JP2000273171A - Production of oxadiazole derivative polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oxadiazole derivative polymer by the condensation reaction of starting materials at a low temperature for a short time by condensing a dicarboxylic acid (A) with a compound (B) selected from a dicarboxylic acid dihydrazide and hydrazinium sulfate in the presence of phosphorus pentoxide, a sulfonic acid, and an sulfonic anhydride. SOLUTION: It is desirable that component A is an aromatic dicarboxylic acid, and component B is an aromatic dicarboxylic dihydrazide. It is desirable that the sulfonic acid is methanesulfonic acid, and the sulfonic acid anhydride is methanesulfonic anhydride. It is desirable that the condensation reaction of component A with component B is performed at 50-130 deg.C for 1-48 hr. The sulfonic acid anhydride is used in an amount of 10-150 pts.wt. per 100 pts.wt. sulfonic acid. To attain a high condensation reaction efficiency, it is desirable to use the sulfonic acid in an amount of 300-3,000 pts.wt. per 100 pts.wt. phosphorus pentoxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat-resistant resin material,
The present invention relates to a method for producing an oxadiazole derivative polymer suitable as a resin material for a separation membrane and a material for an organic electroluminescence device. The present invention relates to a method for producing a polymer.

[0002]

2. Description of the Related Art Hitherto, oxadiazole derivative polymers have been suitably used as heat-resistant resin materials, resin materials for separation membranes, and materials for organic electroluminescence devices. As a method for producing a high molecular weight oxadiazole derivative polymer, fuming sulfuric acid, a mixture of fuming sulfuric acid and chlorosulfonic acid, polyphosphoric acid, and the like are used as a polymerization solvent also serving as a dehydrating condensing agent, and a dicarboxylic acid and a dicarboxylic acid are used. A method is known in which acid dihydrazide and / or hydrazinium sulfate are dehydrated and condensed in one step.

However, in such a method,
When fuming sulfuric acid or chlorosulfonic acid is used as the polymerization solvent also serving as the dehydrating condensing agent, these are substances having high danger and the condensation reaction is carried out at a high temperature, for example, 130 to 18
The operation involves considerable danger, since it must be performed at a temperature of 0 ° C. In addition, when a condensation reaction is performed at a high temperature, side reactions are likely to occur, and the raw materials are likely to deteriorate, so that the obtained polymer may be colored or the reaction system may gel during the condensation reaction. There is a problem that there is. On the other hand, when polyphosphoric acid is used as the polymerization solvent, because of its high viscosity, it is difficult to conduct a condensation reaction without sufficiently stirring the reaction system, and as a result, high reaction efficiency cannot be obtained. There's a problem.

[0004] In order to solve such a problem, a mixture of phosphorus pentoxide and methanesulfonic acid is used as a polymerization solvent also serving as a dehydrating condensing agent, and a condensation reaction between dicarboxylic acid and hydrazinium sulfate is carried out. A method for producing a diazole derivative polymer has been proposed [Jo
urnal of Polymer science:
Part A: Polymer Chemistrr
y, Vol. 26, 159 (1988)]. According to such a method, since it is not necessary to use a highly dangerous substance, the condensation reaction can be performed safely,
Moreover, when an aliphatic dicarboxylic acid is used as a dicarboxylic acid as a raw material, a condensation reaction can be performed at a low temperature, for example, room temperature, so that side reactions and deterioration of the raw material can be suppressed, As a result, an uncolored oxadiazole derivative polymer can be produced. However, when an aliphatic dicarboxylic acid is used as a raw material, the obtained oxadiazole derivative polymer has a thermal decomposition temperature (a 10% weight loss temperature in air).
Is 335 ° C., and the heat resistance is not sufficiently high.
On the other hand, when an aromatic dicarboxylic acid is used as a raw material, it is necessary to carry out a condensation reaction at a high temperature, for example, a temperature of 80 ° C. or higher. There is a problem that the polymer is colored brown, for example.

In US Pat. No. 5,486,592, a mixture of phosphorus pentoxide and methanesulfonic acid is used as a polymerization solvent also serving as a dehydrating condensing agent, and a dicarboxylic acid, a dicarboxylic dihydrazide and / or Alternatively, a method for producing an oxadiazole derivative polymer by performing a condensation reaction with hydrazinium sulfate is disclosed. However, even in such a method, since it is necessary to carry out the condensation reaction at a temperature of 90 ° C. or higher, it is difficult to obtain an uncolored oxadiazole derivative polymer as a result of side reactions and deterioration of the raw materials. is there.

