JPH03255101A - Production of random cycloolefin copolymer - Google Patents

Abstract

PURPOSE:To obtain a random copolymer having a decreased polyethylene content and excellent transparency in good efficiency by copolymerizing ethylene with a specified cycloolefin under a specified agitation condition in the presence of a specified catalyst in a specified liquid phase. CONSTITUTION:A process for forming a random cycloolefin copolymer by copolymerizing ethylene with at least one cycloolefin selected between an unsaturated monomer of formula I (wherein (n) is 0 or 1; (m) is 0 or an integer; R<1> to R<18> are each H, halogen or a hydrocarbon group; R<15> to R<18> may be combined to form a monocyclic or polycyclic ring which may have a double bond; and R<15> and R<18> or R<17> and R<18> may be combined to form an alkylidene group) and an unsaturated monomer of formula II in the presence of a catalyst comprising a soluble vanadium compound and an organoaluminum compound in a hydrocarbon solvent or in a liquid phase comprising said cyloolefin, wherein the reaction solution is agitated at a power requirement of the impeller of 2.7kW/kl or above.

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, there is a strong desire for a method for producing a cyclic olefin random copolymer that can reduce the content of polyethylene contained as impurities.

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 bananium compound and an organoaluminum compound. It is manufactured by copolymerizing using it as a solvent. The present inventors have 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. They discovered that ethylene and the above-mentioned cyclic olefin can be copolymerized and completed 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. III. A method for producing a cyclic olefin random copolymer that can be produced efficiently.
(The purpose is to

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 [I1 or [nl (where n is 0 or 1, m is 0 or a positive integer, R-R18 are each independently a hydrogen atom, a hydrogen atom, or a hydrocarbon group, and R15 to R1g are bonded to each other to form a monocyclic or polycyclic ring. and the monocyclic or polycyclic ring may have a double bond, and R and R or R17 and Rlg may have 15
16 may form an alkylidene group).

[where g is an integer of 0 or 1 or more, m and n
is Oll or 2, R1-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 R'' (or R7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group.] From the group consisting of unsaturated monomers represented by and at least one selected cyclic olefin, in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminium compound, in a hydrocarbon solvent or in a liquid phase consisting of the cyclic olefin. When producing a cyclic olefin random copolymer, the reaction solution is subjected to 2.
It is characterized in that ethylene and the cyclic olefin are copolymerized while stirring and mixing with a stirring power of 7 KW/KL or more.

According to the present invention, when copolymerizing ethylene and the cyclic olefin, ethylene and the cyclic olefin are copolymerized while stirring and mixing the reaction solution with a stirring power of 2.7 KW/KL or more, so that impurities It is possible to produce a cyclic olefin-based random copolymer with a reduced content of polyethylene and excellent transparency.

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 [
n] and ethylene in a hydrocarbon mixed solvent or in a liquid phase consisting of the cyclic olefin, and a vanadium compound and an organoaluminium compound soluble in the solvent? A cyclic olefin-based random copolymer is produced by copolymerizing the reaction solution while stirring and mixing at a specific stirring power or higher in the presence of a catalyst.

(The following is a blank space) The cyclic olefin represented by the above formula [I] used in the present invention is specifically, bicyclo[2,2,11hept-2-ene-derived tetracyclo[4,4,0,12 ,6,1?・IJ-3-dodecene derivative hexacyclo[5,6,l,13. @, 111.13.
Q2.? , Q9. +4]-4-heptadensene derivative book octashif (7[8,8,0,12,*, 14.7.
11+1@, lI3.18Qll, Q10. +? ]-5
- Tococene induction Honpe induction dipentacyclo 6.1.1'・
8, (p, 7, (p・■]-4-hexadecene derivative, main heptacyclo-5-icosene derivative, main heptacyclo-5-heneicosene derivative, main tricyclo[
4,3,0,12・s]-3-decene derivative tricyclo[4,3,0,12・6]-3-undecene derivative pentacyclo[5,5,1,13,8,Q27. Ql13-4-pentadecene derivative Pentacyclopentadecadiene derivative Pentacyclo[4,7,Q, 12, S, 0@
, + 3 , 19 , + 2-3-pentadecene derivative pentacyclo [7, 8, 0, 136,027, 11 +T, QI1. +11. 112 IJ-4-eicosene derivative image and nonacyclo[9,10,1,1,4,7,031,Q2
．． II, Q10.21 3 21, Q10 19.116 8co5-bentacocene derivatives.

