JPH02191603A - Production of cycloolefinic random copolymer - Google Patents

Abstract

PURPOSE:To make possible to stably and continuously operate equipment for long period of time and obtain the subject copolymer having excellent heat resistance, etc., by supplying cycloolefin with specific method in polymerizing ethylene and cycloolefin in liquid phase in polymerization vessel. CONSTITUTION:Ethylene is copolymerized with a compound expressed by the formula (R<1> to R<12> are H or halogen, etc.) in liquid phase in the presence of catalyst and solvent with supplying unsaturated cycloolefin expressed by said compound as a raw material or mixture of said compound and solvent onto inner peripheral wall of polymerization vessel upper than interface between gaseous phase and liquid phase in the polymerization vessel to afford the aimed copolymer. As a concrete method supplying a compound expressed by the formula or a mixture of said compound and solvent, for instance, a method bringing the compound expressed by the formula, etc., into liquid-phase part with introducing along peripheral wall at gaseous phase in the polymerization vessel by spraying said compound, etc., onto said wall from a spray disk installed in gaseous phase part of the polymerization vessel, etc., is shown.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a cyclic olefin random copolymer, and more specifically, to a method for producing a cyclic olefin random copolymer that has excellent heat resistance, heat aging resistance, and various mechanical properties. Regarding the manufacturing method.

Technical Background of the Invention Polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and the like are known as synthetic resins with excellent transparency. For example, polycarbonate is a resin that has excellent heat resistance, heat aging resistance, and impact resistance as well as transparency. However, it has the problem that it is easily attacked by strong alkalis and has poor chemical resistance. Further, polymethyl methacrylate has problems in that it is easily attacked by ethyl acetate, acetone, toluene, etc., swells in ether, and has low heat resistance. Furthermore, although polyethylene terephthalate has excellent heat resistance and mechanical properties, it is susceptible to strong acids and alkalis and is susceptible to hydrolysis.

On the other hand, polyolefins, which are widely used as general-purpose resins, have excellent chemical resistance, solvent resistance, and mechanical properties, but many have poor heat resistance and are transparent because they are crystalline resins. inferior to sex.

Therefore, in general, to improve the transparency of polyolefins, a nucleating agent is added to the reaction system during polyolefin production to refine the polyolefin's crystal structure, or rapid cooling is performed to stop crystal growth. (quenching method) is used, but its effectiveness cannot be said to be sufficient. On the contrary, adding a third component such as a nucleating agent to the reaction system may impair the excellent properties originally possessed by polyolefins, and the rapid cooling method requires large-scale equipment and may cause crystallization. As the temperature decreases, there is a possibility that the heat resistance or rigidity of the polyolefin decreases.

For copolymers of ethylene and bulky comonomers,
For example, US Pat. No. 2,1183,372 discloses copolymers of ethylene and 2,3-dihydroxydicyclopentadiene. This copolymer is
Although it has an excellent balance of rigidity and transparency, it has a problem in that its glass transition temperature is about 100°C and its heat resistance is poor. Further, copolymers of ethylene and 5-ethylidene-2-norbornene also have similar problems.

In addition, in Japanese Patent Publication No. 46-149111, I, 4
．． 5. It-dimethano-1,2,3,4,4! , 5
．． 8.81. - A homopolymer of octahydronaphthalene has been proposed, but this polymer has poor heat resistance and heat aging resistance. Furthermore, Japanese Patent Application Laid-Open No. 12770/1983 includes 1.
4.5.8-dimethano-1,,2,34,435,1!
, a homopolymer of l13-octahydronaphthalene or a copolymer of the cyclic olefin and a norbornene type comonomer has been proposed, but the above publication states that both of these polymers are ring-opening polymers. It is clear from this. Since such ring-opened polymers have unsaturated bonds in the polymer main chain, they have a problem of poor heat resistance and heat aging resistance.

In addition, the present applicant has previously discovered that a cyclic olefin-based random copolymer obtained by copolymerizing ethylene and a specific noble cyclic olefin has excellent transparency, heat resistance,
It is a synthetic resin with well-balanced heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and mechanical properties, and is said to exhibit excellent performance in the field of optical materials such as optical memory disks and optical fibers. Headline, special application already filed in 1933
9-16995, Japanese Patent Application No. 59-220550, Japanese Patent Application No. 59-236828, Japanese Patent Application No. 59-2
This was proposed in Japanese Patent Application No. 361129 and Japanese Patent Application No. 59-242336.

