JPS63225630A - Production of aromatic polyamide-imide - Google Patents

Abstract

PURPOSE:To obtain an aromatic polyamide-imide in good yields and good workability, by reacting an acyl halide derivative of an aromatic tricarboxylic acid anhydride with an aromatic diamine at a specified temperature in a specified organic solvent. CONSTITUTION:An acyl halide derivative of an aromatic tricarboxylic acid anhydride (A) of the formula (wherein Ar is a trivalent aromatic group, and X is Cl, Br or I), e.g., 4-chloroformylphthalic anhydride, and an aromatic diamine (B) (e.g., 4,4'-diaminodiphenyl ether) are dissolved in a solvent (e.g., benzonitrile) which can dissolve components A and B but can not dissolve the formed aromatic polyamide-imide. Components A and B are reacted with each other at a temperature of 80-200 deg.C. Because the formed aromatic polyamide-imide precipitates from the reaction system as the reaction proceeds, it can be easily separated by, e.g., filtration.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing an aromatic polyamide-imide, and more particularly, to a method for producing an aromatic polyamide-imide by a sinking condensation method.

<Conventional technology> Aromatic polyamideimide has excellent heat resistance, mechanical properties,
In addition to having properties similar to those of aromatic polyimides, such as electrical properties, it also has better chemical resistance and mechanical properties than aromatic polyimides, and has recently attracted attention as an important industrial material.

As a typical method for producing aromatic polyamide-imide, a method is known in which an acyl halide derivative of aromatic trihnl acid anhydride and an aromatic diamine are reacted in an organic solvent. A solvent that dissolves aromatic polyamideimide, which is normally produced as an organic solvent, is used.
The reaction is carried out at a relatively low temperature of 60° C. or lower (see JP-A-47-8093).

<Problems to be solved by the invention> However, such conventional methods require a complicated step of isolating solid aromatic polyamide-imide from a viscous solution of aromatic polyamide-imide obtained by reaction. There is a problem that. Generally, to solve such problems, it is considered to apply the so-called precipitation condensation method in which the produced polymer is precipitated during the reaction, but it is possible to apply the so-called precipitation condensation method in which the produced polymer is precipitated during the reaction. Regarding reaction 1ζ, practical precipitation is not possible due to problems such as not being able to obtain aromatic polyamideimide of polymer -lu or low yield! The reality is that the 1-condensation method has not been established.

An object of the present invention is to provide a precipitation condensation method for producing aromatic polyamideimide with a high P content in good yield.

Under such circumstances, the present inventors have developed a practical aromatic composition from acyl halide derivatives of aromatic tricarboxylic acids and aromatic diamines based on the condensation method. As a result of intensive research aimed at establishing a method for producing group polyamideimides, the inventors discovered that the selection of a specific solvent and specific temperature has a significant effect on molecular weight and yield, leading to the completion of the present invention. In other words, the present invention provides an acyl halide derivative of an aromatic tricarboxylic acid anhydride represented by the general formula (wherein Ar is an octavalent aromatic group, and X represents Cg, Br, or I) and an aromatic diamine. In a method for producing an aromatic polyamide-imide by reacting them in an organic solvent, the acyl halide derivative of the aromatic tricarboxylic anhydride and the aromatic diamine are dissolved in the organic solvent, but the resulting aromatic polyamide-imide is dissolved. This is a method for producing aromatic polyamide-imide, which is characterized in that the reaction is carried out at a temperature of 80 to 200°C using a solvent that does not contain alcohol. Incidentally, the aromatic polyamide-imide in the present invention also includes the aromatic polyamide acid which is its precursor, and examples include the octavalent aromatic group Ar in the general formula (I). A preferred specific example of the acyl halide derivative of aromatic tricarboxylic anhydride represented by the general formula CI) used in the present invention is 4-chloroformylphthalic anhydride.

