JPH03172312A - Production of cyclic olefin random copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer excellent in transparency, heat resistance, dielectric properties, etc., narrow in both molecular weight distribution and composition distribution by copolymerization between ethylene and a cyclic olefin in a hydrocarbon solvent in the presence of a specific catalyst under specified conditions. CONSTITUTION:The objective copolymer can be obtained by continuous copolymerization between (A) ethylene and (B) a cyclic olefin of formula I or II (R<1>-R<16> are each H, hydrocarbon, etc.; (n) in the formula I is integer >=0; (l) is 0 or integer >=1; (m) and (n) in the formula II are each 0-2; R<1>-R<15> are each H, halogen, etc.) in a hydrocarbon solvent using catalyst made up of a soluble vanadium compound (e.g. VOCl3) and organoaluminum compound (pref. diethylaluminum chloride) under such condition as to keep the ratio of the Al atoms to the V atoms in the liquid phase of the polymerization system (Al/V) at >=2. The component B is e.g. 5-phenyl-bicyclo[2,2,1]hepto-2-ene.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for producing a cyclic olefin random copolymer. More specifically, the present invention is directed to a cyclic olefin-based random compound that has excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties, and has a narrow molecular weight distribution and composition distribution. The present invention relates to a method for producing a copolymer.

Technical background of the invention A cyclic olefin-based random copolymer consisting of ethylene and a specific bulky cyclic olefin is a synthetic resin with well-balanced optical properties, mechanical properties, and thermal properties.
Moreover, it can be used for applications in the field of optical materials such as optical memory disks and optical fibers, as disclosed in International Application Publication WO 39101950 or Japanese Patent Application Laid-open No. 1-18530.
It is disclosed in the specification of No. 7.

The present inventors investigated to obtain a cyclic olefin-based random copolymer with narrow molecular weight distribution and composition distribution, excellent uniformity, and improved transparency.
/V ratio in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound under specific conditions in a hydrocarbon medium or a liquid phase consisting of a cyclic olefin represented by the above general formula [I] or [n]. The inventors have discovered that the above object can be achieved by carrying out continuous copolymerization, and have arrived at the present invention.

In addition, JP-A-61-272216 discloses that when ethylene and a cyclic olefin different from the cyclic olefin used in the present invention are copolymerized in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound, A method for producing random cyclic olefins is disclosed, which is characterized in that Al 2 /V is maintained at 2 or more and copolymerization is carried out continuously.

Purpose of the Invention The present invention has been made in view of the above points, and provides a material with excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties. The object of the present invention is to provide a method for producing a cyclic olefin random copolymer having a narrow molecular weight distribution, a narrow composition distribution, and excellent uniformity.

Summary of the invention That is, according to the present invention, (a) ethylene, (b) the following formula [I] or [n] 1 16 [wherein R-R may be the same or different, respectively] , hydrogen, hydrocarbon group or) 10 gen,
Also R13 (or R14) and R15 (or R16)
may be linked to each other to form a monocyclic or polycyclic ring, and n is an integer of 0 or more [wherein l is 0 or an integer of 1 or more, m and n are 0.1 or 2,
R-R15 each independently represents a hydrogen atom, a halogen atom,
represents an atom or group selected from the group consisting of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group,
R (or R6) and R9 (or R7) have 1 carbon number
-3 may be bonded via an alkylene group, or may be bonded directly without any group. ] At least one cyclic olefin selected from the group consisting of unsaturated monomers represented by When copolymerizing in a liquid phase consisting of a cyclic olefin represented by [I] or [1] to produce a solution of a cyclic olefin random copolymer, aluminum atoms are substituted for vanadium atoms in the liquid phase of the polymerization reaction system. ratio (Al
/V) is maintained at 2 or more and copolymerization is carried out continuously.

DETAILED DESCRIPTION OF THE INVENTION The method for producing a cyclic olefin random copolymer according to the present invention will be specifically described below.

In the present invention, cyclic olefins such as pentacyclopentadecenes represented by the above general formula [1] or aromatic-containing cyclic olefins represented by the general formula [Ir] and ethylene are mixed in a hydrocarbon solvent. Copolymerization is carried out in the presence or absence of a catalyst consisting of a vanadium compound and an organoaluminum compound soluble in the solvent or in the above-mentioned cyclic olefins.

In producing the cyclic olefin random copolymer as described above, the copolymerization reaction between ethylene and pentacyclopentadecenes or aromatic-containing cyclic olefins is as follows:
It may also be carried out using a hydrocarbon solvent. Examples of hydrocarbon solvents that may be discarded include 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. These solvents can be used alone or in combination.

