JPH03106909A - Cycloolefin random copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain the title copolymer excellent in heat resistance and mechanical strengths by randomly copolymerizing ethylene with a specified pentacyclopenandecene so as to form a specified constitution. CONSTITUTION:Ethylene is randomly copolymerized with a pentacyclo[4.7.0.1<2>,<5>.0<8>,<13>.1<9>,<12>]pentadecene-3 of formula I [wherein R<1-14> are each H, a hydrocarbon group or a halogen atom; and R<11>(R<12>) and R<13>(R<14>) may be combined to form a monocyclic or polycyclic ring] as an isomeric mixture of a molar ratio of an endo isomer to an exo isomer of 80/20-0/100 to form a copolymer consisting of 10-90mol% structural units derived from ethylene and 90-10mol% structural units derived from the pentacyclopentadecene, wherein the structural unit derived from the pentacyclopentadecene has a structure of formula III, and having an intrinsic viscosity in decalin at 135 deg.C of 0.05-10dl/g.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a cyclic olefin random copolymer and a method for producing the same, and more particularly to a cyclic olefin random copolymer having excellent heat resistance and mechanical strength, and Regarding the manufacturing method.

Technical Background of the Invention International Publication No. W089/01950 discloses that a cyclic olefin-based random copolymer obtained by copolymerizing ethylene and pentacyclopentadecenes (cyclic olefins) has excellent transparency. In addition to optical properties such as optical homogeneity and low birefringence, it also has heat resistance,
It is also described that it has excellent chemical resistance, dimensional stability, and mechanical properties.

Pentacyclopentadecenes used as cyclic olefins in producing such random copolymers are obtained by combining dihydrodicyclopentadienes, which are partially hydrogenated products of dicyclopentadiene, and cyclopentadienes as shown in the following formula. It is produced by a Diels-Alder reaction.

Pentacyclopentatadiene Bentadiene Decene end body l1-
^^ Pentacyclobentadecenes obtained by such a Diels-Alder reaction are an isomer of the endo form [IA] shown by the above formula and the exo form [I-Bl] shown by the following formula. However, since the cis-addition between cyclobentadiene and dihydrodicyclopentadienes proceeds preferentially, the endo-isomer [
I-Al is mainly produced, and the exo form [1-Bl is hardly viable.

In the pentacyclopentadecene isomer mixture obtained by the Diels-Alder reaction as described above, the endo isomer [! -^] is present in an amount of 85 mol% or more, often 90 mol% or more.

The present inventors conducted intensive studies to further improve the heat resistance and mechanical strength of the cyclic olefin random copolymer obtained by copolymerizing ethylene and pentacyclobentadecenes, and found that the raw materials The endo isomer [I-^] contained in the pentacyclopentadecene isomer mixture used as is contacted with a solid acid to obtain the exo isomer [1-B]
A cyclic olefin random copolymer obtained by copolymerizing a pentacyclopentadecene isomer mixture with a high exo isomer [I-B] content with ethylene is
It has been found that heat resistance and mechanical strength are dramatically improved.

Purpose of the Invention The purpose of the present invention is to provide a cyclic olefin random copolymer with improved heat resistance and mechanical strength obtained by copolymerizing ethylene and pentacyclopentadecenes, and a method for producing the same. .

Summary of the Invention The cyclic olefin random copolymer obtained by random copolymerization of ethylene and pentacyclopentadecenes according to the present invention comprises (A) ethylene, an endo isomer [■-^] represented by the following formula, and Exo body [I
-Molar ratio with Bl ([I-Al/[I-81)
Pentacyclo [4.
7. 0. , 2, 5. , 11, +3. ,9
．． +2 copentadecene-3 is randomly copolymerized, and CB) the structural unit derived from ethylene is present in an amount of 10 to 90 mol %, and the structural unit derived from the pentacyclopentadecene is 90 to 10 mol %. %, (C) the structural unit derived from the pentacyclopentadecenes has a structure represented by the following formula [II], and (D) 1
At 35°C, the endo isomer [IA] shown in decalin was 0.
．． It is characterized by being 05 to 10 dj/g.

