JPH0551016B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Field of Application> The present invention is directed to a novel thermoplastic fragrance that has good thermal stability and fluidity particularly in the temperature range of 300 to 400°C, can be injection molded, and can give molded products with desirable properties. The present invention relates to a group polyamide-imide copolymer (hereinafter, polyamide-imide is abbreviated as PAI). <Prior art> By polycondensing an aromatic tricarboxylic acid anhydride or its derivative with an aromatic diamine or its derivative, aromatic compounds with excellent heat resistance are generally produced.
It is already well known that PAI can be obtained (for example, Japanese Patent Publication No. 42-15637, Japanese Patent Publication No. 44-15637,
Publication No. 19274, Special Publication No. 1972-2397, Special Publication No. 1973
-4077 Publication, Special Publication No. 50-33120, etc.). In addition, as a modification of these basic PAIs, the acid components include aromatic tricarboxylic acid anhydride or its derivative and aromatic dicarboxylic acid dichloride.
Many proposals have already been made regarding methods of utilizing the ingredients (for example, Japanese Patent Application Laid-Open No. 1988-8894, Japanese Patent Application Publication No. 121397-1972, Japanese Patent Publication No. 16908-1983).
Publication No. 12594, Special Publication No. 12594, Special Publication No. 12594, Special Publication No. 12594
Publication No. 13240, Special Publication No. 49-26316, etc.). In particular, JP-A-50-8894 describes polyamide amic acid (precursor of PAI) synthesized by reacting trimellitic anhydride monochloride/isophthalic acid dichloride with two or more diamines for the purpose of developing functional membrane materials. (open ring form) is disclosed. <Problems to be solved by the invention> However, the aromatic
When PAIs are intended to be used as melt molding materials, they are not necessarily satisfied in terms of the total balance of thermal stability during melt molding, fluidity during melt molding, and physical properties of the melt molded product. It was nothing like that. For example, the general formula synthesized from the three components of trimellitic anhydride/isophthalic acid dichloride/4,4'-diaminodiphenylmethane PAI, represented by It is. This property of unsuitability for melt molding can hardly be improved by copolymerizing other diamine components. In addition, the general formula synthesized from the three components of trimellitic anhydride/isophthalic acid dichloride/metaphenylenediamine Although PAI represented by has practical heat resistance properties, it is not easy to melt and mold due to its high melt viscosity when melted by heating. Also, the general formula synthesized from trimellitic anhydride/isophthalic acid chloride/4,4'-diaminodiphenylsulfone PAI represented by 4,4'-diaminodiphenylsulfone has essentially low polymerization activity, so only a polymer with a low degree of polymerization can be obtained, and is unsatisfactory as a resin for molded articles with practical strength. . In addition, the general formula synthesized from trimellitic anhydride/isophthalic acid dichloride/4,4'-diaminodiphenyl ether (or 4,4'-diaminodiphenyl sulfide) or Although PAI represented by has excellent heat resistance, it is difficult to melt and mold it smoothly because the flow start temperature and thermal decomposition temperature are close to each other. Therefore, the present inventors obtained an aromatic PAI that has good melt moldability by combining good thermal stability and fluidity in the temperature range of 300 to 400°C, and has an excellent balance of physical properties in the molded product. As a result of extensive research aimed at this purpose, the present invention was achieved by discovering that a novel thermoplastic aromatic PAI copolymer having the desired properties can be obtained by combining four specific constituent elements. <Means for solving the problems> That is, the present invention has the following formula:

Structural unit of [formula], B formula Structural unit of C formula Structural unit of and D formula The proportion of each structural unit is 1 mole of (C+D) to 1 mole of (A+B), and
B is 0.90 to 0.05 mol to A 0.10 to 0.95 mol,
D is 0.95 to 0.05 mol relative to C 0.05 to 0.95 mol, and the logarithmic viscosity measured at 30°C at a polymer concentration of 0.5% by weight in N-methyl-2-pyrrolidone solvent is 0.20.
~0.69, and is characterized in that A or B and C or D are alternately connected (however, Z in the formula is 3
A trifunctional aromatic group in which two of the functional groups are bonded to adjacent carbons, R ₁ is an alkyl group having 1 to 4 carbon atoms, an alkoxyl group or a halogen group, X
is a direct combination,

