KR940010965B1 - Cyclic olefin random copolymer and process for preparing same - Google Patents

Abstract

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Description

Cycloolefin Random Copolymer and Method for Producing the Same

1 is copolymerization of ethylene with isomeric mixtures of aromatic groups containing norbornenes, e.g., 1,4-methano-1,4,4a, 9a-tetrahydrofuroene (MTHF), having different endomeric / exomeric ratios. A diagram showing the relationship between the aromatic group-containing norbornene content (mol%) and TMA (softening point) in the ethylene / aromatic group-containing norbornene copolymer obtained by

2 is a diagram showing the relationship between the aromatic group-containing norbornene content (mol%) and the flexural modulus in the ethylene / aromatic group-containing norbornene (MTHF) copolymer.

The present invention relates to a cyclic olefin random copolymer obtained by random copolymerization of ethylene and an aromatic group-containing norbornene and a method for producing the same.

As disclosed in Japanese Patent Application Laid-Open No. 60-178708, Japanese Patent Application No. 59-220550, Japanese Patent Application Nos. 59-236828, 59-236829, 59-242336, and 61-95906, the present applicant The cyclic olefin random copolymer obtained by the copolymerization of cyclic olefin such as ethylene and tetracyclodecene has excellent transparency and balances properties such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric property and mechanical strength. It has been found to exhibit excellent performance in optical materials such as optical memory disks and optical fibers.

In addition, Applicants have found that random copolymers of ethylene and aromatic group-containing norbornenes also have the above excellent properties.

The aromatic group-containing norbornene used in the preparation of the random copolymer as described above can be produced by the Diels-Alder reaction of cyclopentadienes and corresponding olefins. The aromatic group-containing norbornene is obtained as a mixture of isomers containing endosomes (IA) and exoforms (IB), but since the cis addition reaction proceeds predominantly, the endosomes (IA) are mainly formed, and exoforms ) Is formed in small amounts. The isomeric mixture of the aromatic group-containing norbornene obtained by the Diels Alder reaction usually contains at least 85 mol%, and in most cases, at least 90 mol% of an endorse.

MEANS TO SOLVE THE PROBLEM The present inventors conducted the high intensity | strength study to further improve the heat resistance and mechanical strength of the above-mentioned cyclic olefin random copolymer obtained by copolymerization of ethylene and an aromatic group containing norbornene, and an exo body (IB) content Cyclic olefin random copolymers obtained by ethylene copolymerization with an isomeric mixture of relatively more aromatic group-containing norbornene compared to those obtained by ethylene copolymerization with an isomeric mixture of norbornene with an aromatic group containing relatively less exo- (IB) It was found that the heat resistance and mechanical strength were significantly improved.

Since the present invention has been completed on the basis of the above-mentioned and knowledge, an object of the present invention is to provide a cyclic olefin random copolymer having excellent heat resistance and mechanical strength obtained by copolymerization of ethylene and norbornene containing an aromatic group, and a method for producing the same. have.

As for the cyclic olefin random copolymer of this invention obtained by the random copolymerization of ethylene aromatic group containing norbornene, (a) the said copolymer is endo (IA) / of the aromatic group containing norbornene of ethylene and the following general formula (I): Obtained by random copolymerization of an isomeric mixture having an exo (IB) molar ratio ((IA) / (IB)) of 80/20 to 0/100, and (b) a structural unit content of ethylene derived from ethylene of 10 ˜95 mol%, the structural unit content derived from the aromatic group-containing norbornene is 90 to 5 mol%, (c) the structural unit derived from the aromatic group-containing norbornene is represented by the following formula (II) And (d) the intrinsic viscosity (η) measured in 135 ° C decalin of the copolymer is 0.05-10 dL / g.

Endo conductor

Exosomes

Wherein p is an integer of 0 or 1 or more, q and r are each 0, 1 or 2, R ¹ to R ¹⁵ are each independently hydrogen or a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, R ⁵ ( Or R ⁵ ) and R ⁹ (or R ⁷ ) may be bonded to each other or directly bonded to each other via an alkylene group having 1 to 3 carbon atoms, and X ¹ may be directly bonded to each other of Formula (I).

Indicates a part.

Wherein p, q, r and R ¹ to R ¹⁵ are as defined above.

