JPH0373575B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a method for producing a polyesterimide derivative, and more particularly to a novel method for producing a polyesterimide derivative having excellent solubility, processability, and heat resistance. [Technical background of the invention and its problems] Polyimide resin is a heat-resistant resin that was developed relatively recently. It is a molecular compound. Although polyimide resin is a polymer compound with excellent characteristics, the reason why it is not fully utilized in reality is that polyimide resin is insoluble in organic solvents and has difficulties in processability. This is because there is. Therefore, in order to obtain a polyimide molded article, it has the disadvantage that it must be processed in the form of polyamic acid, which is a precursor of polyimide resin. Conventionally, in order to improve such drawbacks, modified polyimide resins having amide bonds, ether bonds, ester bonds, etc. in the same molecule have been developed.
It is used for various purposes. However, such modified polyimide resins still have problems with processability, and because of their low degree of polymerization, they do not have sufficient heat resistance.
-It is still difficult to say that it has sufficient performance for use as a class H electrical insulating material. [Object of the Invention] The object of the present invention is to solve these problems and provide a new method for producing a polyesterimide derivative, which is a high molecular weight polymer with excellent solubility in organic solvents, processability, and heat resistance. It is in. [Summary of the Invention] The present invention has the general formula: HO-Z-NH ₂ [] (wherein Z represents a substituted or unsubstituted divalent aromatic hydrocarbon group or aromatic heterocyclic group). An aromatic compound shown in the figure, in which the hydroxyl group and the amino group are directly bonded to the carbon atoms of the aromatic ring, is defined by the general formula []: (In the formula, A represents a tetravalent aromatic group.) Or General formula []: (In the formula, A is the same as the above group, and R ₁ may be the same or different and represents an alkyl group or phenyl group having 1 to 10 carbon atoms.) React with an anhydride or its derivative; Then, the obtained reaction product has the general formula []: (In the formula, R ₂ may be the same or different and represents a halogen atom.) Reacting with an aromatic acid halide represented by General formula []: (In the formula, Z and A are the same as the groups described above.) This is a method for producing a polyesterimide derivative having a repeating unit represented by the following formula. In the following, the invention will be explained in more detail. The production method of the present invention first comprises an aromatic compound having a hydroxyl group and an amino group directly bonded to a carbon atom of an aromatic ring, and an aromatic tetracarboxylic acid represented by the general formula [] or []. React the dianhydride or its derivative. The reaction conditions at this time are, for example, in an inert gas atmosphere such as nitrogen, under stirring, in a temperature range of -20 to 100°C, more preferably in a temperature range of -10 to 70°C, and in a temperature range of 0.5 to 20°C.
It is preferable that the reaction be carried out for a period of time. The compounding ratio of the reaction raw materials at this time is preferably such that the molar ratio of the compound represented by the general formula [] and the compound represented by the general formula [] or [] is 2:1,
The former may be used in excess of up to 4 mol per 1 mol of the latter. In the present invention, the product obtained by the above reaction is then reacted with an aromatic acid halide represented by the general formula []. The reaction conditions at this time are, for example, in an inert gas atmosphere such as nitrogen, under stirring, at a temperature of 200°C or less, more preferably in a temperature range of -25 to 130°C, for 0.5 to 20 hours. It is preferable that The compounding ratio of the reactants at this time is preferably such that the molar ratio of the product obtained by the reaction to the compound represented by the general formula [] does not exceed 10 mol% relative to the other. , more preferably equimolar amounts. In addition, in the above reaction, if the compound represented by the general formula [] is used in an amount exceeding 2 moles, the compound represented by the general formula [] may be added in an amount equal to the molar amount added in excess. It is preferable to do so. The present invention further provides that it is possible to obtain a target polyesterimide derivative having a repeating unit represented by the general formula [] by subjecting the polyesteramide acid, which is the reaction product obtained by the above reaction, to a dehydration reaction. Become. Such a dehydration reaction can be carried out, for example, by heat-treating the reaction product or by using a dehydration catalyst. In the case of heat treatment,
For example, the obtained reaction product is heated under reduced pressure of 760 to 0.1 mmHg and in a temperature range of 50 to 500°C for 0.5 to 20%
An example is a method of heating for a period of time. In addition, when using a dehydration catalyst, for example, an aliphatic acid anhydride and/or a tertiary amine, etc.