【formula】

[expression] or

[Formula] Y is a direct bond, -O -, -S-, -SO ₂ -,

【formula】

【formula】

[expression] or

[Formula] R ₂ is an alkyl group having 1 to 4 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group, Q is a direct bond, -CO-,
-O-, -S- or _-CH2- , a is 0 or 1
b is 0, 1 or 2, and c is 0 or an integer of 1 to 10. ). The thermoplastic PAI copolymer of the present invention is mainly composed of four units represented by A, B, C and D above. Here, the acid component (A+B) and the diamine component (C+D) are in a substantially equimolar ratio, and the ratio of each structural unit is A0.10 to 0.95 (preferably 0.30 to 0.85).
B is 0.90 to 0.05 (preferably 0.70 to 0.70) per mole
0.15) mole, C0.05~0.95 (preferably 0.30~0.80)
D is 0.95 to 0.05 (preferably 0.78 to 0.78) per mole
0.20) molar range. When the amount of A units is less than 10 mol % of the (A+B) units in the ratio of each of these constituent units, the melt viscosity of the resulting PAI copolymer becomes too high, which is inappropriate. Furthermore, if the amount of A units exceeds 95 mol %, it is not suitable because the modification effect by copolymerization of B units, such as improvement in tensile strength, cannot be obtained substantially.
Furthermore, if the amount of C units in (C+D) exceeds 95 mol%, the toughness will be noticeably insufficient, which is unsuitable. Furthermore, if the C unit content is less than 5 mol %, the thermal properties will be insufficient, which is inappropriate. Note that Z in the above A unit is 2 of the 3 functional groups.
A trifunctional aromatic group in which the functional group is bonded to an adjacent carbon, e.g.

【formula】

【formula】

【formula】

【formula】 【formula】

etc. In addition, the A′ unit when the imide bond in the above A unit remains in the state of an amic acid bond as its ring-closing precursor is present as a part of the A units, for example, up to 50 mol%, preferably up to 30 mol%, within the scope of the present invention. A specific example of the above B unit is

[expression] and

[Formula]. As a specific example of the above C unit, and side chain substituted derivatives thereof, etc. As a specific example of D unit, for example, and side chain substituted derivatives thereof. The PAI copolymer of the present invention can be produced using any of the many general production methods that have been proposed to date, but the following two methods are representative examples of the most practical. can be mentioned. (1) Isocyanate method: A method in which a mixture of an aromatic tricarboxylic acid anhydride and an aromatic dicarboxylic acid is reacted with an aromatic diisocyanate (for example, Japanese Patent Publication No. 51-6770). (2) Acid chloride method: A method in which a mixture of aromatic tricarboxylic acid anhydride chloride and aromatic dicarboxylic acid dichloride is reacted with an aromatic diamine (for example, Japanese Patent Publication No. 16908/1983, Japanese Patent Publication No. 12594/1986)
Publications, etc.). Among the above two methods, the acid chloride method has the advantage that raw materials are relatively easy to procure, and that it is easy to obtain PAI with a high degree of polymerization with excellent linearity (less branched structure) through low-temperature solution polymerization. This is the most recommended manufacturing method. Here, the acid chloride method will be explained in more detail as follows. That is, aromatic tricarboxylic anhydride monochloride/isophthalic acid dichloride (and/
or terephthalic acid dichloride) (10~90/90~
10 molar ratio) mixture 1 mol and aromatic diamine () (R ₁ is an alkyl group having 1 to 4 carbon atoms, an alkoxyl group, or a halogen group, X is a direct bond,

【formula】

[expression] or

[Formula] R ₂ is an alkyl group having 1 to 4 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group, Q is a direct bond, -CO-, -O-, -S- or -CH ₂ -, a is 0 or an integer of 1 to 4, b represents 0, 1 or 2) 10 to 90 (preferably 30 to 2)
80) Mol% and aromatic diamines () (Y is a direct bond, -C-, -S-, -SO ₂ -,

