JPH0469177B2 - - 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 previously discovered a method for producing polyesters, particularly aromatic polyesters, by directly reacting diphenols with dicarboxylic acids and directly reacting hydroxybenzoic acids. With this method, it is also possible to produce polyester using diols other than diphenol, and polyester can also be produced by polycondensation of diol, dicarboxylic acid, and oxyacid having a phenolic hydroxyl group and a carboxyl group in the benzene ring. In these polycondensation reactions, the present invention provides compounds of the general formula () produced by the reaction of an amide compound represented by the general formula () below and a halogenated sulfonyl compound represented by the general formula () below. (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 for producing polyester is characterized by the presence of a quaternary salt represented by (X ² represents a halogen atom). The present inventor conducted further studies and determined that in the polycondensation reaction, the amide compound represented by the general formulas () and () and the halogenated The inventors have discovered that similar results can be obtained by carrying out the reaction using a sulfonyl compound, and have thus arrived at the present invention. That is, the gist of the present invention is that the polycondensation reaction between a dicarboxylic acid and a diol, the polycondensation reaction between an oxyacid having a phenolic hydroxyl group and a carboxyl group in a benzene ring, or the polycondensation reaction between the above oxyacid, a dicarboxylic acid, and a diol, 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 ……( ) (wherein R ⁴ represents an alkyl group, aryl group, aralkyl group or cyclohexyl group, and X ¹ represents a halogen atom), the amide compound and the halogenated sulfonyl compound are used. A method for producing a polyester, which comprises mixing a sulfonyl compound with a sulfonyl compound in the presence of the dicarboxylic acid and/or the oxyacid, and then optionally mixing the diol to perform a polycondensation reaction. The present invention will be explained in detail below. The carboxylic acid used in the present invention has the general formula () HOOC-R ⁹ -COOH ... () (in the formula, R ⁹ is a divalent aromatic group, R ¹⁰ -X ³ -R ¹¹ group

[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] is a group (Y ⁵ to ^{Y 8} represent a hydrogen atom, a halogen atom, or an alkyl group). Also

In the group [Formula], Y ¹ to ^{Y 4} are hydrogen atoms, halogen atoms, or alkyl groups. 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, aromatic dicarboxylic acids such as 2,2-diphenylpropane-4,4'-dicarboxylic acid, 1,4-
Aralkylene dicarboxylic acids such as xylylene dicarboxylic acid and 1,3-xylylene dicarboxylic acid; aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid; Chain aliphatic dicarboxylic acid, 1,4-cyclohexyldicarboxylic acid, 1,3-cyclohexyldicarboxylic acid, 1,
Examples include, but are not limited to, 2-cyclohexyldicarboxylic acid, 1,3-cyclopentyldicarboxylic acid, 1,2-cyclohexyldicarboxylic acid, and the like. Moreover, these may be used as a mixture. The diol has the general formula () HO−R ¹² −OH ... () (In the formula, R ⁵ is a divalent aromatic group or a divalent aliphatic group.

