JPH0562128B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a terpolymerized polyester and a method for producing the same, particularly a direct method for producing the same. [Prior Art] In recent years, there has been an increasing demand for materials with excellent rigidity, heat resistance, and chemical resistance, regardless of whether they are fibers, films, or molded products. It is known that aromatic polyester is a heat-resistant polymer or a highly rigid polymer. However, as a heat-resistant polyester, it has been well known for a long time to produce an aromatic polyester by an interfacial polycondensation method by mixing an organic solvent solution of a mixture of terephthalic acid dichloride and isophthalic acid dichloride with an alkaline aqueous solution of bisphenol A. However, the obtained polyester does not necessarily have sufficient heat resistance. On the other hand, as a highly rigid polyester, a thermoliquid crystalline polymer manufactured using polyethylene terephthalate and acetoxybenzoic acid is well known, but from the viewpoint of heat resistance, the heat distortion temperature is low.
The temperature is 70-80°C, which is not preferable. [Object of the present invention] In view of such drawbacks, the inventors of the present invention conducted intensive studies to find a polyester that is inexpensive and has good heat resistance, and a liquid crystalline polyester that is inexpensive and has heat resistance and high rigidity. We have discovered that a ternary copolycondensate consisting of a group carboxylic acid, an aromatic diol, and an aromatic oxycarboxylic acid has such properties, and have discovered an advantageous manufacturing method for obtaining the terpolymer, and have disclosed the present invention. The invention has been achieved. [Problems to be solved by the invention] That is, the gist of the present invention is to solve the problems of general formulas (A), (B) and (C). -O-R ² -O- -(B) [In the formula, R ¹ , R ² and R ³ are divalent aromatic groups, R ⁴
-X ¹ -R ⁵ group (However, R ⁴ and R ⁵ are divalent aromatic groups, and X ¹ is an oxygen atom, sulfur atom, sulfonyl group, carbonyl group, alkylene group, alkylidene group, ester group, or (indicates a bond, and the hydrogen atoms of the aromatic rings of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be substituted with halogen, hydrocarbon group, alkoxy group or phenoxy group)] Consisting of structural units, the composition ratio of which is general formula (A): general formula (B) = 45:55 to 55:45 (molar ratio), general formula (A): general formula (C) = 5:59 to 95:5 (molar ratio) and 50 at 0.5 g/dl in p-chlorophenol.
In producing an aromatic polyester copolymer whose logarithmic viscosity (ηinh) measured at ℃ is 0.1 dl/g or more, an aromatic dicarboxylic acid represented by the general formula (D) HOOCR ⁶ COOH −(D) general formula ( Aromatic diol represented by E) HOR ⁷ OH −(E) Aromatic oxycarboxylic acid represented by general formula (F) HOR ⁸ COOH −(F) [Formula R ⁶ , R ⁷ and R ⁸ are divalent aromatic Group group, R ⁹ −X ²
-R ¹⁰ group (however, R ⁹ and R ¹⁰ are divalent aromatic groups, X ² is an oxygen atom, a sulfur atom, a sulfonyl group,
Represents a carbonyl group, alkylene group, alkylidene group or ester group, and the hydrogen atoms of the aromatic rings of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are substituted with halogen, hydrocarbon group, alkoxy group, or phenoxy group The general formula for the ternary copolycondensation of
(D): General formula (E) = 45:55 to 55:45 (mole ratio), general formula
(D): General formula (F) = 5:95 to 95:5 (mole ratio) and as a condensing agent Formula (G) The present invention relates to a method for producing an aromatic polyester copolymer, characterized in that the method is carried out using a phosphorus compound represented by: Incidentally, such direct polycondensation of an aromatic dicarboxylic acid, an aromatic diol, and an aromatic oxycarboxylic acid in a tertiary system has not been known at all to date. Next, to explain the present invention in detail, specific examples of the aromatic dicarboxylic acid represented by the general formula (D) used in the present invention 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, diphenylthioether-4,4'-
Dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenylketone-4,4'-dicarboxylic acid, 2,2-diphenylpropane-4,4'-
Examples include dicarboxylic acid and diphenyl-4,4'-dicarboxylic acid, but any aromatic dicarboxylic acid represented by the general formula (D) can be used, or a mixture of these may be used. . Further, specific examples of the aromatic diol represented by the general formula (E) 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
-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, 4,4'-dihydroxydiphenyl, etc., but are not necessarily limited to these. Moreover, these may be used as a mixture. Specific examples of the aromatic oxycarboxylic acid represented by the general formula (F) used in the present invention include p-hydroxybenzoic acid, m-hydroxybenzoic acid, syringic acid, baryric acid, 4-hydroxy-4'-carboxylic acid, diphenyl ether, 4-hydroxy-
4'-Carboxybiphenyl, 2,6-dichloro-
p-hydroxybenzoic acid, 2-chloro-p-hydroxybenzoic acid, 2,6-difluoro-p-hydroxybenzoic acid, salicylic acid, 2-hydroxybenzoic acid
-naphthoic acid, 2-hydroxy-3-naphthoic acid,
Examples include 1-hydroxy-5-naphthoic acid, but any aromatic oxycarboxylic acid represented by the general formula (E) can be used, or a mixture thereof may be used. In the present invention, the compounds represented by the general formulas (D), (E), and (F) are used in a molar ratio of (D):(E) of 45:55 to 55:45.
