JPH0597719A - Isomerization of aromatic group-containing norbornene compound end isomer to exo isomer, mixture of aromatic group-containing norbornene compound isomers and its production - Google Patents

Abstract

PURPOSE:To produce an isomer mixture capable of giving a copolymer having excellent heat-resistance and mechanical strength when copolymerized with ethylene by contacting an endo isomer in a mixture of aromatic group-containing norbornene compound isomers with a solid acid catalyst, thereby isomerizing the endo isomer to exo isomer. CONSTITUTION:An endo isomer of formula II (X<1> is group of formula III) of a compound of formula I [(p) is 0 or integer of >=1; (q) and (r) are 0-2; R<1> to R<15> are H, halogen, aliphatic, alicyclic or aromatic hydrocarbon group or alkoxy; R<5> (or R<6>) and R<9> (or R<7>) may be bonded with each other directly or interposing a 1-3C alkylene] is made to contact with a solid acid catalyst (e.g. an acidic metal oxide) at -5 to +150 deg.C (preferably 0-50 deg.C) to isomerize the endo isomer to an exo isomer expressed by formula IV. When an isomer mixture of the compound of formula I containing >=85mol% of the endo isomer is made to contact with a solid acid catalyst, the endo/exo molar ratio can be changed to 80/20 to 0/100.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for isomerizing an endo-form of an aromatic-containing norbornene to an exo-form, an isomer mixture of an aromatic-containing norbornene, and a method for producing the same.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION The present applicant has previously found that a cyclic olefin random copolymer obtained by copolymerizing ethylene and a cyclic olefin such as tetracyclododecene is excellent in transparency and heat resistance, It is a synthetic resin that has a good balance of heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and mechanical strength, and also has excellent performance in the field of optical materials such as optical memory disks and optical fibers. Heading, already disclosed in JP-A-60-168708, JP-A-61-98780, and JP-A-61-115912.
JP-A-61-115916, JP-A-61-161
It is proposed in Japanese Patent Laid-Open No. 120816 and Japanese Patent Laid-Open No. 62-252407.

The applicant has also found that a copolymer of ethylene and an aromatic-containing norbornene also has the above-mentioned excellent properties. The aromatic-containing norbornenes used for producing such a random copolymer are produced by subjecting cyclopentadiene and corresponding olefins to Diels-Alder reaction. Aromatic-containing norbornenes obtained by the Diels-Alder reaction are obtained as an isomer mixture of an endo isomer [IA] and an exo isomer [IB] represented by the above formula, but cis addition preferentially proceeds. Therefore, the endo body [IA] is mainly produced, and the exo body [IB] is hardly produced. In the aromatic-containing norbornene isomer mixture obtained by the Diels-Alder reaction, the endo isomer [IA] is present in an amount of 85 mol% or more, and most of 90 mol% or more.

The present inventors have earnestly studied to further improve the heat resistance and mechanical strength of the cyclic olefin random copolymer obtained by copolymerizing the above ethylene with the aromatic-containing norbornenes. However, the exo body [I-
It was found that the cyclic olefin-based random copolymer obtained by copolymerizing ethylene with an aromatic-containing norbornene isomer mixture having a large B content is dramatically improved in heat resistance and mechanical strength.

[0005]

The present invention was made based on the above findings, and is for isomerizing an endo isomer [IA] in an aromatic-containing norbornene isomer mixture into an exo isomer [IB]. Aromatic-containing norbornene isomer mixture capable of giving a cyclic olefin-based random copolymer having excellent heat resistance and mechanical strength when copolymerized with ethylene. And a method for manufacturing the same.

[0006]

SUMMARY OF THE INVENTION A method for isomerizing an aromatic-containing norbornene endo-form [IA] to an exo-form [IB] according to the present invention is
It is characterized in that the endo-form [IA] of the aromatic-containing norbornene represented by the following general formula [I] is contacted with a solid acid catalyst to isomerize into the exo-form [IB].

[0007]

[Chemical 7]

(In the formula, p is 0 or an integer of 1 or more, q and r are 0, 1 or 2, and R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom or an aliphatic hydrocarbon group. , An alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and R ⁵ (or R ⁶ ) and R ⁹ (or R
⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group.

[0009]

[Chemical 8]

The aromatic-containing norbornene isomer mixture according to the present invention has a molar ratio ([IA] / [IB]) of the endo isomer [IA] and the exo isomer [IB] represented by the above formula of 80.
It is characterized by being / 20 to 0/100. The method for producing an aromatic-containing norbornene isomer mixture according to the present invention is a method for producing an aromatic-containing norbornene endo-form [IA] and an exo containing the endo-form [IA] represented by the above formula in an amount of 85 mol% or more. The isomer mixture with the isomer [IB] is brought into contact with a solid acid catalyst, and the molar ratio of the endo isomer [IA] and the exo isomer [IB] contained in the isomer mixture ([IA] /
[IB]) is set to 80/20 to 0/100.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for isomerizing an aromatic-containing norbornene endo isomer to an exo-form according to the present invention, an aromatic-containing norbornene isomer mixture, and a method for producing the aromatic-containing norbornene isomer mixture. Will be specifically described. Isomerization Method In the present invention, an aromatic-containing norbornene endo-form [IA] represented by the following formula [IA] is contacted with a solid acid to isomerize to an exo-form represented by the following formula [IB]. There is.

[0012]

[Chemical 9]

(In the formula, p is 0 or an integer of 1 or more, q and r are 0, 1 or 2, and R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom or an aliphatic hydrocarbon group. , An alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and R ⁵ (or R ⁶ ) and R ⁹ (or R
⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group.

[0014]

[Chemical 10]

In the above general formula [I], p is 0 or an integer of 1 or more, preferably 0 to 3. R ^{1 to} R ¹⁵ are each independently an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group. Represent Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aliphatic hydrocarbon group include alkyl groups having 1 to 6 atoms such as methyl group, ethyl group, isopropyl group, isobutyl group, amyl group and hexyl group. As the alicyclic hydrocarbon group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group,
Examples thereof include a cyclohexyl group. Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group, specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group,
Examples thereof include a phenylethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group.

In the above general formula [I], R ⁵ (or R ⁶ ) and R ⁹ (or R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms. It may be directly bonded without the intervening group. Specific examples of the aromatic-containing norbornenes used in the present invention include the following compounds.

[0017]

[Chemical 11]

[0018]

[Chemical formula 12]

[0019]

[Chemical 13]

Aromatic-containing norbornenes as raw materials, that is, endo-forms of aromatic-containing norbornenes [IA]
Can be obtained by the Diels-Alder reaction between cyclopentadiene and the corresponding olefin.
The endo-form of the aromatic-containing norbornenes as described above [I-
As the solid acid used for isomerizing [A] into an exo-form [IB], specifically, silica-alumina (Al ₂ O ₃
+ SiO ₂ is the main component, alumina (the main component is Al ₂ O ₃ ), zeolite (the main component is Na ₂ O + SiO ₂ + Al ₂ O ₃ ), activated clay and the like.

As the solid acid other than the above, there are the following acidic metal oxides or acidic metal sulfides. 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 , CrO ₃ , CrO ₂ Cl
₂ , MoO ₃ , V ₂ O ₃ , WO ₂ Cl _{2 and the} like can be mentioned.

In addition to the above-mentioned inorganic compounds, examples of solid acids include organic compounds such as sulfonic acid group-containing crosslinked polymers such as Amberlyst 15 ^™ , Amberlite XE-284 ^™ , and Nafion-H ^™ . The isomerization reaction of the aromatic-containing norbornene endo-form [IA] to the exo-form [IB] using such a solid acid is carried out by contacting the endo-form [IA] with a solid acid. At this time, the endo form [IA] may be contacted with a solid acid as it is, or the endo form may be contacted with a solid acid in the presence of an organic solvent.

As such an organic solvent, specifically,
Cyclohexane, decalin, hexane, benzene, toluene, carbon tetrachloride, 1,2-dichloroethane, etc. are used. The catalytic reaction between the endo-form [IA] of the aromatic-containing norbornene and the solid acid is −5 to 150 ° C., preferably 0 to
It is desirable to carry out at a temperature of 50 ° C. Although the reaction time varies greatly depending on the reaction temperature and the concentration of the aromatic-containing norbornenes, it is preferably 0.5 to 200 hours, preferably 1 to 100 hours.

The above-mentioned catalytic reaction between the endo-form [IA] of the aromatic-containing norbornene and the solid acid can be carried out batchwise or continuously. When the catalytic reaction between the endo-form [IA] of the aromatic-containing norbornenes and the solid acid is carried out by a batch method, specifically, for example, the following may be carried out. A predetermined amount of aromatic-containing norbornenes, a predetermined amount of an organic solvent if necessary, and a solid acid are charged into a reaction tank equipped with a stirrer, and at a predetermined temperature,
Stir for a predetermined time. Then, the solid / liquid is separated by a filtration method, and the aromatic-containing norbornenes and the organic solvent in the liquid phase are separated by a distillation method.

When the contact reaction between the endo-form [IA] of the aromatic-containing norbornene and the solid acid is carried out in a continuous system, specifically, for example, the following may be carried out. (I) Using an apparatus similar to the above batch type, aromatic-containing norbornenes or aromatic-containing norbornenes diluted with an organic solvent are continuously supplied to a reaction tank, and brought into contact with a solid acid existing in the reaction tank. , A method of continuously extracting an aromatic-containing norbornene or a diluted organic solvent thereof.

(Ii) A method in which aromatic-containing norbornenes or aromatic-containing norbornenes diluted with an organic solvent are supplied from one of the columns (or columns) packed with a solid acid and continuously withdrawn from the other. In both methods (i) and (ii), a distillation method can be used to separate the aromatic-containing norbornenes from the organic solvent after contact with the solid acid.

When the endo-form [IA] of the aromatic-containing norbornenes is contacted with the solid acid catalyst in this manner, the endo-form [IA] is isomerized to the exo-form [IB]. The structure of endo-form [IA] and exo-form [IB] or the molar ratio of endo-form to exo-form in the isomer mixture is ¹ H-NM
It can be determined by measuring R or ¹³ C-NMR.

In the present invention, when the endo-form [IA] of an aromatic-containing norbornene is contacted with a solid acid to isomerize into the exo-form [IB], the endo-form [IA] having a purity of 100% is used as a raw material. It is not necessary, and a mixture of endo isomer [IA] and exo isomer [IB] can be used as a raw material. Isomer Mixture The isomer mixture of the aromatic-containing norbornenes represented by the general formula [I] according to the present invention is a mixture of the endo isomer [IA] and the exo isomer [IB] represented by the above formula, The molar ratio of the endo form [IA] and the exo form [IB] ([I-
A] / [IB]) is 80/20 to 0/100, preferably 70/30 to 5/95.

Such an endo body [IA] and an exo body [I]
-B], the isomer mixture of aromatic-containing norbornenes cannot be directly obtained by the Diels-Alder reaction of cyclopentadiene and olefin, and endo-form [IA] It can be obtained for the first time by isomerizing to the body [IB]. Method for producing isomer mixture 85 mol% or more, in many cases 90 mol% or more, more often 90 mol% or more of endo-form [IA] obtainable by Diels-Alder reaction of cyclopentadiene and corresponding olefin Is contacted with an aromatic-containing norbornene isomer mixture containing 94 mol% or more of the solid-state acid as described above under the conditions described above to isomerize the endo-form [IA] to the exo-form [IB]. As a result, the molar ratio ([IA] / [IB]) of the above endo-form [IA] and exo-form [IB] becomes 80/20 to 0/10.
Aromatic containing norbornene isomer mixtures such as 0 can be prepared.

Production of Cyclic Olefin Random Copolymer Aromatic-containing norbornene isomer such that the molar ratio of the endo-form [IA] and the exo-form [IB] is 80/20 to 0/100. A mixture of ethylene and ethylene in a hydrocarbon solvent or in the absence of a hydrocarbon solvent,
It is possible to produce a cyclic olefin-based random copolymer by copolymerizing in the presence of a catalyst consisting of the solvent or an aromatic-containing norbornene-soluble vanadium compound and an organoaluminum compound, preferably a halogen-containing organoaluminum compound. it can.

Hydrocarbon solvents that may be used in the production of the cyclic olefin-based random copolymer include aliphatic hydrocarbons such as hexane, heptane, octane, and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Hydrogen; aromatic hydrocarbons such as benzene, toluene and xylene can be exemplified.

These solvents can be used alone or as a mixture. Specific examples of the vanadium compound used for producing the cyclic olefin-based random copolymer include VO (OR) _a X _b or V (OR) _c X _d (where R is a hydrocarbon group and X is Halogen, a is 0 ≦ a
≤3, b is a number 0≤b≤3 and 2≤a + b≤3, c is 0≤c≤4, d is a number 0≤d≤4 and 3≤c
+ D ≦ 4. ), A vanadium compound represented by the formula (1) or an electron donor adduct thereof is used.

More specifically, VOCl₃, VO (OC₂
H_Five) Cl₂, VO (OC₂H_Five)₂Cl, VO (O-iso-C₃H
₇) Cl₂, VO (O-n-C_FourH₉) Cl₂, VO (OC
₂H_Five)₃, VOBr₂ , VCl_Four, VOCl₂, VO (O
-n-C_FourH₉)₃, VCl₃・ 2OC₈H ₁₆Banaji such as OH
Umium compounds are used. Also, the soluble vanadium catalyst
Electron donors that may be used in preparing media components
Examples of alcohols, phenols, ketones,
Esters of aldehydes, carboxylic acids, organic acids or inorganic acids
, Ethers, acid amides, acid anhydrides, alkoxy silas
Oxygen-containing electron donors such as amines, ammonia, amines, nits
Examples include nitrogen-containing electron donors such as rils and isocyanates.
You can

More specifically, carbon such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol. Number 1
~ 18 alcohols; phenols, cresols, xylenols, ethylphenols, propylphenols, nonylphenols, cumylphenols, naphthols, and other C6-20 phenols that may have lower alkyl groups; acetone, methyl ethyl ketone, methyl isobutyl Ketones, acetophenones, benzophenones, benzoquinones, and other ketones having 3 to 15 carbon atoms; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, and other aldehydes having 2 to 15 carbon atoms; methyl formate, methyl acetate, Ethyl acetate, vinyl acetate, propyl acetate, octal acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, meta Methyl acrylic acid, dichloroacetic ethyl acetate, methyl methacrylate, ethyl crotonate, cyclohexanecarboxylate, 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 carboxylic acid,
Diethyl nadic acid, Diisopropyl tetrahydrophthalate, Diethyl phthalate, Diisobutyl phthalate, Di-n-butyl phthalate, Di2-ethylhexyl phthalate, γ-
Butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate and other organic acid esters having 2 to 30 carbon atoms; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride and the like having 2 to 1 carbon atoms
Acid halides of 5; methyl ether, ethyl ether,
Ethers having 2 to 20 carbon atoms such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acetic acid amide,
Acid amides such as benzoic acid amide and toluic acid amide;
Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine; nitriles such as acetonitrile, benzonitrile, tolunitrile; ethyl silicate, diphenyldimethoxysilane, etc. Examples thereof include alkoxysilanes. Two or more kinds of these electron donors can be used.

As the organoaluminum compound catalyst component used for producing the cyclic olefin random copolymer, a compound having at least one Al-carbon bond in the molecule is used. For example, the compound represented by the general formula R ¹ _{m ^{al (oR 2) n H p}} X q ... [III] ( wherein R ¹ and R ² are carbon atoms, from 1 to 15
Hydrocarbon groups, including one, preferably one to four, may be the same or different. X is halogen,
m is 0 ≦ m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q
Is a number 0 ≦ q <3, and m + n + p + q = 3
Is. An organoaluminum compound represented by), or the general formula _{^{M 1 AlR 1 4 ... [IV}} ] ( wherein M ¹ is Li, Na, a K, R ¹ are as defined in the general formula [III].) Examples thereof include complex alkylated products of a Group 1 metal and aluminum.

Examples of the organoaluminum compound belonging to the above general formula [III] include the following. General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as those in the general formula [III], and m is preferably a number of 1.5 ≦ m <3.) General formula R ¹ _m AlX _3-m (wherein R ¹ is the same as the above general formula [III], X is halogen, and m is preferably 0 <m <3.) General formula R ¹ _m AlH _{3 -m} (wherein R ¹ is the same as the above-mentioned general formula [III], and 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 those in the general formula [III], X is halogen, 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q
<3, m + n + q = 3. ) And the like can be exemplified.

As the aluminum compound belonging to the general formula [III], more specifically, triethylaluminum,
Trialkylaluminums such as tributylaluminum; Trialkenylaluminums such as triisopropenylaluminum; Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide Besides,
Partially alkoxylated alkylaluminums, dialkylaluminum halides such as diethylaluminium chloride, dibutylaluminum chloride, diethylaluminum bromide, having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 ; Alkyl aluminum sesquihalides such as chloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; Partially halogenated alkyl aluminums such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide and other alkyl aluminum dihalides; Dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; ethyl aluminum Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as umdihydride, propylaluminum dihydride; partially alkoxylated and halogenated such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide, ethylaluminum ethoxy bromide And alkyl aluminum.

Further, it may be a compound similar to the above-mentioned general formula [III], for example, an organoaluminum compound in which two or more aluminums are bound via an oxygen atom or a nitrogen atom. As such a compound, specifically,

[0039]

[Chemical 14]

Examples include the following: Examples of the compound belonging to the general formula [IV] include LiAl (C ₂ H ₅ ) ₄ and LiAl
(C ₇ H _{15) 4} etc. can be exemplified. Among these, it is particularly preferable to use an alkylaluminum halide, an alkylaluminum dihalide or a mixture thereof.

In producing the cyclic olefin random copolymer, the copolymerization reaction of ethylene and the aromatic-containing norbornene 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. It is a range.

The ratio of aluminum atoms to vanadium atoms (Al / V) in the polymerization reaction system is preferably 2 or more, preferably 2 to 50, more preferably 3 to 20. The soluble vanadium compound and the organoaluminum compound are usually diluted with the hydrocarbon solvent or the aromatic-containing norbornenes, and supplied. Here, it is desirable that the soluble vanadium compound is diluted within the above concentration range, but a method of preparing the organoaluminum compound at an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization reaction system and supplying it to the polymerization reaction system is a method. Adopted.

When producing a cyclic olefin-based random copolymer, the concentration of the soluble vanadium compound in the copolymerization reaction system is usually 0.
01-5 mmol / l, preferably 0.05-5
It is in the range of millimoles / liter. Such a copolymerization reaction between ethylene and an aromatic-containing norbornene is carried out by -50
The temperature is -100 to 100 ° C, preferably -30 to 80 ° C, more preferably -20 to 60 ° C.

The reaction time for carrying out the above-mentioned copolymerization reaction (the average residence time of the polymerization reaction mixture in the case of continuous polymerization reaction) varies depending on the kind of the polymerization raw material, the concentration of the catalyst component and the temperature. It is usually 5 minutes to 5 hours, preferably 10 minutes to 3 hours. The pressure during the copolymerization reaction is usually more than 0 and 50 kg / cm ² ,
It is preferably more than 0 and 20 kg / cm ² .

When producing the cyclic olefin random copolymer, the molar ratio of ethylene / aromatic-containing norbornenes is usually 90/10 to 10/90, preferably 85/15 to 40/60. Is desirable. In the above cyclic olefin random copolymer, a small amount of other copolymerizable monomer such as norbornenes other than aromatic-containing norbornenes or ethylene other than ethylene is used as long as the object of the present invention is not impaired. The α-olefin and the like may be copolymerized in an amount of 10 mol% or less of the constitutional unit derived from the aromatic-containing norbornenes.

By carrying out the copolymerization reaction of ethylene and the aromatic-containing norbornenes as described above, a hydrocarbon solvent solution of a cyclic olefin random copolymer or an unreacted cyclic olefin solution is obtained. The concentration of the cyclic olefin-based random copolymer contained in such a copolymer solution is usually 0.5 to 40% by weight, preferably 2.0 to 3%.
It is in the range of 0% by weight, and the produced copolymer solution also contains a soluble vanadium compound component and an organoaluminum compound component which are catalyst components.

The cyclic olefin random copolymer solution thus obtained is usually subjected to a series of treatments from deashing to pelletizing to obtain cyclic olefin random copolymer pellets. .. In the above cyclic olefin-based random copolymer, the constitutional unit derived from the aromatic-containing norbornene has a structure represented by the following formula.

[0048]

[Chemical 15]

(In the formula, p, q, r and R ^{1 to} R ¹⁵ are the same as those in the above general formula [I].) Further, 1 of the ethylene / aromatic-containing norbornenes copolymer obtained by the present invention.
The intrinsic viscosity [η] measured in decalin at 35 ° C is 0.
It is preferably from 05 to 10 dl / g.

[0050]

The molar ratio ([IA] / [IB]) of the endo form [IA] and the exo form [IB] according to the present invention is 80/2.
A cycloolefin random copolymer obtained by copolymerizing ethylene with an aromatic-containing norbornene isomer mixture having a ratio of 0 to 0/100 is a copolymer of ethylene and an aromatic-containing norbornene having the same composition. Aromatic-containing norbornene isomerism in which the endo-form [IA] is present in an amount of 85 mol% or more, often 90 mol% or more, and more often 94 mol% or more when polymerized. Compared with the cyclic olefin random copolymer obtained by copolymerizing the polymer mixture and ethylene, the reaction rate of the aromatic-containing norbornenes during the copolymerization reaction is high, and the physical properties of the copolymer are The glass transition point (Tg) is high, the heat resistance is excellent, 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 use of the aromatic-containing norbornene isomer mixture according to the present invention can reduce the amount of expensive aromatic-containing norbornenes copolymerized. It will be possible.

[0051]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Quantitative method 1,4-methano-1,4,4a, 9a-tetrahydrofluorene (MT
HF) isomer mixture of endo [IA] and exo [I]
The molar ratio with -B] was calculated based on the integrated intensity ratio of the absorption peak of the olefin proton in the obtained spectrum by measuring ¹ H-NMR (in CDCl ₃ , room temperature, TMS standard).

The chemical shifts of olefin protons obtained by ¹ H-NMR measurement of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene are shown in Tables A and B. Also,
¹³ C- of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene
The chemical shifts of carbon obtained by measuring NMR are shown in Tables A and B of Table 1.

[0053]

[Table 1]

[0054]

[Table 2]

Method of Measuring Softening Temperature For the samples for measuring softening temperature obtained by molding the copolymers obtained in the polymerization example and the comparative polymerization example into a sheet having a thickness of 1 mm, a thermomechanical analyzer (manufactured by DuPont) ( Thermomechanical Analyser) was used to measure the thermal deformation behavior. That is, a quartz needle is placed on the sample, and the sample is continuously heated at a temperature rising rate of 5 ° C./min while a weight of 49 g is applied to the measuring needle. The temperature at the time of penetration of 0.635 mm was defined as the softening temperature. (Hereinafter, described as "TMA softening point".) Method for measuring flexural modulus The flexural modulus is measured at a temperature of 23 ° C by ASTM-D7.
The measurement method described in 90 was used.

Method of Measuring Intrinsic Viscosity The measurement of intrinsic viscosity was carried out at a temperature of 135 ° C. using decalin as a solvent.

[0057]

[Reference Example 1] Indene and cyclopentadiene are subjected to Diels-Alder reaction by the method described in JP-B-46-14910 to give 1,4-methano-1,
4,4a, 9a-Tetrahydrofluorene (hereinafter referred to as "MTHF"
Sometimes abbreviated. ) Was synthesized.

The obtained MTHF 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 87 mol%, and the exo form was present in an amount of 13 mol%. The results are shown in Table 2.

[0059]

Reference Example 2 5-phenyl-bicyclo [2.2.1] hept-2-ene (hereinafter referred to as “Ph-BH”) was obtained by subjecting styrene and cyclopentadiene to Diels-Alder reaction in the same manner as in Reference Example 1. May be abbreviated). The obtained Ph-BH was measured by ¹ H-NMR,
The molar ratio of endo-form and exo-form was measured.

The endo form was present in an amount of 92 mol%, and the exo form was present in an amount of 8 mol%. The results are shown in Table 2.

[0061]

Example 1 To a 30-liter reaction tank equipped with a stirrer and a reflux condenser, 1 liter of MTHF obtained in Reference Example 1 and 17 liter of cyclohexane were added and stirred. Zeolite (Zeoram F-9, spherical, 1.8-2.4 mmφ, Na ₂ O.Al ₂ O ₃
2.5 kg of SiO ₂ ) was added, and the mixture was stirred at room temperature for 6 hours to carry out an isomerization reaction of the endo form to the exo form.

After the reaction was completed, the reaction mixture was filtered to separate the catalyst, and the obtained cyclohexane solution of MTHF was distilled under reduced pressure (50 mmHg) to distill cyclohexane to obtain isomerized MTHF. The obtained MTHF
^When analyzed by ¹ H-NMR, the molar ratio of the endo form and the exo form was 41/59. The results are shown in Table 2.

[0063]

Example 2 Example 1 except that the reaction time was 3 hours.
The isomerization reaction of MTHF was carried out in the same manner as in. The results are shown in Table 2.

[0064]

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

[0065]

Example 4 The reaction was carried out in the same manner as in Example 1 except that the Ph-BH obtained in Reference Example 2 was used. Second result
Shown in the table.

[0066]

Example 5 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.

[0067]

Example 6 The reaction was performed in the same manner as in Example 4 except that the silica-alumina used in Example 3 was used as the catalyst and the reaction time was 96 hours. The results are shown in Table 2.

[0068]

[Table 3]

[0069]

Polymerization Example 1 A glass-made polymerization vessel having an internal volume of 1 liter equipped with a stirrer was continuously added from the top of the polymerization vessel to the cyclohexane solution of MTHF obtained in Example 1, and VO as a catalyst.
A solution of (OC ₂ H ₅ ) Cl ₂ in cyclohexane and ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 Cl _1.5 ).
The cyclohexane solution of was supplied so that the concentrations in the polymerization vessel were 60 g / liter, 0.5 mmol / liter and 4.0 mmol / liter, respectively, and ethylene was added from the upper portion of the polymerization vessel at 15 liters / hour and hydrogen. The feed rate was 0.5 liter / hour. On the other hand, the total amount of the polymerization liquid in the polymerization vessel was continuously discharged from the upper portion of the polymerization vessel to 1 liter so that the average residence time was 0.5 hours.

The polymerization reaction was carried out at a polymerization temperature of 10 ° C. by circulating a cooling medium 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 / MTHF random copolymer. The polymerization reaction was stopped by adding a small amount of isopropyl alcohol to the polymerization liquid extracted from the upper part of the polymerization vessel. After that, 5 ml of concentrated hydrochloric acid for 1 liter of water
The aqueous solution to which was added and the polymerization solution were brought into contact with each other at a ratio of 1: 1 using a homomixer under strong stirring to transfer the catalyst residue to the aqueous phase. The above-mentioned mixed solution was allowed to stand still, the aqueous phase was removed, and further washed twice with distilled water to purify and separate the polymerization solution.

Next, the polymerization solution after the reaction was stopped was added to a mixer containing about 3 times by volume of acetone with respect to this polymerization solution with vigorous stirring to precipitate a copolymer, and the precipitated copolymer was further added. Was separated from the solution by filtration. The obtained copolymer was dispersed in acetone so that the concentration was about 50 g / liter, 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 the mixture was heated at 120 ° C. for 24 hours.
It was dried under reduced pressure.

When ¹³ C-NMR was measured for the obtained copolymer of ethylene and MTHF, the ethylene content in the copolymer was 63.0 mol%. The intrinsic viscosity [η] and the TMA softening point are 0.41 dl, respectively.
/ G and 178 ° C. The results are shown in Table 4. Furthermore, FIG. 1 shows the relationship between the aromatic-containing norbornene content (mol%) of the obtained ethylene / MTHF and the TMA softening point, and FIG. 2 shows the aromatic-containing norbornene content (mol%) of the copolymer. The relationship with the flexural modulus is shown.

MT contained in the obtained copolymer
The molar ratio of HF unit endo-form to exo-form is ¹³ C-NM
When measured by R, the endo / exo ratio is 4
The value was 0/60, and the value hardly changed before and after the polymerization.

[0074]

[Polymerization Examples 2 to 8 and Comparative Polymerization Examples 1 and 2] Using the raw materials (aromatic-containing norbornene) shown in Table 3 under the conditions shown in Table 3, the same procedure as in Polymerization Example 1 was conducted. Copolymerization of ethylene and MTHF was performed. The results obtained are shown in Table 4. Further, FIG. 1 shows the relationship between the aromatic-containing norbornene content (mol%) and the TMA softening point of the obtained ethylene / MTHF copolymer, and FIG. 2 shows the aromatic-containing norbornene content (mol%) of the polymer. The relationship with the flexural modulus is shown.

[0075]

[Table 4]

[0076]

[Table 5]

[Brief description of drawings]

1 is an ethylene-aromatic norbornene (MTHF) copolymer obtained by copolymerizing ethylene with an aromatic-containing norbornene (MTHF) isomer mixture having various endo / exo ratios. It is a figure which shows the relationship between the aromatic content norbornene content (mol%) and TMA softening point of.

FIG. 2 is a diagram showing a relationship between an aromatic-containing norbornene content (mol%) of an ethylene / aromatic-containing norbornene (here, MTHF) copolymer and a flexural modulus.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C07C 13/62 8619-4H 13/68 8619-4H 23/30 9280-4H 23/46 9280-4H 25/22 9280-4H // C07B 61/00 300

Claims (3)

[Claims] 1. An aromatic compound characterized in that an endo-form [IA] of an aromatic-containing norbornene represented by the following general formula [I] is contacted with a solid acid catalyst to isomerize into an exo-form [IB]. Method for isomerizing contained norbornenes endo-form [IA] to exo-form [IB]. [Chemical 1] (In the formula, p is 0 or an integer of 1 or more, and q and r
Is 0, 1 or 2, R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R 1 ⁵ (or R ⁶ ) and R ⁹ (or R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms,
Further, they may be directly bonded without any group. [Chemical 2] 2. The molar ratio ([IA] / [IB]) of the endo isomer [IA] and the exo isomer [IB] represented by the following formula is 80.
Aromatic-containing norbornene isomer mixture represented by the following general formula [I], which is / 20 to 0/100. [Chemical 3] (In the formula, p is 0 or an integer of 1 or more, and q and r
Is 0, 1 or 2, R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R 1 ⁵ (or R ⁶ ) and R ⁹ (or R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms,
Further, they may be directly bonded without any group. [Chemical 4] 3. The endo-body [IA] represented by the following formula is 8
An isomer mixture of an endo isomer [IA] and an exo isomer [IB] of an aromatic-containing norbornene represented by the following general formula [I], which is contained in an amount of 5 mol% or more, is contacted with a solid acid catalyst, The molar ratio ([IA] / [IB]) of the endo form [IA] and the exo form [IB] contained in the isomer mixture is 80.
/ 20 to 0/100. A method for producing an aromatic-containing norbornene isomer. [Chemical 5] (In the formula, p is 0 or an integer of 1 or more, and q and r
Is 0, 1 or 2, R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R 1 ⁵ (or R ⁶ ) and R ⁹ (or R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms,
Further, they may be directly bonded without any group. [Chemical 6]