JPH02191602A - Production of cycloolefinic random copolymer - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer having excellent heat resistance, thermal aging resistance and mechanical properties, etc., by copolymerizing ethylene and cycloolefin in hydrocarbon solvent in the absence of gas-phase part is polymerization vessel. CONSTITUTION:In copolymerization of ethylene and cycloolefin expressed by the formula [n is 0 or positive integer; R<1> to R<12> are H, halogen, hydrocarbon, R<9> (or R<10>) and R<11> (or R<12>) may be jointed with each other to form monocyclic or polycyclic] (e.g. 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene) in liquid phase composed of hydrocarbon solvent and in the presence of catalyst to produce cycloolefinic random copolymer, said copolymerization reaction is performed substantially in the absence of gas-phase part in a polymerization vessel generating a solution of said copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for producing a cyclic olefin random copolymer, 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. The present invention relates to a method for producing a random copolymer.

Technical background of the invention and its problems 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, U.S. Pat. No. 2,883,372 discloses copolymers of ethylene and 2,3-dihydroxydicyclopentadiene. Although this copolymer has an excellent balance between 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. 46-14910, 1, 4.5
．． [1-dimethano-1,2,3,4,4I, 5.8
．． 81. - A homopolymer of octahydronaphthalene has been proposed, but this polymer has poor heat resistance and heat aging resistance.

Furthermore, in Japanese Patent Application Laid-Open No. 58-127728,
．． 5.8-dimethano-1,'1.3.4.4 g, 5.
If, a homopolymer of 8g-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 the description.

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 applicant has previously discovered that a cyclic olefin-based random copolymer composed of ethylene and a specific noble cyclic olefin has excellent transparency, as well as heat resistance, heat aging resistance, chemical resistance, and solvent resistance. It has been discovered that it is a synthetic resin with well-balanced properties, dielectric properties, and mechanical properties, and that it exhibits excellent performance in the field of optical materials such as optical memory disks and optical fibers.
Publication No. 59-220550, Japanese Patent Application No. 1983
This was proposed in Japanese Patent Application No. 236828, Japanese Patent Application No. 59-236829, and Japanese Patent Application No. 242336-1982.

By the way, when attempting to produce such a cyclic olefin random copolymer consisting of ethylene and a specific cyclic olefin, 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 ethylene-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 filtered. There was a problem in that a series of ethylene-cyclic olefin random copolymer production equipment including a polymerization vessel and a filtration device could not be operated continuously and stably, such as clogging of the equipment.

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, and it has excellent heat resistance, heat aging resistance, and various mechanical properties. An object of the present invention is to provide a method for producing a cyclic olefin random copolymer.

Summary of the Invention The method for producing a cyclic olefin random copolymer according to the present invention comprises co-coating ethylene with a cyclic olefin represented by the following general formula [1F] in a liquid phase consisting of a hydrocarbon solvent in the presence of a catalyst. When producing a cyclic olefin random copolymer by polymerization, the aforementioned copolymerization is carried out in the presence or absence of a gas phase in a polymerization vessel in which a solution of the cyclic olefin random copolymer is produced. It is characterized by a reaction.

(In the formula, n is 0 or a positive integer, R1-R12
may be the same or different, and are a hydrogen atom, a halogen atom, or a hydrocarbon group, and 9 1f
t 11 or R (or R) and R (or R12) may be bonded to each other to form a monocyclic ring or a polycyclic ring. ) Since the method for producing a cyclic olefin random copolymer board according to the present invention has the above-mentioned characteristics, the copolymerization reaction between ethylene and cyclic olefin can proceed smoothly. A series of ethylene-cyclic olefin random copolymer production equipment including a polymerization vessel can be operated continuously and stably, and the quality is uniform, heat resistance, heat aging resistance, various mechanical properties, etc. A cyclic olefin random copolymer with excellent properties can be produced.

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 a raw material for polymerization is represented by the general formula [1F].

In other words, such a cyclic olefin has the following formula [1a
] It can also be expressed as:

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

■ Formula [Ia]l: R-R"il each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. Here, the halogen atom is: For example, fluorine atom, chlorine atom, bromine atom and iodine atom can be mentioned.Hydrocarbon groups include, each independently, usually an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 5 to 7 carbon atoms. A cycloalkyl group can be mentioned, and specific examples of an alkyl group include a methyl group, an ethyl group, an isopropyl group,
Examples include isobutyl group, pentyl group, and hexyl group, and a specific example of the cycloalkyl group includes cyclohexyl group.

