JPH04130116A - Heat-resistant aromatic polyamide and composition - Google Patents

Abstract

PURPOSE:To obtain an aromatic polyamide improved in moldability, high- temperature mechanical strengths and chemical stability by polymerizing a specified aromatic polyamide oligomer. CONSTITUTION:An aromatic polyamide prepared by polymerizing an aromatic polyamide oligomer of formula I or II (wherein R1 and R2 are each a bivalent aromatic group; A and B are each an aliphatic or aromatic polymerizable unsaturated group, provided that at least either of A and B is a polymerizable unsaturated group comprising a polyamine/cyclic unsaturated acid anhydride adduct; E and F are each an aliphatic or aromatic polymerizable unsaturated group, provided that at least either of E and F is an unsaturated group comprising a polyamine/unsaturated acid chloride condensate; and (n) is 0-15). A thermosetting aromatic polyamide oligomer composition is obtained by mixing the above oligomer with at most 5wt.% radical polymerization initiator.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a heat-resistant synthetic resin, particularly a heat-resistant aromatic polyamide imparted with thermosetting properties, and a thermosetting aromatic polyamide oligomer composition for forming the same. Regarding.

[Conventional technology]

As the demands of the plastics industry become more sophisticated, industrial materials with special properties are required, and this trend is rapidly developing as technology becomes more sophisticated.

The demand for improved heat resistance is felt in plastics, films, fibers,
The aim is to add heat resistance to industrial materials in fields that require heat resistance, such as laminates, laminates, and adhesives, to expand the market, and to expand into a wide range of new fields with new functions.

In response to these demands, a group of synthetic resins called engineering plastics, such as aromatic polyamides, polyimides, polysulfones, and polyphenylene oxides, have already been developed and are now being industrialized as plastics with new functions different from conventional synthetic resins. Aromatic polyamides, known under the name aramid, are one of them, and are now being produced and opening up new areas of demand.

Typical aromatic polyamides include polyparaphenylene terephthalamide (trade name: Kevlar) and polymetaphenylene isophthalamide (product name: Nomex 8 or HT-1) developed by Du Bont.

All of these polyamides are essentially classified as thermoplastic synthetic resins, but they generally have a high melting point, and in some cases the difference between the melting point and the thermal decomposition temperature is small or reversed. Therefore, melt molding is difficult or impossible depending on the structure. On the other hand, a type of polyamide in which an oligomer is prepared as a precursor and then thermally cured has not yet been proposed.

The reason why there was no thermosetting aromatic polyamide was as follows.
- This is thought to be because its melting point was sufficiently higher than that of conventional thermoplastic synthetic resins, and because the introduction of unsaturated bonds was judged to have a high risk of causing undesirable gelation during the molding process. .

[Problem to be solved by the invention]

Aromatic polyamide is an excellent heat-resistant polymer that is relatively stable even at considerably high temperatures, has excellent electrical properties and mechanical strength, and has high chemical stability.

The present invention is an aromatic polyamide that has improved moldability without losing these excellent properties of conventional polyamides, and has further improved mechanical strength and chemical stability at high temperatures, and a thermosetting method for forming the aromatic polyamide. The object of the present invention is to provide a aromatic polyamide oligomer composition.

[Means to solve the problem]

The present inventors found that when molding as a molding material or as a laminate, it has a relatively low melting point, can be molded into a desired shape under heat and pressure, and can be cured under relatively mild conditions. After that, research was conducted to obtain an aromatic polyamide having sufficient heat resistance, mechanical strength, chemical stability, etc., and a thermosetting aromatic polyamide oligomer composition for forming the aromatic polyamide, and -Shipboard CI) or -We discovered a heat-resistant aromatic polyamide obtained by polymerizing aromatic polyamide oligomers that are present in shipyards, and also discovered the above-
We have developed a thermosetting aromatic polyamide oligomer composition in which 5% by weight or less of a radical polymerization initiator is blended with the aromatic polyamide oligomer represented by Funagura CI) and (or) - Funagura [■]. This cured aromatic polyamide has the superior chemical properties of conventional aromatic polyamides.
The present inventors have discovered that it has mechanical properties, is easy to mold, and exhibits excellent characteristics such as less decrease in mechanical strength at high temperatures, and has thus completed the present invention.

