JPH0445103A - Production of cyclic olefinic random copolymer - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer, excellent in transparency, heat resistance, dielectric characteristics, etc., containing no halogen and useful as optical memory disks, etc., by copolymerizing ethylene with a specific cyclic olefin in the presence of a specified halogen-containing catalyst in the liquid phase, and then deashing the resultant copolymer solution with an alcohol. CONSTITUTION:(A) Ethylene is copolymerized with (B) a cyclic olefin composed of an unsaturated monomer expressed by formula I ((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 H, halogen, hydrocarbon, etc.) or formula II ((l) is 0 or a positive integer of >=1; (m) and (n) are 0, 1 or 2; R<1> to R<15> are H, halogen, hydrocarbon, etc.), etc., in the presence of a catalyst formed from a soluble V compound and an organoaluminum compound in which at least either thereof contains a halogen. Copolymerization is then carried out in the liquid phase composed of a hydrocarbon medium and/or the cyclic olefin and the resultant produced copolymer polymerization solution is subsequently brought into contact with alcohols having <=20vol.% water content and then deashed to afford the objective random copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for producing a cyclic olefin random copolymer. More specifically, the present invention provides a cyclic olefin-based random compound that has excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties, and is substantially free of halogen. The present invention relates to a method for producing a copolymer.

Technical background of the invention A cyclic olefin-based random copolymer consisting of ethylene and a specific noble cyclic olefin is a synthetic resin with well-balanced optical properties, mechanical properties, and thermal properties, and is useful for optical memory disks and International application publication W has shown that it can be used for applications in the field of optical materials such as optical fibers.
It is disclosed in O39101950 or Japanese Patent Application Laid-open No. 1-185307.

These proposed cyclic olefin random copolymers contain halogenated cyclic olefins as a by-product when produced using a halogen-containing catalyst; Since the softening temperature of the copolymer is significantly higher than that of ordinary olefin polymers, hydrogen halides such as hydrochloric acid are generated even if the halogen content of the copolymer is small, making it difficult to mold. May corrode equipment, etc. Therefore, in order to remove the halides of the cyclic olefin, a large amount of poor solvent such as acetone is added to the copolymer solution produced by copolymerizing ethylene and cyclic olefin in a liquid phase consisting of a hydrocarbon medium. It is necessary to carry out a complicated treatment such as adding the copolymer to a liquid phase, precipitating the copolymer produced, separating it from the liquid phase, and then extracting the copolymer produced using hot acetone or the like.

Therefore, in the process of producing the cyclic olefin random copolymer, a method for producing a cyclic olefin random copolymer has emerged that can economically produce a cyclic olefin random copolymer that does not actually contain halogen. or requested.

In addition, Japanese Patent Application Laid-Open No. 1992-92208 or Japanese Patent Application No. 1993
No. 25152 discloses that halogens are removed from a cyclic olefin random copolymer solution by contacting the cyclic olefin random copolymer solution obtained by copolymerizing ethylene and a cyclic olefin with a specific adsorbent containing a metal cation. It has been taught that chemical compounds can be removed. However, these methods are methods for removing the halogenated cyclic olefin that has been produced, and do not suppress the by-product of the halogenated cyclic olefin.

Purpose of the Invention The present invention has been made in view of the above points, and provides a material with excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties. The purpose of the present invention is to provide a method for producing a cyclic olefin random copolymer that is substantially free of halogen.

Summary of the Invention The method for producing a cyclic olefin random copolymer according to the present invention comprises (a) ethylene, (b) the following formula [1] or [II] (where n is O or 1, and m is 0 or a positive integer, q is 0 or 1, and R-R and R, Rb
are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R15 to R18 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring is a double may have a bond, or R and R or RI7 and R18 may form an alkylidene group).

and n are 0.1 or 2, and 1,1-Rl5. Each independently represents a hydrogen atom, a /XX rosin group, an aliphatic hydrocarbon group, an aromatic hydrocarbon group (an alkoxy group, R (or R) and R" (or R7) and teeth,
They may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group.

] At least one group-selected cyclic olefin consisting of unsaturated monomers represented by
In the presence of a catalyst containing a halogen in at least one of the sodium compound and the organoaluminum compound, the above-mentioned soluble compound is copolymerized in a hydrocarbon medium and/or a liquid phase consisting of the cyclic olefin to form a cyclic olefin-based random copolymer. The method is characterized in that a solution of the copolymer is produced, and the resulting copolymer solution is brought into contact with an alcohol having a water content of 20% by volume or less, and then deashed.