When attempting to copolymerize such ethylene and a specific cyclic olefin to produce a cyclic olefin random copolymer, a seed-type polymerizer equipped with a stirrer is usually used. When attempting to perform a polymerization reaction between ethylene and cyclic olefin using this stirrer-equipped seed-type polymerization reactor, depending on the reaction conditions, the ethylene component may appear on the wall near the gas-liquid interface in the stirrer-equipped seed-type polymerization reactor. copolymer (hereinafter sometimes referred to as solvent-insoluble copolymer) was likely to be produced. When a solvent-insoluble copolymer is generated on the wall near the gas-liquid interface in the stirrer-equipped seed polymerization vessel, this solvent-insoluble copolymer changes the state of the gas-liquid interface in the stirrer-equipped seed polymerization vessel. If it changes from moment to moment or if the amount of solvent-insoluble copolymer produced is large, the gas-liquid contact area may decrease. As a result, the copolymerization reaction between ethylene and cyclic olefin may not be carried out sufficiently, or the solvent-insoluble copolymer formed and attached to the inner wall of the stirrer-equipped seed polymerization vessel may fall off from the inner wall into the liquid phase. The edylene-cyclic olefin random copolymer produced in the polymerization vessel reaches the extraction line, where it is captured by a filtration device installed in the extraction line, and the solvent-insoluble copolymer thus captured is passed through the filtration device. There was a problem in that a series of ethylene-cyclic olefin random copolymer manufacturing equipment including a polymerization vessel and a filtration device could not be operated continuously and stably.

Purpose of the Invention The present invention aims to solve the problems associated with the prior art as described above, and involves copolymerizing ethylene and a cyclic olefin to produce a cyclic olefin random copolymer. At this time, by performing a copolymerization reaction of ethylene and cyclic olefin in a polymerization vessel set under specific conditions, the copolymerization reaction as described above can proceed smoothly, and a series of ethylene- The cyclic olefin random copolymer production equipment can be operated continuously and stably for a long period of time, and the quality is uniform, with excellent heat resistance, heat aging resistance, and various mechanical properties. The object of the present invention is to provide a method for producing an excellent cyclic olefin random copolymer.

Summary of the Invention The method for producing a cyclic olefin-based random copolymer according to the present invention is to process ethylene and a cyclic olefin represented by the following general formula [I] into a liquid phase in the presence of a catalyst and a solvent in a polymerization vessel. When producing a cyclic olefin random copolymer by copolymerizing in the polymerization vessel, at least one cyclic olefin represented by the general formula [1] or a mixture of the cyclic olefin and the solvent is It is characterized in that ethylene and the cyclic olefin are copolymerized while being supplied to the inner circumferential wall of the polymerization vessel above the liquid phase interface.

(In the formula, n is 0 or a positive integer, and R to R12 may be the same or different, and are a hydrogen atom, a halogen atom, or a hydrocarbon group, or R (or Rlfl) and R11 (or R12) may be combined with each other to form a monocyclic or polycyclic ring.) The method for producing a cyclic olefin random copolymer board according to the present invention has the above-mentioned characteristics. Therefore, the copolymerization reaction between ethylene and cyclic olefin can proceed smoothly, and therefore, the series of ethylene-cyclic olefin random copolymer production equipment including the polymerization vessel can be operated continuously and stably. Moreover, it is possible to produce a cyclic olefin-based random copolymer that is uniform in quality and excellent in heat resistance, heat aging resistance, and various mechanical properties.

DETAILED DESCRIPTION OF THE INVENTION The method for producing a cyclic olefin random copolymer according to the present invention will be specifically explained below in accordance with its production steps.

Raw Material for Polymerization In the method for producing a cyclic olefin random copolymer according to the present invention, the cyclic olefin used as the polymerization raw material is at least an IN cyclic olefin represented by the general formula [1].

(In the formula, 1, n is 0 or a positive integer, and R1 to R[
2 may be the same or different, and 9 is a hydrogen atom, a halogen atom, or a hydrocarbon group.
fil II or R (or R) and R (or R12) may be bonded to each other to form a monocyclic ring or a polycyclic ring. ) In other words, such a cyclic olefin has the following formula [Ia
It can also be expressed as l.

However, in the above formula [1al, n is 0 or 1, and m is 0 or a positive integer.

In formula [1a], R1 to RIll each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. here,
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In addition, examples of the hydrocarbon group include, each independently, an alkyl group usually having 1 to 10 carbon atoms, and a cycloalkyl group having 5 to 7 carbon atoms, and specific examples of the alkyl group include: Examples include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a pentyl group, and a hexyl group, and a specific example of the cycloalkyl group includes a cyclohexyl group.

Furthermore, in the above formula [Ial, any two of R15 to R18 may each jointly form a monocyclic or polycyclic group, and the monocyclic or polycyclic group is It may have a double bond.

Further, R and R or R17 and R18 may each independently form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 10 carbon atoms, and specific examples of such alkylidene groups include ethylidene group, propylidene group, and isopropylidene group.

Such a cyclic olefin can be easily produced by condensing a cyclopentadiene and a corresponding cyclic olefin by a Diels-Alder reaction.

