JP2795486B2 - Cyclic olefin random copolymer and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a cyclic olefin-based random copolymer and a method for producing the same, and more particularly, to a cyclic olefin-based random copolymer excellent in heat resistance and mechanical strength and a method thereof. It relates to a manufacturing method.

Technical background of the invention The present applicant has previously described that a cyclic olefin random copolymer obtained by copolymerizing ethylene and tetracyclododecenes has excellent transparency, heat resistance, heat aging resistance, and chemical resistance. It has been found that it is a synthetic resin with a good balance of properties, solvent resistance, dielectric properties, and mechanical properties, and exhibits excellent performance in the field of optical materials such as optical memory disks and optical fibers. No. 60-168708, Japanese Patent Application No. 59-220550, Japanese Patent Application No. 59-236828, Japanese Patent Application No.
No. 59-236829, Japanese Patent Application No. 59-242336, Japanese Patent Application No. 61-95906
No. proposed.

Tetracyclododecenes used for producing such a random copolymer are produced by subjecting norbornenes and cyclopentadienes to a Diels-Alder reaction as shown in the following formula.

The tetracyclododecenes obtained by such a Diels-Alder reaction are isomers of an endo-form [IA] represented by the above formula and an exo-form [IB] represented by the following formula Although it is obtained as a mixture, the cis-addition of cyclopentadiene and norbornene proceeds preferentially, so that the endo-form [IA] is mainly formed and the exo-form [IB] is hardly formed.

In the tetracyclododecene isomer mixture obtained by the above-described Diels-Alder reaction, the endo-form [IA] contains 85 mol% or more, often 90 mol%.
It is present in the above amounts.

The present inventors have conducted intensive studies to further improve the heat resistance and mechanical strength of a cyclic olefin random copolymer obtained by copolymerizing ethylene and tetracyclododecenes as described above. [I-] contained in the tetracyclododecenes isomer mixture used as
A] is contacted with a solid acid to isomerize to an exo form [IB], and a cyclic olefin obtained by copolymerizing a mixture of tetracyclododecene isomers having a high exo form [IB] content with ethylene. The system random copolymer was found to dramatically improve heat resistance and mechanical strength.

Object of the Invention The present invention has an object to provide a cyclic olefin-based random copolymer having improved heat resistance and mechanical strength obtained by copolymerizing ethylene and tetracyclododecenes, and a method for producing the same. I have.

SUMMARY OF THE INVENTION The cyclic olefin-based random copolymer obtained by random copolymerization of ethylene and tetracyclododecenes according to the present invention comprises: (A) ethylene; and an endo-form [IA] represented by the following formula: Exo form [I
-B] ([IA] / [IB]) is 80/20.
Tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] represented by the following formula as a mixture of isomers is ~0 / 100 [I] dodecene -3
And (B) the structural unit derived from ethylene is present in an amount of 10 to 90 mol%, and the structural unit derived from the tetracyclododecene is in an amount of 90 to 10 mol%. (C) a structural unit derived from the tetracyclododecenes has a structure represented by the following formula [II]; and (D) an intrinsic viscosity [η] measured in decalin at 135 ° C.
It is characterized by being 0.05 to 10 dl / g.

[Wherein, R ^{1 to} R ¹² may be the same or different, and each represents a hydrogen, a hydrocarbon group, or a halogen;
R ⁹ (or R ¹⁰ ) and R ¹¹ (or R ¹² ) may be linked to each other to form a ring. ] [Wherein, R ^{1 to} R ¹² are the same as above. Further, the method for producing a cyclic olefin-based random copolymer in which ethylene and tetracyclododecenes are randomly copolymerized according to the present invention comprises: (A) ethylene and an end product [IA] represented by the above formula. And the exo form [I
-B] ([IA] / [IB]) is 80/20.
Tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] represented by the following formula as a mixture of isomers is ~0 / 100 [I] dodecene -3
(B) in a hydrocarbon solvent or in the absence of a hydrocarbon solvent in the presence of a catalyst comprising a vanadium compound and an organoaluminum soluble in the hydrocarbon or the tetracyclododecenes It is characterized by copolymerization.

