JPS63258927A - Polyamideimide - Google Patents

Abstract

PURPOSE:To obtain a polyamideimide with specified intrinsic viscosity, capable of melt forming, outstanding in mechanical properties, heat and chemical resistances, etc., by reaction between an imidedicarboxylic acid (derivative) and diaminodiphenylsulfone (derivative). CONSTITUTION:The objective polyamideimide having >=50 (pref. >=60)mol.% of recurring unit of formula II with an intrinsic viscosity of >=0.3 (pref. >=0.4), can be obtained by reaction, pref. in the presence of catalyst and stabilizer, at 200-350 deg.C, between (A) an imidedicarboxylic acid of formula I (n is 2-12, pref. even number, esp. 6) and/or its amide-forming derivative (e.g., alkyl ester) and (B) diaminodiphenylsulfone and/or its amide-forming derivative (e.g., N,N'- diacyl diaminodiphenylsulfone) in such a ratio that the whole carboxylic acid equivalent be equal to the whole amine equivalent.

Description

DETAILED DESCRIPTION OF THE INVENTION FIELD OF INDUSTRIAL APPLICATION The present invention relates to a novel polyamideimide, more particularly one that is melt-formable and has excellent mechanical properties.

This invention relates to a novel polyamide-imide that has excellent heat resistance, chemical resistance, dimensional stability, etc., and is useful as engineering plastics.

b. Prior art In recent years, polymers such as polyerthylimide, polyethersulfone, and polyetherketone have been developed as resins that can be melt-molded and have excellent mechanical customization and heat resistance. It is known that non-grade resins with excellent stability have a problem in chemical resistance compared to crystalline resins. Generally, the more polar the polymer, the better the chemical resistance tends to be, and for that purpose, polyamide, polyamideimide, etc. are preferable. In particular, polyamideimide using trimellitic anhydride as a raw material is preferable from the viewpoint of heat resistance, and various studies have been conducted, but if an aromatic one is used as the amine component, the melting point of the polymer becomes too high, making it difficult to mold. Also, if aliphatic materials are used, the Tg etc. will be low and there will be problems with heat resistance.
Therefore, Yona attempted to use a combination of aromatic and aliphatic amine components as a melt-moldable product U8P 4348
513 (Japanese Patent Publication No. 56-501883)). However, according to the studies of the present inventors, all of these examples are systems in which the aliphatic amine component can react as an amide amine, and in such cases, the heat resistance stability and molding stability of the obtained polymer may be affected. was found to be unfavorable as it was markedly reduced.

C1 Object of the Invention Therefore, the object of the present invention is to provide a novel polyamide-imide that can be melt-molded in the usual manner and has excellent mechanical properties such as dimensional stability, heat resistance, and chemical resistance.

d0 Structure and effect of the invention According to the invention, the object of the invention is the following formula (I)...
・・・・・・・・・(I) [In the formula, n is an integer from 2 to 12. ] is the main repeating unit, and the polyamide-imide has an intrinsic viscosity of 0.3 or more.

The polyamide-imide of the present invention contains at least 50 moles of the total repeating units, more preferably at least 60 moles of units represented by the above formula (I). Of course, the partial structure of -Nr-CF''C2>+- in the repeating unit also includes units in which the left and right sides are reversely bonded in the repeating unit of the present invention.

In the above formula, n is preferably an even number, especially n
= 6 is preferred.

The following formula (II) and the following formula (m) -oc-♂-CONH-R'-NH- in a ratio of 50 molar or less, more preferably 60 molar or less
...... (m) [However, R3 and R4 are synonymous with the above-mentioned W and Ze, respectively) and the following formula (IV) and the following formula (v) -QC-R6-NH-...・・・・・・・・・・・・
・・・・・・・・・・・・A repeating unit coated with (V) may be contained.

The above alkylene group having 2 to 12 carbon atoms C1 to +n (wherein is an integer of 2 to 12) is 2,2
．． 4-) Limethylhexamethylene.

2.4.4-) Rimeterhexamethylene etc. has 7 carbon atoms
~15 aralkylene groups include "% C) -an, -, etc. as cycloalkylene groups having 6 to 15 carbon atoms, <→, temo c2 with γ, etc.
Examples of the arylene group having 6 to 15 carbon atoms include C-o-, -5o2-, -s-, -co-, -c-, and the like.

The polyamide-imide of the present invention needs to have an intrinsic viscosity of 0.3 or more, and if it is less than 0.3, the mechanical properties are poor and undesirable. More preferably it is 0.4 or more.

