JPH03255105A - Production of random cycloolefin copolymer - Google Patents

Abstract

PURPOSE:To produce the title copolymer having a decreased PE content and improved transparency by copolymerizing ethylene with a specified cycloolefin and separating solid PE produced as a by-product in a small amount. CONSTITUTION:Ethylene is copolymerized with a cycloolefin of formula I (wherein (n) is 0 or 1; (m) is 0 or a positive 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<16> or R<17> and R<18> may be combined to form an alkylidene group) or formula II (wherein (l) is 0 or an integer of 1 or greater; (m) and (n) are each 0-2; R<1> to R<15> are each H, halogen, an aliphatic or aromatic hydrocarbon group or alkoxy; R<5> or R<6> and R<9> or R<7> may be combined directly or through a 1-3C alkylene group) in the presence of a catalyst comprising a soluble V compound and an organoaluminum compound in a hydrocarbon solvent to obtain a random cycloolefin copolymer solution of a concentration of 5-300g/l. This solution is filtered to separate solid PE produced as a by-product in a small amount, and the random cycloolefin copolymer is precipitated.

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 vanadium 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-based random copolymer that has a reduced content of polyethylene as an impurity and has excellent transparency. The present invention was completed by discovering that it is sufficient to perform an operation to separate and remove a small amount of by-product solid polyethylene from a cyclic olefin random copolymer solution.

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 and Rlg are each independently a hydrogen atom, a norogen atom, or a hydrocarbon group, and R15 to R18 are bonded to each other to form a dicyclic or polycyclic ring. and the monocyclic or polycyclic ring may have a double bond, and R15 and R16 or R17 and R18, n is 0, ■ or 2, and R1- R15 is 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 R'l) have 1 to 1 carbon atoms.
They may be bonded via the alkylene group of 3, or may be bonded directly without any group. ] At least one cyclic olefin selected from the group consisting of unsaturated monomers represented by When copolymerizing to produce a cyclic olefin-based random copolymer in a liquid phase consisting of a cyclic olefin, it includes an operation of separating and removing a small amount of by-product solid polyethylene from the resulting cyclic olefin copolymer solution. It is characterized by

The method for producing a cyclic olefin random copolymer according to the present invention involves separating and removing a small amount of by-product solid polyethylene from the resulting cyclic olefin random copolymer solution when copolymerizing ethylene and a cyclic olefin. Since the process involves a number of steps, it is possible to reduce the content of polyethylene contained as an impurity and to produce a cyclic olefin-based random copolymer with 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 [1] or the general formula [
Cyclic olefins represented by [n] and ethylene are co-coated in a hydrocarbon mixed solvent or in a liquid phase consisting of the above-mentioned cyclic olefin in the presence of a catalyst consisting of a vanadium compound and an organoaluminum compound soluble in the solvent. A cyclic olefin random copolymer is produced by polymerization.

(Hereinafter, blank space) As the cyclic olefin represented by the above formula [11] used in the present invention, in the form of L 4 (L bicyclo [2,2,11
Hept-2-ene derived tetracyclo[4,4,0,1
2・s, lv, +@]-3-dodecene derivative hexacyclo[6, 6, 1, 13, @, 11@th Q2
, ? , Q@, I 4 ]-]4-heptadensene induction book) y 9 Schiff C7[8+8+O+1''', 1''',
1”””, 1”””Q3. @, QI2. +? Co-5-tocosene derivative, pentacyclo[6,6,1,116,Q
2,7,Q・+a]-4-hexadecene derivative, present heptacyclo-5-icosene derivative, present heptacyclo-5-heneicosene derivative, tricyclo[4,3,0,12,6]-]3-decene derivative, tricyclo[4,3 ,0,12・@]-3-undecene derivative pentacyclo[6+5+1+1"'+O"'+O""]
-] 4-Pentadecene-induced main tacyclopentadecadiene-induced imitation pentacyclo[4,7,0,12, S, O opening 1e
, +2]-3-pentadecene derivative pentacyclo[7,8,0,1', 6,02? ,
ll@, 17. Qllll+ 1-methylbicyclo[2,112 +51-4-eicosene derivative image and nonacyclo[9,10,1,1,4,7,03kai,02
111, Q10 3 2 @, Q14 +9. II5 +5l-5-bentacocene derivatives.