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

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

Cyclic olefin random copolymer according to the present invention,
Ethylene and tetracyclo [4,
4,0,1 ^2.5 , 1 ^7.10 ] dodecene-3s are randomly copolymerized, and the tetracyclododecene-3s are obtained by the endo-form [IA] and the exo-form [I -B] is used as an isomer mixture having a molar ratio of 80/20 to 0/100.

In this specification, such a tetracyclododecene-3 isomer mixture will be described first.

Method for producing isomer mixture Endo form [IA] and exo form [I-
B] is 80/20 to 0 to 100, preferably 70/30 to 5/9.
The tetracyclododecenes isomer mixture such as 5 is obtained by a Diels-Alder reaction between cyclopentadienes and norbornenes as described above,
85% by mol or more of endo-form [IA], often 90%
By contacting a tetracyclododecene isomer mixture containing at least mol%, more often at least 94 mol% with a solid acid as described below under the conditions as described below, an endo-form [ IA] to an exo form [IB].

As the tetracycldodecenes used in the present invention,
Specific examples include the following compounds.

As the solid acid used for isomerizing the endo-form [IA] into the exo-form [IB] in the above-mentioned tetracyclododecene isomer mixture, specifically, silica-alumina (Mainly composed of Al ₂ O ₃ + SiO ₂ ), alumina (Al ₂ O ₃
Zeolites (mainly composed of Na ₂ O + SiO ₂ + Al ₂ O ₃ ), activated clay, and the like. There are acidic metal oxide or acidic metal sulfide as a solid acid other than the above, _{specifically, Cr 2 O 3, P 2} O 3, TiO 2, Al 2 O 3 · xCr 2 O 3,
Al ₂ O ₃ .CoO, Al ₂ O ₃ .MnO, Cr ₂ O ₃ .Fe ₂ O ₃ , MoS, MoS ₂ , C
rO ₃ , CrO ₂ Cl ₂ , MoO ₃ , V ₂ O ₃ , WO ₂ Cl _{2 and the} like.
In addition to the above inorganic compounds, Amberlyst 1 as a solid acid
5, organic compounds such as sulfonic acid group-containing crosslinked polymers such as Amberlite XE-284 and Nafion-H.

The exo form [I-] of the endo form [IA] in the tetracyclododecene isomer mixture using such a solid acid.
The isomerization reaction to B] is carried out by bringing the endo form into contact with a solid acid. In this case, the endo form may be brought into contact with a solid acid as it is, or the endo form may be brought into contact with an organic solvent. May be contacted with a solid acid.

As such an organic solvent, specifically, cyclohexane, decalin, hexane, benzene, carbon tetrachloride,
1,2-dichloroethane and the like are used.

The contact reaction between the endo-form [IA] in the tetracyclododecene isomer mixture and the solid acid is desirably performed at a temperature of -5 to 150 ° C, preferably 0 to 50 ° C. In addition, the reaction time varies greatly depending on the reaction temperature, but is not limited to 0.1.
It is desirably about 5 to 200 hours, preferably about 1 to 100 hours.

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

When the contact reaction between the endo-form [IA] in the tetracyclododecene isomer mixture and the solid acid is performed in a batch system, specifically, for example, the following method may be used.

A predetermined amount of tetracyclododecenes, a predetermined amount of an organic solvent and, if necessary, a solid acid are charged into a reaction vessel equipped with a stirrer, and the mixture is stirred at a predetermined temperature for a predetermined time. Thereafter, the solid / liquid is separated by a filtration method, and the tetracyclododecenes and the organic solvent in the liquid phase are further separated by a distillation method.

Further, when the contact reaction between the exo form [IB] in the tetracyclododecene isomer mixture and the solid acid is carried out in a continuous manner, specifically, for example, the following method may be used.

(I) Using a device similar to the batch type described above, tetracyclododecenes or tetracyclododecenes diluted with an organic solvent is continuously supplied to the reaction tank, and the solid acid present in the reaction tank is removed. A method of contacting and continuously extracting tetracyclododecenes or a diluted organic solvent thereof.

(Ii) A method in which tetracyclododecenes or tetracyclododecenes diluted with an organic solvent are supplied from one of columns (or columns) packed with a solid acid, and continuously extracted from the other.

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

When the endo-form [IA] in the tetracyclododecenes isomer mixture is thus contacted with a solid acid catalyst,
The endo-form [IA] isomerizes to the exo-form [IB].