【formula】 【formula】

[expression] or

[Formula] R ₁ , R ₂ , a and Q are the same as above, and c represents 0 or an integer from 1 to 10. ) 0.9 to 1.1 mol of mixed diamine consisting of 90 to 10 (preferably 70 to 20) mol% is dissolved in an organic polar solvent and mixed for about 0.5 to 1 hour at a temperature of -20 to 80°C. If necessary, about 2 to 4 moles of hydrogen chloride scavenger are added to accelerate the polymerization reaction rate, and the polymerization reaction is completed at around room temperature in a reaction time of 0.5 to 10 hours. The polymer produced in this step contains the majority (for example, 50 to 100%) of the A units of the PAI copolymer of the present invention in the amido-amic acid units of the ring-closing precursor. The structure has been converted into a so-called polyamide amino acid. It is also possible to stagger the addition timings of aromatic tricarboxylic anhydride chloride and isophthalic acid chloride (and/or terephthalic acid chloride), in which case the resulting polymer is likely to become a block copolymer. The organic polar solvents used in this first step include N/N-dialkylcarboxylic acid amides such as N/N-dimethylacetamide and N/N-diethylacetamide, N-methylpyrrolidone, tetrahydrothiophene-1,
Heterocyclic compounds such as 1-dioxide, phenols such as cresol and xylenol, and especially N-methylpyrrolidone and N・N-
Dimethylacetamide is preferred. Also, the first
Hydrogen chloride scavengers added to the process include aliphatic tertiary amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine.
cyclic organic bases such as pyridine, lutidine, collidine, and quinoline, and organic oxide compounds such as ethylene oxide, propylene oxide, etc. The polyamideamic acid obtained in the first step is then subjected to a second dehydration ring closure step and converted into the polyamideimide copolymer of the present invention. The dehydration ring closure operation is carried out either by liquid phase ring closure in solution or solid phase thermal ring closure by heating in a solid. There are two types of liquid phase ring closure: a liquid phase chemical ring closure method using a chemical dehydrating agent, and a simple liquid phase thermal ring closure method. The chemical ring closure method uses chemical dehydrating agents such as acetic anhydride, aliphatic anhydrides such as propionic anhydride, _{and P2O5} .
It is carried out at a temperature of 0 to 120°C (preferably 10 to 60°C). In addition, in the liquid phase thermal ring closure method, the polyamide/amic acid solution is heated to 50 to 400℃ (preferably 100 to 250℃).
This is done by heating to. In this case, it is more effective to use an azeotropic solvent useful for water removal, such as benzene, toluene, xylene, chlorobenzene, etc. in combination. Solid phase thermal ring closure is performed by first isolating a polyamide/amic acid polymer from the polyamide/amic acid solution obtained in the first step and heat-treating it in a solid state. As a precipitant for isolating the polyamide/amic acid polymer, a liquid such as water, methanol, etc., which is miscible with the reaction mixture solvent but in which the polyamide/amic acid itself is insoluble, is employed. The heat treatment is selected to ensure the desired ring closure rate and melt fluidity, usually from 150 to 350° C. for 0.5 to 50 hours. If the treatment is carried out in the 250 to 350°C range for too long, the polymer itself tends to form a three-dimensional crosslinked structure, which significantly reduces the fluidity during melting, so care must be taken. In addition, the above aromatic diamine () and ()
Specific examples are shown in the form in which amino groups (-NH ₂ ) are attached to both sides of the divalent aromatic residues shown above as specific examples of the C unit and D unit of the present invention. Although the PAI copolymer targeted by the present invention can be obtained by the detailed production method detailed above, additional components other than those constituting the A unit, B unit, C unit, and D unit are added to the reaction system. forms other copolymerized components
It is possible to copolymerize PAI in combination within a quantitative range that does not significantly reduce the melt processability and physical properties of PAI, and it is within the scope of the present invention. The aromatic PAI copolymer of the present invention has a structure in which the imide unit is partially ring-opened and remains as an amic acid bond, but most of it has a ring-closed structure.
Also, the logarithmic viscosity (ηinh) measured in N-methyl-2-pyrrolidone solvent at a polymer concentration of 0.5% by weight at 30°C.
It is a high polymerization degree polymer with a value of 0.20 to 0.69, preferably 0.25 to 0.69, and can be used for various purposes as described below. Compression molding is performed by dry blending the PAI copolymer powder of the present invention with different polymers, additives, fillers, reinforcing agents, etc. as required, and then drying the powder at 300 to 400°C and under pressure.
It is carried out under conditions of 50-500Kg/ ^cm2 . Pressure molding and injection molding are performed by dry-blending the PAI copolymer of the present invention with different polymers, additives, fillers, reinforcing agents, etc. as necessary, or by extruding the same into pellets. It is fed to an extrusion molding machine or an injection molding machine and carried out under a temperature condition of 300-400°C. In particular, the aromatic PAI of the present invention
