JPH03258815A - Production of cyclic olefinic random copolymer - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer, excellent in optical mechanical, thermal properties, etc., and suitable as optical fiber, etc., by copolymerizing ethylene with a cyclic olefin in the presence of a catalyst of a specific organoaluminum compound. CONSTITUTION:(A) Ethylene and (B) an unsaturated monomer expressed by formula I (R<1> to R<18> are H, halogen, etc.; n is 0 or 1; m is 0 or a positive inte ger) or formula II (R<1> to R<15> are H, alkoxy, etc.; 1 is 0 or an integer; m and n are 0-2) are mixed with (C) a hydrocarbon solvent such as pentane or decane. (D) (i) A soluble vanadium compound and (ii) an organoaluminum compound expressed by formula III (R is >=4C alkyl; n is 1.35-1.65) are added to the resul tant mixture to carry out reaction preferably at -50 to 100 deg.C. Thereby, the objective copolymer is obtained.

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 is directed to the production of a cyclic olefin random copolymer that can reduce the content of polyethylene contained as impurities and has excellent transparency. Regarding the method.

Technical background of the invention A cyclic olefin-based random copolymer consisting of ethylene and a specific bulky cyclic olefin is a synthetic resin with well-balanced optical properties, mechanical properties, thermal properties, etc., and is used for example in optical memory. It is used in the field of optical materials such as disks and optical fibers.

However, when optical memory disks are manufactured from such cyclic olefin-based random copolymers, reading errors may occur, albeit very slightly. The present inventors have conducted intensive studies to reduce reading errors in optical memory disks manufactured from cyclic olefin random copolymers, and have found that some of these reading errors are due to impurities in the cyclic olefin random copolymers. It was found that this is due to the polyethylene contained in Therefore, the emergence of a method for producing a cyclic olefin random copolymer that can reduce the content of polyethylene contained as impurities is strongly desired.

By the way, such a cyclic olefin-based random copolymer is conventionally produced by mixing ethylene and a cyclic olefin with a hydrocarbon such as hexane or heptane or the above-mentioned cyclic olefin in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound. It is manufactured by copolymerizing using it as a solvent. The present inventors conducted intensive studies on a method for producing a cyclic olefin random copolymer that has a reduced content of polyethylene as an impurity and has excellent transparency, and found that a specific organoaluminum compound was used as the organoaluminum compound. This discovery led to the completion of the present invention.

Purpose of the Invention The present invention has been made in view of the prior art as described above, and provides a cyclic olefin random copolymer that can reduce the content of polyethylene contained as impurities and has excellent transparency. It is an object of the present invention to provide a method for producing a cyclic olefin random copolymer that can be produced efficiently.

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 0 or 1, m is 0 or a positive integer, R1-R18 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R15-R18 may be bonded to each other to form a monocyclic or polycyclic ring. The monocyclic or polycyclic ring may have a double bond, and R15 and R16 or R17 and R18 may form an alkylidene group).

[In the formula, l is O or an integer of 1 or more, m and n
is 0.1 or 2, R1 to R15 are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an alkoxy group, and R5 (or R6) and R9 (or ) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group. ] in a hydrocarbon solvent in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminium compound, and at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by When copolymerizing to produce a cyclic olefin random copolymer,
As an organoaluminum compound, RAlCl3-11 (wherein, n is 1.35 to 1.65, and R is a carbon number of 4
It is characterized by using an organoaluminum compound represented by the above linear or branched alkyl group.

According to the present invention, when copolymerizing ethylene and a cyclic olefin, RAA'CA' (where n 3-n n is 1.35 to 1.65 and R is a linear or branched alkyl group having 4 or more carbon atoms), the content of polyethylene contained as an impurity is reduced, and the cyclic olefin random copolymer has excellent transparency. A combination can be produced. Moreover, it is possible to efficiently prevent polyethylene from adhering to the walls of the polymerization vessel and the vicinity of the polymer outlet.

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 [I] or the general formula [
Cyclic olefins represented by II] and ethylene,
A cyclic olefin-based random copolymer is produced by copolymerizing in a hydrocarbon solvent or in a liquid phase consisting of the cyclic olefin in the presence of a catalyst consisting of a vanadium compound soluble in the solvent or the cyclic olefin and a specific organic aluminum compound. Manufactures polymers.