The structure of the endo-form [IA] and the exo-form [IB] or the molar ratio of the endo-form to the exo-form in the mixture of isomers is determined by measuring ¹ H-NMR or ¹³ C-NMR. be able to.

Such endo-form [IA] and exo-form [IB]
A mixture of isomers of tetracyclododecenes having a molar ratio of isomer cannot be directly obtained by the Diels-Alder reaction between cyclopentadiene and norbornene, and the endo-form [IA] is converted to the exo-form. It can be obtained only by isomerizing to [IB].

In the cyclic olefin-based random copolymer as described above according to the present invention, the structural unit derived from ethylene is
Desirably, the constituent units derived from tetracyclododecenes are present in an amount of 10 to 90 mol%, preferably 40 to 85 mol%, and in an amount of 90 to 10 mol%, preferably 60 to 15 mol%. .

In the cyclic olefin-based random copolymer as described above, a small amount of other copolymerizable monomers such as norbornenes other than tetracyclododecenes or α other than ethylene, as long as the object of the present invention is not impaired. -An olefin or the like may be copolymerized in an amount of 10 mol% or less of the constitutional unit derived from tetracyclododecenes.

In the above-mentioned cyclic olefin random copolymer, the structural unit derived from tetracyclododecenes has a structure represented by the following formula [II].

[Wherein, R ^{1 to} R ¹² may be the same or different, and each represents a hydrogen, a hydrocarbon group, or a halogen;
R ⁹ (or R ¹⁰ ) and R ¹¹ (or R ¹² ) may be linked to each other to form a ring. The intrinsic viscosity [η] of the ethylene / tetracyclododecene copolymer obtained in the present invention measured in decalin at 135 ° C. is preferably 0.05 to 10 dl / g.

The endo-form [IA] and the exo-form [I-
B] and the molar ratio [IA] / [IB] is 80/20 to 0/100.
A tetracyclododecene isomer mixture such that
The cyclic olefin-based random copolymer obtained by copolymerizing ethylene and ethylene has an end-form [IA] of at least 85 mol% or more, more than 90 mol%, and more often at least 94 mol%. In comparison with a cycloolefin random copolymer obtained by copolymerizing tetracyclododecene isomer mixture and ethylene present in an amount, ethylene and tetracyclododecene are copolymerized with the same composition. In the case of such a copolymer, the glass transition point (Tg) is high and the heat resistance is excellent, and the flexural modulus (FM) is large and the mechanical strength is excellent. Therefore, in order to obtain the same glass transition point (Tg) or flexural modulus, the tetracyclododecene isomer mixture according to the present invention is used.
It becomes possible to reduce the copolymerization amount of expensive tetracyclododecenes.

Production of Cyclic Olefin-Based Random Copolymer The above-mentioned cyclic olefin-based random copolymer according to the present invention has a molar ratio of the endo-form [IA] to the exo-form [IB] as described above. A mixture of tetracyclododecene isomers such as 80/20 to 0/100 and ethylene,
In a hydrocarbon solvent or in the absence of a hydrocarbon solvent, in the presence of a catalyst comprising a vanadium compound and an organic aminium compound, preferably a halogen-containing organic aluminum compound, which are soluble in the solvent or the tetracyclododecenes. It can be produced by copolymerization.

In producing a cyclic olefin-based random copolymer, a copolymerization reaction between ethylene and tetracyclododecenes is carried out in the presence or absence of a hydrocarbon solvent. Examples of the hydrocarbon solvent that may be used in this case 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. Hydrogen and the like can be exemplified. These solvents can be used alone or as a mixture.

As the vanadium compound, specifically, the general formula VO
(OR) _a X _b or V (OR) _c X _d (where R is a hydrocarbon group, 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c
≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4) or an electron donor adduct thereof. More specifically, VOCl ₃ , VO (OC ₂ H ₅ ) Ol ₂ , V
O (OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , VO (On
−C ₄ H ₉ ) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ , VOCl ₂ , VO
Vanadium compounds such as (On-C ₄ H ₉ ) ₃ and VCl ₃ .2OC ₈ H ₁₇ OH are used.

