JP5330447B2 - Method for producing aromatic polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for production of an aromatic polyester with scarcely any coloration even after heat molding at elevated temperatures and not only maintaining extremely high transparency but also accompanied with high fluidity the same. <P>SOLUTION: The process for production of the aromatic polyester by a reaction of (i) a polyhydric phenol and an aromatic polycarboxylic acid, a halogenide or an anhydride of the same, wherein 0-40 mol% of a compound shown by formula (II): X-C(O)-R is caused to react to the total changed amount of the aromatic polycarboxylic acid, the halogenide or the anhydride of the same, wherein X represents chlorine, bromine or iodine and R represents a group of an aliphatic group, an alicyclic group, a monocyclic aromatic group, a polycyclic aromatic group, a fused aromatic group, a heterocyclic group, or a combination of the same with a proviso at least one hydrogen of the same shall be replaced with fluorine, chlorine, bromine, iodine, an alkoxyl group, a mercapto group, a sulfenato group, a sulfinato group, a sulfo group, an alkoxycarbonyl group, an acyl group, an alkoxysulfinyl group, an alkylthiocarbonyl group, a thiosulfo group, a cyano group, a thiocyano group, an isocyano group, an isocyanoto group, an isothiocyanato group or a nitro group, and (ii) a further reaction of the obtained aromatic polycarboxylic and 3-80 mol% of the compound shown by formula (II) to the total charged amount of (i) the aromatic polycarboxylic acid, the halogenide or the anhydride of the same. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention relates to a method for producing an aromatic polyester , and more particularly to a method for producing an aromatic polyester used for optical applications.

An aromatic polyester obtained from a polyhydric phenol, such as bisphenol A, and an aromatic polycarboxylic acid, an acid halide or an acid anhydride thereof, such as isophthaloyl dichloride or terephthaloyl dichloride, usually has a glass transition temperature. High and good heat resistance. However, the aromatic polyester usually has a low melt fluidity and needs to be heated to a high temperature of 300 ° C. or higher during molding such as injection molding. Therefore, the molded product is colored pale yellow and is not suitable for optical applications such as optical fibers.

In order to prevent such coloring, an attempt has been made to seal the polymer terminal of the aromatic polyester. For example, in a method for producing a wholly aromatic polyester carbonate obtained by polymerizing an aromatic dicarboxylic acid, an aromatic diol, and a diaryl carbonate in a predetermined ratio, at a predetermined time of the polymerization reaction, from the carbonate and the carboxylic acid ester. A method is known in which a predetermined aromatic compound is added to produce a terminally blocked wholly aromatic polyester carbonate (Patent Document 1). In this method, a part of the carboxyl group terminal and hydroxyl group terminal of the aromatic dicarboxylic acid and the aromatic diol are sealed by a transesterification reaction using a melt polycondensation method. Since the melt polymerization method is used, the polymerization reaction temperature is 160 to 320 ° C. at the initial stage of polymerization, and after addition of the end-blocking agent, it is heated to a high temperature of 250 to 360 ° C. Therefore, the obtained polymer has been inevitably colored, which is fatal for optical applications.

In order to prevent coloring deterioration of aromatic polyester, a method using an antioxidant is also known. For example, in the step of producing a predetermined polyarylate by interfacial polycondensation reaction between a divalent aromatic carboxylic acid halide and a divalent phenol comprising a biphenyl structure and a bisphenol structure, an antioxidant is added. A method for producing polyarylate, characterized by being added quantitatively, is disclosed (Patent Document 2). This method is relatively widely practiced as a secondary method for preventing color deterioration of industrial materials used for electronic materials and the like. However, when high optical characteristics are required, there is a limit to the effect of preventing color deterioration.

In a method for producing a polyester having a predetermined molecular weight by reacting an aromatic polyhydric alcohol and an aromatic polycarboxylic acid, an acid halide or an acid anhydride thereof, the formula (II): XC (O ) A method for producing an end-capped polyester in the presence of a compound represented by -R is disclosed (Patent Document 3). In the above formula, X is chlorine, bromine or iodine, and R is a linear or branched alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 30 carbon atoms, or the alkyl group and the aryl Or at least one hydrogen of these groups is fluorine, chlorine, bromine, iodine, alkoxyl group, mercapto group, sulfenato group, sulfinato group, sulfo group, alkoxycarbonyl group , An acyl group, an alkoxysulfinyl group, an alkylthiocarbonyl group, a thiosulfo group, a cyano group, a thiocyano group, an isocyano group, an isocyanato group, an isothiocyanato group, or a nitro group. As a preferred embodiment of R, a phenyl group in which at least one hydrogen is substituted with fluorine, an alkyl group in which at least one hydrogen is substituted with fluorine, and a phenyl in which at least one hydrogen is substituted with a chlorine or alkoxyl group Groups are mentioned. In the examples, fluorobenzoyl chloride, dodecanoyl chloride, chlorobenzoyl chloride and methoxybenzoyl chloride are used as compounds represented by X—C (O) —R. Although the polyester obtained by the method has improved heat resistance, the object of the invention is to freely change the refractive index of the polyester by forming the terminal of the obtained polyester into various structures as described above. There was a thing. As a result, the core material and the clad material of the optical fiber were successfully made suitable.

In the step of interfacial polymerization reaction of a divalent aromatic carboxylic acid halide and a divalent phenol, 5 to 20 mol% of a predetermined quaternary ammonium salt is used as a catalyst with respect to the divalent phenol. A method for producing polyarylate is disclosed in which 3 to 10 mol% of a monovalent carboxylic acid halide is added to divalent phenol before termination of interfacial polymerization (Patent Document 4). The catalyst is not a catalyst having 3 or more butyl groups such as tributylbenzylammonium chloride and tetra-n-butylammonium bromide, which are generally used conventionally, but a quaternary compound having 3 or 4 ethyl groups. Ammonium salt, for example, triethylbenzylammonium chloride, triethylbenzylammonium bromide, triethylbenzylammonium hydroxide, triethylbenzylammonium hydrogensulfate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium hydroxide, tetraethylammonium hydrogensulfate It has been. In addition, the amount used is significantly larger than the conventional amount. The present invention uses a large amount of such a special catalyst and adds a monovalent carboxylic acid halide just before the termination of the one-step reaction, and the residual monomer and its oxidant in the resulting polyarylate are obtained. It tries to reduce as much as possible.
In addition, it is possible to form an anisotropic melt phase consisting of forming a polymer having a repetitive component represented by a predetermined structural formula by a polymerization reaction of an ester-forming monomer and optionally an amide-forming monomer in the polymerization zone. In the method for producing a polyester optionally having an amide bond, (c) HO—Ar—OH and / or an esterified derivative thereof, (d) H ₂ N—Ar—NH ₂ And / or an amidated derivative thereof, (e) HO—Ar—NH ₂ , and / or an esterified and / or amidated derivative thereof, and (f) an aromatic monomer selected from the group consisting of these Present in a molar excess of about 0.25 to 4%, and this excess monomer causes (g) dioxyaryl units, (h) A unit selected from the group consisting of a noaryl unit, (i) an oxyaminoaryl unit, and (j) a mixture thereof, and the terminal of the polymer chain is (k) a hydroxyl end group and / or its esterification A terminal group selected from the group consisting of a derivative, (l) an amino terminal group and / or an amidated derivative thereof, and (m) a mixture thereof. A polyester product capable of forming an anisotropic melt phase, characterized in that it reaches an average chain length and produces a polyester product that, when subjected to subsequent heating, is substantially impossible to further extend. An improved manufacturing method (Patent Document 5) is disclosed. In addition, we focused on aromatic polyesters characterized by high heat resistance, improved their transparency, and tried to produce new heat-resistant aromatic polyester-based plastic optical fibers (Non-patent Document 1), and polymer There is known a report that improves the fluidity by changing the molecular structure and enables the synthesis of an amorphous polyester having improved transparency (Non-patent Document 2).

JP 2004-131598 A JP 2008-214541 A JP 2007-320989 A JP 2006-176651 A JP-A-60-245631 Tahata Masayoshi et al., Preparation of high heat-resistant POF with aromatic polyester, Polymers Conference Proceedings, 2009.9.01, Vol. 58, No. 2, pages 4473-4474, 1L2-18 Takenaka Yasushi et al., Production of high heat-resistant transparent resin by molecular design of aromatic polyester, Proceedings of the High-Technological Conference, 2009.9.01, Vol. 58, No. 2, p. 4134, 3Pa111

The present invention is not colored almost occur even after heat molding at a high temperature, significantly higher holding transparency, moreover showed little birefringence addition, the production of aromatic polyester also having high fluidity A method is provided.

The aromatic polyester obtained by the method described in Patent Document 3 has high heat resistance and transparency, and the aromatic polyester was hardly colored even by treatment at a high temperature. However, even though there was almost no coloration, it was not sufficient for use in optical applications. Accordingly, the present inventors have made various studies in order to obtain an aromatic polyester having higher transparency after the heat treatment. As a result, it has been found that it is necessary to increase the end-capping rate of the aromatic polyester with a substance listed as formula (II) in Patent Document 3, preferably benzoyl chloride. However, in the methods conventionally used for producing aromatic polyesters, as shown in the examples of Patent Document 3, the substances listed as Formula (II) in Patent Document 3 Preferably, even if the amount of benzoyl chloride added is increased, the end-capping rate of the aromatic polyester can be increased, while the molecular weight of the obtained aromatic polyester tends to decrease, and optical applications such as, for example, It was not easy to obtain an aromatic polyester suitable for use in an optical fiber or the like. Therefore, it is highly end-capped with a substance, preferably benzoyl chloride, having a predetermined molecular weight suitable for use in optical applications such as, for example, optical fibers and the like, as described in Patent Document 3 as formula (II) Aromatic polyesters have not existed until now. Therefore, the present inventors have further studied to obtain the aromatic polyester. As a result, an aromatic polyester having a relatively large molecular weight was produced in the first stage, and in the subsequent stage, the terminal hydroxyl group present in the obtained aromatic polyester was further listed as the formula (II) in Patent Document 3. The inventors have found that the above-mentioned predetermined aromatic polyesters can be produced by using a multi-stage method of imparting a known substance, preferably benzoyl chloride, and have completed the present invention. In the present invention, it is preferable to purify the aromatic polyester obtained in the first stage by providing a purification step between the first stage and the second stage. Thereby, the relatively low molecular weight aromatic polyester contained in the aromatic polyester obtained in the first stage can be removed, thereby further increasing the terminal blocking rate of the obtained aromatic polyester. It can be done.

That is, the present invention
(1) (i) In a method for producing an aromatic polyester by reacting a divalent phenol with an acid halide of a divalent aromatic carboxylic acid, the divalent phenol and the divalent aromatic carboxylic acid are produced. The charge ratio of the acid halide of the acid is 1.0 to 5.0 mol of divalent phenol with respect to 1.0 mol of the acid halide of divalent aromatic carboxylic acid, 4 to 40 mol% of the following formula (II) with respect to the total charged amount of the acid halide of the aromatic carboxylic acid:
X-C (O) -R (II)
(In the formula (II), X is chlorine, bromine or iodine, and R is an aliphatic group, alicyclic group, monocyclic aromatic group, polycyclic aromatic group, condensed aromatic group, heterocyclic group. Or at least one hydrogen of these groups is fluorine, chlorine, bromine, iodine, alkoxyl group, mercapto group, sulfenato group, sulfinato group, sulfo group, alkoxycarbonyl group, acyl Group, alkoxysulfinyl group, alkylthiocarbonyl group, thiosulfo group, cyano group, thiocyano group, isocyano group, isocyanato group, isothiocyanato group or nitro group)
And (ii) the obtained aromatic polyester is reacted in an amount of 3 to 80 mol% with respect to the total charged amount of the divalent aromatic carboxylic acid halide in (i). Wherein the terminal is further reacted with the compound represented by the above formula (II) at the terminal represented by the following formula (I):
-C (O) -R (I)
(In formula (I), R is the same as above)
In addition, the polyester terminal blocking rate is 99 % or more, and in addition, the weight average molecular weight (Mw) is 10,000 to 100,000.