The aromatic polyamide oligomer having a polymerizable unsaturated group at the end represented by the above-mentioned - Funazura (1) or the above-mentioned - Funazura (II) is an adduct of a polyvalent amine and a cyclic unsaturated acid anhydride, or an adduct of a polyvalent amine and a cyclic unsaturated acid anhydride, respectively. unsaturated amines consisting of condensates of monovalent amines and unsaturated acid chlorides, or mixtures of such unsaturated amines with other unsaturated amines having aliphatic or aromatic polymerizable unsaturated groups, aromatic diamines, and aromatic It can be synthesized by reacting a group dicarboxylic acid cybaride in the presence of a hydrogen halide acceptor.

Among the aromatic polyamide trigomers having a terminal polymerizable unsaturated group represented by the general formula [1] of the present invention, A and B at both ends are an adduct of a multivalued amine and a cyclic unsaturated acid anhydride. An aromatic polyamide oligomer having a polymerizable unsaturated group consisting of - can be illustrated by the following reaction formula, for example.

Wear.

・First stage lv: unsaturated amine 1'III) synthesis of to O hmm finger in Unsaturated amines mainly composed of (m) ・Second stage: Aromatic polyamide with unsaturated groups oligomer (A) synthesis of (aromatic amine) Isophthalic acid dichloride (Aromatic dicarboxylic acid cybalide) (Aromatic polyamide oligomer) (A) The main component of unsaturated end groups is CH-CH CH-CH or CH-CH CH position CH oc　c-.

oc　c-.

It is expressed as

Furthermore, among the aromatic polyamide oligomers having a polymerizable unsaturated group at the terminal represented by the general formula DI,
An aromatic polyamide oligomer in which E and F at both ends have a polymerizable unsaturated group consisting of a condensate of a polyvalent amine and an unsaturated acid chloride can be represented by the following reaction formula, for example.

・First stage: unsaturated amine [■] synthesis of Unsaturated amines mainly composed of [IV) ・Second stage: Aromatic polyamide with unsaturated groups Oricomer (B) synthesis of (unsaturated amine) Metaphenylenediamine (Aromatic diamine) Isophthalic acid dichloride (Aromatic dicarboxylic acid cybaride) or It is expressed as

In order for the above reaction to proceed smoothly, an acceptor for the by-produced hydrogen chloride is required, and for boat fishing it is convenient to use an aliphatic tertiary amine or a caustic alkali. The amount of hydrogen chloride acceptor (hydrogen halide acceptor) used is preferably equivalent to or more than the equivalent amount of hydrogen chloride produced as a by-product.

In this case, a value of n of about 0 to 15, preferably about 3 to 7, is advantageous for ease of moldability, and polymerization at this stage is not particularly necessary. This reaction is generally carried out by mixing amines in an aqueous phase and aromatic dicarboxylic acid civalide in an inert organic solvent that does not dissolve in water to carry out an interfacial polycondensation reaction, or by dissolving both in an inert organic solvent and performing a low-temperature polycondensation reaction. This can be carried out by a low-temperature solution polycondensation reaction in which condensation is carried out at (for example, 10° C. or lower).

Examples of aromatic diamines that can be used in the present invention include metaphenylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 3.
3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-
Diaminodiphenyl ether, 3.3'-diaminodiphenylsulfone, 4.4'-diaminodiphenylsulfone, dianisidine, 2,4-tolylenecyamine, 2.
4/2.8-) lylene diamine mixture, 1,3-bis(3-aminophenoxy)benzene, etc. can be used, and it is also possible to use a mixture of two or more types.

Polyvalent amines are one of the components used when synthesizing unsaturated amines by addition reaction of polyvalent amines and cyclic unsaturated acid anhydrides or by condensation reaction of polyvalent amines and unsaturated acid chlorides. , general formula (R3), (R3), (R3).

In the formula, D: phenylene group, alkyl-substituted phenylene group, diphenylene group, diphenyl ether group, or naphthylenyl group R3: represents a halogen atom, a hydroxyl group, a lower alkoxy group having 4 or less carbon atoms, or a lower alkyl group having 5 or less carbon atoms,
And R3 may be the same or different from each other and may form a ring.

g: 1 or 2 m: an integer from 0 to 3 α: 0 to 1O1, preferably a polyhydric amine represented by 0 to 3 or - ship stock% formula %) (wherein R3, D, rn, α are as defined above) same.)
Preferably, the general formula % formula % (wherein R3 is H or CH3, α is the same as above or the general formula % formula % (wherein R3 is H or CH3, α is a polyvalent amine represented by the same as above) can give.