DETAILED DESCRIPTION OF THE INVENTION The method for producing a cyclic olefin random copolymer according to the present invention will be specifically described below.

In the present invention, the general formula [1] or the general formula [
11] and ethylene,
A cyclic olefin random copolymer is produced by copolymerizing in a hydrocarbon solvent or in a cyclic olefin liquid phase in the presence of a catalyst consisting of a vanadium compound and an organoaluminium compound soluble in the solvent or the cyclic olefin. ing.

2bicyclo[2,
2,11hept2-ene derivative tetracyclo[4,4,0,1'', 17°10]-3
-Dodecene-induced droplet hexacyclo[6,6,1,1'・JIO・+2.027°014]
-4-Heptadecene derivatized octacyclo[8,8,0,1"・1.14・7 11 Old JB・1.03・$.

012・17] 5-tococene-induced tree pentacyclo[6,6,1,1''',0''・7.09・+4ko4
- Hexadecene derivatization; Table 1 specifically describes the cyclic olefin (For reference (structural formula) % formula %) 5-bentacocene derivation (nonacyclo[10,10°1.1", 114 +1.1 +1 lIO2・+1
．． 041.012・O18. ! O] -5-hexacosene derivatives.

Specific examples of such compounds are listed below. Here is a J example.

(Left below) Bicyclo[2,2,1]hept-2-ene derivatives such as; Tetracyclo[4,4,0,12 5,17 10] dodecene derivatives such as Hexacyclo[6,6 ,1,1",1",0°12.7. o@4] Heptadecene derivatives: Octacyclo [8,8,0,12 9,14 7,11 ■ 6.03 8.0] Tococene derivatives; [6, 6, 1, I”1.0!・7.
09 14] -4-Hexadecene derivative; Heptacyclo-5-heneicosene derivative: tricyclo[4,3,0,1! l'] -3 decene derivatives; tricyclo[4,4,0,12・I]-3 to undecene derivatives;
" ]]4-pentadecene derivatives: pentadichloro[7,4,0,1"', 1'-+
2.0"□IJ3-pentadecene derivative: Natonohebutanechlor [8,7,0,12", 1"Q 2
7, Q 11th] -4-eicosene derivative, 1 5-bentacocene / pear') Mouth [10,9,1,1'7,11th o
, IIs”□L1.02.IO, 012, 21, p14
Meko 5 - Hen 9 Near Se > Heptacyclo such as 4 cavalry [8, 4, 0, 1"・6. p, H, OL H] -
Total hexadecene derivatives; hebutacyclo[8,8,o, 14.7.1 Il such as 5-heneicosene
, Il, I B1, gLl, 012 7] Heneicosene derivatives: nonacyclo[10,10,1,1'・J+4°2
1. 1@1 Book, 02*, 012 2.0 Li2] -]5-hexacosene derivatives: Further, the following can be mentioned.

(The following is a blank space) The cyclic olefin represented by the above formula [I] or [n] can be easily produced by subjecting a cyclopentadiene and a corresponding olefin to a Diels-Alder reaction.

Specifically, the vanadium compound has the general formula VO (
OR) aX5 or V (OR). Xd (however,
R is a hydrocarbon group, 0≦a≦3.0≦b≦3.2≦a+b
A vanadium compound represented by the formula ≦3.0≦C≦4.0≦d≦4.3≦c+d≦4) or an electron donor adduct thereof is used.

More specifically, vOC13, VO(OCH)0g2, VO(OC2H5)20g1 VO(0-1so-CH) Cg2, VO(0-n-
CH) CN2, VO(OCH), VOBr-VCII
4. VOCg, VO(0-n-C4H9) 3,v
Vanadium compounds such as c, p ・20C8H170H are used.

Electron donors that may be used when preparing the soluble vanadium catalyst component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides. Oxygen-containing electron donors such as silanes, alkoxysilanes, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates can be mentioned. More specifically, methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, phenylethyl alcohol 1, isopropyl alcohol, isopropylbenzyl Alcohols with 1 to 18 carbon atoms such as alcohol; phenols with 6 to 20 carbon atoms that may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol: Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and 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 dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, benzoic Ethyl acid, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate,
n-butyl maleate, diisobutyl methylmalonate,
Di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, cisisoprovir tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n phthalate
-butyl, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide,
Organic acid esters with 2 to 3 carbon atoms such as ethylene carbonate; acid halides with 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride: methyl ether, ethyl ether, isopropyl ether, butyl ether , amyl ether, tetrahydrofuran, anisole, diphenyl ether and other ethers having 2 to 20 carbon atoms; acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine, toluic acid Examples include amines such as amide, aniline, pyridine, picoline, and tetramethylenediamine; nitriles such as acetonitrile, benzonitrile, and tolnitrile; and alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane.