Specifically, as the cyclic olefin, the compounds listed in Table 1 or 1.4.5.8-dimethano-1,2,3
, 4, 4s, 5.8. In addition to b-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1
,2,3,4,4! , 5.8.81-octahydronaphthalene, 2-ethyl-1,4,5,8 dimethanol-1,
2,3,4,4g, 5.8.81-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1
,2,3゜4,41.5.8. IIJ-octahydronaphthalene, 2-hexyl-1,4,5, g-dimethano-1,2,3,4,41,5,8,8z-octahydronaphthalene, 2-stearyl-1,4,5 ,8-dimethano-1,2,3,4,4s,S,Lb-off9t:
F of79 lene, 2,3-dimethyl-1,4,5,l
l-dime 9/-1,'1.1゜4, 4g, S, 8.
l1i-octahydronaphthalene, tomethyl-3-ethyl-1,4,5,1 dimethanol-1,2,3+ 4.4
*, s, g.

1g-octahydronaphthalene, 2-chloro-1,4,
S, 8-dimethano-1,2,3,4,48,S, l
, ll*-octahydronaphthalene, 2-bromo-1
, 4,5,8-dimethano-1,2,34,4s, 5.
It, h-octahydronaphthalene, 2-fluoro-1,4,5,ll-dimethano-1,2,3,i,i, 5.8.8g-octahydronaphthalene, 2.3-
Dichloro-1,4,5,g-dimethano-1,2,3,4
,4*,S,8.8*-octahydronaphthalene,
2-cyclohexyl-1,4,5,8-dimethano-12
, 3,4,41,S, 8.8s-octahydronaphthalene, 2-m-butyl-1,4,5,8-dimethano-1
,2,3,4,4*, 5.8.8g-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4I, S, 8.8t- Octahydronaphthalenes such as octahydronaphthalene can be exemplified.

Table 1 Table (Continued Table (Continued Table) (Continued Table (Continued Table) (Continued Table (Continued Table (Continued Table O) Table (Continued Table (Continued Table) - ],) Table 1 (Continued Table (Continued Table) (Continued Table) When producing an olefin-based random copolymer, the ethylene and the cyclic olefin are copolymerized, but in addition to the two essential components, other copolymerization may be carried out as necessary within the scope of not impairing the purpose of the present invention. Possible unsaturated monomer components can also be copolymerized.

Specifically, examples of such copolymerizable unsaturated monomers include propylene, l-butene,
4-Methyl-1-pentene,! -hexene, 1-octene, 1-decene, 1-dodecene, l-tetradecene, 1
-α-olefin having 3 to 20 carbon atoms such as hexadecene, j-octadecene, and l-eicosene; cyclopentene, cyclohexene, and 3-methyl in an amount less than equimolar to the cyclic olefin component unit in the random copolymer to be produced; Cyclohexene, cyclooctene, 31,5,6.7
3-tetrahydrocycloolefin, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2- Norbornene, non-conjugated dienes such as 5-vinyl-2-norbornene, norbornene-2,5-methylnorbornene-2,
5-ethylnorbornene-2,5-isopropylnorbornene-2,5-i-butylnorbornene-2,5-i
Examples include norbornenes such as -butylnorbornene-2,56-dimethylnorbornene-2,5-chloronorbornene-2,2-fluoronorbornene-2,5,6-dichloronorbornene-2.

Solvent In the present invention, when producing a cyclic olefin random copolymer, the copolymerization reaction of ethylene and cyclic olefin is carried out in a hydrocarbon solvent.

Examples of hydrocarbon solvents used in this case include aliphatic hydrocarbons such as hexane, heptane, octane, and kerosene; ring hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; Examples include sexually unsaturated monomers, and a mixed solvent of two or more of these may be used.

Catalyst In the present invention, when producing a cyclic olefin random copolymer, the copolymerization reaction of ethylene and cyclic olefin is carried out in the presence of a catalyst. A catalyst consisting of a vanadium compound and an organoaluminum compound that are soluble in a solvent is used. Specifically, the vanadium compound is represented by the general formula v.

(OR), X, or V (OR) cX, (but
R is a hydrocarbon group, 0≦a≦3.0≦b≦3.2≦a+b
A vanadium compound represented by the formula ≦3.0≦C≦4.0≦d≦4.3≦C+d≦4) or an electron donor adduct thereof is used. More specifically, vOC13, VO(QCH)Cm! z.

■0(OC2H5)20! , VO(0-iso-CiH) ) C12,V
O(0-m-CH) CI 2, ■0(OCH), VOB", vC14, VOCI
,,VO(0-1-C4H,) 3. vCl red 20
Vanadium compounds such as C, H, and 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, isocyanates, and the like 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, isopropyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc. 1 to 18 alcohols; 6 to 20 carbon atoms that may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol, etc.
Ketones with 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone; 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde Aldehydes: methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, ethyl dichloroacetate, methacrylic acid Methyl, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate , amyl toluate, ethyl ethylbenzoate, methyl anisate, lobutyl maleate, diisobutyl methylmalonate, di-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, phthalic acid Organic acid esters having 2 to 30 carbon atoms such as dinoble-butyl, di-2-edylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; acetyl chloride, benzoyl chloride, toluic acid chloride, Acid halides with 2 to 15 carbon atoms such as anisyl chloride; ethers with 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether; acetic acid amide, benzoic acid Acid amides such as amide and toluic acid amide; Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylenediamine; Nitriles such as acetonitrile, benzonitrile, and tolnitrile Examples include alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane. Two or more types of these electron donors can be used.

