JPH09302092A - Production of polyamide-imide resin by direct polymerization process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a high-molecular-weight polyamide-imide(PAI) resin excellent in heat resistance and melt flow and also in hue and physical properties, usable as a thermoplastic molding material, especially a heat-resistant structural material important in the high-tech industries and capable of being extensively used for heat-resistant coating materials, heat-resistant sheets, heat-resistant adhesives, heat-resistant fibers and heat-resistant films.

SOLUTION: An aromatic tricarboxylic acid anhydride is condensed with a diamine in a polar solvent to produce a diimidodicarboxylic acid, which is converted into an intermediate having excellent low-temperature reactivity by using an acyl halogenating agent as a catalyst and the intermediate and a diamine are subjected to a direct polymerization reaction to obtain a high- molecular-weight PAI resin. The reaction can be accomplished at a relatively low temperature, say, 100°C or below and a reaction time with 10hr.

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly economical method for producing a polyamide-imide (hereinafter abbreviated as "PAI") resin. More specifically, it relates to a condensation reaction product of aromatic tricarboxylic anhydride and diamine. A method for producing a PAI resin by producing a certain diimidedicarboxylic acid in a polar solvent, using an acyl halogenating agent as a catalyst to form an intermediate having excellent reactivity, and then performing a direct polymerization reaction with a diamine. Regarding

Further, the present invention relates to a method for producing a high molecular weight PAI resin with a high yield in a short reaction time at a low temperature in a simple production process.

[0003]

2. Description of the Related Art PAI resins have various molecular structures depending on the kinds of monomers used, but trimellitic anhydride (or its derivative) is used as a component of aromatic tricarboxylic acid, and metaphenylenediamine and diamino are used as diamine components. The following general formula (I) obtained by polycondensation by mixing diphenyl ether is used.

[0004]

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Resins such as those represented by are most typical.

The PAI resin of the general formula (I) is
U.S. Pat. No. 4,016,140 and Japanese Unexamined Patent Publication No. Hei 02
No. 18,422, etc., this resin is
As a transparent amorphous resin, it has the following characteristics: (1) The heat distortion temperature is very high at 278 ° C, the long-term heat resistance temperature is over 200 ° C, and the heat resistance is very high.
The usable temperature range is as wide as 200 to 260 ° C. (2) It has high mechanical strength and has excellent rigidity at 200 ° C. or higher, which is about the same as the physical properties of general-purpose engineering plastics at room temperature. Furthermore, the impact resistance is also very excellent. (3) Excellent creep resistance. (4) The linear expansion coefficient is 4 × 10 ^-5 even for non-reinforced products.
When using a filler with a small value of cm / cm · ° C,
The value can be reduced to less than half. (5) Especially excellent in dielectric breakdown strength and volume specific resistance,
Moreover, it has the flame retardancy of UL94V-0 without adding any additives. (6) Since it has excellent self-lubricating property and wear resistance due to its combination with PTFE and graphite and has excellent strength and elastic modulus even at high temperature, it is most suitable as a sliding component used in a harsh environment. (7) It has excellent chemical resistance and is almost stable to hydrocarbon-based solvents, but caution is required for concentrated alkaline aqueous solutions. (8) Excellent resistance to ultraviolet rays and radiation.

A general method for producing PAI resin is polyamic acid (Polyya acid) which is a primary polymer by condensation reaction of aromatic diisocyanate and aromatic tricarboxylic acid anhydride.
micacid) and an isocyanate method for synthesizing PAI [JP-B-44-19,274, US Pat. No. 3,541,038 (1970)] and a condensation reaction of aromatic tricarboxylic acid chloride and aromatic diamine. Acid chloride method for producing PAI. For the acid chloride method, N, N'-dimethylacetamide (hereinafter referred to as "DM
(Hereinafter, simply referred to as "Ac") at room temperature in a non-aqueous polar solvent such as a low temperature homogeneous solution polymerization method (US Pat.
920, 612 (1975)) or a system of water and an organic solvent that is partially soluble in water, such as methyl ethyl ketone, developed by Teijin Chemicals, Japan, and uses triethylamine as an acid acceptor. There is a method such as a low temperature precipitation polymerization method (Japanese Patent Application Laid-Open No. 46-15,513) which is a kind of interfacial polymerization method. As another method for producing a PAI resin, there is a direct polymerization method in which an aromatic diamine and an aromatic tricarboxylic acid are directly reacted in the presence of a dehydration catalyst [US Pat. No. 3,860,559 (1975), JP 58-180,532].