Representative examples of the other component, cyclic unsaturated acid anhydride or unsaturated acid chloride, include the following. First, examples of cyclic unsaturated acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, and 3,6-endomethylene-1,2,3,8-tetrahydro Examples include phthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrahydrophthalic anhydride, and 4-methyltetrahydrophthalic anhydride.

Further, as the unsaturated acid chloride, acrylic acid chloride, methacrylic acid chloride, cinnamic acid chloride, crotonic acid chloride, H-C H-C H OH (in the formula, R is H or CH3) CH20 (in the formula , R is H or CHs).

The reaction ratio of the polyvalent amine and the cyclic unsaturated acid anhydride or unsaturated acid chloride may be such that at least one amine remains in one molecule. That is, when an m-valent polyvalent amine is used, the monovalent cyclic unsaturated acid anhydride or unsaturated acid chloride may be used in an amount of (m-1) moles or less.

This unsaturated amine may be used alone, or a mixture of the unsaturated amine and another unsaturated amine having an aliphatic or aromatic polymerizable unsaturated group may be used. Other unsaturated amines include allylamine, propargylamine, aminostyrene, m-isopropenylaniline, p-isopropenylaniline, and the like. The mixing ratio of other unsaturated amines is preferably 50 mol% or less.

Further, as the aromatic dicarboxylic acid civalide that can be used in the present invention, dichlorides of aromatic dibasic acids are convenient, and representative examples include terephthalic acid dichloride, isophthalic acid dichloride, phthalic acid dichloride, and mixtures thereof.

The aromatic polyamide derived from phthalic acid dichloride has slightly insufficient heat resistance, and when using terephthalic acid dichloride, although the heat resistance of the polymer after heat curing is sufficient, the aromatic polyamide obtained as a precursor Group polyamide oligomers tend to have high melting points and become difficult to handle.From a practical standpoint, isophthalic acid dichloride has the best balanced properties and meets the purpose of the present invention.

Since the synthesis reaction of the aromatic polyamide oligomer having a polymerizable unsaturated group at the terminal represented by the above-mentioned -Funazura [I] or general formula CIr) proceeds relatively stoichiometrically, for example, the above-mentioned ( When synthesizing the aromatic polyamide oligomer of formula A) or formula (B), calculate the desired value for n in formula (A) or formula (B), and then add the necessary amount of formula CIII) or [■ ] unsaturated amine shown by the formula,
Metaphenylene diamine (aromatic diamine) and isophthalic acid dichloride (aromatic dicarboxylic acid civalide)
If precise adjustment is required, the molar ratio can be determined by a simple test.

Aromatic polyamide oligomers having a polymerizable unsaturated group at the terminal other than the aromatic polyamide oligomer having a polymerizable unsaturated group at the terminal represented by the above formula (A) or (B) are also synthesized in the same manner as above. be able to. That is,
- An aromatic polyamide oligomer having a polymerizable unsaturated group at both ends, A and B consisting of an adduct of another polyvalent amine and another cyclic unsaturated acid anhydride, or a general formula In [11), an aromatic polyamide oligomer having a polymerizable unsaturated group at the terminal where E and F at both ends are a condensation product of another polyvalent amine and another unsaturated acid chloride is also reacted in the same manner as above. Can be synthesized.

As already explained, the composition of the aromatic polyamide oligomer obtained by this reaction can be easily selected, and it can be easily molded at a temperature of 200° C. or lower. - The aromatic polyamide oligomer represented by Funakura (1) and the aromatic polyamide oligomer represented by general formula (II) can be used in combination.

The aromatic polyamide oligomer having a polymerizable unsaturated group at the end synthesized according to the present invention can be cured in combination with a radical polymerization initiator, making it possible to significantly improve heat resistance.

When the molding temperature is 100 DEG C. or higher, so-called high-temperature decomposition types such as dicumyl peroxide, t-butyl perbenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroxy octoate, etc. are used. The appropriate amount of the radical polymerization initiator to be used is 5% by weight or less, preferably 1 to 3% by weight, based on the aromatic polyamide oligomer represented by general formula CI] and/or general formula [II). Even if the amount of the radical polymerization initiator used is more than 5% by weight, no special effect is observed.

Further, the combined use of a heptamer copolymerizable with the unsaturated bonds of the aromatic polyamide oligomer of the present invention is possible when the heptamer dissolves the oligomer, and in particular, the above-mentioned general formula [I
] or in the general formula [■], the range of application is wide.