Specific examples of such compounds are shown below.

Bicyclo[2,2,1] such as hept-2- enticement conductor; 2,7.9-) Remethylte hmm Hs 5.10-dimethyltetra Hs 9-ethyl-11,12-dime 9-isobutyl-11,12 5,8,9,10-tetramethy +1]-]3-dodese hmm Methyl-9-ethylte =3-dodecene -3-dodecene eyes]-3-dodecene ” e-co3-dodecene 8-methyltetrashif 8-ethyltetrashif 1・]-]3-dodese -hexyltetracycline CIaHIA ・1・]-]3-dodese N, 17 Il+] 3-Dodecene 7・l@]-3-dodecene -3-dodecene ,1・]-]3-dodese N12 S, 17.11]-3-dodece hmm hmm 8-ethylidene-9-iso One dodecene , 12 6.17 eyes] -3-Dodece hmm S,l? , 11]-3-dodecene 8-n-propylidene-9 8-Impropylidene One dodecene ・I @ ] -] 3- Dodese CH.

Tetracyclo[4,4,0,12.6,1 st.]-3-dodecene derivatives such as [4,4,0,121,1 st.]-3-dodecene; (hereinafter blank) CI(.

8-n-propylidene-9 [4,4,0,12 5,17 1@]-3 1-dodecenecro[4,4,0,12 1@]-3-dodecene7 8-n-propylidene-9 [4 , 4, 0, 12・5.17 Illko3-dodecene2・s, p・I l]−]3-dodecene+4]−4−
Hebutadecene Desendecene Hebutadecene s, +s, Qt, s, Q+2. +t]-5-tocosene derivative; +3. Q2. ? ,Q@,+4] Hexacyclo[6,6,1,136,1・+3,Q2,7,Qll・+4]-4-hebutadecene derivatives such as 4-heptadecene; 3.1@, (
p・QII+7]-5- Tokosen ■, eyes 11! +11. Qll, Ql 2・17]-5-tocosendecene 2・I7] Bentasic O[6,6,1,13,@,02? ,
QII4] -4- Natono t ri 9 'y Fukuro 8, 8.0, 121.1'
-', 1"-1", 1' hexadecene derivatives; tricyclo[4,3,0,12S]-3-decene derivatives such as heptacyclo[8,7,0 5-methyl-tricyclo; 1, Ql2.1 ? ]-5-heneicosene and other hebutacyclo-5-icosene derivatives or hebutacyclo-5-heneicosene derivatives; 10-methyl-
tricyclo[4,4,0,12.5]-3-undecene derivatives such as trisif; pentacyclo[4,7,Q, ilS, Qs, such as 1,3-dimethyl-penta1,6-dimethylbentacene; +3. l11. +2]-
3-pentadecene derivative; to 14,15-dimethylbencosenato f): / 9 Schiff O[6,5,1,1"-",
02·', O'Is]-4-pentadecene derivatives; +5]-hebutacyclo[7,8,0,1", 02.7,111.+7.Q10
．． 1@JI2. lS] -4-eicosene derivatives; diene compounds such as; and cyclic olefins represented by the above formula [n] used in the present invention, specifically, the following 21.111211. Examples include compounds such as Q14゜9.11.

S, I*] -5-bentacocene 121, Q14 1. lIs, le] = nonacyclo[9,10,1,14.? , Q! , II,
Q2, 012. 21,113.2@, Q14. III, 11118]
-5-bentacocene derivatives can be mentioned.

(Margin below) -2-en CH.

can be mentioned.

(The following is a blank space) 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.