(The following is a blank space) Specifically, the cyclic olefin represented by the above formula [r] used in the present invention includes bicyclo[2,2,1]hept-2-ene-derived tetracyclo[4,4,0, 12, S, 1? 1@]-3
-dodecene-derivatized hexacyclo[6,5,l, 13.6.111. +3
．． Q2. ff, QII4co4-heptadensene induction book octacyclo [8, 8, 0, 12・9, 14・7.1st・+s, 1+i, +a, 03・−012・l? ]-5-
Tococene induction book pentacyclo [6, 6, 1, 13, 8,
0”',0'・+4]-4-hexadecene-derivatized heptacyclo-5-icosene derivative, heptacyclo-5-heneicosene derivative, tricyclo[4,3,0,12,6]-]3-decene-derived imitative tricyclo 4.3.0.12・S]-3-undecene derivative pentacyclo[6,5,1,13,6,02,7,O”・
+ 3 ]-] 4-pentadecene derivative imitation pentacyclopentadecadiene derivatized hentasiku o [4,7,0,1", O"=3.1"-
+2]-3-he>Tadecene derivative book pentacyclo[7+8+O+1"'+O"'t1""'
+O eyes 1@, I+2・+s]-4-eicosene induction book and nonacyclo[9,10,1,1,4,7,03,@,0
2.1@, 012.211+3. ”+ O12,”+
1""]-]134 bodies of 5-bentacocene were burned.

Specific examples of such compounds are shown below.

hmm 5.10-dimethyltetra CH.

Bicyclo[2,2,1]hept-2-ene derivatives such as CHa2.7.9-)limethylte9-isobutyl-2,7-9,11,12-trimethylCH.

8-methyltetrashif 8-ethyltetrashif 1-2-3-dodecene 8-hexyltetracy 9-isobutyl-11,12 5, 8, 9, 10 Tetrameth +1]-3-dodecene 8-methyl-9-ethylte 3 Dodesen 3 Dodesen 1＠]-3-dodecene 1 @]-3-dodecene ’　＊　’　・’　”　　　　　　　　-3-F　f　Sen 2 8-ethylidene-9-iso 7・+tB-3-dodecene One dodecene -3-dodecene 12, s, l?・I@]-3-dodese hmm , +1]-3-dodecene s, 1f, I @] 3-Dodecene 12, s, l? , l@]-3-tochise hmm One dodecene 8-n-propylidene-9 8-isopropylidene [4,4,0,12 5,1) eyes] -3 One dodecene One dodecene Black [4,4,0,1' 17・ 1・]-]3-dodese N I @] -3 Dodesen 8-n-propylidene [4,4,0,12 5,17 11 ko 3 CH.

[4,4,0,12・s,1) Item 1-3 Tetracyclo[4,4,0,125,17・I@
]-3-dodecene derivative; (blank below) 8-isopropylidene-dodecene.I']-4-hebutadecene+ 3. Q2, t, Qs +4]-4-hentadecene and other hexacyclo[6,6,1,138,11@, mouthQ2, ? , Ql+decene+a]-4-hebutadecene derivative; 3, +6
, (p, @, Ql 2 , 1 T co-5-descentocene + e, Its + e, Ql, kai Ql heptadecene 2.1)]-]5-decentcocene? ]-5 Octacyclo[8,8,0,1214 y, 1st, +1,11 3, +6. Ql, @, QI2.1? ]-5-tocosene derivatives: heptacyclo-5-icosene derivatives such as heptacyclo[8,7,0 cosene, or heptacyclo-5-heneicosene derivatives.

Pentacyclo such as decene [6,6,1,1”・6.02・〒
, 09+ 4] -4-hexadecene derivatives; tricyclo[4,3,0,12.6]-3-decene derivatives such as 5-methyl-tricyclo1,3-dimethyl-penta; 10-methyl-tricif14,15 -pentacyclo[6,5,1,136, such as tricyclo[4,4,0,12.S]-3-undecene derivatives such as dimethylben
Diene compounds such as 02T, □o31-4 body; pentadecene derivatives; 21.11 2@, Q10.119. ll 5.1] -5-pentacyclo[4,7,0,12,S, O" +3.p・+2] -3-pentadecene derivatives such as 5-bentacosencene: 2@, Q10.+9.lIs] - Nonacyclo[9,10,1,14,7,03,”,02+@,0+
2 2I, 1st, 2a, Q10.1. l16+a] -5-bentacocene-derived cocene derivatives.

(The following is a blank space) +5] Hebutacyclo[7,8,0,1" 6, Q2.?, 1111 17.0 16.112 Is] -4-eicosene derivatives such as -4-eicosene; Also used in the present invention Specific examples of the cyclic olefin represented by the above formula [edited] include the following compounds.