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

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

More specifically, ■0C13, ■0(QCH)CIt2, 5 ■0(OC2H5)2C11 VO(0-i+o-CH) C12, 7 VO(0-n-CH) CA' 2,9 VO (OCH) , V OB r 1V Cl
4.2 5 3 2 VOCI, VO(0-n-C4H,”) 3, ■C
Vanadium compounds such as 1.20C8H and 70H are used.

Electron donors that may be used when preparing the soluble vanadium catalyst component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides. Oxygen-containing electron donors such as silanes, alkoxysilanes, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates can be mentioned. More specifically, the number of carbon atoms in methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol, etc. Alcohols having 1 to 18 carbon atoms, which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol, etc.
20 phenols; acetone, methyl ethyl ketone,
Ketones having 3 to 15 carbon atoms such as methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone;
Aldehydes with 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate , methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, benzoate butyl acid, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate , cyclohexenecarboxylic acid di-n
-Hexyl, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, carbonic acid Carbon number 2 or more, such as ethylene
30 organic acid esters; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride; methyl ether;
Ethers with 2 to 20 carbon atoms such as ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; methylamine, ethylamine, diethylamine, Amines such as tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine; Nitriles such as acetonitrile, benzonitrile, tolnitrile; Alkoxysilanes such as ethyl silicate, diphenyldimethoxysilane, etc. Can be done. Two or more types of these electron donors can be used.

As the organoaluminum compound catalyst component, a compound having at least one AI-carbon bond in the molecule is used, for example, (where R and R2 are the number of carbon atoms, usually 1 to 15,
The hydrocarbon groups preferably contain 1 to 4 and may be the same or different from each other. X is halogen, m is 0≦m≦3,
n is a number of 0≦n<3, p is 0≦n<3, q is a number of 0≦q<3, and m+n+p+q=3), (i) a general formula MAIR ( Here, Ml is Li, 1 Na, and R1 is the first
Examples include complex alkylated products of group metals and aluminum.

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

General formula R', AI (OR2) -s (where R-p and R2 are the same as above. m is preferably 1,
.

(or 1.5≦m<3).

General formula R11AI X31 (wherein R1 is the same as above;

(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
) can be exemplified.

More specifically, aluminum compounds belonging to (1) include trialkylaluminiums such as triethylaluminum and tributylaluminium, trialkenylaluminums such as triisopropenylaluminum, dialkylaluminums such as diethylaluminium ethoxide, dibutylaluminum butoxide, etc. In addition to alkylaluminum sesquialkoxides such as alkoxides, ethylaluminum sesquiethoxide, and butylaluminum sesquibutoxide, partially alkoxylated alkoxides having a uniform composition of 2,50.5 expressed as 2 R' AI (OR> etc.) dialkylaluminum halides such as diethylaluminium chloride, dibutylaluminum chloride, diethylaluminum bromide, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide, ethylaluminum dichloride, Partially halogenated alkyl aluminum such as alkyl aluminum cybarides such as propyl aluminum dichloride, butyl aluminum dibromide etc., dialkyl aluminum hydride such as diethylaluminum hydride, dibutyl aluminum hydride, ethyl aluminum dicdride, probyl aluminum Partially hydrogenated alkyl aluminum such as alkyl aluminum halide such as dihydride, partially alkoxylated and halogenated alkyl aluminum such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy promide For example, compounds similar to (i) such as 2
It may also be an organic aluminum compound in which the above aluminum is bonded. Specifically, such compounds include (C2H5)2 AA' OAl (C2Hs)2,
(C4Hs)2 AI OAl (C4H9)2,6
H5 I can give an example.

As a compound belonging to the above (i), LiAn(CH)
, LiAl (C7H15)4, etc. can be cited as 54 examples. Among these, it is particularly preferable to use alkyl aluminum halides, alkylaluminium cybarides, or mixtures thereof.

In the present invention, the cyclic olefin used as a polymerization raw material has the above general formula [I] or general formula [■]
It is indicated by.

The pentacyclopentadecenes represented by the above general formula [I] used in the present invention have International Publication No. WO3
Synthesized by the method shown in 9101950 publication,
Specifically, the following compounds shown in Table 1 may be mentioned.

Further, the aromatic group-containing cyclic olefins represented by the above general formula [II] used in the present invention are
Specific examples include the following compounds synthesized by the method disclosed in JP 185307 and shown in Table 2.