Further, as the electron donor that may be used when preparing the soluble vanadium catalyst component, alcohol,
Oxygen-containing electron donors such as phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates Body and the like. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol,
C1-C18 alcohols such as phenylethyl alcohol, cumyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol,
C6-20 phenols which may have a lower alkyl group such as propylphenol, nonylphenol, cumylphenol and naphthol; C3-15 phenols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; Ketones; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octal acetate, cyclohexyl acetate; Ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, cyclohexa Carboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate,
Ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisosopropyl tetrahydrophthalate, diethyl phthalate, phthalate Carbon number 2 such as diisobutyl acid, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc.
Organic acid esters having up to 30; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole Ethers having 2 to 20 carbon atoms such as amide, diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline And amines such as tetramethylenediamine; nitriles such as acetonitrile, benzonitrile and trinitrile; and alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane. Kill. Two or more of these electron donors can be used.

As the organoaluminum compound catalyst component, a compound having at least one solid Al-carbon bond in the molecule is used. For example, (i) a general formula R ¹ _m Al (OR ² ) _n H _p X _q (where R ¹ and R ² are hydrocarbon groups each having 1 to 15 carbon atoms, preferably 1 to 4, preferably 1 to 4, which may be the same or different, X is a halogen, m is 0 ≦ m ≦ 3, and n is 0 ≦ n <3, p is 0 ≦
n <3, q is a number of 0 ≦ q <3, and m + n +
p + q = 3 a is) an organoaluminum compound represented by, (ii) the general formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na, K, R
¹ is the same as described above), and a complex alkylated product of a Group 1 metal and aluminum, and the like.

The following can be exemplified as the organoaluminum compound belonging to the above (i).

General formula R ¹ _m Al (OR ² ) _3-m (where R ₁ and R ² are the same as above. M is preferably 1.5
≦ m <3).

General formula R ¹ _m AlX _3-m (where R ¹ is the same as above; X is halogen, m is preferably 0 <m <3).

General formula R ¹ _m AlH _3-m (where R ¹ is the same as above, m is preferably 2 ≦ m <3).

General formula R ¹ _m Al (OR ² ) _n X _q (where R ¹ and R ² are the same as above. X is a halogen, 0 <
m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

In the aluminum compound belonging to (i), more specifically, trialkylaluminum such as triethylaminium and tributylaluminum, trialkenylaluminum such as triisopropenylaluminum,
Diethylaluminum ethoxide, dialkylaluminum alkoxides such as dibutyl aluminum butoxide, ethyl aluminum sesqui ethoxide, in addition to alkylaluminum sesqui alkoxides such as butyl sesquichloride butoxide, an average composition represented by such _{^{R 1 2.5 Al (OR 2)}} 0.5 Having partially alkoxylated alkylaluminum, diethylaluminum chloride, dibutylaluminum chloride, dialkylaluminum halide such as diethylaluminum bromide, ethylaluminum sesquichloride, butylaluminum sesquichloride, alkylaluminum sesquibromide such as ethylaluminum sesquibromide , Ethyl aluminum dichloride, propyl aluminum dichloride, butyl alcohol Partially halogenated alkyl aluminum such as alkyl aluminum dihalide such as luminium dibromide, dialkyl aluminum hydride such as diethyl aluminum hydride, dibutyl aluminum hydride, alkyl aluminum dihydride such as ethyl aluminum dihydride, propyl aluminum dihydride and the like. Partially hydrogenated alkylaluminums such as hydride, ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxybromide can be exemplified. Further, a compound similar to (i), for example, an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. As such a compound, specifically, (C ₂ H ₅ ) ₂ AlOAl (C
_{2 H 5) 2, (C} 4 H 5) 2 AlOAl (C 4 H 9) 2, And the like.

As the compound belonging to the above (ii), LiAl (C
_{2 H 5) 4, LiAl (} C 7 H 15) 4 etc. can be exemplified. Among these, it is particularly preferable to use an alkyl aluminum halide, an alkyl aluminum dihalide or a mixture thereof.

In producing the cyclic olefin-based random copolymer, the copolymerization reaction between ethylene and the above-mentioned tetracyclododecenes is preferably carried out by a continuous method. 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.

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

The soluble vanadium compound and the organoaluminum compound are usually supplied after being diluted with the hydrocarbon solvent or tetracyclododecenes, respectively. here,
The soluble vanadium compound is desirably diluted to the above concentration range, but a method is employed in which the organoaluminum compound is adjusted to an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization reaction system and supplied to the polymerization reaction system. .

