the fixed part was collected by filtration. The obtained solid portion was put into acetone so as to be 40 g /,
Extraction treatment was performed at 60 ° C. for 2 hours. Thereafter, a solid portion was collected by filtration and dried at 130 ° C. and 350 mmHg for 24 hours under a nitrogen flow.

As described above, it was found that an ethylene / TCD-3 copolymer was obtained in an amount of 78 g / hour (that is, 39 g / hour).

The ethylene composition of the copolymer measured by ¹³ C-NMR analysis was 5
8.5mol%, intrinsic viscosity [η] measured in decalin at 135 ° C
Was 0.57 dl / g.

The crystallinity by に よ る -ray diffraction was 0%. The glass transition temperature Tg is obtained from the Dynamic Mechanical Analyzer manufactured by DuPont.
The loss elastic modulus E ″ was measured at a temperature increase of 5 ° C./mm by (DMA), and was 142 ° C. as determined from the peak temperature.
In order to further determine whether the melting point Tm is present, by DuPont 990 type DSC at -120 ° C. at a heating rate of 10 ° C./mm
When measured in the range of 400400 ° C., no melting curve (peak) based on Tm was observed.

 Table 1 shows the obtained results.

Example 2 and Comparative Example 1 Copolymerization of ethylene and TCD-3 was carried out in the same manner as in Example 1 except for the conditions shown in Table 1.

 Table 1 shows the obtained results.

Example 3 In place of TCD-3, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene (abbreviated as MTHF) was used as the cyclic olefin, and the conditions were the same as in Example 1 except for the conditions shown in Table 1. Similarly, a copolymerization reaction of ethylene and MTHF was performed.

 Table 1 shows the obtained results.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08F 232/00-232/08 C08F 210/02 C08F 2/06 C08F 4/68

Claims (1)

(57) [Claims] (1) (a) ethylene, and (b) the following formula [I] or [II] (In the formula, n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom,
A halogen atom or a hydrocarbon group, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond. R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group). [Wherein, is an integer of 0 or 1 or more, and m and n
Is 0, 1 or 2, and R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R ⁵ (or R ⁶ )
R ⁹ (or R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group. And at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by the following formulas in a hydrocarbon solvent in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound: In producing a cyclic olefin-based random copolymer by copolymerization, a solubility parameter (δ value) of a hydrocarbon-based solvent is 7.7 [(cal / cm ³ ) ^1/2 ].
A mixed solvent of the above-mentioned hydrocarbon-based solvent (A) and the hydrocarbon-based solvent (B) having a δ value of 7.5 [(cal / cm ³ ) ^1/2 ] or less, wherein the mixing ratio is (A) / (B) = a mixed solvent having a volume ratio in the range of 45/55 to 0/100 (volume ratio) or the above-mentioned hydrocarbon solvent (B); .