In the present invention, ethylene and pentacyclo[4,7,0,+2508·Ij,
9"12. Pentadecene-3 or aromatic-containing cyclic olefins are randomly copolymerized, and these pentacyclopentadecenes or aromatic-containing cyclic olefins are described in Japanese Patent Application No. 1-244494. As described, the molar ratio of the endo form [1-A] and the exo form [I-B] represented by the following formula is 80/20 to 0/100.
It is desirable to use it as an isomer mixture.

(Here, pentacyclopentadecenes are shown as an example.) Below, the endo isomer [1-A] and the exo isomer [I-
The concept of B] will be explained using pentacyclopentadecenes as an example.

The molar ratio of the endo isomer [I-^] and the exo isomer as described above is 80/20 to O/100, preferably 70/3.
A mixture of isomers of pentacyclopentadecenes having a ratio of 0 to 5/95 can be obtained by the Diels-Alder reaction between cyclopentadiene and dihydrodicyclopentadiene or by dihydrodicyclopentadiene, as described above. 85 mol% or more, in many cases 90 mol% of the endo isomer [I-^], which is obtained by the reaction of dicyclopentadiene, which is thermally decomposed under reaction conditions to produce cyclopentadiene. In more cases, 94
By contacting a mixture of pentacyclopentadecene isomers in an amount of mol % or more with a solid acid as described below under conditions as described below, the endo isomer [1-A] is converted to the exo isomer [l-B1 It can be produced by isomerizing into

Specific examples of the solid acid used when isomerizing the endo isomer [1-A] to the exo isomer [I-B] in the pentacyclopentadecene isomer mixture as described above include:
Silica-alumina (mainly composed of human I2O3+5i02),
Alumina (mainly composed of 81203), zeolite (Na2
o+s i 02+^1203 is the main component), activated clay, etc.

Solid acids other than those mentioned above include the following acidic metal oxides or acidic metal sulfides, specifically, Cr OSP O1
TiO5A120323 23 2 x Cr O, A IO・Co OSA l 2
0 a23 23 ・Mn01Cr O-Fe O, MoS.

Examples include 23 23 MoS, CrO, CrOC1, MoO3, 2322 v O1WO2C12. In addition to the above 3 inorganic compounds, as a solid acid, Amberlyst 15
, Amberlite XE-284, Nafion-H, and other sulfonic acid group-containing crosslinked polymers.

The exo isomer [I-A] of the endo isomer [1-A] in the pentacyclopentadecene isomer mixture using such a solid acid
The isomerization reaction to B] is carried out by bringing the endo isomer into contact with a solid acid. At this time, the endo isomer may be brought into contact with the solid acid as is, or the endo isomer may be brought into contact with the solid acid in the presence of an organic solvent. may be brought into contact with a solid acid.

Specifically, such organic solvents include cyclohexane, decalin, hexane, benzene, carbon tetrachloride,
, 2-dichloroethane, etc. are used.

The contact reaction between the endo isomer [I-^] in the pentacyclopentadecene isomer mixture and the solid acid is preferably carried out at a temperature of -5 to 150°C, preferably 0 to 50°C. Although the reaction time varies greatly depending on the reaction temperature, it is preferably about 0.5 to 200 hours, preferably about 1 to 100 hours.

The contact reaction between the endo isomer [1-A] in the pentacyclopentadecene isomer mixture and the solid acid as described above can be carried out batchwise or continuously.

When the catalytic reaction between the endo isomer [IA] in the pentacyclopentadecene isomer mixture and the solid acid is carried out in a batchwise manner, for example, it may be carried out as follows.

A predetermined amount of pentacyclopentadecenes, an optionally predetermined amount of an organic solvent, and a solid acid are placed in a reaction tank equipped with a stirrer, and the mixture is stirred at a predetermined temperature for a predetermined period of time. after that,
The solid and liquid are separated by a filtration method, and the pentacyclopentadecenes in the liquid phase and the organic solvent are further separated by a distillation method.

Further, when the catalytic reaction between the exo form [I-B] in the pentacyclopentadecene isomer mixture and the solid acid is carried out in a continuous manner, for example, it may be carried out as follows.

(i) Using a device similar to the batch type described above, pentacyclopentadecenes or pentacyclopentadecenes diluted with an organic solvent are continuously supplied to the reaction tank, and the solid acid present in the reaction tank is A method of contacting and continuously extracting pentacyclopentadecenes or their organic solvent diluted products.