15-phenyl-bicyclo[ 2-en can be mentioned.

(The following is a blank space) The cyclic olefin represented by the above formula [1] or [II] can be easily produced by subjecting a cyclopentadiene and a corresponding olefin to a Diels-Alder reaction.

In the present invention, a catalyst formed from a soluble vanadium compound and a specific organic aluminum compound is used when copolymerizing ethylene and cyclic olefins.

Specifically, the vanadium compound is -squeezed VO (
OR), X, or V (OR) cX.

(However, R is a hydrocarbon group, 0≦a≦3.0≦b≦3.
2≦a+b≦3.0≦C≦4.0≦d≦4.3≦c+d
A vanadium compound represented by ≦4) or an electron donor adduct thereof is used.

More specifically, VOCI! 3, ■0(OC2H5)CI2, VO (OC2H5) 2 ci.

VO(0-iso-C3H7) CI 2, VO(0
-n-C4H9)C12, ■0(OCH), VOB[, VCl2.2 5
3 2 VO(1, VO(0-1-C4H9) 3.2 ■CI ・A vanadium compound such as 20C8H170H is 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, the number of carbon atoms in methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol, etc. Alcohols having 1 to 18 carbon atoms, which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol, etc.
20 phenols; acetone, methyl ethyl ketone,
Ketones having 3 to 15 carbon atoms such as methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone;
Aldehydes with 2 to 15 carbon atoms such as acetaldehyde, 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 dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, benzoate butyl acid, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate , cyclohexenecarboxylic acid di-n
-hexyl, diethyl nitrate, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-butyrolactone, coumarin, phthalide, Organic acid esters having 2 to 30 carbon atoms such as ethylene carbonate; acid esters having 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,
Amines such as diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine; acetonitrile,
Nitriles such as benzonitrile and tolnitrile; alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane; and the like. Two or more types of these electron donors can be used.

The organoaluminum compound has the formula RAI CI 3゜ (wherein, n is 1.35 to 1.65, and R has 4 carbon atoms.
An organoaluminum compound represented by the above a-chain or branched alkyl group is used.

As mentioned above, n is 1.35 to 1.65, preferably 1.40 to 1.60.

In the above formula, R is a straight chain or branched alkyl group having 4 or more carbon atoms as described above, but specifically, it includes butyl group, isobutyl group, 5ec-butyl group, )eel-butyl group, n-pentyl group. group, n-hexyl group, n-heptyl group, n-octyl group, etc.

Such organoaluminum compounds such as isobutylaluminum sesquichloride (iBυ1.5AIICI
) to copolymerize ethylene and the cyclic olefin represented by the above formula [IF5.5 or [II], isobutylaluminum dichloride (iBu
Compared to the case where ethylene and the above-mentioned cyclic olefin are copolymerized using A I Cl 2 ) as a catalyst, the polyethylene content contained in the resulting cyclic olefin-based random copolymer is reduced, and the copolymer The transparency of the molded product obtained from the method is improved. Furthermore, the amount of polyethylene deposited on the walls of the polymerization vessel and near the copolymer outlet during polymerization can be significantly reduced.

For example, when ethylene and the above cyclic olefin are copolymerized using 1llu AlCl as a catalyst, ethylaluminum sesquichloride (EI
When AlCl) was used as a catalyst], 5
1.5 As in the above case, the polyethylene content contained in the resulting cyclic olefin random copolymer is reduced, and the transparency of the molded article obtained from the copolymer is improved. Furthermore, the amount of polyethylene deposited on the walls of the polymerization vessel and near the copolymer outlet during polymerization can be significantly reduced.

Note that in this specification, polyethylene includes not only a polyethylene homopolymer but also a copolymer of ethylene and the above-mentioned cyclic olefin having an ethylene content of 90 mol% or more.

As described above, according to the present invention, as an organoaluminum compound catalyst component, a compound of the formula RAICJ (formula n3-n, where n is 1.35 to 1.65, and R is a straight chain or branched alkyl having 4 or more carbon atoms) is used. Since the organoaluminum compound represented by If the disc is manufactured,
Reading errors caused by the disk substrate can be reduced.

A hydrocarbon solvent can also be used when copolymerizing ethylene and the above-mentioned cyclic olefin. Such hydrocarbon solvents include aliphatic hydrocarbons and their halogen derivatives such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene; ring hydrocarbons and their halogen derivatives such as cyclohexane, methylcyclopentane, and methylcyclohexane. Derivative; benzene,
Aromatic hydrocarbons such as toluene and xylene and halogen derivatives such as chlorobenzene are used. These solvents may be used in combination.