Specific examples of such compounds are shown below.

hmm 7-methylbicyclo[2 Bicyclo [2, 2, 11 hept-2- enticement conductor.

2,7.9-) Limethyltene Ha 5.10-dimethyltetra Hs 9-isobutyl-2,7- 11,12-trimethyl9-ethyl-11,12-dime9-isobutyl-11,12 5,8,9 , 10-tetrameth]-3-dodecene 8-methyl-9-ethylte8-chlorotetrasif3 Dodecene 8-promotitrasif 8-fluorotetracy-rich]-]3-dodecene]-3-dodecene 8-methyltetra Schiff 8-ethyltetrasif+s]-3-dodecene 8-hexyltetracy, H8°, +5l-3-dodecenes, 1v, +s]-3-dodecene number 3 dodecene 3 dodecene number 1 3-dodecene, 12 6. 17th 3-dodecene 8 ethylidene-9-iso-dodecene, 12 S, l? Tetracyclo[4, 4,0,1'5.17] 3-dodecene derivative; (blank below) -n Propylidene-9 [4,4,0,12 5,17 + 1]-3 -dodecene1.]-]3- Dodecene-n-propylidene-9 [4,4,0,12,S, 1' Roco 3-dodecene 8-isopropylidene+-]-4-hebutadecene 12-methylhexacyfdecenedeceneheptadecene 3, +6. (p, l, Qj2・+t]-5-tocosene derivatives: hexacyclo[6,6,1,13!, lIl, I
ff, Ql? , Q. +4-co-4-hebutadecene derivative +6. Qj,..., 0blindness 2.1〒]-5-Tokosen+1.1@, 1111@, Qll, QlHs Sen2" Mayu-5-Tokosen+? ]-5-Tococene and other pentacyclo[6,6,1,13・6,02・7
．． Octacyclo [8,8,0,12・,14 ? such as 09+ a] −4− , 111, order, 11 hexadecene derivatives; tricyclo[4,3,0,12 s]-3-decene derivatives such as 5-methyl-tricyclo; -Icosene derivative or hebutacyclo-5-heneicosene derivative: 10-methyl-
tricyclo[4,4,0,12·s]-3-undecene derivatives such as trisif; pentacyclo[4,7,0,12% such as 1,3-dimethyl-pentamethyl substituted pentacyclo1,6-dimethylbentacene , 08 12.111.12] -3-pentadecene derivatives; 14,15-dimethylbencocene etc.
, ＋! ] −] 4-pentadecene derivative; “S] −4-eicosene and other hebutacyclo[7,8,0,1” 6, Q2.7.11・”7,0 +1.16,112 +5] −4− diene compounds such as eicosene derivatives; and cyclic olefins represented by the above formula [II] used in the present invention, specifically, the following compounds such as 21.113 2@, QIj, I@, 11 Can be mentioned.

III] -5-bentacocene 5-phenyl-bicyclo[ 2.,0th”・,116 1.] -5-bentacocene etc. [9, 10, 1, 1'・7. OL・　Q21@,Q10 , tl, l13. ffi・1014 +s, 1+s, +・] -5-bentacocene induction I can lift my body.

(Margin below) CH.

can be mentioned.

(The following is a blank space) The cyclic olefin represented by the above formula [I] 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 an organoaluminum compound is used when copolymerizing ethylene and cyclic olefins.

Specifically, the vanadium compound has the general formula VO (
OR) X or V (OR), X.

@ b (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, ■0C13, ■0(OCH)C12, 5 VO(OC2H5)2C11 VO(0-iso-CH) C12, 7 VO(0-a-CH) CI 2, 9 VO(OCH) , VOB " , VCAI4.2 5
3 2 VOCJ, VO (0-n-c4H9) 3, VCI
- Vanadium compounds such as 20C8H, OH 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, 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, diisopropyl 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 acetyl 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 catalyst component, a compound having at least one A1-carbon bond in the molecule is used, for example, (where R and R2 are the number of carbon atoms, usually 1 to 15,
The hydrocarbon groups preferably contain 1 to 4 and may be the same or different from each other. X is halogen, m is O≦m≦3,
n is a number of O≦n<3, p is a number of O≦n<3, q is a number of 0≦q<3, and m + n + p + q = 3), 1 (i) General Examples include complex alkylated products of Group 1 metals and aluminum represented by the formula MAIR (where Ml is Li, Na, or Ni, and R1 is the same as above).