(The following is a blank space) In the present invention, a catalyst formed from a soluble vanadium compound and a specific organoaluminum compound is used when copolymerizing ethylene and cyclic olefins.

Specifically, the vanadium compound has the general formula VO (
OR) aXb or V(OR). Xd (However, R is a hydrocarbon group, “0≦a53.0′≦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, VOCg3, VO(OC2H5)CI2, VO(OC2H5)2Cg1 VO(0-1so-CH) C(12,7 VO(0-n-CH) CI2, 9 VO(QCH), VOBr 5VCN 4.2
5 3 2VOCj2 ,V
O(0-n-C4H9) 3, vB ・20C8HI
A vanadium compound such as 70H 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 nadic acid, diisosobrobyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc. carbon number 2~
30 organic acid esters; acid halides having 2 to 15 carbon atoms, such as niacetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride; methyl ether;
Ethers with 2 to 20 carbon atoms such as ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether; Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; Methylamine, ethylamine, diethylamine, Amines such as tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine; Nitriles such as acetonitrile, benzonitrile, tolnitrile; Alkoxysilanes such as ethyl silicate, diphenyldimethoxysilane, etc. I can do it. Two or more types of these electron donors can be used.

As the organoaluminum compound, a compound having at least one AM-carbon bond in the molecule is used, for example, (i) a compound having the general formula R'lIl (OR") HXn
p q (Here, R1 and R2 are hydrocarbon groups containing the number of carbon atoms, usually 1 to 15, preferably 1 to 4, and may be the same or different from each other. m≦
3, n is Q5n<3, p is O5n<3, q is 0≦q<3
and m+n+p+q-3), (i) general formula MAUR'4 (here, Ml is Li);

Na, and R1 is the same as above)
Examples include complex alkylated products of group metals and aluminum.

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

2 General formula R/l (OR) 31 (where R1 and R2 are the same as above. m is preferably a number of 1.5≦m<3).

General formula R', A, C) X a-1l (where R
1 is the same as above. X is)\logen, m is preferably 0<
m<3).

General formula R' 1Aj7H,.

(Here, R1 is the same as above. m is preferably 2Sm<3
).

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

More specifically, aluminum compounds belonging to (i) include trialkylaluminiums such as triethylaluminum and tributylaluminium, trialkenylaluminums such as triisopropenylaluminum, dialkylaluminums such as diethylaluminum ethoxide, dibutylaluminum butoxide, etc. In addition to alkyl aluminum sesquialkoxides such as alkoxide, ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide, partially alkoxylated compounds having an average composition of 2.5 to 0.5 expressed as R' A, Q (OR), etc. dialkyl aluminum halides, such as diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride,
Alkylaluminium sesquihalides like ethylaluminum sesquipromide, partially halogenated alkylaluminums such as alkylaluminum cybarides like ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, etc., diethylaluminum hydride, dibutyl partially hydrogenated alkyl aluminum hydrides such as dialkylaluminum hydrides such as aluminum hydride, alkyl aluminum halides such as ethyl aluminum dicdolide, probyl aluminum dihydride;
Partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, and ethyl aluminum ethoxy bromide can be exemplified. Also, compounds similar to ]), such as 2 through an oxygen or nitrogen atom,
It may also be an organic aluminum compound in which the above aluminum is bonded. Specifically, such a compound includes (CH) ApOAI (C2H5)2,52 (C4R5) 2 AD 0Afl (C4R9)
2. I can give an example.

The compound included in (i) above is Lij'fJ (C
H), LiAj? (C7H15) 4 etc. 5
4. Can give examples. Among these, it is particularly preferable to use alkyl aluminum halides, alkylaluminium cybarides, or mixtures thereof.

In the present invention, a hydrocarbon solvent can also be used when copolymerizing ethylene and the above-mentioned cyclic olefin. Such hydrocarbon solvents include pentane,
Aliphatic hydrocarbons and their halogen derivatives such as hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons and their halogen derivatives such as cyclohexane, methylcyclopentane, and methylcyclohexane; benzene, toluene, xylene, etc. Aromatic hydrocarbons and halogen derivatives such as chlorobenzene are used.