Two or more types of these electron donors can be used.

As the organoaluminum compound catalyst component, a compound having at least one AI-carbon bond in the molecule is used, for example, a compound containing 15, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. good. X is halogen, m is 0≦
m≦3, n is 0≦n<3, p is 0≦n<3, q is 0≦q
<3, and m+n+p+q-3)
Organoaluminum compounds represented by (i) complex alkylated products of Group 1 metals and aluminum represented by the general formula MANR (where Ml is Li, Na, or Ni, and R1 is the same as above); I can do it.

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

(Here, R and R2 are the same as above. m is preferably 1
．． 5≦m<3).

(Here, R1 is the same as above. X is /% rogene, m is preferably 0<m<3).

General formula RIH8° (where R1 is the same as above. m is preferably 2≦m<3
).

(Here, R1 and R2 are the same as above.
-3) can be exemplified.

More specifically, the aluminum compounds belonging to (i) include: ■ trialkylaluminum such as triethylaminium and tributylaluminum; trialkenylaluminum such as triisopropenylaluminum;
Dialkyl aluminum alkoxides such as diethylaluminum ethoxide and diethyl aluminum ethoxide; alkylaluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide; Partially alkoxylated alkyl aluminum having a homogeneous composition of 0.5, Dialkyl aluminum halides such as diethylaluminum chloride, dibutyl aluminum chloride, diethylaluminium bromide: ethyl aluminum sesquichloride, butyl aluminum sesquichloride,
Alkylaluminum sesquihalides such as isobutylaluminum sesquichloride, ethylaluminum sesquipromide; alkylaluminum cybarides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, etc.; Alkylaluminum, ■Dialkylaluminum hydride such as diethylaluminum hydride, dibutylaluminum hydride;
Partially hydrogenated alkylaluminiums such as alkylaluminum halodrides such as ethylaluminum dicdolide, probylaluminum dihydride, partially hydrogenated alkylaluminums such as ethylaluminum sesquichloride, butylaluminum butoxychloride, ethylaluminum sesquipromide, etc. Examples include alkoxylated and halogenated alkyl aluminums. It may also be a compound similar to (i), such as an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Specifically, such compounds include (CH) ANOAΩ (C2R5)2, (CH)
AJIIOAΩ (C4H9)2, 6H5 can be exemplified.

Compounds belonging to the above (H) include LiA, Q(CH
), LIAN (C7H15)4, etc. Among these, it is particularly preferable to use alkyl aluminum halides, alkylaluminium cybarides, or mixtures thereof.

In the present invention, at least one of the above-described soluble vanadium compound and organoaluminum compound contains a halogen. Particularly in the present invention, it is preferable that the organoaluminum compound 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 hydrocarbon solvents that may be used for this removal 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. For example, These solvents can be used alone or in combination.

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

Further, other copolymerizable unsaturated monomer components can be copolymerized as necessary within a range that does not impair the purpose of the present invention. Specifically, such copolymerizable unsaturated monomers include less than one mole of cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, etc. with the cyclic olefin component unit in the random copolymer to be produced. cycloolefin, l,4-hexadiene, 4
-Methyl-1,4-hexadiene, 5-methyl-1,4
-hexadiene, 1,7-octadiene, 5-vinyl-
Examples include non-conjugated dienes such as 2-norbornene.

When producing a cyclic olefin random copolymer, the copolymerization reaction between ethylene and the above-mentioned cyclic olefins is preferably carried out in a continuous process. 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.

Further, the ratio (Ai)/V) of aluminum atoms to vanadium atoms in the polymerization reaction system is 2 or more, preferably 2 to 2.
50, particularly preferably in the range of 3 to 20.

The soluble vanadium compound and the organoaluminum compound are usually supplied diluted with the hydrocarbon solvent or the cyclic olefin, respectively. Here, the soluble vanadium compound is preferably diluted to the above concentration range, but the organoaluminum compound may be prepared at an arbitrary concentration, for example, 50 times or less of the concentration in the polymerization reaction system, and then supplied to the polymerization reaction system. Adopted.