The method of the present invention for producing a cyclic olefin random copolymer by random copolymerization of ethylene and an aromatic group-containing norbornene comprises: (a) an endodon (IA) of an aromatic group-containing norbornene represented by the general formula (I). (B) the isomeric mixture having a molar ratio (IA) / (IB) of 80/20 to 0/100, or (b) the hydrocarbon solvent or the aromatic in the absence of a hydrocarbon solvent or in the absence of a hydrocarbon solvent. The copolymerization is carried out in the presence of a catalyst composed of a vanadium compound soluble in the group-containing norbornene and an organoaluminum.

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

Hereinafter, the cyclic olefin random copolymer obtained by the aromatic group containing norbornene and ethylene copolymerization of this invention, and its manufacturing method are demonstrated concretely.

The cyclic olefin random copolymer of the present invention is a random copolymer of the aromatic group-containing norbornene represented by the general formula (I), and the aromatic group-containing norbornene is an endo-body (IA) and an exo-body (IB) represented by the above formula. Is used as an isomer mixture having a molar ratio [(IA) / (IB)] of 80/20 to 0/100.

First, the aromatic group-containing norbornene isomer mixture will be described.

[Method of Preparing Isomer Blends]

As described above, the molar ratio [(I-A) / (IB)] of the endoside (IA) and the exoform (IB) is 80/20 to 0/100, preferably 70/30 to 5/95. The containing norbornene isomer mixture contains at least 85 mole%, in many cases at least 90 mole%, and in many cases 94% of the endothomer (IA) obtainable by the Diels Alder reaction of cyclopentadienes and olefins as described above. The aromatic group-containing norbornene isomer mixture containing in an amount greater than or equal to mole% can be prepared by isomerizing endosomes (IA) with exoforms (IB) by contacting the solid acid with a solid acid under the conditions described below.

Specific examples of the aromatic group-containing norbornene used in the present invention include the following compounds.

5-phenyl-bicyclo- [2.2.1] -hept-2-ene

5-Methyl-5-phenyl-bicyclo- [2.2.1] hept-2-ene

5-benzyl-bicyclo [2.2.1] hept-2-ene

5-tolyl-bicyclo [2.2.1] hept-2-ene

5- (ethylphenyl) -bicyclo- [2.2.1] hept-2-ene

5- (isopropylphenyl) -bicyclo- [2.2.1] hept-2-ene

1,4-Metano-1,4,4a, 9a-tetra-hydrofurouene

1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene

Cyclopentadiene-acenaphthalene adduct

5- (α-naphthyl) -bicyclo [2.2.1] -hept-2-ene

5- (Anthracenyl) -bicyclo [2.2.1] -hept-2-ene

Specific examples of the solid acid used to isomerize the endonomer (IA) of the above-described aromatic group containing norbornene to exo-body (IB) include silica-alumina (which consists essentially of Al ₂ O ₃ + SiO ₂ ) and alumina ( Al ₂ O ₃ ), zeolite (consisting of Na ₂ O + SiO ₂ + Al ₂ O ₃ ) and activated clay.

Solid acids other than those exemplified above include Cr ₂ O ₃ , P ₂ O ₃ , TiO ₂ , Al ₂ O ₃ ㆍ xCr ₂ O ₃ , Al ₂ O ₃ ㆍ CoO, Al ₂ O ₃ ㆍ MnO, Cr ₂ O ₃ and Fe can be cited _{2 O 3, MoS, MoS 2} , CrO 3, CrO 2 Cl, MoO 3, V 2 O 3 and WO ₂ Cl _2, such as the acidic metal oxides, and acidic metal sulfide distribution.

In addition to the inorganic compounds, useful solid acids include, for example, organic compounds such as sulfone group-containing crosslinked polymers such as Amberlite 15 ^TM , Amberlite XE-284 ^TM and Naphyone-H ^TM . Can be mentioned.

The isomerization reaction of said aromatic group containing norbornene to exo body (I-B) using the said solid acid can be performed by making the said end body (I-A) contact with the said solid acid. In this case, the endoromer (I-A) may be brought into direct contact with the solid acid or with the solid acid in the presence of an organic solvent.

Specific examples of the organic solvent that can be used include cyclohexane, decalin, hexane, benzene, toluene, carbon tetrachloride and 1,2-dichloroethane.