In the present invention, ethylene and the cyclic olefin (general formula [
I] or [■]) may be copolymerized, but if necessary, an α-olefin having 3 or more carbon atoms may be copolymerized, and such α-olefins having 3 or more carbon atoms include, for example, Propylene, l-butene, 4-methyl-1-
Pentene, i-hexene, l-octene, l-decene,
1-dodecene, 1-tetradecene, i-hexadecene,
Examples include α-olefins having 3 to 20 carbon atoms, such as 1-octadecene and 1-eicosene.

Further, other copolymerizable unsaturated monomer components may 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, etc. in an amount less than equimolar to the cyclic olefin unit in the random copolymer to be produced. cycloolefin, l,4-hexadiene, 4-
Non-conjugated dienes such as methyl 1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene For example,

When producing a cyclic olefin-based random copolymer, ethylene and the above-mentioned pentacyclopentadecenes (general formula [I]) or aromatic-containing cyclic olefins (
The copolymerization reaction with the general formula [■]) is carried out in a continuous manner.

At this time, the ratio (C/lA11
O^g C1Ag) is set to 50 or less, preferably 40 to 1, more preferably 30 to 1, and the concentration of vanadium compound (COv) supplied to the polymerization tank once and the vanadium compound concentration (Clv) in the polymerization tank are adjusted. It is desirable that the ratio (Cov/C1v) be 10 or less, preferably 8-1, and more preferably 6-1.

The soluble vanadium compound and the organoaluminum compound are usually diluted with the hydrocarbon solvent, pentacyclopentadecenes, or aromatic-containing cyclic olefins, respectively, and then supplied to the polymerization tank.

In the present invention, it is desirable that the ratio of aluminum atoms to sodium atoms (AN/V) in the polymerization reaction system is 2 or more, preferably 2 to 50, particularly preferably 3 to 20.

Further, when producing a cyclic olefin-based random copolymer, the concentration of the soluble nonadium compound in the copolymerization reaction system is usually 0.01 to 5 gram atoms/II, preferably 0.05 as vanadium atoms. ~3 grams atom/
The range is 1.

Such a copolymerization reaction of 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. Further, the pressure when carrying out the copolymerization reaction is usually more than 0 and 50) cg/cd, preferably more than 20) cg/cd. Further, during copolymerization, a molecular weight regulator such as hydrogen may be added to adjust the molecular weight of the resulting copolymer.

When producing a cyclic olefin random copolymer, the molar ratio of ethylene/cyclic olefin is 85/15 to
15/85, more preferably 40/60 to 85/15
It is desirable that it be within the range of .

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 copolymer melting is usually
It ranges from 5 to 300 g/l, preferably from 10 to 200 g/l.

In the invention, when producing a cyclic olefin random copolymer by copolymerizing ethylene and cyclic olefin as described above, the reaction solution is 2.7 KW/KL or more, preferably 3.5 KW/KL or more, and Preferably 4.5~
Ethylene and the above-mentioned cyclic olefin are copolymerized while stirring and mixing with a stirring power of 10 KW/KL.

At this time, it is preferable that the vanadium compound and the organic aluminum compound are each supplied to the tip of the stirring blade.

In the present invention, the stirring power includes, for example, the circulation power for polymerization necessary for external circulation cooling to remove reaction heat.

In the present invention, ethylene and the above-mentioned cyclic olefin are copolymerized while stirring and mixing the reaction solution with a stirring power of 2.7 KW/KL or more, but any known stirring device can be used. Yes, for example, devices equipped with vanes such as anchor type blades, flat plate paddles, slanted blade paddles, propeller blades, blue margin blades, Faudler blades, etc. as agitators, although it is not necessary to provide a baffle plate in these devices. , it is more preferable to have it.

It is also possible to use a helical shaft stirrer or a spiral shaft stirrer with a guide cylinder.

Furthermore, the previous loop type stirring device, which has a function of stirring and mixing the internal liquid by forcibly circulating it using a pump, can also be used.

