JPH0438764B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyester. In particular, it relates to the direct production of polyesters, particularly aromatic polyesters. Polyesters, especially aromatic polyesters, can be produced by interfacial polycondensation or solution polycondensation between diphenols and dicarboxylic acid dihalides, melt polycondensation between diacetates of diphenols and dicarboxylic acids, and melt polycondensation between diphenols and dicarboxylic acid diphenyl esters. , melt polycondensation of p-acetoxybenzoic acids, and melt polycondensation of p-hydroxybenzoic acid phenyl esters are known, but it is generally difficult to produce polyester by directly reacting diphenols and dicarboxylic acids. It is known that As a result of extensive studies, the present inventors have discovered a method for producing polyesters, particularly aromatic polyesters, by directly reacting diphenols with dicarboxylic acids and directly reacting hydroxybenzoic acids. In addition, the present inventor has found that it is also possible to produce polyester using diols other than diphenol with this method, and furthermore, polycondensation of diol, dicarboxylic acid, and oxyacid having a phenolic hydroxyl group and a carboxyl group in the benzene ring. It has been discovered that polyester can also be produced by That is, the gist of the present invention is that in the polycondensation reaction of a dicarboxylic acid and a diol, the polycondensation reaction of an oxyacid having a phenolic hydroxyl group and a carboxyl group in the benzene ring, or the polycondensation reaction of the oxyacid, a diol, and a dicarboxylic acid, the general formula () (In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a cycloalkyl group) and the general formula () R ⁴ −SO ₂ X ¹ ……( ) (In the formula, R ⁴ represents an alkyl group, aryl group, aralkyl group, or cyclohexyl group, and X ¹ represents a halogen atom) General formula () produced by reaction with a halogenated sulfonyl compound represented by (In the formula, R ⁵ , R ⁶ and R ⁷ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group, and R ⁸ represents an alkyl group, an aryl group,
represents an aralkyl group or a cyclohexyl group,
The method of producing a polyester is characterized by the presence of a quaternary salt represented by (X ² represents a halogen atom). To explain the present invention in detail, the dicarboxylic acid used in the present invention has the general formula () HOOC-R ⁹ -COOH ... () (wherein R ⁹ is a divalent aromatic group, -R ¹⁰ -X ³ −R ¹¹ −
basis,

[Formula] represents a divalent aliphatic group). Here, R ¹⁰ and R ¹¹ are divalent aromatic groups, and X ³ represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, or an alkylidene group. As a divalent aromatic group

[Formula] groups (where Y ⁵ to Y ⁸ represent a hydrogen atom, a halogen atom, or an alkyl group) are exemplified. Also,

In the group [Formula], Y ¹ to ^{Y 4} represent a hydrogen atom, a halogen atom, or an alkyl group. Specific examples include terephthalic acid, isophthalic acid,
naphthalene-2,6-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, diphenyl-4,4'-
Dicarboxylic acid, methyl terephthalic acid, methyl isophthalic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenyl thioether-4,4'-dicarboxylic acid, diphenyl sulfone-4,4'-dicarboxylic acid, diphenyl ketone-4 , 4'-dicarboxylic acid, 2,2-diphenylpropane-4,4'-dicarboxylic acid, 1,4
-Aralkylene dicarboxylic acids such as xylylene dicarboxylic acid and 1,3-xylylene dicarboxylic acid; chain aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid; acid, 1,4 cyclohexyl dicarboxylic acid, 1,3 cyclohexyl dicarboxylic acid, 1,2 cyclohexyl dicarboxylic acid,
Examples include, but are not limited to, cycloaliphatic dicarboxylic acids such as 1,3 cyclopentyl dicarboxylic acid and 1,2 cyclohexyl dicarboxylic acid. Moreover, these may be used as a mixture. The diol has the general formula () HO−R ¹² −OH ... () (in the formula, R ¹² is a divalent aromatic group, a divalent aliphatic group,