In addition, a part of the acyl halide derivative of the aromatic tricarboxylic anhydride, usually 50 mol% or less, may be replaced with a diacyl halide derivative of the aromatic dicarboxylic acid to the extent that the excellent properties of the aromatic polyamideimide to be produced are not impaired. Good too.

Examples of aromatic diamines used in the present invention include p-phenylenediamine, m-phenylenediamine,
．． 4-4 ylene diamine, 2.6-) low ylene diamine, 4.4r-diaminodiphenylene in methane, 4.4'
-Diamino diphenyl ether, 8.41-diaminodiphenyl ether, 4.4'-diaminopiphenyl, 8.32-diaminobenzophenone, 8.8'-dimethylbenzidine, 4.4'-diaminodiphenyl sulfide, 3.81-diaminodiphenyl Sulfone, 2.
6-diamitunaphthalene, para-bis(4-aminophenoxy)benzene, meta-bis(4-aminophenoxy)benzene, 4.4/-sulfonylbis(p-phenyleneoxy) diniline, 8.8' -Sulfonylbis(p-phenyleneoxy)dianiline, 4,4'-carbonylbis(p-phenyleneoxy)dianiline, 8
．． 8F -carbonylbis(p-phenyleneoxy)
Examples include dianiline, 4,4'-propylbis(p-7enyleneoxy)dianiline, and the like. Preferred aromatic diamines are 4.42-diaminodiphenyl ether, m-7 22-diamine, 2.6-)ylene diamine, 8.41-diaminodiphenyl ether, 8.
8/-dimethylbenzidine, meta-bis(4-aminophenoxy)benzene, 4゜4'-sulfonylbis(p
-phenyleneoxy)dianiline and 4,41-propylbis(p-phenyleneoxy)dianiline,
Particularly preferred are 4,4I-diaminodiphenyl ether and m-7 enylenediamine.

In carrying out the method of the present invention, each of the acyl halide derivative of aromatic tricarboxylic acid anhydride and the aromatic diamine may be used as a single component, or several components may be used simultaneously. In addition, the acyl halide derivative of aromatic tricarboxylic acid anhydride and the aromatic diamine were used in the reaction at approximately equimolar ratios.
l,ru.

The organic solvent used in the present invention is a solvent that dissolves the acyl halide derivative of aromatic tricarboxylic anhydride and aromatic diamine as raw materials, but does not dissolve the aromatic polyamideimide produced. Examples of such solvents include nitrated aromatic hydrocarbons such as nitrobenzene and 0-nitrotoluene, halogenated aromatic hydrocarbons such as chlorobenzene and 0-dichlorobenzene, cyanated aromatic hydrocarbons such as benzonitrile, Examples include aromatic hydrocarbons such as toluene and xylene, aromatic ketones such as acetophenone, and aromatic ethers such as diphenyl ether. Among these, preferred fi solvents are nitrated aromatic hydrocarbons 8 and cyanated aromatic hydrocarbons, particularly preferred are nitrobenzene, O-nitrotoluene and benzonitrile.

In carrying out the process of the present invention, the above-mentioned reagent is used in such a proportion that the aromatic polyamideimide to be produced has a degree of 8 to 4012%, preferably 5 to 30%. If the usage rate is 1cJ such that alt is lower than 3%, it is higher than the yield% (t is preferable because the fluidity of the reaction system will not be maintained and the polycondensation reaction will not proceed smoothly). do not have.

The eleventh feature of the method of the present invention is that the reaction temperature is about 80 to about 200℃.
It is to be selected within the range of 0. A more preferred reaction temperature is 10G-180°C.

If the reaction temperature is lower than about 80°C, only a low molecular weight aromatic polyamideimide will be produced or the yield will be low, which is not preferred. In addition, the reaction temperature is approximately 200℃
If it is higher than this, side reactions such as gelation may occur, which is not preferable. The necessary reaction time cannot be unconditionally determined as the preferred range varies depending on other conditions, but it is usually 0.1 to
It is 10 hours.

When carrying out the method of the present invention, there are no restrictions on the addition of the molecule 11 regulator and the like to the reaction system.