Furthermore, it is also possible to use a device that stirs by blowing gas and using a jet stream, or by rotating the container itself.

Effects of the Invention In the present invention, when producing a cyclic olefin random copolymer as described above, the polymerization reaction solution is heated at 1.5KW/K.
Since the mixture is stirred and mixed with a stirring power of L or more, the polyethylene content contained in the resulting cyclic olefin random copolymer is reduced, and the transparency of the molded product obtained from the copolymer is improved. Therefore, in the optical memory disk manufactured from the cyclic olefin random copolymer according to the present invention, reading errors caused by the disk substrate are significantly reduced.

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

Example 1 [Catalyst Preparation] VO(QCH) CD 2 was diluted with 5 cyclohexane to prepare a vanadium catalyst having a vanadium concentration of 18.6 mmol/g-cyclohexane. On the other hand, ethylaluminum sesquichloride (Ag (C2H5'
) t,5(1) was diluted with cyclohex(,5) to give an aluminum concentration of 164 mmol/p.
- An organoaluminum catalyst, which is cyclohexane, was prepared.

[Polymerization] A polymerization vessel with a baffle plate and a stirrer with an inner diameter of 700 m+W, a total volume of 570 g, and a reaction volume of 300 g, and a vertical multi-tube cooling unit with a heat transfer area of 19.4 nf. The polymerization solution is extracted from the bottom of the polymerization vessel equipped with a stirrer and a stirrer, and the polymerization solution is circulated to the multi-tube cooler (circulation power IKW/
Using a polymerization equipment system equipped with a circulation line in which the cyclic olefin (KL) is returned to the polymerization reactor and a circulation pump installed in the circulation line, ethylene and a cyclic olefin (hereinafter simply referred to as tetra-dodecene) represented by -3-dodecene are A copolymerization reaction was carried out continuously so as to contain about 1.2 mol % of cyclododecene) and butene-1. When carrying out this reaction, the vanadium catalyst (V catalyst) prepared by the above method was supplied into the polymerization vessel in an amount such that the V catalyst concentration in the polymerization vessel was 0.35 mmol/g. In addition, the V catalyst is diluted in advance using cyclohexane, a polymerization solvent, so that the V catalyst concentration immediately before being supplied to the polymerization vessel is 1.8 times the dilution ratio of the catalyst concentration in the polymerization vessel. and supplied it.

On the other hand, ethylaluminum sesquichloride as an organoaluminum compound was supplied into the polymerization vessel in an amount such that i/V-8.0. In addition, the solution was diluted in advance using cyclohexane, a polymerization solvent, so that the concentration immediately before being supplied to the polymerization vessel was a dilution ratio of 11 relative to the concentration inside the polymerization vessel. These V catalysts and organoaluminum catalysts are supplied near the tip of the upper blade of a stirrer equipped with two stages of six vertical disc turbine blades with a diameter of 0.25 m, where the stirring is strongest, and the dispersion mixing is performed. This was done promptly.

The amount of cyclohexane used as a polymerization solvent was 233 kg/
h into the polymerization vessel. 2.69 kg of ethylene
/h of hydrogen gas as a molecular weight regulator at a rate of 2.2NII/h.
It was supplied to the gas phase in the polymerization vessel in an amount of 1 h. The polymerization solution was strongly stirred with a stirrer at a power of 4.4 KW/kL (total stirring power was 5.4 KW/KL).

The temperature was controlled so that the polymerization temperature was 10° C. by circulating 25% by weight methanol water as a refrigerant through the jacket attached to the outside of the polymerization vessel and the shell side of the multi-tubular cooler.

Nitrogen gas was introduced into the polymerization vessel to control the pressure so that the polymerization pressure was 1.0 Kg/cjG.