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

Further, RIs and R16 or RIf and R1ft may each independently form an alkylidene group. Such alkylidene groups usually have 2 to 2 carbon atoms.
10 alkylidene groups, and specific examples of such alkylidene groups include ethylidene groups, propylidene groups, and isopropylidene groups.

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

Specifically, the cyclic olefins include the compounds listed in Table 1, or l, 4. S, ll-dimethano-1
, 2゜3.4゜41.5.8.8 In addition to 1-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4s, 5.8. 8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4>, 5.8. Im-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,34,4s, 5. L 8g-octahydronaphthalene, 2-hexyl-1,4,5,8-
Dimethano-1,2,3,4,4*, 5.8.8m-octahydronaphthalene, 2-stearyl-1,4,5,
8-dimethano-1,2,3,4,4g, 5.11.8
g-octahydronaphthalene, 2,3-dimethyl-1,
4,5,8-dimethano-1,2,3°4,41. S,
8. l1i-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3
,4,4! , 5.8.81-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3
,4,4t, 5.8.8g-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3
゜4,4i, 5.8.8g-octahydronaphthalene, 2-fluoro-14,5,8-dimethano-1,2,3
,4,41,S, 8.81-octahydronaphthalene, 2,3-dichloro-1,4,S, 8-dimethano-1
2, 34, 4*, 5.8.8! -octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1゜2, 3.4.43.5-8.8*-octahydronaphthalene, 2-1-butyl-1, 4,5,8-dimethano-1,2,3,4,4! , 5.8.81-octahydronaphthalene, 2-isobutyl-1,4,5,8 dimethanol-1,2,3,4,4 hatake, 5.8.81-octahydronaphthalene such as octahydronaphthalene can be exemplified.

Table 1 Table 1゜ (continued table (continued table (continued table)) - (continued table (continued table (continued table (continued table) (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, 1-butene,
4-methyl-1-pentene, l-hexene, 1-octene, l-decene, l-dodecene, 1-tetradecene, 1
- α-olefin having 3 to 20 carbon atoms such as hexadecene, 1-octadecene, 1-eicosene, cyclopentene, cyclohexene, 3 to methyl less than equimolar amount to the cyclic olefin component unit in the random copolymer to be produced Cyclohexe cycloolefin, 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, tomethylnorbornene-2,5-ethylnorbornene-2,5-isopropylnorbornene-2, S-m-butylnorbornene-2,5 Examples include norbornenes such as -i-butylnorbornene-2,5,6-dimethylnorbornene-2 and S-chloronorbornene-2,2-fluoronorbornene-2,5,6-dichloronorbornene-2. can.

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.

Hydrocarbon solvents used in this case include, for example, aliphatic hydrocarbons such as hexane, heptane, octane, and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, and xylene. Examples include hydrogen and the above polymerizable 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 between ethylene and cyclic olefin is carried out in the presence of a catalyst. A catalyst consisting of a vanadium compound and an organoaluminium compound which are soluble in aluminum is used.

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

(However, R is a hydrocarbon group, 0≦a≦3.0≦b≦3.
2≦a+b≦3.0≦C≦4, O≦d≦4.3≦c 4
- vanadium compounds represented by d≦4) or electron donor adducts thereof are used.

