JPH09272730A - Production of high-molecular polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-molecular polymer which is a substantially linear polymer in high yields by using a specified catalyst and a specified oxidizing agent in synthesizing a high-molecular polymer by using an aromatic compound as the monomer and forming fresh C-C bonds. SOLUTION: In producing an organic high-molecular polymer by using an aromatic compound as the monomer and forming fresh C-C bonds in an aromatic ring, the reaction is performed in the presence of a vanadium compound as the catalyst in an atmosphere of oxygen or air. The vanadium compound used is desirably an oxyvanadium complex, especially vanadyl acetylacetonate [VO (acac)2 ] which is highly active. Examples of the aromatic monomers used include benzene, substituted benzene derivatives, naphthalene and substituted naphthalene derivatives. The polymerization reaction is practiced in a solvent (desirably a polar solvent) containing an acid anhydride.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an organic polymer material having high strength and excellent heat resistance.

[0002]

2. Description of the Related Art Certain organic polymer materials are used as engineering plastics in place of metal materials, ceramics, glass, wood, etc., as engineering plastics. On the other hand, demand is rapidly increasing due to features such as excellent workability and cost reduction. Furthermore, due to the characteristics of plastic materials such as ease of processing, electrical insulation, colorability, and the ability to easily control changes in their properties with additives and fillers, etc. Has made it possible to manufacture parts that could not be thought of with conventional materials. On the other hand, as the range of application of engineering plastics expands, the required level of properties gradually increases, and it is expected that new polymer materials having higher properties will appear and be industrialized. In particular, a polymer having a structure in which benzene rings are directly linked in a chain form is expected to have extremely high heat resistance and mechanical properties due to its structure, and synthesis of a high molecular weight polymer has been attempted. For example, a method based on an oxidation reaction using copper powder as a catalyst has been announced. However, the various properties and processability of the polymer greatly depend on the structure of the polymer, that is, whether it is a chain type, a bent type, or a crosslinked type, and the size of the molecular weight. These also need to be controlled. Generally speaking, a cross-linking polymer is often difficult to mold, and a low molecular weight polymer is fragile and has mechanical properties. When the abundance ratios of isomers having different bond positions in the aromatic ring are different,
There is a problem that the thermal characteristics are not constant. Regarding the polymer in which the aromatic ring is directly bonded, so far, the moldability, such as low molecular weight of the product and having a crosslinked structure,
Satisfactory mechanical properties have not yet been obtained, and establishment of a method for stably obtaining a high-molecular chain polymer is essential for practical use. On the other hand, in the case of a polymer in which only the benzene ring is directly bonded, that is, polyparaphenylene, due to its structure, difficulty in processing is expected, and a polymer having a substituted benzene structure or a copolymer with another chemical bond is used. , Investigations are underway to improve the workability. In the case of using substituted benzene as a monomer, the present inventors have already invented a synthetic method using iron halide as an oxidant,
He came to apply for a patent (Japanese Patent Application No. 3-100849). However, in this synthetic method, iron halide is used acyclically as an oxidant, so there is still room for improvement as an industrial method, and the selectivity at the bonding position on the aromatic ring of the product is low. There were challenges.

[0003]

Means for Solving the Problems The inventors of the present invention have been searching for a method for efficiently synthesizing a highly functional engineering plastic, specifically, an organic polymer containing a structure in which an aromatic ring is directly linked, It was found that, by the oxidation reaction using a vanadium compound as a catalyst, the product has a highly regioselective bond and is substantially a chain polymer, and has a large molecular weight, and the polymerization reaction can be performed in a high yield, The present invention has been completed. That is, the present invention uses an aromatic compound as a monomer, and a vanadium compound as a catalyst in synthesizing a high-molecular polymer through the formation of a new carbon-carbon bond,
The present invention relates to a method for producing a high-molecular polymer, which uses oxygen as an oxidant.