The polyamide-imide of the present invention is an imidodicarboxylic acid represented by the following formula (VI) "where n is an integer of 2 to 12" and/or an amide-forming derivative thereof, such as an alkyl ester or an aryl ester acid. It can be produced by reacting the dicarboxylic acid component (7) such as a halide with diaminodiphenylsulfone and/or its amide-forming derivative, such as N,N'-diacyldiaminodiphenylsulfone.

Among the imidodicarboxylic acids represented by the above formula (IV), particularly preferred are compounds in which n is an even number, particularly those in which n is 6. Such imidodicarboxylic acids include, for example, trimellitic anhydride and the corresponding diamine CN1'
b+CHt+N%) can be produced extremely easily by subjecting it to a conventionally known imidization reaction.

When producing the polyamideimide of the present invention, the above formula (V
It is most preferred to use imidodicarboxylic acids represented by T), but amide-forming derivatives of said imidodicarboxylic acids can also be used, such derivatives include methyl,
Examples include lower alkyl esters such as ethyl, and aryl esters such as phenyl and tolyl.

In the present invention, a part of the imidodicarboxylic acid and/or its amide-forming derivative (for example, 30 mol or less,
More preferably, it can be replaced with other dicarboxylic acids or/and aminocarboxylic acids and/or amide-forming derivatives thereof in a proportion of 20 molar or less. Such carboxylic acids include, for example, terephthalic acid.

Inphthalic acid, diphenyl ether dicarboxylic acid, cyphenylsulfonic acid, :I succinic acid, adipic acid, cepatic acid, cyclohexanedicarboxylic acid, and the like.

The following formula (■) [However, R1 in the formula is the same as above. ] dicarboxylic acid, aminobenzoic acid.

The following formula (VW) [However, t is the same as above. ] Examples include aminocarboxylic acids represented by the following.

The polyamideimide of the present invention is the imidodicarboxylic acid (
It can be obtained by reacting a carboxylic acid component containing VI) as a main component and/or its amide-forming derivative with diaminodiphenylsulfonic acid and/or its amide-forming derivative. or a part of the amide-forming derivative thereof, for example, 50 molt or less, more preferably 3 molt.
Other diamines and/or amide-forming derivatives thereof may be substituted in a proportion of 0 molar or less.

Such diamines include m- and p-phenylene.

Diamine, diaminodiphenyl ether.

Diaminodiphenylmethane, Diaminobenzophenone,
Aromatic diamines such as 2.4-diaminotoluene are exemplified. Thus, the present invention can be achieved by condensing a carboxylic acid component containing the imidodicarboxylic acid and/or its amide-forming derivative as a main component with an amine component containing diaminodiphenylsulfone and/or its amide-forming derivative as a main component. The polyamide-imide is produced or the condensation reaction is usually carried out using a carboxylic acid component and an amine component in a ratio such that the total carboxylic acid equivalents and the total amine equivalents are substantially equal. At this time, it is preferable to use a catalyst, a stabilizer, etc. Examples of the catalyst include various phosphorus compounds, boron compounds, heteropolyacids, etc. Specifically, trimethyl phosphite, triethyl phosphite,
Triphenylphosphite.

Examples include triphenylphosphine, phosphoric acid, boric acid, and the like. In addition to the above-mentioned phosphorus compounds, examples of stabilizers include hindered phenol oxidation stabilizers and the like. In addition to the above-mentioned phosphorus compounds, examples of stabilizers include hindered and phenolic oxidation stabilizers.

The reaction is usually carried out at 200 to 350°C, preferably 250 to 33°C.
It is produced by reaction at 0°C. For example, water, acetic acid, phenol, etc. are distilled out of the system. The reaction atmosphere at that time may be normal pressure, increased pressure, or reduced pressure. In the case of normal pressure or pressurized reaction, it is preferable to carry out the reaction under an atmosphere of an inert gas such as nitrogen gas or argon gas.

The most preferred method for producing the polyamideimide of the present invention is the following method. That is, 0.4 to 0.6 mol, more preferably 0.4 to 0.6 mol, and more preferably 0.4 to 0.6 mol per mol of trimellitic anhydride and trimellitic anhydride.
5 moles of the formula Nx(CH2)TINH! (In the formula, n is 2
An integer of ~12) is heated to, for example, 100 to 220°C in the presence of a non-reactive low-molecular-weight compound, preferably an aromatic hydroxy compound such as phenol or cresol, as a solvent in some cases to form a diamine. While distilling water out of the system, the imidization reaction is carried out, and then the reactant is added to the diamine in an amount such that the sum of the diamine is substantially equivalent to the trimellitic anhydride, that is, trimellitic anhydride 1
0.6 to 0.4 mol, preferably 0.5 to mol
The method is characterized in that ~0.4 mol of diaminodiphenylsulfone and/or its amide-forming derivative are thermally condensed under the conditions indicated above, preferably in the presence of a catalyst.