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

General formula R11, lAl (OR2) -m (where R and R2 are the same as above. m is preferably 1
．． 5≦m<3).

General formula R1mAlX31 (where RI is the same as above, X is halogen, m is preferably O<m<3).

General formula R', AI R31 (where R1 is the same as above, m is preferably 2≦m<3
).

(Here, R and R2 are the same as above. X is halogen, 0
<m≦3.0≦n<3.0≦q<3, m+n+q=3
) can be exemplified.

More specifically, aluminum compounds belonging to (1) include trialkylaluminiums such as triethylaluminum and tributylaluminium, trialkenylaluminums such as triisopropenylaluminum, dialkylaluminums such as diethylaluminium ethoxide, dibutylaluminum butoxide, etc. In addition to alkyl aluminum sesquialkoxides such as alkoxide, ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide, partially alkoxylated alkoxides having a homogeneous composition of 2,50.5 expressed as R' AI (OR) etc. Alkylaluminum, dialkylaluminum halides such as diethylaluminium chloride, dibutylaluminum chloride, diethylaluminum bromide, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide, ethylaluminum dichloride, propyl Partially halogenated alkyl aluminum such as aluminum dichloride, alkyl aluminum cybarides such as butyl aluminum dibromide, dialkyl aluminum hydride such as diethyl aluminum hydride, dibutyl aluminum hydride, engineered lylaluminum dihydride, probyl aluminum dihydride, etc. Exemplary partially hydrogenated alkyl aluminum such as alkyl aluminum halide such as hydride, partially alkoxylated and halogenated alkyl aluminum such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy promide can. In addition, compounds similar to (i) such as 2
It may also be an organic aluminum compound in which the above aluminum is bonded. Specifically, such compounds include (C2H5) 2 AI OAl (C2Hs)
2, (C4H5) 2 people 10A1 (C4H9) 2, C6
H,s can be exemplified.

As a compound belonging to the above (i), LiAl(CH)
, LiAl (C7H,5)4, etc. can be cited as 54 examples. Among these, it is particularly preferable to use alkyl aluminum halides, alkylaluminium cybarides, or mixtures thereof.

In the present invention, a hydrocarbon catalyst 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; Aromatics such as benzene, toluene, and xylene Group 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, 1-butene, 4-methyl-l
- List α-olefins having 3 to 20 carbon atoms such as pentene, l-hexene, 1-octene, l-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. be able to.

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, etc. in an amount less than equimolar to the cyclic olefin component unit in the random copolymer to be produced. Cycloolefin, 1,4-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 pentacyclopentadecenes (general formula [■]) 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/IAI
011I CIA/) is 50 or less, preferably 40 to 1, more preferably 30 to 1, and the vanadium compound concentration (Co, ) supplied into the polymerization tank and the vanadium compound concentration (C, ) in the polymerization tank It is desirable that the ratio (Co, /C1,) be 10 or less, preferably 8-1, 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, the ratio of aluminum atoms to vanadium atoms (Al/v) in the polymerization reaction system is 2 or more, preferably 2 to 50. It is particularly desirable that the number is in the range of 3 to 20.

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/l.

Such a copolymerization reaction of ethylene and cyclic olefins is carried out at -50 to 100'C1, preferably -30 to 80C,
Even more preferable! It is carried out at a temperature of -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 during the copolymerization reaction is usually more than 0 and 50 kg/a+f, preferably more than 0 and 20 kg/al. 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 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 a copolymer solution is usually
5-300g/I.

It is preferably in the range of 10 to 200 g/A'.

In the present invention, from the cyclic olefin random copolymer solution obtained by copolymerizing ethylene and cyclic olefin as described above, a small amount of solid polyethylene as a by-product contained in the copolymer solution is separated and removed. are doing.

