KR920009694B1 - Polyarylate resin - Google Patents

Abstract

A polyarylate resin containing thiophene gp. of formula (I) is new. The polyarylate resin has 0.15-0.75 dl/g of intrinsic viscosity. In the formula (I), 0 <= (l/Cl+m+n) <= 1, 0 <= (m/Cl+m+n)

Description

Polyarylate resin

1 shows IR and ¹ H-NMR spectra of the polyarylate resin [PAT-1] of the present invention prepared by Example 1,

2 shows the IR and ¹ H-NMR spectra of the polyacrylate resin [PAR-3] of the present invention prepared by Example 3,

3 is a graph showing the weight change with temperature for the polyarylate resin [PAR-1, PAR-2, PAR-3] of the present invention prepared according to the embodiment,

Figure 4 is a graph showing the weight change with temperature for the polyarylate resin [PAR-4, PAR-5, PAR-6] of the present invention prepared according to the embodiment.

The present invention relates to a polyarylate resin, and more particularly, has excellent physical properties such as heat resistance, mechanical strength, weather resistance, and flame retardancy, and excellent solubility in an organic solvent, which can be used as a coating agent and improves melt processability. The present invention relates to a new polyarylate resin containing a thiophene group represented by the following structural formula (1).

이다.Where

to be.

The polyarylate resin refers to a wholly aromatic polyester resin prepared by condensation polymerization of an aromatic diol and an aromatic dicarboxylic acid.

Therefore, the polyarylate resin has various molecular structures depending on the raw material used, but as represented by the following structural formula (A), bisphenol A (hereinafter referred to as BPA) as an aromatic diol, and aromatic dicarboxylic acid as Resin obtained by condensation polymerization of terephthalic acid (hereinafter referred to as TPA) and isophthalic acid (hereinafter referred to as IPA) is most representative.

Such polyarylate resins of structural formula (A) are described in Japanese Patent Application Laid-Open Nos. 49-101,944 and 55-115,871, which are transparent and amorphous resins and have the following characteristics.

(1) The density of the benzene ring, which is an aromatic group, in the molecular structure is very high, so it is excellent in heat resistance and mechanical strength.

(2) The difference in softening point and pyrolysis temperature is so large that extrusion, blow molding and injection molding are all possible.

(3) The marginal oxygen index is 37%, and the resin itself is excellent in flame retardancy.

(4) Due to its high ability to absorb ultraviolet rays, its internal resistance is good.

(5) Excellent compatibility with other resins, easy to change the composition of the resin, wide range of physical properties.

That is, the polyarylate resin of the structural formula (A) is a kind of special engineering plastics having excellent physical properties, and is used in switches, sockets, microwave parts, relay cases and substrates in the fields of electrical and electronic products, It is widely used as various structural materials and packaging materials such as internal / external parts, optical machine parts, hot air parts such as gas circuit breakers, pump housings, lenses, electronics housings and instrument panels in the automotive field. Almost all polyarylate resins have the structure of Formula (A).

However, the existing polyarylate resin represented by Structural Formula (A) has high heat resistance, but the melt viscosity is so large that it must be melt processed at a high temperature of about 400 ℃, because the melt processing is not very good special processing equipment Since there is a disadvantage that the equipment cost is very expensive. In addition, it is almost insoluble in most organic solvents except for strong acids such as sulfuric acid, so that it is almost impossible to use or form the solution.

Many studies have also been reported to improve such disadvantages of conventional polyarylate resins. That is, US Patent No. 4,126,602 discloses a technique for replacing part of TPA and IPA with aliphatic dicarboxylic acid, and British Patent No. 2,085,458 discloses -O-, -S-,-between two benzene rings. A technique using dicarboxylic acids having flexible structures such as SO—, SO ₂ — and —CO— is disclosed.

In addition, Japanese Patent Application Laid-open Nos. 51-136793 and 56-29684 disclose biphenols, halogen elements, or defects in which a bond of -O-, -S-, -SO- is introduced between two benzene rings instead of BPA. An example using a substituted BPA (or biphenol) has been proposed.

However, most of the modified polyarylate resins have an effect of increasing the flexibility of the chain, thereby lowering the melting molding temperature. However, the thermal stability, the mechanical properties, and the weather resistance of the polymer are severely lowered, thereby making it impractical.

In general, a method of manufacturing a polyarylate resin can be representatively selected as a solution polymerization method, a melt polymerization method and an interfacial polymerization method, which will be described in detail as follows.