In the present invention, it goes without saying that the aromatic polyamide oligomer having an unsaturated group can be used in combination with other polymers as reinforcing agents, filler mold release agents, coloring agents, low shrinkage agents, etc., as required.

The composition blended in this way is highly stable at room temperature, and can of course be blended immediately before use.
For a short period of time, it can be stored with a radical polymerization initiator,
Transport is possible.

Most of the aromatic polyamide oligomers are
Since it has a melting point of 00°C or lower and a lower viscosity than ordinary aromatic polyamides, it can flow even into complex shapes before curing.

However, once it has been polymerized and hardened, it has no melting point or softening point, and as it thermally decomposes, it becomes a polymer whose physical properties are less dependent on temperature.

〔Example〕

Next, examples will be shown below to help understand the present invention.

Synthesis Example 1 Anilix pot - Synthesis of aromatic polyamide oligomer [I] with maleic anhydride adduct at the molecular end.
20.3 g (0.1 mol) of isophthalic acid dichloride and 10Qg of dimethylformamide (DMF) are placed in the fourth separable flask of m1, and the mixture is cooled to 10° C. or lower.

Next, 3,4′-diaminodiphenyl ether (3,4
'DAPE) 111i, 87g (0,0834 mol)
, triethylamine 20.5g (0,203 mol)
, 50 g of DMF were weighed and mixed and added dropwise to the reaction flask. Next, 16.0 g of Anilix and 3 maleic anhydride
．． An adduct prepared by reacting 27 g in 30 g of DMF is added dropwise. During this time, the reaction temperature is kept below 10°C.

After the addition is completed, the dropping funnel is washed with 20 g of DMF, and the washing liquid is added to the reaction flask.

Further, stirring is continued for 2 hours while maintaining the temperature of the reaction mixture at 10° C. or lower.

The reaction mixture is then gradually added to a large amount of water with vigorous stirring to precipitate crystals. The precipitated crystals are suction filtered, washed with water, and then dried.

*Anilix (Mitsui Toatsu Chemicals) Amine value 0.625 (eq/100 g) Synthesis Examples 2 to 6 Synthesize aromatic polyamide oligomers using the same procedure as Synthesis Example 1 except for the formulation shown in the table below. did.

Synthesis Example 7 Synthesis of Aromatic Polyamide Oligomer [■] Terminated with Anilic-methacrylamide Isophthalic acid dichloride was placed in a 500 m1 separable flask equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer. 20.3g
(0.1 mol), dimethylformamide (DMF)
Charge 100g and cool to below 10°C.

Next, 3,4'-diaminodiphenyl ether (3,4
'-DAPE) 16.67f (0,0834 mol),
20.5 g (0,203 mol) of triethylamine,
Weigh and mix 50 g of DMF and drop it into the reaction flask.

Subsequently, 3.48 g of methacrylic acid chloride was added to a solution consisting of 18.0 g of Anilix, 3.37 g of ) ethylamine, and 30 g of DMF.

A solution consisting of 20 g of DMF was added under water cooling, and a reaction mixture of unsaturated amine was added dropwise. During this time, the reaction temperature is kept below 10°C.

After the dropping is completed, the dropping funnel is washed with 20 g of DMF, and the washing liquid is added to the reaction flask.

Further, stirring is continued for 2 hours while maintaining the temperature of the reaction mixture at 10° C. or lower.

The reaction mixture is then gradually added to a large amount of water with vigorous stirring to precipitate crystals. The precipitated crystals are suction filtered, washed with water, and then dried.

Synthesis Example 8 Synthesis of aromatic polyamide oligomer [■] terminated with anilic-cinnamic acid amide Synthesis of Synthesis Example 7 except that cinnamic acid chloride (>95% cone) 5.81z was used instead of 3.48 g of methacrylic acid chloride. Aromatic polyamide oligomer [■] was synthesized by the same operation.

Synthesis Example 9 Synthesis of aromatic polyamide oligomer CIX terminated with anilic-methacrylic acid amide When synthesizing the reaction mixture of unsaturated amines, methacrylic acid chloride 3.4
743 g of methacrylic acid chloride and 6.7 g of triethylamine instead of 8 g and 3.37 g of triethylamine.
Aromatic polyamide oligomer (IX) was synthesized in the same manner as in Synthesis Example 7 except that 3 g was used.

Synthesis Example 10 Synthesis of aromatic polyamide oligomer [X] terminated with anilic-acrylic acid amide 3.48 g of methacrylic acid chloride was used when synthesizing the reaction mixture of unsaturated amines.
and 6.03 g of acrylic acid chloride and 6.731 g of triethylamine instead of 3.37 g of triethylamine.
(Aromatic polyamide oligomer EX) was synthesized in the same manner as in Synthesis Example 7 except that .

Example 1 Aromatic polyamide oligomer obtained in Synthesis Example 1 [131 parts by weight, dicumyl peroxide (2% acetone solution) 1
Parts by weight were added to a test tube, and the temperature was gradually raised to 80° C. for 1 hour to remove acetone and dry. Next, the temperature was raised to 160° C. for 2 hours, and then the temperature was further raised to 200° C. for 5 hours, and an amber-colored, durable, insoluble and infusible bulk polymer was obtained.

The resulting polymer was crushed in a mortar and thermogravimetrically analyzed in air at a heating rate of 10°C/min.
) became like this.

95% weight retention temperature 377°C 90% weight weight retention variable temperature 449°C 500°C Weight retention 78.7% Example 2 Aromatic polyamide oligomer [I] Instead of 1 part by weight, the aromatic compound obtained in Synthesis Example 2 Polyamide oligomer [■] 1
The same operation as in Example was carried out except that parts by weight were used.

The resulting polymer was crushed in a mortar and thermogravimetrically analyzed in air at a heating rate of 10°C/min.
2) became like this.

95% weight retention temperature 420°C 90% weight weight retention variable temperature 465°C 500°C Weight retention 84.4% Example 3 Aromatic polyamide oligomer [I] Instead of 1 part by weight, the aromatic compound synthesized in Synthesis Example 3 Polyamide oligomer [■
] The same operation as in Example 1 was performed except that 1 part by weight was used.

The resulting polymer was crushed in a mortar and thermogravimetrically analyzed in air at a heating rate of 10°C/min.
3) became like this.

95% weight retention temperature 434°C 90% weight weight retention variable temperature 471'C 500°C Weight retention 83.0% Example 4 Aromatic polyamide oligomer [I] 1 part by weight was replaced with the aroma synthesized in Synthesis Example 4 Group polyamide oligomer [■
] The same operation as in Example 1 was performed except that 1 part by weight was used.

The resulting polymer was crushed in a mortar and thermogravimetrically analyzed in air at a heating rate of 10°C/min.
1) became like this.

95% weight retention temperature 375°C 90% weight weight retention variable temperature 455°C 500°C Weight retention 78.8% Example 5 Aromatic polyamide oligomer [Aromatic polyamide oligomer synthesized in Synthesis Example 5 instead of 111 parts by weight [■]
The same operation as in Example 1 was performed except that 1 part by weight was used.

The resulting polymer was crushed in a mortar and thermogravimetrically analyzed in air at a heating rate of 10°C/min.
2) became like this.

95% weight retention temperature 336°C 90% weight weight retention variable temperature 426°C 500°C Weight retention 79.7% Example 6 Aromatic polyamide oligomer [I] Instead of 1 part by weight, the aromatic compound synthesized in Synthesis Example 6 Polyamide oligomer [■
] The same operation as in Example 1 was performed except that 1 part by weight was used.

The resulting polymer was crushed in a mortar and thermogravimetrically analyzed in air at a heating rate of 10°C/min.
3) became like this.

95% weight retention temperature 383°C 90% weight weight retention variable temperature 464°C 500°C Weight retention 84.6% Example 7 Aromatic polyamide oligomer [I] Instead of 1 part by weight, the aromatic compound synthesized in Synthesis Example 7 Polyamide oligomer [■
] The same operation as in Example 1 was performed except that 1 part by weight was used.

The resulting polymer was crushed in a mortar and thermogravimetrically analyzed in air at a heating rate of 10°C/min.
4) It became like this.

95% weight retention temperature 429°C 90% weight weight retention variable temperature 462°C 500°C Weight retention 79.8% Example 8 Aromatic polyamide oligomer [I] Instead of 1 part by weight, the aromatic compound synthesized in Synthesis Example 8 Polyamide oligomer [1
The same operation as in Example 1 was performed except that 31 parts by weight was used.

The resulting polymer was crushed in a mortar and thermogravimetrically analyzed in air at a heating rate of 10°C/min.
1) became like this.

95% weight retention temperature 407°C 90% weight weight retention variable temperature 452°C 500°C Weight retention 77.8% Example 9 Aromatic polyamide oligomer CI] 1 part by weight of the aromatic polyamide synthesized in Synthesis Example 9 Oligomer [■
] The same operation as in Example 1 was performed except that 1 part by weight was used.

The obtained polymer was crushed in a mortar and thermogravimetrically analyzed in air at a heating rate of 10°C/min.
2) became like this.

95% weight retention temperature 415°C 90% weight weight retention variable temperature 462°C 500°C Weight retention 80.5% Example 1O Aromatic polyamide oligomer [I] Instead of 1 part by weight, the aromatic compound synthesized in Synthesis Example 10 Polyamide oligomer [
The same operation as in Example 1 was performed except that 1 part by weight of X) was used.

The obtained polymer was crushed in a mortar and thermogravimetrically analyzed in air at a heating rate of 10°C/min.
3) became like this.

95% weight retention temperature 375°C 90% weight weight retention variable temperature 438°C 500°C Weight retention 80.2% Example 11 100 parts by weight of the oligomer (1) synthesized in Synthesis Example 1 and 2 parts of dicumyl peroxide were After soaking a glass cloth in a solution dissolved in 100 parts of dimethylformamide, 1
A prepreg was prepared by drying at 00° C. for 1 hour. After that, several sheets of this prepreg were stacked together and a pressure of 30 kg/c was applied.
d. After heating and pressure molding at a temperature of 180°C for 1 hour, 200°C
C. for 5 hours to obtain a laminate.

The bending strength of this laminate is 54 kg/mj at 25°C.
Met. Moreover, the bending strength after heating at 200°C for 200 hours was 53 dan/- at 25°C.

〔Effect of the invention〕

Among the engineering plastics that have been developed one after another recently, there is a group of aromatic polyamides called aramids. This group consists of resins with higher melting points, higher hardness, and higher strength than conventional thermoplastic resins, and some resins do not have melting points that make processing and moldability extremely difficult.
Since it is essentially a thermoplastic, it is inevitable that its hardness and mechanical strength will decrease at high temperatures.

The present invention has been carried out with the aim of developing a heat-resistant resin with excellent processability, hardness at high temperatures, and mechanical strength. The objective was achieved by developing a thermosetting aromatic polyamide oligomer obtained by curing.

Furthermore, we have developed a composition suitable for obtaining this aromatic polyamide, and have dramatically improved the moldability of the aromatic polyamide.

[Brief explanation of drawings]

FIGS. 1, 2, and 3 show the results of thermogravimetric analysis of the thermosetting polyamides obtained in Examples. Patent applicant Showa Kobunshi Co., Ltd.

Claims (5)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, R_1 and R_2 are divalent aromatic groups, and A
and B are aliphatic or aromatic polymerizable unsaturated groups. However, at least one of A and B is a polymerizable unsaturated group consisting of an adduct of a polyvalent amine and a cyclic unsaturated acid anhydride. n is a number from 0 to 15. ] A heat-resistant aromatic polyamide obtained by polymerizing an aromatic polyamide oligomer represented by the following. (2) The cyclic unsaturated acid anhydride in the aromatic polyamide oligomer represented by the general formula [I] described in claim (1) ▲ has a mathematical formula, chemical formula, table, etc. ▼ ▲ has a mathematical formula, chemical formula, table, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are H or CH_3. However, at least one of R^1 and R^2 is H. ] The heat-resistant aromatic polyamide according to claim (1). (3) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] [In the formula, R_1 and R_2 are divalent aromatic groups, and E
and F is an aliphatic or aromatic polymerizable unsaturated group. However, at least one of E and F is an unsaturated group consisting of a condensate of a polyvalent amine and an unsaturated acid chloride. n
is a number from 0 to 15. ] A heat-resistant aromatic polyamide obtained by polymerizing an aromatic polyamide oligomer represented by the following. (4) The unsaturated acid chloride in the aromatic polyamide oligomer represented by the general formula [II] according to claim (3) is (
meth)acrylic acid chloride, cinnamic acid chloride, crotonic acid chloride, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are H or CH_3. However, at least one of R^1 and R^2 is H. ] The heat-resistant aromatic polyamide according to claim (3). (5) 5% by weight or less of a radical polymerization initiator based on the aromatic polyamide oligomer represented by the general formula [I] according to claim (1) and/or the general formula [II] according to claim (3) A thermosetting aromatic polyamide oligomer composition.