(i) A method in which pentacyclopentadecenes or pentacyclopentadecenes diluted with an organic solvent are supplied from one side of a tower (or column) packed with a solid acid and continuously extracted from the other side.

(i) In both methods (i), a distillation method can be employed to separate the pentacyclopentadecenes from the organic solvent after contact with the solid acid.

When the endo isomer [IA] in the pentacyclopentadecene isomer mixture is brought into contact with the solid acid catalyst in this way, the endo isomer [IA] is isomerized to the exo isomer [■-8].

The molar ratio of the endo isomer and the exo isomer in the structure or isomer mixture of the endo isomer [IA] and the exo isomer [I-8] can be determined by measuring 'H-NMR or 13CNMR. can.

Such endo-isomer [I-A] and exo-isomer [1-B
] The isomer mixture of pentacyclopentadecenes having a molar ratio of [ It can only be obtained by isomerizing I-^] to the exo form [I-8].

Such endo-isomer [I-A] and exo-isomer [I-A]
8], the molar ratio [IA] / [1-8] is 80/2
A cyclic olefin random copolymer obtained by copolymerizing a pentacyclopentadecene isomer mixture with a ratio of 0 to 0/100 and ethylene is an endo-isomer [I-
^] is present in an amount of 85 mol% or more, often 90 mol% or more, and in many cases 94 mol% or more, and a cyclic compound obtained by copolymerizing ethylene with a pentacyclopentadecene isomer mixture. Compared to olefin-based random copolymers, copolymers made by copolymerizing ethylene and pentacyclopentadecenes with the same composition have higher glass transition points (Tg) and TMA softening points. It has excellent heat resistance, has a large flexural modulus (FM), and has excellent mechanical strength. Therefore, in order to obtain the same glass transition point (Tg) or flexural modulus, the amount of copolymerization of expensive pentacyclopentadecenes can be reduced by using a mixture of isomers of pentacyclopentadecenes as described above. becomes possible.

The same phenomenon as above occurs with aromatic-containing cyclic olefins (general formula [
■]) are also observed.

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

Further, other copolymerizable unsaturated monomer components can be copolymerized as necessary within a range that does not impair the purpose of the present invention. Specifically, such copolymerizable unsaturated monomers include cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, in an amount less than equimolar to the cyclic olefin component unit in the random copolymer to be produced.
3a, 5.67a-tetrahydro-4,7-methano-1)1-indene(-fin, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl
Examples include non-conjugated dienes such as -1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene.

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

At that time, the concentration of the soluble vanadium compound supplied to the polymerization reaction system is usually 10 times or less, preferably 1 to 7 times, more preferably 1 to 5 times the concentration of the soluble vanadium compound in the polymerization reaction system. range.

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

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

Here, the soluble vanadium compound is preferably diluted to the above concentration range, but the organoaluminum compound may be prepared at an arbitrary concentration, for example, 50 times or less of the concentration in the polymerization reaction system, and then supplied to the polymerization reaction system. Adopted.

Further, when producing a cyclic olefin random copolymer, the concentration of the soluble vanadium compound in the copolymerization reaction system is usually 0.01 to 5 gram atoms/l, preferably 0.05 to 3 gram atoms/l as vanadium atoms. It is in the range of gram atom/1.

Such a copolymerization reaction of ethylene and pentacyclopentadecenes or aromatic-containing cyclic olefins is carried out at -5
It is carried out at a temperature of 0 to 100°C, preferably -30 to 80°C, more preferably -20 to 60°C.

The reaction time for carrying out the above copolymerization reaction (
In the case of a continuous polymerization reaction, the average residence time of the polymerization reaction mixture varies depending on the type of polymerization raw material, the concentration of the catalyst component, and the temperature, but is usually 5 minutes to 5 hours, preferably 1 hour.
It ranges from 0 minutes to 3 hours. Further, the pressure during the copolymerization reaction is usually more than 0 and 50 kg/ClIr, preferably more than 0 and 20 kg/car. Furthermore, during copolymerization, a molecular weight regulator such as hydrogen can be added under pressure in order to adjust the molecular weight of the resulting copolymer.

When producing a cyclic olefin-based random copolymer, the molar ratio of ethylene/pentacyclopentadecenes (or aromatic-containing cyclic olefins) is 9971 to 1/
99, preferably from 90/10 to 10/90, more preferably from 40/60 to 85/15.

When ethylene is copolymerized with pentacyclopentadecenes or aromatic-containing cyclic olefins as described above, a solution of a cyclic olefin random copolymer is obtained. The concentration of the cyclic olefin random copolymer contained in such a copolymer solution is usually 2.0 to 2.0.
100% by weight, preferably in the range 40-60% by weight.

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

The cyclic olefin random copolymer obtained in this way is immaculate or crystalline, but among the cyclic olefin random copolymers, it does not have a DSC melting point, and from the results of X-ray diffraction measurements, Amorphous copolymers are preferred. Further, the glass transition point (Tg) of the cyclic olefin random copolymer is usually in the range of 10 to 240°C, preferably 20 to 200°C.

The cyclic olefin random copolymer obtained in the present invention has transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance,
It has excellent dielectric properties and various mechanical properties, and its molecular weight distribution and composition distribution are narrow and uniform, so for example, its low molecular weight product is used as a synthetic wax for waxing, pine shaft impregnating agent, paper processing agent, and size. agent, rubber anti-aging agent, cardboard waterproofing agent, chemical fertilizer slowing agent, heat storage agent,
Ceramic binders, paper capacitors, electrical insulation materials such as electric wires and cables, neutron moderators, textile processing aids, water repellents for building materials, paint protection agents, polishing agents, thixotropy agents, pencil and crayon lead hardening agents, Carbon ink base material, toner for electrostatic copying, lubricant for synthetic resin molding, mold release agent,
It can be used in fields such as resin coloring aids, hot melt adhesives, and lubricating greases.

In addition, its polymers are used in optical fields such as optical lenses, optical disks, optical fibers, and glass window applications, water tanks for electric irons, microwave oven products, liquid crystal display substrates, printed circuit boards, high frequency circuit boards, transparent conductive sheets, etc. Electrical fields such as films, medical fields such as syringes, pipettes, animal cages, thermometers, beakers, petri dishes, graduated cylinders, bottles, artificial indirects, chromatography carriers, chemical fields, gas separation membranes, ultrafiltration membranes, reverse It can be used in a variety of fields including separation membranes such as osmotic membranes and gas-liquid separation membranes, camera bodies, housings for various instruments, films, helmets, toys, and stationery.

On the other hand, when the cyclic olefin content is about 20 mol % or less, it can be used in fields utilizing shape memory, vibration damping materials, or tubes.

Specifically, fittings for odd-shaped pipes, laminate materials for the inside and outside of pipes and rods, pins for tightening optical fiber connectors,
Casts, containers, various gap prevention materials for automobile bumpers, vibration damping materials (soundproofing materials) as laminates with metal surface materials, medical tubes, wrap films, protective films (metal plates,
It can be used in various fields such as heat sealable films (pipes, etc.).

Effects of the Invention The cyclic olefin random copolymer obtained by the method of the present invention has excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties, and has a low molecular weight. It is characterized by narrow distribution and composition distribution and excellent uniformity.

EXAMPLES Hereinafter, the method of the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Ethylene and pentacyclo[4,7,O,+2・5.19′120
8″13., -pentadecene (hereinafter abbreviated as PCPD-3)
A copolymerization reaction was carried out. In other words, from the top of the polymerization vessel
A cyclohexane solution of PD-3 was converted into PCP in a polymerization vessel.
0.41 per hour so that the D-3 concentration is 60 g/I. A cyclohexane solution of vO(OC2H5)C12 was used as a catalyst, and the vanadium concentration in the polymerization vessel was 0. 5o+mol
/AT 0.51 per hour (the concentration of vanadium supplied at this time is 2.86 times the concentration in the polymerization vessel), a cyclohexane solution of ethylaluminum 7C1) cyclohexane (AI (C2H5) 1.5 15) When the aluminum concentration in the polymerization vessel is 4.
On+mol/A! Cyclohexane and cyclohexane were continuously fed into the polymerization vessel at a rate of 0.41/hour and 0.71/hour so that That is, the sample is continuously extracted (so that the average residence time is 0.5 hours). In addition, using a bubbling pipe in the polymerization system, 20% of ethylene was added per hour.
11 Nitrogen is fed at a rate of 101/hour and hydrogen at a rate of 0.51/hour. The copolymerization reaction was carried out at 10° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel. When the copolymerization reaction is carried out under the above conditions, ethylene/PCPD
A polymerization reaction mixture containing a -3 random copolymer is obtained. A cyclohexane/isopropyl alcohol (1/1) mixed solution was added to the polymerization solution taken out from the bottom of the polymerization vessel to stop the polymerization reaction. Then, 5 parts of concentrated hydrochloric acid to 1 part of water
ml of the aqueous solution and the polymerization solution were brought into contact at a ratio of 1:1 under strong stirring using a homomixer, and the catalyst residue was transferred to a water tank. The above mixed solution was allowed to stand, and after removing the water tank, it was further washed twice with distilled water to purify and separate the polymerization solution.

