JP2008255265A - Method for producing aromatic polyester pellet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing pellets which are little discolored and are excellent in transparency. <P>SOLUTION: This method for producing aromatic polyester pellets comprises mixing an aromatic polyester with one or more solvents selected from the group consisting of dichloromethane, trichloromethane, 1,2-dichloroethane and chlorobenzene, stirring the mixture at a temperature of 15 to 50°C, simultaneously evaporating the solvent in an inactive gas atmosphere, and then cutting and/or crushing the resultant aromatic polyester mass. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a method for producing aromatic polyester pellets.

Conventionally, when producing aromatic polyester pellets, an aromatic polyester powder is supplied to a pelletizer and heated and melted at a high temperature of 300 ° C. or higher, and then the aromatic polyester is extruded and cut (Patent Document 1).

In this method, the aromatic polyester deteriorates due to heat-melting at a high temperature and turns yellow (yellowing), and a pellet having excellent transparency cannot be obtained. Conventionally, aromatic polyester has been exclusively used only as a heat-resistant resin, and thus yellowing of such aromatic polyester has not been a problem.

However, in recent years, various uses relating to aromatic polyesters have been developed. For example, in the use of optical fibers, yellowing of aromatic polyesters has become a major problem.

JP 2003-285320 A

The present invention provides a method for producing pellets with less coloring and excellent transparency.

The inventors of the present invention have made various studies in order to solve the coloring problem of the conventional method for producing aromatic polyester pellets. As a result, by adding a predetermined solvent to the aromatic polyester and evaporating the solvent under a predetermined temperature and inert gas atmosphere while stirring the resulting solution, pellets with less coloring and excellent transparency are obtained. The present invention has been completed by finding that it can be produced.

That is, the present invention
(1) The aromatic polyester is mixed with one or more solvents selected from the group consisting of dichloromethane, trichloromethane, 1,2-dichloroethane, and chlorobenzene, and the resulting solution is stirred at a temperature of 15 to 50 ° C. However, this is a process for producing aromatic polyester pellets in which the solvent is evaporated under an inert gas atmosphere, and then the resulting aromatic polyester mass is cut and / or crushed.

As a preferred embodiment,
(2) The method according to (1) above, wherein the concentration of the solution is 0.2 to 1.0 g / ml.
(3) The method according to (1) above, wherein the concentration of the solution is 0.4 to 0.8 g / ml.
(4) The method according to any one of (1) to (3) above, wherein the solvent is dichloromethane.
(5) The method according to any one of (1) to (4) above, wherein the temperature at which the solvent is evaporated is 25 to 47 ° C.
(6) The method according to any one of (1) to (4) above, wherein the temperature at which the solvent is evaporated is 35 to 45 ° C.
(7) The method according to any one of (1) to (6) above, wherein the time for evaporating the solvent is 12 to 72 hours,
(8) The method according to any one of (1) to (6) above, wherein the time for evaporating the solvent is 24-48 hours,
(9) The method according to any one of (1) to (8) above, wherein the aromatic polyester obtained by cutting is further heated at 40 to 100 ° C. under reduced pressure.

According to the method of the present invention, aromatic polyester pellets with little coloring and excellent transparency can be obtained. In addition, there is no thermal degradation of the aromatic polyester. In addition, since conventional heat melting is not performed, thermal energy can be saved and the manufacturing process can be simplified.

In the method of the present invention, an aromatic polyester obtained by polymerization, preferably an aromatic polyester powder, is mixed with one or more solvents selected from the group consisting of dichloromethane, trichloromethane, 1,2-dichloroethane and chlorobenzene. To produce a solution. Of these solvents, dichloromethane is preferably used. The upper limit of the concentration of the solution is preferably 1.0 gram / milliliter, more preferably 0.7 gram / milliliter, still more preferably 0.5 gram / milliliter, and the lower limit is preferably 0.2 gram / milliliter, more preferably 0.4 gram / milliliter. It is. If the above upper limit is exceeded, the aromatic polyester powder cannot be sufficiently dissolved, and if it is less than the above lower limit, not only the amount of the solvent used is increased, but a particularly remarkable effect is not obtained.

The temperature at which the solvent is evaporated from the solution obtained by mixing the aromatic polyester with the solvent has an upper limit of 50 ° C., preferably 47 ° C., more preferably 45 ° C., and a lower limit of 15 ° C., preferably 25 ° C. More preferably, it is 35 ° C. If the upper limit is exceeded, the aromatic polyester after evaporation of the solvent turns yellow and becomes colored, and if it is less than the lower limit, it takes a long time to evaporate the solvent. The pressure at the time of solvent evaporation is not particularly limited as long as the solvent can be evaporated at the above temperature. The upper limit is preferably 103 kPa, more preferably 101 kPa, and the lower limit is preferably 10 kPa, more preferably 50 kPa. The upper limit of the time required for solvent evaporation is preferably 72 hours, more preferably 60 hours, still more preferably 48 hours, and the lower limit is preferably 12 hours, more preferably 18 hours, still more preferably 24 hours. If the upper limit is exceeded, the solvent is completely evaporated and processing becomes difficult, and if it is less than the lower limit, the solvent cannot be removed sufficiently.

The evaporation is performed in an inert gas atmosphere with stirring. Stirring is carried out at a rotational speed such that the resulting aromatic polyester becomes agar-like after the solvent has evaporated from the solution. As the inert gas, for example, nitrogen, argon or the like is used.

The embodiment of the present invention will be described with reference to FIG. First, the aromatic polyester powder (1) is mixed with one or more solvents (2) selected from the group consisting of dichloromethane, trichloromethane, 1,2-dichloroethane and chlorobenzene, and a solution having the above-mentioned predetermined concentration ( 3) is prepared. The solution (3) is then placed in a container (4), for example a flask with a stirrer. Next, while stirring the solution, the solvent is evaporated under a predetermined temperature and pressure condition, and preferably with an inert gas such as nitrogen or argon flowing. Thereafter, the aromatic polyester lump (5) remaining in the container can be taken out and pelletized by cutting with a ceramic cutter (6) or the like, for example. The pellet (7) can be heated at 40 to 100 ° C. under reduced pressure to further remove the solvent.

In the present invention, the aromatic polyester is obtained by reacting an aromatic polyhydric alcohol with an aromatic polycarboxylic acid, an acid halide or an acid anhydride thereof. Aromatic polyhydric alcohols and aromatic polycarboxylic acids, their acid halides or acid anhydrides are known. The production method thereof is known and is described in detail, for example, in Patent Document 1 described above.