An example of this method is imidization in a temperature range of 0.1 to 10 hours. The amount of aliphatic acid anhydride used in the above reaction is per equivalent of polyesteramic acid.
The amount is preferably 0.2 to 3 mol, more preferably 0.3 to 2 mol. When the amount of aliphatic acid anhydride used is less than 0.2 mol, the amount of unreacted polyesteramic acid increases, while when it exceeds 3 mol, side reactions occur and it becomes difficult to obtain the target compound. Specific examples of the aliphatic acid anhydride used in this dehydration reaction include acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, succinic anhydride, glutaric anhydride, and the like. In addition, when using a tertiary amine, the amount used is per equivalent of polyesteramic acid.
The amount is preferably 0.005 to 1.2 mol, more preferably 0.02 to 0.7 mol. If the amount of tertiary amine used is less than 0.005 mol, the effect of increasing the reaction rate is not sufficient, while if it exceeds 1.2 mol,
It becomes difficult to obtain the target product due to side reactions. Specific examples of this tertiary amine include trialkylamines having an alkyl group having 3 to 20 carbon atoms such as trimethylamine, triethylamine, tributylamine, N,N-diethylcyclohexylamine, N,N-dimethylbenzyl amine,
N-methylpiperidine, 1,4-diazabicyclo[2,2,2]-octane, 1,8-diazabicyclo[5,4,0]-7-undecene, N-methylmorpholine, pyridine, α-pyricone, β- Picoline and the like can be mentioned. Furthermore, when the aliphatic acid anhydride and the tertiary amine are used together, the amount used is within the range of the amount of each of the two compounds used alone per equivalent of the polyesteramic acid. preferable. If the amount used is less than 0.2 mol for aliphatic acid anhydride and less than 0.005 mol for tertiary amine, unreacted polyesteramic acid will increase, while if both compounds exceed 3 mol and 1.2 mol, respectively, It becomes difficult to obtain the desired product due to undesirable side reactions. In order to increase the reaction rate of this dehydration reaction,
It is preferable to use the following compound in an amount of 5.0×10 ⁻⁴ to 1.0 mol, more preferably 1.0×10 ⁻³ to 0.5 mol, per equivalent of polyesteramic acid. Specific examples of this compound include sodium acetate, manganese acetate, magnesium acetate, cobalt acetate, nickel acetate, cobalt stearate,
Examples include acetylacetonate complexes of copper, nickel, cobalt and manganese. Although it is possible to use the bulk polymerization method in which the polymerization reaction is carried out without a solvent in the production method of the present invention, a solution polymerization method in which the reaction is carried out in the presence of an organic solvent is preferred. The amount of solvent used in such polymerization reaction is not particularly limited as long as it is sufficient to form a homogeneous solution system, but it is preferable to use an amount containing the polymer component in the range of 0.05 to 50% by weight to achieve a high molecular weight. It is possible to obtain a reaction product with . This organic solvent is preferably one that does not react with the reaction raw materials, and specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N,
N-diethylacetamide, N-methyl-2-pyrrolidone, N-methyl-caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine,
Dimethylsulfone, hexamethylphosphoramide, tetramethylenesulfone, formamide, N
- selected from the group consisting of methylformamide, butyrolactone, sulfolane, N-acetyl-2-pyrrolidone, dioxane, nitrobenzene, chlorobenzene, tetrahydrofuran, cellosolve, methyl cellosolve, dichloromethane, chloroform, acetone and methyl ethyl ketone. One or more types may be used. It is also possible to use it in combination with a poor solvent such as benzene, toluene, xylene, cyclohexane and benzonitrile. In addition, it is also possible to add a known terminator to such a reaction, such as phenol, aniline, or a derivative thereof, in order to adjust the molecular weight of the produced polymer. In addition, tertiary amines such as trimethylamine, triethylamine, benzyldimethylamine, ethylene oxide, propylene oxide, etc. may be added to neutralize the halogen acid by-produced in the polyesteramic acid production reaction and promote the polymerization reaction. It is possible, and the amount used is preferably in the range of 1.0 to 5 mol per 1 mol of the aromatic acid halide used. In addition, in the production method of the present invention, a compound represented by the general formula [] and the general formula [] or []