As described above, in the conventional method, when an aromatic dicarboxylic acid is used as a raw material, a condensation reaction cannot be carried out at a low temperature. It has been difficult to produce an oxadiazole derivative polymer having high heat resistance.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and its object is to provide:
It is an object of the present invention to provide a method capable of performing a condensation reaction of a raw material at a low temperature and in a short time and reliably producing a non-colored oxadiazole derivative polymer. Another object of the present invention is to provide a method capable of reliably producing an uncolored oxadiazole derivative polymer having high heat resistance.

[0008]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and found that phosphorus pentoxide, sulfonic acid and sulfonic anhydride are used as polymerization solvents also serving as dehydrating condensing agents. It has been found that by using a mixture of the above, the condensation reaction can be carried out at a low temperature even when an aromatic dicarboxylic acid is used as a raw material, thereby completing the present invention.

That is, the process for producing an oxadiazole derivative polymer of the present invention comprises subjecting a condensation reaction between the following component (A) and the following component (B) in the presence of phosphorus pentoxide, sulfonic acid and sulfonic anhydride. It is characterized by performing. Component (A): dicarboxylic acid, Component (B): at least one compound selected from dicarboxylic acid dihydrazide and hydrazinium sulfate

In the method for producing an oxadiazole derivative polymer according to the present invention, the sulfonic acid is preferably methanesulfonic acid, and the sulfonic anhydride is preferably methanesulfonic anhydride. Further, it is preferable to use an aromatic dicarboxylic acid as the component (A). Further, it is preferable to use an aromatic dicarboxylic acid dihydrazide as the component (B). Also, 50-130 ° C
It is preferable to carry out a condensation reaction between the component (A) and the component (B) at the temperature described above. Further, it is preferable to use sulfonic anhydride in a ratio of 10 to 150 parts by weight with respect to 100 parts by weight of sulfonic acid.

[0011]

According to such a method, in addition to phosphorus pentoxide and sulfonic acid as a polymerization solvent also serving as a dehydrating condensing agent, a sulfonic anhydride is further used. The condensation reaction with the dicarboxylic acid dihydrazide and / or hydrazinium sulfate as the component (B) can be performed at a low temperature and in a short time, thereby suppressing the occurrence of side reactions and the deterioration of the raw materials. Thus, an uncolored oxadiazole derivative polymer can be reliably obtained. Further, by using an aromatic dicarboxylic acid as the component (A) or using an aromatic dicarboxylic acid dihydrazide as the component (B), an oxadiazole derivative polymer having high heat resistance can be reliably obtained.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for producing an oxadiazole derivative polymer of the present invention will be described in detail. In the method for producing an oxadiazole derivative polymer of the present invention, phosphorus pentoxide (P) is used as a polymerization solvent also serving as a dehydrating condensing agent (hereinafter, also referred to as a “dehydrating polymerization solvent”).
A mixture of ₂ O ₅ ), sulfonic acid and sulfonic anhydride is used.

As the sulfonic acid used as one component of the dehydrating polymerization solvent, the sulfonic acid is liquid at the condensation reaction temperature, and contains phosphorus pentoxide, the raw materials used (components (A) and (B)), and the produced polymer. Is not particularly limited as long as it can sufficiently dissolve, and specific examples thereof include methanesulfonic acid, ethanesulfonic acid,
Examples thereof include 2-propanesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid, and fluorosulfonic acid. Of these, methanesulfonic acid is preferably used from the viewpoint of cost, availability, safety, and the like. The use ratio of the sulfonic acid is not particularly limited, but from the viewpoint of obtaining a high condensation reaction efficiency, 300 to 3000 per 100 parts by weight of phosphorus pentoxide.
It is preferable to use sulfonic acid in such a ratio as to become parts by weight.

The sulfonic anhydride used as one component of the dehydrating polymerization solvent is not particularly limited as long as it can be dissolved in the sulfonic acid used, and specific examples thereof include methanesulfonic anhydride. Products, trifluoromethanesulfonic anhydride, p-toluenesulfonic anhydride and the like. Of these, methanesulfonic anhydride is preferably used from the viewpoints of cost, availability, and reactivity.