Examples of the aromatic polyhydric alcohol include 2,2′-dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, and 2,2′-bis- ( 4-hydroxyphenyl) propane [bisphenol A], 2,4'-dihydroxydiphenylmethane, bis- (4-hydroxyphenyl) methane, bis- (2-hydroxyphenyl) methane, bis- (4-hydroxy-2,6- Dimethyl-3-methoxyphenyl) methane, 1,1-bis- (4-hydroxyphenyl) ethane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, 1,2-bis- (4-hydroxyphenyl) ethane 1,1-bis- (4-hydroxy-2-chlorophenyl) ethane, 1,1'-binaphthalene-2,2'-diol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4- Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6- Hydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 9,9-bis (4-hydroxyphenyl) fluorene 9,9-bis (5-methyl-4-hydroxyphenyl) fluorene, 1,2- (9-oxofluorene) diol, 1,5- (9-oxofluorene) diol, 1,6- (9-oxo Fluorene) diol, 1,7- (9-oxofluorene) diol, 2,3- (9-oxofluorene) diol, 2,7- (9-oxofluorene) diol, 2,2-bis- (4-hydroxy) Naphthyl) propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) pentane, 3,3-bis- (4-hydroxyphenyl) Phenylmethane, para-α, α'-bis- (4-hydroxyphenyl) -para-diisopropylbenzene, bi Su- (4-hydroxyphenyl) ether, 4,3'-dihydroxydiphenyl ether, 4,2'-dihydroxydiphenyl ether, 2,2'-dihydroxydiphenyl ether, 2,3'-dihydroxydiphenyl ether, 4,4'-dihydroxy-2 , 6-Dimethyldiphenyl ether, bis- (hydroxynaphthyl) ether, 3,4'-dihydroxydiphenyl, bis- (4-hydroxyphenyl) sulfone, bis- (3-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenylsulfone Catechol, 3-methyl catechol, 4-methyl catechol, 3-ethyl catechol, 4-ethyl catechol, 3-n-propyl catechol, 4-n-propyl catechol, 3- (t-butyl) catechol, 3-n- Pentylcatechol, 4-n-pentylcatechol, 4- (1,1-dimethylpropyl) catechol, 4-hexylcatechol, 4-cyclohexylcatechol 4- (1,1,3,3-tetramethylbutyl) catechol, 4-nonylcatechol, 3,4-dimethylcatechol, 3,5-dimethylcatechol, 3,6-dimethylcatechol, 4,5- Dimethylcatechol, 4-methyl-5-ethylcatechol, 3-chlorocatechol, 4-chlorocatechol, 3-bromocatechol, 4-bromocatechol, 3-fluorocatechol, 4-fluorocatechol, 3,5-dichlorocatechol, 4 , 5-dichlorocatechol, 3,4-dichlorocatechol, 3,4-dibromocatechol, 3,5-dibromocatechol, 4,5-dibromocatechol, 4-chloro-5-nitrocatechol, 3-chloro-6-methoxy Catechol, 5-bromo-4-nitrocatechol, 4-bromo-5-methylcatechol, 3-bromo-5- (t-butyl) catechol, 3,4,5-trichlorocatechol, 3,4,5-tribromo Catechol, 3,4,6-tribromocatechol, tetrac Locatechol, tetrabromocatechol, 3-aminocatechol, 4-aminocatechol, 3- (2-aminoethyl) catechol, 4- (2-methylaminoethyl) catechol, 4- (2-dimethylaminoethyl) catechol, 4- (2-aminoethyl) catechol, 6-amino-4- (2-aminoethyl) catechol, 3-nitrocatechol, 3,4-dinitrocatechol, 3,4-dinitrocatechol, 4,5-dinitrocatechol, 3- Nitro-6-methoxycatechol, 4-nitro-3-methoxycatechol, 5-nitro-3-methylcatechol, 4-methoxycatechol, 6-methoxycatechol, 4- (2-hydroxyethyl) catechol, 3-propioxycatechol , 3-butyroxycatechol, 3,4-dimethoxycatechol, 3,6-dimethoxycatechol, 5-methoxy-3- (t-butyl) catechol, 3-ethoxy- (t-butyl) catechol, 3,4,6 -Trimethoxyca Tecor, resorcinol, 2-chlororesorcinol, 4-chlororesorcinol, 5-chlororesorcinol, 2,4-dichlororesorcinol, 4,6-dichlororesorcinol, 2,4,6-trichlororesorcinol, 2-bromo-4-chlororesorcinol 4-bromo-2-chlororesorcinol, 4-chloro-5-methylresorcinol, 6-chloro-4-ethylresorcinol, 2-chloro-4-butylresorcinol, 6-chloro-4-butylresorcinol, 6-chloro- 4-cyclohexylresorcinol, 2,4-dichloro-5-methylresorcinol, trichlororesorcinol, 2-bromoresorcinol, 4-bromoresorcinol, 5-bromoresorcinol, 2,4-dibromoresorcinol, 4,6-dibromoresorcinol, 2, 4,6-tribromoresorcinol, 6-bromo-4-butylresorcinol, 2-iodoresor Nord, 4-iodoresorcinol, 5-iodoresorcinol, 4,6-diiodoresorcinol, 2,4,6-triiodoresorcinol, 2-aminoresorcinol, 5-aminoresorcinol, 4-amino-2,5-dimethylresorcinol 4-benzaminoresorcinol, 5-mercaptoresorcinol, 5-methylthioresorcinol, 5-ethylthioresorcinol, 5-propylthioresorcinol, 5-propylthioresorcinol, 5-butylthioresorcinol, 2-benzsulfonylresorcinol, resorcinol monoacetate , Resorcinol monobenzoate, 2-nitroresorcinol, 4-nitroresorcinol, 5-nitroresorcinol, 2,4-dinitroresorcinol, 4,6-dinitroresorcinol, 2,4,6-trinitroresorcinol, tetranitroresorcino , 6-nitro-5-methoxyresorcinol, 2-nitro-5-methoxyresorcinol, 4-nitro-5-methoxyresorcinol, 2,4-dinitro-5-methylresorcinol, 2,4,6-trinitro-5 -Methylresorcinol, 2-methoxyresorcinol, 4-methoxyresorcinol, 5-methoxyresorcinol, 2,3-methoxyresorcinol, 2,5-methoxyresorcinol, 2-methoxy-5-methylresorcinol, 5-methoxy-4-methylresorcinol 5-methoxy-6-methylresorcinol, 5-ethoxyresorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 5-ethylresorcinol, 2-n-propyl Resorcinol, 4-n-propyl resorcinol, 5-n-propyl resorcinol, 2- (2-propenyl ) Resorcinol, 4- (2-propenyl) resorcinol, 4- (2-methylethenyl) resorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 5-n-butylresorcinol, 2-n-butylresorcinol, 4 -tert-butylresorcinol, 2-n-pentylresorcinol, 4-n-pentylresorcinol, 5-n-pentylresorcinol, 4- (1-methylbutyl) resorcinol, 5- (2-methyl-1 -Ethylpropyl) resorcinol, 2-n-hexylresorcinol, 4-n-hexylresorcinol, 5-n-hexylresorcinol, 4- (4-methylpentyl) resorcinol, 5- (4-methylpentyl) resorcinol, 5 -(1,1-dimethylbutyl) resorcinol, 5- (1,2-dimethylbutyl) resorcinol, 5- (1-methyl-1-pentenyl) resorcinol, 4-cyclohexylresorcinol, 4-phenylresorcinol 4-heptylresorcinol, 