The copolymer has an excellent balance of thermal stability and flow properties in the 300-400°C range, and is useful for extrusion molding and injection molding. In addition, by further subjecting the molded product obtained by heating and melting molding the PAI copolymer of the present invention to heat treatment under high-temperature conditions, a molded product with further improved physical properties such as heat distortion temperature, tensile strength, bending strength, and friction and wear properties can be obtained. Obtainable. Such heat treatment conditions include heating the molded product to 200°C or higher and below the glass transition temperature of the molded product.
In particular, it is appropriate to heat the molded product at a temperature of 220°C or higher and lower than (glass transition temperature -5°C) of the molded product for 5 hours or more, especially 10 hours or more. If the heat treatment temperature exceeds the glass transition temperature of the molded article, the molded article is undesirably deformed during the heat treatment and has a strong tendency to impair its practicality. There are no particular restrictions on the equipment for this heat treatment, but a normal electric heating oven can suffice to achieve the purpose. For film and fiber manufacturing applications, the polymerization-finished solution can be applied in a dry or wet-dry casting process, or the isolated polymer can be melt-molded with appropriate additives as required. . Laminated boards are made by impregnating cloth or mat made of glass fiber, carbon fiber, asbestos fiber, etc. with a polymer solution, and then precuring it by drying/heating to obtain a prepreg.
It is manufactured by pressing under conditions of 50-300 kg/cm ² at ℃. For paint applications, different types of solvents may be added and mixed to the polymerization-completed solution as needed, and then the concentration may be adjusted and used for practical use as is. The composition of the present invention may contain the following fillers in an amount of 70% by weight or less, if necessary. (a) Wear resistance improvers: graphite, carborundum, silica powder, molybdenum disulfide, fluorine resin, etc. (b) Reinforcers: glass fiber, carbon fiber, boron fiber, silicon carbide fiber, carbon whisker, asbestos Fibers, asbestos, metal fibers, etc.
(c) Flame retardant improvers: antimony trioxide, magnesium carbonate, calcium carbonate, etc. (d) Electrical property improvers: clay, mica, etc. (e) Tracking resistance improvers: asbestos, silica, graphite, etc. f) Acid resistance improvers: barium sulfate, silica, calcium metasilicate, etc. (g) Thermal conductivity improvers: Metal powders such as iron, zinc, aluminum, copper, etc. (h) Others: glass beads, glass spheres, carbonic acid calcium, alumina,
It includes synthetic and natural compounds that are stable at temperatures above 300°C, such as talc, diatomaceous earth, hydrated alumina, mica, shirasu balloons, asbestos, various metal oxides, and inorganic pigments. <Examples> Hereinafter, the present invention will be further described in detail using Examples and Comparative Examples. Note that the value of the logarithmic viscosity, which is a guideline for the molecular weight of the polymer, was measured in N-methyl-2-pyrrolidone solvent at a polymer concentration of 0.5% and a temperature of 30°C. The melt viscosity of the polymer was determined by using a "Koka-type Flow Tester" manufactured by Shimadzu Corporation. A sample that had been dried to an absolutely dry state was placed in a cylinder heated to 360°C and left there for 8 minutes. Apply a load to the nozzle in the center of the die (diameter 0.5 mm, length 1
Measured by extrusion method from mm). Further, the glass transition temperature was measured using a PerkinElmer Model 1B DSC device. Note that measurements of various physical properties were performed according to the following methods. Bending strength (FS)...ASTM D790 Heat distortion temperature (HDT)...ASTM D648−56
(18.56Kg/cm ² ) Example 1 In a separable glass flask with an internal volume of 5 equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, 2.
-Bis(p-aminophenyl)propane 81.5g
(0.36 mol), 168.3 g (0.84 mol) of 4,4'-diaminodiphenyl ether (DDE) and anhydrous N,
3000 g of N-dimethylacetamide was charged and stirred to obtain a homogeneous solution. The reaction mixture is cooled to -10°C in a dry ice/acetone bath and 60.9 g (0.30 mol) of terephthalic dichloride is added followed by 189.55 g (0.90 mol) of trimellitic anhydride to maintain the temperature between -10 and -5°C. It was added in small portions at a similar speed. After continuing stirring at 20°C for an additional hour, 152 g (1.5 moles) of anhydrous triethylamine was added in portions at a rate sufficient to maintain the temperature below about 30°C. Next, the polymerized liquid is gradually poured into water under high-speed stirring to precipitate the polymer into particles.Then, the precipitated polymer is crushed into a fine powder using an impact crusher, and then thoroughly washed with water and dehydrated. and then in a hot air dryer
After drying at 150° C. for 5 hours and then at 200° C. for 3 hours, about 385 g of polymer powder having a logarithmic viscosity of 0.69 was obtained. The theoretical structural formula and molecular formula of the copolymer obtained here are as follows, and it has a structure in which A or B units and C or D units are alternately connected.Elemental analysis of the copolymer The results showed good agreement with the theoretical values as shown in Table 1. A

