JP3128786B2 - Method for isomerizing an aromatic-containing norbornene endo-form into an exo-form, mixture of aromatic-containing norbornenes isomer, and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

Background of the Invention The present applicant has previously reported that a cyclic olefin random copolymer obtained by copolymerizing ethylene and a cyclic olefin such as tetracyclododecene has excellent transparency, heat resistance, It is a synthetic resin with a good balance of heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and mechanical strength, and exhibits excellent performance in the field of optical materials such as optical memory disks and optical fibers. Heading, JP-A-60-168708, JP-A-61-98780, JP-A-61-115912
JP, JP-A-61-115916, JP-A-61-115916
No. 120816 and JP-A-62-252407.

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

The present inventors have intensively studied to further improve the heat resistance and mechanical strength of a cyclic olefin random copolymer obtained by copolymerizing ethylene and an aromatic-containing norbornene as described above. However, the exo form [I-
B] It has been found that a cyclic olefin random copolymer obtained by copolymerizing an aromatic-containing norbornene isomer mixture having a large content with ethylene has remarkably improved heat resistance and mechanical strength.

[0005]

SUMMARY OF THE INVENTION The present invention has been made based on the above findings and is intended to isomerize an endo-form [IA] to an exo-form [IB] in an aromatic-containing norbornene isomer mixture. Aromatic-containing norbornene isomer mixtures that can provide a cyclic olefin-based random copolymer having excellent heat resistance and mechanical strength when copolymerized with ethylene while providing a method of And a method for manufacturing the same.

[0006]

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

[0007]

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(Where p is an integer of 0 or 1 ;
And r are 0, 1 or 2, and 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 and an alkoxy group, wherein R ⁵ (or R ⁶ ) and R ⁹ (or R ⁷ ) are bonded via an alkylene group having 1 to 3 carbon atoms. And it may be directly bonded without any group.

[0009]

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The aromatic-containing norbornene isomer mixture according to the present invention has a molar ratio ([IA] / [IB]) of the endo-form [IA] to the exo-form [IB] of 70 represented by the above formula.
/ 30 to 5/95 . The method for producing an aromatic-containing norbornene isomer mixture according to the present invention is characterized in that the endo-form [IA] represented by the above formula contains 85 mol%
The isomer mixture of the endo-form [IA] and the exo-form [IB] of the aromatic-containing norbornenes contained in the above amounts is brought into contact with a solid acid catalyst to form the endo-form [IA] contained in the isomer mixture And the molar ratio of the exo form [IB] ([IA] / [I
-B]) is set to 70/30 to 5/95 .

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for isomerizing an aromatic-containing norbornene endo-isomer into an exo-form, an aromatic-containing norbornene isomer mixture, and a method for producing the aromatic-containing norbornene isomer mixture according to the present invention will be described below. Will be specifically described. In the present invention, an aromatic-containing norbornene endo-form [IA] represented by the following formula [IA] is isomerized to an exo-form represented by the following formula [IB] by contact with a solid acid. I have.

[0012]

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(Wherein p is an integer of 0 or 1 ;
And r are 0, 1 or 2, and 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 and an alkoxy group, wherein R ⁵ (or R ⁶ ) and R ⁹ (or R ⁷ ) are bonded via an alkylene group having 1 to 3 carbon atoms. And it may be directly bonded without any group.

[0014]

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Here, in the above general formula [I], p is an integer of 0 or 1 , and preferably an integer of 0 to 3. R ^{1 to} R ¹⁵ each independently represent 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 an alkyl group having 1 to 6 atoms such as a methyl group, an ethyl group, an isopropyl group, an isobutyl group, an amyl group, and a hexyl group. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group, and specific examples include a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

In the above 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. May be directly bonded without the intervention of the group of Specific examples of aromatic-containing norbornenes used in the present invention include the following compounds.

[0017]

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[0018]

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[0019]

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Aromatic Norbornenes as Raw Materials, That is, End-Forms of Aromatic Norbornenes [IA]
Can be obtained by the Diels-Alder reaction of cyclopentadienes with the corresponding olefins.
End-forms of the above aromatic-containing norbornenes [I-
The solid acid used when isomerizing A] to the exo form [IB] includes, specifically, silica-alumina (Al ₂ O ₃
+ SiO ₂ as a main component), alumina (Al ₂ O ₃ as a main component), zeolite (Na ₂ O + SiO ₂ + Al ₂ O ₃ as a main component), activated clay, and the like.

Other solid acids other than those mentioned above include 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 _Two
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.

