JPH0379374B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyesteramide. More specifically, it relates to a method for directly producing polyesteramide. For polyesteramides, there are reports of interfacial or solution polycondensation of aminophenol with dicarboxylic acid dihalide, melt polycondensation of aminophenol diacetate and dicarboxylic acid, and melt polycondensation of aminophenol and dicarboxylic acid diphenyl ester. However, there is no known method for producing polyesteramide by directly reacting aminophenol and dicarboxylic acid. As a result of extensive research, the present inventors have discovered a method for producing polyesteramide by directly reacting aminophenol or aminoalcohol with dicarboxylic acid. The gist of the present invention is to produce a polyesteramide by polycondensing an organic compound having an amino group and an alcoholic or phenolic hydroxyl group in the molecule with a dicarboxylic acid having a benzene ring in the molecule. General formula during reaction

The present invention relates to a method for producing a polyesteramide, which is characterized by the presence of a phosphorus compound represented by the formula: (wherein R ¹ represents an aryl group). To explain the present invention in detail, as an organic compound having an amino group and an alcoholic or phenolic hydroxyl group in the molecule, the general formula

[Formula] (wherein R ² is a divalent aromatic group, a divalent aliphatic group,

[Formula] represents a group or a −R ⁴ −X ² − R ⁵ − group, where R ³ is a hydrogen atom, an aliphatic group, or
Examples include compounds represented by (representing an aromatic group). Here, R ⁴ and R ⁵ are a divalent aliphatic group or a divalent aromatic group, and X ² is 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] (Y ¹ to ^{Y 4} represent a hydrogen atom, a halogen atom, or an alkyl group). 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, 3,5-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-diphenyl)
- Aromatic hydroxyamines (aminophenols) such as propane; ethanolamine, 3-amino-n-propanol, N-methylethanolamine, 3-aminoisobutanol, 8-amino-n
- aliphatic hydroxyamines such as octanol, q-amino-n-nonanol and 1,4-
Examples include xylylene amino alcohol and 1,3-xylene amino alcohol, but it is preferable to use aromatic hydroxyamine (aminophthanol). A carboxylic acid having a benzene ring in the molecule has the general formula HOOCR ⁶ COOH (where R ⁶ is a divalent aromatic group,

[Formula] group or -R ⁷ -X ³ -R ⁸ - group) is mentioned. Here, R ⁷ and R ⁸ are divalent aromatic groups, and X ³ is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, or an alkylidene group. As a divalent aromatic group, R ⁴
and the same aromatic group as R ⁵ are exemplified. 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-xylylene dicarboxylic acid, 1,3-xylylene dicarboxylic acid, and the like. As the phosphorus compound used in the present invention, any compound represented by the general formula shown above can be used. Specific examples include diphenyl chlorophosphate, dinonylphenyl chlorophosphate,
Dibenzyl chlorophosphate, dibutyl chlorophosphate, dicyclohexyl chlorophosphate, dihexyl chlorophosphate,
Examples include dioctyl chlorophosphate, didodecyl chlorophosphate, diphenyl bromophosphate, diphenylfluorophosphate, and the like, but phosphates containing a chlorine atom as a halogen atom are preferred. 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. During polymerization, it may be sufficient to simply mix and heat the two types of monomers and the phosphorus compound, but generally it is appropriate to heat the monomer and the phosphorus compound in a polar organic solvent or a base, and for this purpose Solvents used include o-dichlorobenzene, chloroform, chlorobenzene, carbon tetrachloride, dichloromethane, chlorinated solvents such as tetrachloroethane, N-methylpyrrolidone, dimethylacetamide, δ-butyrolactone, dimethyl Polar organic solvents such as sulfoxide, sulfolane, hexamethylphosphoramide, aromatic hydrocarbons such as benzene, toluene, xylene, bases such as pyridine, 2-methylimidazole, N-methylimidazole triethylamine, quinoline, isoquinoline, etc. can be mentioned. Moreover, these can also be used in combination with a solvent such as N-methylpyrrolidone. In many cases, it is preferable to add additives to adjust the solubility and swelling properties of the polymer produced during polymerization, and auxiliary agents to increase the degree of polymerization.
By adding alkali or alkaline earth metal halides, such as LiCl, CaCl ₂ , MgCl ₂ , LiBr, etc., polyesteramides with a high degree of polymerization can be obtained. Polymerization is carried out in the above-mentioned system by heating and stirring at a temperature above room temperature and below 200°C, preferably between 80°C and above 120°C. 1-20% by weight
is appropriate. 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. Example 1 Isophthalic acid (5 mmol, 0.831 g) and chlorophosphate diphenyl ester (12 mmol, 3.22 g)
Lithium chloride (10ml) is added to a solution of pyridine (10ml).
mol, 0.42 g) and p-aminophenol (5 m
Pyridine solution (15 ml) in which mol, 0.55 g) was dissolved.
After heating at a constant temperature for a certain period of time, the reaction solution was poured into methanol and the precipitated polymer was pulverized, thoroughly washed with methanol, separated and dried to obtain the results shown in Table 1. The yield was almost quantitative, and the logarithmic viscosity (ηinh) was measured at 30°C in a 0.5wt% N-methylpyrrolidone solution as a measure of the molecular weight of the produced polymer.

[Table] Example 2 Example 1 except that the amount of lithium chloride was changed
In the same manner as above, the reaction was carried out at 120°C for 4 hours, and the quantitative yields shown in Table 2 were obtained. Table 2 LiCl (mmol) ηinh (dl/g) 0 0.20 1.0 0.55 1.5 0.74 2.0 0.80 3.0 0.11 Example 3 Same as Example 1 except that the amount of chlorophosphate diphenyl ester was changed, 120°C, 4 After a time reaction, quantitative yields as shown in Table 3 were obtained. Table 3 Diphenyl chlorophosphate ηinh (dl/g) Ester (mmol) 11 0.16 12 0.80 13 0.72

Claims (1)

[Scope of Claims] 1. When producing polyesteramide by polycondensing an organic compound having an amino group and an alcoholic or phenolic hydroxyl group in the molecule and a dicarboxylic acid having a benzene ring in the molecule,
A method for producing polyesteramide, which comprises causing a phosphorus compound represented by the general formula [Formula] (wherein R ¹ represents an aryl group) to be present during the polycondensation reaction.