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

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

The reaction time for carrying out the above copolymerization reaction (
In the case of a continuous polymerization reaction, the average residence time of the polymerization reaction mixture varies depending on the type of polymerization raw material, the concentration of the catalyst component, and the temperature, but is usually 5 minutes to 5 hours, preferably 1 hour.
It ranges from 0 minutes to 3 hours. In addition, the pressure when carrying out the copolymerization reaction is usually higher than 0 and 50 kg/cd,
Preferably it exceeds 0 and 20 kg/c-. In addition, during copolymerization, a molecular weight regulator such as hydrogen may be present in order to adjust the molecular weight of the resulting copolymer.

When producing a cyclic olefin random copolymer, the molar ratio of ethylene/cyclic olefins supplied to the reaction system is usually in the range of 90/10 to 10/90, preferably 20/80 to 85/15. It is desirable that there be.

When the copolymerization reaction of ethylene and cyclic olefins is carried out as described above, a solution of a cyclic olefin random copolymer is obtained. The concentration of the cyclic olefin random copolymer contained in such a copolymer solution is usually
2.0-300 grams/it, preferably 10-100
gram/II, 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, the cyclic olefin random copolymerization solution obtained in this way has a water content of 20% by volume or less, preferably 5% by volume or less, more preferably 5000% by volume or less.
It is characterized by being deashed after being brought into contact with alcohols having a concentration of ppm or less.

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

The amount of alcohol added to the polymerization solution is preferably 5 times or more the total number of moles of vanadium and aluminum used as catalysts in the polymerization, and the upper limit is an amount that does not precipitate the polymer. Usually, 1.5ml to 20ml per 1g of polymerization solution
ml is the preferred range.

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

The deashing treatment can be carried out by a conventionally known method, for example, by adding water to a cyclic olefin random copolymer solution. The water used in the deashing process may contain acid or alkali.

Through such deashing treatment, catalyst components are decomposed and removed.

A cyclic olefin random copolymer can be obtained by a conventional method from a cyclic olefin random copolymer solution that has been deashed as described above, but in order to obtain a copolymer from the above copolymer solution, For example, the copolymer can be precipitated and recovered by distillation of the solvent or by bringing the polymerization solution under high temperature and pressure and then flashing it to normal pressure. It is also possible to precipitate and separate the copolymer by adding it to a polar solvent such as acetone, but there is no particular limitation.

In the present invention, as described above, when an alcohol having a water content of 20% by volume or less and a cyclic olefin random copolymer polymerization solution are brought into contact with each other and then deashed, the formation of halogenated cyclic olefins is prevented. Can be suppressed.

Therefore, the cyclic olefin random copolymer obtained by deashing the resulting cyclic olefin random copolymer solution and precipitating it by the method described above does not substantially contain halogen.

It is not clear why halogenated cyclic olefins are not produced by deashing after contacting an alcohol with a water content of 20% by volume or less with a cyclic olefin random copolymer polymerization solution. However, alcohols and halogen-containing organoaluminum compounds or halogen-containing vanadium compounds react to decompose the halogen-containing organoaluminum compounds or halogen-containing vanadium compounds, and the decomposed halogen-containing organoaluminum compounds or halogen-containing vanadium compounds are dissolved in water. This is thought to be due to the fact that halogenated cyclic olefins are not produced even when the halogenated cyclic olefins are brought into contact with the cyclic olefins. On the other hand, when a halogen-containing organoaluminum compound or a halogen-containing vanadium compound is brought into contact with water without contacting with alcohol, the halogen-containing organoaluminum compound or halogen-containing vanadium compound decomposes and reacts with the cyclic olefin, resulting in halogenation. It is thought that cyclic olefins are produced.

The cyclic olefin random copolymer which is obtained in this manner and which does not substantially contain halogen is non-polymerized or crystalline, but among the cyclic olefin random copolymers, it has no DSC melting point and no A non-crystalline copolymer is also preferred based on measurement results by linear 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.
15-30/70, preferably 90/10-40/60
is within the range of Further, the glass transition point (Tg) of the cyclic olefin random copolymer is usually 10 to 260°C,
Preferably it is in the range of 20 to 200°C.

Effects of the Invention In the present invention, ethylene and a cyclic olefin are copolymerized in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound and 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 deashed after being brought into contact with an alcohol having a water content of 20% by volume or less, resulting in a cyclic olefin random copolymer containing substantially no halogen. Combination can be obtained efficiently.

EXAMPLES Next, the method of the present invention will be specifically explained by examples, but the present invention is not limited to these examples.

The chlorine content ((l content) in the polymer was determined by burning the polymer using an oxygen flask method and quantifying the generated HCfi using an ion chromatography method.

