JPH058215B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyesteramides or polyamides. In particular, it relates to the direct production of polyesteramides or polyamides, particularly aromatic polyesteramides or aromatic polyamides. It is generally considered difficult to directly synthesize aromatic polyesteramides and aromatic polyamides. However, although this is possible by using a phosphorus compound as a condensing agent, there is a drawback that the cost of the phosphorus compound used in this case is high. As a result of intensive studies to find an inexpensive condensing agent to replace phosphorus compounds, the present inventor found that polyesteramide and polyamide can be easily produced by using a sulfonyl compound represented by the general formula [] as a condensing agent. I discovered that. That is, the gist of the present invention is to produce polyesteramide or polyamide by polycondensation reaction of aromatic hydroxyamine and aromatic dicarboxylic acid or polycondensation reaction of aromatic diamine and aromatic dicarboxylic acid. (In the formula, R ¹ , R ² and R ³ are hydrogen atoms, alkyl groups,
amide compound or/and general formula (representing an aryl group, aralkyl group, or cycloalkyl group) [] (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,
aryl group, aralkyl group or cycloalkyl group) and ^the general formula [] ^{R 6} _−SO ² The present invention relates to a method for producing polyesteramide or polyamide using a mixture with a halogenated sulfonyl compound represented by (representing a halogen atom). To explain the present invention in detail, the dicarboxylic acid used in the present invention has the general formula [] HOOC-R ⁷ -COOH ... [] (wherein R ⁷ is a divalent aromatic group, -R ⁸ -X ² −R ⁹ − group,

[Formula] represents a group). Here, R ⁸ and R ⁹ 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, or an alkyl group) can be mentioned. 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, aromatic dicarboxylic acids such as 2,2-diphenylpropane-4,4'-dicarboxylic acid, 1,4-
Examples include, but are not limited to, aralkylene dicarboxylic acids such as xylylene dicarboxylic acid and 1,3-xylylene dicarboxylic acid. Moreover, these may be used as a mixture. As an organic compound having an amino group and an alcoholic or phenolic hydroxyl group in the molecule, the general formula [] (In the formula, R ¹⁰ is a divalent aromatic group,

[Formula] represents a group or a -R ¹² -X ³ -R ¹³ - group, and Y ⁹ to Y ¹² represent a hydrogen atom, a halogen atom, or an alkyl group. R ¹¹ represents a hydrogen atom, an aliphatic group or an aromatic group). Here, R ¹² and R ¹³ are divalent aromatic groups, and X ³ is an oxygen atom, a sulfur atom,
Sulfonyl group, carbonyl group, alkylene group, alkylidene group or none. As a divalent aromatic group,

[Formula] groups (Y ¹³ to ^{Y 16} represent a hydrogen atom, a halogen atom, or an alkyl group) are exemplified. Specific examples include 4-aminophenol, N-methyl 4-aminophenol, 4-amino-4'-hydroxydiphenyl, 3-aminophenol, N
-phenyl-3-aminophenol, 3-methyl-4-hydroxy-4'-amino-diphenyl,
3,5-dimethyl-4-hydroxy-4'-amino-diphenyl, 3-methyl-4-hydroxy-
3'-Methyl-4'-amino-diphenyl, 3-methyl-4-hydroxy-4'-aminodiphenyl ether, 3,5-dimethyl-4-hydroxy-4'-
Amino-diphenyl ether, 3-methyl-4-
Hydroxy-3'-methyl-4'-amino-diphenyl ether, 4-hydroxy-4'-amino-diphenyl ether, 3-methyl-4-hydroxy-
4'-amino-diphenyl sulfide, 3-methyl-4-hydroxy-4'-amino-diphenylmethane, 3,5-dimethyl-4-hydroxy-4'-
Amino-diphenylmethane, 2,2-(3-methyl-4-hydroxy-4'-amino-diphenyl)
-propane, 2,2'-(3,5-dimethyl-4-
hydroxy-4′-aminodiphenyl)-propane,
2,2-(3,5-dimethyl-4-hydroxy-
3'-Methyl-4'-amino-diphenyl)propane, 2,2-(3-isopropyl-4-hydroxy-4'-amino-diphenyl)-propane, 2,
2'-(3-tert-butyl-4-hydroxy-4'-amino-diphenyl)-propane, 2,2-(3-chloro-4-hydroxy-4'-amino-diphenyl)-propane, 2,2 -(3-methyl-4-hydroxy-4'-amino-diphenyl)-butane, 3,
3'-(3-Methyl-4-hydroxy-4'-amino-diphenyl)-pentane, 1,1-(3-methyl-4-hydroxy-4'-amino-diphenyl)cyclohexane, 2,2-(4 -Hydroxy-4'-
Aromatic hydroxyamines (aminophenols) such as amino-diphenyl)-propane and 1,
Examples include 4-xylylene amino alcohol and 1,3-xylylene amino alcohol. The diamine used to produce polyamide has the general formula [] H ₂ NR ¹⁴ -NH ₂ ... [] (In the formula, ¹⁴ is a divalent aromatic group or a divalent aliphatic group.