In the present invention, the use ratio of sulfonic anhydride is 10 to 150 parts by weight per 100 parts by weight of sulfonic acid.
It is preferably in parts by weight. When this proportion is less than 10 parts by weight, it is difficult to carry out the condensation reaction at a low temperature, and a long reaction time is required, so that it may be difficult to obtain an uncolored polymer. . On the other hand, when this ratio exceeds 150 parts by weight, the obtained dehydrating polymerization solvent contains the raw materials [component (A) and component (B)].
Component] and the resulting polymer have low solubility, which may make it difficult to obtain a high molecular weight oxadiazole derivative polymer.

In the present invention, from the viewpoint of obtaining a high condensation reaction efficiency, phosphorus pentoxide, sulfonic acid,
Heating a mixture with sulfonic anhydride in advance within a temperature range of 50 to 150 ° C. and sufficiently dissolving phosphorus pentoxide and sulfonic anhydride in sulfonic acid, and then serving as a dehydrating polymerization solvent. Is preferred. Such a dehydrating polymerization solvent is composed of raw materials [component (A) and component (B)] 10
It is preferably used in a ratio of 1000 to 10000 parts by weight with respect to 0 parts by weight.

In the production method of the present invention, a condensation reaction of the following components (A) and (B) is carried out in the above-mentioned dehydrating polymerization solvent. Component (A): dicarboxylic acid, Component (B): at least one compound selected from dicarboxylic acid dihydrazide and hydrazinium sulfate

The dicarboxylic acid for constituting the component (A) is not particularly limited, and an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid can be used. An oxadiazole derivative having high heat resistance can be used. In terms of obtaining a polymer, aromatic dicarboxylic acids are preferred. Specific examples of particularly preferred aromatic dicarboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid,
2,6-naphthalenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-
Pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 2,2′-biphenyldicarboxylic acid, 9-fluorenone-2,7-dicarboxylic acid, ,
1,3-trimethyl-3-phenylindane-4 ', 5
-Dicarboxylic acid, stilbene-4,4'-dicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 4,
4′-dicarboxydiphenyl sulfone, 4,4′-dicarboxydiphenyl sulfide, 2,2-bis (4-
(Carboxyphenyl) hexafluoropropane and 2,2-bis (4-carboxyphenyl) propane. These aromatic dicarboxylic acids may have a substituent such as an alkyl group or an alkoxy group having 1 to 10 carbon atoms as long as the heat resistance of the obtained oxadiazole derivative polymer is not impaired. These dicarboxylic acids can be used alone or in combination of two or more.

The dicarboxylic acid dihydrazide for constituting the component (B) is not particularly limited.
Although aromatic dicarboxylic acid dihydrazide and aliphatic dicarboxylic acid dihydrazide can be used, it is preferable to use aromatic dicarboxylic acid dihydrazide from the viewpoint that an oxadiazole derivative polymer having high heat resistance can be obtained. Specific examples of particularly preferred aromatic dicarboxylic acid dihydrazide include phthalic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 1,4-
Naphthalenedicarboxylic acid dihydrazide, 2,3-naphthalenedicarboxylic acid dihydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide, 2,3-pyridinedicarboxylic acid dihydrazide, 2,4-pyridinedicarboxylic acid dihydrazide, 2,5-pyridinedicarboxylic acid dihydrazide,
2,6-pyridinedicarboxylic acid dihydrazide, 3,5-
Pyridinedicarboxylic acid dihydrazide, 4,4'-biphenyldicarboxylic acid dihydrazide, 2,2'-biphenyldicarboxylic acid dihydrazide, 9-fluorenone-2,7
-Dicarboxylic acid dihydrazide, 1,1,3-trimethyl-3-phenylindane-4 ', 5-dicarboxylic acid dihydrazide, stilbene-4,4'-dicarboxylic acid dihydrazide, 4,4'-dihydrazinocarbonyl diphenyl ether, 4 4,4'-dihydrazinocarbonyldiphenylsulfone, 4,4'-dihydrazinocarbonyldiphenylsulfide, 2,2-bis (4-hydrazinocarbonylphenyl) hexafluoropropane,
2-bis (4-hydrazinocarbonylphenyl) propane and the like can be mentioned. These aromatic dicarboxylic acid dihydrazides may have a substituent such as an alkyl group or an alkoxy group having 1 to 10 carbon atoms as long as the heat resistance of the obtained oxadiazole derivative polymer is not impaired. . These dicarboxylic acid dihydrazides can be used alone or in combination of two or more.