[Formula] group or -R ¹³ -X ⁴ -R ¹⁴ - group) is mentioned. R ¹³ and R ¹⁴ are the above R ¹⁰ and
R represents the same meaning as ¹¹ , X ⁴ represents the same meaning as X ³ above,
Y ⁹ to ^{Y 12} have the same meanings as Y ¹ to ^{Y 4} above. Specific examples include hydroquinone, resorcinol, methylhydroquinone, chlorohydroquinone, acetylhydroquinone, acetoxyhydroquinone,
Nitrohydroquinone, dimethylaminohydroquinone, 1,4-dihydroxynaphthol, 1,
5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, 2,7-dihydroxynaphthol, 2,2'-
Bis(4-hydroxyphenyl)propane, 2,
2'-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2'-bis(4-hydroxy3,5-dichlorophenyl)-propane, 2,
2'-bis(4-hydroxy-3-methylphenyl)-propane, 2,2'-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)-methane, bis(4-hydroxy- 3,5-dimethylphenyl)-methane, bis(4-hydroxy-3,5-dichlorophenyl)-methane, bis(4-hydroxy-3,5-
dibromophenyl)-methane, 1,1-bis(4
-hydroxyphenyl)cyclohexane, 4,
4'-dihydroxydiphenylbis(4-hydroxyphenyl)-ketone, bis(4-hydroxy-
3,5-dimethylphenyl)-ketone, bis(4
-hydroxy-3,5-dichlorophenyl)-ketone, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxy-3-chlorophenyl) sulfide, bis(4-hydroxyphenyl) sulfone, bis(4- Hydroxy-3,5-
dichlorophenyl) ether, 1,4-butanediol, 1,4-cyclohexanediol, 1,
Examples include, but are not limited to, 6-hexamethylene diol, 1,4-cyclohexanedimethanol, xylidene-1,4-diol, 1,3-cyclohexanediol, and the like. Moreover, these may be used as a mixture. As an oxyacid having a phenolic hydroxyl group and a carboxyl group in the benzene ring, the general formula

A compound represented by the formula: (wherein Z ¹ to ^{Z 4} represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group) can be used.
Specific examples include p-hydroxybenzoic acid, m-hydroxybenzoic acid, Schuringer's acid, vanillic acid, 4-hydroxy-4'-carboxydiphenyl ether, 4-hydroxy-4'-carboxybiphenyl, 2,6- dichloro-p-hydroxybenzoic acid, 2-chloro-p-hydroxybenzoic acid,
Examples include hydroxybenzoic acids such as 2,6-difluoro-p-hydroxybenzoic acid. These may be a mixture. As the amide compound used in the present invention, any of those represented by the general formula () above can be used, but N,N-dimethylformamide,
N,N-diethylformamide, N,N-dibutylformamide, N-methylformamide, formamide, N,N-dimethylacetamide, N,
N-diethylacetamide, N-methylacetamide, acetanilide, N,N-diphenylformamide, benzoylamide, N,N-dimethylbenzoylamide, N-methylbenzoylamide, N,N-diethylacetamide and other general formulas In (), R ¹ , R ² and R ³ are particularly preferably hydrogen atoms, alkyl groups and aryl groups. As the sulfonyl compound used in the present invention, any compound represented by the general formula () can be used, but p-toluenesulfonyl chloride, phenylsulfonyl chloride, p-bromophenylsulfonyl chloride, p-nitrophenyl chloride, enylsulfonyl chloride, p-chlorophenylsulfonyl chloride, m-chlorophenylsulfonyl chloride, 2,4,6-trimethylphenylsulfonyl chloride, 2,4,6-triisopropylsulfonyl chloride, methanesulfonyl chloride,
ethanesulfonyl chloride, p-toluenesulfonium bromide, p-toluenesulfonyl iodide, p-toluenesulfonyl fluoride,
Particularly preferred are those in the general formula () in which R ⁴ is an aryl group, an alkyl group, or a benzyl group, such as benzylsulfonyl chloride. The amount of the amide compound to be used is 1/50 mole or more per mole of diol or oxyacid, and the amount of the sulfonyl compound to be used is 2 to 4 times the mole, preferably 2 to 4 times the mole of diol or oxyacid. It is necessary to use ~3 times the molar amount. During polymerization, the amide compound and sulfonyl compound are reacted in advance with a base alone or in a base and a solvent to produce the compound of formula () in the system (the amount produced is 1/1 per mole of diol or oxyacid).
A suitable method is to mix and add the monomers (dicarboxylic acid and diol or/and oxyacid) after 50 mol or more, and the reaction temperature is usually about 0 to 50°C, preferably about room temperature. Bases used for this purpose include pyridine,
α-picoline, β-picoline, γ-picoline,
3,5-lutidine, 3,4-lutidine, 2,4-
Lutidine, 2,6-lutidine, 2,3-lutidine, 2,5-lutidine, 2,4,6-collidine,
Examples include quinoline, isoquinoline, dimethylaniline, etc., but any tertiary amine can be used. Examples of solvents include chlorinated solvents such as chlorobenzene, O-dichlorobenzene, carbon tetrachloride, dichloromethane, and tetrachloroethane, dimethylformamide, dimethylacetamide, N-methylpyrrolid, γ-butyrolactone, dimethylsulfoxide, sulfolane, and hexane. Examples include polar solvents such as methylphosphoramide, and aromatic hydrocarbons such as benzene, toluene, and xylene.
Polycondensation temperature varies depending on the solvent, but is usually 80 to 200
The temperature is preferably about 100 to 120°C. In the present invention, additives such as LiCl, CaCl ₂ , MgCl ₂ , LiBr, etc., which are used as additives to adjust the solubility and swelling properties of the polymer produced during polymerization, and as auxiliary agents to increase the degree of polymerization, are used. Polyesters with a high degree of polymerization and a very narrow molecular weight distribution can be easily obtained without the addition of alkali or alkaline earth metal halides. The system during polymerization varies depending on the combination of monomers, solvents, and additives used, such as homogeneous, precipitation, and gel-like systems. This can be carried out by reprecipitation in a solvent, reprecipitation with water alone, washing, and the like. The present invention will be explained in detail below with reference to Examples. All viscosities (ηinh) in the following examples are phenol/sym-tetrachloroethane (60/
40, weight ratio), a 0.5 wt% polymer solution was measured at 30°C. Example 1 N,N-dimethylformamide (10 mmol) was added to a solution of p-toluenesulfonic acid chloride (13 mmol) in pyridine (10 ml), stirred at room temperature for 30 minutes, and reacted, followed by isophthalic acid (2.5 mmol). A solution of terephthalic acid (2.5 mmol) in pyridine (10 ml) was added and reacted for 10 minutes. The reaction mixture was further heated in an oil bath at 120°C for 10 minutes,
Bisphenol A (5 mmol) dissolved in pyridine (10 ml) was added dropwise to this solution over 20 minutes, and the mixture was further reacted in an oil bath at 120°C for 3 hours. The reaction solution was diluted with pyridine and then poured into methanol to separate the polymer, yielding a polymer in almost quantitative yield. The viscosity (ηinh) of the polymer was 1.15 dl/g. Examples 2 to 7, Comparative Example 1 Table 1 was prepared in the same manner as in Example 1 except that the amount of N,N-dimethylformamide (DMF) was changed.
The results shown are obtained.