First, solution polymerization produces aromatic dicarboxylic acid in the form of acid chloride, which is then reacted in solution in the presence of aromatic diol and pyridine or triethylamine. That is, when preparing a polyarylate resin such as formula (A), TPA and IPA are replaced with perephthaloyl chloride (hereinafter referred to as TPC) and isophthaloyl chloride (hereinafter referred to as IPC) in the form of acyl chloride and then aromatic As a method of condensation polymerization in the presence of a diol and a solvent, it is classified into a low temperature solution polymerization method and a high temperature solution polymerization method according to the reaction solvent and the reaction temperature. Here, representative examples of the low temperature solution polymerization include US Pat. Nos. 3,234, 168, 4,049, 629, and 4,051, 107. In these patents, tetrahydrofuran is used as a solvent. Disclosed is a technique for condensation polymerization at 10 ° C to 30 ° C. On the other hand, as a high temperature solution polymerization method, a high boiling point solvent such as dichloroethylbenzene or ditoylmethane is used and condensation polymerization at a high temperature of 215 ° C to 220 ° C is described in US Patent Nos. 3,133,898, 3,702,838, 3,733,306 and the like. However, such a solution polymerization method is difficult to obtain a polymer having a high molecular weight, and the recovery and purification cost of the solvent is high, and thus there is a problem in economical production.

Secondly, the melt polymerization method is a method of condensation polymerization of diacetate compounds of aromatic diols, diphenyl esters of aromatic dicarboxylic acids or aromatic dicarboxylic acids, and aromatic diols at a high temperature of 220 캜 to 330 캜 in the presence of a catalyst. Patent Publication Nos. 53-35796 U.S. Patent Nos. 3,317, 464, 3,975, 487 and 3,553, 167 and the like, wherein as the polymerization reaction proceeds, the melt viscosity in the reactor rapidly increases, making stirring difficult. Therefore, it is difficult to obtain a heavy polymer having a large molecular weight. In addition, since the polymerization reaction proceeds at a high temperature, there is a problem in that the color of the polymer becomes poor due to simultaneous thermal decomposition or side reaction of the polymer.

Third, the interfacial polymerization method is heated by dissolving aromatic dicarboxylic acid chloride of aromatic dicarboxylic acid in an organic solvent such as methane dichloride which is not mixed with water, and then adding aromatic diol to a solution dissolved in aqueous solution of caustic soda. It is a method of superposing | polymerizing, stirring stirring. In this case, a phase transfer catailylst such as trimethyl ammonium bromide may be used as necessary. [S.C.Temin, in ‘Interfacial Synthesis’ed. F. Mellich and C. E. Carraher, Dekker, New York, 1977, Vol. II, p.27; H. -B. Tsai and Y.-D. Lee, J. Polym. Scl., Polym. Chem. Ed. 1987, 25, 1505; US Patent No. 4,229,565 and the like. This polymerization process proceeds very quickly even at room temperature, yields a high molecular weight polymer, the purity of the raw material is not so much a problem, and the equivalence ratio between the reactants does not necessarily have to be identical. Accordingly, in the present invention, in the preparation of a new polyarylate resin including a thiophene bond structure, intensive studies have been carried out using the interfacial polymerization method among the above-mentioned methods. Method was adopted.

On the other hand, the synthesis of 5-membered heterocylic aromatic polymers such as thiophene and furan and pyrrole has been conducted by researchers since the early 1960s. Reference; V. P. Sarzhevskaya, et al., Chem. Abstr., 59, 6526 (1983); H. Hopff and K. Krieger. Makromol, Chem., 47, 93 (1967); J. A. Moore and J. E. Kelly, Polym. Preper., 15 (2), 442 (1974); P. M. Heeetizes and G. J. Kok, Chem. Abstr., 83, 114977t (1976); S.-K.Kwon. K.-Y.Choi. and S.K.Choi. J. Polym. Sci., Pt A, 25 1781 (1987).

The main purpose of this work is to synthesize new polymers that have heat resistance comparable to existing wholly aromatic polymers. That is, the five-membered heterocyclic aromatic compound is less than 36 Kcal / mol, which is the resonance stability energy of benzene, but has some aromaticity and various addition reactions. It has been a target of research because it has many interesting points.

Also, among these heterocyclic aromatic polymers, polymers having a thiophene bond structure are known to have relatively superior thermal stability (P. M. Heertijes and G. J. Kok, Chem. Abstr., 83, 114977t (1976)).