In the present invention, ethylene and the cyclic olefin (general formula [
I] or [■]) is copolymerized, but if necessary, an α-olefin having 3 or more carbon atoms may be copolymerized, and such olefins having 3 or more carbon atoms may be copolymerized. α
-Olefins include, for example, propylene, 1-butene, 4-methyl 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
Examples include α-olefins having 3 to 20 carbon atoms, such as 1-hexadecene, 1-octadecene, and 1-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 cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, and other cyclopentene in an amount less than equimolar to the cyclic olefin component unit in the random copolymer to be produced. Olefin, 1,4-hexadiene, 4-methyl 1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl −
Examples include non-conjugated dienes such as 2-norbornene.

When producing a cyclic olefin random copolymer, ethylene and the above cyclic olefin (general formula [1
] or general formula [11]) is preferably 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. Preferably within the range.

In the present invention, the ratio of aluminum atoms to vanadium atoms in the polymerization reaction system (Al /V) l;! , 2 or more,
It is preferably in the range of 2 to 50, particularly preferably 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 gram atoms/l, preferably 0.05 to 3 gram atoms/l as vanadium atoms. It is in the range of gram atom/I.

Such a copolymerization reaction between ethylene and olefins is
It 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. Further, the pressure when carrying out the copolymerization reaction is usually more than 0 and 50 kg/a11, preferably more than 0 and 20 kg/aLr. 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 olefin supplied to the copolymerization reaction is usually in the range of 85/15 to 1/99, more preferably in the range of 85/15 to 40/60. 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
10-300g/I.

Preferably it is in the range of 20 to 200 g/J.

The copolymer solution thus obtained is treated according to a conventional method to obtain a cyclic olefin random copolymer.

The cyclic olefin random copolymer obtained in this way is immaculate or crystalline, but among the cyclic olefin random copolymers, it does not have a DSC melting point, and from the results of X-ray diffraction measurements, Amorphous copolymers are preferred. Further, the ethylene/cyclic olefin molar ratio of the cyclic olefin random copolymer obtained by the method of the present invention is usually in the range of 9515 to 30/70, preferably 90/10 to 40/60. In addition, the glass transition point (Tg) of the cyclic olefin random copolymer
is usually in the range of 10 to 240°C, preferably 20 to 200°C.

Effects of the Invention According to the present invention, when copolymerizing ethylene and a cyclic olefin, RAICl (where n 3-n is 1.35 to 1.65 and R is a linear or branched alkyl group having 4 or more carbon atoms), the content of polyethylene contained as an impurity is reduced, and the cyclic olefin random copolymer has excellent transparency. A combination can be produced. Moreover, it is possible to efficiently prevent polyethylene from adhering to the walls of the polymerization vessel and the vicinity of the polymer outlet.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A copolymerization reaction of ethylene and tetracyclo[4,4,0,+2゛5] was carried out continuously using a polymerization vessel with a capacity of 11 equipped with a stirring blade. That is, TCD-
The cyclohexane solution of No. 3 was added at 0.41 g/hour so that the TCD-3 concentration in the polymerization vessel was 60 g/l. As a catalyst, a solution of 0(OC2H5)CI2 in cyclohexane was fed at 0.51/hour so that the vanadium concentration in the polymerization vessel was 0.5 mmol/l (at this time, the supplied vanadium concentration was 2% of the concentration in the polymerization vessel). .86 times), isobutylaluminum sesquichloride (A I (i -C4
A cyclohexane solution of CI) was diluted with 1.5
1.5 0.41 and cyclohexane per hour so that the aluminum concentration in the bundle is 4.0 mmol/l.
71, respectively, into the polymerization vessel continuously, and on the other hand, from the top of the polymerization vessel, so that the polymerization liquid in the polymerization vessel was always 11 (i.e., the average residence time was 0.5 hours). pulled out continuously. In addition, ethylene, 2011 nitrogen per hour, and 1011 hydrogen per hour were supplied to the polymerization system using a bubbling tube at a rate of 0.51 per 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, a polymerization reaction mixture containing an ethylene-TCD-3 random copolymer is obtained. A cyclohexane/isopropyl alcohol (1/I) mixed solution was added to the polymerization solution taken out from the top of the polymerization vessel to stop the polymerization reaction.