[Formula] - ( C ₉ H ₄ N ₂ O ₃ -) B

[Formula] - ( C ₈ H ₆ N ₂ O ₂ -) C

[Formula] - (C ₁₅ H ₁₄ -) D

[Formula] - (C ₁₂ H ₈ O -) A/B/C/D = 0.9/0.3/0.36/0.84 (molar ratio) = 75/25/30/70 (molar ratio)

[Table] Next, the obtained copolymer powder was added with 0.5% by weight of tetrafluoroethylene resin (Asahi Glass Co., Ltd. "Afron Polymist F-5") as a sun protection agent and titanium oxide.
After adding 0.5% by weight, Brabender Plastograph extruder (processing temperature 340-360℃)
The operation of extruding the pellets while melting and kneading was performed twice to obtain uniformly blended pellets. Next, the obtained pellets are compression molded (processing temperature 330-360℃, pressure 50℃).
~100Kg/cm ² ) to prepare test pieces and measure their physical properties, and the results shown in Table 2 below were obtained.

[Table] Next, the compression molded test piece obtained under the same conditions as above was placed in a hot air dryer and dried at 150°C for a day and night, then heated to 245°C.
When heat treatment was performed for 24 hours at 255°C and then for 48 hours at 255°C, the physical properties after the heat treatment were as shown in Table 3 below, and were significantly improved compared to the results in Table 2.