As the organoaluminum compound catalyst component used in the present invention, a compound having at least one A/= carbon bond in the molecule is used, for example, A/= carbon bond, preferably 1 to 1 carbon bond.
The hydrocarbon groups containing 4 groups may be the same or different from each other. X is halogen, m is O≦m≦3, n is 0≦n<3
, p is a number of 0≦n<3, q is a number of 0≦q<3, and m + n+1) 10=3), and RI is the organoaluminum compound, Na, represented by ) is the same as
Examples include complex alkylated products of group metals and aluminum.

Examples of the organoaluminum compounds belonging to the above (1) include the following.

General formula R', A7 (OR2) t1 (where R and R2 are the same as above. m is preferably 1
．． 5≦m<3).

General formula R', At X31 (wherein R1 is the same as above;

General formula R' lAI H,.

(Here, 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
).

More specifically, aluminum compounds belonging to (i) include trialkylaluminiums such as triethylaluminum and tributylaluminium, trialkylaluminums such as triisopropylaluminum, dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide, In addition to alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, partially alkoxylated alkylaluminums having a homogeneous composition of 2,50.5 expressed as R' AI (OR) etc. ,
Dialkyl aluminum halides such as diethylaluminum chloride, dibutyl aluminum chloride, diethylaluminium bromide, alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquipromide, ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum Partially halogenated alkyl aluminum hydrides such as alkyl aluminum cybarides such as dibromide, dialkyl aluminum hydrides such as diethylaluminum hydride, dibutyl aluminum hydride, alkyl aluminum halides such as ethyl aluminum dicdride, probylaluminum dihydride Partially hydrogenated aluminum alkyls such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide and the like may be exemplified. It may also be a compound similar to (i), such as an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Specifically, such compounds include (C2H5
)2A! OA1 (C2H5)2, (C4R9)2 A
An example is n OAR(C4Hg )2.

As a compound belonging to the above (i), LiAJ (C2R
5) 4, x, tAi (C7HI3) 4, etc. can be exemplified. Among these, it is particularly preferable to use alkyl aluminum halides, alkylaluminium cybarides, or mixtures thereof.

In the method for producing a cyclic olefin random copolymer according to the present invention, the copolymerization reaction is carried out in a continuous manner as described below. At that time, the concentration of the soluble vanadium compound supplied to the polymerization reaction system is usually 10 times or less, preferably 7 times or less, the concentration of the soluble vanadium compound in the polymerization reaction system.
It is in the range of 1 to 1 times, more preferably 5 to 1 times.

Furthermore, the ratio of aluminum atoms to vanadium atoms (A7/V) in the polymerization reaction system is 2 or more, preferably 2 to 2.
50, particularly preferably in the range of 3 to 20.

The soluble vanadium compound and the organoaluminum compound are each usually supplied diluted with the hydrocarbon solvent. 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.

In the method for producing a cyclic olefin random copolymer according to the present invention, the concentration of the soluble vanadium compound in the copolymerization reaction system is usually 0.01 as vanadium atoms.
It ranges from ~5 g atoms/l, preferably from 0.05 to 3 g atoms/l.

Polymerization In the present invention, when producing a cyclic olefin random copolymer, a copolymerization reaction of ethylene and a cyclic olefin is carried out using the above-mentioned polymerization raw materials and in the presence of the above-mentioned solvent and catalyst. When carrying out this reaction, for example, a polymerization vessel equipped with a stirrer is used. This polymerization vessel with a stirrer includes, for example, a multi-tubular cooler to keep the polymerization temperature constant, and a polymerization solution that is drawn out from the bottom of the polymerization vessel with a stirrer and circulated through the multi-tubular cooler. Then, a circulation line that returns to the polymerization vessel with a stirrer and a circulation pump installed in the circulation line are provided.

A liquid phase part and a gas phase part exist in the polymerization vessel marked L,
In addition to ethylene present in the gas phase, hydrogen gas as a molecular weight regulator may also be present, and an inert gas may also be present in the gas phase. On the other hand, in the liquid phase, cyclic olefin,
A solvent and a catalyst are present.

Among these components present in the polymerization vessel, at least a portion of the cyclic olefin or at least a portion of both the cyclic A reflex and the solvent are present in the inner periphery W of the polymerization vessel above the gas-liquid phase interface within the polymerization vessel. (inner circumferential wall of the gas phase part in the polymerization vessel), travels along the inner wall, and is introduced into the liquid phase.

As a specific method for supplying a cyclic olefin or a mixture of the cyclic olefin and a solvent to the upper inner circumferential wall from the gas-liquid phase interface in the polymerization vessel, the following method may be mentioned, for example.

(a) A spray disk is provided in the gas phase in the polymerization vessel, and a cyclic olefin or a mixture of the cyclic olefin and a solvent is flowed down or sprayed from the spray disk toward the inner peripheral wall of the gas phase in the polymerization vessel. A method in which the gas is transmitted through the inner circumferential wall of the gas phase and mixed into the liquid phase.