and (D):(F) in a molar ratio of 5:95 to 95:5.
Use at a ratio of The ternary polycondensation reaction of these compounds is carried out in a solvent, but in the present invention, it is necessary to have diphenylchlorophosphate, which is a phosphorus compound represented by formula (G), in the reaction system as a condensing agent. be. By the presence of such a phosphorus compound, the polycondensation reaction of the three component compounds can be promoted, and an excellent polyester terpolymer can be directly obtained in one step of the reaction. 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-
Chlorinated solvents such as dichlorobenzene, carbon tetrachloride, dichloromethane, tetrachloroethane, dimethylformamide, dimethylacetamide, N
Examples include polar solvents such as -methylpyrrolide, γ-butyrolactone, dimethylsulfoxide, sulfolane, and hexamethylphosphoramide, and aromatic hydrocarbons such as benzene, toluene, and xylene. As mentioned above, by making the phosphorus compound exist in the reaction system, the compounds represented by the general formulas (A), (B), and (C) can be copolycondensed, but during polymerization, the amide compound, Or, if an alkali or alkaline earth metal halide, or a mixture thereof is further present in the reaction system,
It is more preferred since it is easy to obtain a high polymer. When an amide compound is present in the present invention,
General formula (H) (wherein R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a cycloalkyl group) or/and the general formula (I) (In the formula, R ¹⁶ represents an optionally branched alkylene group having 3 or more carbon atoms, and R ¹⁷ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group.) Specific examples include N,N-dimethylformamide, N,N-diethylformamide, N,N-dibutylformamide, N-methylformamide, formamide,
N,N-dimethylacetamide, N,N-diethylacetamide, N-methylacetamide, acetanilide, N,N-diphenylformamide,
In the general formula (H), R ¹³ , R ¹⁴ and R ¹⁵ are hydrogen atoms, alkyl groups and aryl groups, such as benzoylamide, N,N-dimethylbenzoylamide, N-methylbenzoylamide and NN-diethylacetamide. Particularly preferred. Also, as a compound represented by general formula (I), N-methyl-2-
Pyrrolidone is preferred from the viewpoint of cost. 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, and strontium chloride. If so, you can use either one. Among them, it is preferable to use lithium bromide, lithium, and idodide because a polymer with a high degree of polymerization can be obtained. When polymerizing using such an alkali or alkaline earth metal halide, a base alone or a base and another solvent may be combined with a phosphorus compound represented by formula (G) and an alkali or alkaline earth metal halide. When dropped into a solution consisting of an aromatic dicarboxylic acid, an aromatic diol, an aromatic oxycarboxylic acid, and a base, or a solution consisting of a base and another solvent, it becomes a polymer with a very high degree of polymerization. is obtained. In addition, when an amide compound is present, a mixture of an aromatic dicarboxylic acid, an aromatic diol, and an aromatic oxycarboxylic acid is added to a solution containing an amide compound, a phosphorus compound, a base, or a solvent in addition to the base. Compound,
It is preferable to dissolve it in at least one solvent selected from and other solvents and add this at once. In the former case, a reaction signal is generated by forming a complex between an alkali or alkaline earth metal halide, a phosphorus compound, and a base, and in the latter case, a Vilsmeier complex is generated from an amide compound and a phosphorus compound. It is presumed that the reaction is progressing. 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, 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. [Effects of the Invention] According to the method of the present invention, the structural unit consisting of the structural units represented by the general formulas (A), (B) and (C), and the general formula (A):
(B) has a molar ratio of 45:55 to 55:45, general formula (A):(C) has a molar ratio of 5:95 to 95:5, and p-chlorophenol Medium 0.50.5g/dl
It is possible to easily obtain an excellent aromatic polyester terpolymer having heat resistance or heat resistance and high rigidity, the logarithmic viscosity (ηinh) measured at 50° C. being 0.1 dl/g or more. Furthermore, the method of the present invention can directly obtain an excellent polyester terpolymer, so it can be produced at low cost and is an industrially advantageous method. Hereinafter, the present invention will be explained in detail with reference to Examples. Example 1 DMF (5 mL) was added to a solution of diphenylchlorophosphate (12 mmol) in pyridine (10 mL), and the mixture was stirred at room temperature for 30 minutes. Isophthalic acid (2.5 mmol) and bisphenol A (2.5 mmol) were added to this mixture.