[Table] Comparative Examples 1 and 2 271.6 g (1.2 mol) of 2,2-bis(p-aminophenyl)propane or
The same operations as in the first half of Example 1 were performed except that 240.3 g (1.2 mol) of DDE was used alone, and 400 g of polymer powder with a logarithmic viscosity of 0.62 (this is referred to as Comparative Example 1) and a polymer powder with a logarithmic viscosity of 0.43 were obtained. 370 g of combined powder (this is referred to as Comparative Example 2) was obtained. Next, using the obtained polymer, 0.5% by weight of tetrafluoroethylene resin and 0.5% by weight of titanium oxide were blended in the same manner as in Example 1.
When the polymer obtained in Comparative Example 2 did not develop a smooth melted state, the rotational torque value applied to the extruder shaft exceeded the allowable limit of the device. As a result, melt-kneading was virtually impossible. On the other hand, although the polymer obtained in Comparative Example 1 could be made into pellets, when this pellet was compression molded under the same conditions as in the second half of Example 1, the bending strength of the molded product obtained was 630 kg. It was extremely small, measuring / ^cm2 . In this way, if each of the diamines used in Example 1 were used alone, it would be difficult to melt mold the polymer (Comparative Example 2), or melt molding is possible, but the strength is very low compared to Example 1. Only a molded article (Comparative Example 1) was obtained. Example 2 165.4 g of 4,4'-(p-phenylenediisopylidene)bisaniline was placed in the same apparatus as in Example 1.
(0.48 mol), DDE144.2g (0.72 mol) and anhydrous
3000 g of NN,N'-dimethylacetamide was charged and stirred to obtain a homogeneous solution. The reaction mixture was cooled to -10°C in a dry ice/acetone bath and 176.9 g (0.84 mol) of trimellitic anhydride chloride was added followed by 73.1 g (0.36 mol) of isophthalic acid dichloride at a temperature between -10 and -5°C. It was added in small portions at a rate that maintained the same amount. Thereafter, the same reaction operations and post-treatment operations as in Example 1 were performed, and the logarithmic viscosity was
400 g of 0.59 polymer powder was obtained. The theoretical structural formula and molecular formula of the copolymer obtained here are as follows, and it has a structure in which A or B units and C or D units are alternately connected, and the elements of the copolymer The analytical results also showed good agreement with the theoretical values. A

[Formula] - ( C ₉ H ₄ N ₂ O ₃ -) B

[Formula] - ( C ₈ H ₆ N ₂ O ₂ -) C ―(C ₂₄ H ₂₄ ―) D

[Formula] - (C ₁₂ H ₈ O -) A/B/C/D = 0.84/0.36/0.48/0.72 (molar ratio) = 70/30/40/60 (molar ratio) Next, the obtained copolymer Similar to Example 1, using a combination of 0.5% tetrafluoroethylene resin and titanium oxide.
After blending 0.5%, a melt-kneading operation was performed to obtain pellets. Next, test pieces were prepared by compression molding the pellets under the same conditions as in Example 1, and physical properties were measured, and the results shown in Table 4 below were obtained. Table 3 also shows the physical properties of this test piece after it was heat treated under the same conditions as in Example 1. It is clear that the physical properties are improved by heat treatment.

[Table] Example 3 311.4 g of 4,4'-bis(p-aminophenoxy) diphenyl sulfone was placed in the same apparatus as in Example 1.
(0.72 mol) and 3000 g of anhydrous N,N-dimethylacetamide were charged and stirred to obtain a homogeneous solution.
The reaction mixture was heated in a dry ice/acetone bath.
Cooled to 10℃, 73.1g of terephthalic acid dichloride
(0.3 mol) was added in small portions at such a rate that the temperature was maintained at -10 to -5°C. 40.5 g (0.4 mole) of anhydrous triethylamine was then added dropwise at a rate sufficient to maintain the temperature below about 0.degree. After dripping
After continuing stirring at 20°C for 1 hour, 4,4′-bis(p-aminophenoxy)diphenylsulfone
103.8g (0.24mol) and 3,3'-dimethyl-
4,4'-diaminobiphenyl 51.0g (0.24mol)
was added and dissolved. The reaction mixture was then cooled again to -10°C in a dry ice/acetone bath, and 176.9 g (0.84 mol) of trimellitic acid chloride was added in small portions at a rate such that the temperature was maintained between -10 and -5°C. , and then stirring was continued for 1 hour at 20°C. The obtained reaction mixture was subjected to the same post-treatment operation as in Example 1, and 560 g of polymer powder having a logarithmic viscosity of 0.48 was obtained. The theoretical structural formula and molecular formula of the copolymer obtained here are as follows, and it has a structure in which A or B units and C or D units are alternately connected.Elemental analysis of the copolymer The results also showed good agreement with the theoretical values. A