After the reaction product with the compound represented by is precipitated from the reaction system by a precipitation method using a poor solvent such as water or alcohol, or by a separation operation such as an extraction operation using an extraction solvent, This includes a method in which the reaction product is made to act on a compound represented by the general formula []. However, from the viewpoint of shortening the reaction process, it is preferable to subject the reaction product as it is to the reaction with the compound represented by the general formula [] without separating it. The aromatic compound having a hydroxyl group and an amino group directly bonded to an aromatic carbon atom used in the production method of the present invention is represented by the above formula [ ], where Z is substituted or unsubstituted. One or more aromatic groups selected from the group consisting of divalent aromatic hydrocarbon groups or aromatic heterocyclic groups. Specific examples of compounds having such hydroxyl groups and amine groups include o(m or p)-aminophenol, 2-amino-p-cresol, 4-amino-
m-cresol, 6-amino-m-cresol,
4-amino-2,6-dimethylphenol, 2,
2-(4′-aminophenol-4″-hydroxyphenyl)propane, 2,2-(3′-methyl-4′-
Aminophenyl-4″-hydroxyphenyl)propane, 2,2-(3′-methyl-4′-aminophenyl-3″-methyl-4″-hydroxyphenyl)propane, 3-amino-4-hydroxybiphenyl,
4-amino-4'-hydroxybiphenyl, 2,2
-(3′-aminophenyl-4″-hydroxyphenyl)propane, 1-amino-5-naphthol, 1
-amino-7-naphthol, 2-amino-5-naphthol, 6-amino-1-naphthol, 2-amino-4-hydroxy-6-methylpyrimidine,
Examples include 2-amino-3-hydroxypyridine, 2-amino-6-hydroxypyridine, etc. Furthermore, the hydrogen atom bonded to the carbon atom of these compounds may be a fluorine atom, a chlorine atom, a bromine atom, a cyano group, Substituted with at least one substituent selected from the group consisting of a nitro group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an acetoxy group having 1 to 5 carbon atoms, and a phenyl group. It may also be a compound that has been In the present invention, one or more selected from the group consisting of these are used. The aromatic tetracarboxylic dianhydride or its derivative used in the production method of the present invention is represented by the above formula [ ] or [ ], where A is a tetravalent aromatic group, particularly an aromatic One or more tetravalent aromatic groups selected from the group consisting of hydrocarbon groups or divalent aromatic hydrocarbon groups bonded via ether bonds, sulfide bonds, or sulfone groups. Specific examples of aromatic tetracarboxylic dianhydrides or derivatives thereof include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3', 4,4'-diphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-
diphenyltetracarboxylic dianhydride, 2,2-
Bis(3',4'-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, perylene
Aromatic tetracarboxylic dianhydrides such as 3,4,9,10-tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride; and 1,2,4,5 -diethyl ester of tetracarboxybenzene, 1,4-dimethoxycarbonyl-2,5-dicarboxybenzene, 1,5
-diisopropylcarbonyl-2,4-dicarboxybenzene, dimethyl ester of 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,
Diethyl ester of 6-naphthalenetetracarboxylic acid, diethyl ester of 2,2',3,3'-diphenyltetracarboxylic acid, 2,2-bis(3,4
-Dicarboxyphenyl)propane diethyl ester, bis(3,4-dicarboxyphenyl)
Diethyl ester of sulfone, dimethyl ester of 1,1-bis(2,3-dicarboxyphenyl)ethane, diethyl ester of bis(2,3-dicarboxyphenyl)methane, 3,3',4,
Diethyl ester of 4'-benzophenonetetracarboxylic acid, diethyl ester of bis(3,4-dicarboxyphenyl) ether and bis(3,
Examples include aromatic tetracarboxylic acid derivatives such as diethyl ester of 4-dicarboxyphenyl sulfide, and one or more selected from the group consisting of these may be used. The aromatic acid halide used in the production method of the present invention is represented by the above formula [], where R ₂ is selected from the group consisting of fluorine atom, chlorine atom, bromine atom, etc. Represents one or more types. Specific examples of aromatic acid halides used include isophthalic acid dichloride, terephthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dibromide, isophthalic acid difluoride, terephthalic acid difluoride, etc. One or more types selected from the group. EXAMPLES Below, the present invention will be described in more detail with reference to Examples. In the Examples, the logarithmic viscosity was calculated using the following formula: Logarithmic viscosity=natural logarithm (solution flow time/solvent flow time)/concentration. In the formula, the concentration indicates the concentration of the polymer in the solution, and the logarithmic viscosity indicates the concentration of the polymer in the solution per 1 g of the polymer.