[0008] However, in the production of PAI by the isocyanate method, gelation occurs during the reaction, and it is difficult to obtain a linear high molecular weight polymer due to the formation of a side reaction product, and it is very difficult to control the reaction. Therefore, the PAI resin produced by this method has a reduced melt flowability and poor moldability, has very low mechanical properties and heat resistance, and is difficult to use in applications such as molding materials.

The low temperature homogeneous solution polymerization method of the acid chloride method is a method in which a high molecular weight polymer can be obtained by using an expensive acid chloride as a raw material, and polyamic acid which is a primary polymer This is a two-step reaction in which after production, imidization is carried out either by heating again or by using a dehydration catalyst, and it is necessary to remove the halogen compound produced during the reaction. Therefore, it is disadvantageous in terms of price, and on top of that, it is almost impossible to modify the molecular structure of the resin.

The low-temperature precipitation polymerization method, like the low-temperature homogeneous solution polymerization method, utilizes a very expensive acid chloride, and uses methyl ethyl ketone and water as reaction solvents to precipitate polyamic acid and to perform ring closure. Reaction,
Since the produced PAI has a large molecular weight distribution and only a polymer having a relatively low molecular weight is obtained, it has little practical value.

Not only that, but also in the isocyanate method and the acid chloride method, since both acid chloride and diisocyanate are sensitive to water and are very difficult to handle, water must be thoroughly shut off also in the reaction process. There is a drawback that.

Therefore, the PAI resin direct polymerization method is a method of directly reacting an aromatic diamine and an aromatic tricarboxylic acid anhydride or a derivative thereof by using a polymerization dehydration catalyst. Much research has been carried out because it is the simplest process and is advantageous in terms of cost such as raw material cost and manufacturing process cost, and it is a method that is easy to secure and handle monomers.

The polymerization catalyst used in this method is a phosphoric acid-based catalyst such as phosphoric acid or polyphosphoric acid (Japanese Patent Publication No. 63-2).
7,527, JP-A-62-297,329, JP-B-63-108,027, JP-A-2-115,229.
Boric acid and boric acid anhydride such as boric acid anhydride (French Patent No. 1,515,066, JP-A-58-180,
532) or phosphoric acid triesters such as triphenyl phosphite (US Pat. No. 3,860,559)
Etc. are used, and there is a method of adding two or more kinds of these catalysts (JP-A-64-51438), and it is known that these polymerization catalysts have different polymerization effects depending on the kind. . However, in order to obtain a polymer having a high molecular weight, it is necessary to use an expensive polymerization catalyst in the same molar ratio as the reactant monomer and carry out the reaction at a high temperature of 200 ° C. or higher for a long time. Therefore, N- which is a high boiling solvent
A resin having a high molecular weight and a high viscosity even when methylpyrrolidone (hereinafter abbreviated as "NMP"), sulfolane, nitrobenzene, benzonitrile, 1,3-dimethyl-2-imidazolidinone, etc. is used. When the monomer and the monomer react with each other at a high temperature for a long time, they become charred and adhere to the inner wall of the reactor or decompose in the reactor, resulting in a tar-like substance and a large amount of it. Polymerization catalyst mixed with the polymer, these deteriorate the hue,
It causes deterioration of the physical properties of PAI. In particular, since expensive polymerization catalysts must be used in large amounts and these polymerization catalysts cannot be recovered, the production cost of the PAI resin becomes high, which is not economical.

The S. Maiti and A. Ray et al Mak
romol. Chem. Rapid Commun. 2,649-653
(1981) reported that N, N-dimethylformamide (hereinafter abbreviated as "DME") solvent added with thionyl chloride and lithium chloride was used, and pyridine (hereinafter abbreviated as "Py"). Was developed as an acid acceptor and reacted at 0 to 5 ° C. In this method, PA having a very low molecular weight was developed.
Only I can be obtained, and it is not economical to use an expensive metal salt.