The contact of the endodon (I-A) of the aromatic group-containing norbornene with a solid acid is preferably performed at -5 to 150 캜, preferably at 0 to 50 캜. The contact time is about 0.5 to 200 hours, preferably about 1 to 100 hours, but this time varies greatly depending on the contact temperature and the concentration of the norbornene containing aromatic group.

Contact of the endodon (I-A) of the aromatic group-containing norbornene with a solid acid can be carried out batchwise or continuously.

The batchwise operation of the contact of the endodon (I-A) of the aromatic group norbornene with a solid acid can be carried out by the following method, for example.

A predetermined amount of norbornene containing an aromatic group, a predetermined amount of an organic solvent and a predetermined amount of a solid acid are added to a reactor equipped with a stirring blade, and the contents of the reactor are stirred at a predetermined temperature for a predetermined time. Next, the reaction mixture is separated into solid and liquid by filtration, and the aromatic group-containing norbornene and the organic solvent in the liquid phase are separated from each other by distillation.

Continuous operation of the contact of the end group (I-A) of the aromatic group-containing norbornene with the solid acid can be carried out by the following method, for example.

(Iii) continuously feeding the aromatic group-containing norbornene or the aromatic group-containing norbornene diluted with the organic solvent to the reactor using the same reactor as used in the batch operation, while contacting with the solid acid present in the reactor. The aromatic group-containing norbornene or the organic solvent-diluted aromatic group-containing norbornene is withdrawn from the reactor.

(Ii) continuously supplying the aromatic group-containing norbornene or the aromatic group-containing norbornene diluted with the organic solvent through one end thereof to the column (or column) loaded with the solid acid, and the aromatic-containing norbornene or this A dilution of and the contact of the solid acid is withdrawn through the other end of the column.

In the above methods (iii) and (ii), norbornene containing aromatic groups after contact with the solid acid can be separated from the organic solvent by distillation.

The endo-body (I-A) isomerized to the exo-body (I-B) by contacting the endomeric (I-A) of the aromatic group-containing norbornene with the solid acid catalyst.

The structure of endosomes (IA) and exoforms (IB) or endosomes (IA) / exoforms (IB) molar ratio in the isomeric mixture can be determined by ¹ H-NMR or ¹³ C-NMR measurements.

The isomeric mixture of the aromatic-containing norbornene in which the (IA) / (IB) molar ratio is as described above cannot be obtained directly from the Diels-Alder reaction of cyclopentadiene and olefin, and the endomer (IA) of the isomeric mixture is subjected to the acid catalyst treatment. Can be obtained only when isomerized to exo body (IB).

[Cyclic olefin random copolymer]

The cyclic olefin random copolymer of the present invention is obtained by random copolymerization of ethylene and the aromatic group-containing norbornene represented by the general formula (I), and the aromatic group-containing norbornene is formed of endosomes (IA) and exoforms (IB). ) Is an isomer mixture having a molar ratio ((IA) / (IB)) of 80/20 to 0/100.

In the cyclic olefin random copolymer of the present invention, the structural unit content derived from ethylene is 10 to 95 mol%, preferably 40 to 85 mol%, and the structural unit content derived from the aromatic-containing norbornene is 90 to 5 mol%. Preferably it is 60-15 mol%.

A small amount of other copolymerizable monomers, such as norbornene derivatives other than norbornene containing the aromatic group, or α-olefins other than ethylene, may be used in the cyclic olefin random copolymer, so long as the object of the present invention is not impaired. Up to 10 mole% of the structural units derived from the group-containing norbornene can be polymerized.

In the cyclic olefin random copolymer, the structural unit derived from the aromatic group-containing norbornene has a structure represented by the following general formula (II).

Wherein p, q, r and R ¹ to R ¹⁶ are as defined in general formula (I) above.

Preferably the intrinsic viscosity ((eta)) measured in 135 degreeC decalin of the said ethylene / aromatic group containing norbornene copolymer obtained by this invention is 0.05-10 dL / g.

[Production of Cyclic Olefin Random Copolymer]

In the cyclic olefin random copolymer of the present invention, the endo- (endo) (IA) / exo (IB) molar ratio ((IA) / (IB)) of ethylene and the aromatic group-containing norbornene is 80/20 to 0/100. The presence of a catalyst comprising an isomeric mixture comprising a vanadium compound and an organoaluminum compound, preferably a halogen-containing organoaluminum compound, soluble in the hydrocarbon solvent or in the absence of a hydrocarbon solvent, of the hydrocarbon solvent or the norbornene containing the aromatic group. It can manufacture by copolymerizing under the following.