As a preferred embodiment,
(2) The amount of the compound represented by the step (ii) Formula (II) in is from 3 to 50 mol%, the (1) Symbol placement process for producing aromatic polyesters,
(3) the amount of the compound represented by the step (ii) Formula (II) in is 3 to 35 mol%, the (1) Symbol placement process for producing aromatic polyesters,
(4) The amount of the compound represented by the step (ii) formula in (II) is 3 to 20 mol%, the (1) Symbol method for producing the mounting of the aromatic polyester,
( 5 ) R in the above formula (II) is a monocyclic aromatic group, polycyclic aromatic group, condensed aromatic group or heterocyclic group, or at least one hydrogen of these groups is fluorine, chlorine , The method for producing an aromatic polyester according to any one of (1) to ( 4 ) above, which is a group substituted by a bromine, iodine or alkoxyl group,
( 6 ) The above formula (II), wherein R is a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, or a group in which one hydrogen of these groups is substituted with a fluorine, chlorine, or methoxyl group, (1) The manufacturing method of the aromatic polyester as described in any one of ( 4 ),
( 7 ) In the above formula (II), R is a phenyl group, a naphthyl group, or a group in which one hydrogen of these groups is substituted with a fluorine, chlorine, or methoxyl group. 4 ) A process for producing an aromatic polyester according to any one of
( 8 ) The method for producing an aromatic polyester according to any one of (1) to ( 4 ), wherein R in the formula (II) is a phenyl group or a naphthyl group.
( 9 ) The method for producing an aromatic polyester according to any one of (1) to ( 4 ), wherein R in the formula (II) is a phenyl group,
( 10 ) The method for producing an aromatic polyester according to any one of (1) to ( 9 ), wherein X in the formula (II) is chlorine,
(11) between the step (i) and step (ii), step purifying the product liquid after the reaction obtained in (i) further including (iii), above (1) to (10) A method for producing the aromatic polyester according to any one of the above,
( 12 ) Step (iii) is a purification of the aromatic polyester according to ( 11 ) above, wherein the solution containing the aromatic polyester is separated from the product solution after the reaction, and subjected to the reaction of the step (ii). Production method,
( 13 ) The aromatic polyester according to ( 11 ) above, wherein the step (iii) is a purification comprising washing the product solution after the reaction to obtain a solution containing the aromatic polyester, and subjecting it to the reaction of the step (ii) Manufacturing method,
( 14 ) The method for producing an aromatic polyester according to ( 13 ) above, wherein the washing of the product liquid is carried out with water,
( 15 ) The method for producing an aromatic polyester according to the above ( 11 ), wherein the step (iii) is purification by separating the aromatic polyester from the product solution after the reaction, and subjecting it to the reaction of the step (ii),
( 16 ) In step (iii), a solution containing the aromatic polyester is obtained from the product solution after the reaction, and then the aromatic polyester is separated from the solution and subjected to the purification in step (ii). A method for producing an aromatic polyester according to ( 11 ) above,
( 17 ) In step (iii), the reaction solution is washed to obtain a solution containing the aromatic polyester, and then the aromatic polyester is separated from the solution, which is then used in the reaction of step (ii). The method for producing an aromatic polyester according to the above ( 11 ), which is purification to be provided,
( 18 ) The method for producing an aromatic polyester according to the above ( 17 ), wherein the washing of the product liquid is carried out with water,
(19) a divalent phenol is bisphenol A, acid halide of the divalent aromatization carboxylic acid is terephthaloyl dichloride and / or isophthaloyl dichloride, any of the above (1) to (18) One method can be mentioned.

The process for producing the aromatic polyester of the present invention is remarkably high in transparency and hardly colored even after being processed at a high temperature, not only maintaining remarkably high transparency, but also having high fluidity. Moreover, the aromatic polyester which has also can be manufactured . Therefore, the aromatic polyester obtained by the method of the present invention is extremely useful for optical applications such as optical fibers.

FIG. 1 is an NMR chart of an aromatic polyester end-capped with benzoyl chloride. ( Reference Example 1) FIG. 2 is an NMR chart of an aromatic polyester end-capped with benzoyl chloride. (Comparative Example 2) FIG. 3 is an NMR chart of an aromatic polyester end-capped with benzoyl chloride. (Comparative Example 2) FIG. 4 is an NMR chart of an aromatic polyester end-capped with benzoyl chloride. ( Reference Example 1) FIG. 5 is an NMR chart of an aromatic polyester end-capped with benzoyl chloride. (Example 5) FIG. 6 is an NMR chart of an aromatic polyester end-capped with 1-naphthoyl chloride. (Example 10) FIG. 7 is an NMR chart of a compound in which two hydroxyl groups present at both ends of 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] are sealed with 1-naphthoyl chloride, respectively.

The process for producing an aromatic polyester of the present invention, first, a process for the preparation of aromatic polyesters by reacting an (i) a divalent phenol and a divalent aromatization acid halide of carboxylic acid, 2 4-40 mol% of the following formula with respect to the total charged amount of the acid halide of the valence of aromatization carboxylic acid (II):
X-C (O) -R (II)
(In the formula (II), X is chlorine, bromine or iodine, and R is an aliphatic group, alicyclic group, monocyclic aromatic group, polycyclic aromatic group, condensed aromatic group, heterocyclic group. Or at least one hydrogen of these groups is fluorine, chlorine, bromine, iodine, alkoxyl group, mercapto group, sulfenato group, sulfinato group, sulfo group, alkoxycarbonyl group, acyl Group, alkoxysulfinyl group, alkylthiocarbonyl group, thiosulfo group, cyano group, thiocyano group, isocyano group, isocyanato group, isothiocyanato group or nitro group)
In shown the step of reacting with a compound and then, the aromatic polyester obtained (ii),. 3 to the total charged amount of the divalent aromatization carboxylic acid halide of the acid in (i) And further reacting with 80 mol% of the compound represented by the above formula (II). In the compound represented by the above formula (II), R is a monocyclic aromatic group, a polycyclic aromatic group, a condensed aromatic group or a heterocyclic group, or at least one hydrogen of these groups is fluorine. A compound which is a group substituted by a chlorine, bromine, iodine or alkoxyl group, wherein R is a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group or one hydrogen of these groups is fluorine, chlorine, Or a compound that is a group substituted with a methoxyl group, and R is a phenyl group, a naphthyl group, or a compound in which one hydrogen of these groups is substituted with a fluorine, chlorine, or methoxyl group Are more preferable, and compounds in which R is a phenyl group or a naphthyl group are further preferable, and in particular, compounds in which R is a phenyl group are preferable. X is preferably chlorine. As the compound represented by the formula (II), benzoyl chloride and naphthoyl chloride are preferable, and benzoyl chloride is particularly preferable.

Here, the amount of the compound of formula (II) in step (i), the upper limit is, with respect to the total charged amount of the divalent aromatization acid halide of carboxylic acid, 40 mol%, preferably Is 30 mol%, more preferably 20 mol%, still more preferably 15 mol%, and the lower limit is 4 mol%. If the above upper limit is exceeded, the weight average molecular weight of the resulting aromatic polyester will be low, and the aromatic polyester as the final product will not be suitable for optical applications. The amount of the compound of formula (II) in step (ii), the upper limit is, with respect to the total charged amount of the divalent aromatization acid halide of carboxylic acid in step (i), 80 Mol%, preferably 50 mol%, more preferably 35 mol%, still more preferably 20 mol%, and the lower limit is 3 mol%, preferably 5 mol%, more preferably 7 mol%, still more preferably 10 mol%. %. If it is less than the said minimum, a hydroxyl group may remain in the terminal of the aromatic polyester obtained, and coloring may be produced when it processes at high temperature. On the other hand, even if the above upper limit is exceeded, the amount of the compound represented by the formula (II) that can be incorporated into the end of the aromatic polyester becomes almost constant, and a significant improvement in coloring prevention after processing at high temperature cannot be expected.

Known conditions can be used as the production conditions for the aromatic polyester in step (i) of the present invention. The reaction temperature is preferably 5 to 60 ° C, more preferably 10 to 50 ° C, still more preferably 20 to 30 ° C, and the reaction time is preferably 10 to 180 minutes, more preferably 20 to 120 minutes, still more preferably. Is 30 to 90 minutes. The reaction pressure is preferably 0.01 to 2 MPa, more preferably 0.08 to 0.12 MPa. Manufacture can be either batch or continuous. The conditions in step (ii) are the same as those in step (i) above. In step (ii), a predetermined amount of the compound represented by the formula (II) can be reacted at once, but the predetermined amount of the compound represented by the formula (II) is divided and used. And it can also be made to react in steps. In the production of the aromatic polyester in step (i) of the present invention, dihydric phenols, and divalent aromatization acid halide of carboxylic acid charged amount ratio of divalent aromatization carboxylic acid acid halide compound 1. 1 mol of divalent phenol with respect to 0 mol. 0-5.0 mol der is, it is favorable preferable is 1.1 to 3.0 moles.

In steps (i) and (ii), conventionally known catalysts can be included in known amounts. As the catalyst, a quaternary ammonium salt represented by the following formula can be used. The amount of the catalyst added is preferably 0 to 10 mol%, more preferably 0.001 to 5 mol%, based on the amount of charged polyphenol in step (i) in both steps (i) and (ii). More preferably, it is 0.005-1 mol%.