The following method was used to clean the inner wall of the polymerization vessel. In other words, the receiver with a hole partially drilled in the gas phase part of the shaft that connects the agitator and the agitating blade is a dish (spray disk).
was installed. Then, cyclohexane solvent was fed into this spray disk in an amount of 30 Kg/h, tetracyclododecene in an amount of 14.2 Kg/h, and butene-i in an amount of 0.41 Kg/h. ,
The shaft was rotated, and cyclohexane, tetracyclododecene, and butene-1 were scattered from the holes in the spray disk by the centrifugal force generated by the rotation of the shaft, and sprayed onto the inner wall of the polymerization vessel. The sprayed tetracyclododecene, cyclohexane, and butene-1 passed along the inner wall and mixed into the liquid phase.

When the copolymerization reaction of ethylene, tetracyclododecene, and butene-1 was carried out continuously under the above-mentioned conditions, the concentration of the ethylene-tetracyclododecene-butene-1 copolymer was 4.0 to 4.0. A 3% by weight cyclohexane solution was obtained.

[Deashing] Boiler water at 80°C and a NaOH solution with a concentration of 4% by weight as a pH adjuster were added to the copolymer solution of ethylene and tetracyclododecene extracted from the polymerization vessel.
The copolymerization reaction was stopped and the catalyst residue remaining in the copolymer solution was removed (deashed) from the copolymer solution.

After deashing, the copolymerization solution was stored in a stirrer-equipped container with an inner diameter of 900 m+g and an effective volume of 1.0 rrr, and water at room temperature was poured through a jacket attached to the outside of the container for about 30 minutes. Cooled to ~40°C.

[Filtration] The copolymer solution thus obtained was filtered to 261 kg.
/ h to a filter containing 34 nominally 1 μm Kotton thread-wound filters (vertical wind filters manufactured by Nippon Seiki Co., Ltd.) with an outer diameter of 63.5 m, an inner diameter of 28 m, and a length of 1 m. Continuously filtered.

Next is the nominal 2μ with an outer diameter of 25 mm and a length of 750 m+s.
The sample was supplied at a rate of 261 kg/h to a filter containing 15 tube-type filters made of laminated metal mesh made of SUS 304 (Fuji Filter Co., Ltd. vertical type Fuji Plate ■ filter), and filtered continuously.

Furthermore, it has a nominal 0.5 mm outer diameter and a length of 510 m+*.
3 μm SUS 804 metal nonwoven fabric pleated filter (PSPO3 filter manufactured by Brunswick)
261K by connecting in series two filters containing three
g/h and filtered continuously.

[Precipitation] Acetone was added to the thus filtered copolymer solution to precipitate the copolymer, and the obtained copolymer was separated.

After extracting unreacted monomers from the obtained cyclic olefin random copolymer, the copolymer is separated and dried,
Pelletized and dried.

When a cyclic olefin random copolymer was produced as described above, the filter medium remained clogged for 9 days due to polyethylene, which is thought to be produced during the polymerization reaction.

Furthermore, when an optical disc was manufactured from the obtained cyclic olefin random copolymer, reading errors were significantly reduced compared to when an optical disc was manufactured from the copolymer obtained in Comparative Example 1, which will be described later.

Comparative Example 1 In Example 1, the polymerization solution was heated to 1.6KW/K using a stirrer.
Stirring with stirring power of L (total stirring power is 2.6KW/K
L) L, except that the AN catalyst concentration immediately before being supplied to the polymerization vessel was 80 times the catalyst concentration in the polymerization vessel,
The same procedure as in Example 1 was carried out.

When a cyclic olefin random copolymer was produced as described above, the furnace material was clogged for two days with polyethylene, which is thought to be produced during the polymerization reaction.

Claims (1)

[Claims] 1. (a) Ethylene, (b) The following formula [I] or [II] ▲There are numerical formulas, chemical formulas, tables, etc.▼[I] (In the formula, n is 0 or 1, and , 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^1^8 are , 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^1^6 and, 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 copolymerizing to produce a cyclic olefin random copolymer in a liquid phase consisting of a cyclic olefin, ethylene and the above cyclic olefin are mixed while stirring the reaction solution with a stirring power of 2.7 KW/KL or more. A method for producing a cyclic olefin random copolymer, the method comprising copolymerization.