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

Such a copolymerization reaction between ethylene and tetracyclododecenes is carried out at a temperature of -50 to 100C, preferably -30 to 80C, and more preferably -20 to 60C.

The reaction time for carrying out the copolymerization reaction as described above (in the case of a continuous polymerization reaction, the average residence time of the polymerization reaction mixture) varies depending on the type of the polymerization raw material, the concentration of the catalyst component and the temperature, but is usually 5 minutes to 5 hours, preferably
The range is from 10 minutes to 3 hours. The pressure at which the copolymerization reaction is carried out is usually more than 0 and 50 kg / cm ² , preferably 0
Over 20 kg / cm ² .

When producing a cyclic olefin-based random copolymer, the molar ratio of ethylene / cyclic olefin is usually 90%.
It is desirably in the range of / 10 to 10/90, preferably 40/60 to 85/15.

When a copolymerization reaction of ethylene and a cyclic olefin is performed as described above, a solution of a cyclic olefin-based random copolymer is obtained. The concentration of the cyclic olefin-based random copolymer contained in such a copolymer solution is usually
It is in the range of 2.0 to 100% by weight, preferably 40 to 60% by weight, and the resulting copolymer solution also contains a soluble vanadium compound component and an organoaluminum compound component as catalyst components.

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

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Quantitative methods tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] dodecene -3 such isomers endo isomer in the mixture [I-A] with the exo isomer [I-
The molar ratio with [B] was calculated based on the ¹ H-NMR (in CDCl ₃ , room temperature, based on TMS) and the integrated intensity ratio of the absorption peak of the olefin proton in the obtained spectrum.
Table 2 tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] dodecene -
¹ showed a chemical shift of the olefin proton obtained by ¹ H-NMR measurement.

Also in Table 2, tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] showed ¹³ C-NMR chemical shifts of the carbon obtained by measuring dodecene -3.

Further, Table 3 shows the chemical shift of carbon obtained by measuring ¹³ C-NMR of the ethylene-tetracyclododecene copolymer.

Measurement method of softening temperature About the sample for softening temperature measurement obtained by shape | molding each copolymer obtained by the polymerization example and the comparative polymerization example into a 1 mm-thick sheet form, the thermomechanical analyzer (Thermomechanical Analyzer) by DuPont Was used to measure the thermal deformation behavior. That is, a quartz needle was placed on the sample, and the sample was continuously heated at a rate of 5 ° C./min while a load of 49 g was applied to the measurement needle. The temperature at the time of penetration into mm was defined as the softening temperature. (Hereinafter referred to as TMA softening point) Measurement method of flexural modulus The flexural modulus was measured at a temperature of 23 ° C according to the measuring method described in ASTM-D790.

Measurement method of intrinsic viscosity The intrinsic viscosity was measured at a temperature of 135 ° C using decalin as a solvent.

Examples Reference Example 1 Norbornene and cyclopentadiene were obtained by
By Diels-Alder reaction by the process of 14910 JP, tetracyclo [4,4,0,1 ^2.5, 1
^7.10 ] Dodecene-3 Was synthesized.

The obtained tetracyclododecene-3 was measured by ¹ H-NMR, and the molar ratio of the endo-form and the exo-form was measured.
The endo form was present in an amount of 94.9 mol%, and the exo form was present in an amount of 5.1 mol%.

 Table 4 shows the results.

Reference Example 2 By subjecting 5-ethyl-2-norbornene and cyclopentadiene to a Diels-Alder reaction in the same manner as in Reference Example 1, 8-ethyl-tetracyclo [4,4,
0,1 ^2.5 , 1 ^7.10 ] dodecene-3 Was synthesized.

The obtained tetracyclododecene-3 was measured by ¹ H-NMR, and the molar ratio of the endo-form and the exo-form was measured.
The endo form was present in an amount of 97.3 mol%, and the exo form was present in an amount of 2.7 mol%.

 Table 4 shows the results.

