JPS58154729A - Aromatic polyamide-polyimide block copolymer with improved moldability - Google Patents

Abstract

PURPOSE:The titled copolymer showing both good heat stability and good fluidity in the temperature range of 300-400 deg.C, prepared by using an aromatic diamine component formed by combining at least two kinds of aromatic diamine compounds. CONSTITUTION:An aromatic polyamide obtained by reacting a mixture of at least two kinds of aromatic diamines of formulaI(wherein A is an unsubstituted or substituted phenylene, naphthylene, anthrylene or a bicyclic aromatic hydrocarbon bonded by a bridging member), e.g., a mixture of 4,4'-diaminodiphenylmethane and m-phenylene diamine, with an aromatic dicarboxylic acid dihalide compound of formula II (wherein X is a halogen and B is A) is reacted with an aromatic polyamic acid obtained by reacting a mixture containing at least two kinds of the above aromatic diamines with an aromatic tetracarboxylic dianhydride of formula III, wherein Y is O, S, CH2 or the like. The formed block copolymer is imidated to obtain the titled copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aromatic polyamide-polyimide block copolymer with improved moldability.

It is already well known that polyamide block copolymers have good electrical, thermal and mechanical properties. However, the aromatic polyamide-polyimide block copolymers that have been proposed so far are insufficient in terms of thermal stability during melt molding and fluidity during melt molding.
Only compression molding was possible; extrusion and injection molding were completely impossible.

For example, a terminal amine polyamide block with an average molecular weight of 5,000 synthesized from isophthalic acid dichloride and m-phenylenediamine, 3.3:4.4'-benzophenonetetracarboxylic dianhydride, and 4.4'-diaminodiphenyl ether. Average molecular weight synthesized from 3.
The polyamide-polyimide block copolymer obtained by imidizing the polyamide-polyamic acid block copolymer obtained by reacting the terminal acid anhydride of 000 with the polyamic acid block can be substantially extruded or injection molded. It is impossible to do so.

The present inventors conducted studies aimed at obtaining an aromatic polyamide-polyimide block copolymer that has both good thermal stability and fluidity in the temperature range of 300 to 400°C, and found that aromatic polyamide block and a copolymer obtained by combining two or more aromatic diamine compounds in the aromatic polyamic acid block is a new thermoplastic aromatic polyamide-polyimide block copolymer having the desired physical properties. The present invention was achieved by discovering that this is a combination.

That is, the novel thermoplastic polyamide-polyimide block copolymer of the present invention is a terminal acid anhydride obtained by reacting a mixture of two or more aromatic diamines and a dicarboxylic acid civalide with a tetracarboxylic dianhydride. A is obtained by copolymerizing a monopolyamic acid or a terminal amine polyamic acid, and then converting it into hydrogen.

In the present invention, the aromatic diamine has the general formula (1)% formula%
(In the formula, A is an unsubstituted or substituted phenylene group, naphthylene group, or anthrylene group and represents a bicyclic aromatic group connected by a bridge member), for example, o-lm- or p-phenylenediamine, those in which the benzene nucleus is further substituted with a dihalogen or an alkyl group, such as diaminotoluenes, 1,3-diamino-4-tribenzene, 1,3-diamino-4-to-7 zene, 3-diamino-4-isopropylbenzene, etc., and other 1,5-
or 1,8-diaminonaphthalene, 1゜2-11,4
-11,5-11,8- or 46-cyamitsuanthracene, further two phenyl groups are -〇-1-8-, -
For example, 2,2'-13,5'- or 4. 4'-cya epsilonobenzophenone, 3.3'- or 4.4'-diaminodiphenyl ether, 4.4'-diaminodiphenylthioether, 4.4'-diaminodiphenylmethane, 2
．． 2'-16,3'- or 4,4'-diaminoazobenzene, 5,5'- or 4,4'-cyamitudiphenylsulfone, 4°4'-diaminotorundyl, 2,2'
- or 4,4'-diaminostyl pair.

In the present invention, two or more types of aromatic diamine components are used in the aromatic polyamide block and the aromatic polyamic acid block, so two or more types of aromatic diamines as described above are appropriately selected and used. In particular, the following combinations of two or more aromatic diamines are preferred. That is, m-phenylenediamine and 4,4'-diaminodiphenylmethane and m-phenylenediamine, m-phenylenediamine and 4,4'-diaminodiphenylthioether, m-phenylenediamisi and 4,4'-diaminodiphenyl sulfo7. A mixture of two types, such as 2.4-diaminotoluene and diaminodiphenylsulfone, '4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether and 3+ diamino diphenyl ketone, 4.4'-diaminodiphenyl ether, 4. Diaminodiphenylsulfone and m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ketone and m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4/4'-diaminodiphenylmethane It is a mixture of three types such as m-phenylenediamine.