In general, however, these 5-membered ring heterocyclic aromatic polymers are far less thermally stable than conventional benzene aromatic polymers.

Accordingly, the present inventors introduced the inflexible linkage between two thiophene rings (ie, dithienyl alkane) into the molecular chain, thereby providing excellent physical properties such as thermal stability and mechanical properties of the entire polymer. However, the present invention has been completed as a result of continuous research in the determination that the polyarylate resin having good melt processability or high solubility in solvents can be synthesized.

Therefore, in order to improve the deficiency of the existing polyarylate resin, the present invention introduces a thiophene bond structure into the molecular chain by interfacial polymerization, so that the general properties of the conventional resin are excellent at the same level and melt processability. The purpose of the present invention is to provide a polyarylate resin having a new structure with improved solubility in organic solvents.

Hereinafter, the present invention will be described in detail.

This invention contains the thiophene group represented by following structural formula (I), It is characterized by the polyarylate resin whose intrinsic viscosity (eta) in is 0.15-0.75 dl / g.

In the above formula, the correlation of l, m, n is as described above.

The polyarylate resin according to the present invention containing the thiophene group represented by the above structural formula (I) has an initial decomposition at 325 ° C to 405 ° C, has a glass transition point of 165 ° C to 183 ° C, sulfuric acid, CHCL3, It is characterized by dissolving in an organic solvent such as m-cresol or DMF. Tensile strength was found to be usually 6.0-7.4 kg / mm2.

The present invention will be described in more detail with reference to the manufacturing method as follows.

In order to prepare a novel polyarylate resin according to the present invention, 2,2-bis (5-chlorocarbonyl-2-thienyl) propane represented by the following structural formula (II) as an aromatic dicarboxylic acid carbonyl chloride component (Hereinafter referred to as "BCTP"), 2,5-dichlorocarbonylthiophene represented by the following general formula (III) (hereinafter referred to as "DCCT"), and TPC and IPC can be prepared by interfacial polymerization with BPA. .

At this time, the interfacial condensation polymerization reaction is preferably carried out at a temperature of 5 ° C to 20 ° C, preferably at 8 ° C to 15 ° C under stirring.

On the other hand, BCTP used in the present invention can be synthesized through the reaction of the following several steps, 2,2-bis (5-acetyl-2) represented by the following structural formula (IV) by reacting thiophene and acetone Thienyl) propane (hereinafter referred to as "BATP") was prepared, followed by bromoform oxidation to give 2,2-bis (5-carboxy-2-thienyl) propane (hereinafter referred to as "BCBTP"). ), And then finally, BCTP can be synthesized by acid chlornation with thionyl chloride.

In synthesizing the BCTP of the structural formula (II), the reaction was performed at a temperature of 60 to 80 ° C., preferably at a temperature of 70 ° C., in the presence of 70 to 75% sulfuric acid in the reaction of thiophene and acetone. In the case of acetylating the BTP synthesized by the formula (IV), reflux in the presence of 85% H ₃ PO ₄ to prepare the BATP of the formula (V).

BATP thus prepared can be reacted by the Badger method [J. Chem. Soc. 4165 (1954)] in the presence of Br ₂ / NaOH or HCl for about 24 hours to prepare BCBTP of formula (VI) When it is acylated by refluxing with thionyl chloride for 24 hours, BCTP is prepared.

On the other hand, DCCT (2,5-thiophene dicarbonyl chloride) of the formula (III), which is another compound used in the present invention can be prepared by the following simple reaction.

That is, when the adipic acid and thionyl chloride is refluxed for about 24 hours in the presence of a pyridine solvent, DCCT of the above formula (III) is prepared.

BCTP and DCCT prepared as described above are used as reactants in the present invention. For example, isophthaloyl chloride (IPC) and BCTP and DCCP are mixed with bisphenol A (BPA), sulfate chloride and trimethylbenzyl ammonium bromide. After dropwise addition and interfacial polymerization reaction at a temperature of 5 ° C. to 20 ° C. for about 1 hour, a polyarylate resin having a new structure containing a thiophene group of the above formula (I) is a poly-containing terephthaloyl chloride. Compared to acrylates, which do not dissolve in common organic solvents and dissolve only in strong acids such as sulfuric acid, they are very good in solubility and thus can be easily prepared by solvent casting as well as coatings. It will have a big characteristic.