5-heptylresorcinol, 5- (1-methylhexyl) resorcinol, 4-phenylmethylresorcinol, 2-octylresorcinol, 4-octylresorcinol, 5-octylresorcinol, 4- (1-methyl (Heptyl) resorcinol, 4- (1,1,3,3-tetrabutyl) resorcinol, 4- (2-phenylethyl) resorcinol, 5-nonylresorcinol, 5- (1-methyloctyl) resorcinol, 5- (1,1 -Dimethylheptyl) resorcinol, 5- (1,2-dimethylheptyl) resorcinol, 5- (1,2,4-trimethylhexyl) resorcinol, 4-decylresorcinol, 5- (1-methylnonyl) resorcinol, 2,4- Dimethylresorcinol, 2,5-dimethylresorcinol, 4,5-dimethylresorcinol, 4,6-dimethylresorcinol, 4-ethyl-2-methylresorcinol 5-ethyl-2-methylresorcinol, 2-ethyl-4-methylresorcinol, 5-ethyl-4-methylresorcinol, 6-ethyl-4-methylresorcinol, 5-ethenyl-4-methylresorcinol, 2,4- Dimethylresorcinol, 5-methyl-4-propylresorcinol, 2-methyl-5-sec-butylresorcinol, 4,6-di (isopropyl) resorcinol, 4-ethyl-6-pentylresorcinol, 4,6-di- (tert-butyl) resorcinol, 2-methyl-4- (benzyl) resorcinol, 2,4,5-trimethylresorcinol, 2,4,6-trimethylresorcinol, 4,5,6-trimethylresorcinol, 4,6-dimethyl -5-sec-butylresorcinol, tetramethylresorcinol, 2-hydroxyethylresorcinol, 5-trifluoromethylresorcinol, hydroquinone, phenylhydroquinone, chlorohydroquinone , Methylhydroquinone, trifluorohydroquinone, tetrafluorohydroquinone, 2-chloro-3-methoxyhydroquinone, 2-chloro-5-methoxyhydroquinone, 2-chloro-6-methoxyhydroquinone, 2,3-dichlorohydroquinone, 2,5- Dichlorohydroquinone, 2,6-dichlorohydroquinone, trichlorohydroquinone, tetrachlorohydroquinone, bromohydroquinone, 3-bromo-2,6-dimethylhydroquinone, 2,5-dibromohydroquinone, 2,6-dibromohydroquinone, tribromohydroquinone, iodo Hydroquinone, 2,6-diiodohydroquinone, tetraiodohydroquinone, nitrohydroquinone, 2,6-dinitrohydroquinone, methoxyhydroquinone, 2-methoxy-3-methylhydroquinone, 2-methoxy-5-methylhydroquinone, 3-methoxy-2 -Methylhydroquinone, 5-methoxy-2-methyl Luhydroquinone, 2-methoxy-6-propylhydroquinone, 2-methoxy-5-propenylhydroquinone, 2,3-dimethoxyhydroquinone, 2,5-dimethoxyhydroquinone, 2,6-dimethoxyhydroquinone, phenoxyhydroquinone, mercaptohydroquinone, acetylhydroquinone Benzoylhydroquinone, hydroxymethylhydroquinone, methylhydroquinone, 2-methyl-6-ethylhydroquinone, 2-methyl-5-isopropylhydroquinone, 2-methyl-5-cyclohexylhydroquinone, 2,3-dimethylhydroquinone, 2,5-dimethyl Hydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, tetramethylhydroquinone, ethylhydroquinone, 2,6-diethylhydroquinone, vinylhydroquinone, 5-ethoxyresorcinol, 2-methylresorcinol, 4-methylresorcino 5-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 5-ethylresorcinol, 2-n-propylresorcinol, 4-n-propylresorcinol, 5-n-propylresorcinol, 2- (2-propenyl) Resorcinol, 4- (2-propenyl) resorcinol, 4- (1-methylethenyl) resorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 5-n-butylresorcinol, 5-sec-butylresorcinol, 4- tert-butylresorcinol, 2-n-pentylresorcinol, 4-n-pentylresorcinol, 5-n-pentylresorcinol, 4- (1-methylbutyl) resorcinol, 5- (2-methyl-1-ethylpropyl) resorcinol, 2 -n-hexyl resorcinol, 4-n-hexyl resorcinol, 5-n-hexyl resorcinol, 4- (4-methylpentyl) resorcinol, 5- (4-methylpentyl) resorcinol, 5- (1,1-dimethylbutyl) resorcinol, 5- (1,2-dimethylbutyl) resorcinol, 5- (1-methyl-1-pentenyl) resorcinol, 4-cyclohexyl Resorcinol, 4-phenylresorcinol, 4-heptylresorcinol, 5-heptylresorcinol, 5- (1-methylhexyl) resorcinol, 4-phenylmethylresorcinol, 2-octylresorcinol, 5-octylresorcinol, 4- (1-methylheptyl ) Resorcinol, 4- (1
, 1,3,3-tetramethylbutyl) resorcinol, 4- (2-phenethyl) resorcinol, 5-nonylresorcinol, 5- (1-methyloctyl) resorcinol, 5- (1,1-dimethylheptyl) resorcinol, 5 -(1,2-dimethylheptyl) resorcinol, 5- (1,2,4-trimethylhexyl) resorcinol, 4-decylresorcinol, 5- (1-methylnonyl) resorcinol, 2,4-dimethylresorcinol, 2,5- Dimethylresorcinol, 4,5-dimethylresorcinol, 4,6-dimethylresorcinol, 4-ethyl-2-methylresorcinol, 5-ethyl-2-methylresorcinol, 2-ethyl-4-methylresorcinol, 5-ethyl-4- Methyl resorcinol, 6-ethyl-4-methyl resorcinol, 5-ethenyl-4-methyl resorcinol, 2,4-dimethyl resorcinol, 5-methyl-4-propyl resorcinol, 2-methyl-5-sec- Tilresorcinol, 4,6-diisopropylresorcinol, 4-ethyl-6-pentylresorcinol, 4,6-di-tert-butylresorcinol, 2-methyl-4- (benzyl) resorcinol, 2,4,5-trimethylresorcinol, 2,4,6-trimethylresorcinol, 4,5,6-trimethylresorcinol, 4,6-dimethyl-5-sec-butylresorcinol, tetramethylresorcinol, 2-hydroxyethylresorcinol, 5-trifluoromethylresorcinol, n- Propylhydroquinone, isopropylhydroquinone, 1-propenylhydroquinone, 2-propenylhydroquinone, 2,5-diisopropylhydroquinone, 4-butylhydroquinone, 4-butylhydroquinone, 2,3-di (tert-butyl) hydroquinone, 2,5-di (tert-butyl) hydroquinone, 2,6-di (tert-butyl) hydroquinone, 2-methyl-2-propenyl hydroxyl , Hexylhydroquinone, 4-methylpentylhydroquinone, cyclohexylhydroquinone, 4-phenylmethylhydroquinone, octylhydroquinone, 2,2'-methylidenebisphenol, 3,3'-methylidenebisphenol, 4,4'-methylidenebisphenol, 2,2'-methylidenebis (4-methylphenol), 2,2'-methylidenebis (5-methylphenol), 2,2'-methylidenebis (6-methylphenol), 4,4'-methylidene (2-methylphenol) ), 4,4'-methylidene (3-methylphenol), 2,2'-methylidenebis (4,6-dimethylphenol), 2,2'-methylidenebis (3,5-dimethylphenol), 4,4'- Methylidenebis (2,6-dimethylphenol), 3,3'-methylidenebis (2,4,6-trimethylphenol), 2,2'-methylidenebis (4-propylphenol), 4,4'-methylidenebis (2-propyl) Phenol), 4,4'-methylide Bis (2-methyl-6-ethylphenol), 2,2'-methylidenebis (3,4,5,6-tetramethylphenol), 4,4'-methylidenebis (2,3,5,6-tetramethylphenol) ), 2,2'-methylidenebis (4-tert-butylphenol), 4,4'-methylidenebis (2-methyl-5-isopropylphenol), 4,4'-methylidenebis (3-methyl-6-isopropylphenol), 4,4'-methylidenebis (5-methyl-6-isopropylphenol), 2,2'-methylidenebis (4-tert-butyl-6-methylphenol), 2,2'-methylidenebis (6-tert-butyl-4 -Methylphenol), 4,4'-methylidenebis (4-tert-butyl-6-methylphenol), 4,4'-methylidenebis (2-tert-butyl-5-methylphenol), 2,2'-methylidenebis ( 3,4-dimethyl-6-isopropylphenol), 2,2'-methylidenebis (6-tert-butyl-4-methylphenol), 2,2'-methylidenebis (4- (1,1,3,3-tetramethyl) Butyl) phenol), 2,2'-methylidenebis (4,6-di-tert-butylphenol), 2,2'-methylidenebis (4,6-tert-butylphenol), 4,4'-methylidenebis (2,6- Di-tert-butylphenol), 4,4'-methylidenebis (3,5-di-tert-butylphenol), 2,2'-methylidenebis (4-chlorophenol), 4,4'-methylidenebis (2-chlorophenol) 2,2'-methylidenebis (4-bromophenol), 2,2'-methylidenebis (4,6-dichlorophenol), 2,2'-methylidenebis (4,5-dichlorophenol), 3,3'-methylidenebis (4,5-dichlorophenol), 4,4'-methylidenebis (2,5-dichlorophenol), 4,4'-methylidenebis (2,6-dichlorophenol), 2,2'-methylidenebis (4,6- Dibromophenol), 4,4'-methylidenebis (2,6-dibromophenol), 2,2'-methylidenebis (3,4,6-trichlorophenol), 3,3'-methylidenebis (2,4 , 6-trichlorophenol), 2,2'-methylidenebis (6-bromo-4-chlorophenol), 2,2'-methylidenebis (4-bromo-6-nitrophenol), 2,2'-methylidenebis (6- Chloro-4-nitrophenol), 2,2'-methylidenebis (4-nitrophenol), 4,4'-methylidenebis (2-nitrophenol), 2,2'-methylidenebis (4,6-dinitrophenol), 3 , 3'-methylidenebis (6-methoxyphenol), 4,4'-methylidenebis (2-methoxyphenol), 2,2'-methylidenebis (4-chloro-6-methylphenol), 2,2'-methylidenebis (6 -Chloro-4-methylphenol), 4,4'-methylidenebis (2-chloro-6-methylphenol), 2,2'-methylidenebis (6-bromo-4-methylphenol), 4,4'-methylidenebis ( 6-bromo-2-methylphenol), 2,2'-methylidenebis (4-chloro-3,5-dimethylphenol), 2,2'-methylidenebis (3-chloro-4, 6-dimethylphenol), 2,2'-methylidenebis (6-bromo-4,5-dimethylphenol), 4,4'-methylidenebis (2-chloro-3,5,6-trimethylphenol), 2,2 ' -Methylidenebis (4-chloro-6-isopropylphenol), 2,2'-methylidenebis (6-chloro-4-tert-butylphenol), 2,2'-methylidenebis (4-chloro-3-methyl-6-isopropylphenol) ), 2,2'-methylidenebis (4-chloro-6-tert-butyl-3-methylphenol), 2,2'-methylidenebis (4,6-dichloro-3-methylphenol), 2,2'-methylidenebis (6-nitro-4-tert-butylphenol), 4,4'-isopropylidenebisphenol, 2,2'-isopropylidenebis (5-methylphenol), 4,4'-isopropylidenebis (2-methylphenol) 4,4′-isopropylidenebis (2-cyclohexylphenol), 4,4′-isopropylidenebis (2,6-dibromophenol), 4'-isopropylidenebis (2-nitrophenol), 4,4'-isopropylidenebis (2,6-dinitrophenol), 4,4'-butanediylbis (2-methylphenol), 4,4'-butylidene Bisphenol, 2,2'-butylidenebis (6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-2-methylphenol), 4,4'-sec-butylidenebisphenol 4,4'-sec-butylidenebis (3-methylphenol), 2,2'-sec-butylidenebis (3-methyl-6-isopropylphenol), 2,2'-sec-butylidenebis (6-tert-butyl- 4-methylphenol), 4,4'-isobutylidenebisphenol, 4,4'-isobutylidenebis (6-tert-butyl-4-methylphenol), 4,4 '-(1,3-cyclohexanediyl ) Bisphenol, 4,4'-cyclohexylidene bisphenol, 4,4'-cyclohexylidene bis (2-chlorophenol), 4,4'-cyclohexyl Denbis (2,6-dichlorophenol), 2,2'-thiobisphenol, 4,4'-thiobisphenol, 4,4'-thiobis (2-methylphenol), 2,2'-thiobis (4,5- Dimethylphenol), 2,2'-thiobis (4,6-dimethylphenol), 4,4'-thiobis (2,6-dimethylphenol), 2,2'-thiobis (6-tert-butyl-4-methyl) Phenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'-thiobis (4-fluorophenol), 2,2'-thiobis (4-chlorophenol), 4, 4'-thiobis (3-chlorophenol), 2,2'-thiobis (4-chloro-5-methylphenol), 2,2'-thiobis (4,6-dichlorophenol), 4,4'-thiobis ( 2-bromophenol), 2,2'-thiobis (5-nitrophenol), 4,4'-sulfinylbisphenol, 4,4'-sulfinylbis (2-methylphenol), 4,4'-sulfinylbis (2 -tert-butyl-5-methylphenol), 4,4 '-Sulfinylbis (2-chlorophenol), 4,4'-sulfinylbis (4-chlorophenol), 2,2'-sulfinylbis (4,6-dichlorophenol), 4,4'-sulfinylbis (2 -Bromophenol), 2,2'-sulfonylbisphenol, 4,4'-sulfonylbisphenol, 4,4'-sulfonylbis (2-methylphenol), 4,4'-sulfonylbis (2,5-dimethylphenol) 4,4′-sulfonylbis (2-tert-butyl-5-methylphenol), 4,4′-sulfonylbis (2-chlorophenol), 4,4′-sulfonylbis (3-chlorophenol), 4 , 4'-sulfonylbis (2-bromophenol), 4,4'-sulfonylbis (2-nitrophenol), 2,3'-oxybisphenol, 2,2'-ethanediyl dimercaptobisphenol, 4,4 ' -Methylidenebiscatechol, 4,4'-methylidenebisresorcin, 4,4'-ethylidenebisresorcin, 2,2 ' -Propanediylbisresorcin, 2,2'-butanediylbisresorcin, 2,2'-pentanediylbisresorcin, 2,2'-methylidenebis (6-chlororesorcin), 2,2'-methylidenebis (4-chloro- 6-nitroresorcin), 4,4′-sulfinbisresorcin, 2,2′-ethanediylbishydroquinone, 4,4′-sulfonylbishydroquinone and the like. Among these, 2,2′-bis- (4-hydroxyphenyl) propane [bisphenol A] is particularly preferred, and other compounds containing a wholly aromatic hydroxyl group having a rigid molecular structure containing no alkylene chain in the main chain, For example, biphenols, binaphthalenediols, dihydroxynaphthalenes, dihydroxyfluorenes, dihydroxyoxofluorenes, catechols, resorcinols, hydroquinones and the like are preferably used.