[0015]

The object of the present invention is to epoch-makingly solve the above-mentioned problems of the PAI production technology by the known direct polymerization method, and to improve heat resistance, melt fluidity, solubility and economical efficiency. An object is to provide a method for producing an excellent high molecular weight PAI resin.

[0016]

The production method of the present invention comprises the steps of dissolving an aromatic tricarboxylic acid anhydride and a diamine in a polar solvent to produce a diimidecarboxylic acid, and then using an acyl halogenating agent as a catalyst to obtain a nucleophilic group. This is a method of producing a high molecular weight PAI resin by adding an diamine as a nucleophilic agent after forming an intermediate having excellent reactivity with the agent.

More specifically, in the present invention, an aromatic tricarboxylic acid anhydride and a diamine are dissolved in a polar solvent such as NMP, water generated by heating is removed in the form of an azeotropic mixture, and the ring is closed to diimide dicarboxylic acid. After the acid is produced, it is separated as a solid or remains in a state of being dissolved in a solvent, and an acyl halogenating agent such as thionyl chloride (hereinafter abbreviated as “TC”) used as a polymerization catalyst is NMP. Dissolved in a polar solvent such as
After cooling to the following to form a complex, the temperature is raised to room temperature and the solid diimidedicarboxylic acid prepared as described above is added, or the diimidedicarboxylic acid NMP solution is added and allowed to react at room temperature within 1 hour. To form an intermediate, and then add diamine and carry out an amidation reaction at 100 ° C. or less to obtain an intrinsic viscosity of 0.1 to 2.5 dL within 10 hours.
/ G (solvent: DMAc, temperature: 30 ° C., concentration 0.5 g /
dL) is a method for producing a PAI resin.

The aromatic tricarboxylic acid anhydride used in the present invention is represented by the following general formula (II).

[0019]

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Further, diimidedicarboxylic acid, which is a condensate of aromatic tricarboxylic acid and diamine, has the general formula (II
I).

[0021]

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The diamine used in the present invention is represented by the general formula (IV).

[0023]

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These compounds may be used alone or, if necessary, as a mixture of two or more kinds. Among these, in consideration of physical properties such as heat resistance and melt fluidity of the produced resin and economical efficiency such as cost, oxy- which is a condensate of trimellitic anhydride and 4,4'-diaminodiphenyl ether. Bis (N- (4-
(Phenylene) -trimellitimide) [OBTI], metaphenylene-bis (N-trimellitimide) which is a condensation polymer with metaphenylenediamine, 4,4-diaminodiphenyl ether (ODA), 4,4'-diaminodiphenylmethane (MDA), Metaphenylenediamine (m-
It has been found that PAI resins obtained utilizing PDA) and isophoronediamine (IPDA) are excellent.

Examples of the catalyst usable in the present invention include organic or inorganic acyl halogenating agents such as thionyl chloride (TC), paratoluenesulfonyl chloride (TsCl), sulfuryl chloride, cyanuryl chloride and phosphorus trichloride. Thionyl chloride is superior in terms of cost and performance.

The reaction solvent used in the present invention forms a complex with an organic or inorganic acyl halogenating agent,
A polar solvent which easily induces acylation,
P, N-methylimidazole (NMI), N-ethylpyrrolidone, N-phenylpiperidone, N-methylcaprolactam, N, N'-ethylenedipyrrolidone, hexamethylphosphoric triamide, N-ethylalphapyridone,
There are N, N'-dimethylacetamide, N, N-dimethylpropionamide, etc., and the most excellent solvents are NMP and N.
MI, HMPA, etc.

As the acid acceptor used in the present invention, tertiary amines and alkylene oxides can be used, and as tertiary amines, pyridine (Py), alpha-picoline, 2,6-lutidine, triethylamine ( TE
A) and the like, and alkylene oxides include propylene oxide (PO), ethylene oxide, butylene oxide and the like. This acid acceptor produces H generated during the reaction.
Reacting with Cl to form a salt or halohydrin compound,
It removes HCl. These are used in amounts of 1 to 1.5 mol per mol of theoretically calculated HCl.