More specifically, voc! 3, VO(QCH)C12, VO(QC2H,) 2C1, VO(0-ito-C3Ht) C12,'/O(
0-s-Cf() CI! , VO(QCH) ,V
OBt 1VCI 4. VOCI, VO(0-f
i-C4H,) 3, VCJ-20C8H, 70H
Vanadium compounds such as 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, methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol , C1-18 alcohols such as cumyl alcohol and isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol,
Bu[j-Vylphenol, Nonylphenol, Cumilf 1
Phenols having a lower alkyl group such as alcohol and naphthol and having 6 to 20 carbon atoms; Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; acetaldehyde, propionaldehyde, octyl aldehyde , aldehydes having 2 to 15 carbon atoms, such as benzaldehyde, tolualdehyde, and naphthaldehyde. Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate,
Methyl butyrate, 1 tyl chlorate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl dichloroacetate, methyl methacrylate, 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, koji-butyl maleate, methylmalonic acid Diisobutyl, di-n-hexyl cyclohexenecarboxylate, diethyl nazic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-·dyrolactone, coumarin Organic acid esters having 2 to 30 carbon atoms, such as , phthalide, and ethylene carbonate; Acid halides and ides having 2 to 15 carbon atoms, such as acetyl chloride, benzoyl chloride, toluyl chloride, and anisyl chloride; methyl ether, ethyl Ding. ethyl, isopropyl nitrogen, butyl ether, methyl ether, tetrahydrofuran, anisole,
Ethers with 2 to 20 carbon atoms such as Schiff's ether; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine , picoline, tetramethylenediamine, and other nitriles; ethyl silicate, diphenyldimethoxysilane, and other alkoxysilanes; and the like. Two or more types of these electron donors can be used.

In the organoaluminum compound catalyst component 1 used in the present invention, a compound having at least one AI carbon bond in the molecule is used, for example, (here, R1 and R2 are the number of carbon atoms, usually 1 to 15, , preferred, <ha]~4
These hydrocarbon groups may be the same or different from each other. X is halogen! ] ] is 0≦m≦3, n is 0≦n<
3, p is a number of 0≦n<3, q is a number of 0≦q<3, and rn+n+p+q=3), (i) a general formula MAIR (where Ml is Ll, Examples include complex alkylated products of Group 1 metals represented by Ni, Ni, and R1 is the same as above) and aluminum.

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

(Here, R1 and R2 are the same as above. m is preferably a number of 1,5≦m<3).

General formula R', A/X3□ (where R1 is the same as above; X is halogen; In is preferably Q<m<3);

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

General formula R', A/ (OR2) X++q (where R1 and R2 are the same as above, X is halogen,
Q<rn≦3, 0≦n<3, 0≦q<3, m+n
+ q = 3).

Aluminum compounds belonging to (i) include, more specifically, trialkyl aluminum such as triethyl aluminum and tributyl aluminum, trialkenyl aluminum such as triisopropyl aluminum, dialkyl aluminum alkoxide such as diethylaluminium ethoxide, dibutyl aluminum butoxide, etc. , ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, as well as partially alkoxylated alkylaluminums with an average composition expressed as R12, sAI (OR), etc. ,
dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminium bromide, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide, ethylaluminum dichloride, propylaluminum dichloride, Partially halogenated alkylaluminiums such as alkylaluminum cybarides such as butylaluminum dibromide, dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, ethylaluminum dicdride, probylaluminum dihydride, etc. Examples include partially hydrogenated aluminum alkyls such as alkylaluminium haladride, partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide. 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:
(C,H,), AI OAJ (C2H5) 2,
(C4H,) and Al OAI (C4H,) 2 are examples.

Compounds belonging to (i) above include LiAl(CH
), L+A7 (C,)j, 5)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 (Al/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.
~5 grams atom/! , preferably in the range of 0.05 to 3 gram atoms/1.

Polymerization In the present invention, in the presence of the above solvent and catalyst,
A copolymerization reaction between ethylene and cyclic olefin is carried out,
First, the polymerization vessel used in carrying out the copolymerization reaction of ethylene and cyclic olefin will be explained.

The polymerization vessel used may be a seed type polymerization vessel equipped with a stirrer, or a tubular loop type polymerization vessel having a function of forcibly circulating the copolymer solution using a pump.

In the present invention, regardless of which polymerization vessel is used, when producing the copolymer, ethylene and cyclic onophine are co-coated under conditions such that there is substantially no gas phase within the polymerization vessel. Carry out polymerization.

By carrying out the polymerization reaction in such a manner that there is substantially no gas phase in the polymerization vessel, the content of the solvent-insoluble copolymer, that is, the ethylene component, is high, and the amount of ethylene that can be used when carrying out the polymerization reaction is high. It is possible to make it difficult to generate a copolymer that is insoluble in the hydrocarbon solvent used in the polymerization vessel.