[Formula] - ( C ₉ H ₄ N ₂ O ₃ -) B

[Formula] - ( C ₈ H ₆ N ₂ O ₂ -) C

[Formula] - (C ₁₄ H ₁₂ -) D King (C ₂₄ H ₁₆ O ₄ S-) A/B/C/D = 0.84/0.36/0.96/0.24 (mole ratio) = 70/30/80/20 (mole ratio) Next obtained copolymer After blending 0.5% by weight of tetrafluoroethylene resin and 0.5% by weight of titanium oxide in the same manner as in Example 1 using the same method as in Example 1, a melt-kneading operation was performed to obtain pellets. Next, this pellet was compression molded under the same conditions as in Example 1 to create a test piece.
When physical properties were measured, the results shown in Table 5 below were obtained.

[Table] Examples 4 to 7 Two types of diamines shown in Table 6 and N,N-dimethylacetamide were added to the same apparatus as in Example 1.
3000g was added and stirred to obtain a homogeneous solution. This mixture was cooled in an ice bath, and 48.7 g (0.24 mol) of powdered terephthalic acid dichloride and 24.4 g (0.12 mol) of isophthalic acid dichloride were added in small portions at a rate that the internal temperature did not exceed 30°C, and the addition was completed. After 10~
The reaction was continued for an additional 30 minutes at 30°C. followed by powder
176.9g (0.84 mol) of TMAC was added in small portions at a rate that the internal temperature did not exceed 30℃, and then
Stirring was continued for an hour to complete the polymerization reaction. Next, the polymerization finished liquid was gradually poured into water under high-speed stirring to precipitate the polymer into powder, which was thoroughly washed/dehydrated, and then heated in a hot air dryer at 150°C for 5 hours, followed by drying at 220°C for 5 hours. It was dried at ℃ for 3 hours. The polymers obtained here each consisted of theoretical structural units as shown in Table 6, and the elemental analysis results also showed good agreement with the theoretical values. Next, the obtained polymer is compression molded (processing temperature 330-400℃, pressure 50-100℃)
When test pieces were prepared and physical properties were measured ^, the results shown in Table 6 were obtained.

【table】

【table】

【table】

[Table] <Effects of the Invention> The PAI of the present invention has good melt moldability by having good thermal stability and fluidity in the temperature range of 300 to 400°C, and the physical property balance of the molded product is good. This makes it possible to produce high-performance materials and molded articles with high molding productivity through extrusion molding and injection molding. Utilizing their excellent heat resistance and mechanical properties, these materials and molded articles can be used to manufacture electrical and electronic components,
It is widely used in fields such as aerospace equipment parts, automobile parts, and office equipment parts.

Claims (1)

[Claims] 1 A structural unit of formula [formula], B formula Structural unit of C formula Structural unit of and D formula It consists of structural units, and the proportion of each structural unit is (A
+B) (C+D) is 1 mole per mole, and B is 0.90 to 0.05 to A0.10 to 0.95 mole.
mol, D is 0.95 to 0.05 mol to C 0.05 to 0.95 mol, in N-methyl-2-pyrrolidone solvent,
A thermoplastic aromatic polyamide-imide copolymer having a polymer concentration of 0.5% by weight, a logarithmic viscosity of 0.20 to 0.69 measured at 30°C, and characterized in that A or B and C or D are alternately connected. (However, Z in the formula is a trifunctional aromatic group in which two of the three functional groups are bonded to adjacent carbons,
R ₁ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, X is a direct bond, [Formula] [Formula] or [Formula] Y is a direct bond, -O-, -S-, -SO ₂ - ,
[Formula] [Formula] [Formula] or [Formula] R ₂ is an alkyl group having 1 to 4 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group, Q is a direct bond, -CO-, -O-, -S- or _-CH2- , a is 0 or an integer of 1 to 4, b is 0, 1 or 2, and c is 0 or an integer of 1 to 10. )