Examples of hydrocarbon solvents used in the production of the cyclic olefin random copolymers of the present invention include aliphatic hydrocarbons such as hexane, heptop, octane and kerosene; Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Aromatic hydrocarbons, such as benzene, toluene, and xylene, etc. can be illustrated. These solvents can be used alone or in combination.

As the vanadium compound which is soluble in the hydrocarbon solvent or the aromatic group-containing norbornene and used in the preparation of the cyclic olefin random copolymer of the present invention, the general formula VO (OR) _a X _b or V (OR) _c X _d ( R is a hydrocarbon group, X is a halogen, a vanadium compound represented by 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4), or an electron donor adduct thereof .

More specifically VOCl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , VO (OnC ₄ H ₉ ) Cl ₂ Vanadium compounds such as, VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ , VOCl ₂ , VO (OnC ₄ H ₉ ) ₃ and VCl ₃ 2OC ₉ H ₁₆ OH are used.

Further, electron donors used in the preparation of the soluble vanadium catalyst component include alcohols, phenols, ketones, aldehydes, carbon acids, esters of organic or inorganic acids, acid amides, acid anhydrides, alkoxysilanes, and the like. And nitrogen-containing electron donors such as oxygen electron donors, ammonia, amines, nitriles, and isocyanates.

More specifically, carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol, etc. 18 alcohols; Phenols having 6 to 20 carbon atoms which may have lower alkyl groups such as phenol, cresol, chiselenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol; Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetone phenone, benzophenone, and benzoquinone; Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde benzoaldehyde, tolualdehyde, naphthaldehyde: methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, propionate Ethyl, methyl butyrate, ethyl gil acetate, methyl crawlo acetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexane carbonate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclobenzoate Hexyl, Phenyl Benzoate, Benzyl Benzoate, Methyl Toluate, Ethyl Toluate, Amyl Toluate, Ethyl Ethyl Benzoate, Methyl Anisate, N-butyl Maleate, Diisobutyl Methyl Malonic Acid, Di-N-hexyl Cyclohexene Carbonate, Diethyl nitrate, tetrahydrophthalic acid diisopropyl, diethyl phthalate, diisobutyl phthalate, di-butyl phthalate, phthalate Dean, 2-ethylhexyl, γ- butyrolactone, ester of an organic acid having a carbon number of 2 to 30 acids, such as lactone, coumarin, phthalide lead carbonate, ethylene at a δ- ballet; Acid halides having 2 to 15 carbon atoms, such as acetyl chloride, benzoyl chloride, toluic acid chloride and aniseic acid chloride; C2-C20 ethers, such as methyl ether, 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; Amines such as methylamine, ethylamine, diethylamine, trimethylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylenediamine; Nitriles such as acetonitrile, benzonitrile and tolunitrile; Alkoxysilanes, such as ethyl silicate and diphenyldimethoxysilane, etc. are mentioned. These electron donors can be used in combination of 2 or more types.

As the organoaluminum compound catalyst component used in the preparation of the cyclic olefin random copolymer of the present invention, a compound having at least one Al-carbon bond in a molecule is used. For example, the following formula (III)

R ¹ _m Al (OR ² ) _n H _p X _q (III)

Where R ¹ and R ² are hydrocarbons containing 1 to 15 carbon atoms, usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and may be the same or different from each other. X is halogen, m is 0 ≦ m ≦ 3, and n is 0 ≦ n ≦ 3, p is 0 ≦ p ≦ 3, q is a number of 0 ≦ q ≦ 3, m + n + p + q = 3), and the following general formula (IV)

M ¹ AlR ¹ ₄ (IV)

And complex alkyl compounds of Group I metals and aluminum, wherein M ¹ is Li, Na or K, and R ¹ is as defined in formula (III) above.

The following can be illustrated as an organoaluminum compound represented by said general formula (III).