(b) A nozzle is provided in the gas phase in the polymerization vessel, and a cyclic olefin or a mixture of the cyclic olefin and a solvent is directly flowed down or sprayed from this nozzle toward the inner circumferential wall of the gas phase in the polymerization vessel. A method in which the gas is transmitted through the inner circumferential wall of the gas phase and mixed into the liquid phase.

In both methods (a) and (b), flowing down or spreading may be performed continuously or intermittently.

In this way, by supplying a cyclic olefin or a mixture of the cyclic olefin and a solvent to the inner circumferential wall of the polymerization vessel above the gas-liquid phase interface in the polymerization vessel, the content of the edinone component can be reduced to the original value. It is possible to suppress the formation of a copolymer (solvent-insoluble copolymer) that is insoluble in one or more solvents used than the cyclic olefin random copolymer according to the invention (solvent-insoluble copolymer) on the inner peripheral wall.

When a mixture of a cyclic olefin and a solvent is supplied to the inner circumferential wall of the gas phase in the polymerization vessel, this solvent and the solvent in the liquid phase in the polymerization vessel are usually the same, but may be different.

Further, in order to always maintain the interface between the liquid phase portion and the gas phase portion at the same position, it is preferable to automatically control the liquid level using a liquid level control valve.

In the present invention, the copolymerization reaction of ethylene and cyclic olefin is carried out at -50 to 100°C, preferably -30 to 80°C.
, more preferably at a temperature of -20 to 60°C.

In the present invention, the copolymerization reaction of ethylene and the cyclic olefin 7 is usually carried out in a continuous manner. In that case, ethylene and cyclic olefin as polymerization raw materials, copolymerizable components to be copolymerized as necessary, soluble vanadium compound components as catalyst components, organoaluminum compound components, and hydrocarbon solvent are continuously supplied to the polymerization reaction system. The polymerization reaction mixture is continuously extracted from the polymerization reaction system.

When carrying out the above copolymerization 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 10 minutes to 3 hours. It is a range of time. In addition, the pressure when carrying out the copolymerization reaction is usually over 0 and 50 kg/
al, preferably 20 kg/al above O.

When producing the cyclic olefin random copolymer according to the present invention, the ethylene/cyclic olefin molar ratio is
Usually 99/1 to 1/99, preferably 98/2 to 2
/98, more preferably in the range of 90/10 to 10/90.

When the copolymerization reaction of ethylene and cyclic olefin is carried out as described above, a solution of a cyclic olefin random copolymer in a hydrocarbon solvent is obtained.

As described above, in the cyclic olefin random copolymer obtained by copolymerizing ethylene and the cyclic olefin, the cyclic olefin forms a structure represented by the general formula [11].

General formula (In formula [111, n and R1-R12 are the same as in formula [1] above.) To express the structure represented by formula [11] more specifically, the following formula [I[al] expressed.

... [II al However, in the above formula [11a], n and m and R1,, RH have the same meaning as in the above formula [1al].

The concentration of the cyclic olefin random copolymer contained in such a copolymer solution is usually in the range of 2.0 to 100% by weight, preferably 40 to 60% by weight, and the resulting copolymer solution It also contains a soluble vanadium compound component and an organoaluminum compound component, which are catalyst components.

The hydrocarbon solvent solution of the cyclic olefin random copolymer obtained as described above is usually subjected to a series of treatments, from deashing to pelletization, as described below. A pellet is obtained.

Usually, for example, an aqueous sodium hydroxide solution with a concentration of 5 to 40% by weight is added to the polymer solution extracted from the deashing polymerization vessel to stop the polymerization reaction and remove the catalyst residue remaining in the polymer solution. Removed (decalcified) from the coalescing solution.

Next, the deashed polymer solution is usually temporarily stored in a predetermined stirrer-equipped container before entering the next precipitation step.

A predetermined amount of the polymer solution that has undergone the precipitation-deashing process and a predetermined amount of a precipitation solvent, such as acetone, are usually supplied to a precipitation drum equipped with a stirrer (first precipitation drum), and are heated at a predetermined temperature and under stirring.
The polymer is deposited into a first deposition drum.

Next, the acetone dispersion of the polymer precipitated in the first precipitation drum is normally supplied to a precipitation drum (second precipitation drum) equipped with a baffle plate and a stirrer, and the polymer is precipitated again.

Filtration Separation The dispersion obtained in the second precipitation drum is filtered and separated into a filtrate and a solid content as a wet cake of the polymer obtained by the polymerization reaction. The filtrate contains unreacted monomers and solvents such as cyclohexane used in the polymerization step and acetone used in the precipitation step.

The separated filtrate is separated into each component and reused.

Extraction Next, a solution (copolymer dispersion) in which the polymer wet cake is dispersed in a solvent such as acetone is heated under pressure in an extraction tank.

In this way, by heating the copolymer dispersion liquid, the unreacted top material remaining in the polymer wet cake described above can be removed.
can be extracted into a solvent.