When producing the copolymer using a seed polymerization reactor equipped with a stirrer, various methods can be adopted to ensure that there is substantially no gas phase in the polymerization reactor. It is preferable to install a nozzle for extracting the copolymer solution from the polymerization vessel as high as possible in the upper part of the polymerization vessel, so that even if a gas phase exists, the gas phase can be quickly discharged from the polymerization vessel. Furthermore, in order to control the amount of the obtained copolymer extracted, it is preferable to automatically control the amount using a pressure control valve instead of using a liquid level control valve as in the conventional method.

In order to prevent the copolymer from entering the seal surface of the agitator's shaft seal, such as a mechanical seal, and causing the copolymer to leak from the shaft seal, for example, a flushing liquid is poured into the shaft seal. It is preferable to take measures such as:

When producing the copolymer using a loop-type polymerization vessel, if a gas phase exists around a pump for forced circulation of the polymer solution, so-called cavitation occurs, and the copolymer solution Since forced circulation of the copolymer solution becomes difficult, it is difficult to confirm whether the inside of the polymerization vessel is substantially filled with the copolymer solution by observing the flow rate of the copolymer solution inside the loop type polymerization vessel. can. When extracting the copolymer from the polymerization vessel, it is preferable to extract the copolymer while automatically controlling the pressure using a pressure control valve.

In addition, when using either the stirrer-equipped seed type polymerization vessel or the loop type polymerization vessel described above, the pressure inside the polymerization vessel, which is automatically controlled by a pressure control valve, is determined by the amount of gas phase. As the number decreases, the fluctuation becomes larger. Therefore, if a large fluctuation range of pressure is recorded in the pressure record inside the polymerization vessel, it can be easily confirmed that there is substantially no gas phase inside the polymerization vessel.

Furthermore, in terms of material balance, the product of the amount of hydrocarbon solvent supplied to the polymerization reactor per unit time and the solubility of ethylene in the hydrocarbon solvent is larger than the amount of unreacted ethylene per unit time. By selecting the polymerization temperature and pressure, it is also possible to set a state in which substantially no gas phase exists. However, in practice, it is possible to carry out the polymerization reaction while confirming that there is virtually no gas phase in the polymerization reactor by checking the fluctuation range of the pressure in the polymerization reactor and the current consumption of the pump in the loop reactor. preferable.

In the present invention, when producing a cyclic olefin-based random copolymer, the above-mentioned polymerization raw materials are used under conditions where there is substantially no gas phase in the polymerization vessel, and the solvent is A copolymerization reaction between ethylene and a cyclic olefin is carried out in the presence of a catalyst and a catalyst.
It is carried out at a temperature of 0 to 100°C, preferably -30 to 80°C, more preferably -20 to 60°C.

In the present invention, when producing a cyclic olefin random copolymer, the copolymerization reaction of ethylene and cyclic olefin is
It is usually performed using the continuous method. 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 performing the copolymerization reaction is usually over 0 and 50 kg.
/al, preferably greater than 0 and 20 kg/+a/.

When producing the cyclic olefin random copolymer according to the present invention, the ethylene/cyclic olefin molar ratio is
Usually 99/work 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.

In the cyclic olefin random copolymer obtained by reacting ethylene and the cyclic olefin, the cyclic olefin forms a structure represented by the general formula [I].

General formula (In the formula, n, R' to R12 are the same as in the above formula [1].) If the structure represented by this formula [1] is expressed more specifically, the structure represented by the following formula [nal] It will be done.

However, in the above formula [nal, n and m and R1 to R18 have the same meanings as in the above formula [1a].

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 1 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 (deashed) from the polymer 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 produced 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.

By heating the copolymer dispersion in this manner, unreacted monomers remaining in the polymer wet cake can be extracted into the 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: Centrifugation as described above] The J (polymer (wet cake)) obtained through the two-culm process is first dried under normal pressure using a normal pressure dryer.

When performing such normal pressure drying, the drying temperature is usually 100~.
Steam at a temperature of 190° C. is passed through an atmospheric dryer to heat the copolymer wet cake.

The normal pressure drying time varies depending on the speed of the copolymer wet cake being moved in the normal pressure dryer, but is usually 5 to 60 minutes.

1″ of the copolymer dried under normal pressure as described in -I-
! The cake 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. By heating and drying the wet cake of the copolymer in this manner, a powder of the copolymer can be obtained.