Formula R ¹ _m Al (OR ² ) _3-m

(Wherein R ¹ and R ² are as defined in formula (III) above, m is preferably 1.5 ≦ m ≦ 3)

Formula R ¹ _m AlX _3-m

(Wherein R ¹ is as defined in formula (III) above, m is preferably 0 <m <3)

Formula R ¹ _m AlH _3-m

Where R ¹ is as defined in formula (III) above, m is preferably 2 ≦ m <3)

Formula R ¹ _m Al (OR ² ) _n X _p

(Wherein R ¹ and R ² are as defined in formula (III) above, X is halogen, 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3) What is displayed can be illustrated.

As an aluminum compound represented by said Formula (III), More specifically, Trialkyl aluminum, such as triethyl aluminum or tributyl aluminum; Trialkenyl aluminum, such as triisopropenyl aluminum; Dialkyl aluminum alkoxides such as diethyl aluminum ethoxide or dibutyl aluminum butoxide; Alkylaluminum sesquialoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxy and partially alkoxylated alkylaluminum, diethylaluminum chloride, having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 , Dialkyl aluminum halides such as dibutyl aluminum chloride and diethyl aluminum bromide; Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride or ethylaluminum sesquibromide; Partially halogenated alkylaluminum such as alkylaluminum dihalide such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide and the like; Dialkyl aluminum hydrides such as diethyl aluminum hydride or dibutyl aluminum hydride; Partially hydrogenated alkyl aluminum such as alkyl aluminum dihydride such as ethyl aluminum dihydride and propyl aluminum dihydride; Partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxychloride, butyl aluminum butoxychloride, ethylaluminum ethoxybromide and the like can be exemplified.

The organoaluminum compound catalyst component used in the preparation of the cyclic olefin random copolymer of the present invention is also a compound similar to the compound represented by the general formula (III), for example, organoaluminum in which two or more aluminums are bonded via an oxygen atom or a nitrogen atom. It may be a compound. The same compound as _{Specifically, (C 2 H 5) 2} AlOAl (C 2 H 5) 2, (C 4 H 9) 2 AlOAl (C 4 H 9) 2, Etc. can be illustrated.

Examples of the compound of formula (IV) include LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₂ H ₁₅ ) ₄ , and the like. Of these, preference is given to using alkylaluminum halides, alkyl aluminum dihalides or mixtures thereof.

When manufacturing the cyclic olefin random copolymer of this invention, it is preferable to perform copolymerization reaction of ethylene and a cyclic olefin by a continuous method.

In this case, the concentration of the soluble vanadium compound supplied to the polymerization reaction system is usually in the range of 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.

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

The soluble vanadium compound and the organoaluminum compound are usually diluted with the hydrocarbon solvent or the aromatic group-containing norbornene and fed to the copolymerization reaction system, respectively.

In this case, the soluble vanadium compound is preferably diluted in the above concentration range, but the organoaluminum compound is diluted to any concentration, for example, 50 times or less of the concentration in the polymerization reaction system.

When producing the cyclic olefin random copolymer of the present invention, the concentration of the soluble vanadium compound in the copolymerization reaction system is usually 0.01 to 5 mmol / L, preferably 0.05 to 3 mmol / L in terms of vanadium atoms.

The copolymerization reaction of ethylene and the aromatic group-containing norbornene is carried out at a temperature of -50 to 100 ° C, preferably -30 to 80 ° C, particularly preferably -20 to 80 ° C.

The reaction time when performing the copolymerization reaction as described above (in the case of continuous polymerization reaction, 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 reaction temperature, but is usually 5 minutes to 5 hours. Preferably, it is the range of 10 minutes-3 hours. Moreover, the pressure at the time of performing a copolymerization reaction is 0 or more and 50 kg / cm <2> or less normally, Preferably it is 0 or more and 20 kg / cm <2> or less.

The molar ratio of ethylene / aromatic group-containing norbornene used in producing the cyclic olefin random copolymer is usually in the range of 90/10 to 10/90, preferably in the range of 85/15 to 40/60.

In the cyclic olefin random copolymer obtained by the above method, a small amount of other copolymerizable monomers within a range that does not impair the object of the present invention, for example, norbornenes other than the aromatic group-containing norbornene or α-olene other than ethylene The fin may be copolymerized in an amount of 10 mol% or less of the structural unit derived from the aromatic group-containing norbornene.