Two or more types of extraction tanks can also be used in parallel.

Centrifugal Separation The copolymer can be separated by solid-liquid separation of the copolymer dispersion that has undergone the above-mentioned extraction process, usually using a centrifugal separator.

Drying The copolymer (wet cake) obtained through the above-described centrifugation step is first dried under normal pressure using a normal pressure dryer.

When performing such normal pressure drying, the drying temperature is usually 100 to 1.
Steam at a temperature of 90° C. is passed through an atmospheric dryer to heat the copolymer wet cake.

In addition, this normal pressure drying time varies depending on the speed of the copolymer wet cake moving in the normal pressure dryer, but
Usually, it is 5 to 60 minutes.

The copolymer wet cake dried under normal pressure as described above is then vacuum dried using a vacuum dryer.

When performing such vacuum drying, a vacuum dryer is usually heated using steam at a temperature of 100 to 190°C.

Vacuum drying time is usually 1 to 4 hours. The final pressure during vacuum drying is usually 1 to 30 To+t. By heating and drying the wet cake of the copolymer in this manner, a powder of the copolymer can be obtained.

In addition, by adding a heating step to the cyclic olefin random copolymer solution obtained through the deashing step as described above, and flash drying after sufficiently removing the solvent,
The copolymer may be dried.

Pelletization The copolymer powder obtained through the drying process as described above is melted using an extruder, and then made into pellets using a pelletizer.

Effects of the Invention In the method for producing a cyclic olefin random copolymer according to the present invention, even if the copolymerization reaction of ethylene and cyclic olefin is carried out continuously for a long period of time, the solvent-insoluble copolymer, i.e. The formation of a copolymer with a high content of ethylene component and insoluble in hydrocarbon solvents is suppressed. Furthermore, the occurrence of blockage or the like in the line for extracting the copolymer from the polymerization vessel due to the solvent-insoluble copolymer is less likely than in normal production methods. Therefore, according to the method for producing a cyclic olefin random copolymer according to the present invention, the above-described series of apparatuses can be operated continuously for a long period of time.

Further, according to the present invention, it is possible to produce a cyclic olefin-based random copolymer that is uniform in quality and excellent in heat resistance, heat aging resistance, various mechanical properties, and the like.

Next, the method for producing a cyclic olefin random copolymer according to the present invention will be specifically explained using Examples, but the present invention is not limited to these Examples.

The proportion of crosslinked copolymers present in the cyclic olefin random copolymers obtained in Examples and Comparative Examples was determined by the following method.

Gel fraction: A cyclic olefin random copolymer is dissolved in xylene, and the roughness is 0.45 μm and 10
The gel fraction was determined by filtering through a μm filter and measuring the increase in filter weight.

Example 1 [Catalyst Preparation] VO(QCH)C10 was diluted with hexante, and the vanadium concentration was 6.7 mmol/! -A vanadium catalyst, which is cyclohexane, was prepared.

On the other hand, ethylaluminum sesquichloride (” (0
2H5)1.5 1.5C/ ) was diluted with cyclohexane to give an aluminum concentration of 107 mmol/l-
An organoaluminum catalyst, which is hexane, was prepared.

[Polymerization] A polymerization vessel with a stirrer having an inner diameter of 700 mm, a total capacity of 560 mm, a reaction volume of 280 mm, and a heat transfer area of 1 mm.
A circulation line that extracts the polymerization solution from the bottom of the polymerization vessel with a 9.4rrf vertical multitubular cooler and a stirrer, circulates the polymerization solution through the multitubular cooler, and returns it to the polymerization vessel. A copolymerization reaction was continuously carried out with a cyclic olefin (hereinafter sometimes simply referred to as tetracyclododecene) shown in the circulation line. When carrying out this reaction, the vanadium catalyst (V catalyst) prepared by the above method is polymerized in an amount such that the V catalyst concentration with respect to cyclohexane used as a polymerization solvent is 0.6 mmol/l in a polymerization vessel. Supplied into the vessel. In addition, this (1) catalyst is diluted in advance using cyclohexane, the polymerization solvent, so that the V catalyst concentration immediately before being supplied to the polymerization vessel is less than twice the dilution ratio of the catalyst concentration in the polymerization vessel. was supplied.

On the other hand, ethylaluminum sesquichloride, which is an organoaluminum compound, was supplied into the polymerization vessel in such an amount that AI/V=8.0. Cyclohexane used as a polymerization solvent was supplied into the polymerization vessel in an amount of 205 kg/H. Ethylene was supplied in an amount of 2.84 kg/H, hydrogen gas as a molecular weight regulator was supplied in an amount of 0.2N17H to the gas phase in the polymerization vessel, and tetracyclododecene was supplied in an amount of 300 g/H to the liquid phase in the polymerization vessel. Supplied to the department.

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.

Polymerization pressure is 1. Nitrogen gas was introduced into the polymerization vessel and the pressure was controlled so that the pressure was 0 kg/alG.

