JPH0477014B2 - - 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 are hydrogen atoms, alkyl groups,
An amide compound represented by (representing an aryl group, aralkyl group or cycloalkyl group) or general formula () (In the formula, R ⁴ represents an optionally branched alkylene group having 3 or more carbon atoms, and R ⁵ represents a hydrogen atom, an alkyl group,
Indicates an aryl group, an aralkyl group or a cycloalkyl group. ) and the general formula () (In the formula, R ⁶ and R ⁷ are an alkyl group, an aryl group,
represents an aralkyl group or a cyclohexyl group,
A method for producing a polyester, which comprises reacting in advance a halogenated phosphorus compound represented by (X ¹ represents a halogen atom), and then mixing and reacting the above dicarboxylic acid with a diol or/and oxyacid. exists in To explain the present invention in detail, the dicarboxylic acid used in the present invention has the general formula () HOOC-R ³ -COOH ... () (wherein R ³ is a divalent aromatic group, -R ⁹ -X ² −R ¹⁰ − group,

[Formula] represents a divalent aliphatic group). Here, R ⁹ and R ¹⁰ are divalent aromatic groups, and X ² represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, an alkylidene group, or none.
As a divalent aromatic group,

[Formula] groups (where Y ⁵ to ^{Y 8} represent a hydrogen atom, a halogen atom, an alkoxy group, or an alkyl group) can be mentioned. Also,

In the group [Formula], Y ¹ to ^{Y 4} represent a hydrogen atom, a halogen atom, an alkoxy group or an alkyl group. Specific examples include terephthalic acid, isophthalic acid,
naphthalene-2,6-dicarboxylic acid, naphthalene-1,5-dicarphonic 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, aromatic dicarboxylic acids such as diphenyl-4,4'-dicarboxylic acid, 1,4-xylylene dicarboxylic acid, 1 , aralkylene dicarboxylic acids such as 3-xylylene dicarboxylic acid, chain aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superic acid, azelaic acid, 1,4 cyclohexyl dicarboxylic acid acid, 1,3 cyclohexyldicarboxylic acid,
Examples include, but are not limited to, cycloaliphatic dicarboxylic acids such as 1,2 cyclohexyl dicarboxylic acid, 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 ¹¹ is a divalent aromatic group, a divalent aliphatic group,