By copolymerizing ethylene with an aromatic group-containing norbornene as described above, a hydrocarbon solvent solution of a cyclic olefin random copolymer and an unreacted cyclic olefin solution are obtained. The concentration of the cyclic olefin random copolymer contained in such a copolymer solution is usually in the range of 0.5 to 40% by weight, preferably 2.0 to 30% by weight, and the soluble vanadium compound component and the organoaluminum compound component are also included in the copolymer solution. It is contained.

The solution of the cyclic olefin random copolymer of the present invention obtained as described above is usually subjected to a series of processes from deliming to pelletizing to obtain pellets of the cyclic olefin random copolymer.

The present invention obtained by copolymerization of an isomeric mixture of the aromatic group-containing norbornene with ethylene having an molar ratio ((IA) / (IB)) of endo- (IA) to exo- (IB) of 80/20 to 0/100 Of cyclic olefin random copolymers and endomers (IA) of at least 85 mole%, in most cases at least 90 mole% and at least 94 mole% of isomer mixtures of norbornene containing aromatic groups. Comparing the cyclic olefin random copolymers with each other, both are the same in terms of the composition of ethylene and the aromatic group-containing norbornene, but the copolymer of the present invention has a higher monomer reaction rate of the aromatic group-containing norbornene during the copolymerization reaction, The transition temperature Tg is high, the heat resistance is excellent, and the mechanical strength is excellent, as evidenced by the greater flexural modulus (FM). Therefore, when a cyclic olefin random copolymer having the same glass transition temperature (Tg) or flexural modulus (FM) is required, the air content of the expensive aromatic group-containing norbornene can be reduced by using the aromatic group-containing norbornene isomer mixture of the present invention. Can be reduced.

By the manufacturing method of the cyclic olefin random copolymer of this invention, the above-mentioned cyclic olefin random copolymer can be manufactured efficiently.

EXAMPLE

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

[How to measure]

The molar ratio of endo- (IA) to exo- (IB) of the isomeric mixture of 1,4-methano-1,4,4a, 9a-tetrahydrofurouene (hereinafter referred to as “MTHF”) ((IA) / (IB)) it is calculated by the integral intensity ratio of the absorption peak of the olefin proton of the spectrum obtained by ¹ H-NMR measurement (by in CDCl _3, room temperature, TMS).

Tables 1a and 1b show chemical shifts of olefin protons obtained by ¹ H-NMR measurement of MTHF, respectively.

Tables 1a and 1b show chemical shifts of carbon obtained by ¹³ C-NMR measurement of MTHF, respectively.

TABLE 1a

1,4-Metano-1,4,4a, 9a-tetrahydrofurouene ¹ H-NMR and ¹³ C-NMR chemical shift (based on TMS)

TABLE 1b

¹ H-NMR and ¹³ C-NMR Chemical Shifts of 1,4-Methano-1,4,4a, 9a-tetrahydrofurouene (TMS Standards)

[Measuring method of softening temperature]

The thermal strain kinetics were measured using a thermo mechanical analyzer manufactured by DuPont for the samples for softening temperature measurement obtained by molding each copolymer obtained in the examples and the comparative examples into a Schiff phase of 1 mm in thickness. That is, the quartz needle is placed vertically on the sample, the sample is continuously heated up at a temperature increase rate of 5 ° C./min with a weight of 49 g. The temperature at which the measuring needle is infiltrated into the sample is 0.635 mm. It was set as softening temperature. (Hereinafter, it is called "TMA softening temperature.")

[Measuring Method of Flexural Modulus]

The measurement of the flexural modulus was performed at the temperature of 23 degreeC according to the measuring method of ASTM-D790.

[Measurement of Ultimate Viscosity]

The intrinsic viscosity was measured at 135 degreeC in decalin used as a solvent.

Reference Example 1

1,4-Metano-1,4,4a, 9a-tetrahydrofuroene (MTHF) was prepared by the Diels Alder reaction of indene and cyclopentadiene by the method disclosed in Japanese Unexamined Patent Publication No. 46-14910. .

MTHF obtained above was measured by <^1> H-NMR and the quantity of an endobody and an exo body was measured. The contents of endo and exo were 87 mol% and 13 mol%, respectively. The results are shown in Table 2.

Reference Example 2

5-phenyl-bicyclo (2,2,1) hept-2-ene (hereinafter referred to as "Ph-BH") by the Diels Alder reaction of styrene and cyclopentadiene by the same method as in Reference Example 1 Manufactured.