In the above formula, Y represents H, an ethyl group, a butyl group or a benzyl group, X represents Cl, Br, I, OH or HSO ₄ , and n is an integer of 1 to 8, preferably 3 to An integer of 8 is shown. Examples of the quaternary ammonium salt include tetrabutylammonium fluoride, tetrabutylammonium fluoride hydrate, tetraethylammonium fluoride hydrate, tetraethylammonium fluoride tetrahydrofluoride, tetraethylammonium fluoride trihydrofluoride, Tetrabutylammonium chloride, tetrapropylammonium chloride, tetrapentylammonium chloride, acetylchlorin chloride, (3-acrylamidopropyl) trimethylammonium chloride, benzalkonium chloride, benzoylchlorin chloride, benzylcetyldimethylammonium chloride hydrate, N-benzylcinchone Nidium chloride, benzyldimethylphenyl ammonium Chloride, benzyldimethylstearylammonium chloride, benzyldimethyltetradecylammonium chloride, N-benzylquinidinium chloride, N-benzylquininium chloride, benzyltributylammonium chloride, benzyltriethylammonium chloride, benzyltrimethylammonium chloride, carbamyloline chloride, Chlorocholine chloride, (3-chloro-2-hydroxypropyl) triethylammonium chloride, choline chloride, n-decyltrimethylammonium chloride, diallyldimethylammonium chloride, dichloromethylenedimethylammonium chloride, dimethyldistearylammonium chloride, dodecyltrimethylammonium chloride, n-Hexadecyltrimethyl Ammonium chloride, hexamethonium chloride dihydrate, lauroyl chlorin chloride, methacholine chloride, methacroyl choline chloride, (2-methoxyethoxymethyl) triethylammonium chloride, β-methylcholine chloride, methyltriethylammonium chloride, n-octyltrimethylammonium Chloride, phenyltrimethylammonium chloride, phenyltriethylammonium chloride, phosphochlorin chloride calcium salt, phosphochlorin chloride sodium salt, stachydrin hydrochloride, succinic chloride, tetra-n-amylammonium chloride, tetra-n-butylammonium chloride , Tetradecyldimethylbenzylammonium chloride, tetraethylammonium Um chloride, tetramethylammonium chloride, trimethyl [2,3- (dioleoyloxy) propyl] ammonium chloride, trimethylstearylammonium chloride, trimethyltetradecylammonium chloride, trimethyl [3- (triethoxysilyl) propyl] ammonium chloride, tri- n-octylmethylammonium chloride, trioxymethylammonium chloride, tetrapropylammonium bromide, tetrapentylammonium bromide, acetylchlorin bromide, benzoyl chlorin bromide, benzyltri-n-butylammonium bromide, benzyltriethylammonium bromide, benzyltrimethylammonium bromide, bromo Choline bromide, cetyldimethylethyl ammonium Bromide, choline bromide, decamethonium bromide, decyltrimethylammonium bromide, didecyldimethylammonium bromide, dilauryldimethylammonium bromide, dimethyldimyristylammonium bromide, dimethyldioctylammonium bromide, dimethyldipalmitylammonium bromide, dimethyldistearylammonium bromide, Dodecyltrimethylammonium bromide, (ferrocenylmethyl) dodecyldimethylammonium bromide, (ferrocenylmethyl) trimethylammonium bromide, hexadecyltrimethylammonium bromide, hexamethonium bromide, hexyldimethyloctylammonium bromide, hexyltrimethylammonium bromide, methacholine bromide , Neo Stigmine bromide, n-octyltrimethylammonium bromide, phenyltrimethylammonium bromide, stearyltrimethylammonium bromide, tetraamylammonium bromide, tetra-n-butylammonium bromide, tetra-n-decylammonium bromide, tetradecyltrimethylammonium bromide, Tetraethylammonium bromide, tetraheptylammonium bromide, tetrahexylammonium bromide, tetramethylammonium bromide, tetra-n-propylammonium bromide, tetra-n-propylammonium bromide, 3- (trifluoromethyl) phenyltrimethylammonium bromide, trimethylvinylammonium Bromide, ballesamate bromide, acetylcholine Odide, acetylthiocholine iodide, benzoylcholine iodide, benzoylthiocholine iodide, benzoyltriethylammonium iodide, butyrylcholine iodide, butyrylthiocholine iodide, decamethinium iodide, N, N-dimethylmethyleneammonium iodide Dide, 1,1-dimethyl-4-phenylpiperazinium iodide, ethyltrimethylammonium iodide, ethyltri-n-propylammonium iodide, (ferrocenylmethyl) trimethylammonium iodide, (2-hydroxyethyl) triethyl Ammonium iodide, β-methylcholine iodide, O-β-naphthyloxycarbonylcholine iodide, phenyltriethylammoni Mu-iodide, tetra-n-amylammonium iodide, tetrabutylammonium iodide, tetraethylammonium iodide, tetraheptylammonium iodide, tetra-n-hexylammonium iodide, tetramethylammonium iodide, tetra-n-octylammonium iodide Dide, tetra-n-propylammonium iodide, 3- (trifluoromethyl) phenyltrimethylammonium iodide, trimethylphenylammonium iodide, benzyltriethylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, n-hexadecyltrimethylammonium Hydroxide, hexadecyltrimethylammonium hydroxide , Phenyltrimethylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, tetrahexylammonium hydroxide, tetramethylammonium hydroxide, tetrapropylammonium hydroxide, 3- (trifluoromethyl) phenyltrimethylammonium hydroxide, Tris (2-hydroxyethyl) methylammonium hydroxide, acetylcholine perchlorate, benzyltrimethylammonium dichloroiodate, benzyltrimethylammonium tetrachloroiodate, benzyltrimethylammonium tribromide, betaine anhydrus, betaine hydrochloride, bis (tetra- n-Butylammonium) dichro Mate, bis (tetra-n-butylammonium) tetracyanodiphenoquinodimethanide, 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide, L-carnitine, 3-[(3-colamidopropyl ) Dimethylammonio] -1-propanesulfonate, cyclophenyltrimethylammonium (trifluoromethanesulfonyl) imide, denatonium benzoate, n-dodecyldimethyl (3-sulfopropyl) ammonium hydroxide inner salt, N-fluoro-N ′ -(Chloromethyl) triethylenediaminebis (tetrafluoroborate), hexadecyltrimethylammonium hexafluorophosphate, hexadecyltrimethylammonium perchlorate, hexadecyltrimethylammonium Um tetrafluoroborate, (methoxycarbonylsulfamoyl) triethylammonium hydroxide inner salt, methyltri-n-octylammonium bis (trifluoromethanesulfonyl) imide, methyltri-n-octylammonium hydrogen sulfate, neostigmine methyl sulfate, Octadecyldimethyl (3-sulfopropyl) ammonium hydroxide inner salt, phenyltrimethylammonium tribromide, proponylchlorin p-toluenesulfonate, tetrabutylammonium azide, tetrabutylammonium bifluoride, tetrabutylammonium borohydride, tetrabutylammonium Bromodiaiodide, tetrabutylammonium dibromoaurate, tetrabuty Ammonium dibromochloride, tetrabutylammonium dibromoiodide, tetrabutylammonium dichloroaurate, tetrabutylammonium dichlorobromide, tetrabutylammonium difluorotriphenyl silicate, tetrabutylammonium difluorotriphenylstannate, tetrabutylammonium dihydrogen trifluoride, Tetrabutylammonium diiodate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetrabutylammonium perchlorate, tetrabutylammonium perlenate, tetrabutylammonium phosphate, tetrabutylammonium salicylate, tetrabutylammonium tetra Rafluoroborate, tetrabutylammonium tetraphenylborate, tetrabutylammonium thiocyanate, tetrabutylammonium tribromide, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium triiodide, tetraethylammonium borohydride, tetraethylammonium perchlorate, tetraethylammonium tetrafluoro Borate, tetraethylammonium p-toluenesulfonate, tetraethylammonium trifluoromethanesulfonate, tetramethylammonium acetate, tetramethylammonium borohydride, tetramethylammonium hexafluorophosphate, tetramethylammonium hydrogen sulfate , Tetramethylammonium perchlorate, tetramethylammonium sulfate, tetramethylammonium tetrafluoroborate, tetramethylammonium p-toluenesulfonate, tetramethylammonium triacetoxyborohydride, tetrapropylammonium pearlate, tetramethylammonium tetrafluoroborate, etc. Can be mentioned. Of these, tetra-n-butylammonium bromide, tetrabutylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium chloride, tetrapentylammonium bromide, tetrapentylammonium chloride and the like are preferably used.

The method for producing an aromatic polyester of the present invention further includes a step (iii) of purifying the product solution obtained after the reaction obtained in the step (i) between the steps (i) and (ii). Can do. The purification in step (iii) includes purification for separating the solution containing the aromatic polyester from the reaction product produced in step (i), and from the reaction product produced in step (i). The purification which isolate | separates aromatic polyester itself is mentioned. In the former purification, the solution containing the obtained aromatic polyester is fed to the reaction of step (ii), while in the latter purification, the obtained aromatic polyester itself is fed to the reaction of step (ii). Is done. The method for carrying out these purifications is not particularly limited, and conventionally known methods can be used. As purification for separating the solution containing the aromatic polyester from the product solution after the reaction produced in the step (i), for example, the product solution after the reaction produced in the step (i) is preferably water, for example, A method is used in which a solution containing an aromatic polyester, preferably an organic phase containing an aromatic polyester, is obtained by washing with ion exchange water. Further, as purification for separating the aromatic polyester itself from the reaction product produced in step (i), for example, the reaction product produced in step (i) is preferably water, for example, A method of washing with ion exchange water to obtain a solution containing an aromatic polyester, preferably an organic phase containing an aromatic polyester, and then separating the aromatic polyester from the solution is used. Here, as a method for separating the aromatic polyester from the solution, for example, a method is used in which the solution is mixed with a solvent containing alcohol such as methanol to precipitate the aromatic polyester, which is filtered and separated. be able to.