In addition to the above 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. In this case, the endo-form [IA] may be directly contacted with a solid acid, 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 and the like are used. The contact reaction between the endo-form [IA] of the aromatic-containing norbornene and the solid acid is carried out at -5 to 150C, preferably 0 to 150C.
It is desirable to carry out at a temperature of 50 ° C. The reaction time varies greatly depending on the reaction temperature and the concentration of the aromatic-containing norbornenes, but it is desirably 0.5 to 200 hours, preferably about 1 to 100 hours.

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

Further, when the contact reaction between the endo-form [IA] of the aromatic-containing norbornene and the solid acid is carried out in a continuous manner, specifically, for example, the following method may be used. (I) Using the same apparatus as in the batch system, aromatic-containing norbornenes or aromatic-containing norbornenes diluted with an organic solvent are continuously supplied to the reaction tank and brought into contact with the solid acid present in the reaction tank. And continuously extracting aromatic-containing norbornenes or a diluted organic solvent thereof.

(Ii) A method in which an aromatic-containing norbornene or an aromatic-containing norbornene diluted with an organic solvent is 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 employed to separate the aromatic-containing norbornenes after contact with the solid acid from the organic solvent.

When the endo-form [IA] of the aromatic-containing norbornene is brought into contact with the solid acid catalyst in this manner, the endo-form [IA] is isomerized 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 ¹ H-NM
It can be determined by measuring R or ¹³ C-NMR.

In the present invention, when the endo-form [IA] of the aromatic-containing norbornene is brought into contact with a solid acid to isomerize to the exo-form [IB], the endo-form [IA] having a purity of 100% is used as a raw material. There is no need to use a mixture of the endo-form [IA] and the exo-form [IB] as a raw material. 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-form [IA] and the exo-form [IB] represented by the above formula, The molar ratio of the endo-form [IA] to the exo-form [IB] ([I-
A] / [IB]) is preferably from 70/30 to 5/95.

The endo-form [IA] and the exo-form [I
A mixture of isomers of aromatic-containing norbornenes having a molar ratio of -B] cannot be directly obtained by the Diels-Alder reaction between cyclopentadiene and olefin, and the end-form [IA] is exo- It can be obtained only by isomerizing to the form [IB]. Method for producing isomer mixture Endo-form [IA] obtainable by Diels-Alder reaction of cyclopentadiene with corresponding olefin is at least 85 mol%, often at least 90 mol%, more often at least 90 mol% In the above, an isomer mixture of aromatic-containing norbornenes containing not less than 94 mol% is brought into contact with the above-mentioned solid acid under the above-mentioned conditions to convert the endo-form [IA] into the exo-form [IB]. Thus, the molar ratio ([IA] / [IB]) between the endo-form [IA] and the exo-form [IB] is 70/30 to 5/95.
A mixture of aromatic-containing norbornenes isomers can be prepared.

Production of cyclic olefin-based random copolymer Aromatic-containing norbornene isomer whose molar ratio between endo-form [IA] and exo-form [IB] is 70/30 to 5/95 The mixture, ethylene, in a hydrocarbon solvent or in the absence of a hydrocarbon solvent, comprises a vanadium compound and an organoaluminum compound, preferably a halogen-containing organoaluminum compound, which are soluble in the solvent or the aromatic-containing norbornenes. By copolymerizing in the presence of a catalyst, a cyclic olefin-based random copolymer can be produced.

Examples of the hydrocarbon solvent which may be used in producing the cycloolefin random copolymer include aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Hydrogen; examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene;

These solvents can be used alone or as a mixture. The vanadium compound used in manufacturing the cycloolefin random copolymer, specifically, the general formula VO (OR) _a X _b or V (OR) _c X _d (wherein, R is a hydrocarbon group, X is Halogen, a is 0 ≦ a
≦ 3, b is a number of 0 ≦ b ≦ 3 and 2 ≦ a + b ≦ 3, c is a number of 0 ≦ c ≦ 4, d is a number of 0 ≦ d ≦ 4 and 3 ≦ c
+ D ≦ 4. ) Or an electron donor adduct thereof.

More specifically, VOCl_Three, VO (OC_Two
H_Five) Cl_Two, VO (OC_TwoH_Five)_TwoCl, VO (O-iso-C_ThreeH
₇) Cl_Two, VO (On-C_FourH₉) Cl_Two, VO (OC
_TwoH_Five)_Three, VOBr_Two , VCl_Four, VOCl_Two, VO (O
-n-C_FourH₉)_Three, VCl_Three・ 2OC₈H ₁₆Vanaji such as OH
Compound is used. In addition, the soluble vanadium
Electron donors that may be used when preparing medium components
Alcohols, phenols, ketones, alcohols
Esters of aldehydes, carboxylic acids, organic or inorganic acids
, Ethers, acid amides, acid anhydrides, alkoxysilas
Oxygen-containing electron donors such as ammonia, ammonia, amines, nitrite
Examples include nitrogen-containing electron donors such as rils and isocyanates.
I can do it.