The combination of two or more aromatic diamines in the aromatic polyamide block and aromatic polyamide acid block is
They may be the same or different.

The ratio of each component in the mixture of two or more aromatic diamines can be selected arbitrarily, but each component must be contained in a range of 5 to 95 mol, preferably 10 to 90 mol.

In the present invention, the aromatic dicarboxylic acid dichloride has the general formula (II) (wherein, (representing a bicyclic aromatic radical).

For example, examples where X is chlorine include inophthalic acid cyclolide, terephthalic acid dichloride, 1.3-1
1.4- or 1,5-naphthalenedicarboxylic acid dichloride, 1.5-11.4- or 1,5-anthracenedicarboxylic acid dichloride, 3.3'- or 4.4
'-diphenyl ether dicarboxylic acid dichloride, 3
．． 3'- or 4,4'-benzophenone dicarboxylic acid dichloride, 5.5'- or 4,4'-diphenylthioether dicarboxylic acid dichloride), 3.5'-
Examples include 444,4'-diphenylsulfonedicarboxylic acid diquaride 1.5,5'- or 4,4'-biphenyldicarboxylic acid dichloride.

Usually, as the dicarboxylic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, etc. are used alone or in combination.

In addition, in the present invention, the tetracarbo/acid dianhydride has the general formula (1) (wherein, Y is -o-, -s-, -c-, -aH2-, -
5o2- group), such as benzophenonetetracarboxylic dianhydride, bisdicarpoxyphenyl ether dianhydride, bis-dicarboxyphenylthioether dianhydride, bis-dicarboxyphenylmethane dianhydride. Examples include bis-dicarboxyphenyl sulfone dianhydride, bis-dicarboxyphenylpropani dianhydride, his-dicarboxyphenyl hexafluoropro, panni anhydride, etc., and these can be used alone or in combination of two or more. It will be done.

The aromatic polyamide in the present invention is a mixture of two or more selected from the above-mentioned aromatic amines and one or more selected from the above-mentioned aromatic dino-carboxylic acid dino-ride compounds. A terminal amine polyamide or an acid terminal polyamide can be obtained by reacting in the following manner.

That is, two or more aromatic diamines and a dicarboxylic acid dino-ride are reacted in a solvent at a temperature range of -20 to 40°C, preferably in a temperature range of -10 to 20°C.

The solvents used are N,N'-dimethylacetamide, N
-Methylpyrrolidone, N,N'-diethylacetamide, N,N'-dimethylmethoxyacetamide, N-acetyl-2-pyrrolidone, dimethyl sulfoxide, N-methyl-ε-prolactam, hexasol, which are anhydrous use something The amount used is such that the polymer concentration is in the range of 5 to 40% by weight, preferably in the range of 10 to 25% by weight.

The reaction is usually carried out by dissolving a mixture of two or more aromatic diamines in an anhydrous polar solvent, and gradually adding dicarboxylic acid civalide under a nitrogen atmosphere to cause the reaction.

Trimethylamine,
Aliphatic tertiary amines such as triethylamine, tripropylamine, and tributylamine, cyclic organic bases such as pyridine, picoline, and lutidine, alkali metal hydroxides, alkali metal carbonates, alkaline earth metal oxides, etc. Inorganic bases, organic oxide compounds such as ethylene oxide, propylene oxide, etc. are used.

The reaction is completed in 10 minutes to 2 hours after the entire amount of added dicarboxylic acid dichloride is dissolved.

In the above reaction, 0.99 for aromatic diamine
If a dicarboxylic acid cybaride is used in a molar ratio of ~0.050, it is possible to obtain an amine-terminated polyamide, while if an aromatic diamine is used in a molar ratio of 0.99 to 0.050 to the dicarboxylic acid cybaride, a polyamide with an acid halide terminal can be obtained. can.

Moreover, the aromatic polyamic acid in the present invention is also
A mixture of two or more selected from the above aromatic amines and one or more selected from the above aromatic tetracarboxylic dianhydrides are reacted as follows to produce a terminal acid anhydride polyamide. Obtained as acid or terminal amine polyamic acid.