Ph-BH obtained above was measured by ¹ H-NMR to determine the amounts of the endo and exo bodies. The contents of endo and exo were 92 mol% and 8 mol%, respectively. The results are shown in Table 2.

Example 1

1 L of MTHF and 17 L of cyclohexane obtained in Reference Example 1 were added and stirred to a 30 L reaction tank equipped with a stirring device and a reflux condenser. To the obtained solution, 6 kg of zeolite (manufactured by Tosho Corporation, Zelam F-9, spherical, 1.8 to 2.4 mm in diameter, Na ₂ O.Al ₂ O ₃ and 2.5SiO ₂ ) was added, stirred at room temperature for 6 hours to obtain an endosomal exo-body. Isomerization reaction was carried out.

After completion of the reaction, the reaction mixture was filtered to separate the catalyst, and the cyclohexane solution of MTHF obtained was distilled off under reduced pressure (50 mmHg) to distill cyclohexane to obtain isomerized MTHF. As a result of analyzing the obtained MTHF by ¹ H-NMR, the molar ratio of the endo- / exo body was 41/59. The results are shown in Table 2.

Example 2

The isomerization reaction of MTHF was performed like Example 1 except having made reaction time into 3 hours. The results are shown in Table 2.

Example 3

As the catalyst, the amount of cyclohexane and the catalyst was determined using silica-alumina (manufactured by Shinagawa Hakurengas Co., Ltd., Segado 0W, granular, 0.5 to ₂ mmØ, Al ₂ O ₃ .mSiO ₂ nH ₂ O to Al (OH) ₃ ). The reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 4.0 L and 3 kg, and the reaction time was changed to 69 hours. The results are shown in Table 2.

Example 4

The reaction was carried out in the same manner as in Example 1 except that PhBh obtained in Reference Example 2 was used instead of MTHF. The results are shown in Table 2.

The reaction was carried out in the same manner as in Example 4 except that the reaction time was changed to 3 hours. The results are shown in Table 2.

Example 6

As a catalyst, the reaction was carried out in the same manner as in Example 4 except that the reaction time was changed to 96 hours using silica-alumina in Example 3. The results are shown in Table 2.

TABLE 2

a) Tosho Sase, Trade Name: Zeolam F-9, Spherical, 1.8-2.4mmØ, Na ₂ O · Al ₂ O ₃ ㆍ 2.5SiO ₂

b) Shinagawa Hakurenga Co., Ltd. Trade Name: Segard 0W, Granular, 0.5-2mmØ, Al ₂ O ₃ ㆍ mSiO ₂ ㆍ nH ₂ O + Al (OH) ₃

Example 7

A cyclohexane solution of MTHF obtained in Example 1, a cyclohexane solution of VO (OC ₃ H ₅ ) Cl ₂ as a catalyst, and ethylaluminum sacquichloride (Al) A cyclohexane solution of (C ₂ H ₅ ) _1.5 Cl _1.5 ) was fed to a concentration of 6-g / l, 0.5 mmol / l and 40 mmol / l in the polymerization reactor, and 15 l / of ethylene at the top of the polymerization reactor. At the time, hydrogen was supplied at a feed rate of 0.5 liter / hour. On the other hand, the reaction mixture was taken out continuously so that the whole quantity of the polymerization liquid in a polymerization reactor might be 1 liter in the lower part of a polymerization reactor, and the average residence time might be 0.5 hour.

The polymerization reaction was carried out by circulating a refrigerant in a cooling jacket installed outside the polymerization reactor and maintaining the polymerization temperature at 10 ° C.

The copolymerization reaction was carried out under the same reaction conditions as above to obtain a polymerization reaction mixture containing an ethylene / MTHF random copolymer. The polymerization reaction was stopped by adding a small amount of isopropyl alcohol to the polymerization liquid continuously removed from the lower portion of the polymerization reactor.

Next, the catalyst residue was moved into the water phase by stirring the aqueous solution to which 5 ml of concentrated hydrochloric acid was added to 1 L of water, and the said polymerization liquid by stirring with a homomixer. The mixture was allowed to stand to remove the aqueous phase, and then washed twice with distilled water to purify and separate the polymerization solution.