In addition, by preparing a polymer having a lower glass transition point than the conventional polyarylate and exhibiting the same level of initial decomposition, a polyarylate resin having excellent heat resistance, electrical properties, and mechanical properties can be manufactured while lowering the molding temperature. .

Such a present invention will be described in detail based on the following examples.

Preparation Example 1 Synthesis of 2,2-bis (2-thienyl) propane (BTP)

When thiophene is reacted with acetone under a concentrated sulfuric acid catalyst, 2,2-bis (2-thienyl) propane can be obtained as shown in formula (VII). The specific reaction sequence is 72-75% dark sulfur solution. To 2.0 mol of thiophene and 1.0 mol of acetone were added and reacted at 70 ° C. for 4 hours with stirring. The reaction mixture was transferred to a separatory funnel, the product was separated, and distilled under reduced pressure to obtain a titleless compound, colorless 2,2-bis (2-thienyl) propane.

Boiling Point: 89 ℃ / 0.3mmHg

Yield: 45%

Preparation Example 2 Synthesis of BATP by Acetylation of BTP]

1.5 mol of acetic anhydride is added to a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler and a dropping funnel, and then 0.2 mol of 2,2-bis (2-thienyl) propane is slowly added through the dropping funnel. 10 g of 85% ortho-hosphoric acid is added to the mixed solution, and the mixture is refluxed for 3 hours with stirring.

200cc of cooling water is added to the reaction mixture to completely hydrolyze unreacted acetic anhydride, and carbon trichloride is added to extract the product. The extracted product was dried over anhydrous calcium dichloride and the solvent was evaporated to separate the product. The mixture was recrystallized several times with ethanol-petroleum ether to obtain 2,2-bis (5-acetyl-2-thienyl) propane.

Melting Point: 72 ℃

Yield: 55%

Preparation Example 3 Synthesis of BCBTP by Bromoform Oxidation of BATP

2,2-bis (5-carboxy-2-thienyl) propane was described by Badger et al. [J. Chem. Soc, 4165 (1954)] d to synthesize.

Melting Point: 275 ℃

Yield: 60%

Preparation Example 4 Synthesis of BCTP by Acylation of BCBTP

40 cc of thionyl chloride was slowly added to 0.1 mol of 2,2-bis (5-carboxy-2-thienyl) propane and then refluxed for 24 hours with stirring. Unreacted thionyl chloride was distilled off and distilled under reduced pressure to obtain 2,2-bis (5-chlorocarbonyl-2-thienyl) propane.

Boiling Point: 195 ~ 197 ℃ / 3.0mmHg

Preparation Example 5 Synthesis of DCCT

83 g (0.5 mol) of adipic acid and 180 ml (2.5 mol) of thionyl chloride were added to the reaction vessel and stirred at room temperature. 4.85 ml (0.06 mol) of pyridine was slowly added thereto, followed by reflux for 24 hours, and then unreacted thionyl chloride was distilled off.

Hot n-hexane was added to the reaction residue to dissolve it, and then filtered to remove gummy sulfur of the unmelted melt. The filtrate was subjected to fractional distillation under reduced pressure to obtain the product (boiling point: 94-96 ° C./0.1torr, yield: 56%) and recrystallized from n-hexane to give 52 g (49-5%: yield) of white needle-like 2 , 5-thiophene dicarbonylchloride was obtained.

Melting Point: 44.5 ~ 45.5 ℃

Example 1

18.24 g (0.08 mole) of bisphenol A, 0.16 g of hydrosulfite and 0.11 g of trimethyl benzyl amo Add chromium bromide and start stirring at a speed of 900 rpm.

To this was slowly added a solution of 8.12 g (0.04 mole) of isophthaloyl chloride and 17.92 g (0.04 mole) of 2,2-bis (5-chlorocarbonyl-2-thienyl) propane in 160 ml of methane dichloride. Add.

Interfacial condensation polymerization is carried out for 1 hour while maintaining the temperature in the reactor at 10 ° C using a temperature controller. After the polymerization reaction is completed, the reaction mixture is added to 500 ml of acetone to precipitate the polymer, followed by filtration and separation.

The separated polymer was washed several times with water and acetone, and then dried in a vacuum dryer at 60 ° C. for 24 hours to obtain a polymer of white powder.

The yield is 95.1% and 30 ° C. in concentrated sulfuric acid. The intrinsic viscosity of 0.75 dl / l was measured as a concentration of 0.5 g / dl.