In the method for producing an oxadiazole derivative polymer according to the present invention, the ratio of the component (A) to the component (B) is 40:
It is preferably from 60 to 60:40, particularly preferably from 45:55 to 55:45.

The conditions for the condensation reaction between the component (A) and the component (B) are preferably a reaction temperature of 50 to 130 ° C. and a reaction time of 1 to 48 hours, more preferably a reaction time of 1 to 48 hours. Temperature is 60-100 ° C, reaction time is 2-2
4 hours. By satisfying these conditions,
An uncolored oxadiazole derivative polymer can be produced with high efficiency and certainty. (A) component and (B)
When the reaction temperature with the component is lower than 50 ° C, (A)
Since the condensation reaction between the component and the component (B) cannot proceed rapidly, it may be difficult to produce the oxadiazole derivative polymer with high temporal efficiency.
On the other hand, the reaction temperature between the component (A) and the component (B) is 130 ° C.
In the case where it exceeds 3, since side reactions and deterioration of the raw materials are likely to occur, it may be difficult to obtain an uncolored oxadiazole derivative polymer.

In the condensation reaction between the components (A) and (B), the molecular weight of the obtained oxadiazole derivative polymer is adjusted in order to improve the durability of the obtained oxadiazole derivative polymer. For this purpose, the terminal of the oxadiazole derivative polymer may be blocked using a terminal blocking agent. Examples of such terminal blocking agents include benzoic acid, 1-naphthoic acid, 2-naphthoic acid and 4-naphthoic acid.
Aromatic monocarboxylic acids such as biphenylcarboxylic acid and 2-pyridinecarboxylic acid, or hydrazides of these aromatic monocarboxylic acids can be used. These compounds can be used alone or in combination of two or more. Further, the usage ratio of the terminal blocking agent is preferably 0.001 to 0.25 mol per 1 mol of the obtained oxadiazole derivative polymer.

The oxadiazole derivative polymer obtained as described above has no coloring and has a high molecular weight. Also, by using an aromatic dicarboxylic acid as the component (A) or using an aromatic dicarboxylic acid dihydrazide as the component (B), the obtained oxadiazole derivative polymer has high heat resistance. Therefore, such an oxadiazole derivative polymer can be suitably used as a heat-resistant resin, a resin for a separation membrane, and a material for an organic electroluminescence device.

[0024]

EXAMPLES The present invention will now be described with reference to specific examples according to the method for producing the oxadiazole derivative polymer of the present invention, but the present invention is not limited to these examples.

Example 1 In a 100 ml flask, 16 g of methanesulfonic acid and methanesulfonic anhydride 1 were placed.
6 g was added, and the system was heated to 100 ° C. with stirring using a stirrer to sufficiently dissolve methanesulfonic anhydride in methanesulfonic acid. Thereafter, while maintaining the temperature of the solution at 100 ° C., 3.6 g of phosphorus pentoxide was added to and dissolved in the solution to prepare a dehydrating polymerization solvent. Then, the dehydrating polymerization solvent is cooled to 70 ° C., and 1,117 g of 1,1,3-trimethyl-3-phenylindane-4 ′, 5-dicarboxylic acid is added to the dehydrating polymerization solvent as the component (A). (3.44mm
ol) and 0.6679 g (3.44 mmol) of terephthalic acid dihydrazide as the component (B). Thereafter, when the system was stirred with a stirrer while maintaining the temperature of the system at 70 ° C., the viscosity of the system gradually increased, and the progress of the condensation reaction was confirmed. Then, a reaction liquid was obtained by performing a condensation reaction until the viscosity of the system became constant (3 hours).