The obtained polymerization liquid was brought into contact with three times the amount of acetone under strong stirring, and the solid portion was collected by filtration and thoroughly washed with acetone. After that, the obtained solid part was 40g/j! The mixture was poured into acetone and reacted at 60°C for 2 hours.

After that, the solid part was collected by filtration, and heated under nitrogen flow for 13 minutes.
It was dried for 24 hours at 0°C and 1350++ unHg.

In the manner described above, ethylene/PCPD-3 copolymer was obtained at a rate of 76 g/hour (ie, 38 g/l).

The ethylene composition of the copolymer measured by 3C-NMR analysis was 60.5 mol%, and the intrinsic viscosity measured in decalin at 135°C [η is 0. 61 dl 7g, iodine value is 1.0
Met.

The crystallinity by X-ray diffraction was 0%, and the transparency was 3.1% as measured on a 1M sheet using a haze meter according to ASTM D 1003-52.

The glass transition temperature Tg is D7namicM manufactured by DuPont.
The loss modulus E' was measured by mechanical analysis (DMA) at a heating rate of 5°C/M, and was found to be 149°C from the peak temperature. Roughly speaking, the melting point Tm was measured in the range of -1206C to 400C using a DuPont 990 type DSC at a heating rate of 10C/10C, and no melting curve (peak) was observed.

These results are summarized in Table 3.

Examples 2 to 4 Copolymerization was carried out continuously in the same manner as in Example 1 except that the copolymerization conditions were changed as shown in Table 3. The obtained physical properties are shown in Table 3.

Example 5 Instead of PCPD~3 as the cyclic olefin, 1.4-
A copolymer was synthesized in the same manner as in Example 1 except for using methanol-1,h,4,4a-tetrahydrofluorene (MTI (abbreviated as F)).The physical properties of the obtained copolymer are shown in Table 3.
It was shown to.

Comparative Example 1 A sufficiently dried 500 ml separable flask was equipped with a stirring blade, a gas blowing tube, a thermometer, and a dropping funnel, and the flask was sufficiently purged with nitrogen. 250 ml of cyclohexane, which had been dehydrated and dried using a molecular sieve, was placed in this flask. P as a cyclic olefin in a flask under nitrogen flow.
7.5g of CP D-3.

Ethylaluminum sesquichloride (AI (02C1)
0.1255 mmol of 0(OCH)C12 was added to H5) 1.5 1.5 0-t. A mixed gas of dry ethylene IQ//h+ and nitrogen 401/br was passed through a gas blowing tube into a flask controlled at 10° C. for 10 minutes. The copolymerization reaction was started by dropping ethylaluminum sesquichloride from the dropping funnel, and the batch copolymerization reaction was carried out at 10° C. for 30 minutes while passing the mixed gas. 5 ml methanol
was added to the polymerization solution to stop the copolymerization reaction, and the polymerization solution was poured into a large amount of methanol and acetone to precipitate the copolymer. After washing with acetone, the copolymer was vacuum-dried at 80°C overnight to precipitate the copolymer. A total of 3.4 g was obtained. The physical properties of the obtained copolymer were measured in the same manner as in Example 1.

The results are shown in Table 4.

Claims (1)

[Claims] 1. (a) Ethylene, (b) The following formula [I] or [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [In the formula, R^1~ Each of R^1^6 may be the same or different and is hydrogen, a hydrocarbon group, or a halogen, and R^1^3 (or R^1^4) and R^
1^5 (or R^1^6) may be linked to each other to form a monocyclic or polycyclic ring, and n is an integer of 0 or more. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [II] [In the formula, l is an integer of 0 or 1 or more, m and n
is 0, 1 or 2, and R^1 to R^1^5 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group. Represents an atom or group, R^5 (or R
^6) and R^9 (or R^7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group. ] At least one cyclic olefin selected from the group consisting of unsaturated monomers represented by When copolymerizing to produce a solution of a cyclic olefin random copolymer in a liquid phase consisting of a cyclic olefin represented by [I] or [II],
A method for producing a cyclic olefin random copolymer, which comprises continuously copolymerizing while maintaining the ratio of aluminum atoms to vanadium atoms (Al/V) in the liquid phase of a polymerization reaction system to 2 or more.