The structure of the prepared polyarylate (PAR-1) was confirmed from the IR and ¹ H-NMR spectrum shown in FIG.

Example 2

18.24 g (0.08 mol) of 8.12 g (0.04 mol) of terephthaloyl chloride and 17.92 g (0.04 mol) of 2,2-bis (5-chlorocarbonyl-2-thienyl) propane were carried out in the same manner as in Example 1. Was stirred dropwise at 10 ° C. for 1 hour to obtain polyarylate (PAR-2).

The yield was 78.6% and the intrinsic viscosity of 0.70 dl / g was measured in a concentrated sulfuric acid at a concentration of 30 g and 0.5 g / dl.

Example 3

The same procedure as in Example 1, except that 6.5 g (0.032 mol) of terephthaloyl chloride, 6.5 g (0.032 mol) of isophthaloyl chloride, and 7.17 (0.016 mol) of 2,2-bis (5-chlorocarbonyl-2 -Thienyl) propanol 18.24 g (6.08 mol) of bisphenol A was dripped at 10 degreeC for 1 hour, and the polyarylate was obtained.

The yield was 89.4% and was measured at a concentration of 0.5 g / dl at 30 ° C. in concentrated sulfuric acid to give an intrinsic viscosity of 0.73 dl / g. The structure of the produced polyacrylate (PAR-3) was confirmed from the spectrum shown in FIG.

Example 4

In the same manner as in Example 1 except that 8.12 g (0.04 mol) of terephthaloyl chloride and 10.64 g (0.04 mol) of 2.5-thiophene dicarbonyl chloride were added dropwise to 18.24 g (0.08 mol) of bisphenol A. It stirred for 1 hour, and obtained polyarylate (PAR-4).

The yield was 75% and the intrinsic viscosity of 0.30 dl / g was measured at a concentration of 0.5 g / dl at 30 ° C. in concentrated sulfuric acid.

Example 5

Perform the same procedure as in Example 1, except that 6.5 g (0.032 mol) of terephthaloyl chloride, 6.5 g (0.032 mol) of isophthaloyl chloride and 3.62 g (0.016 mol) of 2,5-thiophene dicarbonyl chloride were added to 18.24. The polyarylate (PAR-6) which stirred at 10 degreeC for 1 hour was obtained by dripping g (0.08 mol) bisphenol A.

The yield was 60% and was measured at a concentration of 0.5 g / dl at 30 ° C. in concentrated sulfuric acid and showed an intrinsic viscosity of 0.74 dl / g.

Example 6

In the same manner as in Example 1, 8.12 g (0.04 mol) of isophthaloyl chloride and 10.64 g (0.04 mol) of 2,5-thiophene dicarbonyl chloride were added dropwise to 18.24 g (0.08 mol) of bisphenol A. It stirred at 10 degreeC for 1 hour, and obtained polyarylate (PAR-6).

The yield was 94.8% and the intrinsic viscosity of 0.75dl / g was obtained when the concentration of 0.5g / dl was measured at 30 ° C in concentrated sulfuric acid.

Example 7

9.74 (0.048 mol) of isophthaloyl chloride and 7.17 g (0.016 mol) of 2,2-bis (5-chlorocarbonyl-2-thienyl) propane and 2,5-thiophene 4,26 g (0.016 mol) of dicarbonyl chloride was added dropwise to 18.24 g (0.08 mol) of bisphenol A by stirring at 10 ° C. for 1 hour to obtain polyarylate (PAR-7).

The yield was 65% and was measured at a concentration of 0.5 g / dl in concentrated sulfuric acid at a concentration of 0.58 dl / g.

Example 8

9.74 g (0.048 mol) of terephthaloyl chloride, 7.17 g (0.016 mol) of 2,2-bis (5-chlorocarbonyl-2-thienyl) propane and 2.5-thiophene dica 4.26 g (0.016 mol) of carbonyl chloride was added dropwise to 18.24 g (0.08 mol) of bisphenol A by stirring at 10 ° C. for 1 hour to obtain polyarylate (PAR-8).

The yield was 55% and the intrinsic viscosity of 0.15 dl / g was measured at a concentration of 0.5 g / dl at 30 ° C. in concentrated sulfuric acid.