Examples of aromatic polycarboxylic acids include phthalic acid, dimethyl phthalate, diphenyl phthalate, isophthalic acid, dimethyisophthalic acid isophthalate, di (cyanomethyl) isophthalate, diphenyl isophthalate, and di (2,4-dinitroisophthalate). Phenyl), isophthalic acid (1,1-dioxobenzothiophen-3-yl), di (3-benzoisoxazolyl) isophthalate, di (2-benzothiazolyl) isophthalate, isophthalic acid (1-benzotriazolyl) Dithioisophthalic acid S, S'-dipropyl, dithioisophthalic acid S, S'-di (p-nitrophenyl), dithioisophthalic acid S, S'-di (2-benzoxazolyl), dithioisophthalic acid S, S'-di (2-benzothiazolyl), 4-methylisophthalic acid, dimethyl isophthalate, 5-methylisophthalic acid, dimethyl 5-methylisophthalate, 4,5-dimethylisophthalic acid, 4,6- Methyl isophthalic acid, 4-chloroisophthalic acid, dimethyl 4-chloroisophthalate, 5-chloroisophthalic acid, dimethyl 5-chloroisophthalate, 4,6-dichloroisophthalic acid, dimethyl 4,6-dichloroisophthalate, 4-bromo Isophthalic acid, 4,6-dibromoisophthalic acid, dimethyl 4,6-dibromoisophthalate, terephthalic acid, dimethyl terephthalate, di (cyanomethyl) terephthalate, diphenyl terephthalate, di (3-benzoisoxazolyl) terephthalate , Di (2-benzothiazolyl) terephthalate, 2-methyl terephthalic acid, dimethyl 2-methyl terephthalate, 2,5 dimethyl terephthalic acid, 2,6-dimethyl terephthalic acid, dimethyl 2,6-dimethyl terephthalate, 2-chloro Terephthalic acid, dimethyl 2-chloroterephthalate, 2,5-dichloroterephthalic acid, dimethyl 2,5-dichloroterephthalate, Lachloroterephthalic acid, dimethyl tetrachloroterephthalate, 2-bromoterephthalic acid, dimethyl 2-bromoterephthalate, 2,5-dibromoterephthalic acid, diethyl 2,5-dibromoterephthalate, 2,2'-diphenyldicarboxylic acid, 3,3'-diphenyldicarboxylic acid, 3,4'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl ether, 1,2-naphthalene Dicarboxylic acid, 1,2-naphthalenedicarboxylic acid dimethyl, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid dimethyl, 1,5-naphthalenedicarboxylic acid, 1,5-naphthalene Dimethyl dicarboxylate, 1,6-naphthalenedicarboxylic acid, dimethyl 1,6-naphthalenedicarboxylate, 1,6-naphthalenedicarboxylic acid diphenyl, 1,7-naphthalene Carboxylic acid, 1,7-naphthalenedicarboxylic acid dimethyl, 1,8-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid dimethyl, 1,8-naphthalenedicarboxylic acid diphenyl, 2,3-naphthalenedicarboxylic acid, 2,3- Dimethyl naphthalenedicarboxylate, 2,3-naphthalenedicarboxylic acid diphenyl, 2,6-naphthalenedicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid diphenyl, 2,7-naphthalenedicarboxylic acid, 2, Diphenyl 7-naphthalenedicarboxylate, 1,2- (9-oxofluorene) dicarboxylic acid, dimethyl 1,2- (9-oxofluorene) dicarboxylate, dimethyl 1,5- (9-oxofluorene) dicarboxylate, 1, 6- (9-oxofluorene) dicarboxylic acid, 1,6- (9-oxofluorene) dicarboxylic acid dimethyl, 1,7- (9-oxofluorene) dicarboxylic acid, 1,7- (9-oxofluorene) dicarboxylic acid Dimethyl rubonate, 2,3- (9-oxofluorene) dicarboxylic acid, dimethyl 2,3- (9-oxofluorene) dicarboxylate, 2,7- (9-oxofluorene) dicarboxylic acid, 2,7- (9 -Oxofluorene) dimethyl dicarboxylate, 1,4-anthracene dicarboxylic acid, 1,5-anthracene dicarboxylic acid, diethyl 1,5-anthracene dicarboxylate, 1,8-anthracene dicarboxylic acid, 1,9-anthracene dicarboxylic acid, 2 1,3-anthracene dicarboxylic acid, 9,10-anthracene dicarboxylic acid, dimethyl 9,10-anthracene dicarboxylate, 1,2-anthraquinone dicarboxylic acid, dimethyl 1,2-anthraquinone dicarboxylate, 1,3-1,2-anthraquinone Dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 1,5-anthraquinone dicarboxylic acid, dimethyl 1,5-anthraquinone dicarboxylate, 1,5-anthraquinone dicarboxylate diphenyl, 1, 6-anthraquinone dicarboxylic acid, 1,7-anthraquinone dicarboxylic acid, 1,8-anthraquinone dicarboxylic acid, 2,3-anthraquinone dicarboxylic acid, 2,7-anthraquinone dicarboxylic acid, 2,3-biphenyl dicarboxylic acid, 2,3- Dimethyl biphenyl dicarboxylate, 2,5-biphenyl dicarboxylic acid, 2,6-biphenyl dicarboxylic acid, 3,4-biphenyl dicarboxylic acid, dimethyl 3,4-biphenyl dicarboxylate, 3,4-biphenyl dicarboxylic acid, 3,4- Dimethyl biphenyl dicarboxylate, 3,4-biphenyl dicarboxylic acid, 2,2'-biphenyl dicarboxylic acid, dimethyl 2,2'-biphenyl dicarboxylate, diphenyl 2,2'-biphenyl dicarboxylate, 2,4'-biphenyl dicarboxylic acid 2,4'-biphenyldicarboxylic acid dimethyl, 3,3'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid dimethyl, 3,4'-biphenyldicarboxylic acid Dimethyl 3,4′-biphenyldicarboxylate, 4,4′-biphenyldicarboxylic acid, dimethyl 4,4′-biphenyldicarboxylate, diphenyl 4,4′-biphenyldicarboxylate, 1,5-biphenylenedicarboxylic acid, 1, Dimethyl 5-biphenylene dicarboxylate, 1,8-biphenylene dicarboxylic acid, dimethyl 1,8-biphenylene dicarboxylate, 2,6-biphenylene dicarboxylic acid, dimethyl 2,6-biphenylene dicarboxylate, 2,7-biphenylene dicarboxylic acid, 2 Dimethyl 2,7'-biphenylenedicarboxylate, 2,2'-dimethyl-4,4'-biphenyldicarboxylic acid, diethyl 2,2'-dimethyl4,4'-biphenyldicarboxylate, 4,4 "-p-terphenyldicarboxylic acid Dimethyl 4,4 ′ ″-p-quaterphenyl dicarboxylate, 4,4 ′ ″-p-quaterphenyl dicarboxylic acid, 2,2′-methylene dibenzoic acid, 2,2′-methylene dibenzoic acid Dimethyl acid, 2,4'-me Len dibenzoic acid, dimethyl 2,4'-methylene dibenzoate, 3,3'-methylene dibenzoic acid, 4,4'-methylene dibenzoic acid, dimethyl 4,4'-methylene dibenzoate, 4,4 '-Isopropylidene dibenzoic acid, 2,2'-bibenzyldicarboxylic acid, dimethyl 2,2'-bibenzyldicarboxylate, dimethyl 3,3'-bibenzyldicarboxylate, 4,4'-bibenzyldicarboxylic acid, Dimethyl 4,4'-bibenzyldicarboxylate, 2,2'-trans-stilbene dicarboxylic acid, dimethyl 2,2'-trans-stilbene dicarboxylate, diphenyl 2,2'-trans-stilbene dicarboxylate, 2,4 ' -trans-stilbene dicarboxylic acid, 4,4'-trans-stilbene dicarboxylic acid, 4,4'-trans-stilbene dicarboxylic acid, 2,4'-trans-stilbene dicarboxylic acid, 4,4'-trans-stilbene dicarboxylic acid 4,4'-trans-dimethyl stilbene dicarboxylate, 2,2'-transicarboxylic acid, 2,2'-transicarbo Dimethyl acid, 2,4′-transicarboxylic acid, 4,4′-transicarboxylic acid, dimethyl 4,4′-transicarboxylate, pseudo-p-dicarboxy [2,2] paracyclophane, 4,4 '-Carbonyldibenzoic acid, 3,3'-oxydibenzoic acid, 4,4'-oxydibenzoic acid, dimethyl 4,4'-oxydibenzoate, diphenyl 4,4'-oxydibenzoate, 4 , 4'-thiodibenzoic acid, 4,4'-sulfonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid dimethyl, 3,3'-dithiodibenzoic acid, 4,4'-dithiodibenzoic acid, Diethyl 4,4'-dithiodibenzoate, 2,2'-3,3'-dithiodibenzoic acid, 2,2'-azobenzenedicarboxylic acid, dimethyl 2,2'-azobenzenedicarboxylate, 3,3'- Azobenzene dicarboxylic acid, dimethyl 3,3'-azobenzenedicarboxylate, 4,4'-azobenzenedicarboxylic acid, dimethyl 4,4'-azobenzenedicarboxylate, homophthalic acid, homophthalate Dimethyl acid, homoisophthalic acid, dimethyl homoisophthalate, homoterephthalic acid, dimethyl homoterephthalate, o-phenylene diacetate, diethyl o-phenylene diacetate, m-phenylene diacetate, diethyl m-phenylene diacetate, p-phenylene Diacetic acid, diethyl p-phenylenediacetate, 3,3'-o-phenylenedipropionic acid, diethyl 3,3'-o-phenylenedipropionic acid, 3,3'-m-phenylenedipropionic acid, 3,3 '-M-Phenylenedipropionic acid diethyl, 3,3'-p-phenylenedipropionic acid, 3,3'-p-phenylenedipropionic acid diethyl, 2-carboxycinnamic acid, 3-carboxycinnamic acid, 4-carboxy Cinnamic acid, diethyl 4-carboxycinnamate, 3t, 3't-o-phenylene diacrylic acid, 3t, 3't-o-phenylene diacrylate, 3t, 3't-m-phenylene diacrylic acid, 3t, 3't-m-fe Dimethyl diacrylate, 3t, 3't-p-phenylene diacrylic acid, 3t, 3't-p-phenylene diacrylate, m-phenylene propiolic acid, dimethyl m-phenylene propiolate, 1,4 -Naphthalene diacetic acid, 1,5-naphthalene diacetic acid, 1,5-naphthalene diacetate dimethyl, 3,3 '-(1,4-naphthalene) dipropionic acid, 3,3'-(1,4-naphthalene) Diethyl dipropionate, 4,4'-biphenyldiacetic acid, diethyl 4,4'-biphenyldiacetate, 3,3 '-(4,4'-biphenyl) dipropionic acid, 3,3'-[4,4 '-(Methylenedi-p-phenylene)] dipropionic acid, 4,4'-bibenzyldibutyric acid, 3,3'-(4,4'-bibenzyl) dipropionic acid, 4,4 '-(oxydi-p- Phenylene) dibutyric acid, 3,3 '-"4,4'-(oxydi-p-phenylene)" dipropionic acid, 3,3 '-[4,4'-(oxydi-p-phenylene)] dibutyric acid, Diphenyls Hondicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,3-furandicarboxylic acid, 2,3-furandicarboxylic acid dimethyl, 2,4-furandicarboxylic acid, 2,4-furandicarboxylic acid dimethyl, 2,5- Flange carboxylic acid, 2,5-furandicarboxylate dimethyl, 2,5-furandicarboxylate diphenyl, 3,4-furandicarboxylate, 3,4-furandicarboxylate dimethyl, 3,4-diphenyl-2,5-flange Carboxylic acid, 3,4-diphenyl-2,5-furandicarboxylic acid dimethyl, 3,3 '-(2,5-furan) dipropionic acid, 3,3'-(2,5-furan) dipropionic acid dimethyl 2,5-cis-tetrahydrofuran dicarboxylic acid, dimethyl 2,5-cis-tetrahydrofuran dicarboxylate, 3,3 '-(2,5-cis-tetrahydrofuran) dipropionic acid, 3,3'-(2,5- cis-tetrahydrofuran) diethyl dipropionate, 2,3- Offendicarboxylic acid, dimethyl 2,3-thiophene dicarboxylate, 2,4-thiophene dicarboxylic acid, dimethyl 2,4-thiophene dicarboxylate, 2,5-thiophene dicarboxylic acid, dimethyl 2,5-thiophene dicarboxylate, 2,5 Diphenyl thiophene dicarboxylate, 3,4-thiophene dicarboxylic acid, dimethyl 3,4-thiophene dicarboxylate, 3,4-diphenyl-2,5-thiophene dicarboxylic acid, 3,4-diphenyl-2,5-thiophene dicarboxylic acid Dimethyl, 2,5-thiophenediacetic acid, 3,3 '-(2,5-thiophene) dipropionic acid, diethyl 3,3'-(2,5-thiophene) dipropionate, 2,5-cis-tetrahydro Thiophene dicarboxylic acid, diethyl 2,5-cis-tetrahydrothiophene dicarboxylate, 3,4-cis-tetrahydrothiophene dicarboxylic acid, 3,4-cis-tetrahydrothiophene dicarboxylic acid Dimethyl acid, 1,1-dioxo-2,5-cis-tetrahydrothiophene dicarboxylic acid, diethyl 1,1-dioxo-2,5-cis-tetrahydrothiophene dicarboxylate, 2,6-4H-pyrandicarboxylic acid, 4-oxo -2,6-4H-pyrandicarboxylic acid, diethyl 4-oxo-2,6-4H-pyrandicarboxylate, 2,6-cis-tetrahydropyrandicarboxylic acid, dimethyl 2,6-cis-tetrahydropyrandicarboxylate, 2 , 6-cis-tetrahydrothiopyrandicarboxylic acid, dimethyl 2,6-cis-tetrahydrothiopyrandicarboxylate, 1,1-dioxo-2,6-cis-tetrahydrothiopyrandicarboxylic acid, 1,1-dioxo-2 Dimethyl 6-cis-tetrahydrothiopyrandicarboxylate, 2,8-dibenzofurandicarboxylic acid, dimethyl 2,8-dibenzofurandicarboxylate, 3,7-dibenzofurandicarboxylic acid, 3,7-diben Dimethyl zofurancarboxylate, 4,6-dibenzofurandicarboxylic acid, dimethyl 4,6-dibenzofurancarboxylate, 2,8-dibenzothiophene dicarboxylic acid, 5,5-dioxo-2,8-dibenzothiophene dicarboxylic acid, 9-oxo- 1,8-xanthene dicarboxylic acid, 9-oxo-2,7-xanthene dicarboxylic acid, dimethyl 9-oxo-2,7-xanthene dicarboxylate, 1,6-dibenzo [1,4] dioxin dicarboxylic acid, 1,6 -Dibenzo [1,4] dioxin dicarboxylate, 2,7-dibenzo [1,4] dioxin dicarboxylic acid, 2,7-dibenzo [1,4] dioxin dicarboxylate, 2,8-dibenzo [1,4 ] Dioxin dicarboxylic acid, 2,8-dibenzo [1,4] dioxin dicarboxylic acid dimethyl, 1,6-phenoxathiin dicarboxylic acid, 4,6-phenoxathiin dicarboxylic acid, dimethyl 4,6-phenoxathiin dicarboxylic acid 10,10-dioxo-1,6- Enoxydine dicarboxylic acid, dimethyl 10,10-dioxo-1,6-phenoxydine dicarboxylate, 10,10-dioxo-1,9-phenoxydine dicarboxylic acid, 10,10-dioxo-1,9-phenoxydine dicarboxylic acid Dimethyl acid, 10,10-dioxo-2,8-phenoxine dicarboxylic acid, Dimethyl 10,10-dioxo-2,8-phenoxine dicarboxylate, 10,10-dioxo-4,6-phenoxine dicarboxylic acid, 2 , 7-thianthenedicarboxylic acid, 2,7-thianthenedicarboxylic acid dimethyl, 10,10-dioxo-1,9-thianthenedicarboxylic acid, 5,5,10,10-tetraoxo-2,7-thiandylene dicarboxylic acid Acid, dimethyl 5,5,10,10-tetraoxo-2,7-thianthylene dicarboxylate, 10-oxo-10-phenyl-2,8-phenoxaphosphine dicarboxylic acid, 9-oxabicyclo [3.3.1] nonane Dimethyl-2,6-dicarboxylate, 9-oxabicyclo [3.3.1] nonane-2,6-dicarbo Diphenyl acid, 2,4,6,8-tetraoxaspiro [5.5] undecane-3,9-dicarboxylic acid, dimethyl 2,4,6,8-tetraoxaspiro [5.5] undecane-3,9-dicarboxylate, 2,4,6,8-tetraoxaspiro [5.5] undecane-3,9-diacetic acid, 2,4,6,8-tetraoxaspiro [5.5] undecane-3,9-diethyl acetate, 2,3 -Pyrrole dicarboxylic acid, dimethyl 2,3-pyrrole dicarboxylate, 2,4-pyrrole dicarboxylic acid, dimethyl 2,4-pyrrole dicarboxylate, 2,5-pyrrole dicarboxylic acid, 2 Dimethyl 1,5-pyrrole dicarboxylate, 1-methyl-2,5-pyrrole dicarboxylic