JPH0530850B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing polyesteramide.

More specifically, it relates to a method for directly producing polyesteramide.

[Conventional technology]

Regarding polyesteramides, there are reports on interfacial polycondensation of aminophenol and carboxylic acid dihalide, melt polycondensation of solution polycondensed aminophenol diacetate and dicarboxylic acid, and melt polycondensation of aminophenol and diphenyl dicarboxylate. The present inventor also discovered that aminophenol and dicarboxylic acid can be directly polycondensed, and filed an application for the invention. (Japanese Unexamined Patent Publication No. 59-25821) [Purpose of the Invention] After that, as a result of further intensive studies on the production of polyesteramide, a method for easily producing polyesteramide having a structure different from the polyesteramide produced by the production method previously filed was developed. I found out.

That is, the gist of the present invention is a dicarboxylic acid represented by the general formula (A) HOOCR ¹ COOH - (A), a diol represented by the general formula (B) HOR ² OH - (B), a dicarboxylic acid represented by the general formula (C) Oxycarboxylic acid HOR ³ COOH ―(C), diamine represented by general formula (D) Aminocarboxylic acid represented by general formula (E) Hydroxyamine represented by general formula (F) [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁷ and R ⁹ are divalent aromatic groups, R ¹¹ -X ¹ -R ¹² groups, (However, R ¹¹ and R ¹²
is a divalent aromatic group, and X ¹ represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, an ester group, or a direct bond. ) represents a xylylene group or a divalent aliphatic group. (However, R ¹ ,
R ² , R ³ , R ⁴ , R ⁷ , R ⁹ , R ¹¹ , R ¹² and the hydrogen atoms of the aromatic ring of the xylylene group may be substituted with a halogen, a hydrocarbon group, an alkoxy group or a phenoxy group), and R ⁵ , R ⁶ , R ⁸ and R ¹⁰ represent a hydrogen atom, an aliphatic group or an aromatic group. ] In
Polyesteramide is produced by combining two or more components of general formulas (A), (B), (C), (D), (E) and (F) (excluding combinations of only A and F). For this, the general formula (G) (In the formula, R ¹¹ and R ¹² represent an aromatic group, an aliphatic group, or an aralkyl group, X ¹ represents a halogen atom, and Y ¹ , Y ² and Z ¹ represent an oxygen atom or a sulfur atom.) The present invention relates to a method for producing polyesteramide, characterized in that it is carried out using a phosphorus compound.

[Structure of the invention]

To explain the present invention in detail, any of the carboxylic acids represented by the general formula (A) can be used as the carboxylic acid used in the present invention, and specific examples include terephthalic acid, isophthalic acid, and naphthalic acid.
2,6-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, methylterephthalic acid, methylisophthalic acid,
diphenyl ether-4,4'-dicarboxylic acid, diphenyl thioether-4,4'-dicarboxylic acid,
Diphenylsulfone-4,4'-dicarboxylic acid, diphenylketone-4,4'-dicarboxylic acid, 2,2
- Aromatic dicarboxylic acids such as diphenylpropane-4,4'-dicarboxylic acid, aralkylene dicarboxylic acids such as 1,4-xylylene dicarboxylic acid and 1,3-xylylene dicarboxylic acid, malonic acid, and succinic acid. , chain aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, 1,4 cyclohexyl dicarboxylic acid, 1,3 cyclohexyl dicarboxylic 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.

Any of the diols represented by the general formula (B) can be used, but 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-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, 1,4-butanediol, 1,4-cyclohexanediol, 1,6-hexamethylenediol, 1,4-cyclohexanedimethanol, xylidene-1,4-diol , 1,3-cyclohexanediol, etc., but are not necessarily limited to these. Moreover, these may be used as a mixture.

As the oxycarboxylic acid, any of those represented by the general formula (C) can be used, and specific examples thereof include p-hydroxybenzoic acid, m-hydroxybenzoic acid, Schulinger's acid, vanillic acid, and 4-hydroxy-4' -carboxydiphenyl ether, 4
-Hydroxy-4'-carboxybiphenyl, 2,
6-dichloro-p-hydroxybenzoic acid, 2-chloro-p-hydroxybenzoic acid, 2,6-difluoro-p-hydroxybenzoic acid, 2-hydroxy 6-naphthoic acid, 2-hydroxy 3-naphthoic acid, 1- Examples include hydroxy 4-naphthoic acid, 4-hydroxylcyclohexanecarboxylic acid, 3-hydroxycyclohexanecarboxylic acid, β-hydroxyethyl acetic acid, and ω-hydroxycaproic acid, but a mixture of these may be used.

Any diamine represented by the general formula (D) can be used, and specific examples include metaphenylenediamine, paraphenylenediamine, 2,2-bis(4-aminophenyl)propane, 4,4 '-Diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfide,
4,4'-diaminodiphenylsulfone, 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,
Examples include m-xylylene diamine, p-xylylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, 2,2-dimethylpropylene diamine, 1,4-diaminocyclohexane, etc., and these can be used alone or as a mixture. You can.