R3 i9 l [In the formula, R - R14 may be the same or different, and represent hydrogen, a hydrocarbon group, or a halogen, and R11 (or R12) and R13 (or R1
and 4) may be linked to each other to form a monocyclic or polycyclic ring. ] R4R5R6R10 [In the formula, R-R14 is the same as above. ]1 Furthermore, the method for producing a cyclic olefin random copolymer in which ethylene and pentacyclopentadecenes are randomly copolymerized according to the present invention includes (A) ethylene and the endo isomer [A^] represented by the above formula. and exo body [I
- The molar ratio with Bl ([I-^]/[I-B co) is 80
/20 to O/100 pentacyclo [4. 7. 0
．． , 2, 5. , 8, 13. ,9. 12]
(B) in a hydrocarbon solvent or in the absence of a hydrocarbon solvent, in the presence of a catalyst consisting of a vanadium compound and an organoaluminum soluble in the hydrocarbon or the pentadecene-3 class; It is characterized by copolymerizing with.

According to the present invention, a cyclic olefin random copolymer having excellent heat resistance and mechanical strength can be obtained.

DETAILED DESCRIPTION OF THE INVENTION The cyclic olefin random copolymer and the method for producing the same according to the present invention will be explained in detail below.

The cyclic olefin random copolymer according to the present invention comprises ethylene and pentacyclo [4.
7. 0. 1" 5.08゜13.,9・12] pentadecene-3 is randomly copolymerized, and this pentacyclopentadecene is composed of the endo form [I-A] shown by the above formula and the exo form It is used as an isomer mixture in which the molar ratio with [I-8] is 80/20 to O/100.

In this specification, first, such a pentacyclopentadecene isomer mixture will be explained.

Method for producing isomer mixture Endo-isomer [IA] and exo-isomer [I-B] as described above
] and (7) mo/l, the ratio is 8 0/2 0-0/1 0
The isomer mixture of pentacyclopentadecenes, preferably from 70/30 to 5/95, can be prepared by the Diels Alder reaction of cyclopentadienes with dihydrodicyclopentadienes or by dihydrodicyclopentadienes, as described above. The endo-isomer [1
-A] in an amount of 85 mol% or more, often 90 mol% or more, and even more often 94 mol% or more, with a solid acid as described below. It can be produced by isomerizing the endo isomer [I-^] into the exo isomer [I-8] by contacting it under conditions as described below.

The pentacyclobentadecenes used in the present invention are synthesized by the method shown in International Publication No. WO89/01950, and specifically include the following compounds shown in Table 1.

Specifically, the solid acid used when isomerizing the endo isomer [IA] to the exo isomer [1-B] in the pentacyclopentadecene isomer mixture as described above is silica alumina. (ht 2 03 +Si02
is the main component), alumina (the main component is A12 03), zeolite (the main component is N120+Si02+^l2 03)
, activated clay, etc.

Solid acids other than those mentioned above include the following acidic metal oxides or acidic metal sulfides, specifically, CrO 1P O
STiO, AI20323 2i 2 xCr203, AI O ●CoO1Al20323 ●MnOSCr O ●Fe203, MoS123 M o S 2 , C r O , C r O C
Examples include I SM o 0 3, 3 2 2 v O SWO2Cl2, and the like. In addition to the above 23 inorganic compounds, as a solid acid, Amberlyst 15
, Amber Light I! Examples include organic compounds such as sulfonic acid group-containing crosslinked polymers such as -284 and Nafion-H.

The exo isomer [IA] of the endo isomer [IA] in the pentacyclobentadecene isomer mixture using such a solid acid.
The isomerization reaction to I-8] 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 an organic solvent. It may be contacted with a solid acid in the presence of the solid acid.

Specifically, such organic solvents include cyclohexane, decalin, hexane, benzene, carbon tetrachloride,
．． 2-dichloroethane or the like is used.