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

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, that is, the ethylene component, remains on the inner wall of the polymerization vessel. The formation of a copolymer with a large content 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-mentioned series of apparatuses can be operated continuously for a long period of time.

The polymerization vessel used in the method for producing a cyclic olefin random copolymer according to the present invention is applicable not only to the production of the cyclic olefin random copolymer shown in the present invention, but also to It can also be used as a polymerization vessel when producing a polymer using an olefin random copolymer composition (Japanese Patent Application No. 309).For example, for parallel polymerization or series polymerization. Each can also be used as a polymerization vessel.

Effects of the Invention The method for producing a cyclic olefin random copolymer according to the present invention comprises combining ethylene and a cyclic olefin represented by the above general formula [I] in a liquid phase consisting of a hydrocarbon solvent in the presence of a catalyst. When producing a cyclic olefin random copolymer by copolymerization, the above-described copolymerization reaction is carried out in a state where there is substantially no gas phase in a polymerization vessel in which a solution of the cyclic olefin random copolymer is produced. The copolymerization reaction can proceed smoothly, and a series of ethylene-cyclic olefin random copolymer production equipment including the polymerization vessel can be operated continuously and stably. , uniform quality, heat resistance,
A cyclic olefin random copolymer having excellent heat aging resistance and various mechanical properties can be produced.

(The following is a blank space) The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

[Example] The physical properties of the cyclic olefin random copolymers obtained in Examples and Comparative Examples were determined by the following method.

[Polymer basic physical property measurement method] Measured at VFR, 260° C., and a load of 2160 g.

[η]; Intrinsic viscosity was measured at 135°C using an Atlantic viscometer.

Copolymer composition [mol%]; Absorption band based on cyclic olefin component (1026c11-') by infrared spectroscopy (7) Peak height measurement,
The content of the cyclic olefin component was determined.

Moreover, the content of the ethylene component was determined as the residual cyclic olefin component.

Ash content [^sk V, kl, CI]: Determined by X-ray diffraction method.

Volatile component [VM]: Change in weight was measured under the conditions of 300° C., ITo++, and 1 hour, and expressed in weight %.

Unreacted cyclic olefin content: The obtained cyclic olefin random copolymer was dissolved in cyclohexane and quantified by gas chromatography.

Softening point [TMAl i penetration test Dw pea1 component, the softening point temperature was measured using a thermomechanical analyzer at a heating rate of 5° C./min.

Molecular weight distribution [Mv/Mu]; determined by GPC method.

Example 1 [Catalyst Preparation CO(OC2H5)C12 was diluted with cyclohexane,
A vanadium catalyst was prepared with a vanadium concentration of 6.7 mmol/l-cyclohexane.

On the other hand, ethylaluminum sesquichloride (A7 (
C2H,)1. s C1) was diluted with 1.5 cyclohexane to give an aluminum concentration of 107 mmol/l.
- An organoaluminum catalyst which is hexane was prepared.

[Polymerization] The inner tube size is 4B, the outer tube size is 6B, the total length of the tube is 32 m, and a vertical loop reactor is used. Sesquichloride was supplied into the polymerization vessel in an amount such that AJ/V=8.0. Cyclohexane used as a polymerization solvent was
It was supplied into the polymerization vessel in an amount of g/H. 4.55 ethylene
5NJ/H of hydrogen gas as a molecular weight regulator in an amount of kg/H.
was supplied into the polymerization vessel in an amount of

Tetracyclodepletion of the cyclic olefin described above. ) was carried out continuously. When carrying out this reaction, the vanadium catalyst (V catalyst) prepared by the above method was used in a polymerization vessel at a catalyst concentration of 0.6 mmol/! with respect to cyclohexane used as a polymerization solvent. It was supplied into the polymerization vessel in an amount such that Moreover, the vanadium 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 less than twice the dilution ratio of the catalyst concentration in the polymerization vessel. and supplied it.

On the other hand, when carrying out the ethylaluminum reaction of the organoaluminum compound, the polymerization temperature was controlled at 10°C.

The polymerization temperature was controlled by circulating methanol water having a concentration of 25% by weight as a refrigerant in the double tube outer tube portion of the loop reactor. In addition, the rotation speed of the circulation pump was controlled by an inverter so that the flow rate of methanol water in the pipe was 5 m/s.

