JP2953531B2 - 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 provides a cyclic olefin-based random excellent in transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and various mechanical properties, and substantially containing no halogen. The present invention relates to a method for producing a copolymer.

TECHNICAL BACKGROUND OF THE INVENTION A cyclic olefin-based random copolymer composed of ethylene and a specific bulky cyclic olefin is a synthetic resin in which optical properties, mechanical properties, and thermal properties are balanced, and an optical memory disk or the like. International application publication that can be used for applications in the field of optical materials such as optical fibers
W089 / 01950 or JP-A-1-185307.

When the cyclic olefin-based random copolymers proposed in the above are produced using a catalyst containing a halogen, they contain a cyclic olefin halide as a by-product, and when the copolymer is thermoformed. Since the softening temperature of the copolymer is significantly higher than that of ordinary olefin-based polymers, even if the halogen content of the copolymer is small, hydrogen halide such as hydrochloric acid is generated, and molding is performed. The machine may corrode. Then, in order to remove the halide of the cyclic olefin, a large amount of a poor solvent such as acetone is added to a copolymer solution produced by copolymerizing ethylene and the cyclic olefin in a liquid phase composed of a hydrocarbon medium. After the addition, the resulting copolymer is precipitated and separated from the liquid phase portion, and then a complicated process such as extraction of the resulting copolymer with hot acetone or the like is required.

For this reason, in the process for producing the cyclic olefin random copolymer, the emergence of a method for producing a cyclic olefin random copolymer capable of economically producing a cyclic olefin random copolymer substantially free of halogens Is required.

Incidentally, Japanese Patent Application Laid-Open No. 1-92208 or Japanese Patent Application No.
No. 25152 discloses that a cyclic olefin-based random copolymer solution obtained by copolymerization of ethylene and a cyclic olefin is brought into contact with a specific adsorbent containing a metal cation, so that a halogen is produced from the cyclic olefin random copolymer solution. It is taught that chlorides can be removed. However, these methods are methods for removing the halogenated cyclic olefin once formed,
It cannot suppress by-product of the halogenated cyclic olefin.

Effects of the Invention The present invention has been made in view of the above points, and is excellent in transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and various mechanical properties. It is another object of the present invention to provide a method for producing a cyclic olefin random copolymer substantially containing no halogen.

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]. (Wherein, 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. Is formed from a soluble vanadium compound and an organoaluminum compound, and at least one of the soluble vanadium compound and the organoaluminum compound is halogenated. In a hydrocarbon medium and / or a liquid phase comprising the cyclic olefin to form a solution of a cyclic olefin random copolymer in the presence of a catalyst containing It is characterized in that the combined solution is contacted with an alcohol having a water content of 20% by volume or less and then decalcified.

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 cyclic olefin represented by the above general formula [I] or the general formula [II] and ethylene are
In a hydrocarbon solvent or a cyclic olefin liquid phase, copolymerization is performed in the presence of a catalyst comprising a vanadium compound and an organoaluminum compound soluble in the solvent or the cyclic olefin to produce a cyclic olefin-based random copolymer. ing.

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; Hexacyclo 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.

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, VOC 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 17
A vanadium compound such as 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, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, phenylethyl alcohol, isopropyl alcohol,
C1-18 alcohols such as isopropylbenzyl alcohol; C6-20 phenols which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol. C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde Classes: 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, benzoate Octyl acid, 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 nadicate, diisosopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-phthalate
-Butyl, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide,
Organic acid esters having 2 to 30 carbon atoms such as ethylene carbonate;
C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride; C2 to C2 such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether 20 ethers; acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylenediamine Nitriles such as acetonitrile, benzonitrile and trinitrile; and alkoxysilanes such as ethyl silicate and 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
+ P + q = 3 a is) an organoaluminum compound represented by, (ii) the general formula M ¹ AR ¹ ₄ (wherein M ¹ is Li, Na, K, and
R ¹ is the same as described above) and a complex alkylated product of a Group 1 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).