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

When carrying out the contact reaction between the endo isomer [IA] in the pentacycpentadecene isomer mixture and the solid acid in a batchwise manner, the reaction may be carried out, for example, 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 pentacyclobentadecenes and the organic solvent in the liquid phase are further separated by a distillation method.

Further, when the catalytic reaction between the exo form [I-B] in the mixture of pentacyclopentadecene isomers and the solid acid is carried out in a continuous manner, the reaction may be carried out, for example, 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 brought into contact with the solid acid present in the reaction tank. A method of 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.

In both methods (t) and (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 manner, the endo isomer [IA] is isomerized to the exo isomer [I-B].

The structures of endo isomer [I-Al and exo isomer [I-8] or the molar ratio of endo isomer and exo isomer in the isomer mixture are determined by H-NMR or l3c-NM.
It can be determined by measuring R.

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

Cyclic olefin random copolymer In the above-mentioned cyclic olefin random copolymer according to the present invention, the structural unit derived from ethylene is 1
It is desirable that the structural units derived from pentacyclobentadecenes are present in an amount of 0 to 90 mol%, preferably 40 to 85 mol%, and 90 to 10 mol%, preferably 60 to 15 mol%. .

In addition, in the above-mentioned cyclic olefin random copolymer, a small amount of other copolymerizable monomers such as norbornenes other than pentacyclopentadecenes, such as 5-ethylidene −
2-norbornene, dicyclopentadiene, tetracyclo [4. 4. 0. +2゜5. ,7. 10,
A small amount of dodecene-3 or an α-olefin other than ethylene may be copolymerized.

In the above-mentioned cyclic olefin-based random copolymer, the structural unit derived from pentacyclopentadecenes has a structure as shown by the following formula [n].

[In the formula, Rl-R14 is the same as above. ] Furthermore, it is preferable that the endo isomer [IA] of the ethylene/pentacyclopentadecene copolymer obtained by the present invention in decalin at 135° C. is 80/g.

The molar ratio [I-^]/CI-8] of the endo-isomer [■-^] and the exo-isomer [I4] according to the present invention is 8 0/2 0 to O
A cyclic olefin-based random copolymer obtained by copolymerizing a pentacyclopentadecene isomer mixture having a ratio of
Cyclic compound obtained by copolymerizing ethylene with a mixture of pentacyclobentadecene isomers in which A] is present in an amount of 85 mol% or more, often 90 mol% or more, and even more often 94 mol% or more. 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, and has a large flexural modulus (FM) and excellent mechanical strength. Therefore, in order to obtain the same glass transition temperature (TI) or flexural modulus,
By using the isomer mixture of pentacyclopentadecenes according to the present invention, it is possible to reduce the amount of copolymerization of expensive pentacyclopentadecenes.

Production of Cyclic Olefin Random Copolymer The above-mentioned cyclic olefin random copolymer according to the present invention comprises the above-mentioned endo form [I-A] and exo form [I-A].
-B], a pentacyclobentadecene isomer mixture having a molar ratio of 80/20 to 0/100;
ethylene in a hydrocarbon solvent or in the absence of a hydrocarbon solvent, a catalyst consisting of a vanadium compound and an organic aminium compound, preferably a halogen-containing organoaluminum compound, which is soluble in the solvent or in the pentacyclopentadecenes. It can be produced by copolymerization in the presence of.

When producing a cyclic olefin random copolymer, the copolymerization reaction of ethylene and pentacyclopentadecenes is carried out in the presence or absence of a hydrocarbon solvent. Hydrocarbon solvents that may be used at this time include:
Examples 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.

These solvents can be used alone or in combination.

Specifically, the vanadium compound has the general formula VO
(OR) X or v(OR)cXd! b (However, R is a hydrocarbon group, 0≦a≦3, 0≦b≦3,
2≦a'+b≦3, O≦C≦4, O≦d≦4, 3≦c+
A vanadium compound represented by d≦4) or an electron donor adduct thereof is used.