As the aminocarboxylic acid, any of those represented by the general formula (E) can be used, and specific examples include glycine, glycylglycine, alanine, phenylalanine, α-aminobutyric acid, valine, leucine, isoleucine, α- Aminoenanthic acid, α-
Aminocaprylic acid, α-aminoundecanoic acid, α
-aminostearic acid, α-aminocerotic acid,
α-aminomeric acid, β-alanine, β-aminobutyric acid, γ-aminovaleric acid, ω-aminoenanthic acid, 4-aminocyclohexanecarboxylic acid, m-
Aminobenzoic acid, p-aminobenzoic acid, p-(4
-aminophenyl)benzoic acid, p-(4-aminobenzyl)benzoic acid, and the like.
Moreover, these may be used in combination.

As the hydroxyamine, any of those represented by the general formula (F) can be used, and specific examples thereof 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' -Amino-
Aromatic hydroxyamines (aminophenols) such as diphenyl)-propane; ethanolamine,
3-amino-n-propanol, N-methylethanolamine, 3-aminoisobutanol, 8-
Aliphatic hydroxyamines such as amino-n-octanol, p-amino-n-nonanol and 1,4-xylylene amino alcohols, 1,3
-xylylene amino alcohol, etc., but it is preferable to use aromatic hydroxyamine (aminophenol). Moreover, these may be used in combination.

As the phosphorus compound used in the present invention, a phosphorus compound represented by general formula (G) is used. In this general formula (G), an aryl group is generally used as the aromatic group, and an alkyl group or a cycloalkyl group is generally used as the aliphatic group.

Specific examples thereof include diphenyl chlorofusphate, dinonylphenyl chlorofusphate, dibenzyl chlorofusphate, dibutyl chlorofusphate, dicyclohexyl chlorofusphate, dihexyl chlorofusphate, and dioctyl chlorofusphate. Phate, didodecyl chlorophosphate, diphenylbromophosphate, diphenyl fluorophosphate, phenylbutyl chlorophosphate, benzyl octyl chlorophosphate, diphenyl chlorothiophosphate, dinonilph Examples include enylchlorothiophosphate and dibenzylchlorothiophosphate, and any of those represented by the general formula (G) can be used, or they may be used in combination.

As the solvent used in the present invention, it is preferable to use a base or a combination of a base and another solvent. Such bases include, for example, pyridine, α-
Picoline, β-picoline, γ-picoline, 3,5
-lutidine, 3,4-lutidine, 2,4-lutidine, 2,6-lutidine, 2,3-lutidine, 2,
Examples include 5-lutidine, 2,4,6-collidine, quinoline, isoquinoline, dimethylaniline, etc., but any tertiary amine can be used.

Other solvents include chlorobenzene, o-dichlorobenzene, carbon tetrachloride, dichloromethane,
Chlorinated solvents such as tetrachloroethane, dimethylformamide, dimethyl-acetamide, N-
Examples include polar solvents such as methylpyrrolidone, γ-butyrolactone, dimethylsulfoxide, sulfolane, and hexamethylphosphoramide, and aromatic hydrocarbons such as benzene, toluene, and xylene.

As mentioned above, polyesteramide can be obtained by allowing the phosphorus compound to exist in the reaction system, but if an alkali or alkaline earth metal halide, or a mixture thereof, is further present in the reaction system during polymerization, , is more preferable since it is easy to obtain a high polymer.

Specific examples of alkali and alkaline earth halides used in the reaction include lithium chloride, lithium bromide, lithium iodide, calcium chloride, magnesium chloride, rubidium chloride, strontium chloride, etc.; If so, you can use either one.

In the present invention, a phosphorus compound and an alkali metal halide or an alkaline earth metal halide are dissolved in a solvent, and the general formulas (A), (B), (C), (D), (E) are
A compound selected from All known polymerization methods used in polycondensation reactions using solvents can be used, such as a method in which a compound having an acid group is brought into contact in a solvent in advance and a solution of a compound having a hydroxyl group and an amino group is added thereto. . Moreover, the above-mentioned alkali metal halide or alkaline earth halide does not necessarily have to be present. The amount of the phosphorus compound to be used is selected from a range of 1 to 20 equivalents of phosphorus per 1 equivalent of ester bond and 1 equivalent of amide bond to be produced.

Polycondensation temperature varies depending on the solvent, but is usually 80~
A temperature of about 200°C, preferably about 100 to 120°C is employed.

The system during polymerization varies depending on the combination of monomers used, such as homogeneous system, precipitation system, gel-like system, and types of solvents and additives. This can be carried out by reprecipitation in a solvent, reprecipitation with water alone, washing, etc.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention is not particularly limited to the examples unless it goes beyond the gist of the present invention.