That is, an aromatic tetracarboxylic acid anhydride is suspended in the same polar solvent as above, an aromatic diamine solution is added, and the temperature range is 0 to 100°C, preferably 0 to 40°C.
React at a temperature range of

In this reaction, if the aromatic diamine is used in a molar ratio of 05 to 099 to the aromatic tetracarboxylic dianhydride, the terminal acid anhydride polyamic acid can be A terminal amine polyamic acid can be obtained by using aromatic tetracarboxylic acid anhydride in a molar ratio of 0.099.

In the synthesis of these aromatic polyamides and aromatic polyamic acids, it is possible to obtain target products with arbitrary amide-imide ratios by adjusting the molar ratios of diamine to dicarboxylic acid dichloride and tetracarboxylic dianhydride to cyabane, respectively. can.

After the obtained aromatic polyamide-containing reaction solution is treated with a dehydrochlorination agent, it is added to the separately obtained aromatic boroamic acid-containing reaction solution to synthesize an aromatic polyamide-polyamic acid block copolymer.

Further, it is imidized in the presence of a dehydrating agent and a catalyst or without a catalyst to obtain a polyamide-polyimide block copolymer. Further, the desired polymer is separated and precipitated by a conventional method and dried.

That is, more specifically, in synthesizing an aromatic polyamide-polyamic acid block copolymer, when the aromatic polyamide is a terminal amine polyamide, an aromatic polyamic acid obtained as a terminal acid anhydride polyamic acid is used; In the case of acid halide polyamide, terminal amine polyamic acid is used.

The copolymerization reaction is carried out at a temperature of 0 to 80°C, preferably 10 to 30°C, with sufficient stirring.

The average molecular weight of the polyamide and polyamic acid part of the copolymer is determined by the molar ratio of the raw material, the aromatic diamine mixture and the aromatic dicarboxylic acid civalide, and the raw material, the aromatic diamine mixture and the aromatic tetracarboxylic acid dicarboxylate. There is a theoretical value determined by the molar ratio of the anhydride used. However, in reality, the average molecular weight of the obtained polyamide and polyamic acid can be indirectly indicated by their respective intrinsic viscosities. The intrinsic viscosity of the polyamide or polyamic acid obtained as described above varies somewhat depending on the purity of the raw materials and reaction conditions, but in general, the use of high-purity raw materials, an appropriate raw material molar ratio, low reaction temperature, etc. Alternatively, the average molecular weight expressed by the intrinsic viscosity of the polyamic acid and the theoretical average molecular weight are made to be quite similar.

When the polyamide and polyamic acid in the present invention are reacted at a molar ratio such that the theoretical average molecular weight is 3.000, their respective intrinsic viscosities (0.5 weight 11%, N,
in N-dimethylacetamide at 35°C) from 0.22 to
Located near 026 and 025-032.

Then, the polyamic acid block portion of the obtained aromatic polyamide-polyamic acid copolymer is dehydrated and imidized by either liquid phase imidization in a solution or solid phase thermal imidization by heating in a solid phase. Further, liquid phase imidization includes liquid phase chemical imidization using a chemical dehydrating agent and azeotropic imidization using an azeotropic solvent.

Chemical imidization is carried out by adding acetic anhydride or propionic anhydride to a polyamide-polyamic acid block copolymer solution at a reaction temperature of 0 to 120°C, preferably 20 to 80°C, in the presence or absence of a catalyst. . Catalysts used in this case include triethylabane, trilobylamine, pyridine, picolines, lutidines, N, N'
-Dimethylaniline, N,N'-diethylaniline, and other tertiary organic bases.

Azeotropic imidization is a process in which a polyamide-polyamide block copolymer solution is heated to 40 to 200°C and water is removed azeotropically in the presence of toluene, xylene, chlorobenzene, etc. under normal pressure or reduced pressure. Isolation of the polymer from the polymer mixture is carried out by known methods. That is,
The polymer mixture is poured into a solvent that is miscible with the reaction mixture other than the aromatic polyamide-polyimide block copolymer. A suitable solvent is methanol,
Examples include acetone, acetonitrile, dioxane, and water.

In solid phase thermal imidization, first, an aromatic polyamide-polyamic acid block copolymer is isolated.

Isolation of the copolymer is carried out by known methods.