[Formula] group or R ¹² -X ⁴ - R ¹⁴ group) can be mentioned. R ¹³ and R ¹⁴ have the same meanings as R ¹⁰ and R ¹¹ , X ⁴ has the same meaning as X ³ , and Y ⁹ to ^{Y 12} have the same meaning as Y ¹ to ^{Y 4} . Specific examples include hydroquinone, resorcinol, methyl, hydroquinone, 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-hydroxy 3,5
-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, 1,6-hexamethylenediol, 1,4-cyclohexanedimethanol, xylidene-1,4-diol, Examples include 1,3-cyclohexanediol, but are not necessarily limited thereto. 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,
In the general formula () such as N,N-diethylacetamide, R ¹ , R ² and R ³ are hydrogen atoms,
Particularly preferred are alkyl 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, p-toluenesulfonyl chloride,
Phenylsulfonyl chloride, p-bromophenylsulfonyl chloride, p-nitrophenylsulfonyl chloride, p-chlorophenylsulfonyl chloride, m-chlorophenylsulfonyl chloride, 2,4,6.Trimethylphenylsulfonyl chloride, 2,4 ,6, In the general formula () shown above, R Particularly preferred are those in which ⁴ is an aryl group, an alkyl group, or a benzyl group. The amount of the amide compound to be used is 1/50 mole or more based on the carboxyl group, and the amount of the sulfonyl compound to be used is 1 to 4 times the mole, preferably 1 to 1.5 times the mole of the carboxyl group. It is necessary to use In the method of the present invention, the amide compound and the sulfonyl compound are mixed with the dicarbonate under conditions that do not substantially produce the quaternary salt represented by the general formula (), that is, the amide compound and the halogenated sulfonyl compound are After mixing in the presence of the acid and/or the oxyacid, if necessary, the diol is mixed to perform a polycondensation reaction. Specifically, as such conditions, first, any of the following ~ The dicarboxylic acid and/or the oxyacid and the amide compound and sulfonyl compound are mixed by the method shown in . Such conditions include the case where a) an amide compound and a sulfonyl compound, and a) the dicarboxylic acid and/or the oxyacid are mixed substantially simultaneously [for example, in the base (and solvent) described below,
Examples include a method of adding the three components (-) at the same time, a method of adding the base (and solvent) after supplying these three components into a reaction vessel], () amide compound and) dicarboxylic acid and/or
or oxyacid, then) when mixing with a sulfonyl compound, a) when mixing a sulfonyl compound and) dicarboxylic acid and/or oxyacid, and then) mixing with an amide compound, then diol is added to these mixtures. The polycondensation reaction is carried out with (or without) addition. For this polymerization, the amide compound, sulfonyl compound, dicarboxylic acid, and/or the above oxyacid are mixed in the base alone or in a base and a solvent using the method described above (heating may be performed during or after mixing as the case may be), and the diol is added or added. It reacts without
When adding a diol, the diol can be used as a base alone or dissolved in a mixture of a base and a solvent, if necessary. Bases used for these purposes include pyridine, α-picoline, β-picoline, γ-picoline, 3,5-lutidine, 3,4-lutidine,
2,4-lutidine, 2,6-lutidine, 2,3-
Examples include lutidine, 2,5-lutidine, 2,4,6-collidine, 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-methylpyrrolide, γ-butyrolactone, dimethylsulfoxide sulfolane, and hexamethyl Examples include polar solvents such as phosphoramide, aromatic hydrocarbons such as benzene, toluene, and xylene. The polymerization temperature varies depending on the solvent, etc., but is usually 80 to 200℃.
temperature, preferably about 100 to 120°C. In addition, in this method, it is used as an additive to adjust the solubility and swelling properties of the polymer produced during polymerization, and as an auxiliary agent to increase the degree of polymerization.
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 such as Licl, Cacl ₂ , Mgcl ₂ , LiBr, etc. The system during polymerization varies depending on the combination of monomers used, solvents, additives, etc., such as homogeneous system, precipitation system, gel-like system, etc. 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/sy-tetrachloroethane (60/40,
(weight ratio), 0.5 wt% polymer solution, measured at 30°C. Example 1 p-toluenesulfonic acid chloride (13 mmol)
was added to a solution of isophthalic acid (2.5 mmol) in pyridine (10 ml) containing N ₁ N-dimethylformamide (3 mmol), left under stirring at room temperature for 10 minutes, and then further stirred at 120 °C.
Heat for 10 minutes to make a homogeneous solution. Add bisphenol A (5 mmol) to this solution in pyridine (10 ml).
The solution was added dropwise over 20 minutes, and then reacted at 120°C for 3 hours. After diluting the reaction solution with pyridine, it was poured into methanol to separate the polymer, and the polymer was obtained in almost quantitative yield. ηinh. was 1.45. Example 2 The reaction was carried out in the same manner as in Example 1 except that N ₁ N-diethylformamide (3 mmol) was used instead of N ₁ N-dimethylformamide (3 mmol). The ηinh. of the polymer was 1.41. Example 3 In Example 1, the reaction was carried out in the same manner as in Example 1 except that trimethylbenzenesulfonyl chloride (13 mmol) was used instead of p-toluenesulfonic acid chloride (13 mmol), and ηinh.1.33
of polymer was obtained. Example 4 p-Toluenesulfonyl chloride (13 mmol) was dissolved in pyridine (10 ml) and stirred at room temperature for 30 minutes. This solution was dissolved in p-oxybenzoic acid (5 ml).
mol) and Schuringer's acid (5 mmol),
Pyridine (10 ml) heated in an oil bath at 120°C and N,
The mixture was added to a mixed solution of N-dimethylformamide (10 ml) and reacted for 3 hours in an oil bath at 120°C. The separation of the polymer was carried out in the same manner as in Example 1, with a quantitative yield of 1.41 dl/g of ηinh (in p-chlorophenol,
A polymer having a temperature of 50° C.) was obtained.

Claims (1)

[Scope of Claims] 1 Polycondensation of dicarboxylic acids and diols, polycondensation of oxyacids having a phenolic hydroxyl group and carboxyl group on the benzene ring, or polycondensation of the above oxyacids, dicarboxylic acids, and diols, generally 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 ……( ) (wherein R ⁴ represents an alkyl group, aryl group, aralkyl group or cyclohexyl group, and X ¹ represents a halogen atom), the amide compound and the halogenated sulfonyl compound are used. A method for producing polyester, which comprises mixing a sulfonyl compound in the presence of the dicarboxylic acid and/or the oxyacid, and then optionally mixing the diol to perform a polycondensation reaction.