As the aluminum compound belonging to (i), more specifically, trialkylaluminum such as triethylaminium and tributylaluminum; trialkenylaluminum such as triisopropenylaluminum; dialkylaluminum such as diethylaluminum ethoxide and dibutylaluminum butoxide alkoxide; ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride butoxide; in _{^{addition, R 1 2.5 a (OR 2}} )
Partially alkoxylated alkylaluminum, diethylaluminum chloride, dibutylaluminum chloride, dialkylaluminum halide such as diethylaluminum bromide having an average composition represented by _0.5 or the like; ethylaluminum sesquichloride, butylaluminum sesquichloride, isobutylaluminum Alkyl aluminum sesquihalides such as sesquichloride, ethyl aluminum sesquibromide; alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; partially halogenated alkyl aluminum, diethyl aluminum Dialkylaluminum hydride such as hydride and dibutylaluminum hydride Alkyl aluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; partially hydrogenated alkylaluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and partially alkoxy such as ethylaluminum ethoxybromide And halogenated alkyl aluminum. 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 the compound belonging to the above (ii), LiA (C ₂ H ₅ )
₄ , LiA (C ₇ H ₁₅ ) _{4 and the} like. Among these, it is particularly preferable to use an alkyl aluminum halide, an alkyl alnium dihalide or a mixture thereof.

In the present invention, at least one of the soluble vanadium compound and the organoaluminum compound as described above contains a halogen. In particular, in the present invention, the organoaluminum compound preferably contains a halogen.

In the present invention, the copolymerization reaction between ethylene and the cyclic olefin represented by the above formula [I] or [II] is carried out in the presence or absence of a hydrocarbon solvent.
Examples of the hydrocarbon solvent that may be used in this case include: aliphatic hydrocarbons such as hexane, heptane, octane, and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, and xylene. And the like. These solvents can be used alone or as a mixture.

In the present invention, ethylene and the cyclic olefin are copolymerized, but if necessary, an α-olefin having 3 or more carbon atoms may be copolymerized, and as such an α-olefin having 3 or more carbon atoms. Is, for example, propylene, 1-
Butene, 4-methyl-1-pentene, 1-hexene, 1
Α-olefins having 3 to 20 carbon atoms, such as -octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

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 a copolymerizable unsaturated monomer include cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, and the like in an amount less than the molar amount of the cyclic olefin component unit in the generated random copolymer. Cycloolefin, 1,4-hexadiene, 4
Non-conjugated dienes such as -methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene and 5-vinyl-2-norbornene can be exemplified.

In producing the cyclic olefin-based random copolymer, it is preferable that the copolymerization reaction between ethylene and the above-mentioned cyclic olefin is carried out 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. Range.

The ratio (A / V) of aluminum atoms to vanadium atoms in the polymerization reaction system is 2 or more, preferably 2 to 5
0, particularly preferably in the range of 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 to the above concentration range, but there is a method in which the organoaluminum compound is adjusted to an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization reaction system and supplied to the polymerization reaction system. Adopted.

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

Such a copolymerization reaction of ethylene and a cyclic olefin 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 olefins supplied to the reaction system is usually 90/10 to 10/90, preferably 20/80 to 8
It is desirable to be in the range of 5/15.

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 2.0 to 300 g / m, preferably 10 to 100 g / m.
And the resulting copolymer solution contains a soluble vanadium compound component and a halogen-containing organoaluminum compound component which are catalyst components.

In the present invention, after the cyclic olefin random copolymer polymerization solution thus obtained is brought into contact with an alcohol having a water content of 20% by volume or less, preferably 5% by volume or less, more preferably 5000 ppm or less. Characterized by decalcification.

As the alcohols, methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol, ethylene glycol and the like are used.

The amount of alcohol added to the polymerization solution was 5 times the total number of moles of vanadium and aluminum used as the catalyst in the polymerization.
Times or more is preferable, and the amount at which the polymer does not precipitate is the upper limit. Usually, the preferred range is 1.5 ml to 20 ml per 1 polymerization solution.

After bringing the cyclic olefin-based random copolymer polymerization solution into contact with an alcohol having a water content of 20% by volume or less in this manner, a deashing treatment is applied to the copolymer solution.

The demineralization treatment can be performed by a conventionally known method, for example, by adding water to a cyclic olefin-based random copolymer solution. The water used in the demineralization treatment may contain an acid or an alkali.

By such a deashing treatment, the catalyst component is decomposed and removed.

A cyclic olefin random copolymer can be obtained from the cyclic olefin random copolymer solution to which the deashing treatment has been added as described above according to a conventional method.To obtain a copolymer from the copolymer solution, For example, there is a method of precipitating and recovering a copolymer by a method such as distillation of a solvent or a method in which a polymerization solution is heated to a high temperature and a high pressure and then flushed under a normal pressure. Into a polar solvent such as acetone to precipitate and separate the copolymer, and there is no particular limitation.

In the present invention, as described above, when the alcohol having a water content of 20% by volume or less is contacted with a cyclic olefin-based random copolymer polymerization solution and then decalcified, the formation of a halogenated cyclic olefin is caused. Can be suppressed.
Therefore, the cyclic olefin-based random copolymer obtained by decalcifying the obtained cyclic olefin-based random copolymer solution and then precipitating by the above-described method does not substantially contain a halogen.

It is not clear why halogenated cyclic olefins are not generated by deashing after contacting alcohols having a water content of 20% by volume or less with a cyclic olefin-based random copolymer polymerization solution, The alcohols react with the halogen-containing organic aluminum compound or the halogen-containing vanadium compound to decompose the halogen-containing organic aluminum compound or the halogen-containing vanadium compound. This is considered to be because halogenated cyclic olefin is not generated even when contacted with olefin. On the other hand, when the halogen-containing organoaluminum compound or the halogen-containing vanadium compound is brought into contact with water without contacting with alcohols, the halogen-containing organoaluminum compound or the halogen-containing vanadium compound decomposes and reacts with the cyclic olefin to form a halogenated compound. It is considered that a cyclic olefin is formed.

The cyclic olefin-based random copolymer substantially free of halogen obtained in this way is amorphous or crystalline, but among the cyclic olefin-based random copolymers, they have no DSC melting point and Amorphous copolymers are also suitable from the results of measurement by line diffraction. Furthermore, the ethylene / cyclic olefin molar ratio of the cyclic olefin random copolymer obtained by the method of the present invention is usually 95/5.
~ 30/70, preferably 90/10 ~ 40/60. The glass transition point (Tg) of the cyclic olefin-based random copolymer is usually in the range of 10 to 260 ° C, preferably 20 to 200 ° C.

Effect of the Invention In the present invention, ethylene and a cyclic olefin are formed from a soluble vanadium compound and an organoaluminum compound, and are copolymerized in the presence of a catalyst containing a halogen in at least one of the soluble vanadium compound and the organoaluminum compound. The resulting cyclic olefin random copolymer polymerization solution is demineralized after being brought into contact with an alcohol having a water content of 20% by volume or less, so that the cyclic olefin random copolymer substantially containing no halogen is contained. Coalescence can be obtained efficiently.

EXAMPLES Next, the method of the present invention will be specifically described with reference to examples, and the present invention is not limited to these examples.

The chlorine content (C content) in the polymer was determined by a method in which the polymer was burned by an oxygen flask method and HC generated was quantified by an ion chromatography method.