[Formula] group or -R ¹² -X ³ -R ¹³ - group). R ¹² and R ¹³ have the same meanings as R ⁹ and R ¹⁰ , X ³ has the same meaning as X ² , and Y ⁹ to ^{Y 12} have the same meaning as Y ¹ to ^{Y 4} . 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'-pis(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-hydroxy phenyl)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-hydroxyphenyl)-ketone,
-Hydroxy-3,5-dichlorophenyl)ether, 4,4'-dihydroxydiphenyl, 1,4
-butanediol, 1,4-cyclohexanediol, 1,6-hexamethylenediol, 1,4
-Cyclohexane dimethanol, xylidene-
Examples include 1,4-diol, 1,3-cyclohexanediol, and the like, but are not necessarily limited to these. 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 element, an alkyl group, or an alkoxy group) can be used.
Specific examples include p-hydroxybenzoic acid, m-hydroxybenzoic acid, syringic acid, vanillic acid,
4-Hydroxy-4'-carboxydiphenyl ether, 4-hydroxy-4'-carboxybiphenyl, 2,6-dichloro-p-hydroxybenzoic acid, 2-chloro-p-hydroxybenzoic acid, 2,
Examples include hydroxybenzoic acids such as 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 () or/and () can be used, but N,N-dimethylformamide, N,N-dimethylformamide, N, N-dibutylformamide, N-methylformamide, formamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methylacetamide, acetanilide,
N,N-diphenylformamide, benzoylamide, N,N-dimethylbenzoylamide, N-
In the general formula () shown above, R ¹ , like methylbenzoylamide and N,N-diethylacetamide,
Particularly preferred are those in which R ² and R ³ are hydrogen atoms, alkyl groups, and aryl groups. Also general formula ()
From the viewpoint of cost, N-methyl 2-pyrrolidone is preferred as the compound represented by the formula. As the phosphorus compound used in the present invention, any compound represented by the general formula () can be used, but specific examples include diphenyl chlorophosphate, dinonylphenyl chlorophosphate, and dibenzyl chlorphosphate. Fuosphate, dibutyl chlorofuosphenate, dicyclohexyl chlorofuosphate, dihexyl chlorofuosphate, dioctyl chlorofuosphate, didodecyl chlorofuosphate, diphenylbromophosphate, diphenyl fluorophosphate phenylbutyl Examples include chlorophosphate and benzyl octyl chlorophosphate, but phosphate containing a chlorine atom as a halogen atom is preferred. 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 phosphorus compound to be used is 2 to 10 times the mole of diol or oxyacid, preferably 2
It is necessary to use ~4 times the molar amount. During polymerization, the amide compound and phosphorus compound are reacted in advance with a base alone or in a base and a solvent.
A method of mixing and heating the monomers (dicarboxylic acid and diol or/and oxyacid) after generating a quaternary salt in the system (the amount of generation is 1/50 mole or more per 1 mole of diol or oxyacid). is suitable, 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-
Examples include lutidine, 2,3-lutidine, 2,5-lutidine, 2,4,6-collidine, quinoline, isoquinoline, dimethylaniline, and 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, aromatic hydrocarbons such as benzene, toluene, and xylene. Polycondensation temperature varies depending on the solvent, but is usually 80-200℃
temperature, preferably about 100 to 120°C. In addition, in the present invention, LiCl, CaCl ₂ , MgCl _{2 ,} LiBr, etc. 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. 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. 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. Examples 1 to 4, Comparative Example 1 Diphenyl chlorophosphate (13 mmol)
N,N-dimethylformamide (DMF, 0-26 mmol) was added to a solution of pyridine (10 ml) and stirred at room temperature for 30 minutes. A solution of p-hydroxybenzoic acid (5 mmol) and syringic acid (5 mmol) in pyridine (20 ml) was added to this mixture.
The reaction was carried out for 3 hours in an oil bath at 120°C. After the reaction is complete,
By injection into methanol, the following ηinh (in p-chlorophenol, 0.5
%, measured at 50°C) was obtained. The results are shown in Table-1.

[Table] Examples 5 to 11 Example 1 except that DMF was 26 mmol and the ratio of p-oxybenzoic acid and syringic acid was changed.
By operating in the same manner as above, polymers of ηinh shown in Table 2 below were synthesized in quantitative yields.

[Table] Examples 12 to 15 Example 1 except that DMF was 26 mmol and the solvent for dissolving the monomer oxyacid was changed.
By operating in the same manner as above, a polymer having the following ηinh was obtained in quantitative yield. The results are shown in Table-3.

[Table] Example 16 The same procedure as in Example 1 was performed except that vanillic acid (5 mmol) was used instead of syringic acid (5 mmol) and DMF was changed to 26 mmol, and the quantitative yield was ηinh of 0.73. dl/g of polymer was obtained. Example 17 Diphenyl chlorophosphate (12 mmol)
DMF (5 mmol) was added to a solution of pyridine (10 ml), and the mixture was stirred at room temperature for 30 minutes. Add isophthalic acid (2.5 mmol) and terephthalic acid (2.5 mmol) to this mixture.
A solution of bisphenol A (5 mmol) in pyridine (10 ml) was added and heated at room temperature for 10 minutes, and then heated in an oil bath at 120°C for 10 minutes. The mixture was added dropwise and further heated in an oil bath at 120°C for 3 hours. After the reaction,
The reaction solution was poured into methanol and ηinh (phenol/1,1,2,2-tetrachloroethane, 3/
2 (weight ratio), 0.5%, measured at 30℃) is 0.84dl/
g of polymer was obtained in quantitative yield.

Claims (1)

[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 are hydrogen atoms, alkyl groups,
An amide compound represented by (representing an aryl group, an aralkyl group or a cycloalkyl group) or/and the general formula () (In the formula, R ⁴ represents an optionally branched alkylene group having 3 or more carbon atoms, and R ⁵ represents a hydrogen atom, an alkyl group,
Indicates an aryl group, an aralkyl group or a cycloalkyl group. ) and the general formula () (In the formula, R ⁶ and R ⁷ are an alkyl group, an aryl group,
represents an aralkyl group or a cyclohexyl group,
¹ represents a halogen atom), and then reacts the dicarboxylic acid with a diol or/and an oxyacid. Law.