Next, the resulting reaction solution was cooled to room temperature, and then slowly poured into about 300 ml of cold water in a beaker to precipitate a powdery solid product. The resulting solid product is filtered off using filter paper, water,
After washing with an aqueous solution of sodium hydrogen carbonate, water and methanol in that order, it was dried in vacuum. The solid product obtained is white, weighs 1.52 g and the yield is 99%.
% Was extremely high. In addition, infrared spectroscopy was performed on the obtained solid product to find that the wave number was 2958.
cm ^-1, 1614cm ^-1, 1577cm ^-1 and 155
A characteristic peak at 0 cm ^-1 was observed.
It was confirmed that the solid product was an oxadiazole derivative polymer having a repeating unit represented by the following formula (1). FIG. 1 shows the measured IR spectrum. In this IR spectrum, the horizontal axis represents the wave number (cm
^-1 ), and the vertical axis indicates transmittance (%).

[0027]

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The logarithmic viscosity η _inh (measurement condition: solvent: sulfuric acid, temperature 30 ° C., concentration 0.5 g / dl) of the obtained oxadiazole derivative polymer was measured.
A value of 60 dl / g was obtained. The glass transition temperature of the obtained oxadiazole derivative polymer was determined by DSC.
When measured using (measurement conditions: heating rate: 10 ° C./min., Atmosphere: nitrogen stream), a high value of 337 ° C. was obtained. In addition, 5% weight loss temperature of the obtained oxadiazole derivative polymer (measurement condition: heating rate 10 ° C.)
/ Min. , In the air) using TGA, a high value of 461 ° C. was obtained.

<Comparative Example 1> 32 g of methanesulfonic acid and 3.6 g of phosphorus pentoxide were placed in a 100 ml flask, and this system was stirred for 100 hours using a stirrer.
By heating to ℃ and sufficiently dissolving phosphorus pentoxide in methanesulfonic acid, a comparative dehydrating polymerization solvent was prepared. Next, the dehydrating polymerization solvent is cooled to 70 ° C., and 1,1,3-trimethyl-
3-phenylindane-4 ', 5-dicarboxylic acid 1.1
17 g (3.44 mmol) and 0.6679 g (3.44 mmol) of terephthalic dihydrazide were added. Thereafter, the system was stirred with a stirrer while maintaining the temperature of the system at 70 ° C., but no increase in the viscosity of the system was observed, and it was confirmed that the condensation reaction hardly proceeded. Thereafter, when the system was heated to 120 ° C. while continuing to stir with a stirrer, the viscosity of the system gradually increased, and the progress of the condensation reaction was confirmed. Then, while maintaining the temperature of the system at 120 ° C., a condensation reaction was performed until the viscosity of the system became constant (11 hours) to obtain a reaction solution.

The obtained reaction liquid was subjected to the same operation as in Example 1 to obtain a powdery solid product.
The solid product was light brown, weighed 1.49 g, and the yield was 98%. When the obtained solid product was subjected to infrared spectroscopy, it had a spectrum similar to that of the oxadiazole derivative polymer obtained in Example 1, and was represented by the above formula (1). It was confirmed that the polymer was an oxadiazole derivative polymer having a repeating unit. When the logarithmic viscosity η _inh (measurement condition: solvent: sulfuric acid, temperature 30 ° C., concentration 0.5 g / dl) of the obtained oxadiazole derivative polymer was measured, a value of 0.37 dl / g was obtained. . When the glass transition temperature of the obtained oxadiazole derivative polymer was measured using DSC (measurement condition: heating rate: 10 ° C./min., Atmosphere: nitrogen stream), a value of 336 ° C. was obtained. 5% weight loss temperature of the obtained oxadiazole derivative polymer (measurement condition: heating rate 10 ° C. /
min. , In air) using TGA,
A value of 443 ° C. was obtained.

Example 2 According to the formulation shown in Table 1,
A white powdery solid product was obtained in the same manner as in Example 1, except that the components (A) and (B) were used. When infrared spectroscopy was performed on the obtained solid product, the results confirmed that the solid product was an oxadiazole derivative polymer having a repeating unit represented by the following formula (2). Was. Further, the yield, yield, logarithmic viscosity η of the obtained oxadiazole derivative polymer
Table 2 shows _{in h} , glass transition temperature and 5% weight loss temperature.