That is, the reaction solution is poured into a precipitating agent such as methanol, acetone, water, etc. to precipitate the copolymer. This is done by heat-treating the solid powder. The heat treatment is
Normally 120℃~550℃, 01~760 tnrx
Hg is selected from the conditions of 0.5 to 50 hours so as to ensure the desired imidization rate and melting fluidity. However, care must be taken because long-term treatment in the range of 250 to 350° C. significantly reduces the fluidity of the copolymer itself when it is melted.

The aromatic polyamide-polyimide block copolymer of the present invention has a structure in which the imide units are substantially ring-closed, and when it is a polyamide-polyamic acid block copolymer,
It is a highly polymerized polymer with a logarithmic viscosity of 06 or more, preferably 035 or more, measured at a polymer concentration of 05% by weight and 35°C in N,N'-dimethylacetamide, and can be used in various conditions as shown below. .

At that point, the pellets to which different polymers, additives, fillers, reinforcing agents, etc. are added as necessary, or pelletized by extruding the pellets, are fed to an extrusion molding machine or an injection molding machine and heated at 300 to 400 °C. It is carried out under temperature conditions. In particular, the wholly aromatic polyamide-polyimide block copolymer of the present invention has excellent thermal stability and fluidity in the 600 to 400°C range, and is useful for extrusion molding and injection molding.

The present invention will be explained below with reference to Examples and Comparative Examples.

Example-1 A. Production of polyamide with amine end groups 4.4'-
Diaminodiphenylmethane 125J3S' (0,63
54 mol) and m-phenylenediamine 61M1f
(0,6353 mol) of anhydrous N,N'-dimethylacetamide 900 mol in a 5 t reactor equipped with a stirrer, a thermometer, a dropwise addition tube with a pressure equalization tube and a nitrogen inlet tube.
completely dissolved in rul. The internal temperature of the reactor was cooled to -15 to -5°C in a salt-ice bath, and solid isophthalic acid dichloride 2343r (1,154 mol) was added under a nitrogen atmosphere.
was added portionwise to the above solution. At that time, the reaction solution temperature was 5
The addition rate was adjusted to keep the temperature below °C.

After the addition was complete, the viscous reaction solution was stirred at 10° C. for 1 hour. Next, propylene oxide 141 was added to this reaction mixture.
t (242 mol) to 280 ml of anhydrous N,N'-dimethylacetamide! The diluted solution was added dropwise to the reaction solution while keeping the temperature of the solution below 10°C. After completion of the dropwise addition, the reaction solution was stirred at 10° C. for 1 hour to obtain a polyamide having terminal amine groups and an average molecular weight of 5.000 based on theoretical calculation. The intrinsic viscosity of this substance, that is, the intrinsic viscosity expressed by ηinh (the same applies hereinafter) (in the above formula, the 4-self natural logarithm, η,
= viscosity of the solution (05% by weight of polymer in N,N'-dimethylacetamide), η. = viscosity of the solvent (N, N'-dimethylacetamide), C = concentration of the polymer solution expressed in 7 of the polymer per 100 of the solvent, the temperature of viscosity measurement is 55°C) is 025 Met. Furthermore, a part of the obtained polyamide solution was separated and dried, and an infrared absorption spectrum was measured, and a clear absorption attributable to amide was obtained at 1650 crrL-'. This indicates that an aromatic boria compound was synthesized by the reaction of an aromatic diamine and an aromatic carboxylic acid dichloride, accompanied by dehydrochlorination.

B. Production of polyamic acid with acid anhydride termination In the same reactor as in A, 3. s', 4.4'-benzopheno/
Tetracarboxylic dianhydride 262.69 (0,815
mol) of anhydrous N, N'-dimethylacetamide 70
It was suspended in 0ml. 4.4'-diaminodiphenylmethano 694f (0,550 mol) and m-phenylenediamine 57.8? (0.55 mol) anhydrous N,
A solution of N'-dimethino and acetamide dissolved in 460 m/ml was added dropwise at 5 to 20°C under a nitrogen atmosphere. The viscosity increases as the amine solution is added, and when 75% of the amine solution is added, anhydrous N, sodimethylacetamide 5 is added to adjust the viscosity.
[Added 10 ml. After dropping, the reaction mixture was heated to 20~
After stirring at 25°C for 1 hour, the average molecular weight based on theoretical calculation with terminal acid anhydride groups was 3. Doll's polyamic acid was obtained.

The intrinsic viscosity of this product was 0.29. Furthermore, a part of the obtained polyamic acid solution was extracted, treated with acetic anhydride, imidized, separated, dried, and measured for infrared absorption spectrum. Clear absorption due to the imide group was obtained at 1775α-1. This indicates that aromatic polyamic acid was produced by the reaction between aromatic diamine and aromatic tetracarboxylic dianhydride, and was transformed into aromatic polyimide by dehydration reaction.

C. Production of boria middle polyimide block copolymer The polyamide solution having amine end groups obtained by A was added to the solution of the polyamic acid having acid anhydride ends obtained by B under a nitrogen atmosphere at 15°C to 20°C. It was added with a feed pump in about 60 minutes.

After the addition was completed, the mixture was further stirred at 201-25°C for 2 hours.

A viscous solution of a polyamide-polyamic acid block copolymer having an intrinsic viscosity (concentration 05 wt 1 N in N'-dimethylacetamide, temperature 65 DEG C.) of 076 was obtained. Add β-picoline 758 f (0,0815
After adding 25Of (245 mol) of acetic anhydride, the mixture was stirred at 40 to 50°C for 4 hours to obtain a suspension of polyamide-polyimide block copolymer. The resulting suspension was gradually poured into water under high-speed stirring to thoroughly pulverize the copolymer, and then washed with water, dehydrated, and washed with methanol.
Subsequently, it was dried at 120°C for 12 hours under reduced pressure to obtain a polyamide and polyimide part average molecular weight of 5.0 based on theoretical calculations.
A yellow powder 6601 of boria middle polyimide block copolymer No. 00 was obtained. The melt viscosity of the obtained polymer powder measured at 350° C. using a drop-down flow tester was 7.6×10′ voids, which was at a sufficiently practical level as a resin for melt molding.

In addition, after uniformly adding 2 parts of 47-ethylene oxide resin and 7'% of titanium oxide to the copolymer powder for anti-seizure purposes, it was pelletized and put into an injection molding machine to create an injection molded test piece. . Measure its physical properties (TISK6810
) The bending stress (Kr/crtt, 23℃) was 1.7X103, and the bending modulus (K9/cni, 23℃)
is 3.2X10', tensile strength (Kg/c!).

23℃) is 1.10 x 10”, compressive strength (Kq/c
rti, 23℃) is 1.25 x 103, Izod impact strength KrcrrL/cm, 23℃) is 65,
It exhibited excellent physical properties with a heat distortion temperature of 265°C.

Examples 2 to 5 A mixture of 4,4'-diaminodiphenyl ether and m-7 enyle/diamine, isophthalic acid chloride, and terephthalic acid were prepared by mixing aromatic polyamides as shown in Table 1 in the same manner as in Example-1. Synthesized from a mixture of acid chlorides. In addition, aromatic polyamic acid: 3.5:
It was synthesized from a diamine mixture mixed with 4.4'-benzophenone tetracarboxylic dianhydride as shown in Table 1.

This was copolymerized in the same manner as in Example 1(C) to obtain an aromatic polyamide polyimide Pronk copolymer. Table 1 shows the obtained /dichloride molar ratio, intrinsic viscosity, and intrinsic viscosity and melt viscosity of the copolymer.

Comparative Example-1 In the same manner as in Example-'1, 4,4'-diaminodiphenyl ether 276 f (0,1380 mol), isophthalic acid chloride 125 f (0, (16158 mol)) and terephthalic acid chloride 125 f CO,06
A polyamide was synthesized from a mixture of s, s
A polyamic acid was synthesized from 4,4'-benzophenone tetracarboxylic anhydride 5o45r (0,0945 mol) and 4,4'-diaminodiphenyl ether 16f (0,08 mol). This was treated in the same manner as in Example 1(C) to obtain a polyamide/polyimide block copolymer 852 containing a single aromatic diamine and having an average molecular weight of 3,000 for both the polyamide part and the polyimide part.

The intrinsic viscosity (ηinh) of the polyamide-polyamic acid block copolymer was (]83.

The polyamide-polyimide block copolymer had a melt viscosity of 1.05 x 10' voids measured by an up-and-down flow tester, which was unsuitable as a melt-molding resin.

Comparative Examples 2 to 4 Polyamide-polyimide block copolymers having a single aromatic diamine as shown in Table 1 were synthesized by the method of Example 1. Table 1 shows the intrinsic viscosity of polyamide and polyamic acid, and the viscosity of the obtained polyamide-polyimide block copolymer.

In Table 1, ηinh: Intrinsic viscosity, which is calculated by the following formula.

111 m natural logarithm η1: Viscosity (35° C.) of the solution (05% by weight of the polymer in N,N′-dimethylacetamide) η. : Viscosity of the solvent (N, N'-dimethylacetamide) (35°C) C: Polymer solution concentration η expressed as 1 of polymer per iomg of solvent : Melt measured at 350°C with a high-low flow tester Viscosity (unit: poise) Examples 6 to 14 Polyamide-polyimide block copolymers using a mixture of two or more aromatic diamines shown in Table 2 were obtained in the same manner as in Example 1. . Table 2 shows the results of measuring the intrinsic viscosity of polyamide and polyamic acid and the viscosity of the obtained copolymer.

Comparative Example 5 A polyamide-polyamic acid block copolymer made of a single diamine was synthesized in the same manner as in Comparative Examples 1 and 2. Both were mixed so that the molar composition was 1:1 and sufficiently stirred to obtain a uniform mixed solution of a uniform polyamide-polyamic acid block copolymer. This was treated in the same manner as in Example 1 (C), and the aromatic diamino was single, and the average molecular weight of both the polyamide part and the polyimide part was 3 based on theoretical calculations.
,000 of a polyamide-polyimide block copolymer was obtained. The intrinsic viscosity of the polyamide-polyamic acid block copolymer made of 4,4'-diaminodiphenyl ether was OBO, and that of the copolymer made of m-phenylenediamine was 059. The melt viscosity of the polyamide-polyimide block copolymer mixture was 150 x 10' poise as measured by a high-down flow tester. The melt viscosity of the mixture does not decrease until it can be used for melt molding.

Example 15 A. Production of polyamide with acid chloride end groups A polyamide block with acid chloride end groups was prepared by the method of Example 1A, and 66.19 g of isophthalic acid dichloride (
03256 mol), 4. Ediaminone phenyl ether 35.959 (0,1795-E: #), 2.
4-Toluenediamine 21.939 (0,1795 mol), anhydrous N, N'~dimethylacetamide 400
mJ, cooled to =15°C to -5°C, and added 65.9Of (0
, 6512 mol) was added to react and synthesize. The produced triethylamine hydrochloride was separated from P.

B. Production of amine-terminated polyamic acid block Amine-terminated polyamic acid block was prepared using the method of Example 1B in 3. s', 4.4'-benzophenonetetracarboxylic dianhydride 752 f (0,2334 mol), 4
．． 4'-diaminodiphenyl ether20. Of (0
, 1 mol) and 2.4-) luenediamine 122F (0
, 1 mol) in anhydrous N,N'-dimethylacetamide.

C. Production of polyamide-polyamic acid block copolymer The polyamide obtained in A and B and the polyamic acid solution were mixed and reacted at 10 to 20°C to obtain a polyamide-polyamic acid block copolymer.

Furthermore, it was imidized by the same imidization method as in Example 10, and the average molecular weight of both the polyamide part and the polyimide part was 3.
,000 polyamide-polyimide block copolymers were produced.

The intrinsic viscosity of this polyamide-polyimide block copolymer was 06B, and the melt viscosity of the polyamide-polyimide block copolymer at 350°C measured by an up-and-down flow tester was 8.9×10' poise.

patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1) (a) an aromatic polyamide obtained by reacting a mixture of two or more aromatic diamines with an aromatic dicarboxylic acid sybaride compound, and (b) a mixture of two or more aromatic diamines and an aromatic An aromatic polyamide-polyimide with improved moldability, which is obtained by subsequently imidizing an aromatic polyamide-polyamic acid block copolymer obtained by reacting an aromatic polyamic acid obtained by reacting with a group tetracarboxylic dianhydride. Block copolymer. 2) Aromatic diamine has the general formula (I) H2N+A+Na2(D (wherein A is an unsubstituted or substituted phenylene group, naphthylene group, anthrylene group, or a bicyclic aromatic group connected by a bridge member) The copolymer according to claim 1, wherein the aromatic dicarboxylic acid dino-ride compound is represented by the general formula (II) (wherein, X is a rogen atom). , B is an unsubstituted or substituted phenylene group/naphthylene group.・The copolymer according to claim 1, which is represented by an anthrylene group or a bicyclic aromatic group connected by a crosslinking member. 4) Aromatic tetracarboxylic dianhydride has the general formula l (aya, 7yuni.-1-8--ki-1-6□2-1) -C(CF3) 2-1-c(cH3) a2, -so,
- The copolymer according to claim 1, which is represented by any one of the following groups.