Thereafter, an aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to water 11 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 a water tank. The above mixed solution was allowed to stand, and after removing the water tank, it was further washed twice with distilled water to purify and separate the polymerization solution.

The degree of turbidity of the in-system polymerization solution during polymerization was observed, and it was determined that there was no turbidity as it was a brownish-colored transparent solution. Furthermore, after the continuous polymerization reaction had been carried out for 3 hours, it was observed that no polymer (polyethylene) was attached to the vicinity of the polymerization liquid outlet at the top of the polymerization vessel.

The obtained polymerization liquid 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. Thereafter, the obtained solid portion was poured into acetone at a concentration of 40 g/l and reacted at 60° C. for 2 hours. After that, the solid part was collected by filtration, and heated at 130 °C under nitrogen flow.
It was dried at 350 mmHg for 24 hours.

As described above, ethylene/TCD-3 copolymer was obtained at a rate of 70 g/hour (ie, 35 g/J).

The ethylene composition of the copolymer measured by 13C-NMR analysis was 59.0 mol%, the intrinsic viscosity [η] measured in decalin at 135°C was Q, 57 dl/g, and the iodine value was 1.0. Further, the crystallinity by X-ray diffraction was 0%.

The glass transition temperature Tg is D7nxmicM manufactured by DuPont.
echanicxl^nx17se+ (D MA)
The loss elastic modulus E I + was measured at a heating rate of 5° C./■, and was determined from the peak temperature to be 151° C. Furthermore, the melting point Tm was determined by DuPont 990 type DSC at a heating rate of 10°C/120°C to 40°C.
When measured in the range of 0°C, no melting curve (peak) was observed.

In addition, as a means of evaluating the amount of trace amounts of polyethylene contained in the copolymer, the obtained copolymer was dissolved in cyclohexane, and the light transmittance of the polymer solution was measured according to ASTM
It was measured using a haze meter based on D 1003-52. That is, 1.0 g of the copolymer was dissolved in 10 ml of cyclohexane, and the light transmittance of the solution was measured using a quartz cell with an optical path length of 20 tlI1 (the light transmittance of cyclohexane alone was taken as 100%).9
It was 4%.

These results are shown in Table 1.

Examples 2 to 5 A copolymerization reaction of ethylene and TCD-3 was carried out in the same manner as in Example 1 except for the conditions shown in Table 1.

The results obtained are shown in Table 1.

Note that the organoaluminum compound iBu AlCl used in Example 4 is
1.6 Luminium dichloride C+Bu AN C12) and isobutylaluminum sesquichloride (iBa,, 5
A 2/8 (molar ratio) mixture with AI CI , 5') was prepared in advance and used in the polymerization reaction. In addition, iBu A j! of Example 5 CI 1.4 is 1.6 flu AlCl,,5/iBu 2At CI as above
A mixture of = 8/21.5 (molar ratio) was prepared in advance and used.

Example 6 TCD-3 was used as the cyclic olefin to be subjected to the copolymerization reaction.
14-methano-1,4, which is a Diels-Alder reaction adduct of cyclopentadiene and indene.
A copolymerization reaction was carried out in the same manner as in Example 1 except that 41,91-tetrahydrofluorene (abbreviated as MTIIF) was used.

Table 1 shows the results obtained.

Comparative Examples 1 to 3 A copolymerization reaction of ethylene and TCD-3 was carried out in the same manner as in Example 1 except for the conditions shown in Table 1.

The results obtained are shown in Table 1.

Note that iBu AlCl, which is an organoaluminum compound used in Comparative Examples 2 and 3, and 1,25
1.75 iBu AlCl are 1 and 75, respectively.
1.25 iBu AJ C1/iBu AlCl =5
/20 +, 5 1.5 5 (molar ratio), 1BIIAICI /1, 5
A mixture of 1.5 +11++ 2A/C/ = 515 (molar ratio) was prepared in advance and used.

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, R^1 to R^1^8 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R^1^5 to R^1 ^0 may be combined with each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, and R^1^5 and R^ With 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 When a cyclic olefin-based random copolymer is copolymerized in a liquid phase consisting of a cyclic olefin, R_nAlCl_3_-_n (where n is 1.35 to 1.65 and R has 4 carbons
A method for producing a cyclic olefin-based random copolymer, characterized by using an organoaluminum compound represented by the above linear or branched alkyl group. 2. The method for producing a cyclic olefin random copolymer according to claim 1, wherein an organoaluminum compound in which R is an isobutyl group or a hexyl group is used.