Expressed in number of dl. As a diluting solvent, N-methyl-
The values measured at 30°C using 2-pyrrolidone are listed. Example 1 10.91 g of pyromellitic anhydride was dissolved in 100 ml of N,N-dimethylacetamide, and the solution was heated at 5°C.
After cooling to, under stirring, p-aminophenol 22.73
g was gradually added and stirring continued for an additional 2 hours. Then add 10.15% of terephthalic acid dichloride to this solution.
After gradually adding 3.0 g of propylene oxide, stirring was continued for 4 hours to obtain a viscous polyesteramic acid solution. Note that all of the above reactions were conducted under a nitrogen atmosphere. This solution was applied onto a glass plate to form a solution film with a thickness of 0.6 mm, and the film was dried at 120° C. for 1 hour in a nitrogen atmosphere to produce a film. Thereafter, this film was heated under vacuum from 150°C to 300°C at a rate of 1°C per minute, and at this temperature
Hold for 30 minutes. As a result, a strong and flexible film was obtained. When this film was subjected to 1R spectrum and elemental analysis, it was confirmed that it was a polyesterimide derivative. Example 2 10.91 g of pyromellitic anhydride was dissolved in 120 ml of anhydrous N,N-dimethylformamide, and this solution was dissolved.
After cooling to 10°C and stirring, 2,2(4′-aminophenyl-4″-hydroxyphenyl)propane22.73
g was gradually added and stirring was continued for an additional 3 hours. Next, 10.15 g of an equimolar mixture of terephthalic acid dichloride and isophthalic acid dichloride was gradually added to this solution, followed by 16 g of triethylamine, and the solution was further stirred at 20°C for 5 hours to form a viscous polyesteramic acid solution. I got it. Note that all of the above reactions were conducted under a nitrogen atmosphere. Thereafter, the same operation as in Example 1 was performed, and a strong and flexible film was obtained. When this film was analyzed in the same manner as in Example 1, it was confirmed that it was a polyesterimide derivative. In this example, the logarithmic viscosity of the polyesteramic acid obtained was 1.3 dl/g. Furthermore, in order to compare the resin obtained by the above reaction with a conventional modified polyimide resin, test pieces were prepared for each and tested for solubility, processability, and heat resistance. The test conditions were: for solubility, the solvent was 10% sulfuric acid, 38% concentrated hydrochloric acid, trichlorethylene, methyl ethyl ketone, the immersion temperature was room temperature, and the immersion time was 10 days; for processability, the heating temperature was 330℃, Compression molding with a pressure of 1000Kg/ ^cm2 , and heat resistance at a temperature of 300Kg/cm2.
Aging for 100 hours at ℃ was performed. the result,
It was confirmed that the product of the present invention had almost no change compared to before the test, and was significantly superior to the conventional product. Example 3 Using the same sample as in Example 2, a reaction was carried out under the same conditions to obtain a polyesteramic acid solution. Then, acetic anhydride was added to this solution as a dehydration catalyst.
Add 12 g and 10 g of β-picoline, and add 1.5 g at 5°C.
Stir for hours. This solution was added to a thoroughly stirred mixed solution of 700 ml of methanol and 700 ml of water to obtain a uniform precipitate. Separate this precipitate and
After thorough washing with a solution of water and methanol, it was dried at 80° C. under vacuum to obtain 36.9 g of a yellowish brown powder. When this powder was analyzed by the same method as in Example 1, it was confirmed that it was a polyesterimide derivative, and the yield was 96%. Example 4 110 ml of anhydrous N,N-dimethylformamide
Dissolve 16.1 g of 3',4,4'-benzophenonetetracarboxylic dianhydride, cool the solution to 10°C, and dissolve 2,2-(4'-aminophenyl-
22.73 g of 4"-hydroxyphenyl)propane was slowly added and stirring was continued for 5 hours. To this solution was added 15 g of triethylamine, and further 10.15 g of isophthalic acid dichloride was gradually added.