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, the cyclohexane solvent was supplied into the spray disk at a rate of 50 kg/H, and the tetracyclododecene was supplied at a rate of 12.66 kg/H, and the shaft was rotated to release the cyclohexane and tetracyclododecene into the shaft. The centrifugal force generated by the rotation of the machine caused the spray to scatter through the holes in the spray disk, and was sprayed onto the inner wall of the polymerization vessel. The sprayed tetracyclododecene and cyclohexane passed along the inner wall and mixed into the liquid phase.

When a copolymerization reaction of ethylene and tetracyclododecene was carried out continuously under the above conditions, a cyclohexane solution of an ethylene/tetracyclodotecene copolymer was obtained.

[Deashing] Add boiler water and an Ng OH solution with a concentration of 25% by weight as a pH adjuster to the copolymer solution of ethylene and tetracyclododecene extracted from the polymerization vessel to stop the copolymerization reaction. At the same time, the catalyst residue remaining in the copolymer solution was removed (deashed) from the copolymer solution.

Before the copolymer solution after deashing is entered into the next precipitation operation, the inner diameter is 900mm and the effective volume is i, 0rrf.
It was stored in a container with a stirrer.

[Precipitation] The copolymer solution after deashing was added in an amount of 265 kg/H, and the precipitation solvent (acetone, moisture 1.0% by weight) was added in an amount of 1060 kg/H.
kg/H was fed to the first precipitation drum. This first precipitation drum has an inner diameter of 450 mm and an effective volume of 10
01 precipitation drum, and a baffle plate and a stirrer are provided inside.

The stirrer installed in this precipitation drum had six turbine blades, and the rotational speed of the stirrer during this precipitation was 600 rpm. The liquid temperature at the time of precipitation was 30 to 35°C. The precipitated copolymer dispersion is allowed to overflow and is then supplied to a second precipitation drum with an inner diameter of 1.3 m and an effective volume of 2.7 d, which is equipped with a baffle plate and a stirrer, and further contains unprecipitated ethylene and cyclic olefin. A copolymer dispersion liquid was obtained by precipitating a copolymer with At this time, the rotational speed of the stirrer attached to the second precipitation drum was 200+pm.

[Filtration separation] The outer diameter is 70 m, the inner diameter is 50 m, and the length is 1 m.
The copolymer dispersion obtained in the second precipitation drum described above was supplied to a vertical type filtration machine (CF-26 model) manufactured by Nippon Schumatsuha Co., Ltd., which consisted of 13 ceramic filters, and was filtered. The filtrate was supplied to a distillation system, and the unreacted monomer and the solvents cyclohexane and acetone were separated and purified and reused. Due to the above filtration operation, the wet cake that adheres to the outer surface of the ceramic filter of the filter (also mainly contains a copolymer of ethylene and cyclic olefin and acetone) is subjected to intermittent backwashing using acetone. By doing so, it was allowed to fall into the extraction tank provided at the bottom of the filter.

In other words, the wet cake that adheres to the outer surface of the cylindrical ceramic filter is heated to 4 to 5 kg using nitrogen gas.
Acetone was blown from an acetone holding drum pressurized to g/cd through a cylindrical ceramic filter in an amount of approximately 2001 g/cd and dropped into an extraction tank. Note that the above-mentioned backwashing was performed at approximately 30 minute intervals.

[Extraction] The extraction tank that receives the wet cake containing the copolymer of ethylene and cyclic olefin and acetone that has fallen from the filter and the acetone used for backwashing has an inner diameter of 1850 mm and an effective An extraction tank with a baffle plate and a stirrer with a volume of 6+1 was used. Using such an extraction tank, the above fallen F was heated under pressure at a temperature of 78°C for 2 hours. Tetracyclododecene remaining in the wet cake was extracted into acetone.

When carrying out the process, two extraction tanks A and B are used, and one extraction tank A is used to heat a solution (copolymer dispersion liquid) in which a polymer wet cake is dispersed in acetone. When extracting unreacted monomers (-), the other extraction tank B receives the polymer wet cake and acetone that have fallen from the filter, and conversely, one extraction tank B is used to collect the polymer wet cake and acetone that have fallen from the filter. When the copolymer dispersion is heated and the unreacted monomers are extracted, the polymer wet cake and acetone that fall from the filter are transferred to the other extraction tank A.
Extraction tanks A and B were used alternately.

[Centrifugal fraction 11111 After performing the extraction process as described above, the copolymer dispersion was transferred to a super decanter manufactured by Tomoe Kogyo Co., Ltd. (model number P-4400).
) to separate the copolymer into a wet cake.

"Drying": First, the wet cake of the copolymer that has gone through the centrifugation process as described above was dried in an ordinary pressure dryer (manufactured by Nara Kikai Co., Ltd., NP
D SW W type) was used to dry under normal pressure.

During this atmospheric drying, the copolymer wet cake was heated by passing steam at a temperature of 120° C. through the jacket and screw of the atmospheric dryer.

This normal pressure drying time was determined by the conveyance speed of the copolymer wet cake by the screw installed in the normal pressure dryer, and was actually 20 to 30 minutes.