acid, dimethyl 1-methyl-2,5-pyrrole dicarboxylate, 1-phenyl-2,5-pyrrole Dicarboxylic acid, dimethyl 1-phenyl-2,5-pyrrole dicarboxylate, 3,4-pyrrole dicarboxylic acid, dimethyl 3,4-pyrrole dicarboxylate, 1-methyl-3,4-pyrrole Dicarboxylic acid, 1-methyl-3,4-pyrrole Diethyl dicarboxylate, 1-phenyl-3,4-pyrrole dicarboxylic acid, diethyl 1-phenyl-3,4-pyrrole dicarboxylate, diethyl 3,5-dimethyl-2,4-pyrrole dicarboxylate, 2,5-dimethyl-3,4-pyrrole dicarboxylic acid, diethyl 2,5-dimethyl-3,4-pyrrole dicarboxylate, 1,2,5-trimethyl-3,4-pyrrole dicarboxylic acid 1,2,5-trimethyl-3,4-pyrrole dicarboxylate, 1-methyl-2,5-pyrrolediacetic acid, 1-methyl-2,5-pyrrolediacetate, 3,3'- Dimethyl (2,5-pyrrole) dipropionate, 3,3 '-(1-methyl-2,5-pyrrole) dipropionic acid, 3,3'-(1-methyl-2,5-pyrrole) dipropion Dimethyl acid, diethyl 3,3 '-(1-phenyl-2,5-pyrrole) dipropionate, diethyl 1-methyl-2,5-cis-pyrrolidinedicarboxylate, 1-phenyl-2,5-cis-pyrrolidine Diethyl dicarboxylate 1-methyl-2,5-pyrrolidine diacetate, 3,3 '-(1-methyl-2,5-pyrrolidine) dipropionic acid, 3,3'-(1-methyl-2,5-pyrrolidine) di Diethyl propionate, diethyl 2,5-indole dicarboxylate, 2,6-indole dicarboxylic acid, diethyl 2,6-indole dicarboxylate, 9-methyl-1,8-carbazole dicarboxylic acid, 2,6-carbazole dicarboxylic acid, Diethyl 2,6-carbazoledicarboxylate, 3,6-carbazoledicarboxylic acid, diethyl 3,6-carbazoledicarboxylate, 9-methyl-3,6-carbazoledicarboxylic acid, diethyl 9-methyl-3,6-carbazoledicarboxylate 3,4-pyrazole dicarboxylic acid, dimethyl 3,4-pyrazole dicarboxylate, 2-methyl-3,4-pyrazole dicarboxylic acid, 1-phenyl-3,4-pyrazole dicarboxylic acid, 1-phenyl-3,4 -Dimethyl pyrazole dicarboxylate, 2-phenyl-3,4-pyrazole dicarboxylic acid, dimethyl 2-phenyl-3,4-pyrazole dicarboxylate, 3,5-pyrazole dicarboxylic acid, dimethyl 3,5-pyrazole dicarboxylate, 1- Methyl-3,5-pyrazoledicarboxylic acid, dimethyl 1-methyl-3,5-pyrazoledicarboxylate, 1-phenyl-3,5-pyrazoledicarboxylic acid, dimethyl 1-phenyl-3,5-pyrazoledicarboxylate, 4, 5-imidazole dicarboxylic acid, 4,5-imidazole dicarboxylic acid diphenyl, 1-methyl-4,5-imidazole dicarboxylic acid, dimethyl 1-methyl-4,5-imidazole dicarboxylate, 1-phenyl-4,5-imidazole dicarboxylic acid Acid, diethyl 1-phenyl-4,5-imidazole dicarboxylate, 2,3-pyridinedicarboxylic acid, 2,3-pyridinedicarboxylic acid di Methyl, 2,3-pyridinedicarboxylic acid diphenyl, 2,4-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid dimethyl, 2,4-pyridinedicarboxylic acid diphenyl, 2,5-pyridinedicarboxylic acid, 2,5-pyridine Dimethyl dicarboxylate, 2,5-pyridinedicarboxylic acid diphenyl, 2,6-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid dimethyl, 2,6-pyridinedicarboxylic acid diphenyl, 3,4-pyridinedicarboxylic acid, 3,4 Dimethyl pyridine dicarboxylate, 3,5-pyridinedicarboxylic acid, diphenyl 3,5-pyridinedicarboxylate, 2,6-dimethyl-3,5-pyridinedicarboxylic acid, 2,4,6-trimethyl-3,5-pyridine Dicarboxylic acid, dimethyl 2,5-piperidinedicarboxylate, diethyl 2,3-piperidinedicarboxylate, 2,6-cis-piperidinedicarboxylic acid, 2,6-cis-piperidinedicar Dimethyl acid, 1-methyl-2,6-cis-piperidinedicarboxylic acid, 1-methyl-2,6-cis-piperidinedicarboxylate, diethyl 3,5-piperidinedicarboxylate, 2,6-cis-piperidine Acetic acid, 1-methyl-2,6-cis-piperidinediacetic acid, 1-methyl-2,6-cis-piperidinediacetic acid diethyl ester, 2,3-quinolinedicarboxylic acid, dimethyl 2,3-quinolinedicarboxylate, 2, 4-quinoline dicarboxylic acid, dimethyl 2,4-quinoline dicarboxylate, 2,6-quinoline dicarboxylic acid, 3,7-quinoline dicarboxylic acid, 4,8-quinoline dicarboxylic acid, dimethyl 4,8-quinoline dicarboxylate, 5, 6-quinoline dicarboxylic acid, dimethyl 5,6-quinoline dicarboxylate, 5,8-quinoline dicarboxylic acid, 6,7-quinoline dicarboxylic acid, dimethyl 6,7-quinoline dicarboxylate, 6,8-quinoline dicarboxylic acid, 7, 8-Quinori Dicarboxylic acid, 2,2'-bipyridine-4,4'-dicarboxylic acid, 2,2'-bipyridine-4,4'-dicarboxylic acid dimethyl, 2,2'-bipyridine-5,5'-dicarboxylic acid, 2 Dimethyl 2,2'-bipyridine-5,5'-dicarboxylate, 2,2'-bipyridine-6,6'-dicarboxylic acid, dimethyl 3,3'-bipyridine-2,2'-dicarboxylate, 4,5- Pyridazine dicarboxylic acid, 4,5-pyrimidine dicarboxylic acid, 4,6-pyrimidine dicarboxylic acid, 2,3-pyrazine dicarboxylic acid, 2,3-pyrazine dicarboxylic acid dimethyl, 2,5-pyrazine dicarboxylic acid, 2,5-pyrazine Dimethyl dicarboxylate, diphenyl 2,5-pyrazine dicarboxylate, 2,6-pyrazine dicarboxylic acid, dimethyl 2,6-pyrazine dicarboxylate, dimethyl 1,4-piperazine diacetate, 3,3 '-(1,4-piperazine ) Dimethyl dipropionate, 1,6-phenazine dicarboxylic acid, 1,6-phenazine And dimethyl dicarboxylate. Among them, wholly aromatic polycarboxylic acids having a rigid molecular structure containing no alkylene chain in the main chain, such as phthalic acids, terephthalic acids, isophthalic acids, biphenyldicarboxylic acids, naphthalenedicarboxylic acids, oxofluorenedicarboxylic acids, anthracene Dicarboxylic acids, anthraquinone dicarboxylic acids, biphenylene dicarboxylic acids, terphenyl dicarboxylic acids, quaterphenyl dicarboxylic acids, azobenzene dicarboxylic acids, furandicarboxylic acids, thiophene dicarboxylic acids, pyran dicarboxylic acids, dibenzofurandicarboxylic acids, dibenzothiophene dicarboxylic acids, xanthene dicarboxylic acids , Dibenzo [1,4] dioxin dicarboxylic acids, phenoxathiin dicarboxylic acids, thianthylene dicarboxylic acids, phenoxafo Findicarboxylic acids, pyrrole dicarboxylic acids, indole dicarboxylic acids, carbazole dicarboxylic acids, pyrazole dicarboxylic acids, imidazole dicarboxylic acids, pyridine dicarboxylic acids, quinoline dicarboxylic acids, bipyridine dicarboxylic acids, pyrimidine dicarboxylic acids, pyrazine dicarboxylic acids, phenazine dicarboxylic acids, etc. are preferred . Moreover, the acid halide or acid anhydride of said aromatic polycarboxylic acid can also be used. Examples of the acid halide of the aromatic polycarboxylic acid include phthaloyl dichloride and naphthoyl dichloride. Of these, preferably phthaloyl dichloride, such as isophthaloyl dichloride or terephthaloyl dichloride, is used.