Example 9

In the same manner as in Example 1, 4.06 g (0.02 ml) of terephthaloyl chloride, 4.06 g (0.02 mol) of isophthaloyl chloride and 8.96 g (0.02 mol) of 2,2-bis (5-chlorocarbonyl- 2-thienyl) propane and 5.32 (0.02 mol) of 2,5-thiophendicarbonyl chloride were added dropwise to 18.24 g (0.08 mol) of bisphenol A. 9) was obtained.

The yield was 64%, and the intrinsic viscosity of 0.72 dl / g was obtained when measured at a concentration of 0.5 g / dl at 30 ° C. in concentrated sulfuric acid.

Comparative Example 1

In the same manner as in Example 1, 12.18 g (0.06 mol) of terephthaloyl chloride and 4.06 g (0.02 mol) of isophthaloyl chloride were added dropwise to 18.24 g (0.08 mol) of bisphenol A for 1 hour at 10 ° C. It stirred and obtained polyarylate (PAR-1C).

The yield was 93% and was measured at a concentration of 0.5 g / dl at 30 ° C. in concentrated sulfuric acid and showed an intrinsic viscosity of 0.71 dl / g.

Comparative Example 2

In the same manner as in Example 1, 16.24 g (0.08 mol) of terephthaloyl chloride was added dropwise to 18.24 g (0.08 mol) of bisphenol A, followed by stirring at 10 ° C. for 1 hour to form polyarylate (PAR-2C). Got it.

The yield was 65% and was measured at a concentration of 0.5 g / dl at 30 ° C. in concentrated sulfuric acid, and showed an intrinsic viscosity of 0.43 dl / g.

The polyarylate prepared by the above embodiment has the following characteristics.

[Solubility]

Table 1 shows the results of solubility experiments of the polyarylate prepared by the above examples.

In general, polyarylate containing terephthaloyl chloride does not dissolve in general organic solvents, but dissolves only in strong acids such as sulfuric acid.

However, polyarylates prepared by reacting terephthaloyl chloride used as monomers with monomers containing thiophene groups (Examples 2, 4, 5, 8, 9) were partially or completely dissolved in most organic solvents. .

In addition, polyarylates containing isophthaloyl chloride (Examples 1, 3, 6, 7) were also partially or completely dissolved in most organic solvents. Therefore, the film can be easily produced by the solvent casting.

In addition, the use as a coating is also considered to be very large.

TABLE 1

* In Table 1, ○: dissolution, △: partial dissolution, ×: insoluble.

[Molecular Weight, Thermal Analysis, Tensile Strength]

Table 2 shows the molecular weight, thermal analysis, and tensile strength test results of the polyarylate synthesized by the above examples.

The polyarylate prepared as shown in Table 2 has a glass transition point around 169 to 183 ° C and does not show a significant weight change even when heated from 320 to around 410 ° C (Attachments 3 and 4). Reference)

Therefore, the polyarylate prepared according to the present invention has a lower glass transition point than the conventional polyarylate and obtains a polymer exhibiting the same level of initial decomposition, thereby lowering the molding temperature and having excellent heat resistance, electrical properties, and mechanical properties. Can be confirmed.

TABLE 2

* Tg: glass transition temperature

DT: Initial decomposition temperature

T.S. The tensile strength

Claims (6)

Intrinsic viscosity (eta) h containing the thiophene group represented by following structural formula (I) is 0.15-0.75 dl / g, The polyarylate resin characterized by the above-mentioned.

In the above formula,

The polyarylate resin according to claim 1, wherein the polyarylate resin has an initial decomposition at 327 ° C to 405 ° C and has a glass transition point of 165 ° C to 183 ° C. The polyarylate resin according to claim 1 or 2, wherein the polyarylate resin is partially or completely dissolved in an organic solvent of sulfuric acid, CHCl ₃ , m-cresol or DMF. 3. The polyarylate resin according to claim 1 or 2, wherein the polyarylate resin has a phosphorus strength of 6.0 to 7.4 kg / mm ² . As the aromatic dicarboxylic acid component, 2,2-bis (5-chlorocarbonyl-2-thienyl) propane represented by the following structural formula (II) or 2,5-dichlorocarbonyl represented by the following structural formula (III) A method for producing a polyallylate resin containing a thiophene group represented by the following general formula (I) by interfacial polymerization with bisphenol A using thiophene, terephthaloyl chloride and isofnaloyl chloride.

However, in the above formula

The method for producing a polyarylate resin according to claim 5, wherein the interfacial polycondensation reaction is carried out at a temperature of 5 ° C to 20 ° C under stirring.

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