In the production method of the present invention, 0.5 mol of the diamine is used per 1 mol of the aromatic tricarboxylic acid to prepare the diimidedicarboxylic acid, and then the same number of diamines are reacted. To produce PAI resin. At this time, the tertiary amine or alkylene oxide can be added simultaneously with the diamine or after the diamine is added. Reactant concentration is 5
It is 50 wt%, preferably 10 to 20 wt%. 5 wt%
If it is less than 50% by weight, the economy is low. The amount of the catalyst used is 170 to 230 mol% based on the number of moles of the monomer, especially 1
90-210 mol% is suitable and outside this range,
Almost no progress of the polymerization reaction is observed. The reaction temperature during the polymerization reaction is 0 to 100 ° C., and the reaction time is 0.5 to 10 hours. Especially in the temperature range from room temperature to 50 ℃,
Reaction times within 2 hours are preferred.

[0029]

The PAI resin produced according to the present invention has a temperature of 30 ° C.
Has an intrinsic viscosity of 0.1 dL / g or more measured at a concentration of 0.5 g / dL of DMAc.
It can be used for films and coatings. Such a PAI resin manufacturing method has a simple manufacturing process, is easy to secure and handle a monomer, and uses an inexpensive catalyst, which is advantageous in terms of raw material cost and manufacturing process cost. However, there is no decrease in solubility due to side reactions and deterioration in hue and physical properties due to the inclusion of tar-like substances, etc., and only thermoplastic molding materials, especially major heat-resistant structural materials in advanced industries such as electrical and electronic, space and aviation. Not heat resistant paint, heat resistant sheet, heat resistant adhesive, heat resistant slide material,
Widely applicable to heat resistant fibers and heat resistant films.

[0030]

The present invention will be described in detail below with reference to examples.

Example 1 In a 30 liter reactor equipped with a stirrer, a nitrogen inlet, a temperature controller and a cooler, 0.7 kg (3.5 mol) of 0.7 kg (3.5 mol) was gradually added while gradually passing nitrogen gas. Diaminodiphenyl ether, 0.16 kg (1.
5 mol) of metaphenylenediamine, 1.92 kg (10
Mol) trimellitic anhydride and 10 liters of NMP
Were mixed and stirred at room temperature. After 1 hour, 2 liters of xylene was added, heated to 180 ° C., and water generated during the reaction was removed as an azeotrope using a Dean-Stark trap to prepare a diimidedicarboxylic acid mixture.

Further, in a 25 liter reactor equipped with a stirrer and a nitrogen inlet, while passing nitrogen gas,
1.22 kg (10.25 mol) of thionyl chloride and 10 liter of NMP were mixed and cooled to 5 ° C or lower. After 0.5 to 1 hour, the temperature was raised again to room temperature and added all at once to the reactor containing the dicarboxylic acid-NMP mixture prepared above. Then, after stirring at 25 ° C for 1 hour, 0.7 kg (3.5 mol) of diaminodiphenyl ether, 0.16 kg (1.5 mol) of metaphenylenediamine and 1.25 L of NMP were added, and nitrogen gas was added. The reaction was carried out at room temperature for 2 hours in the presence of.
The reaction mixture was isolated by precipitation in a blender with excess distilled water and filtration. After washing the isolated polymer several times with water and methanol, 12
A yellow powder polymer was obtained by drying in a vacuum dryer at 0 ° C. for 24 hours. PAI manufactured as described above
Resin was dissolved in DMAc at a concentration of 0.5 g / dL and
The intrinsic viscosity measured at ° C was 1.05 dL / g.
The prepared PAI was dissolved in DMAc to a solid content of 10 wt% and applied on a glass plate.
C. and 250.degree. C. for 1 hour, respectively, and further cured at 300.degree. C. for 10 minutes to produce a pale tan PAI film.