A copolymer solution of ethylene and cyclic olefin (hereinafter sometimes simply referred to as copolymer solution) obtained under the conditions described above was extracted from the loop reactor. When drawing out this copolymer solution, the pressure was controlled so that the pressure on the suction side of the circulation pump was 41 cg/1fflG using a pressure control valve attached to the drawing line of the loop reactor. In addition, when the above-mentioned reaction was carried out, the range of pressure change was within ±1 kg1a1, and no cavitation occurred around the pump.

[Deashing] Boiler water and Ns OH solution with a concentration of 25% by weight were added as a regulator to the copolymer solution of ethylene and tetracyclododecene extracted from the polymerization vessel to stop the polymerization reaction. At the same time, the catalyst residue remaining in the copolymer solution was removed (deashed) from the copolymer solution.

The copolymer solution after deashing is heated to an inner diameter of 900 m and an effective volume of 1.0 M before entering the next precipitation operation.
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 overflowed and supplied to a second precipitation drum with an inner diameter of 1.3 m and an effective volume of 2.7 rrf, 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 20 Orpm.

[Filtration and Separation] A vertical filtration machine (CF-26 type) manufactured by Nihon Schumatsuha Co., Ltd., consisting of 13 ceramic filters with an outer diameter of 70 m, an inner diameter of 50K11, and a length of 1 m, was used.
The copolymer dispersion obtained in the second precipitation drum described above was supplied and 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. Along with the above filtration operation,
By performing intermittent backwashing using acetone, wet cake mainly containing ethylene and cyclic olefin copolymer and acetone attached to the outer surface of the ceramic filter of the filter can be removed by intermittent backwashing using acetone. It was dropped into an extraction tank.

In other words, the wet cake that had adhered to the outer surface of the cylindrical ceramic filter was heated to 4 to 5 kg using nitrogen gas.
From an acetone holding drum pressurized to g/cd to a cylindrical ceramic filter approximately 2001/1
The acetone was blown out twice and dropped into the 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 above-mentioned filter and the acetone used for backwashing has an inner diameter of 1850 m and an effective volume. A 6M extraction tank with a baffle plate and a stirrer was used. Using such an extraction tank, the fallen material was heated under pressure at a temperature of 78° C. for 2 hours, and the tetracyclododecene remaining in the copolymer wet cake was extracted into acetone. In addition, when performing this extraction process, two extraction tanks A and B are used, and one extraction tank A is used to prepare a solution (copolymer dispersion liquid) in which the polymer wet cake is dispersed in acetone. When heating and extracting unreacted particles,
The other extraction tank B receives the copolymer wet cake and acetone that have fallen from the filter, and conversely, the copolymer dispersion is heated using one extraction tank B to extract unreacted monomers. During this process, extraction tanks A and B were used alternately, with the other extraction tank A receiving the copolymer wet cake and acetone that had fallen from the filter.

[Centrifugation] After 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).
The wet cake of the copolymer was separated by solid-liquid separation using a .

[Drying] The wet cake of the copolymer that has undergone the centrifugation process as described above is first dried in a normal pressure dryer (manufactured by Nara Kikai, NPD-3).
It was dried under normal pressure using a vacuum cleaner (W-W type).

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 was then dried under atmospheric pressure.
Vacuum drying was performed using a vacuum dryer (manufactured by Tamade Kikai Co., Ltd., capacity 2n (vacuum stirring dryer)).

During this vacuum drying, the copolymer wet cake 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 LO Torr.

As described above, the copolymer powder obtained by drying the copolymer cake was temporarily stored in a powder silo with a capacity of 2 ryf.

[Pelletizing] Using a twin-screw extruder (TEX-44 manufactured by Nippon Steel Corporation), the polymer powder was melted and then pelletized. When performing this pelletizing, a hot-cut pelletizer was used.

A series of equipment as described above, from the copolymerization reaction process of ethylene and cyclic olefin to the pelletizing process of ethylene-cyclic olefin random copolymer, is continuously operated for two months to produce a cyclic olefin random copolymer. did. Thereafter, when the polymerization vessel used in the above-described operation was disassembled and inspected, no particularly noticeable dirt was detected inside the polymerization vessel.