The copolymer wet cake dried under normal pressure as described above was then vacuum dried using a vacuum dryer (manufactured by Doyo Kikai, vacuum stirring dryer with a capacity of 2n11).

During this vacuum drying, the wet cake of the copolymer was heated by passing steam at a temperature of 140° C. through the jacket and stirring blade of the vacuum dryer.

Further, the vacuum drying time was 2.5 hours.

The final pressure during vacuum drying was actually 5 to 10 T'o++. The copolymer powder obtained by drying the copolymer weight cake as described above was added to a volume of 2rrf.
It was temporarily stored in a powder silo.

[Pelletizing] Using a twin-screw extruder (TEX-44 manufactured by Nippon Steel Corporation), the copolymer powder was melted and then pelletized. When performing this pelletizing, a hot-cut pelletizer was used. In addition, when performing the above pelletizing, in order to remove fine foreign matter in the molten polymer,
A filter with a mesh size of 5 μm or 10 μm was installed between the extruder and the pelletizer.

When the series of equipment described above, from the ethylene and cyclic olefin copolymerization process to the ethylene-cyclic olefin random copolymer pelletization process, was operated continuously for two months, the circulation pump became unstable. Ta.

Therefore, when we stopped the equipment, opened the polymerization vessel, and inspected it, we found that a football-sized lump had formed at the feed nozzle of the catalyst. It was assumed that the formation of this lump made the liquid delivery by the circulation pump unstable. Additionally, a copolymer of ethylene and cyclic olefin, which is insoluble in cyclohexane, was found to be attached to the gas-liquid interface in the polymerization vessel in an oblique pattern. however,
The life of the polymer filter installed between the extruder and the pelletizer with a mesh roughness of 10 μm was one month.

Table 2 shows the proportion of cyclohexane insoluble content (gel fraction) in the copolymer obtained by the above polymerization method, and also the operating life of the polymerization vessel and the Table 2 shows the lifespan of polymer filters.
Shown below.

Comparative Example 1 In the polymerization process of Example 1, the receiver limited the liquid supplied to the tray to only the solvent cyclohexane, except that tetracyclododecene was supplied from the multi-tubular cooler to the line connected to the polymerization vessel. When a copolymerization reaction of ethylene and tetracyclododecene was continuously carried out under the same conditions as in the polymerization process of Example 1, a cyclohexane solution of an ethylene-tetracyclododecene copolymer was obtained. Hereinafter, a series of steps from the deashing step to the pelletizing step were performed in the same manner as in Example 1 to produce an ethylene-tetracyclododecene copolymer.

When the above operation was continued for three weeks, the current consumption of the circulation pump became unstable. When the circulation pump was opened, a copolymer insoluble in cyclohexane clogged inside the circulation pump was detected. Therefore, when the above-described operation was stopped and the inside of the polymerization vessel was inspected, a copolymer insoluble in cyclohexane was detected adhering to the gas-liquid interface of the polymerization vessel in an oblique pattern. Therefore, it was assumed that the pump was clogged because the cyclohexane-insoluble copolymer formed at the gas-liquid interface of the polymerization vessel peeled off and flowed out of the polymerization vessel, clogging the circulation pump. Further, when the composition of the copolymer insoluble in cyclohexane was analyzed, the content of the ethylene component was 90%.

Table 2 shows the percentage of cyclohexane insoluble content (gel fraction) in the copolymer obtained using the polymerization method described above, and also shows the operating life of the polymerization vessel and the life of the polymer filter described above. Shown in 2.

Table 2

Claims (1)

[Claims] 1. In a polymerization vessel, in the presence of a catalyst and a solvent, ethylene and an unsaturated cyclic olefin represented by the following general formula [I] are copolymerized in a liquid phase to form a cyclic olefin system. When producing a random copolymer, an unsaturated cyclic olefin represented by the general formula [I] or a mixture of the cyclic olefin and a solvent is applied to the inner peripheral wall of the polymerization vessel above the gas-liquid phase interface in the polymerization vessel. A method for producing a cyclic olefin random copolymer characterized by copolymerizing ethylene and the cyclic olefin while supplying ethylene: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, n is 0 or a positive integer, R^1~R^
1^2 may be the same or different,
Is it a hydrogen atom, a halogen atom or a hydrocarbon group, or R
^9 (or R^1^0) and R^1^1 (or R^1
^2) may be bonded to each other to form a monocyclic or polycyclic ring. ) 2. By flowing or spraying an unsaturated cyclic olefin or a mixture of the cyclic olefin and a solvent toward the inner circumferential wall of the polymerization vessel above the gas-liquid phase interface in the polymerization vessel, the gas and liquid in the polymerization vessel can be reduced. 2. The method according to claim 1, wherein the supply is carried out on the inner circumferential wall of the polymerization vessel above the phase interface. 3. The method according to claim 1, wherein the solvent is an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon. 4. The method according to claim 1, wherein the catalyst comprises a vanadium compound and an organoaluminum compound soluble in a solvent.