[0004]

Hereinafter, the present invention will be described in detail. The above-mentioned aromatic monomer used in the present invention has a skeleton structure such as benzene, naphthalene, anthracene, phenanthrene, and fluorene as an aromatic ring structure. These aromatic rings have the general formula Ar- (X-Ar)
_As represented by _n , (n = 0 to 6), it includes one having a structure in which two or more aromatic rings are bound alone or in combination. Wherein Ar represents the aromatic ring of the general formula -C _n H _2n as X - (n = 0~20) alkylene represented by,
_{-OC n H 2n - (n =} 0~20) oxyalkylene represented by,
-OC _n H _2n O- (n = 1-20) represented by dioxyalkylene,-(C _n H _2n O) _{n '} -(n = 1-20, n' = 1-10) represented by poly Oxygen-containing alkylene such as (oxyalkylene), -S
Examples thereof include sulfur-containing atomic groups such as-, -SO-, and -SO _2- . More specifically, for example, biphenyl, terphenyl, diphenylmethane, 1,2-diphenylethane,
1,3-diphenylpropane, 1,4-diphenylbutane,
1,5-diphenylpentane, 1,6-diphenylhexane, 1,8-diphenyloctane, diphenyl ether,
Benzylphenyl ether, 2-phenethylphenyl ether, di (2-phenethyl) ether, 3-phenylpropylphenyl ether, di (3-phenylpropyl) ether, 1,2-diphenoxyethane, 1,3-diphenoxypropane, 1,4-diphenoxybutane, 1,5-
Diphenoxypentane, 1,6-diphenoxyhexane,
1,4-Diphenoxybenzene and the like, and benzene derivatives such as diphenyl sulfide, diphenyl sulfoxide, and diphenyl sulfone, binaphthyl, ternaphthyl, dinaphthylmethane, 1,2-naphthylethane, 1,3-dinaphthylpropane, 1, 4-dinaphthylbutane, 1,5-dinaphthylpentane, 1,6-dinaphthylhexane, 1,8-dinaphthyloctane, dinaphthyl ether, benzyl phenyl ether, 2-phenethyl phenyl ether, di (2
-Phenethyl) ether, 3-phenylpropyl phenyl ether, di (3-naphthylpropyl) ether, 1,
2-Dinaphthoxyethane, 1,3-Dinaphthoxypropane, 1,4-Dinaphthoxybutane, 1,5-Dinaphthoxypentane, 1,6-Dinaphthoxyhexane, 1,4-Dinaphthoxy Benzene, naphthalene derivatives such as dinaphthyl sulfide, dinaphthyl sulfoxide, dinaphthyl sulfone, 4,4'-di (phenoxy) diphenyl sulfone, 4,4'-di (1-naphthoxy) diphenyl sulfone, etc. included. Various substituents may be introduced into these aromatic rings for the purpose of enhancing reactivity, controlling solubility in a solvent, or controlling thermoplasticity to enhance processability. For example, by introducing an alkoxyl group, it is possible to improve the properties such as increasing the reactivity and making it solvent-soluble to facilitate the production of a film from a solution. Examples of such substituents include the general formula C _n H _{2n + 1} O- (n =
Other alkoxyl group represented by 1 to 12), an alkyl group (general formula _{C n H 2n + 1 -,} n = 1~12) , and the like.