During the condensation reaction with the dicarboxylic acid represented by the general formula (Vl) generated in the imidization reaction, 70% of the total acid component
The aforementioned other dicarboxylic acids in a proportion of at least 80 mol, more preferably at least 80 mol.

Aminocarboxylic acids may be added and a portion of the diaminodiphenylsulfone may be replaced by the other aromatic diamines, for example in a proportion of up to 50 molar, more preferably up to 30 molar. In these cases, it goes without saying that the acid component and the amine component must be used in equivalent amounts to the extent that a substantially linear polymer can be formed.

The polyamideimide of the present invention can be melt-molded and the resulting polymer is of poor quality. For example, in general formula (I), any polymer in which n=6 and 4,4'-diaminodiphenylmethane 1414'-diaminodiphenyl ether etc. is used instead of the diaminodiphenylsulfone component is crystalline and has a melting point of 350°C or higher. It is expensive and cannot be melt-molded.

If necessary, the polyamide-imide of the present invention may be blended with an ultraviolet absorber, a coloring agent, a pigment, a lubricant, various fillers, fillers, and the like.

EXAMPLES The present invention will be explained below with reference to Examples. In the examples, "part" means the rt measured part, and the intrinsic viscosity was measured in N-methylpyrrolidone at 35 DEG C. and C=0.59/di. Also,
The secondary transition point (Tg) of the polymer was measured using DSC at a heating rate of 10° C./min.

Example 1 384 parts of trimellitic anhydride and 116 parts of hexamethylene diamine were placed in a reactor having a distillation system equipped with a stirrer, a vacuum line, and a nitrogen inlet.

Prepare 1100 parts of phenol and heat to 140 to 20 parts in a nitrogen stream.
The reaction was carried out at 0° C. for 2 hours, and the produced water was distilled off from the system. Next, 248 parts of 4,4'-diaminodiphenylsulfone was added to the reaction product.

Add 1.2 parts of triphenyl phosphite and heat at 300°C.
heated to. The reaction mixture became homogeneous 1 minute after heating,
Water began to distill out. After reacting for another hour at the same temperature, the reaction temperature was increased to 310'CK6, and the pressure in the system was gradually reduced to 1101IIIu for about 15 minutes. The reaction continued for 20 minutes.

The obtained polymer was transparent and had an intrinsic viscosity of 0.44.
'rg was 219°C. Moreover, this polymer permeated into solvents such as acetone and triclene xylene and was stable without any major change.

Example 2 In Example 1, hexamethylene diamine was 104.4
272 parts, 4,4'-diaminophenyl sulfone
．． A reacted polymer was obtained in exactly the same manner except that the amount was changed to 8 parts. The obtained polymer had an intrinsic viscosity of 0.40, was amorphous, and had a Tg of 224°C.

Example 3 In a reactor similar to Example 1, 185.6 parts of N,N'-hexamethylenebis-trimellitimide, 99.2 parts of 3,3'-diaminodiphenyl ether, and 0.5 parts of triphenyl phosphate were added. During preparation, the mixture was heated to 300°C. The rest was condensed under the same conditions as in Example 1 to obtain a polymer. The obtained polymer had an intrinsic viscosity of txO, 43, and was of poor quality.
'rg was 197°C.

Example 4 Into the same reactor as in Example 1, 280 parts of N,N'-dodecamethylene bistrimeritimid diphenyl ester, 4
．． 99.2 parts of 4'-diaminodiphenylsulfone and 0.3 parts of triphenylphosphine were charged and heated to 300°C. The only thing left to do is to set the vacuum reaction time at about 1 mm and 11 g to 110
The reaction was carried out in the same manner as in Example 1, except that the reaction time was changed to 7 g, 164° C., with an intrinsic viscosity of 0.45 and a poor quality.

Furthermore, this polymer remained stable even when permeated with active agents such as acetone, trichlene, and xylene without any change.

Claims (1)

[Claims] The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼……(I) [However, in the formula, n is an integer from 2 to 12. ] is the main repeating unit, and the intrinsic viscosity is 0.3
or more polyamideimide.