(Example)
In the following examples, the present invention will be described in more detail, but the present invention is not limited to these examples.

The average particle size, bulk density and absorbance (coloring degree) of the aromatic polyester pellets were measured as follows.

Average particle diameter: Using a stereomicroscope (SZXILLB2-100 manufactured by OLYNPUS) with a magnification of 16 times, the long diameter of 100 arbitrarily selected pellets was measured, and the average value was taken as the average particle diameter.

Bulk density: measured in accordance with JIS K6911.

Absorbance (ΔI): The obtained pellet was dissolved in chloroform so as to have a concentration of 0.2 g / milliliter, and the absorbance was measured with a UV spectrum of 400 nm using a cell having an optical path length of 20 mm.

(Synthesis Example 1)
Production of aromatic polyester A reactor equipped with a stirrer was charged with 1,100 parts by weight of water, then 38 parts by weight of 2,2-bis (4-hydroxyphenyl) propane, and 0.6 parts by weight of p-tert-butylphenol. Part and 14 parts by weight of sodium hydroxide were dissolved (aqueous phase). Separately, 1,300 parts by mass of dichloromethane was charged into another container, and then 31 parts by mass of an equimolar mixture of terephthalic acid chloride and isophthalic acid chloride and 1.1 parts by mass of benzoyl chloride were dissolved (organic phase). After the organic phase was added to the aqueous phase in the reactor with stirring, a polycondensation reaction was carried out at room temperature for 1 hour. After the reaction, the aqueous phase and the organic phase were separated, and washing with water was repeated until the organic phase became neutral. The obtained dichloromethane solution of the aromatic polyester is supplied to 4,000 parts by mass of a 9/1 mixture (volume ratio) of methanol and pure water at a rate of 1.3 kg / hour with stirring to precipitate the aromatic polyester powder. I let you. Subsequently, it filtered and 55 mass parts of aromatic polyester powder was obtained. The weight average molecular weight of the aromatic polyester powder was 50,000.

(Synthesis Example 2)
Production of aromatic polyester The same procedure as in Synthesis Example 1 was performed except that 3.2 parts by mass of benzoyl chloride was used instead of 2.1 parts by mass. 55 parts by weight of aromatic polyester powder was obtained. The weight average molecular weight of the aromatic polyester powder was 25,000.

(Synthesis Example 3)
Production of aromatic polyester The procedure was the same as in Synthesis Example 1 except that benzoyl chloride was not used. 55 parts by weight of aromatic polyester powder was obtained. The aromatic polyester powder had a weight average molecular weight of 150,000.

(Example 1)
The aromatic polyester powder having a weight average molecular weight of 50,000 produced in Synthesis Example 1 was dissolved in dichloromethane (methylene chloride) to prepare a solution having a concentration of 0.4 g / ml. 2 liters of the solution was placed in a 10 liter flask and placed in a constant temperature bath at 45 ° C. Next, while maintaining the temperature, the contents were stirred at a rotational speed of 100 rpm for 2 days while flowing nitrogen gas, and methylene chloride was slowly distilled off. An agar-like aromatic polyester lump which was translucent and contained almost no bubbles was obtained at the bottom of the flask. Next, the aromatic polyester was cut with a ceramic cutter to produce 3 mm square pellets. The obtained pellets were dried under reduced pressure at 60 ° C. for about 80 hours to obtain a product. The product had an average particle size of 3.9 mm and a bulk density of 0.56 grams / cc. The pellet was translucent, but the absorbance (ΔI) was 0.02, and no discoloration was observed.

(Example 2)
The same procedure as in Example 1 was performed except that an aromatic polyester powder having a weight average molecular weight of 25,000 was used. The aromatic polyester lump remaining at the bottom of the flask was fragile, and when cut with a ceramic cutter, it became fine powder and could not be pelletized. Therefore, the aromatic polyester mass was left to dry under environmental conditions. The dried aromatic polyester mass was very hard. The aromatic polyester mass was crushed with a hammer, and then passed through a sieve having a mesh size of 2.8 mm square and 4.0 mm square to remove particles of 2.8 mm under and 4.0 mm over. The obtained aromatic polyester particles were dried under reduced pressure at 60 ° C. for about 80 hours to obtain a product. The product had an average particle size of 3.2 mm and a bulk density of 0.50 grams / cc. The pellet was milky white, but the absorbance (ΔI) was 0.02, and no discoloration was observed.

(Example 3)
The same operation as in Example 1 was carried out except that an aromatic polyester powder having a weight average molecular weight of 150,000 was used. By the same treatment as in Example 1, pellets having an average particle diameter of 3.8 mm and a bulk density of 0.57 g / cc were obtained. The pellet was translucent, but the absorbance (ΔI) was 0.02, and no discoloration was observed.

(Comparative Example 1)
The same operation as in Example 1 was conducted except that methylene chloride was distilled off in an air atmosphere without flowing nitrogen gas. The aromatic polyester mass obtained at the bottom of the flask was extremely hard on the surface, while the methylene chloride still remained in the interior and was extremely inhomogeneous. Although it was transparent, it could not be pelletized.

(Comparative Example 2)
The same procedure as in Example 1 was carried out except that methylene chloride was distilled off without stirring. The aromatic polyester mass obtained at the bottom of the flask was extremely hard on the surface, while the methylene chloride still remained in the interior and was extremely inhomogeneous. Although it was transparent, it could not be pelletized.

(Comparative Example 3)
The same operation as in Example 1 was performed except that the temperature of the thermostatic bath was set to 60 ° C. A large amount of air bubbles, a bulk density as low as 0.24 g / cc, a non-uniform particle shape, and satisfactory pellets were not obtained.

Since the aromatic polyester pellets produced by the method of the present invention are not colored and are transparent, they are useful in electrical / electronic materials and optical materials such as optical fibers, spectacle lenses, imaging lenses and coatings.

FIG. 1 is a diagram showing an embodiment of the present invention.

Explanation of symbols

1． Aromatic polyester powder
2． One or more solvents selected from the group consisting of dichloromethane, trichloromethane, 1,2-dichloroethane and chlorobenzene;
3． solution
Four. container
Five. Aromatic polyester mass
6． Ceramic cutter
7． pellet

Claims (3)

The aromatic polyester is mixed with one or more solvents selected from the group consisting of dichloromethane, trichloromethane, 1,2-dichloroethane, and chlorobenzene, and the resulting solution is stirred while being stirred at a temperature of 15 to 50 ° C. A process for producing aromatic polyester pellets, wherein the solvent is evaporated under an active gas atmosphere, and then the resulting aromatic polyester mass is cut and / or crushed. 2. The method according to claim 1, wherein the concentration of the solution is 0.2 to 1.0 gram / milliliter. 3. The method according to claim 1 or 2, wherein the solvent is dichloromethane.

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