To remove the solid polyethylene contained in the cyclic olefin random copolymer solution from the copolymer solution,
For example, a method of filtering the copolymer solution by passing it through a filter, a method of subjecting the copolymer solution to a centrifugal separation operation,
It can be removed by adsorption to diatomaceous earth, activated carbon, alumina, etc., it can be removed using membranes such as ultrafiltration membranes or reverse osmosis membranes, it can be suspended in a liquid such as a flotation machine, and a gas is blown into it.
A method of attaching solid polyethylene to floating bubbles and removing it, heating a copolymer solution and rapidly cooling it to agglomerate the solid polyethylene particles to a large particle size. The copolymer solution is brought to a high temperature and high pressure state, separated into a solution phase mainly composed of the copolymer and a solution phase containing a large amount of molten polyethylene, and only the former phase is separated. The method of doing so is adopted.

Note that the polyethylene produced when ethylene and cyclic olefin are copolymerized is sparingly soluble in hydrocarbon solvents or cyclic olefin solvents, and therefore exists as a fine particulate solid. On the other hand, the cyclic olefin random copolymer produced is dissolved in a hydrocarbon solvent or a cyclic olefin solvent. Therefore, by carrying out the above operation, only polyethylene can be removed.

Here, in this specification, polyethylene refers to not only polyethylene homopolymers but also combinations of ethylene and the above-mentioned cyclic olefins, which have an ethylene content of 90 mol% or more and have a crystal peak of 50°C or more by DSC measurement. Contains polymers.

In the present invention, as described above, when copolymerizing ethylene and cyclic olefin, an operation is performed to separate and remove a small amount of by-product solid polyethylene from the resulting cyclic olefin random copolymer solution. 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.

The cyclic olefin solution that has been subjected to the operation to remove solid polyethylene as described above is treated according to a conventional method,
A cyclic olefin random copolymer is obtained.

The cyclic olefin random copolymer thus obtained is preferably an amorphous copolymer having a DSC melting point and also from the results of measurements by X-ray diffraction.

Furthermore, the ethylene/cyclic olefin molar ratio of the cyclic olefin random copolymer according to the present invention is usually 951.
The range is from 5 to 30/70, preferably from 90/10 to 40/60, and more preferably from 85/15 to 40/60. Further, the glass transition point (Tg) of the cyclic olefin random copolymer is usually 10 to 240°C, preferably 20 to 240°C.
The range is 200°C.

Effects of the Invention According to the present invention, when copolymerizing ethylene and cyclic olefin, an operation is performed to separate and remove a small amount of by-product solid polyethylene from the resulting cyclic olefin random copolymer solution. The content of polyethylene contained as an impurity is reduced, and when used as a substrate for an optical disk, reading errors caused by the substrate can be reduced.

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

[Test method] A spiral with a grouped diameter of 130+ was obtained from the cyclic olefin random copolymer obtained in the Examples and Comparative Examples.
An am disk substrate is created, and SiNx/TbFeCo/S iNx/
A14 layer film (thickness of each layer (mm'); 1100/250/
A film with a composition of 300/400°Tb/Fe/Co; 71/23/6a1m%) was formed, and the pit error rate (BER) of the disk was measured under the following conditions.

Evaluation conditions Write frequency IM Hz Write pulse width 500ns Erase power
10mW write power 8m
W reproduction power 1.5mW bias magnetic field 3000eBER measurement area radius 4
0-45m Example 1 [Catalyst Preparation] ■ Dilute 0(OC2H5)C12 with cyclohexane,
A vanadium catalyst was prepared with a vanadium concentration of 18.6 mmol/l cyclohexane. On the other hand, ethylaluminum sesquichloride (Ai' (C2Hs) +
, s + , sCI ) was diluted with cyclohexane to give an aluminum concentration of 164 mmol/7
! - An organoaluminum catalyst, which is cyclohexane, was prepared.