Next, to the mixer containing about three times the volume of acetone with respect to the polymerization solution, the polymerization solution after the reaction was stopped was added to precipitate the copolymer, and the precipitated copolymer was separated from the solution by filtration. The copolymer obtained as a powder was dispersed in acetone such that its concentration was about 50 g / l, and the mixture was heated for about 2 hours at the boiling point of acetone. After treatment, the copolymer was separated from acetone by filtration and dried under reduced pressure at 120 ° C for 24 hours.

As a result of measuring ¹³ C-NMR of the obtained copolymer of ethylene / MTHF, the ethylene content in the copolymer was 63.0 mol%. The intrinsic viscosity (η) and TMA softening temperature of the copolymer were 0.41 dL / g and 178 ° C, respectively.

The results are shown in Table 4.

The molar ratio of endo and exo of MTHF contained in the obtained copolymer was measured by ¹³ C-NMR. The endo / exo ratio was 40/60, and this value did not change substantially before and after polymerization.

[Examples 8-14 and Comparative Examples 1-2]

Copolymerization of ethylene and MTHF was carried out in the same manner as in Example 7 using the raw materials (aromatic group-containing norbornene) as shown in Table 3 under the conditions as shown in Table 3.

The obtained results are shown in Table 4.

The relationship between the aromatic group-containing norbornene content (mol%) and TMA softening temperature of the ethylene / MTHF copolymer obtained in FIG. 1 is shown, and the aromatic group-containing norbornene content (mol%) and bending of the copolymer of FIG. The relationship with the elasticity modulus (FM) was shown.

TABLE 3

TABLE 4

[Examples 15-17 and Comparative Example 3]

Ethylene and Ph-BH were copolymerized in the same manner as in Example 7 using the raw materials (Ph-BH) as shown in Table 5 under the conditions as shown in Table 5.

It can be seen that the copolymers obtained in Examples 15 to 17 using Ph-BH containing a large amount of exo-body were improved in both the TMA softening temperature and the flexural modulus as compared with the copolymer obtained in Comparative Example 3.

TABLE 5

TABLE 6

Claims (2)

In the cyclic olefin random copolymer obtained by the random copolymer of ethylene and an aromatic group containing norbornene, (a) The said copolymer is endo of ethylene and the aromatic group containing norbornene of the following general formula (I) (IA) Obtained by random copolymerization of an isomer mixture having a molar ratio (IA) / (IB) of 80/20 to 0/100 / (exo), and (b) the copolymer has a structural unit content derived from ethylene. 10 to 95 mole%, 90 to 5 mole% of the structural unit derived from the aromatic group-containing norbornene, and (c) the structural unit derived from the aromatic group-containing norbornene is represented by the following general formula (II). (D) a cyclic olefin random copolymer characterized in that the intrinsic viscosity (η) measured in 135 ° C decalin of the copolymer is 0.05-10 dL / g: Endo conductor Exosomes Wherein p is 0 or an integer of 1 or more, q and r are each 0, 1 or 2, R ¹ to R ¹⁵ are each independently hydrogen or a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, R ⁵ (Or R ⁶ ) and R ⁹ (or R ⁷ ) may be bonded to each other through an alkylene group having 1 to 3 carbon atoms, or may be directly bonded to each other, and X ¹ may be a compound of Formula (I) Part.) Wherein p, q, r and R ¹ to R ¹⁵ are as defined above. In the method for producing a random copolymer of ethylene and an aromatic group-containing norbornene, (a) the endoether (IA) / exo- (IB) molar ratio of ethylene and the aromatic group-containing norbornene represented by the general formula (I) ( (B) Vanadium compounds soluble in the hydrocarbon solvent or in the aromatic group-containing norbornene in the presence of a hydrocarbon solvent or in the absence of a hydrocarbon solvent. Method for producing a cyclic olefin random copolymer characterized in that the copolymerization in the presence of a catalyst consisting of and organic aluminum: Endo conductor Exosomes Wherein p is 0 or an integer of 1 or more, q and r are each 0, 1 or 2, R ¹ to R ¹⁵ are each independently hydrogen or a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, R ⁵ (Or R ⁶ ) and R ⁹ (or R ⁷ ) may be bonded to each other through an alkylene group having 1 to 3 carbon atoms, or may be directly bonded to each other, and X ¹ may be a compound of Formula (I) Part.)