Example 1 Diphenylchlorophosphate (DPCP)
Mixtures (10 mmol) of p-aminobenzoic acid (PAB) and syringic acid (SGA) with various compositions were prepared by preheating a solution of pyridine (10 mL) containing (13 mmol) and lithium chloride (10 mmol) at 120°C for 5 minutes. (20 mL) after dropping into the solution over a period of 30 minutes.
After heating at 120°C for 3 hours, the reaction solution was diluted with pyridine and poured into methanol to obtain a polymer powder with a quantitative yield and logarithmic viscosity (ηinh) shown in Table 1.

Table 1 PAB (mol%) ηinh ^a) 100 0.26 ^b) 90 0.46 80 1.37 70 2.33 60 3.44 50 4.17 40 2.17 ^c) 30 2.83 ^c) 10 1.42 ^c) 0 0.36 ^c) a) 0.5% concentration, 5% LiCl b) 0.5% concentration in concentrated sulfuric acid, measured at 30°C c) 0.5% concentration in p-chlorophenol, 50
Measurement at °C Example 2 The results shown in Table 2 were obtained in the same manner as in Example 1 except that various oxycarboxylic acids were used instead of SGA. ηinh was measured at 30°C at a concentration of 0.5% by weight in DMAc (containing 5% by weight of LiCl) Table 2 Oxycarboxylic acids (mol%) ηinh p-oxybenzoic acid (40) 0.37 m-oxybenzoic acid ( 50) 0.54 〃 (60) 0.44 p-hydroxycinnamic acid (40) 1.39 Vanillic acid (50) 1.13 Example 3 Isophthalic acid (2.5 mmol), terephthalic acid (2.5 mmol), bisphenol A instead of PAB and SGA A polymer with ηinh=0.62 was obtained in quantitative yield in the same manner as in Example 1 except that 4,4'-oxydianiline (4.0 mmol) and 4,4'-oxydianiline (1.0 mmol) were used. ηinh was measured at 30°C in phenol/sym-tetrachloroethane (6/4, weight ratio).

Example 4 A solution of isophthalic acid (2.5 mmol) and terephthalic acid (2.5 mmol) in pyridine (10 mL) to a solution of DPCP (13 mmol) and LiCl (10 mmol) in pyridine (10 mL)
After adding the solution and heating and stirring at room temperature for 20 minutes and then at 120°C for 10 minutes, a solution of bisphenol A (4.0 mmol) and 4,4'-oxydianiline (1.0 mmol) in pyridine (10 mL) was added over 10 minutes. and dripped it. The reaction solution was further heated at 120°C for 3 hours to give ηinh=1.17 (phenol/sym-tetrachloroethane=6/4,
(weight ratio) measured at 30°C) was obtained in quantitative yield.

Example 5 A reaction was carried out in the same manner as in Example 3 except that methylhydroquinone was used instead of bisphenol A, and ηinh
=1.15 polymer was obtained.

Example 6 A reaction was carried out in the same manner as in Example 4 except that methylhydroquinone was used instead of bisphenol A, and ηinh
=1.2 polymer was obtained.

〔Effect of the invention〕

The polyester amide obtained according to the present invention is useful as a high-rigidity polymer and a heat-resistant polymer,
It also has great industrial value.

Claims (1)

[Claims] 1 Dicarboxylic acid represented by the general formula (A), HOOCR ¹ COOH - (A) diol represented by the general formula (B), HOR ² OH - (B) a diol represented by the general formula (C) Oxycarboxylic acid, HOR ³ COOH - (C) Diamine represented by general formula (D), Aminocarboxylic acid represented by general formula (E), Hydroxyamine represented by general formula (F), [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁷ and R ⁹ are divalent aromatic groups, R ¹¹ -X ¹ -R ¹² groups, (However, R ¹¹ and R ¹²
is a divalent aromatic group, and X ¹ represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, an ester group, or a direct bond. ) represents a xylylene group or a divalent aliphatic group. (However, R ¹ ,
R ² , R ³ , R ⁴ , R ⁷ , R ⁹ , R ¹¹ , R ¹² and the hydrogen atoms of the aromatic ring of the xylylene group may be substituted with a halogen, a hydrocarbon group, an alkoxy group or a phenoxy group), and R ⁵ , R ⁶ , R ⁸ and R ¹⁰ represent a hydrogen atom, an aliphatic group or an aromatic group. ] In which two or more components of general formulas (A), (B), (C), (D), (E) and (F) are combined (excluding combinations of only A and F) to produce polyesteramide. In doing so, the general formula (G) (In the formula, R ¹¹ and R ¹² represent an aromatic group, an aliphatic group, or an aralkyl group, X ¹ represents a halogen atom, and Y ¹ , Y ² and Z ¹ represent an oxygen atom or a sulfur atom.) 1. A method for producing an aromatic polyester amide, characterized in that the method is carried out using a phosphorus compound.