Stirring was performed at ℃ for 7 hours to obtain a viscous polyesteramic acid solution. The logarithmic viscosity of this polymer was measured and found to be 0.92 dl/g. Thereafter, a film was produced in the same manner as in Example 1, and a strong and flexible film was obtained.
When this film was analyzed in the same manner as in Example 1, it was confirmed that it was a polyesterimide derivative. Furthermore, regarding the film obtained as above,
Measurement of film elongation at 25℃
11.8%, and its tensile strength was measured to be 832 Kg/cm ² . Examples 5 to 8 In Example 3, 2,2-(3'-methyl-4'-aminophenyl-4''- Hydroxyphenyl) propane 25.3g
(Example 5), 2,2-(3′,3″-dimethyl-4′-
27.93 g of aminophenyl-4″-hydroxyphenyl)propane (Example 6), 2,2-(3′-chloro-
4′-aminophenyl-4″-hydroxyphenyl)
26.18 g of propane (Example 7) or 2,2-(3'-
A reaction similar to Example 3 was carried out using 22.73 g of aminophenyl-3'-hydroxyphenyl)propane (Example 8). A film was prepared using the obtained reaction solution in the same manner as in Example 1.
In each case, strong and flexible films were obtained. When these films were analyzed in the same manner as in Example 1, they were confirmed to be polyesterimide derivatives. Note that Table 1 shows the logarithmic viscosity of the polyesteramic acid and the yield of the polyesterimide derivative.

[Table] Examples 9 to 13 In Example 3, instead of N,N-dimethylformamide, 150 ml of tetrahydrofuran (Example 9), 150 ml of dioxane (Example 10), N,N
-A reaction similar to Example 3 was carried out using 120 ml of dimethylacetamide (Example 11), 130 ml of dimethyl sulfoxide (Example 12), or 130 ml of N-methyl-2-pyrrolidone (Example 13). When films were prepared from the obtained reaction solutions in the same manner as in Example 1, tough and flexible films were obtained. When these films were analyzed in the same manner as in Example 1, they were confirmed to be polyesterimide derivatives. Note that Table 2 shows the logarithmic viscosity of the polyesteramic acid and the yield of the polyesterimide derivative.

〔Effect of the invention〕

According to the method of the present invention, a polyesterimide derivative which is a heat-resistant high polymer with excellent solubility and processability can be obtained. The polyesterimide derivative having such excellent properties produced by the method of the present invention can be used, for example, as an impregnating varnish or a wire coating varnish in the state of a solution in a polar organic solvent, and can also be used as a film by removing the solvent. and fibers can be produced. Furthermore, this film is transparent and has excellent water resistance, heat resistance, electrical and mechanical properties, and these properties can be further improved by uniaxial or biaxial stretching. Therefore, the polyesterimide derivative produced according to the present invention also has uses such as electrical parts such as insulating tapes, sheets, and magnetic tapes. In addition, the polyesterimide derivative obtained by the method of the present invention has superior processability and heat resistance compared to conventional modified polyimide resins, so it can be used in various molding methods, such as gears, bearings, housings, electrical It can be widely used in fields such as electronic components and electronic components.

Claims (1)

[Claims] 1. An aromatic compound represented by the general formula: HO-Z-NH ₂ (wherein Z represents a substituted or unsubstituted divalent aromatic hydrocarbon group or aromatic heterocyclic group) An aromatic compound having a hydroxyl group and an amino group directly bonded to a ring carbon atom is defined by the general formula: (In the formula, A represents a tetravalent aromatic group.) Or, general formula: (In the formula, A is the same as the above group, and R ₁ may be the same or different and represents an alkyl group or phenyl group having 1 to 10 carbon atoms.) react with an anhydride or a derivative thereof; then, the obtained reaction product is (In the formula, R ₂ may be the same or different and represents a halogen atom.) Reacting with an aromatic acid halide represented by General formula: (In the formula, Z and A are the same as the groups described above.) A method for producing a polyesterimide derivative having a repeating unit represented by the following. 2. The method for producing a polyesterimide derivative according to claim 1, wherein the dehydration treatment is performed by heating. 3. The method for producing a polyesterimide derivative according to claim 1, wherein the dehydration treatment is performed using an aliphatic acid anhydride and/or a tertiary amine.