More specifically, carbon such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl alcohol, etc. Number 1
Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol; acetone, methylethylketone, methylisobutyl C3 to C15 ketones such as ketone, acetophenone, benzophenone and benzoquinone; C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and 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, 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-hexyl cyclohexenecarboxylate,
Diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-
Organic acid esters having 2 to 30 carbon atoms such as butyrolactone, δ-valerolactone, coumarin, phthalide and ethylene carbonate; 2 to 1 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride
5 acid halides; methyl ether, ethyl ether,
Ethers having 2 to 20 carbon atoms such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acetate 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 and the like Alkoxysilanes and the like can be mentioned. Two or more of these electron donors can be used.

Further, as the organoaluminum compound catalyst component used in manufacturing the cycloolefin random copolymer, a compound having one Al- carbon bond in at least the molecule is used, for example, 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
, Preferably 1 to 4 hydrocarbon groups, which 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 satisfying 0 ≦ q <3, and m + n + p + q = 3
It 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].) And a complex alkylated product of a Group 1 metal and aluminum.

The following are examples of the organoaluminum compound belonging to the above general formula [III]. General formula R ¹ _m Al (OR ² ) _{3 -m} (where R ¹ and R ² are the same as in the general formula [III], and m is preferably a number of 1.5 ≦ m <3) formula R ¹ _m AlX _3-m (wherein R ¹ is the same as the general formula [III], X is a halogen, m is preferably 0 <m <3.) the general formula R ¹ _m AlH _{3 -m} (where R ¹ is the same as in the general formula [III], and m preferably satisfies 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. ) 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; Besides,
R ¹ _2.5 Al as having an average composition represented by (OR ²⁾ _0.5, partially alkoxylated alkyl aluminum, diethyl aluminum chloride, dibutyl aluminum chloride, dialkyl aluminum halides such as diethyl aluminum bromide, ethyl aluminum sesqui Alkyl aluminum sesquihalides such as chloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; ethylaluminum Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as uranium dihydride and propylaluminum dihydride; partially alkoxylated and halogenated such as ethylaluminum ethoxychloride, butylaluminum butoxycyclolide and ethylaluminum ethoxybromide Can be exemplified.

A compound similar to the general formula [III], 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,

[0039]

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And the like. Compounds belonging to the general formula [IV] include LiAl (C ₂ H ₅ ) ₄ , LiAl
(C ₇ H ₁₅ ) _{4 and the} like. 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 aromatic-containing norbornenes 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.

The ratio (Al / V) of aluminum atoms to vanadium atoms in the polymerization reaction system is desirably 2 or more, preferably 2 to 50, and more preferably 3 to 20. The soluble vanadium compound and the organoaluminum compound are usually supplied after being diluted with the hydrocarbon solvent or the aromatic-containing norbornenes, respectively. Here, it is desirable to dilute the soluble vanadium compound to the above concentration range, but there is a method 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. Adopted.

When a cyclic olefin-based random copolymer is produced, the concentration of the soluble vanadium compound in the copolymerization reaction system is usually 0.1 as vanadium atom.
01 to 5 mmol / l, preferably 0.05 to 3
It is in the range of mmol / l. Such a copolymerization reaction between ethylene and an aromatic-containing norbornene is -50.
To 100 ° C, preferably -30 to 80 ° C, more preferably -20 to 60 ° C.

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

In producing the cyclic olefin-based random copolymer, the molar ratio of ethylene / the aromatic-containing norbornenes is usually in the range of 90/10 to 10/90, preferably in the range of 85/15 to 40/60. It is desirable. In the above-mentioned cyclic olefin-based random copolymer, a small amount of other copolymerizable monomers such as norbornenes other than aromatic norbornenes or ethylene other than ethylene, as long as the object of the present invention is not impaired. An α-olefin or the like may be copolymerized in an amount of 10 mol% or less of the structural unit derived from the aromatic-containing norbornene.

When the copolymerization reaction of ethylene and the aromatic-containing norbornenes is carried out 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 from 0.5 to 40% by weight, preferably from 2.0 to 3% by weight.
In the range of 0% by weight, 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 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 random copolymer. . In the cyclic olefin-based random copolymer as described above, the structural unit derived from the aromatic-containing norbornenes has a structure represented by the following formula.

[0048]

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(In the formula, p, q, r and R ^{1 to} R ¹⁵ are the same as those in the above formula [I].) Also, one of the ethylene / aromatic-containing norbornenes copolymers obtained by the present invention
The intrinsic viscosity [η] measured in decalin at 35 ° C. is 0.3.
It is preferably from 0.05 to 10 dl / g.

[0050]

According to the present invention, the molar ratio ([IA] / [IB]) between the endo-form [IA] and the exo-form [IB] is 70/3.
In a cyclic olefin random copolymer obtained by copolymerizing an aromatic-containing norbornene isomer mixture of 0 to 5/95 and ethylene, ethylene and the aromatic-containing norbornene have the same composition. When polymerized, the endo-form [IA] is 85 mol% or more, often 90 mol% or more, and more often 94 mol%.
The reaction rate of the aromatic-containing norbornenes during the copolymerization reaction compared to the cyclic olefin-based random copolymer obtained by copolymerizing ethylene with the aromatic-containing norbornenes isomer mixture present in the above amount As for the physical properties of the 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, if the aromatic-containing norbornene isomer mixture according to the present invention is used, the amount of expensive aromatic-containing norbornenes can be reduced. It becomes 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
Endo-form [IA] and exo-form [I] in the HF) isomer mixture
-B] was measured based on ¹ H-NMR (in CDCl ₃ , room temperature, based on TMS), and calculated based on the integrated intensity ratio of the absorption peak of the olefin proton in the obtained spectrum.

The chemical shifts of olefin protons obtained by measuring ¹ H-NMR 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.

[0053]

[Table 1]

[0054]

[Table 2]

Method of Measuring Softening Temperature A sample for measuring the softening temperature obtained by molding each of the copolymers obtained in the polymerization examples and the comparative polymerization examples into a sheet having a thickness of 1 mm was subjected to a thermomechanical analyzer (manufactured by DuPont). The thermal deformation behavior was measured using a Thermomechanical Analyzer). 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 when penetrating 0.635 mm was defined as the softening temperature. (Hereinafter referred to as “TMA softening point”.) Method for measuring flexural modulus The flexural modulus was measured at a temperature of 23 ° C. using ASTM-D7.
The measurement was performed according to the measurement method described in No. 90.

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

[0057]

Reference Example 1 Indene and cyclopentadiene were subjected to a Diels-Alder reaction according to the method described in JP-B-46-14910 to give 1,4-methano-1,
4,4a, 9a-tetrahydrofluorene (hereinafter “MTHF”
May be abbreviated. ) Was synthesized.

The obtained MTHF was measured by ¹ H-NMR, and the molar ratio between 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 By subjecting styrene and cyclopentadiene to a Diels-Alder reaction in the same manner as in Reference Example 1, 5-phenyl-bicyclo [2.2.1] hept-2-ene (hereinafter referred to as "Ph-BH") May be abbreviated). The obtained Ph-BH was measured by ¹ H-NMR,
The molar ratio between the endo-form and the 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 1 liter of MTHF obtained in Reference Example 1 and 17 liter of cyclohexane were added to a 30 liter reaction tank equipped with a stirrer and a reflux condenser, followed by stirring. The resulting solution zeolite (manufactured by Tosoh Corporation, Zeolam F-9, _{spherical, 1.8~2.4mmφ, Na 2 O · Al} 2 O 3 ·
6 kg of 2.5 SiO ₂ ) was added thereto, and the mixture was stirred at room temperature for 6 hours to carry out an isomerization reaction of an endo-form to an exo-form.

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

[0063]

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

[0064]

Example 3 As a catalyst, silica-alumina (manufactured by Shinagawa White Brick Co., Ltd., Segard OW, granular, 0.5 to ₂ mmφ, Al ₂
O ₃ · mSiO ₂ · nH with _{2 O + Al (OH) 3} ), and changing the amount of cyclohexane and the catalyst, respectively 4.0 liters and 3 kg, except for changing the reaction time to 96 hours, as in Example 1 The reaction was carried out. Second result
It is shown in the table.

[0065]

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

[0066]

Example 5 A 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 carried out 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 changed to 96 hours. The results are shown in Table 2.

[0068]

[Table 3]

[0069]

[Polymerization Example 1] A cyclohexane solution of MTHF obtained in Example 1 was continuously introduced from the upper part of a polymerization vessel into a glass polymerization vessel having an internal volume of 1 liter equipped with a stirring device, and VO was used as a catalyst.
(OC ₂ H ₅ ) Cl ₂ in cyclohexane and ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 Cl _1.5 )
Is supplied so that the concentrations in the polymerization vessel are 60 g / L, 0.5 mmol / L, and 4.0 mmol / L, respectively. From the top of the polymerization vessel, ethylene is supplied at 15 L / hour and hydrogen is supplied. The feed was at a feed rate of 0.5 liter / hour. On the other hand, the polymerization solution was continuously extracted from the upper portion of the polymerization vessel so that the total amount of the polymerization solution in the polymerization vessel was 1 liter 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. The 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. Then, 5 ml of concentrated hydrochloric acid per liter of water
Was added to the polymerization solution at a ratio of 1 to 1 using a homomixer under vigorous stirring to transfer the catalyst residue to the aqueous phase. The mixture was allowed to stand, and after removing the aqueous phase, the mixture was further washed twice with distilled water, and the polymerization liquid was purified and separated.

Next, the polymer solution after the termination of the reaction was added to a mixer containing about 3 times the volume of acetone with respect to the polymer solution under vigorous stirring to precipitate a copolymer. Was separated from the solution by filtration. The obtained copolymer was dispersed in acetone so as to have a concentration of about 50 g / liter, and the mixture was subjected to a heat treatment at the boiling point of acetone for about 2 hours. After the treatment, the copolymer was separated from acetone by filtration, and was
Drying under reduced pressure was performed.

The obtained copolymer of ethylene and MTHF was subjected to ¹³ C-NMR measurement to find that the ethylene content in the copolymer was 63.0 mol%. The intrinsic viscosity [η] and the TMA softening point were 0.41 dl, respectively.
/ G and 178 ° C. The results are shown in Table 4. 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.

The MT contained in the obtained copolymer was
The molar ratio between the endo-form and the exo-form of the HF unit is ¹³ C-NM
As measured by R, the endo / exo ratio was 4
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 In the same manner as in Polymerization Example 1 under the conditions shown in Table 3 using the starting materials (aromatic-containing norbornene) shown in Table 3 Copolymerization of ethylene and MTHF was performed. Table 4 shows the obtained results. 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 the drawings]

FIG. 1 is an ethylene / aromatic-containing norbornene (here, MTHF) copolymer obtained by copolymerizing an aromatic-containing norbornene (here, MTHF) isomer mixture having various endo- / exo-form ratios with ethylene. FIG. 2 is a graph showing the relationship between the content of aromatic-containing norbornene (mol%) and the TMA softening point.

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

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C07C 13/64 C07C 13/64 // C07B 61/00 300 C07B 61/00 300 (56) References JP-A-55-72122 JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 5/22 C07C 13/42 C07C 13/64 CA (STN)

Claims (3)

(57) [Claims] 1. An aromatic compound, which is obtained by isomerizing an endo-form [IA] of an aromatic-containing norbornene represented by the following general formula [I] into an exo-form [IB] by contact with a solid acid catalyst. A method for isomerizing a contained norbornene endo-form [IA] to an exo-form [IB]. Embedded image Wherein p is an integer of 0 or 1 , q and r are 0, 1 or 2, and R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic group. A hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group,
R ⁵ (or R ⁶ ) and R ⁹ (or R ⁷ ) each have 1 carbon atom
They may be bonded via an alkylene group of 1 to 3, or may be directly bonded without any group. Embedded image 2. The molar ratio ([IA] / [IB]) between the endo-form [IA] and the exo-form [IB] represented by the following formula is 70.
/ 30 to 5/95 , an aromatic-containing norbornene isomer mixture represented by the following general formula [I]: Embedded image Wherein p is an integer of 0 or 1 , q and r are 0, 1 or 2, and R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic group. A hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group,
R ⁵ (or R ⁶ ) and R ⁹ (or R ⁷ ) each have 1 carbon atom
They may be bonded via an alkylene group of 1 to 3, or may be directly bonded without any group. Embedded image 3. An endo-form [IA] represented by the following formula:
An isomer mixture of an endo-form [IA] and an exo-form [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]) between the endo-form [IA] and the exo-form [IB] contained in the isomer mixture is 70.
/ 30 to 5/95 , a method for producing an aromatic-containing norbornene isomer. Embedded image Wherein p is an integer of 0 or 1 , q and r are 0, 1 or 2, and R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic group. A hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group,
R ⁵ (or R ⁶ ) and R ⁹ (or R ⁷ ) each have 1 carbon atom
It may be bonded via an alkylene group of (1) to (3), or may be directly bonded without any group. Embedded image