Using one of the polymerization vessel equipped with Example 1 [Polymerization stirring blades, continuously ethylene and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene (hereinafter TCD-3 substantially) Was carried out. That is, the cyclohexane capacity of TCD-3 was 0.4 per hour from the top of the polymerization vessel so that the TCD-3 concentration in the polymerization vessel was 60 g /, and a cyclohexane solution of VO (OC ₂ H ₅ ) C ₂ was used as a catalyst in the polymerization vessel. 0.5 hourly (the vanadium concentration supplied at this time is 2.86 times the concentration in the polymerization reactor), and ethyl aluminum sesquichloride (A (C ₂ H ₅ ) _1.5 C _1.5 ) With a cyclohexane solution of 4.0mmo
l / h and cyclohexane were continuously fed into the polymerization machine at a rate of 0.7 / h, and 0.4 / h, respectively.
On the other hand, the polymerization solution in the polymerization vessel is continuously withdrawn from the upper portion of the polymerization vessel so that the polymerization liquid is always 1 (that is, the average residence time is 0.5 hours). In addition, ethylene is supplied at a rate of 20 per hour, nitrogen is supplied at a rate of 10 per hour, and hydrogen is supplied at a rate of 0.5 per hour using a bubbling tube for 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 is performed under the above conditions,
A polymerization reaction mixture (polymerization liquid) containing the ethylene / TCD-3 random copolymer was obtained.

[Addition of alcohol] To the polymerization liquid 1 withdrawn from the upper part of the polymerization vessel, 3.3 ml of methanol (water content: 310 ppm) was added and stirred vigorously for 5 minutes.

[Deashing] Thereafter, an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to water 1 was brought into contact with the polymerization solution at a ratio of 1 to 1 under vigorous stirring using a homomixer to transfer a catalyst residue to an aqueous layer. The mixture was allowed to stand, and after removing the aqueous layer, the mixture was further washed twice with distilled water, and the polymer solution was purified and separated. (A part of this polymerization solution was taken out and dried at 130 ° C. under reduced pressure for 24 hours to remove the solvent component, and the C content in the polymer at this point was measured and found to be 35.4 ppm.) Precipitation] The polymer solution obtained by the above-described deashing operation was brought into contact with a three-fold amount of acetone under vigorous stirring, and the solid portion was collected by filtration and sufficiently washed with acetone. (Take out part of the polymer,
The polymer was dried at 130 ° C. under reduced pressure for 24 hours. The C content of the polymer at this time was measured, and it was 7.0 ppm. [Acetone Extraction] Thereafter, the fixed part obtained in the above precipitation step was put into acetone so as to be 40 g /, and subjected to a reaction treatment at 60 ° C. for 2 hours. Thereafter, the solid portion was collected by filtration, and under nitrogen flow,
It was dried at 130 ° C. and 350 mmHg for 24 hours.

As described above, an ethylene / TCD-3 copolymer was obtained at an amount of 96 g / h (that is, 48 g / h). The ethylene content of the obtained copolymer is 61.5 mol%, the intrinsic viscosity [η]
Is 0.54 dl / g, w / n by GPC measurement is 2.50, crystallinity by Χ-ray diffraction is 0%, and glass transition temperature Tg of DSC method is 137.
° C.

The C content in the polymer is the detection limit of the above measurement method.
At 5 ppm or less, it was found that C was not substantially contained.

 Table 1 shows the results.

Examples 2 to 4 Copolymers were synthesized in the same manner as in Example 1 except that the copolymerization conditions of Example 1 were left as they were, and the types and amounts of alcohols were changed as shown in Table 1.

 Table 1 shows the results.

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

Claims (1)

(57) [Claims] (1) (a) ethylene, and (b) the following formula [I] or [II] (Wherein, 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. Is formed from a soluble vanadium compound and an organoaluminum compound, and at least one of the soluble vanadium compound and the organoaluminum compound is halogenated. In a hydrocarbon medium and / or a liquid phase comprising the cyclic olefin to form a solution of a cyclic olefin random copolymer in the presence of a catalyst containing A method for producing a cyclic olefin-based random copolymer, which comprises contacting the combined solution with an alcohol having a water content of 20% by volume or less and then removing the ash.