Examples of such molecular weight regulators include monofunctional compounds such as monocarboxylic halides such as benzoyl chloride and monoamines such as aniline. The addition of a molecular weight regulator is related to the terminal structure of the aromatic polyamideimide produced, and often contributes to the stabilization of the aromatic polyamideimide.

As the reaction format, either a batch type or a flow type can be adopted.

Thus, in carrying out the method of the present invention, the acyl halide derivative of the aromatic tricarboxylic acid hydrate and the aromatic diamine are heated at the reaction temperature in the organic solvent to undergo a polycondensation reaction. As the polycondensation reaction progresses, the produced aromatic polyamide-imide precipitates, and the reaction system becomes a slurry. Additionally, during this time, hydrogen halide released by the flea ζ is generated. The hydrogen halide is removed from the system in the presence of an inert gas carrier such as nitrogen gas, if necessary. The resulting slurry is subjected to a conventional solid-liquid separation process such as transient separation or centrifugation to isolate the solid aromatic polyamide-imide. The solid aromatic polyamide-imide is washed with the solvent used in the reaction or with a solvent that does not dissolve the aromatic polyamide-imide, such as T-cetone, methanol, or water, or subjected to treatment such as steam stripping, as necessary. A powdered or granular aromatic polyamide imide product is obtained through ordinary drying processes such as , vacuum drying, and fluidized drying.

<Examples> Hereinafter, the method of the present invention will be explained in detail with reference to Examples, but the scope of the present invention is not limited by these Examples.

Note that the intrinsic viscosity ([η]) in the examples is a value measured in N-methylpyrrolidone at 26°C.

Amino l diphenyl ether 60.0 in a separable flask equipped with an outlet and a stirrer
f (0,8 mol), 4-rialoformyl anhydride 68.2 f (0,8 mol) and benzonitrile 50
I prepared 0 d. The system was stirred while slowly introducing nitrogen gas from the nitrogen inlet tube, and the temperature of the reaction mixture was raised to 160° C. by external heating. Stirring was continued for 4 hours using this F4 power while removing generated hydrogen chloride and water from the distillation port to the outside of the reaction system. After cooling, the resulting nine-viscosity slurry was poured into 1 g of methanol, and the resulting solid was separated by filtration. The solid was washed once with boiling methanol and 8 times with water, and then dried under reduced pressure at 200°C for 8 hours.
Aromatic polyamideimide 97.8 F in the form of a yellow-green powder was obtained.

The aromatic polyamideimide has an intrinsic viscosity of 0.62 di/
It was a high value of f.

Example 2-6. Comparative Examples 1 to 2 The reaction temperature and benzonitrile in Example 1 were
Aromatic polyamide-imide was produced in the same manner as in Example 1, except that the reaction shown in the table was carried out once and the organic solvent was changed. Table 1 shows the yield and intrinsic viscosity of the aromatic polyamideimide obtained.

``Sl, \, Table 1 As is clear from the examples above, the method 1ζ of the present invention is a simple process that does not require the complicated process of isolating a high molecular weight compound from a viscous solution of the high molecular weight compound. Aromatic polyamideimide having a high PWk can be obtained in a good yield through a process that can be used in a suitable manner.The industrial value of the aromatic polyamide thus obtained is extremely large.

Claims (1)

[Claims] An aromatic compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [ I ] (In the formula, Ar is a trivalent aromatic group, and X is Cl, Br, or I.) In a method for producing aromatic polyamideimide by reacting an acyl halide derivative of tricarboxylic anhydride and an aromatic diamine in an organic solvent, the acyl halide derivative of aromatic tricarboxylic anhydride and the aromatic diamine are used as the organic solvent. 1. A method for producing aromatic polyamide-imide, characterized in that the reaction is carried out at a temperature of 80 to 200° C. using a solvent that dissolves the aromatic polyamide-imide but does not dissolve the produced aromatic polyamide-imide.