More specifically, vOC13, ■0(OC H )Cl2, 25 VO (QC2H5), CI, VO (0-iso- C3H,) Cl 2, VO (
0-n- C4H,)Cl2,VO(OCH
), VO Br SVCI 4, 2 5
3 2V O C l -
A vanadium compound such as VO(0-n-C4H9)3,2VCI-20C8H170H is used.

Electron donors that may be used when preparing the soluble vanadium catalyst include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, alcohols, acid amides, etc. Examples include oxygen-containing electron donors such as , acid anhydrides, and alkoxysilanes, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol Alcohols having 1 to 18 carbon atoms such as cumyl alcohol and isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol,
Phenols with 6 to 20 carbon atoms that may have a lower alkyl group, such as probylphenol, nonylphenol, cumylphenol, and naphthol; 3 to 15 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, penzophenone, and benzoquinone. Ketones; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, blobionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, proyl acetate, octal acetate, acetic acid cyclohexyl,
Ethyl probionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, benzoic acid Brovil, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, methyl Diisobutyl malonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisobutyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, ditoptyl phthalate, di-2 phthalate
- Organic acid esters with 2 to 30 carbon atoms such as ethylhexyl, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; 2 to 30 carbon atoms such as acetyl chloride, penzoyl chloride, toluyl chloride, anisyl chloride, etc. 15 acid halides; 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 amide, toluic acid Acid amides such as amides; methylamine, ethylamine,
Amines such as diethylamine, tributylamine, biperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine; acetonitrile,
Nitriles such as penzonitrile and tolnitrile; alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane; and the like. 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, a compound containing 15, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. good. X is halogen, m is O≦
m≦3, n is O≦n<3, p is 0≦n<3, q is 0≦q
<3, and m+n+p+q=3)
an organoaluminum compound represented by I1 (i) a first compound represented by the general formula MAtR (where Ml is Li, 4 Na, K, and R1 is the same as above);
Examples include complex alkylated products of group metals and aluminum.

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

(Here, R and R2 are the same as above. m is preferably l (or 1.5≦m<3).

General formula RIIIAIIX31 (wherein R1 is the same as above, X is halogen, and m is preferably 0<m<3).

(Here, Rl is the same as above. m is preferably 2≦m<3
).

Gen, 0<m≦3, 0≦n<3, O≦q<3, m +
Examples include those expressed by n + Q = 3).

More specifically, the aluminum compounds belonging to (i) include trialkyl aluminum such as triethylaminium and triptylaluminium, trialkenyl aluminum such as triisopropenyl aluminum, dialkyl such as diethylaluminum ethoxide, dibutyl aluminum butoxide, etc. Aluminum alkoxides, partially alkoxylated aluminum alkyls such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminium bromide, ethylaluminum sesquichloride , alkylaluminum sesquihalides such as butylaluminum sesquichloride, ethylaluminum sesquipromide, ethylaluminum dichloride,
Probylaluminum dichloride, butylaluminum dipromide, etc. Partially halogenated alkyl aluminum dihalides such as alkyl aluminum dihalides, dialkyl aluminum hydrides such as diethylaluminum hydride, diptylaluminum hydride, alkyl aluminum dihydrides such as ethyl aluminum dihydride, probylaluminum dihydride, etc. Examples include partially hydrogenated aluminum alkyls, ethylaluminum ethoxy chloride, butylaluminum poxychloride, ethylaluminum ethoxybromide and the like. 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 ) AIOAl (C2H5)2,2 5
2 (C H ”) A70Al (C4H9)2
, 4 5 2 examples can be given.

As a compound belonging to the above (i), LiA1(C
H), LiAI (C7H1s)4, etc.
5 4 I can give examples. Among these, it is particularly preferable to use alkyl aluminum halides, alkylaluminium dihalides, or mixtures thereof.

When producing a cyclic olefin random copolymer, the copolymerization reaction between ethylene and the above pentacyclopentadecenes is preferably 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 addition, the ratio of aluminum atoms to vanadium atoms (Al/V) in the polymerization reaction system is 2 or more, preferably 2.
-50, particularly preferably 3-20.