[A polymerization vessel with a baffle plate and a stirrer having an inner diameter of 700 mm, a total volume of 570 mm, and a reaction volume of 300 mm;
Heat transfer area is 19.4rr! A vertical multi-tube cooler, a circulation line that extracts the polymerization solution from the bottom of the polymerization reactor with a stirrer, circulates the polymerization solution through the multi-tube cooler, and returns it to the polymerization reactor, and a circulation line. Using a polymerization equipment system equipped with a circulation pump installed inside, ethylene and 3-
dodecene) (hereinafter sometimes simply referred to as tetracyclododecene) and butene-1
The copolymerization reaction was carried out continuously so as to contain about 1.2 mol% of . 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/l. Moreover, the V immediately before being supplied to the polymerization vessel
This (1) catalyst was diluted and supplied in advance using cyclohexane as a polymerization solvent so that the catalyst concentration was 1.8 times the dilution ratio as compared to the catalyst concentration in the polymerization vessel.

On the other hand, ethylaluminum sesquichloride as an organoaluminum compound was supplied into the polymerization vessel in an amount such that AA'/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. The point where these (1) catalysts and organic aluminum catalysts are supplied is a 6.
A stirrer equipped with two stages of vertical disc turbine blades was designed to have the strongest stirring near the tip of the upper stage blade, so that dispersion and mixing could be carried out quickly.

The amount of cyclohexane used as a polymerization solvent was 233 kg/
h into the polymerization vessel. 2.69 kg of ethylene
/h, hydrogen gas as a molecular weight regulator was added to 2.2NA'/h.
It was supplied to the gas phase in the polymerization vessel in an amount of 1 h. The polymerization solution was strongly stirred using a stirrer with a power of 4.3 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/cd-G.

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-1 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, a cyclohexane solution with a concentration of ethylene-tetracyclododecene-butene-1 copolymer of 34 g/l was found. was gotten.

[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.

The copolymerization solution after deashing is heated to a temperature of 900 mm, and the inner diameter is 900 mm.
The effective volume is 1. Orr! It was stored in a container equipped with a stirrer, and cooled to about 30 to 40° C. by running room temperature water through a cage attached to the outside of the container.

[Filtration] The copolymer solution thus obtained was filtered at 261 kg/
h amount, the outer diameter is 63.5Dl! The sample was supplied to a filter containing 34 thread-wound filters (vertical wind filters manufactured by Nippon Roki Co., Ltd.) each having an inner diameter of 28 m and a length of 1 m, each having a nominal diameter of 1 μm, and was continuously filtered.

Next, the outer diameter is 641III111, the inner diameter is 51-1, the length is 47
261 kg/h was applied to a filter containing three depth-type filters (BX filter manufactured by Polston) made of borosilicate glass microfiber non-woven fabric with a nominal 2 μm.
, and was continuously filtered.

The differential pressure at this time was 1.5 kg/ad or less.

Next, a filter containing three depth-type filters (AQ filter manufactured by Bolston) made of borosilicate glass microfiber with a nominal diameter of 0.9 μm and having an outer diameter of 59 plates, an inner diameter of 51 plates, and a length of 476 m was loaded at 261 kg/h. , and was continuously filtered. The differential pressure at this time is 1.5 kg
It was below Zal.

1. A depth-type filter (manufactured by Polston Co., Ltd., A
261 kg/h to a filter containing three AQ filters)
, and was continuously filtered. The differential pressure at this time is 1
．． It was set to 5 kg/al or less.

Finally, a nominal 0.3 with an outer diameter of 61 m and a length of 510+ om.
1μm SO8304 metal nonwoven fabric pleated filter (Brunswick PSPO3 filter)
It was supplied to the filter containing the present invention at a rate of 261 kg/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.

[Classification] Before filling the pellets dried as described above into a product container, 1/1/2 of the pellets are separated using an air classifier.
Fine particles weighing 10 or less, specifically, pellet abrasion powder generated during pellet drying, small-sized pellets, crushed pellet fragments, fine foreign matter adhering to the pellets, etc. were removed.

The classifier uses a 370m long zigzag wind classifier.
Nitrogen gas was supplied from the bottom at 30 to 4 ONm3/h1, and the pellets were dropped from the top at a rate of 300 kg/h to remove fine particles.

After creating a substrate using the cyclic olefin random copolymer thus obtained, an optical disc was manufactured and the pit error rate (BER) was measured as described in the test method. there were.