Example 1 [Polymerization] Ethylene and tetracyclo[4,4,0,1"517"101
A copolymerization reaction of 3-dodecene (hereinafter abbreviated as TCD-3) was carried out. That is, a cyclohexane solution of TCD-3 is poured from the top of the polymerization vessel until the TCD-3 concentration in the polymerization vessel is 60 g/
0.4N/hour, VO (OC2
H5) A cyclohexane solution of C112 was added every hour to a vanadium concentration of 0.5 mmol/I in the polymerization vessel.
, 5g (the concentration of vanadium supplied at this time is 2.86 times the concentration in the polymerization vessel), a cyclohexane solution of ethylaluminum sesquichloride (Ag (C2H5)15CD) was added to the aluminum concentration in the polymerization vessel, or 4g.
．． 0.49 and cyclohexane are each continuously fed into the polymerization machine at a rate of 0.7g/hour so that the concentration is 0 mmol/Ω, and on the other hand, from the top of the polymerization vessel, the amount of polymerized liquid in the polymerization vessel is constantly fed to 1 g. (i.e., with an average residence time of 0.5 hours). Also,
Using a bubbling tube in the polymerization system, ethylene was added at 2 (01
, nitrogen at a rate of 10 g/hour and hydrogen at a rate of 0.5 g/hour. The copolymerization reaction was carried out at 10° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel.

When the copolymerization reaction is carried out under the above conditions, ethylene/TCD-3
A polymerization reaction mixture (polymerization liquid) containing a random copolymer was obtained.

[Addition of Alcohol] 3.3 ml of methanol (hydrous Ji: 310 ppI11) was added to the polymerization liquid IR extracted from the upper part of the polymerization vessel, and the mixture was vigorously stirred for 5 minutes.

[Deashing] Thereafter, an aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 g of water was brought into contact with the polymerization solution at a ratio of 1:1 under strong stirring using a homomixer, and the catalyst residue was transferred to the aqueous layer. The above mixture was allowed to stand, and after removing the aqueous layer, it was further washed twice with distilled water to purify and separate the polymerization liquid. (A portion 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 CΩ content in the polymer at this point was measured and found to be 35.4 ppm.) Precipitation of Polymer] The polymerization liquid obtained in the above deashing operation was brought into contact with three times the amount of acetone under strong stirring, and the solid portion was collected by filtration and thoroughly washed with acetone. (Take out a part of the polymer and
After drying at 0°C under reduced pressure for 24 hours, the 0g content in the polymer at this point was determined to be 7.01) pffl
Met. ) [Acetone extraction] Then, the solid part obtained in the above precipitation step was extracted with 40g/
The mixture was poured into acetone so as to become D and reacted at 60° C. for 2 hours. Thereafter, the solid portion was collected by filtration and dried at 130° C. and 35 C1 amHg for 24 hours under nitrogen flow.

As described above, ethylene/TCD-3 copolymer was obtained in an amount of 96 g/hour (ie, 48 g/g). The ethylene content of the obtained copolymer was 61.5 mol%, the intrinsic viscosity [η was 0.54 dI/g, and Mw was determined by GPC measurement.
/Mn is 2,50, crystallinity by X-ray diffraction is 0
%, and the glass transition temperature Tg by DSC method was 137°C.

In addition, the 0g content in the polymer is the detection limit S of the above measurement method.
It was found that C9 was not substantially contained at pp■ or less.

These results are shown in Table 1.

Examples 2 to 4 Copolymers were synthesized in the same manner as in Example 1, with the same copolymerization conditions as in Example 1, except that the type and amount of alcohol were changed as shown in Table 1.

These results are shown in Table 1.

Claims (1)

[Claims] 1. (a) Ethylene, (b) The following formula [I] or [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R^1 to R^1^8 and R^a, R^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, and R^1^5 to R^1^8 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond. Also, R^1^5 and R^1^6, or R^1^7
and R^1^8 may form an alkylidene group). ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [II] [In the formula, l is an integer of 0 or 1 or more, m and n
is 0, 1 or 2, R^1 to R^1^5 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) and R^9 (or R^7) may be bonded via an alkylene group having 1 to 3 carbon atoms,
Alternatively, they may be directly bonded without any group intervening. At least one cyclic olefin selected from the group consisting of unsaturated monomers represented by: Copolymerizing in a hydrocarbon medium and/or a liquid phase consisting of the cyclic olefin in the presence of a catalyst containing the cyclic olefin to produce a solution of the cyclic olefin random copolymer, and the resulting copolymer weight A method for producing a cyclic olefin random copolymer, which comprises contacting a combined solution with an alcohol having a water content of 20% by volume or less, and then deashing the mixture.