The polymerization conditions and representative values of the basic physical properties of the obtained copolymer are summarized in Table 2.

A copolymer of ethylene and methyltetracyclododecene was produced in the same manner as in Example 1, except that the same operation as in Example 1 was carried out for three consecutive weeks.

After the above-described continuous operation was completed, the polymerization vessel used during this operation was disassembled and inspected, and no particularly noticeable dirt was detected inside the polymerization vessel.

Similar to Example 1, the polymerization conditions and representative values of the basic physical properties of the obtained copolymer are summarized in Table 2.

Comparative Example 1 The same operation as in Example 1 was performed except that the polymerization apparatus system used in the polymerization step was changed as follows.

[Polymerization] The inner diameter is 700am and the total capacity is 560! And the reaction volume is 280! A polymerization vessel with a stirrer and a heat transfer area of 1
9.4d vertical multi-tubular cooler, a circulation line that extracts the polymerization solution from the bottom of the polymerization vessel, circulates the polymerization solution through the multi-tubular cooler, and returns it to the polymerization vessel; and the circulation line. A copolymerization reaction of ethylene and tetracyclododecene was carried out in the following manner using a polymerization apparatus system consisting of a circulation pump for circulating the polymerization solution.

This copolymerization reaction was carried out under the following conditions.

The vanadium catalyst prepared by the method of Example 1 was
The vanadium catalyst concentration relative to the polymerization solvent (cyclohexane) in the polymerization vessel is 0.6 mmol/! It was supplied into the polymerization tank in an amount such that In addition, when supplying this vanadium catalyst to the polymerization vessel, the vanadium catalyst concentration immediately before supply is 2 times the dilution ratio relative to the catalyst concentration in the polymerization vessel.
This vanadium catalyst was diluted in advance with cyclohexane, which is a polymerization solvent, so that the volume was less than twice that.

On the other hand, ethylaluminum sesquichloride, an organoaluminum compound, was fed into the polymerization vessel at a rate such that A7/V=8.0. Cyclohexane used as a polymerization solvent was supplied into the combiner in an amount of 200 kg/H.

Ethylene was supplied in an amount of 4.55 kg/'H, N2 as a molecular weight regulator was supplied in an amount of 0.2 Nl/H to the gas phase in the polymerization vessel, and tetracyclododecene was supplied to the liquid phase in the polymerization vessel. was supplied in an amount of 10.1 kg/H.

During this reaction, the polymerization temperature was maintained at 10°C. The temperature was controlled to 10° C. by circulating 25% methanol water as a refrigerant through the shell of a salmon, soot, and multi-tube cooler installed outside the polymerization reactor. The pressure was controlled by introducing N2 gas into the system so that the polymerization pressure was 1, Q kg/adG.

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

After the deashing step, the copolymer was produced through the same steps as in Example 1. Table 2 shows typical values of the basic physical properties of the copolymer thus obtained.

When the above operation was continued for three weeks, the current consumption of the circulation pump became unstable. When the circulation pump was opened, it was found that the circulation pump was clogged with a copolymer insoluble in cyclohexane.

Therefore, when the above-mentioned operation was stopped and the interior of the polymerization vessel was inspected, a copolymer insoluble in cyclohexane was found adhering to the gas-liquid interface of the polymerization vessel in an oblique shape. Therefore, the clogging of the circulation pump is caused by a copolymer that is insoluble in cyclohexane formed at the gas-liquid interface of the polymerization vessel, peeling off from the gas-liquid interface of the polymerization vessel, flowing out of the polymerization vessel, and clogging the circulation pump. Estimated.

In addition, when the composition of the copolymer insoluble in cyclohexane was analyzed, the content of ethylene component was 901, +6 ◇ Table 2 Polymerization conditions, etc.

Claims (1)

[Claims] 1) In the presence of a catalyst, in a liquid phase consisting of a hydrocarbon solvent,
When producing a cyclic olefin random copolymer by copolymerizing ethylene and a cyclic olefin represented by the general formula [I] below, a substantial amount of A method for producing a cyclic olefin random copolymer characterized by carrying out the copolymerization reaction described above in the absence of a gas phase: ▲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. )