[Formula] (Y ¹⁷ to ^{Y 20} represent a hydrogen atom, a halogen atom, or an alkyl group), -R ¹⁵ -
X ⁴ −R ¹⁶ − group) where R ¹⁵ and R ¹⁶ are divalent aromatic groups,
X ⁴ is 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] (Y ²¹ and Y ²⁴ represent a hydrogen atom, a halogen atom, or an alkyl group). Specific examples include metaphenylenediamine, paraphenylenediamine, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfide. , 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenyl ketone, 1,5-diaminonaphthalene, 3,3'-dimethylbenzidine,
2,6-diaminonaphthalene, 4,4'-diaminodiphenyl ether, m-xylylenediamine,
Examples include p-xylylenediamine, which can be used alone or as a mixture. Moreover, any of the compounds of the general formula [] can be used, and is not limited to these specific examples. 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-diethylformamide, 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,
It is particularly preferable that R ² and R ³ are a hydrogen atom, an alkyl group or an aryl group. Also general formula []
From the viewpoint of cost, N-methyl 2-pyrrolidone is preferred as the compound represented by the formula. 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, p-toluenesulfonyl bromide, p-toluenesulfonyl iodide, p-toluenesulfonyl fluoride, Examples include benzylsulfonyl chloride. The amount of the amide compound used should be 1/50 mole or more per mole of dicarboxylic acid or aminocarboxylic acid, and the amount of the sulfonyl compound used should be 2 to 10 times the mole per mole of dicarboxylic acid or aminocarboxylic acid. , preferably 2 to 4 times the molar amount. For polymerization, it is appropriate to mix the amide compound and sulfonyl compound with a base alone or with a base and a solvent, and then mix and heat the monomers.
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,
-picoline, 3,5-lutidine, 3,4-lutidine, 2,4-lutidine, 2,6-lutidine, 2,
3-lutidine, 2,5-lutidine, 2,4,6-
Examples include 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-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, as additives for adjusting the solubility and swelling properties of the polymer produced during polymerization,
and very narrow molecular weight distribution polyesters with high degree of polymerization without the addition of alkali or alkaline earth metal halides such as LiCl, CaCl ₂ , MgCl ₂ , LiBr, etc. used as auxiliaries to increase the degree of polymerization can be easily obtained. 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. Example 1 N,N-dimethylformamide (DMF, 5 mmol) was added to a solution of p-toluenesulfonyl chloride (13 mmol) in pyridine (10 ml) and left under stirring at room temperature for 30 minutes. This solution was added to a solution of isophthalic acid (5 mmol) in pyridine (10 ml) at room temperature for 10 minutes, and then in an oil bath at 120°C for 10 minutes.
After heating for minutes, a solution of p-aminophenol (5 mmol) in pyridine (10 ml) was added and heated in a 120° C. oil bath for 3 hours. ηinh was 0.69 in quantitative yield by injecting the reaction solution into methanol.
dl/g of polyesteramide was obtained. In addition, the viscosity (ηinh) in Examples 1 to 9 was 30% in N-methylpyrrolidone (0.5%).
Measured in °C. Examples 2 and 3, Comparative Example 1 The following results were obtained by operating in the same manner as in Example 1 except that the amount of DMF was changed.

[Table] Example 4 A polymer with ηinh of 0.27 dl/g was obtained in quantitative yield by the same procedure as in Example 1 except that p-aminophenol was changed to m-aminophenol. Example 5 A polymer with ηinh of 0.95 dl/g was produced in the same manner as in Example 1 except that a mixture of isophthalic acid (2.5 mmol) and terephthalic acid (2.5 mmol) was used instead of isophthalic acid. Obtained. Example 6 The procedure was as in Example 1 except that a mixture of isophthalic acid (2.5 mmol) and terephthalic acid (2.5 mmol) was used instead of isophthalic acid and m-aminophenol was used instead of p-aminophenol. A polymer with a quantitative yield of ηinh of 0.40 dl/g was obtained. Example 7 A polymer with a quantitative yield of ηinh of 0.62 dl/g was obtained by the same procedure as in Example 1 except that N,N-diethylformamide was used instead of DMF. Examples 8 and 9 Polymers were obtained in quantitative yield in the same manner as in Example 1, except that the following compounds were used in place of p-toluenesulfonyl chloride.

[Table] Examples 10, 11 The following diamine was used instead of p-aminophenol, and after adding a pyridine solution of isophthalic acid, the diamine ( 5 mmol) and then heat to 100℃.
Example 1 except that the reaction was carried out for 3 hours in an oil bath of
The following polyamide was obtained in quantitative yield by operating in the same manner as above.

【table】

Claims (1)

[Claims] 1. In the production of polyesteramide or polyamide by the reaction of polycondensation of aromatic hydroxyamine and aromatic dicarboxylic acid or polycondensation of aromatic diamine and aromatic dicarboxylic acid, general formula [] (In the formula, R ¹ , R ² and R ³ are hydrogen atoms, alkyl groups,
amide compound or/and general formula (representing an aryl group, aralkyl group, or cycloalkyl group) [] (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 sulfonyl halides represented by ^the general formula ^{[ ]} R ⁶ −SO ₂ 1. A method for producing polyesteramide or polyamide, characterized by using a mixture with a compound.