mol) and p-hydroxybenzoic acid (5 m
A solution of pyridine (20 mL) in which mol) was dissolved was added, and the mixture was reacted for 3 hours in an oil bath at 120°C. The reaction solution was poured into methanol to obtain a polymer with a quantitative yield of ηinh (0.5% in p-chlorophenol, measured at 50°C) of 0.60 dl/g. Examples 2 to 5 The following results were obtained in the same manner as in Example 1, except that the dicarboxylic acid, diol, and oxycarboxylic acid were changed as shown below.

[Table] Measurement.
Example 6 Diphenyl chlorophosphate (13 mmol) was added to a solution of lithium bromide (10 mmol) in pyridine (20 mL), and the mixture was stirred at room temperature for 30 minutes. This solution was added dropwise over 30 minutes to a solution of isophthalic acid (2.5 mmol), bisphenol A (2.5 mmol) and p-oxybenzoic acid (5 mmol) in pyridine (10 mL) which had been heated in advance at 120°C.
The reaction was carried out in an oil bath at ℃ for 3 hours. In the same manner as in Example 1, a polymer with ηinh of 0.64 dl/g was obtained in quantitative yield. Examples 7 to 11 The following results were obtained in the same manner as in Example 6, except that the dicarboxylic acid, diol, and oxycarboxylic acid were changed as shown below.

[Table] Measurement.

Claims (1)

[Claims] 1 General formulas (A), (B) and (C) -O-R ² -O- -(B) [In the formula, R ¹ , R ² and R ³ are divalent aromatic groups, R ⁴
-X ¹ -R ⁵ group (However, R ⁴ and R ⁵ are divalent aromatic groups, and X ¹ is an oxygen atom, sulfur atom, sulfonyl group, carbonyl group, alkylene group, alkylidene group, ester group, or (indicates a bond, and the hydrogen atoms of the aromatic rings of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be substituted with halogen, hydrocarbon group, alkoxy group or phenoxy group)] Consisting of structural units, the composition ratio of which is general formula (A): general formula (B) = 45:55 to 55:45 (molar ratio), general formula (A): general formula (C) = 5:95 to 95:5 (molar ratio) and 50 at 0.5 g/dl in p-chlorophenol.
In producing an aromatic polyester copolymer whose logarithmic viscosity (ηinh) measured at ℃ is 0.1 dl/g or more, an aromatic carboxylic acid represented by the general formula (D) HOOCR ⁶ COOH −(D) general formula ( Aromatic diol represented by E) HOR ⁷ OH −(E) Aromatic oxycarboxylic acid represented by general formula (F) HOR ⁸ COOH −(F) [Formula R ⁶ , R ⁷ and R ⁸ are divalent aromatic Group group, R ⁹ −X ²
-R ¹⁰ group (however, R ⁹ and R ¹⁰ are divalent aromatic groups, X ² is an oxygen atom, a sulfur atom, a sulfonyl group,
Represents a carbonyl group, alkylene group, alkylidene group or ester group, and the hydrogen atoms of the aromatic rings of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are substituted with halogen, hydrocarbon group, alkoxy group, or phenoxy group The general formula for the ternary copolycondensation of
(D): General formula (E) = 45:55 to 55:45 (mole ratio), general formula
(D): General formula (F) = 5:95 to 95:5 (mole ratio) and as a condensing agent Formula A method for producing an aromatic polyester copolymer, characterized in that the method is carried out using a phosphorus compound represented by: