JPH0333175B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to an aromatic polyester amide and a method for producing the same, and more particularly to a novel aromatic polyester amide with excellent solubility, processability, and heat resistance, and a method for producing the same. [Technical background of the invention and its problems] Aromatic polyesters and aromatic polyamides have been known as engineering plastics. The former has low hygroscopicity and excellent moist heat properties, but has poor thermal stability and is difficult to mold.
Furthermore, it has the disadvantage of being susceptible to hydrolysis. Although the latter has excellent heat resistance, it is generally highly hygroscopic and has a high melting point, making it extremely difficult to mold. Therefore, in order to eliminate the drawbacks of aromatic polyester and aromatic polyamide and to obtain a polymer that combines the excellent properties of both, research has been carried out on aromatic polyester amide having ester bonds and amide bonds in the same molecule. I was able to proceed. As a result of this research, for example, in Japanese Patent Publication No. 39-26012, 2,2-bis(4'-hydroxyphenyl)propane, hexamethylene diamine and phthalic acid dichloride (isophthalic acid dichloride: terphthalic acid dichloride = 50:50) A method for obtaining aromatic polyesteramides is disclosed. Although this polymer had a softening temperature of 228 to 236°C, its thermal stability at high temperatures was poor and unsatisfactory. Special Public Service 1977
-19237 publication discloses that an aromatic polyester amide is obtained from 2,2-bis(4'-hydroxyphenyl)propane, 2,2-bis(4'-aminophenyl)propane, and terephthaloyl chloride by an interfacial polymerization method. Although the second-order rearrangement temperature of this polymer is 262°C, the decomposition temperature is as low as 350°C or higher, and it also has the disadvantage of being poorly soluble in many organic solvents. Furthermore, in Japanese Patent Publication No. 54-20555, isophthalic acid chloride,
A method for obtaining an aromatic polyesteramide from 4-amino-4'-hydroxydiphenyl ether and 4,4'-diaminodiphenyl ether is disclosed, but this polymer has a low degree of polymerization and a high decomposition temperature.
The temperature was as low as 365℃. As described above, conventional aromatic polyesteramides have various drawbacks, are still unsatisfactory as heat-resistant polymers, and have not yet been put into practical use industrially. [Object of the invention] The object of the present invention is to eliminate such drawbacks and improve solubility,
An object of the present invention is to provide a novel aromatic polyesteramide, which is a high molecular weight polymer with excellent processability and heat resistance, and a method for producing the same. [Summary of the invention] The present invention has the following formula: Structural unit denoted by (), formula: Structural unit represented by () and formula: A structural unit represented by (), (wherein R ₁ to R ₁₂ may be the same or different, and each represents a hydrogen atom, a halogen atom,
Nitro group, phenyl group, cyano group, carbon number 1-5
represents an alkyl group or an alkoxy group having 1 to 5 carbon atoms; R ₁₃ and R ₁₄ may be the same or different, and each represents a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms;
5 represents an alkyl group; Z ₁ to _{Z 3} may be the same or different, and each represents a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a cycloalkylene having 5 to 15 carbon atoms; (n ₁ represents 0 or 1, n ₂ represents 0, 1 or 2) an aromatic polyester amide in which each unit is connected by an amide bond and/or an ester bond, wherein the molar ratio of the sum of formula () and formula () to formula () is 1:1.1 to 1.1: 1. The molar ratio of formula () to formula () is 99:1 to 1:
99 and a weight average molecular weight of 2000 or more, and a method for producing the same. In the substituents R ₁ to _{R 14} in the aromatic polyesteramide of the present invention, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and the alkyl having 1 to 5 carbon atoms is a methyl group, an ethyl group. , propyl group, isopropyl group, butyl group,
Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a tert-butoxy group, and a pentoxy group. In the substituents _Z1 to _Z3 , the cycloalkylene group having 5 to 15 carbon atoms refers to a cyclopentylene group, a cyclohexylene group, a cycloheptalene group, a cyclooctylene group, a cyclononylene group, a cyclodecarylene group, and a cycloundecarylene group. , cyclotridecarylene group, cyclotetradecarylene group, cyclopentadecarylene group, etc., and the alkylene group having 1 to 7 carbon atoms includes methylene group, ethylene group, propylene group, butylene group, amylene group, hexylene group,
Pentamethylene group or 1-methylhexamethylene group, etc., and alkylidene groups having 2 to 7 carbon atoms include ethylidene group, isoethylidene group, propylidene group, butylidene group, pentylidene group, hexylidene group, heptylidene group, isoethylidene group. ,
These include isopropylidene group, isobutylidene group, isopentylidene group, isohexylidene group, and isoheptylidene group, and alkenylene groups having 2 to 7 carbon atoms include menylene group, propenylene group, 1-butenylene group, 2-butenylene group, 1-methyl -2-
These include butenylene group, 1,1-dimethyl-2-butenylene group, 1-methylene-3,3-dimethylpropylene group, 3-methyl-3-ethylpropylene group, and 2-methyl-2-butenylene group. The aromatic polyester amide of the present invention has a polymerization degree of 3 or more, preferably 7 or more.
Further, the weight average molecular weight is 2000 or more, preferably 4000 or more. Note that the present invention can include various structures depending on the composition of the raw materials used and the manufacturing method, and the reactivity of the compounds used as reaction raw materials. Examples include polymers, random copolymers, and combinations of these polymers, and depending on the combination of raw material compositions described below, the molar ratio of the sum of formula () and formula () to formula () is 1:1.1. ~1.1:1,
The molar ratio of formula () to formula () is 99:1 ~
The range is 1:99. Depending on the specific structure of the present invention, various solvents such as methylene chloride, chlorobenzene, chloroform, tetrahydrofuran, cyclohexanone, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N dimethylacetamide, sulfolane, etc. , hexamethylphosphoramide or pyridine, etc., and has an improved softening temperature.
It has a high decomposition temperature of 400℃. In addition, it has excellent compatibility with other resins and miscibility with various fillers,
It has characteristics such as easy molding. Therefore, the present invention takes advantage of such properties to process processes such as varnish formation, film formation by casting from a solution, extrusion molding, injection molding, compression molding, fiber formation, paper manufacturing, and sheet formation as a solution or melt. It has a wide range of industrial uses, such as electrical insulation materials, electronic component molding materials, heat-resistant adhesives, and paints. For example, an aromatic polyester amide (obtained in Example 2) having the structure of the following formula, which is one of the compounds of the present invention, Weight average molecular weight is 23000 (degree of polymerization p ₁ + p ₂ = 65.3)
The softening temperature was 273°C, and the 5% weight loss temperature measured using a thermobalance was 439°C. The method for producing aromatic polyester amide according to the present invention has the following formula: Structural unit denoted by (), formula: Structural unit represented by () and formula: A structural unit represented by (), (wherein R ₁ to R ₁₂ may be the same or different, and each represents a hydrogen atom, a halogen atom,
Nitro group, phenyl group, cyano group, carbon number 1-5
represents an alkyl group or an alkoxy group having 1 to 5 carbon atoms; R ₁₃ and R ₁₄ may be the same or different, and each represents a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms;
5 represents an alkyl group; Z ₁ to _{Z 3} may be the same or different, and each represents a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group,
Cycloalkylene group having 5 to 15 carbon atoms, 1 to 1 carbon atoms
7 alkylene group, an alkylidene group having 2 to 7 carbon atoms, or an alkenylene group having 2 to 7 carbon atoms;
n ₁ represents 0 or 1, n ₂ represents 0, 1 or 2), each unit is connected by an amide bond and/or an ester bond, and the formula () and the formula () for the formula () The total molar ratio of
1.1 to 1.1:1, the molar ratio of formula () to formula () is in the range of 99:1 to 1:99, and the weight average molecular weight is 2000 or more, the method for producing an aromatic polyester amide, comprising: : [In the formula, R ₁₅ and R ₁₆ are halogen atoms, hydroxy groups, or groups: R ₁₇ -O- (In the formula, R ₁₇ has 1 carbon number
-5 represents an alkyl group or phenyl group; R ₁ to R ₄ , Z ₁ and n ₁ are the same as the above-mentioned groups] An aromatic dicarboxylic acid or a derivative thereof represented by the general formula: (In the formula, R ₅ to R ₈ and Z ₂ are the same as the groups described above.) Aromatic hydroxyamino compound and general formula: (In the formula, R ₉ to R ₁₄ , Z ₃ and n ₂ have the same meanings as above) and the total amount of compound () and compound () to compound () in molar ratio. It is characterized by polycondensation at a ratio of 1:1.1 to 1.1:1. Below, the method for producing an aromatic polyester amide according to the present invention will be explained in more detail. The aromatic dicarboxylic acid or its derivative used in the production method of the present invention is represented by the above general formula (). Specific examples of this compound include terephthalic acid, isophthalic acid, 4,4'-diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4-diphenyl sulfide dicarboxylic acid, 2, 2-diphenyl-propane-4′,4″-
Examples include dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'-diphenylketone dicarboxylic acid, and phthalic acid. Derivatives of these dicarboxylic acids include terephthalic acid dichloride, terephthalic dibromide, and isophthalic acid dichloride. ,
Dibromide isophthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diphenyl terephthalate, dimethyl isophthalate, diethyl isophthalate, diphenyl isophthalate, and the like may be mentioned. Furthermore, these compounds are compounds in which the hydrogen atom of the benzene nucleus is substituted with at least one substituent selected from the group consisting of a bromine atom, a methyl group, an ethyl group, and a cyano group, which are inert to polycondensation. Good too.
In the present invention, one or more selected from the group consisting of these are used.
In addition, as other dicarboxylic acids or derivatives thereof, for example, naphthalene carboxylic acid or derivatives thereof can also be used. The aromatic hydroxyamino compound used in the production method of the present invention is represented by the general formula ().
Specific examples of this compound include 4-hydroxy-
4'-aminodiphenyl, 4-hydroxy-4'-aminodiphenylmethane, 2,2-(4'-hydroxy-4''-aminodiphenyl)propane, 2,2-
(4-hydroxy-4′-aminodiphenyl)butane, 1,1-(4′-hydroxy-4″-aminodiphenyl)cyclohexane, 2,2-(4′-hydroxy-3″-methyl-4″-aminodiphenyl)propane , 2,2-(4′-hydroxy-3″,5″-dimethyl-4′-aminodiphenyl)propane, 2,2
-(4′-hydroxy-3″-bromo-4″-aminodiphenyl)propane, 2,2-(4′-hydroxy-3″-cyano-4″-aminodiphenyl)propane, 2,2-(4′-hydroxy −3″−methoxy−
4″-aminodiphenyl)propane, 3-methyl-
4-hydroxy-4'-aminodiphenyl, 3,
3'-dimethyl-4-hydroxy-4'-aminodiphenyl, 3,5-dimethyl-4-hydroxy 4'-
Aminodiphenyl, 3-methyl-4-hydroxy-4'-aminodiphenyl sulfide, 3-methyl-4-hydroxy-4'-aminodiphenylmethane, 3,5-dimethyl-4-hydroxy-4'-aminodiphenyl enylmethane, 2,2-(3-methyl-
4-Hydroxy-4'-aminodiphenyl)propane, 2,2-(3',3''-dimethyl-4'-hydroxy-4''-aminodiphenyl)propane, 2,2-
(3′,5′-dimethyl-4′-hydroxy-4″-aminodiphenyl)propane, 2,2-(3′-ethyl-
4′-hydroxy-4″-aminodiphenyl)propane, 2,2-(3′-tert-butyl-4-hydroxy-4″-aminodiphenyl)propane, 2,2-
(3′-chloro-4′-hydroxy-4″-aminodiphenyl)propane, 2,2-(3′,3″-dichloro-
4′-hydroxy-4″-aminodiphenyl)propane, 2,2-(3′,3″-dibromo-4′-hydroxy-4″-aminodiphenyl)propane, 2,2-
(3′,5′,3″,5″-tetrabromo-4′-hydroxy-4″-aminodiphenyl)propane, 3,3-
(4'-hydroxy-4''-aminodiphenyl)pentane, 4-methyl-2,4-(4'-hydroxy-
4″-aminodiphenyl)-1-pentene, 4-methyl-2,4-(4′-hydroxy-4″-aminodiphenyl)-2-pentene or 4-methyl-2,
Examples include 4-(4'-hydroxy-3''-methyl-4''-aminodiphenyl)-1-pentene. In the present invention, one or more selected from the group consisting of these are used. The aromatic diamino compound used in the production method of the present invention is represented by the above general formula (). Specific examples of this compound include m-phenylenediamine,
p-phenylenediamine, 2,4-tolylenediamine, 4,4'-diaminodiphenyl, 4,4'-
Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diamino-diphenyl sulfide, 4,4'-di-(N-ethylamino)diphenyl ether, 4,4'- Diaminodiphenylmethane, 2,2-(4′,4″-diaminodiphenyl)propane, 2,2-(4′,4″-di-N-
Methylaminodiphenyl)propane, 1,4-bis(4'-aminophenoxy)benzene, 4-methyl-2,4-bis(4'-aminophenyl)-1-
Pentene, 4-methyl-2,4-bis(4'-aminophenyl)-2-pentene, α,α'-(4,4'-
diaminophenyl)-p-diisopropylbenzene, α,α'-diaminodiphenyl)-p-diisobutylbenzene, α,α'-(4,4'-diaminodiphenyl)-m-diisopropylbenzene, 1,
5-diaminonaphthalene, imino-di-p-phenylenediamine, 4-methyl-2,4-bis(4'-aminophenyl)pentane, 4,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl Examples include ketone or 3,3'-diaminodiphenylsulfone, and furthermore, the hydrogen atom of the aromatic nucleus of this aromatic diamino compound is a chlorine atom, bromine atom, methyl group, ethyl group, which is inert to polycondensation.
The compound may be substituted with at least one substituent selected from the group consisting of a phenyl group, a cyano group, and a nitro group. In the present invention, one or more selected from the group consisting of these are used. Furthermore, as other aromatic diamino compounds, for example, 1,5-diaminonaphthalene, 5 (or 6)-amino-1-
(4'-aminophenyl)-1,3,3-trimethylindane and the like can also be used. The manufacturing method of the present invention can be implemented in various ways. That is, for example, (1) a method of carrying out a polycondensation reaction in a homogeneous solution in the presence of an inert organic solvent and a tertiary amine using an aromatic dicarboxylic acid or a derivative thereof as a starting material; (2) a method of carrying out a polycondensation reaction as a starting material; The polycondensation reaction is carried out in a heterogeneous solution in the presence of an inert organic solvent and an aqueous solution of a basic compound, optionally with the addition of a tertiary amine as a catalyst, using an aromatic dicarboxylic acid or its derivative as a catalyst. and (3) a method in which the polycondensation reaction is carried out by melting without a solvent under heating and reduced pressure. The reaction conditions for each of the above reactions will be explained in detail below. The mixing ratio of the reaction raw materials in the present invention is that of the aromatic hydroxyamino compound represented by the above formula () and the aromatic diamino compound represented by the above formula () to the aromatic dicarboxylic acid or its derivative represented by the above formula (). The molar ratio of the total amount is 1:
The ratio is preferably 1.1 to 1.1:1. That is, the amount of compound () used is most preferably equimolar to the total amount of compound () and compound (), and it is possible to use it in excess or deficiency within the range of 10 mol% or less. . If the amount of these compounds used is outside this range, it will be difficult to obtain a polymer having a desired degree of polymerization. or,
The amount of compound () used is in the range of 99 to 1 mol% based on the total amount of compound () and compound (). If the amounts of these two compounds used are out of this range, the significance of using both of them will be lost, and the resulting aromatic polyesteramide will become difficult to mold. In the reaction (1), first, an aromatic dicarboxylic acid represented by the general formula () or a derivative thereof is reacted with an aromatic hydroxyamino compound represented by the general formula (). The reaction conditions at this time are to react in an inert gas atmosphere such as nitrogen, under stirring, in a temperature range of -40 to 120°C, more preferably in a temperature range of -20 to 100°C, for 0.5 to 12 hours. It is preferable that Next, the product obtained by the above reaction is reacted with an aromatic diamino compound represented by the general formula (). The reaction conditions at this time are, for example, in an inert gas atmosphere such as nitrogen, under stirring, in a temperature range of -40 to 120°C, more preferably in a temperature range of -20 to 80°C, and in a temperature range of 0.5 to 13
It is preferable that the reaction be carried out for a period of time. The reaction (2) involves the reaction of an aromatic dicarboxylic acid or its derivative represented by the general formula (), an aromatic hydroxyamino compound represented by the general formula (), and an aromatic diamino compound represented by the general formula (). The reaction conditions for this reaction in one step are, for example,
It is preferred that the reaction be carried out under stirring at a temperature range of -40 to 100°C, more preferably in a temperature range of -20 to 80°C, for 0.1 to 12 hours. Examples of the inert organic solvent used in the reactions (1) and (2) above include methylene chloride, chloroform, carbon tetrachloride, 1,1,2-trichloroethane, chlorobenzene, benzene, toluene,
One or two selected from the group consisting of xylene, tetrahydrofuran, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, pyridine, and m-cresol. These include the above. or,
The tertiary amine used in the reaction (1) above is preferably used in an amount equivalent to or more than the amount of acid as a by-product, and is used as a catalyst if necessary in the reaction (2) above. The tertiary amine used is 1 for the aromatic dicarboxylic acid or its derivative.
It is preferably from ×10 ⁻³ to 10% by weight. Specific examples of this tertiary amine include triethylamine, tri-n-propylamine, tri-n-butylamine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethylaniline, N,N-
Examples include one or more selected from the group consisting of dimethyl-m (or p-)-toluidine, quinoline, and pyridine. Furthermore, the above
The amount of the basic compound used in the reaction (2) is preferably greater than the equivalent amount of the acid to be produced as a by-product. Specific examples of the basic compound include one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal hydrogen carbonates. The polycondensation reaction of (3) is carried out between an aromatic dicarboxylic acid represented by the general formula () or a derivative thereof, an aromatic hydroxyamino compound represented by the general formula (), and an aromatic diamino compound represented by the general formula (). This process is carried out in a single step in a molten state without a solvent. The reaction conditions at this time are a temperature range of 10 to 400°C, more preferably a temperature range of 50 to 350°C,
The reaction is preferably carried out at a pressure range of 400 to 0.001 mmHg, more preferably 200 to 0.002 mmHg, for 3 to 50 hours. This polycondensation reaction is continued until the desired melt viscosity is reached. In addition, it is also possible to use a basic catalyst in this reaction. The amount used in this case is 1.0× for aromatic dicarboxylic acid or its ester.
A range of 10 ^-3 to 10% by weight is preferred. Specific examples of the basic catalyst include alkali metals, alkali metal hydroxides, oxides, alcoholates, phenolates, and aliphatic or aromatic carboxylates of alkali metals or alkaline earth metals. EXAMPLES Below, the present invention will be described in more detail with reference to Examples. In the Examples, the logarithmic viscosity was calculated by the following formula: Logarithmic viscosity=natural logarithm (solution flow time/dissolved flow time)/concentration. In the formula, the concentration indicates the concentration of the polymer in the solution, and the logarithmic viscosity is expressed in grams of polymer per 100 ml of solution. N-methyl-2-pyrrolidone was used as the diluting solvent, and the values measured at 30°C are listed. The softening temperature and 5% weight loss temperature were determined by differential thermal analysis and thermobalance, and the weight average molecular weight was determined by high performance liquid chromatography. The present invention will be explained below with reference to Examples. In the case of a homogeneous solution system, the Examples were carried out under a nitrogen atmosphere while preventing moisture from entering the system. Moreover, all parts indicate parts by weight. Example 1 11.37 parts of 2,2-(4′-hydroxy-4″-aminodiphenyl)propane was added to 300 parts of tetrahydrofuran.
11.2 parts of triethylamine was added.
This solution was maintained at -10°C, and 20.30 parts of terephthalic acid dichloride was gradually added in powder form while thoroughly stirring.Then, the temperature of the reaction solution was raised from -10°C to 25°C over 1 hour, and at this temperature. Stirring was continued for 3 hours. Next, the reaction solution was maintained at 5 DEG C., and a solution of 5.356 parts of m-phenylenediamine dissolved in 40 parts of N,N-dimethylacetamide was added dropwise, and stirring was continued at this temperature for 4 hours. The reaction solution gradually became viscous. The mother liquor from which the by-produced triethylamine hydrochloride was removed was dropped into thoroughly stirred methanol to precipitate a polymer, which was thoroughly washed with methanol and dried under reduced pressure. When the obtained polymer was analyzed in the same manner as in Example 2, it was confirmed that it was an aromatic polyester amide. The yield of this aromatic polyesteramide is
The weight average molecular weight was 9000 at 27.4 parts (yield = 92%). This aromatic polyesteramide is dioxane, N,N-dimethylformamide, N,N-
Soluble in organic solvents such as dimethylacetamide, softening temperature is 243℃, 5% weight loss temperature is 451℃
It was hot. Example 2 22.73 parts of 2,2-(4′-hydroxy-4″-aminodiphenyl)propane was added to 750 parts of tetrahydrofuran.
30 g of triethylamine was added to the solution. This solution was kept at -15℃ and terephthalic acid dichloride was added.
25.38 parts were added in powder form. After the addition was completed, the temperature of the reaction solution was raised from -15°C to 25°C over 1 hour, and stirring was continued at this temperature for 4 hours. Next, the reaction solution was kept at 5°C and 4,4'-diaminophenyl ether was added.
A solution of 5.005 parts dissolved in 250 parts of tetrahydrofuran was gradually added dropwise, and stirring was continued at this temperature for 4 hours. Thereafter, a polymer was obtained in the same manner as in Example 1. The yield of the obtained polymer was 41.6 parts (yield 94%),
The logarithmic viscosity was 1.03 and the weight average molecular weight was 23.000. This polymer was confirmed to be an aromatic polyester amide having the structure of the following formula based on infrared absorption spectrum, ¹ H nuclear magnetic resonance spectrum, and elemental analysis. (The average value of p ₁ +p ₂ is 65.3.) Infrared absorption spectrum As shown in Figure 1, absorption characteristic of the carbonyl of the amide group was observed at 1650 cm ^-1 and carbonyl characteristic of the ester group was observed at 1740 cm ^-1 . ^1H nuclear magnetic resonance absorption spectrum (solvent
DMSOD ₆ ) Chemical shifts (δ values) are respectively
1.69ppm is −CH ₃ , 3.83ppm is

[Formula] 7.21 to 8.30 ppm was found to have resonance absorption attributed to -H of the benzene nucleus, and the absorption area intensity matched the proton number ratio. Elemental analysis value (%) C H N count value 76.43 5.15 4.77 Analysis value 76.37 5.17 4.75 The softening temperature of this polymer was 273°C, and the 5% weight loss temperature was 439°C. . A light yellow, transparent and strong film was obtained by forming an aromatic polyesteramide into a film from an N,N-dimethylformamide solution by a casting method. Compression molding and injection molding were also possible. Example 3 9.092 parts of 2,2-(4'-hydroxy-4''-aminodiphenyl)propane and 2.002 parts of 4,4'-diaminodiphenyl ether were dissolved in 300 parts of cyclohexanone, and 4.4 g of sodium hydroxide was dissolved in 50 parts. A solution of 10.15 parts of isophthalic acid chloride dissolved in 80 parts of cyclohexanone was injected into the above reaction solution which was kept at 20°C and stirred vigorously.Then, 0.15 parts of triethylamine was added. The viscous reaction mixture was diluted with 100 parts of cyclohexanone and acidified with dilute phosphoric acid, and the organic phase was separated from the aqueous phase and the organic phase was thoroughly washed with water. After that, it was poured into methanol to precipitate the polymer.The precipitate was washed with methanol and then dried under reduced pressure.The obtained polymer was analyzed in the same manner as in Example 2, and it was found that it was an aromatic polyester amide. The yield of this aromatic polyesteramide was 16.5 parts (yield 93%), and the logarithmic viscosity was
It was 1.01. This aromatic polyester amide had a softening temperature of 239°C and a 5% weight loss temperature of 440°C. This polymer was compression molded at 200°C and 300 kg/cm ² to obtain a transparent and tough molded product. Examples 4 to 10 Aromatic polyesteramides were obtained in the same manner as in Example 2 or 3 using various aromatic hydroxyamino compounds, aromatic diamino compounds, and iso- or terephthalic acid dichloride. The results are shown in the table.