【table】

[Table] Examples 8 to 16 The procedure was repeated in the same manner as in Example 1 except that the amount of DMF was 3 mmol, the dropping time of bisphenol was 10 minutes, and the dicarboxylic acid and diol were changed as shown below. The results shown in 2 were obtained.

[Table] Examples 17 to 19 The following results were obtained in the same manner as in Example 1, except that 3 mmol of the amide compound shown below was used instead of DMF.

[Table] Examples 20 to 23 The procedure was carried out in the same manner as in Example 1, except that a halogenated sulfonyl compound as shown below was used instead of p-toluenesulfonyl chloride, and the amount of DMF was 3 mmol. The following results were obtained.

[Table] Example 24 After dissolving p-toluenesulfonyl chloride (13 mmol) in pyridine (10 ml), let it stand for 20 minutes, add DMF (20 mmol) and leave it under stirring at room temperature for 30 minutes. This solution was combined with p-oxy-benzoic acid (5 mmol) and Schulinger's acid (5 mmol).
mmol) was dissolved, added to a mixed solution of pyridine (10 ml) and DMF (10 ml) heated in a 120°C oil bath, and reacted for 3 hours in a 120°C oil bath. The separation of the polymer was carried out in the same manner as in Example 1, with a quantitative yield of 2.0 dl/g of ηinh (in p-chlorophenol, 50
A polymer was obtained having a temperature of 100° C.). Examples 25 to 28 The following results were obtained in the same manner as in Example 24, except that the mixing ratio of DMF and pyridine for dissolving the monomer oxyacid was changed.

【table】

Claims (1)

[Scope of Claims] 1 In the polycondensation reaction of a dicarboxylic acid and a diol, the polycondensation reaction of an oxyacid having a phenolic hydroxyl group and a carboxyl group in the benzene ring, or the polycondensation reaction of the oxyacid, a dicarboxylic acid, and a diol, the general formula () (In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a cycloalkyl group) and the general formula () R ⁴ −SO ₂ X ¹ ……( ) (In the formula, R ⁴ represents an alkyl group, aryl group, aralkyl group, or cyclohexyl group, and X ¹ represents a halogen atom) General formula () produced by reaction with a halogenated sulfonyl compound represented by (In the formula, R ⁵ , R ⁶ and R ⁷ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group, and R ⁸ represents an alkyl group, an aryl group,
represents an aralkyl group or a cyclohexyl group,
A method for producing polyester, characterized by the presence of a quaternary salt represented by (X ² represents a halogen atom).