As the polyhydric phenol, various known polyhydric phenols such as divalent, trivalent and tetravalent can be used. For example, 2,2′-dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 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, -Dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 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-oxofluorene) diol, 1,7- (9-oxofluorene) diol, 2,3- (9-oxofluorene) diol, 2,7- (9-oxofluorene) Diol, 2,2-bis- (4-hydroxynaphthyl) 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, bis- (4-hydroxyphenyl) ether, 4,3 '-Dihydroxydiphenyl ether, 4,2'-dihydroxydiphenyl ether, 2,2'-dihydroxydiphenyl ether, 2,3'-hydroxydiphenyl ether, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether, bis- (hydroxynaphthyl) ether 3,4'-dihydroxydiphenyl, bis- (4-hydroxy Phenyl) sulfone, bis- (3-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, catechol, 3-methylcatechol, 4-methylcatechol, 3-ethylcatechol, 4-ethylcatechol, 3-n-propyl Catechol, 4-n-propylcatechol, 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, -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-methoxycatechol, 5-bromo-4-nitrocatechol, 4 -Bromo-5-methylcatechol, 3-bromo-5- (t-butyl) catechol, 3,4,5-trichlorocatechol, 3,4,5-tribromocatechol, 3,4,6-tribromocatechol, Tetrachlorocatechol, tetrabromocatechol, 3-aminocatechol, 4-amino Tecole, 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-methoxy Catechol, 5-nitro-3-methylcatechol, 4-methoxycatechol, 6-methoxycatechol, 4- (2-hydroxyethyl) catechol, 3-propoxycatechol, 3-butyroxycatechol, 3,4-dimethoxycatechol, 3,6-dimethoxycatechol, 5-methoxy-3- (t-butyl) cate , 3-ethoxy- (t-butyl) catechol, 3,4,6-trimethoxycatechol, 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 Nord, 5-bromoresorcinol, 2,4-dibromoresorcinol, 4,6-dibromoresorcinol, 2,4,6-tribromoresorcinol, 6-bromo-4-butylresorcinol, 2-iodoresorcinol, 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, Tetranitroresorcinol, 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 Lucinol, 5-methoxy-4-methylresorcinol, 5-methoxy-6-methylresorcinol, 5-ethoxyresorcinol, 2-methylresorcinol, 4-methylresorcinol, 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- (2- Methylethenyl) resorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 5-n-butylresorcinol, 2-n-butylresorcinol, 4-tert-butylresorcinol, 2-n-pentylles Lucinol, 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-cyclohexylresorcinol, 4-phenylresorcinol, 4-heptylresorcinol, 5-heptylresorcinol, 5- (1- Methylhexyl) resorcinol, 4-phenylmeth Tilresorcinol, 2-octylresorcinol, 4-octylresorcinol, 5-octylresorcinol, 4- (1-methylheptyl) 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-butyl resorsi , 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, iodohydroquinone, 2,6- Diiodohydroquinone, tetraiodohydroquinone, nitrohydroquinone, 2,6-dinitrohydroquinone, methoxyhydroquinone, 2-methoxy-3-methylhydroquinone, 2-methoxy-5-methylhydroquinone, 3-methoxy-2-methylhydroquinone, 5- Methoxy-2-methylhydroquinone, 2-methoxy-6-propylhydroquinone, 2-methoxy-5-propenylhydroquinone, 2,3-dimethoxyhydroquinone, 2,5-dimethoxyhydroquinone, 2,6-dimethoxyhydroquinone, phenoxyhydroquinone, mercapto Hydroquinone, acetylhydroquinone, benzoylhydroquinone, hydroxymethylhydroquinone, methylhydroquinone, 2-methyl-6-ethylhydroquinone, 2-methyl-5-isopropylhydroxyl Down, 2-methyl-5-cyclohexyl hydroquinone, 2,3-dimethyl hydroquinone, 2,5-dimethyl hydroquinone, 2,6-di
Methylhydroquinone, trimethylhydroquinone, tetramethylhydroquinone, ethylhydroquinone, 2,6-diethylhydroquinone, vinylhydroquinone, 5-ethoxyresorcinol, 2-methylresorcinol, 4-methylresorcinol, 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- ert-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, 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 -Dimethyl resole Sinol, 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-propyl resorcinol, 2-methyl-5-sec-butylresorcinol, 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-se -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-propenylhydroquinone Hexylhydroquinone, 4-methylpentylhydroquinone, cyclohexylhydroquinone, 4-phenylmethylhydroquinone, octylhydroquinone, 2,2′-methylidenebisphenol, 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-propylphenol), 4,4'-methylidenebis (2-methyl-6-) Tilphenol), 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-tetramethylbutyl) phenol), 2,2′-methylidenebis (4,6-di-tert-butylphenol), 2,2′-methylidenebis (4,6-tert- Butylphenol), 4,4′-methylidenebis (2,6-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'-methylidene Bis (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-methyl) Phenol), 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'-isopropylidene Denbis (5-methylphenol), 4,4′-isopropylidenebis (2-methylphenol), 4,4′-isopropylidenebis (2-cyclohexylphenol), 4,4′-isopropylidenebis (2,6 -Dibromophenol), 4,4'-isopropylidenebis (2-nitrophenol), 4,4'-isopropylidenebis (2,6-dinitrophenol), 4,4'-butanediylbis (2-methylphenol), 4,4′-butylidenebisphenol, 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'-se c-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'-cyclohexylidenebisphenol, 4,4'-cyclohexylidene Bis (2-chlorophenol), 4,4′-cyclohexylidenebis (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-tertbutyl-4-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methyl) Phenol), 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′- Sulfinyl bis (2-chlorophenol), 4,4′-sulfinyl bis (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-nitro) Phenol), 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′-sulfonylbis Hydroquinone, 2,6,2'-trihydroxybiphenyl, 3,5,3'-trihydroxybiphenyl, 3,4,4'-trihydroxybiphenyl, 2,4,4'-trihydroxydiphenyl ether, 2,4 4′-trihydroxydiphenylmethane, 1,1′-binaphthalene-2,3,2′-triol, 1,2,3-triol Droxynaphthalene, 1,3,5-trihydroxynaphthalene, 1,4,5-trihydroxynaphthalene, 1,5,6-trihydroxynaphthalene, 1,6,7-trihydroxynaphthalene, 1,7,8- Trihydroxynaphthalene, 2,6,2 ′, 6′-tetrahydroxybiphenyl, 3,5,3 ′, 5′-tetrahydroxybiphenyl, 3,4,3 ′, 4′-tetrahydroxybiphenyl, 2,4, 2 ', 4'-tetrahydroxydiphenyl ether, 2,2'-bis- (2,4-hydroxyphenyl) propane, 2,4,2', 4'-tetrahydroxydiphenylmethane, bis- (2,4-hydroxyphenyl) ) Methane, bis- (2,6-hydroxyphenyl) methane, bis- (2,4-hydroxy-2,6-dimethyl-3-methoxyphenyl) meta 1,1-bis- (2,4-hydroxyphenyl) ethane, 1,1-bis- (2,4-hydroxyphenyl) cyclohexane, 1,2-bis- (2,4-hydroxyphenyl) ethane, , 1-bis- (4,6-hydroxy-2-chlorophenyl) ethane, 1,1′-binaphthalene-2,3,2 ′, 3′-tetraol, 1,2,3,4-tetrahydroxynaphthalene, etc. Is mentioned. Among these, 2,2′-bis- (4-hydroxyphenyl) propane [bisphenol A] is particularly preferable. In addition, a wholly aromatic hydroxyl group-containing compound 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.

As the aromatic polyvalent carboxylic acid, various known aromatic polyvalent carboxylic acids such as divalent, trivalent and tetravalent can be used. For example, phthalic acid, dimethyl phthalate, diphenyl phthalate, isophthalic acid, dimethyl isophthalate, di (cyanomethyl) isophthalate, diphenyl isophthalate, di (2,4-dinitrophenyl) isophthalate, 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, 5-methylisophthalic acid Dimethyl tartrate, 4,5-dimethylisophthalic acid, 4,6-dimethylisophthalic acid, 4-chloroisophthalic acid, dimethyl 4-chloroisophthalate, 5-chloroisophthalic acid, dimethyl 5-chloroisophthalate, 4,6- Dichloroisophthalic acid, dimethyl 4,6-dichloroisophthalate, 4-bromoisophthalic 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-methylterephthalic acid, dimethyl 2-methylterephthalate, 2,5-dimethylterephthalic acid, 2,6 -Dimethylterephthalic acid, 2,6-dimethylterephthalate Dimethyl acid, 2-chloroterephthalic acid, dimethyl 2-chloroterephthalate, 2,5-dichloroterephthalic acid, dimethyl 2,5-dichloroterephthalate, tetrachloroterephthalic 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-naphthalenedicarboxylic acid, dimethyl 1,2-naphthalenedicarboxylic acid, 1,3-naphthalene Dicarboxylic acid, 1,4-naphthalenedicarboxylic 1,4-naphthalenedicarboxylic acid dimethyl, 1,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid dimethyl, 1,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid dimethyl, 1,6-naphthalenedicarboxylic acid Acid diphenyl, 1,7-naphthalenedicarboxylic 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-naphthalenedicarboxylic acid dimethyl, 2,3-naphthalenedicarboxylic acid diphenyl, 2,6-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid dimethyl, 2,6-naphthalenedicarboxylic acid diphenyl, 2, 7-Naphthalenical Bonic acid, 2,7-naphthalenedicarboxylic acid diphenyl, 1,2- (9-oxofluorene) dicarboxylic acid, 1,2- (9-oxofluorene) dicarboxylic acid dimethyl, 1,5- (9-oxofluorene) dicarboxylic acid Dimethyl acid, 1,6- (9-oxofluorene) dicarboxylic acid, dimethyl 1,6- (9-oxofluorene) dicarboxylate, 1,7- (9-oxofluorene) dicarboxylic acid, 1,7- (9- Dimethyl oxofluorene) dicarboxylate, 2,3- (9-oxofluorene) dicarboxylic acid, dimethyl 2,3- (9-oxofluorene) dicarboxylate, 2,7- (9-oxofluorene) dicarboxylic acid, 2,7 -(9-oxofluorene) dicarboxylic acid dimethyl, 1,4-anthracene dicarboxylic acid, 1,5-anthracene dicarboxylic acid, 1,5- Diethyl nthracene dicarboxylate, 1,8-anthracene dicarboxylic acid, 1,9-anthracene dicarboxylic acid, 2,3-anthracene dicarboxylic acid, 9,10-anthracene dicarboxylic acid, dimethyl 9,10-anthracene dicarboxylic acid, 1,2 -Anthraquinone dicarboxylic acid, 1,2-anthraquinone dicarboxylic acid dimethyl, 1,3-1,2-anthraquinone dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 1,5-anthraquinone dicarboxylic acid, 1,5-anthraquinone dicarboxylic acid dimethyl 1,5-anthraquinone dicarboxylic acid 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-biphenyldicarboxylic acid, dimethyl 2,3-biphenyldicarboxylic acid, 2,5-biphenyldicarboxylic acid, 2,6-biphenyldicarboxylic acid, 3,4-biphenyldicarboxylic acid, 3,4-biphenyldicarboxylic acid Dimethyl acid, 3,4-biphenyl dicarboxylic acid, dimethyl 3,4-biphenyl dicarboxylate, 3,4-biphenyl dicarboxylic acid, 2,2′-biphenyl dicarboxylic acid, dimethyl 2,2′-biphenyl dicarboxylic acid, 2,2 '-Biphenyldicarboxylic acid diphenyl, 2,4'-biphenyldicarboxylic acid, 2,4'-biphenyldicarboxylic acid dimethyl, 3,3'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid dimethyl, 3,4'- Biphenyl dicarboxylic acid, dimethyl 3,4'-biphenyl dicarboxylate, 4, '-Biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid dimethyl, 4,4'-biphenyldicarboxylic acid diphenyl, 1,5-biphenylenedicarboxylic acid, 1,5-biphenylenedicarboxylic acid dimethyl, 1,8-biphenylenedicarboxylic acid 1,8-biphenylene dicarboxylic acid dimethyl, 2,6-biphenylene dicarboxylic acid, 2,6-biphenylene dicarboxylic acid dimethyl, 2,7-biphenylene dicarboxylic acid, 2,7-biphenylene dicarboxylic acid dimethyl, 2,2′-dimethyl 4,4′-biphenyldicarboxylic acid, diethyl 2,2′-dimethyl4,4′-biphenyldicarboxylate, 4,4 ″ -p-terphenyldicarboxylic, 4,4 ′ ″-p-quaterphenyldicarboxylic Dimethyl acid, 4,4 ′ ″-p-quaterphenyl dicarboxylic acid, 2,2′-methyl Len dibenzoic acid, dimethyl 2,2′-methylene dibenzoate, 2,4′-methylene 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'-benzyldicarboxylate, 3 Dimethyl 3,3′-bibenzyldicarboxylate, 4,4′-bibenzyldicarboxylic acid, dimethyl 4,4′-bibenzyldicarboxylate, 2,2′-trans-stilbene dicarboxylic acid, 2,2′-trans-stilbene Dimethyl dicarboxylate, diphenyl 2,2′-trans-stilbene dicarboxylate, 2,4′-trans-stilbene dicarboxylic acid, 4,4′-trans-stilbene dica Rubonic acid, 4,4′-trans-stilbene dicarboxylic acid, 2,4′-trans-stilbene dicarboxylic acid, 4,4′-trans-stilbene dicarboxylic acid, dimethyl 4,4′-trans-stilbene dicarboxylic acid, 2, 2′-transidicarboxylic acid, 2,2′-transidicarboxylic acid dimethyl, 2,4′-transidicarboxylic acid, 4,4′-transidicarboxylic acid, 4,4′-transidicarboxylic acid dimethyl, pseudo-p-di Carboxy [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, dimethyl 4,4′-sulfonyldibenzoate, 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′-azobenzenedicarboxylic acid, dimethyl 3,3′-azobenzenedicarboxylate, 4,4′-azobenzenedicarboxylic acid, dimethyl 4,4′-azobenzenedicarboxylate, homophthalic acid Dimethyl homophthalate, homoisophthalic acid, dimethyl homoisophthalate, homoterephthalic acid, dimethyl homoterephthalate, o-phenylene diacetate, o-phenylene diacetate, m-phenylene diacetate, diethyl m-phenylene diacetate, p -Phenylene diacetate, diethyl p-phenylene diacetate, 3,3'-o-phenylene dipropionic acid, 3,3′-o-phenylene dipropionic acid diethyl, 3,3′-m-phenylene dipropionic acid, 3,3′-m-phenylene dipropionic acid diethyl, 3,3′-p-phenylene dipropionic acid, Diethyl 3,3′-p-phenylenedipropionate, 2-carboxycinnamic acid, 3-carboxycinnamic acid, 4-carboxycinnamic acid, 4-carboxycinnamic acid diethyl, 3t, 3′t-o-phenylene diacrylic acid 3t, 3't-o-phenylene diacrylic acid dimethyl, 3t, 3't-m-phenylene diacrylic acid, 3t, 3't-m-phenylene diacrylic acid dimethyl, 3t, 3't-p- Phenylene diacrylic acid, 3t, 3′t-p-phenylene diacrylate dimethyl, m-phenylene propiolic acid, dimethyl m-phenylene propiolate, 1,4-naphthalene Diacetic acid, 1,5-naphthalenediacetic acid, 1,5-naphthalenediacetate dimethyl, 3,3 ′-(1,4-naphthalene) dipropionic acid, 3,3 ′-(1,4-naphthalene) dipropion Diethyl acid, 4,4′-biphenyl diacetic acid, diethyl 4,4′-biphenyl diacetate, 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, diphenylsulfone Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,3-flanged Boronic acid, dimethyl 2,3-furandicarboxylic acid, 2,4-furandicarboxylic acid, dimethyl 2,4-furandicarboxylic acid, 2,5-furandicarboxylic acid, dimethyl 2,5-furandicarboxylate, 2,5- Flanged carboxylate diphenyl, 3,4-furandicarboxylic acid, 3,4-furandicarboxylic acid dimethyl, 3,4-diphenyl-2,5-furandicarboxylic acid, 3,4-diphenyl-2,5-furandicarboxylic acid dimethyl 3,3 ′-(2,5-furan) dipropionic acid, dimethyl 3,3 ′-(2,5-furan) dipropionic acid, 2,5-cis-tetrahydrofuran dicarboxylic acid, 2,5-cis- Dimethyl tetrahydrofurandicarboxylate, 3,3 ′-(2,5-cis-tetrahydrofuran) dipropionic acid, 3,3 ′-(2,5-cis- Trahydrofuran) diethyl dipropionate, 2,3-thiophenedicarboxylic acid, dimethyl 2,3-thiophenedicarboxylic acid, 2,4-thiophenedicarboxylic acid, dimethyl 2,4-thiophenedicarboxylic acid, 2,5-thiophenedicarboxylic acid Dimethyl 2,5-thiophene dicarboxylate, diphenyl 2,5-thiophene dicarboxylate, 3,4-thiophene dicarboxylic acid, dimethyl 3,4-thiophene dicarboxylate, 3,4-diphenyl-2,5-thiophene dicarboxylic acid, Dimethyl 3,4-diphenyl-2,5-thiophenedicarboxylate, 2,5-thiophenediacetic acid, 3,3 ′-(2,5-thiophene) dipropionic acid, 3,3 ′-(2,5-thiophene) ) Diethyl dipropionate, 2,5-cis-tetrahydrothiophene dicarboxylic acid, 2 Diethyl 5-cis-tetrahydrothiophene dicarboxylate, 3,4-cis-tetrahydrothiophene dicarboxylic acid, dimethyl 3,4-cis-tetrahydrothiophene dicarboxylate, 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, 4-oxo-2,6- 4H-pyrandicarboxylic acid diethyl, 2,6-cis-tetrahydropyrandicarboxylic acid, 2,6-cis-tetrahydropyrandicarboxylic acid dimethyl, 2,6-cis-tetrahydrothiopyrandicarboxylic acid, 2,6-cis-tetrahydrothio Dimethyl pyrandicarboxylate 1,1-dioxo-2,6-cis-tetrahydrothiopyrandicarboxylic acid, dimethyl 1,1-dioxo-2,6-cis-tetrahydrothiopyrandicarboxylate, 2,8-dibenzofurandicarboxylic acid, 2,8-dibenzofuran Dimethyl dicarboxylate, 3,7-dibenzofurandicarboxylic acid, dimethyl 3,7-dibenzofurandicarboxylate, 4,6-dibenzofurandicarboxylic acid, dimethyl 4,6-dibenzofurandicarboxylate, 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 dica Rubonic acid, 1,6-dibenzo [1,4] dioxin dicarboxylic acid dimethyl, 2,7-dibenzo [1,4] dioxin dicarboxylic acid, 2,7-dibenzo [1,4] dioxin dicarboxylic acid dimethyl, 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, 4,6- Dimethyl phenoxathiin dicarboxylate, 10,10-dioxo-1,6-phenoxine dicarboxylic acid, dimethyl 10,10-dioxo-1,6-phenoxine dicarboxylate, 10,10-dioxo-1,9-phenoxine Dicarboxylic acid, dimethyl 10,10-dioxo-1,9-phenoxine dicarboxylate, 10,10- Oxo-2,8-phenoxine dicarboxylic acid, dimethyl 10,10-dioxo-2,8-phenoxine dicarboxylic acid, 10,10-dioxo-4,6-phenoxine dicarboxylic acid, 2,7-thianthenedicarboxylic acid Dimethyl 2,7-thiandienedicarboxylate, 10,10-dioxo-1,9-thiandylene dicarboxylic acid, 5,5,10,10-tetraoxo-2,7-thiandienedicarboxylic acid, 5,5,10 , 10-Tetraoxo-2,7-thianthylene dicarboxylic acid dimethyl, 10-oxo-10-phenyl-2,8-phenoxaphosphine dicarboxylic acid, 9-oxabicyclo [3,3,1] nonane-2,6- Dimethyl dicarboxylate, 9-oxabicyclo [3,3,1] nonane-2,6-dicarboxylate diphenyl, 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-diacetate diethyl, 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, Dimethyl 2,5-pyrrole dicarboxylate, 1-methyl-2,5-pyrrole dicarboxylic acid, dimethyl 1-methyl-2,5-pyrrole dicarboxylate, 1-phenyl-2,5-pyrrole Rudicarboxylic acid, 1-phenyl-2, Dimethyl 5-pyrrole dicarboxylate, 3,4-pyrrole dicarboxylic acid, dimethyl 3,4-pyrrole dicarboxylate, 1-methyl-3,4-pyrrole dicarboxylic acid, 1-methyl-3, Diethyl 4-pyrrole dicarboxylate, 1-phenyl-3,4-pyrrole dicarboxylic acid, diethyl 1-phenyl-3,4-pyrrole dicarboxylate, 3,5-dimethyl-2,4-pyrrole dicarboxylic acid Diethyl acid, 2,5-dimethyl-3,4-pyrrole dicarboxylic acid, diethyl 2,5-dimethyl-3,4-pyrrole dicarboxylate, 1,2,5-trimethyl-3,4-pyrrole Ludicarboxylic acid, 1,2,5-trimethyl-3,4-pyrroledicarboxylic acid diethyl 1-methyl-2,5-pyrroldiacetic acid, 1-methyl-2,5-pyrrolediacetate dimethyl, 3,3 '-(2,5-pyro ) Dimethyl dipropionate, 3,3 ′-(1-methyl-2,5-pyrrole) dipropionic acid, dimethyl 3,3 ′-(1-methyl-2,5-pyrrole) dipropionate, 3, , 3 ′-(1-phenyl-2,5-pyrrole) dipropionate diethyl, 1-methyl-2,5-cis-pyrrolidine dicarboxylate, 1-phenyl-2,5-cis-pyrrolidine dicarboxylate, 1-methyl-2,5-pyrrolidinediacetate diethyl, 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-carbazole dicarboxylate, 3,6-carbazole dicarboxylic acid, diethyl 3,6-carbazole dicarboxylate, 9-methyl-3,6-carbazole dicarboxylic acid, 9-methyl- Diethyl 3,6-carbazole dicarboxylate, 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-pyrazole dicarboxylic acid dimethyl, 2-phenyl-3,4-pyrazole dicarboxylic acid, 2-phenyl-3,4-pyrazole dicarboxylic acid dimethyl, 3,5-pyrazole dicarboxylic acid, 3,5- Dimethyl pyrazole dicarboxylate, 1-methyl-3,5-pyra Dicarboxylic acid, 1-methyl-3,5-pyrazole dicarboxylic acid dimethyl, 1-phenyl-3,5-pyrazole dicarboxylic acid, 1-phenyl-3,5-pyrazole dicarboxylic acid dimethyl, 4,5-imidazole dicarboxylic acid, 4 , 5-imidazole dicarboxylic acid diphenyl, 1-methyl-4,5-imidazole dicarboxylic acid, 1-methyl-4,5-imidazole dicarboxylic acid dimethyl, 1-phenyl-4,5-imidazole dicarboxylic acid, 1-phenyl-4 Diethyl 2,5-imidazoledicarboxylate, 2,3-pyridinedicarboxylic acid, dimethyl 2,3-pyridinedicarboxylate, diphenyl 2,3-pyridinedicarboxylate, 2,4-pyridinedicarboxylic acid, dimethyl 2,4-pyridinedicarboxylate 2,4-pyridinedicarboxylic acid diphenyl, 2,5- Lysine dicarboxylic acid, dimethyl 2,5-pyridinedicarboxylate, diphenyl 2,5-pyridinedicarboxylate, 2,6-pyridinedicarboxylic acid, dimethyl 2,6-pyridinedicarboxylate, diphenyl 2,6-pyridinedicarboxylate, 3, 4-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid dimethyl, 3,5-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid diphenyl, 2,6-dimethyl-3,5-pyridinedicarboxylic acid, 2,4, 6-trimethyl-3,5-pyridinedicarboxylic acid, dimethyl 2,5-piperidinedicarboxylate, diethyl 2,3-piperidinedicarboxylate, 2,6-cis-piperidinedicarboxylic acid, dimethyl 2,6-cis-piperidinedicarboxylate 1-methyl-2,6-cis-piperidinedicarboxylic acid Dimethyl 1-methyl-2,6-cis-piperidinedicarboxylate, diethyl 3,5-piperidinedicarboxylate, 2,6-cis-piperidinediacetic acid, 1-methyl-2,6-cis-piperidinediacetic acid, 1- Methyl-2,6-cis-piperidinediacetate, 2,3-quinoline dicarboxylic acid, dimethyl 2,3-quinoline dicarboxylate, 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-quinoline dicarboxylic acid, 2,2′-bipyridine-4,4′-dicarboxylic acid, dimethyl 2,2′-bipyridine-4,4′-dicarboxylate, 2,2 ′ -Bipyridine-5,5'-dicarboxylic acid, 2,2'-bipyridine-5,5'-dicarboxylic acid dimethyl, 2,2'-bipyridine-6,6'-dicarboxylic acid, 3,3'-bipyridine-2 Dimethyl 2,2'-dicarboxylate, 4,5-pyridazine dicarboxylic acid, 4,5-pyrimidine dicarboxylic acid, 4,6-pyrimidine dicarboxylic acid, 2,3-pyrazine dicarboxylic acid, dimethyl 2,3-pyrazine dicarboxylate, 2 , 5-pyrazinedicarboxylic acid, dimethyl 2,5-pyrazinedicarboxylate, diphenyl 2,5-pyrazinedicarboxylate, 2,6-pyrazinedicarboxylic acid, 2,6-pyrazinedicar And dimethyl 1,4-piperazine diacetate, dimethyl 3,3 ′-(1,4-piperazine) dipropionate, 1,6-phenazine dicarboxylic acid, dimethyl 1,6-phenazine dicarboxylate and the like. . Among them, wholly aromatic polycarboxylic acids having a rigid molecular structure not containing an 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, thiophenedicarboxylic acids, pyrandicarboxylic acids, dibenzofurandicarboxylic acids, dibenzothiophenedicarboxylic acids, xanthenedicarboxylic acids Acids, dibenzo [1,4] dioxin dicarboxylic acids, phenoxathiin dicarboxylic acids, thianthylene dicarboxylic acids, phenoxy Examples include phosphine dicarboxylic 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. It is done. Moreover, the acid halide or acid anhydride of said aromatic dicarboxylic acid can also be used. Examples of the acid halide of aromatic dicarboxylic acid include phthaloyl dichloride and naphthoyl dichloride. Of these, preferably phthaloyl dichloride, such as isophthaloyl dichloride or terephthaloyl dichloride, is used.