In addition, the cyclic olefin random copolymer obtained in Example 1 was dissolved in cyclohexane in an amount of 34 g/l, and the polymer solution was passed through a fluororesin filter (Granfil ■ manufactured by Kurashiki Boseki Co., Ltd.). The solid polyethylene trapped in the filter contains 2.0 pp of the copolymer.
It was m.

When the polymer solution is passed through the filter, the temperature is about 35°C and the differential pressure is 1. 6 kg/ad or less, and the flow rate of the polymer solution was about 300 kg/hr-of.

Furthermore, the fluororesin filter has a filtration area of 0.87
d, and the flow rate characteristics (25℃ ethyl alcohol (viscosity 1
．． 09cp) was as follows.

Example 2 The same procedure as in Example 1 was carried out except that the filtration step was performed as follows.

[Filter the copolymer solution at 261. kg/h, and the outer diameter is 53
．． The sample was supplied to a filter containing 34 nominally 5 μm thread-wound filters (vertical wind filters manufactured by Nippon Roki Co., Ltd.), each having an inner diameter of 2811III+1 and a length of 1 m, for continuous filtration.

Next, a filter containing 15 SUS 3Q4 laminated metal mesh tube filters (vertical Fuji Plate ■ filters manufactured by Fuji Filter Co., Ltd.) with a nominal 2 μm outer diameter and a length of 750 mm was loaded with 261 kg/h. , and was continuously filtered.

In addition, a filter containing 3 depth-type filters made of borosilicate glass microfiber (No.
continuous filtration. The allowable differential pressure at this time was 1.5 kg/ad or less.

Finally a nominal 0.3 with an outer diameter of 61+am and a length of 510m.
The sample was fed at a rate of 261 kg/h to a filter containing three μm SUS 304 metal nonwoven fabric pleated filters (PSP03 filters manufactured by Brunswick) for continuous filtration.

After creating a substrate using the obtained cyclic olefin random copolymer, an optical disc was manufactured, and the pit error rate (BER) was measured in the same manner as in Example 1.
It was 4.7×10'.

Further, the amount of solid polyethylene contained in the cyclic olefin random copolymer obtained in Example 2 was 5.8 pp
It was m.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the filtration step was performed as follows.

[Filtration] The copolymer solution was filtered at a rate of 261 kg/h and an outer diameter of 63.
5+n, an inner diameter of 28 m, a length of 1 m, and a nominal 5 μm thread-wound filter (vertical wind filter manufactured by Nippon Roki Co., Ltd.) was supplied to a filter containing 34 filters for continuous filtration.

Next, the outer diameter is 25 mm and the length is 510 mm, which is a nominal 2 μm.
The sample was fed at a rate of 261 kg/h to a filter containing 15 SUS 304 laminated metal mesh tube filters (vertical Fuji Plate ■ filters manufactured by Fuji Filter Co., Ltd.), and filtered continuously.

Furthermore, the outer diameter is 61 fins and the length is 750 mm, which is a nominal 0.3μ.
m SUS 304 metal nonwoven fabric pleated filter (PSP03 filter manufactured by Brunswick)
Using two filters containing three filters, connected in series, 261k
g/h and filtered continuously.

In these filtration operations, solid polyethylene was not filtered out.

After creating a substrate using the cyclic olefin random copolymer thus obtained, an optical disc was manufactured, and the pit error rate (BER) was measured in the same manner as in Example 1, and it was found to be 1.1. It was ×105.

Further, the amount of solid polyethylene contained in the cyclic olefin random copolymer obtained in Comparative Example 1 was measured in the same manner as in Example 1, and was found to be 10.8 ppm.

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) , 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, R^1^5 to R^1^8 may combine 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^ With 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 copolymerizing to produce a cyclic olefin random copolymer in a liquid phase consisting of a cyclic olefin, from the resulting cyclic olefin random copolymer solution,
A method for producing a cyclic olefin random copolymer, the method comprising the step of separating and removing a small amount of solid polyethylene produced as a by-product. 2. The method for producing a cyclic olefin random copolymer according to claim 1, wherein the operation for separating and removing solid polyethylene is a filtration operation.