In the following, the content of the present invention will be specifically described by taking the case of using 1,4-dialkoxybenzene as a monomer as an example. As a vanadium compound catalyst for alkoxy substituted benzene, an oxygen-containing vanadium complex such as vanadyl acetylacetonate VO (acac) ₂ ,
An oxovanadium complex containing vanadyl bis (1-phenyl-2,4-butanedioate), vanadyl tetraphenylporphinate, vanadyl oxalate VO (COO) ₂ , vanadyl sulfate VOSO ₄ , etc. has high catalytic activity, Vanadyl acetylacetonate shows high activity. The amount of the catalyst added is preferably 0.1 to 100 mol% with respect to the monomer, and particularly preferably 1 to 10 mol% from the viewpoint of the balance between activity and economy. The polymerization reaction is performed in an atmosphere of pure oxygen as an oxidant or air. It is considered that the main polymerization reaction involves a process of disproportionation of the catalyst vanadium compound under strongly acidic conditions, and it is necessary to add a strong acid to the solution. Examples of the strong acid include methanesulfonic acid, fluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and alkylbenzenesulfonic acid. The addition amount of these strong acids is 0.1 to 100 times, preferably 1 to 10 times the molar amount of the vanadium catalyst. These strong acids may be used alone or in combination of two or more. Vanadium (IV) disproportionates to vanadium (III) and vanadium (V) under strongly acidic conditions, and vanadium (V) becomes a direct oxidative active species. On the other hand, vanadium (III) also becomes vanadium (IV) due to oxygen and cyclically becomes a catalytically active species. Regarding the amount of addition of these acids, it is necessary to adjust the amount of addition in consideration of the fact that if the amount of addition of the acid is small, the activity is not sufficient, and when it is excessive, side reactions such as unfavorable crosslinking reaction occur.

In order to remove water produced as the condensation reaction proceeds, an excess of acid anhydride is added to the reaction system. Here, the acid anhydride is various organic acid anhydrides such as trifluoroacetic anhydride, trichloroacetic anhydride, fluoroacetic anhydride, chloroacetic anhydride, dichloroacetic anhydride, and difluoroacetic anhydride, and these may be used alone or in combination. Used. The amount added is required to be at least 1 time the molar amount of the monomer, but the upper limit is not particularly specified. The solvent is selected from a monomer, a catalyst, and a compound that is generally a polar solvent from the viewpoint of easily dissolving the above-mentioned acid and is inactive in the polymerization reaction. Examples of polar solvents used include dichloromethane, 1,2-dichloroethane, nitrobenzene, dinitrobenzene, dimethyl sulfoxide, dimethylformamide and the like. The above-mentioned polymerization reaction temperature is not particularly limited, and the reaction is usually performed at room temperature, but may be heated if necessary.

[0007]

INDUSTRIAL APPLICABILITY According to the present invention, an aromatic polymer having excellent mechanical and heat resistance can be produced at low cost,
The polymer thus produced is expected to be applied as a molded product, fiber or filler, or film having high strength and excellent heat resistance.

[0008]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Example 1 An oxygen supply pipe and a septum cap were attached to a two-necked flask, 0.66 g of vanadyl acetylacetonate was put therein, and then the inside of the flask was replaced with oxygen. Subsequently, 50 ml of nitrobenzene, 13.9 ml of trifluoroacetic anhydride and 0.44 ml of trifluoromethanesulfonic acid were added to the flask through the septum cap, and the mixture was stirred for about 1 hour. Then, 17.8 g of 1,5-di (1-naphthoxy) pentane dissolved in 0.1 liter of nitrobenzene was added, and the mixture was stirred at room temperature for 15 hours. The reaction product was poured into 5 liters of methanol containing 5% hydrochloric acid, and the precipitate was collected. The precipitate was purified by the reprecipitation method from chloroform to methanol. The yield was 100%. When the structure of the product was examined by NMR and IR, formation of a polymer represented by the following formula I was confirmed. The weight average molecular weight of the polymer produced by gel filtration was 53,000, and the number average molecular weight was 1.
1,000. The thermal decomposition temperature determined by thermogravimetric analysis was 395 ° C in nitrogen and 380 ° C in air. The glass transition temperature determined by DSC was 142 ° C.