The aromatic polyester obtained by the method for producing an aromatic polyester of the present invention has, at its end, the following formula (I):
-C (O) -R (I)
(In the formula (I), R is an aliphatic group, an alicyclic group, a monocyclic aromatic group, a polycyclic aromatic group, a condensed aromatic group, a heterocyclic group, or a group consisting of a combination thereof. Or at least one hydrogen of these groups is fluorine, chlorine, bromine, iodine, alkoxyl group, mercapto group, sulfenato group, sulfinato group, sulfo group, alkoxycarbonyl group, acyl group, alkoxysulfinyl group, alkylthiocarbonyl group, thiosulfo group. A group substituted by a group, a cyano group, a thiocyano group, an isocyano group, an isocyanato group, an isothiocyanato group or a nitro group)
It has the structure shown by. As the structure represented by the formula (I), R is a monocyclic aromatic group, a polycyclic aromatic group, a condensed aromatic group or a heterocyclic group, or at least one hydrogen of these groups is fluorine, Structures that are groups substituted by chlorine, bromine, iodine, or alkoxyl groups are preferred, where R is a phenyl group, naphthyl group, anthranyl group, phenanthryl group, or one hydrogen of these groups is fluorine, chlorine, or A structure that is a group substituted with a methoxyl group is more preferable, and a structure that is a phenyl group, a naphthyl group, or a group in which one hydrogen of these groups is substituted with fluorine, chlorine, or a methoxyl group is still more preferable. A structure in which R is a phenyl group or a naphthyl group is more preferable, and a structure in which R is a phenyl group (benzoyloxy group) is particularly preferable. Further, the higher the polyester end-capping rate, the better, and it is 90% or more, preferably 92% or more, more preferably 95% or more, and further preferably 99% or more. When the polyester end-capping rate is less than the above lower limit, coloring after molding at a high temperature cannot be sufficiently suppressed. Here, the polyester end-capping rate refers to the structure represented by the formula (I) with respect to the sum of the number of polyhydric phenol residues present at the end of the aromatic polyester and the number of structures represented by the formula (I). Indicates the percentage of the number. Details of the measurement and calculation methods are given in the examples below.

The lower limit of the weight average molecular weight (Mw) of the aromatic polyester obtained by the method of the present invention is 3,000, preferably 5,000, more preferably 10,000, still more preferably 20,000, and even more preferably 25. , 000. The upper limit is 1,000,000, preferably 500,000, more preferably 250,000, still more preferably 100,000, still more preferably 80,000, and particularly preferably 60,000. If it is less than the said minimum, it is not suitable for the use as an optical material.

The lower limit of the melt flow rate (MFR, unit: g / 10 min, measurement conditions: 320 ° C., 10.0 kg load) of the aromatic polyester obtained by the method of the present invention is preferably 15.0, more preferably 30.0. More preferably, it is 50.0, and still more preferably 60.0. A higher melt flow rate value is preferable because molding becomes easier. Therefore, there is no particular limitation on the upper limit. If it is less than the said minimum, since shaping | molding becomes difficult, it is not preferable.

Dihydric phenol residues contained in the aromatic polyester obtained by the process of the present invention, residues of divalent aromatization acid halide of carboxylic acid, and the structure represented by the formula (I), aromatic making the polyester, obtained by reacting a divalent phenol, a compound represented by the divalent aromatization carboxylic acid halide compound and the formula of the acid (II). Dihydric phenol and an acid halide of the bivalent aromatization carboxylic acids are known either.

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

(Example)
Each property of the aromatic polyester was measured as follows.

<Weight average molecular weight (Mw)>
It measured using Shimadzu GPC LC20AT type | mold. A column in which a total of 3 columns, Shodell KF802, KF804 and KF806, were connected in series was used. Chloroform for liquid chromatography was used as an elution solvent. A commercially available polystyrene having a known molecular weight was used as a standard substance.

<Absorbance (Abs.)>
The sample was heat-treated at 260 ° C. for 1 hour using an electric furnace Muffle Furnace FP21 (trademark) manufactured by Yamato Scientific Co., Ltd. The sample was dissolved in a concentration of 200 mg / 5 ml with chloroform for absorption analysis [UVASOL (trademark), manufactured by Merck & Co., Ltd.], and then UV spectrophotometer V-550 (trademark) manufactured by JASCO Corporation was used. Absorbance at a wavelength of 400 nm was measured.

<Melt flow rate (MFR, g / 10 min)>
A melt indexer F-W01 (trademark) manufactured by Toyo Seiki Seisakusho was used. Here, in Reference Examples 1 to 4 and Comparative Examples 1 and 2, a temperature of 320 ° C. and a 10.0 kg load was measured as a standard, and in Examples 5 to 9 and Comparative Examples 3 to 4, the temperature was 260 ° C. and 10.0 kg. The load was measured as a standard.

<Polyester end sealing rate>
In measuring the polyester end-capping rate, an FT-NMR apparatus JNM-ECA500 (trademark) manufactured by JEOL Ltd. was used. The polyester end-capping rate is determined by NMR analysis in terms of the methyl proton peak (2) (around 1.75 ppm) of the bisphenol A residue contained in the aromatic polyester and the bisphenol A residue present at the end of the aromatic polyester. Two proton peaks (1) (near 6.73 ppm) present in the ortho position relative to the hydroxyl group, and two each present in the benzoyl chloride residue of the bisphenol A residue present at the end of the aromatic polyester The peak of proton (3) (proton present in m-position (3,5-position) with respect to ester group, 7.50 to 7.53 ppm) and peak (4) (o-position with respect to ester group) Calculation was made based on protons present at (2,6-position) (8.16 to 8.18 ppm). Here, the peak (2) is used as an index of all bisphenol A residues contained in the aromatic polyester, and the peak (1) is used as an index of a bisphenol A residue having a hydroxyl terminal contained in the aromatic polyester. The peak (3) and the peak (4) were used as indicators of a bisphenol A residue having a benzoyl group end contained in an aromatic polyester. The polyester end-capping rate is the sum of the area ratios of the above peak (3) and peak (4), and the area ratio of the above peak (3) and peak (4) and the area ratio of peak (1). The value divided by the total is shown as a percentage.

For better understanding, a method for calculating the polyester end-capping rate will be described based on NMR charts of aromatic polyesters produced in Reference Example 1 and Comparative Example 2 (FIGS. 1 and 2 and 3 respectively). To do. In Comparative Example 2 (FIGS. 2 and 3), the area ratio of peak (2) observed near 1.75 ppm is 6.0, and the area ratio of peak (1) recognized near 6.73 ppm is 0.01675. And the area ratio of the peak (3) observed at 7.50 to 7.53 ppm and the peak (4) observed at 8.16 to 8.18 ppm is 0.09816 and 0.09672 respectively. Assuming that all bisphenol A residues are 1, the number of bisphenol A residues having hydroxyl terminal ends is 0.008375 (0.01675 / 2) from the area ratio of peak (1). On the other hand, from the area ratio of peak (3) and peak (4), the number of bisphenol A residues having a benzoyl group terminal (shown as “BC uptake ratio” in Table 1) was 0.04872 [ (0.09816 + 0.09672) / 4]. From these results, the end capping rate was calculated to be 85.3% [0.04872 × 100 / (0.04872 + 0.008375)].

In Reference Example 1 (FIG. 1), the area ratio of the peak (2) observed near 1.75 ppm is 6.0 (not shown), and the area ratio of the peak (1) recognized near 6.73 ppm is The area ratio of the peak (3) observed at 7.415 and 7.50-7.53 ppm and the peak (4) observed at 8.16-8.18 ppm is 0.10648 and 0.13454, respectively. . Assuming that all bisphenol A residues are 1, the number of bisphenol A residues having a hydroxyl terminal is 0.002075 (0.00415 / 2) from the area ratio of peak (1). On the other hand, from the area ratio of the peak (3) and the peak (4), the number of bisphenol A residues having a benzoyl group terminal (shown as “BC uptake ratio” in Table 1) was 0.060255 [ (0.1064 + 0.13454) / 4]. From these results, the terminal blocking rate was calculated to be 96.7% [0.060225 × 100 / (0.060225 + 0.002075)].

<Heat resistance degradation>
As a result of the absorbance (Abs.) Measurement, an absorbance of less than 0.05 was evaluated as good heat deterioration resistance (G), and an absorbance of 0.05 or more was evaluated as poor heat deterioration resistance (B).

[Preparation of aromatic polyester (I)]
A reaction vessel equipped with a stirrer was prepared, and the inside of the reaction vessel was replaced with nitrogen gas. Next, 4.4 liters of water was placed in the reaction vessel, and 346 grams (1.515 moles) of 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] and 121 grams of sodium hydroxide (3. 030 mol) and 0.977 g (0.003 mol) of tetra-n-butylammonium bromide as a catalyst were added and dissolved with sufficient stirring. Here, tetra-n-butylammonium bromide used as a catalyst was 0.2 mol% with respect to the total amount of bisphenol A.

Separately, prepare a container equipped with a stirrer, put 4 liters of methylene chloride in the container, and add 123 grams (0.606 mol) of a one-to-one mixture of terephthaloyl dichloride and isophthaloyl dichloride, Thoroughly stirred to dissolve.

Next, the entire amount of the substance in the latter container was added to the former reaction container, and reacted by stirring and mixing at 25 ° C. for 1 hour. After completion of the reaction, the entire amount of the substance in the reaction vessel was transferred to a separatory funnel, and the organic layer was extracted and separated. The same amount of ion-exchanged water was added to the separated organic layer and stirred for 10 minutes, and then transferred to a separatory funnel to remove the aqueous layer. This operation of washing the organic layer with ion-exchanged water was repeated three times to obtain 4 liters of organic phase (I). The obtained organic phase (I) was dropped into 4 times amount of methanol to precipitate and precipitate a polymer. The precipitated polymer was collected by filtration, and then dried at 120 ° C. for 12 hours under reduced pressure in a vacuum dryer to obtain 120 g of aromatic polyester (I).

[Preparation of Aromatic Polyester (II)]
A reaction vessel equipped with a stirrer was prepared, and the inside of the reaction vessel was replaced with nitrogen gas. Subsequently, 33 liters of water was placed in the reaction vessel, and further, 1145.5 grams (5.000 moles) of 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] and 400.0 grams of sodium hydroxide ( 10.00 mol) and 0.366 g (0.001136 mol) of tetra-n-butylammonium bromide as a catalyst were added and dissolved with sufficient stirring. Here, tetra-n-butylammonium bromide used as a catalyst was 0.023 mol% with respect to the total amount of bisphenol A.

Separately, prepare a container equipped with a stirrer, put 30 liters of methylene chloride in the container, and further 922.76 grams (4.546 mol) of a one-to-one mixture of terephthaloyl dichloride and isophthaloyl dichloride, and 77.0 grams of benzoyl chloride (0.548 mol, 12 mol% based on the total amount of terephthaloyl dichloride and isophthaloyl dichloride charged) was added and dissolved with sufficient stirring.