The soluble vanadium compound and the organoaluminum compound are usually supplied diluted with the hydrocarbon solvent or pentacyclopentadecenes, 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/It, preferably 0.05 to 3 gram atoms/It as vanadium atoms. gram atom/l
is within the range of

Such a copolymerization reaction of ethylene and pentacyclopentadecenes is carried out at -50 to 100°C, preferably -30 to 100°C.
It is carried out at a temperature of 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/al, preferably more than 0 and 20 kg/Ci.

When producing a cyclic olefin random copolymer, the molar ratio of ethylene/pentacyclobentadecenes is as follows:
Usually, the range is preferably 90/10 to 10/90, preferably 40/60 to 85/15.

When the copolymerization reaction between ethylene and betacyclobentadecenes is carried out as described above, a solution of a cyclic olefin random copolymer is obtained. The concentration of the cyclic olefin random copolymer contained in such a copolymer solution is usually 2.0 to 100% by weight, preferably 40 to 6% by weight.
The resulting copolymer solution also contains a portion of a soluble vanadium compound and an organoaluminium compound component as a catalyst.

The solution of the cyclic olefin random copolymer obtained as described above is usually subjected to a series of treatments ranging from deagglomeration to pelletization to obtain pellets of the cyclic olefin random copolymer.

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

Quantification method Pentacyclo [4. 7. 0. +2゜5.08・I
j t9, 12] pentadecene-3 (Pct' (abbreviated as l)) The molar ratio of the endo isomer [IA] and the exo isomer [IB] in the isomer mixture is 'C-NMR (C6
D6 (at room temperature, TMS standard) was measured and calculated based on the integrated intensity ratio of the absorption peak of olefin carbon in the obtained spectrum. Table 2 shows pentacyclo [4.
7. 0. 12°5O8, Ij, 9. 12]
The chemical shift of olefin protons obtained by measuring IH-NMR of pentadecene-3 (PCFD) and the chemical shift of carbon obtained by measuring 13C-NMR are shown.

Furthermore, Table 3 shows the 13C of ethylene-PCPD copolymer.
-The chemical shift of carbon obtained by measuring NMR is shown.

Method for Measuring Softening Temperature Samples for measuring softening temperature obtained by molding each of the copolymers obtained in the polymerization examples and comparative polymerization examples into a sheet with a thickness of 1 mI1 were measured using a DuPont thermomechanical analyzer (ThermomechsnicxlAn!).
Thermal deformation behavior was measured using a microcomputer (lrser). That is, a quartz needle was placed on the sample, and the sample was heated continuously at a heating rate of 5°C/min with a load of 49 g applied to the measuring needle until the measuring needle was in the sample. .63
The temperature when the penetration was 5 mm was defined as the softening temperature. (TMA
Measuring method of flexural modulus (hereinafter referred to as softening point) The flexural modulus was measured at a temperature of 23°C using ASTJ-07
The measurement was carried out according to the method described in 90.

Method for Measuring Intrinsic Viscosity Intrinsic viscosity was measured at a temperature of 135° C. using decalin as a solvent.

Examples Reference Example 1 and the obtained dihydrodicyclopentadiene (aOl
) and dicyclopentadiene according to International Publication No. WO8.
Performed by the method described in 9/01950 publication Example 1,
Pentacyclo[4. 7. O. 12"5.0g.+
3.9, +2, and entadecene-3 (abbreviated as PCPD) were obtained.

The obtained PCPD was measured by 13C-NMR, and the molar ratio of the endo isomer and the exo isomer was determined. End body is 9
The exo form was present in an amount of 5.7 mol% and 4.3 mol%.

The results are shown in Table 4.

Reference Example 2 In Reference Example 1, when the partially hydrogenated product of dicyclopentadiene was combined, the ratio of the endo isomer and the exo isomer of dimethyl-PCPD obtained from dicyclopentadiene was 97.0 mol%/3, It was O mol%.

The results are shown in Table 4.

Synthesis Example 1 In a 30 l reaction tank equipped with a stirring device and a reflux condenser,
PCPD ljl obtained in Reference Example 1 and cyclohexane 171 were added and stirred.

Add zeolite (manufactured by Toyo Soda Co., Ltd., Zeolum) to the obtained solution.
F-9, spherical "1-1.s~2.4mφ, Ni2
0.AlO a2.5SiO2) 12 kg was added and stirred at room temperature for 236 hours to carry out an isomerization reaction of the endo isomer to the exo isomer.

After the reaction was completed, the reaction mixture was filtered to separate the catalyst, and the resulting cyclohexane solution of PCPD was filtered under reduced pressure (5G++a
Cyclohexane was distilled off under H1) to obtain isomerized PCPD.

When the obtained PCPD was analyzed by 'C-NMR, the molar ratio of the endo isomer and the exo isomer was 42.8/57.2.
Met.

The results are shown in Table 4.

Synthesis Example 2 The isomerization reaction of PCPD was carried out in the same manner as in Synthesis Example 1 except that the reaction time was 3 hours.

The results are shown in Table 4.

Synthesis Example 3 As a catalyst, silica alumina (manufactured by Shinagawa Shirorenga Co., Ltd., Segard OW, granular, 0.5 to 2 mm φ, AI OL
1mSiO *nll20+AI (OH) ) was used at 2 3 2 3, and the amounts of cyclohexane and catalyst were 4.01 and 3 kg, respectively.
The reaction was carried out in the same manner as in Synthesis Example 1, except that the reaction time was changed to 96 hours.

The results are shown in Table 4.

Synthesis Example 4 The reaction was carried out in the same manner as in Synthesis Example 1 except that dimethyl-PCPD obtained in Reference Example 2 was used.

The results are shown in Table 4.

Synthesis Example 5 The reaction was carried out in the same manner as in Synthesis Example 4 except that the reaction time was changed to 3 hours.

The results are shown in Table 4.

Synthesis Example 6 The reaction was carried out in the same manner as Synthesis Example 4 except that the silica alumina used in Synthesis Example 3 was used as a catalyst and the reaction time was 96 hours.

The results are shown in Table 4.

Example 1 A cyclohexane solution of PCPD obtained in Synthesis Example 1 was added continuously from the top of the polymerization vessel to a 2-liter glass polymerization vessel equipped with a stirring device, and VO(QC H )CA'2 was added as a catalyst.
cyclohexane solution 25 and ethylaluminum sesquichloride (AICI
) cyclohexane solution "2 '5) 1.5 1.5, the concentration in the polymerization vessel was 60 g/l, 0, 5 mmol/1, 4, respectively.
．． Ethylene was supplied from the top of the polymerization vessel at a rate of 151/hour and hydrogen at a rate of 0.51/hour. On the other hand, the total amount of polymerization liquid in the polymerization vessel continuously from the bottom of the polymerization vessel becomes 11, and the average residence time is 0.5.
I pulled it out in time.

The polymerization reaction was carried out at a polymerization temperature of 10° C. by circulating a refrigerant through a cooling jacket provided outside the polymerization vessel.

A copolymerization reaction was carried out under the above reaction conditions to obtain a polymerization reaction mixture containing an ethylene/PCPD random copolymer. The polymerization reaction was stopped by adding a small amount of isopropyl alcohol to the polymerization liquid taken out from the bottom of the polymerization vessel. Next, this polymerization solution is rotated in a mixer containing about 3 times the volume of acetone, and the polymerization solution after the reaction has been stopped is added thereto to precipitate the copolymer, and then the precipitated copolymer is filtered. It was separated from the solution by The resulting copolymer was dispersed in acetone to a concentration of about 50 g/I, and the mixture was further heated at the boiling point of acetone for about 2 hours. After the treatment, the copolymer was separated from the acetone by filtration and dried under reduced pressure at 120° C. for 24 hours.

Regarding the obtained copolymer of ethylene and PCPD, "C-
When NMR was measured, the ethylene content in the copolymer was 62.0 mol%. Further, the intrinsic viscosity [η] and TMA softening temperature were 0.40 dl/g and 183°C, respectively.

The results are shown in Tables 5 and 6.