[0032]

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Example 3 According to the formulation shown in Table 1,
Using component (A) and component (B), the reaction temperature is 60 ° C.
A white powdery solid product was obtained in the same manner as in Example 1 except for changing the above. When infrared spectroscopy was performed on the obtained solid product, the results confirmed that the solid product was an oxadiazole derivative polymer having a repeating unit represented by the following formula (3). Was. Table 2 shows the yield, yield, logarithmic viscosity η _{in h} , glass transition temperature and 5% weight loss temperature of the obtained oxadiazole derivative polymer.

[0034]

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Comparative Example 2 According to the formulation shown in Table 1,
A light brown powdery solid product was obtained in the same manner as in Comparative Example 1, except that the components (A) and (B) were used.
When the obtained solid product was subjected to infrared spectroscopy, it had a spectrum similar to that of the oxadiazole derivative polymer obtained in Example 2, and the solid product was represented by the above formula (2). It was confirmed that the polymer was an oxadiazole derivative polymer having the represented repeating unit. Further, the yield, yield, logarithmic viscosity η _{in h} , glass transition temperature and 5% of the obtained oxadiazole derivative polymer were obtained.
Table 2 shows the percent weight loss temperature. In addition, reaction temperature 60-7.
An attempt was made to conduct a condensation reaction between the component (A) and the component (B) under the condition of 0 ° C., but no increase in the viscosity of the system was observed, and it was confirmed that the condensation reaction hardly proceeded.

Comparative Example 3 The components (A) and (B) were mixed under the same conditions as in Comparative Example 1 except that the components (A) and (B) were used according to the formulation shown in Table 1. Was attempted, but the system was colored brown and the color was only darkened, no increase in the viscosity of the system was observed, and the condensation reaction did not proceed. And even after 11 hours, the oxadiazole derivative polymer could not be obtained.

[0037]

[Table 1]

[0038]

[Table 2]

As is clear from the above results, Example 1
According to Nos. 3 to 3, it was confirmed that an oxadiazole derivative polymer having no coloring and having high heat resistance was obtained. Further, from the value of the logarithmic viscosity η _inh , it is understood that these oxadiazole derivative polymers have a high molecular weight. On the other hand, in Comparative Examples 1 and 2, since a high reaction temperature is required for the condensation reaction between the component (A) and the component (B) to proceed, the obtained oxadiazole derivative polymer is It became pale brown. From the value of the logarithmic viscosity η _inh , these oxadiazole derivative polymers had a lower molecular weight than the oxadiazole derivative polymers according to Examples 1 to 3.

[0040]

As described above, according to the present invention,
As a polymerization solvent also serving as a dehydration condensing agent, to use a mixture of phosphorus pentoxide, sulfonic acid and sulfonic anhydride,
The condensation reaction between the dicarboxylic acid as the component (A) and the dicarboxylic acid dihydrazide and / or hydrazinium sulfate as the component (B) can be carried out at a low temperature and in a short time, whereby side reactions and raw material Deterioration is suppressed, and as a result, an uncolored oxadiazole derivative polymer can be reliably produced. Also,
By using an aromatic dicarboxylic acid as the component (A) or using an aromatic dicarboxylic acid dihydrazide as the component (B), it is possible to reliably produce an oxadiazole derivative polymer having high heat resistance.

[Brief description of the drawings]

FIG. 1 is a diagram showing an IR spectrum of an oxadiazole derivative polymer obtained in Example 1.

FIG. 2 is a view showing an IR spectrum of the oxadiazole derivative polymer obtained in Example 2.

FIG. 3 is a view showing an IR spectrum of the oxadiazole derivative polymer obtained in Example 3.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kohei Goto 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. F term (reference) 4J043 PA02 QB59 SA24 SB01 TA12 TB01 ZB13 ZB21

Claims (3)

[Claims] 1. Production of an oxadiazole derivative polymer, wherein a condensation reaction of the following component (A) and the following component (B) is carried out in the presence of phosphorus pentoxide, sulfonic acid and sulfonic anhydride. Method. Component (A): dicarboxylic acid Component (B): at least one compound selected from dicarboxylic dihydrazide and hydrazinium sulfate 2. The method for producing an oxadiazole derivative polymer according to claim 1, wherein an aromatic dicarboxylic acid is used as the component (A). 3. The method for producing an oxadiazole derivative polymer according to claim 1, wherein an aromatic dicarboxylic acid dihydrazide is used as the component (B).