Synthesis Example 1 In a 30 reactors equipped with a stirrer and a reflux condenser,
Tetracyclo obtained in Reference Example 1 [4,4,0,1 ^2.5, 1 ^7.10]
Dodecene-3 (hereinafter sometimes abbreviated as TCD-3)
1 and cyclohexane 17 were added and stirred. Zeolite (manufactured by Tosoh Corporation, Zeolam F-
9, _{spherical, 1.8~2.4mmφ, Na 2 O · Al} 2 O 3 · 2.5SiO 2) 12kg
Was added and the mixture was stirred at room temperature for 6 hours to carry out an isomerization reaction of the endo form into the exo form.

After completion of the reaction, the reaction mixture was filtered to separate the catalyst, and the obtained cyclohexane solution of TCD-3 was reduced in pressure (50 mmHg).
Cyclohexane is distilled off under reduced pressure to give isomerized TC.
D-3 was obtained.

When the obtained TCD-3 was analyzed by ¹ H-NMR, the molar ratio between the endo form and the exo form was 44.2 / 55.8.

 Table 4 shows the results.

Synthesis Example 2 An isomerization reaction of TCD-3 was performed in the same manner as in Synthesis Example 1 except that the reaction time was changed to 3 hours.

 Table 4 shows the results.

Synthesis Example 3 As a catalyst, silica-alumina (manufactured by Shinagawa White Brick Co., Ltd., Cegard OW, granular, 0.5 to ₂ mmφ, Al ₂ O ₃ .mSiO ₂ .nH ₂ O +
The reaction was carried out in the same manner as in Synthesis Example 1 except that the amounts of cyclohexane and the catalyst were changed to 4.0 and 3 kg, respectively, and the reaction time was changed to 96 hours using Al (OH) ₃ .

 Table 4 shows the results.

Synthesis Example 4 8-ethyl-tetracyclo [4,4,
0,1 ^2.5 , 1 ^7.10 ] The reaction was carried out in the same manner as in Synthesis Example 1 except that dodecene-3 (abbreviated as 8E-TCD-3) was used.

 Table 3 shows the results.

Synthesis Example 5 A reaction was performed in the same manner as in Synthesis Example 4 except that the reaction time was changed to 3 hours.

 Table 4 shows the results.

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

 Table 4 shows the results.

Example 1 A cyclohexane solution of TCD-3 obtained in Synthesis Example 1 was continuously fed from the upper part of a polymerization vessel into two glass polymerization vessels equipped with a stirrer, and cyclohexane of VO (OC ₂ H ₅ ) Cl ₂ was used as a catalyst. Solution and ethyl aluminum sesquichloride (Al
A cyclohexane solution of (C ₂ H ₅ ) _1.5 Cl _1.5 ) was supplied such that the concentration in the polymerization vessel became 60 g /, 0.5 mmol /, and 4.0 mmol /, respectively, and ethylene was fed from the top of the polymerization vessel at 15 / hour. Hydrogen was fed at a feed rate of 0.5 / hour. On the other hand, the polymerization solution was continuously extracted from the lower part of the polymerization vessel so that the total amount of the polymerization liquid in the polymerization vessel was 1, and the average residence time was 0.5 hour.

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 / TCD-3 random copolymer. The polymerization reaction was stopped by adding a small amount of isopropyl alcohol to the polymerization liquid extracted from the lower part of the polymerization vessel.
Next, the mixture is rotated in a mixer containing about three times the volume of acetone with respect to the polymerization liquid, and the polymerization liquid after the reaction is stopped is added thereto to precipitate a copolymer, and the precipitated copolymer is filtered. To separate from the solution. The obtained copolymer is
The mixture was dispersed in acetone so as to have a concentration of about 50 g /, and the mixture was heated at the boiling point of acetone for about 2 hours. After the treatment, the copolymer was separated from acetone by filtration, and dried under reduced pressure at 120 ° C. for 24 hours.

About the obtained copolymer of ethylene and TCD-3, ¹³ C-
According to NMR measurement, the ethylene content in the copolymer was 6
0.7 mol%. The intrinsic viscosity [η] and the TMA softening temperature were 0.37 dl / g and 180 ° C., respectively.

Table 5 shows the results. FIG. 1 shows the relationship between the tetracyclododecene-3 content (mol%) and the softening temperature of the obtained ethylene / tetracyclododecene-3 copolymer, and FIG. 2 shows the copolymer. Of tetracyclododecene
3 shows the relationship between the content (mol%) and the flexural modulus.