In addition, when the molar ratio of the endo isomer and the exo isomer of PCPD contained in the obtained copolymer was measured by 13C-NMR, the endo isomer/exo isomer ratio was 4 2/5 8, and the value There was almost no change before and after polymerization.

Examples 2 to 8, Comparative Examples 1 to 2 Using the raw materials (PCPDs) shown in Table 5,
Copolymerization of ethylene and PCPDs was carried out in the same manner as in Example 1 under the conditions shown below.

The results obtained are shown in Table 6.

As shown in the above Examples and Comparative Examples, endo body [
I-A] is present in an amount of 85 mol% or more, often 90 mol% or more, and even more often 94 mol% or more, by copolymerizing ethylene with a mixture of pentacyic pentadecene isomers. Compared with the obtained cyclic olefin random copolymers (Comparative Examples 1 and 2), the molar ratio of the endo form [I-^] and the exo form [I-B co] according to the present invention [I-A]/ [I-8] is 8 0/2 0~0/
Cyclic olefin random copolymers (Examples 1 to 8) obtained by copolymerizing a pentacyclopentadecene isomer mixture such as 100 with ethylene, ethylene and pentacyclopentadecene are In the case of a copolymer made by copolymerizing with almost the same composition, the TMA softening point is high and the heat resistance is excellent, and the flexural modulus (FM
) becomes large, indicating that the mechanical strength is excellent.

Examples 9 to 11, Comparative Example 3 Using raw materials (dimethyl PCPD) as shown in Table 7,
Copolymerization of ethylene and dimethyl PCPD was carried out in the same manner as in Example 1 under the conditions shown in Table 7.

The results obtained are shown in Table 8.

The copolymers using dimethyl PCPD with a high exo-isomer [I-B] content obtained in Examples 9 to 11 were prepared in Comparative Example 3.
It can be seen that both the TMA softening point and flexural modulus are improved compared to the copolymer obtained in .

Claims (1)

[Scope of Claims] 1) (A) Ethylene, the endo isomer [I-A] and the exo isomer [I-A] represented by the following formula:
-B], the molar ratio ([I -A]/[I -B]) is 8
Pentacyclo[4,7,0. ＿１
2,5__. _08,13_. _19,12] pentadecene-3 is randomly copolymerized, (B) the structural unit derived from ethylene is present in an amount of 10 to 90 mol%, and the structural unit derived from the pentacyclopentadecene is present in an amount of 90 to 10 mol%, (C) the structural unit derived from the pentacyclopentadecene has a structure represented by the following formula [II], (D) the limit measured in decalin at 135 ° C. Viscosity [η]
A cyclic olefin-based random copolymer obtained by random copolymerization of ethylene and pentacyclopentadecenes, characterized in that the cyclic olefin random copolymer is 0.05 to 10 dl/g. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[ I -B] [In the formula, R^1 to R^1^4 may be the same or different, and represent hydrogen, a hydrocarbon group, or It is a halogen, and also R^1^1 (or R^1^2) and R^
1^3 (or R^1^4) may be linked to each other to form a monocyclic or polycyclic ring. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [III] [In the formula, R^1 to R^1^4 are the same as above. ]2
) (A) Ethylene, the endo isomer [I-A] and the exo isomer [I
-B], the molar ratio ([I -A]/[I -B]) is 8
Pentacyclo[4.7.0_. ＿
12,5__. _08,13_. _19,12] pentadecene-3 from (B) a vanadium compound and an organoaluminum soluble in the hydrocarbon or the pentacyclopentadecene in a hydrocarbon solvent or in the absence of a hydrocarbon solvent. A method for producing a cyclic olefin random copolymer obtained by random copolymerization of ethylene and the pentacyclopentadecenes, the method comprising copolymerizing in the presence of a catalyst. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I -B] [In the formula, R^1 to R^1^4 are each the same may be hydrogen, a hydrocarbon group, or a halogen, and R^1^1 (or R^1^2) and R^
1^3 (or R^1^4) may be linked to each other to form a monocyclic or polycyclic ring. ]