【table】

〔Effect of the invention〕

First, the aromatic polyester amide of the present invention is soluble in various organic solvents, and has excellent solubility such as compatibility with other synthetic resins and miscibility with various fillers. Secondly, by utilizing such excellent solubility, it also has processability in that it is easy to mold.For example, it can be made into varnish, film from solution, and various moldings as solution or melt. It is possible. Third, it has excellent heat resistance with high softening and decomposition temperatures, and therefore has a wide range of industrial uses such as electrical insulation materials, electronic component molding materials, heat-resistant adhesives, and paints. Therefore, it can be said that the aromatic polyester amide and the method for producing the same according to the present invention have great industrial value.

[Brief explanation of the drawing]

FIG. 1 shows the infrared absorption spectrum of the aromatic polyesteramide obtained in Example 2.

Claims (1)

[Claims] 1 Formula: The structural unit represented by the formula: Structural unit represented by and formula: Structural unit represented by (in the formula, R ₁ to R ₁₂ may be the same or different, and each represents a hydrogen atom, a halogen atom,
Nitro group, phenyl group, cyano group, carbon number 1-5
represents an alkyl group or an alkoxy group having 1 to 5 carbon atoms; R ₁₃ and R ₁₄ may be the same or different, and each represents a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms;
5 represents an alkyl group; Z ₁ to _{Z 3} may be the same or different, and each represents a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a cycloalkylene having 5 to 15 carbon atoms; (n ₁ represents 0 or 1, n ₂ represents 0, 1 or 2) an aromatic polyester amide in which each unit is connected by an amide bond and/or an ester bond, wherein the molar ratio of the sum of formula () and formula () to formula () is 1:1.1 to 1.1: 1. The molar ratio of formula () to formula () is 99:1 to 1:
99 and a weight average molecular weight of 2000 or more. 2 formula: The structural unit represented by the formula: Structural unit represented by and formula: Structural unit represented by (in the formula, R ₁ to R ₁₂ may be the same or different, and each represents a hydrogen atom, a halogen atom,
Nitro group, phenyl group, cyano group, carbon number 1-5
represents an alkyl group or an alkoxy group having 1 to 5 carbon atoms; R ₁₃ and R ₁₄ may be the same or different, and each represents a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms;
5 represents an alkyl group; Z ₁ to _{Z 3} may be the same or different, and each represents a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a cycloalkylene having 5 to 15 carbon atoms; (n ₁ represents 0 or 1, n ₂ represents 0, 1 or 2) an aromatic polyester amide in which each unit is connected by an amide bond and/or an ester bond, wherein the molar ratio of the sum of formula () and formula () to formula () is 1:1.1 to 1.1: 1. The molar ratio of formula () to formula () is 99:1 to 1:
99 and a weight average molecular weight of 2000 or more, the method comprises: [In the formula, R ₁₅ and R ₁₆ represent a halogen atom, a hydroxyl group, or a group: R ₁₇ -0- (in the formula, R ₁₇ represents an alkyl group having 1 to 5 carbon atoms or a phenyl group); R ₁ to R ₄ , Z ₁ and n ₁ are the same as the above-mentioned groups] An aromatic dicarboxylic acid or a derivative thereof represented by the general formula: (In the formula, R ₅ to R ₈ and Z ₂ are the same as the above-described groups) and an aromatic hydroxyamino compound represented by the general formula: (In the formula, R ₉ to R ₁₄ , Z ₃ and n ₂ have the same meanings as above.) A method for producing an aromatic polyester amide, which comprises polycondensing an aromatic diamino compound represented by the following formula.