[0009]

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Example 2 In a flask as shown in Example 1, 1.99 g of vanadyl acetylacetonate was placed, and the inside of the flask was replaced with oxygen. Then, 30 ml of 1,2-dichloroethane, 27.8 ml
Add trifluoroacetic anhydride and 0.66 g of trifluoromethanesulfonic acid and stir for about 1 hour. After that, 70
22.2 g of 1,4-di-n-butoxybenzene dissolved in 1,2-dichloroethane (ml) was added, and the mixture was stirred at room temperature for 20 hours. The product was recovered and purified as in Example 1. NMR
It was found that the structure of the product obtained by the IR method and elemental analysis was almost 100% selectively as shown in the following formula II. The weight average and number average molecular weights of the produced polymer are 30,000, 12,000 and 10%, respectively, and the thermal decomposition temperature is 385 ° C in nitrogen.
Met.

[0011]

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Example 3 In the reaction vessel shown in Example 1, 25.1 g of 4,4'-di (1-naphthoxy) diphenyl sulfone, 1.32 g of vanadyl acetylacetonate, 13.9 ml of trifluoroacetic anhydride, 0.
Polymerization was carried out according to the procedure of Example 1 at room temperature using 88 ml of trifluoromethanesulfonic acid and 150 ml of nitrobenzene. The product was purified by a recrystallization method with acetone and methanol to obtain a polymer with a yield of 100%. The structure of the product was determined by IR and elemental analysis and found to be a polymer represented by the following formula III. The weight average and number average molecular weights of the produced polymer were 6,400,
3,500.

[0013]

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Example 4 In place of pure oxygen in Example 1, polymerization was carried out according to the procedure of Example 1 while circulating air.
And similar results were obtained. However, the reaction rate was slightly slower than that of Example 1, and the polymerization time was 20 hours.

Example 5 Polymerization was carried out according to the procedure of Example 2 while circulating air instead of pure oxygen in Example 2.
And similar results were obtained. However, the reaction rate was slightly slower than that in Example 2, and the polymerization time was 30 hours.

Example 6 Polymerization was carried out according to the procedure of Example 3 while flowing air instead of pure oxygen in Example 3, and Example 3 was thus obtained.
And similar results were obtained. However, the reaction rate was slightly slower than that in Example 3, and the polymerization time was 40 hours.

Claims (14)

[Claims] 1. A vanadium compound is used as a catalyst in the production of an organic polymer using an aromatic compound as a monomer to form a new carbon-carbon bond in an aromatic ring. Production method. 2. The method for producing a high molecular polymer according to claim 1, wherein the reaction is performed in an oxygen or air atmosphere in producing the high molecular polymer. 3. The method for producing a high molecular polymer according to claim 1, wherein the vanadium compound is an oxovanadium complex. 4. The method for producing a polymer according to claim 3, wherein the oxovanadium complex is vanadyl acetylacetonate VO (acac) ₂ . 5. The method for producing a high molecular polymer according to claim 1, wherein the monomer is benzene or a benzene derivative having a substituent. 6. The method for producing a high molecular polymer according to claim 5, wherein the monomer is a benzene derivative having an alkoxy or oxyalkylene substituent. 7. The method for producing a high molecular polymer according to claim 6, wherein the alkoxy substituent is a butoxy group. 8. The method according to claim 1, wherein the monomer is naphthalene or a naphthalene derivative having a substituent.
A method for producing a high molecular polymer according to the item. 9. The naphthalene derivative in which the monomer contains an alkoxy or oxyalkylene substituent.
A method for producing the high molecular polymer described. 10. The method for producing a polymer according to claim 9, wherein the monomer is dinaphthyl alkylene ether. 11. The method for producing a high molecular polymer according to claim 10, wherein the monomer is 1,5-di (1-naphthoxy) pentane. 12. The method for producing a high molecular polymer according to claim 8, wherein the monomer is selected from diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone and their derivatives. 13. The method for producing a high molecular polymer according to claim 1, wherein the polymerization reaction is carried out in a solvent containing an acidic compound. 14. The method for producing a high molecular polymer according to claim 1, wherein the polymerization reaction is carried out in a solvent containing an acid anhydride.