Next, the entire amount of the substance in the latter container was added to the former reaction container, and reacted by stirring and mixing at 25 ° C. for 1 hour. After completion of the reaction, the organic layer was extracted from the total amount of substances in the reaction vessel and separated. The separated organic layer was returned again to the reaction vessel from which the aqueous layer had been removed, the same amount of ion-exchanged water was added and stirred for 10 minutes, and then the aqueous layer was removed. This operation of washing the organic layer with ion-exchanged water was repeated three times to obtain 30 liters of organic phase (II). The obtained organic phase (II) was dropped into 100 liters of methanol to precipitate and precipitate a polymer. The precipitated polymer was collected by filtration, and then dried at 120 ° C. for 12 hours under reduced pressure in a vacuum dryer to obtain 1,200 grams of aromatic polyester (II).

( Reference Example 1)
In a 500 milliliter eggplant-shaped flask equipped with a stirrer, 200 milliliters of water was placed. Mmol) and dissolved with sufficient stirring.

Separately, 200 ml of methylene chloride was placed in a container equipped with a stirrer, and further 12 grams of the aromatic polyester (I) prepared above and 0.426 grams of benzoyl chloride (3 mmol, 1 / of aromatic polyester (I)). 10 scale preparation, 5 mol% with respect to the total required amount of 0.0606 mol of terephthaloyl dichloride and isophthaloyl dichloride) was added and dissolved with sufficient stirring.

Next, the entire amount of the substance in the latter container was added to the former eggplant-shaped flask and allowed to react by stirring at 25 ° C. for 1 hour. Thereafter, the same treatment as in the preparation of the above aromatic polyester (I) was carried out to obtain an aromatic polyester.

The ¹ H-NMR measurement result of the aromatic polyester is shown in FIG. As the NMR apparatus, an FT-NMR apparatus JNM-EX270 (trademark) manufactured by JEOL Ltd. was used. From the ¹ H-NMR chart of FIG. 4, absorption peaks (7) and (8) derived from hydrogen of the incorporated benzoyl group [4-H near 7 ppm (p-position with respect to ester group (4-position)) (Protons present in FIG. 4 due to overlapping peaks), 3-H and 5-H (m-position (3,5-position) with respect to the ester group) in the vicinity of 7.51 ppm And 2-H and 6-H (protons present in the o-position (2,6-position) with respect to the ester group)] were observed near 8.17 ppm. It was confirmed that the end of the aromatic polyester thus obtained was sealed with benzoyl chloride.

( Reference Example 2)
0.639 grams of benzoyl chloride (4.5 mmol, 7.5 mol with respect to the total required amount of 0.0606 mol of terephthaloyl dichloride and isophthaloyl dichloride in 1/10 scale preparation of aromatic polyester (I) The aromatic polyester was obtained in the same manner as in Reference Example 1 except that it was changed to).

( Reference Example 3)
0.852 grams of benzoyl chloride (6.0 mmol, 10.0 mol for the total required amount of 0.0606 mol of terephthaloyl dichloride and isophthaloyl dichloride in 1/10 scale preparation of aromatic polyester (I) The aromatic polyester was obtained in the same manner as in Reference Example 1 except that it was changed to).

( Reference Example 4)
1.064 grams of benzoyl chloride (7.5 mmol, 12.5 moles relative to 0.0606 moles of total required amount of terephthaloyl dichloride and isophthaloyl dichloride in 1/10 scale preparation of aromatic polyester (I) The aromatic polyester was obtained in the same manner as in Reference Example 1 except that it was changed to).

(Comparative Example 1)
Except that benzoyl chloride was not added (it is 0 mol% with respect to a total required amount of 0.0606 mol of terephthaloyl dichloride and isophthaloyl dichloride in 1/10 scale preparation of aromatic polyester (I)). In the same manner as in Reference Example 1, an aromatic polyester was obtained.

(Comparative Example 2)
0.213 grams of benzoyl chloride (1.5 mmol, 2.5 mol with respect to the total required amount of 0.0606 mol of terephthaloyl dichloride and isophthaloyl dichloride in 1/10 scale preparation of aromatic polyester (I) The aromatic polyester was obtained in the same manner as in Reference Example 1 except that it was changed to).

(Example 5)
In a 500 milliliter eggplant-shaped flask equipped with a stirrer, 200 milliliters of water was placed. Mmol) and dissolved with sufficient stirring.

Separately, in a vessel equipped with a stirrer, 12 grams of the aromatic polyester (II) prepared above and 0.213 grams of benzoyl chloride (1.5 mmol, dichloride in 1/100 scale preparation of the aromatic polyester (II) The total required amount of terephthaloyl and isophthaloyl dichloride was 0.04546 mol, and 3.3 mol%.) Was added and dissolved with sufficient stirring.

Next, the entire amount of the substance in the latter container was added to the former eggplant-shaped flask, and reacted by stirring and mixing at 25 ° C. for 1 hour. Thereafter, the same treatment as in the preparation of the above aromatic polyester (I) was carried out to obtain an aromatic polyester.

The ¹ H-NMR measurement result of the aromatic polyester is shown in FIG. As the NMR apparatus, an FT-NMR apparatus JNM-EX270 (trademark) manufactured by JEOL Ltd. was used. From the ¹ H-NMR chart of FIG. 5, absorption peaks (7) and (8) derived from hydrogen of the incorporated benzoyl group [4-H near 7 ppm (p-position (4-position) with respect to ester group) (Protons present in FIG. 5 due to overlapping peaks), 3-H and 5-H (m-position (3,5-position) with respect to the ester group) in the vicinity of 7.51 ppm And 2-H and 6-H (protons present in the o-position (2,6-position) with respect to the ester group)] were observed near 8.17 ppm. It was confirmed that the end of the aromatic polyester thus obtained was sealed with benzoyl chloride.

(Example 6)
0.426 grams of benzoyl chloride (3 mmol, 6.6 mol% with respect to the total required amount of 0.04546 mol of terephthaloyl dichloride and isophthaloyl dichloride in 1/100 scale preparation of aromatic polyester (II) Aromatic polyester was obtained in the same manner as in Example 5 except that it was changed to (1).

(Example 7)
0.639 grams of benzoyl chloride (4.5 mmol, 9.9 moles per 0.04546 moles of the total charge of terephthaloyl dichloride and isophthaloyl dichloride in 1/100 scale preparation of aromatic polyester (II) The aromatic polyester was obtained in the same manner as in Example 5, except that the aromatic polyester was changed.

(Example 8)
0.852 grams of benzoyl chloride (6.0 mmol, 13.2 mol relative to the total required amount of 0.04546 mol of terephthaloyl dichloride and isophthaloyl dichloride in 1/100 scale preparation of aromatic polyester (II) The aromatic polyester was obtained in the same manner as in Example 5, except that the aromatic polyester was changed.

Example 9
1.064 grams of benzoyl chloride (7.5 mmol, 16.5 moles relative to the total charge of 0.04546 moles of terephthaloyl dichloride and isophthaloyl dichloride in 1/100 scale preparation of aromatic polyester (II) The aromatic polyester was obtained in the same manner as in Example 5, except that the aromatic polyester was changed.

(Comparative Example 3)
Except that benzoyl chloride was not added (it is 0 mol% with respect to the required total amount of 0.04546 mol of terephthaloyl dichloride and isophthaloyl dichloride in the 1/100 scale preparation of aromatic polyester (II)). In the same manner as in Example 5, an aromatic polyester was obtained.

(Comparative Example 4)
0.021 gram of benzoyl chloride (0.15 mmol, 0.33 mol with respect to the total required amount of 0.04546 mol of terephthaloyl dichloride and isophthaloyl dichloride in 1/100 scale preparation of aromatic polyester (II) The aromatic polyester was obtained in the same manner as in Example 5, except that the aromatic polyester was changed.

(Comparative Example 5)
Bisphenol A, sodium hydroxide and tetra-n-butylammonium bromide were 37.67 grams (0.165 mole), 14.0 grams (0.35 mole) and 0.01209 grams (0.0375 mole), respectively. And in a separate container, in addition to 30.46 grams (0.15 moles) of a one-to-one mixture of terephthaloyl dichloride and isophthaloyl dichloride, 4.22 grams of benzoyl chloride. The reaction was carried out in the same manner as in the preparation of the aromatic polyester (I), except that 0.03 mol (20 mol% with respect to the total amount of terephthaloyl dichloride and isophthaloyl dichloride charged) was added.

After completion of the reaction, the entire amount of the substance in the reaction vessel was transferred to a separatory funnel, and the organic layer was extracted and separated. The same amount of ion-exchanged water was added to the separated organic layer and stirred for 10 minutes, and then transferred to a separatory funnel to remove the aqueous layer. This operation of washing the organic layer with ion-exchanged water was repeated three times to obtain 1 liter of organic phase (III). The obtained organic phase (III) was dropped into 4 times amount of methanol to precipitate and precipitate a polymer. The precipitated polymer was collected by filtration, and then dried in a vacuum dryer under reduced pressure at 120 ° C. for 12 hours to obtain 37.9 g of aromatic polyester (III). This aromatic polyester (III) had a weight average molecular weight Mw of 6,700 and a number average molecular weight Mn of 3,400.

The above Reference Examples 1 to 4, for each aromatic polyesters prepared in Examples 5-9 and Comparative Examples 1 to 5, weight average molecular weight (Mw), the absorbance (Abs.at 400nm), benzoyl chloride (BC) uptake The quantity ratio, polyester terminal blocking rate (%) (abbreviated as “terminal blocking rate” in Table 1), melt flow rate (MFR, g / 10 min), and heat deterioration resistance were determined. The results are shown in Table 1.

表１中、「Ｂｉｓ−Ａ」は、ビスフェノールＡを示し、「ＦＣ」は、二塩化テレフタロイル及び二塩化イソフタロイルの両者（１：１の混合物）を示し、「ＢＣ」は、塩化ベンゾイルを示す。また各モル％は、ＦＣ１００モル％に対する比として算出したものである。ＭＦＲ値は、参考例１〜４及び比較例１〜２では、温度３２０℃、１０．０ｋｇ荷重で測定した値であり、実施例５〜９及び比較例３〜４では、温度３２０℃、１０．０ｋｇ荷重で測定すると著しく大きな値となり測定不能であったことから、温度２６０℃、１０．０ｋｇ荷重で測定した値である。また、比較例５は一段階反応である。比較例５において、ＭＦＲ値は重量平均分子量が低いことから著しく高い値となり、温度２６０℃、１０．０ｋｇ荷重の条件においても測定不能であった。

In Table 1, “Bis-A” represents bisphenol A, “FC” represents both terephthaloyl dichloride and isophthaloyl dichloride (1: 1 mixture), and “BC” represents benzoyl chloride. Each mol% is calculated as a ratio to FC 100 mol%. The MFR value is a value measured at a temperature of 320 ° C. and a 10.0 kg load in Reference Examples 1 to 4 and Comparative Examples 1 and 2, and in Examples 5 to 9 and Comparative Examples 3 to 4, the temperature is 320 ° C., 10 ° C. It was a value measured at a temperature of 260 ° C. and a 10.0 kg load because it was extremely large and could not be measured when measured at a load of 0.0 kg. Comparative Example 5 is a one-step reaction. In Comparative Example 5, the MFR value was remarkably high because the weight average molecular weight was low, and measurement was impossible even at a temperature of 260 ° C. and a 10.0 kg load.

In Reference Examples 1 to 4, benzoyl chloride was not added in step (i), but the amount of benzoyl chloride added was changed within the scope of the present invention in step (ii). The end sealing rate of the obtained aromatic polyester was high. All of the absorbances showed very good values, good heat resistance and good coloration after heat treatment. The MFR value was also good.

On the other hand, Comparative Example 1 was one in which benzoyl chloride was not added in any of steps (i) and (ii), and Comparative Example 2 was not added benzoyl chloride in step (i). In ii), benzoyl chloride is added within the range of the present invention. In any case, the absorbance was remarkably bad, it was found that the heat deterioration was poor, and the coloring after the heat treatment was remarkable.