When the molar ratio between the endo-form and the exo-form of TCD-3 contained in the obtained copolymer was measured by ¹³ C-NMR, the endo-form / exo-form ratio was 41/59. The value hardly changed before and after the polymerization.

Examples 2 to 8, Comparative Examples 1 and 2 Raw materials (tetracyclododecene-3) as shown in Table 5
Was used to copolymerize ethylene and tetracyclododecene-3 in the same manner as in Example 1 under the conditions shown in Table 5.

 Table 6 shows the obtained results.

FIG. 1 shows the relationship between the tetracyclododecene-3 content (mol%) and the softening temperature of the obtained ethylene / tetracyclododecene-3 copolymer, and FIG. 2 shows the tetracyclododecene-3 copolymer. The relationship between the content of dodecene-3 (mol%) and the flexural modulus is shown.

Examples 9 to 11, Comparative Example 3 Ethylene was produced in the same manner as in Example 1 using the starting material (8-ethyl-tetracyclododecene-3) shown in Table 7 under the conditions shown in Table 7. And 8-ethyl-tetracyclododecene-3 were copolymerized.

 Table 8 shows the obtained results.

The copolymer using 8-ethyl-tetracyclododecene-3 having a high exo-form [IB] content obtained in Examples 9 to 11 was different from the copolymer obtained in Comparative Example 3 in comparison with the copolymer obtained in Comparative Example 3. It can be seen that both the TMA softening point and the flexural modulus have been improved.

[Brief description of the drawings]

FIG. 1 shows the tetracyclododecene of an ethylene / tetracyclododecene-3 copolymer obtained by copolymerizing ethylene with a tetracyclododecene-3 isomer mixture having various endo / exo isomer ratios. FIG. 2 is a graph showing the relationship between the -3 content (mol%) and the softening temperature. FIG. 2 shows the relationship between the tetracyclododecene-3 content (mol%) and the bending of the ethylene / tetracyclododecene-3 copolymer. It is a figure showing the relation with elastic modulus.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akira Mizuno 6-1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Hiroo Wamura Waki-machi, Kuga-gun, Yamaguchi Prefecture No. 6 1-2 Ki, Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-64-54011 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 210/02 C08F 232/00 Registry (STN) CA (STN)

Claims (2)

(57) [Claims] (1) (A) ethylene, an endo-form [IA] and an exo-form [I-
B] and the molar ratio ([IA]] / [IB]) is 80/20.
Tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] represented by the following formula as a mixture of isomers is ~0 / 100 [I] dodecene -3
And (B) the structural unit derived from ethylene is present in an amount of 10 to 90 mol%, and the structural unit derived from the tetracyclododecene is in an amount of 90 to 10 mol%. (C) a structural unit derived from the tetracyclododecenes has a structure represented by the following formula [II]; and (D) an intrinsic viscosity [η] measured in decalin at 135 ° C.
A cyclic olefin-based random copolymer obtained by random copolymerization of ethylene and tetracyclododecenes, wherein the copolymer is 0.05 to 10 dl / g. [Wherein, R ^{1 to} R ¹² may be the same or different, and each represents a hydrogen, a hydrocarbon group, or a halogen;
R ⁹ (or R ¹⁰ ) and R ¹¹ (or R ¹² ) may be linked to each other to form a ring. ] [Wherein, R ^{1 to} R ¹² are the same as above. ] (A) ethylene, an endo-form [IA] represented by the following formula and an exo-form [I-
B] and the molar ratio ([IA]] / [IB]) is 80/20.
Tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] represented by the following formula as a mixture of isomers is ~0 / 100 [I] dodecene -3
(B) in a hydrocarbon solvent or in the absence of a hydrocarbon solvent in the presence of a catalyst comprising a vanadium compound and an organoaluminum soluble in the hydrocarbon or the tetracyclododecenes A process for producing a cycloolefin random copolymer obtained by random copolymerization of ethylene and said tetracyclododecenes, characterized by copolymerizing. [Wherein, R ^{1 to} R ¹² may be the same or different, and each represents a hydrogen, a hydrocarbon group, or a halogen;
R ⁹ (or R ¹⁰ ) and R ¹¹ (or R ¹² ) may be linked to each other to form a ring. ]