In Examples 5 to 9, benzoyl chloride was added within the scope of the present invention in step (i), and the amount of benzoyl chloride added was varied within the scope of the present invention in stage (ii). The end sealing rate of the obtained aromatic polyester was very large. All of the absorbances showed very good values, good heat resistance and good coloration after heat treatment. The MFR value was also good.

On the other hand, Comparative Example 3 was obtained by adding no benzoyl chloride in the stage (ii), and Comparative Example 4 was obtained by adding benzoyl chloride in the stage (ii) within the range of the present invention. In any case, the absorbance was remarkably bad, it was found that the heat deterioration was poor, and the coloring after the heat treatment was remarkable. Thus, it was found that the aromatic polyester of the present invention cannot be obtained even if the two-step reaction is employed unless the reaction is carried out using a predetermined amount or more of benzoyl chloride in the step (ii). In Comparative Example 5, an aromatic polyester was produced using a one-step reaction. Even if the amount of benzoyl chloride added is increased in a one-step reaction, the weight average molecular weight of the obtained aromatic polyester is lowered, and the aromatic polyester as in the present invention cannot be obtained. This means that the aromatic polyester described in Patent Document 3 is not an aromatic polyester having a high molecular weight, a high end-capping rate, and a very low coloration after heating, like the aromatic polyester of the present invention. That means.

(Example 10)
A reaction vessel equipped with a stirrer was prepared, and the inside of the reaction vessel was replaced with nitrogen gas. Next, 1.1 liters of water was placed in the reaction vessel, and 37.67 grams (0.165 mole) of 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], sodium hydroxide 14.0 Grams (0.35 mol) and 24.18 milligrams (0.075 mmol) of tetra-n-butylammonium bromide as a catalyst were added and dissolved with sufficient stirring. Here, tetra-n-butylammonium bromide used as a catalyst was 0.05 mol% with respect to the total amount of bisphenol A.

Separately, prepare a container equipped with a stirrer, put 1 liter of methylene chloride in the container, and further, 15.23 grams (0.075 mole) terephthaloyl dichloride and 15.23 grams (0.075 mole) isophthaloyl dichloride. ) And 1-naphthoyl chloride 8.58 grams (0.045 moles, 30.0 mole percent based on 0.15 moles total charge of terephthaloyl dichloride and isophthaloyl dichloride) .) Was added and dissolved with sufficient stirring.

Next, the entire amount of the substance in the latter container was added dropwise to the former reaction container over 5 minutes, and the mixture was stirred and mixed at 25 ° C. for 30 minutes to react. After completion of the reaction (the reaction of step (i)), the organic layer was extracted from the total amount of the substance in the reaction vessel and separated. The separated organic layer was washed 3 times with 300 ml of water. Next, the organic layer was dropped into a mixed solvent of 4 liters of methanol and 250 ml of water under stirring to precipitate a polymer. The precipitated polymer was recovered by filtration, and then dried at 120 ° C. under reduced pressure for 12 hours in a vacuum dryer to obtain 57.7 g of aromatic polyester (yield 97%).

In a reaction vessel equipped with a stirrer, 110 ml of water and 1.4 g (0.035 mol) of sodium hydroxide were placed. Separately, 6 grams of the aromatic polyester produced above was dissolved in 90 ml of methylene chloride and added to the former container. Next, 7.3 milligrams (0.02 mmol) of tetra-n-butylammonium bromide was added and dissolved by stirring for 5 minutes. Next, 0.86 g of 1-naphthoyl chloride (4.5 mmol, 30.0 mol% with respect to 0.15 mol of the total charged amount of terephthaloyl dichloride and isophthaloyl dichloride) was chlorinated in the solution. A solution dissolved in 20 ml of methylene was added dropwise over 1 minute, and the reaction was continued by further stirring for 1 hour. After completion of the reaction (reaction in step (ii)), the organic layer was extracted from the total amount of substances in the reaction vessel and separated. The separated organic layer was washed 3 times with 50 ml of water. Next, the organic layer was dropped into a mixed solvent of 400 ml of methanol and 25 ml of water with stirring to precipitate a polymer. The precipitated polymer was collected by filtration, and then dried at 120 ° C. for 12 hours under reduced pressure in a vacuum dryer to obtain 5.69 grams of aromatic polyester.

The obtained aromatic polyester had a weight average molecular weight of 40,000 and a terminal blocking rate of 99.6%. The MFR value was 1.26 g / 10 min as measured at a temperature of 260 ° C. and a 10.0 kg load, which was good. When measured at a temperature of 320 ° C. and a load of 10.0 kg, it was extremely high and could not be measured.

(Example 11)
Example except that the amount of tetra-n-butylammonium bromide used in the reaction of step (i) was changed from 24.18 milligrams (0.075 millimoles) to 14.51 milligrams (0.045 millimoles). This was carried out in the same manner as in No. 10. The resulting aromatic polyester had a weight average molecular weight of 24,000 and a terminal blocking rate of 99.3%. The MFR value was 22.4 g / 10 min as measured at a temperature of 260 ° C. and a 10.0 kg load, which was good. When measured at a temperature of 320 ° C. and a load of 10.0 kg, it was extremely high and could not be measured.

In the above Examples 10 and 11, the end capping rate of the aromatic polyester is measured as follows. In measuring the polyester end-capping rate, an FT-NMR apparatus JNM-ECA500 (trademark) manufactured by JEOL Ltd. was used. Peak of the two protons present in the 1-naphthoyl chloride residue of the bisphenol A residue present at the end of the aromatic polyester (11) (proton present in the 5-position with respect to the ester group, around 7.95 ppm) And peak (12) (proton present at the 4-position with respect to the ester group, near 8.13 ppm), and at the ortho position relative to the hydroxyl group of the bisphenol A residue present at the end of the aromatic polyester The calculation was based on the peak of two protons (13) (around 6.73 ppm). Here, the peak (13) is used as an index of all bisphenol A residues contained in the aromatic polyester, and the peak (11) and the peak (12) are 1-naphthoyl chloride contained in the aromatic polyester. It was used as an indicator of bisphenol A residues having a base end. The polyester end-capping rate is the sum of the area ratios of the peak (11) and peak (12), and the area ratio of the peak (11) and peak (12) to the area ratio of the peak (13). The value divided by the total is shown as a percentage.

In FIG. 6, the NMR chart of the aromatic polyester obtained in Example 10 was shown. The area ratio of the peak (11) observed near 7.95 ppm is 0.0609, the area ratio of the peak (12) recognized near 8.13 ppm is 0.0714, and is observed near 6.73 ppm. The area ratio of the peak (13) is 0.0005. Assuming that all bisphenol A residues are 1, the number of bisphenol A residues having a hydroxyl terminal is 0.00025 (0.0005 / 2) from the area ratio of the peak (13). On the other hand, from the area ratio of peak (11) and peak (12), the number of bisphenol A residues having a 1-naphthoyl chloride terminal is 0.06615 [(0.0609 + 0.0714) / 2]. From these results, the end capping rate was calculated to be 99.6% [0.06615 × 100 / (0.06615 + 0.00025)].

Moreover, when measuring the end-capping rate in Examples 10 and 11, the attribution of each peak is the two hydroxyl groups present at both ends of 2,2-bis (4-hydroxyphenyl) propane [bisphenol A]. Each compound was sealed with 1-naphthoyl chloride and determined based on NMR measurements of the material. The apparatus used is an FT-NMR apparatus JNM-ECA500 (trademark) manufactured by JEOL Ltd. as described above. FIG. 7 shows the chart and each attribution.

The aromatic polyester obtained by the method for producing an aromatic polyester of the present invention not only has heat resistance, but is not easily colored at the time of molding, not only has excellent optical properties, but also has high fluidity. Yes. Therefore, it is extremely useful not only for optical fibers but also for optical applications such as lenses, optical elements, and display substrates. In addition, it can also be used for materials that particularly require heat resistance, such as automobile parts and electronic precision parts.

1 Peak of two protons present in the ortho position relative to the hydroxyl group of the bisphenol A residue 2 Peak of methyl proton of the bisphenol A residue 3 Two protons present in the benzoyl chloride residue of the bisphenol A residue Peak 4 of (proton present in m-position (3,5-position) with respect to ester group) Two protons present in benzoyl chloride residue possessed by bisphenol A residue (o-position relative to ester group) (Proton present in the (2,6-position)) Peak 5 Isophthaloyl dichloride peak 6 Terephthaloyl dichloride peak 7 Benzoyl chloride peak 8 Benzoyl chloride peak 11 Bisphenol A residue present at the end of the aromatic polyester Proton present in the 1-naphthoyl chloride residue Peak 12 of the proton (existing in the 4-position with respect to the ester group) present in the 1-naphthoyl chloride residue of the bisphenol A residue present at the end of the aromatic polyester. Peaks of two protons that are ortho to the hydroxyl group

Claims (6)

(I) In a method for producing an aromatic polyester by reacting a divalent phenol with an acid halide of a divalent aromatic carboxylic acid, the divalent phenol and the acid of the divalent aromatic carboxylic acid The charged amount ratio of halide is 1.0 to 5.0 mol of divalent phenol with respect to 1.0 mol of acid halide of divalent aromatic carboxylic acid, and divalent aromatic carboxylic acid 4 to 40 mol% of the following formula (II) with respect to the total amount of acid halides of acid:
X-C (O) -R (II)
(In the formula (II), X is chlorine, bromine or iodine, and R is an aliphatic group, alicyclic group, monocyclic aromatic group, polycyclic aromatic group, condensed aromatic group, heterocyclic group. Or at least one hydrogen of these groups is fluorine, chlorine, bromine, iodine, alkoxyl group, mercapto group, sulfenato group, sulfinato group, sulfo group, alkoxycarbonyl group, acyl Group, alkoxysulfinyl group, alkylthiocarbonyl group, thiosulfo group, cyano group, thiocyano group, isocyano group, isocyanato group, isothiocyanato group or nitro group)
And (ii) the obtained aromatic polyester is reacted in an amount of 3 to 80 mol% with respect to the total charged amount of the divalent aromatic carboxylic acid halide in (i). Wherein the terminal is further reacted with the compound represented by the above formula (II) at the terminal represented by the following formula (I):
-C (O) -R (I)
(In formula (I), R is the same as above)
And a polyester terminal blocking ratio of 99 % or more, and in addition, a method for producing an aromatic polyester having a weight average molecular weight (Mw) of 10,000 to 100,000. The method for producing an aromatic polyester according to claim 1, wherein the reaction temperature in steps (i) and (ii) is 5 to 60 ° C, and the reaction time is 10 to 180 minutes. R in the above formulas (I) and (II) is a monocyclic aromatic group, a polycyclic aromatic group, a condensed aromatic group or a heterocyclic group, or at least one hydrogen of these groups is fluorine, The method for producing an aromatic polyester according to claim 1 or 2, wherein the aromatic polyester is a group substituted by a chlorine, bromine, iodine or alkoxyl group. R in the above formulas (I) and (II) is a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, or a group in which one hydrogen of these groups is substituted with a fluorine, chlorine, or methoxyl group. The manufacturing method of the aromatic polyester of Claim 1 or 2. The step (iii) further comprising the step (iii) of purifying the product solution after the reaction obtained in the step (i) between the step (i) and the step (ii). A method for producing an aromatic polyester. The aromatic according to any one of claims 1 to 5, wherein the divalent phenol is bisphenol A, and the acid halide of the divalent aromatic carboxylic acid is terephthaloyl dichloride and / or isophthaloyl dichloride. A method for producing polyester.

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