Example 2 Using the same reactor as in Example 1 and using NMI instead of NMP as a reaction solvent, a dicarboxylic acid was produced. In a 25 liter reactor equipped with a stirrer and a nitrogen inlet, 1.90 kg (10.0 mol) of tosyl chloride and 10 liter of NMI were added while passing nitrogen gas, and the mixture was cooled to 10 ° C or lower. . After 1 hour, the temperature was raised to room temperature and added all at once to the reactor containing the diimidocarboxylic acid prepared above. Then, after stirring at 25 ° C for 1 hour,
0.70 kg (3.5 mol) of diaminodiphenyl ether, 0.16 kg (1.5 mol) of metaphenylenediamine and 5 liters of NMI were added thereto, and the powdered PAI polymer was prepared by the same method as in Example 1. Obtained. The PAI polymer was dissolved in DMAc at a concentration of 0.5 g / dL and the intrinsic viscosity measured at 30 ° C. was 0.95 dL / g.

Example 3 The same reactor as in Example 1 was charged with 0.
63 kg (3.15 mol) of diaminodiphenyl ether, 0.15 kg (1.35 mol) of metaphenylenediamine, 1.73 kg (9.0 mol) of trimellitic anhydride and 10 liters of NMP were added, and the mixture was kept at room temperature for 1 hour. Stir,
The mixture was heated to 180 ° C. and imidized to produce a diimidedicarboxylic acid mixture.

Further, in a separate reactor of 25 liters equipped with a stirrer and nitrogen inlet, 1.10 kg (9.23 mol) of thionyl chloride and 10 liters of NMP were added while passing nitrogen gas. Cooled to below 5 ° C. After 1 hour, the temperature was raised to room temperature and 0.38 kg (2
After stirring at room temperature for 1.5 hours with 0.63 kg (3.15 mol) of diaminodiphenyl ether and 0.15 kg (1.35 mol) of metaphenylenediamine, Example 1 was added. PAI in powder form was obtained by the same method as described above. The intrinsic viscosity measured by dissolving this PAI in DMAc at a concentration of 0.5 g / dL was 0.72 dL / g.

Example 4 In the same reactor as in Example 1,
00 kg (5 mol) of diaminodiphenyl ether, 1.
92 kg (10 mol) of trimellitic anhydride and 12 liters of metacresol were added, and the mixture was stirred at 80 to 90 ° C.
The temperature was raised to. After about 1 hour, 2 liters of toluene were added and heated to 160 ° C. to remove water formed during the reaction as an azeotrope. After the reaction, the precipitate formed by cooling was filtered and washed with methanol and acetone 2-3 times. After drying in a vacuum dryer at 120 ° C. for 24 hours, 2.67 kg of oxy-bis (N- (4-phenylene) -trimellitimide) [OBTI] (yield 97.5%,
mp: 374 ° C.) was obtained. Separately, 0.54 kg (5 mol) of metaphenylenediamine in the same reactor as in Example 1,
1.92 kg (10 mol) of trimellitic anhydride and 18
Lithium meta-cresol and meta-phenylene-bis (N-trimellitimide) by the same method as above.
[BTI] 2.05 kg (yield 90%, mp: 398 ° C)
I got

Further, in a 30 liter reactor equipped with a stirrer, a nitrogen inlet and a condenser, 1.18 kg (10.0 mol) of thionyl chloride and 20 liter of NMP were added while passing nitrogen gas. Cooled to below 5 ° C. After 1 hour, warm to room temperature and as above, 1.92 kg (3.5 mol) OBTI, 0.68 kg
(1.5 mol) of BTI and 10 liters of NMP were added, and the mixture was stirred at room temperature for 1 hour. Then 0.70kg
(3.5 mol) diaminodiphenyl ether, 0.1
6 kg (1.5 mol) of metaphenyldiamine and 10
1 liter of NMP was added, and the mixture was vigorously stirred at room temperature for 2 hours. Then, the reaction product was treated in the same manner as in Example 1 to obtain a PAI powder. The intrinsic viscosity measured by dissolving this PAI powder in DMAc was 0.85 dL / g.

[Embodiment 5] By the same method as in Embodiment 4, O
BTI was obtained. In the same 30 liter reactor as in Example 1, 0.85 kg (5 mol) of isoprene diamine was mixed with 8 liters of DMAc and dissolved, and then cooled to a low temperature of 10 ° C or lower. Then 1.93 kg (10.05
(Mol) trimellitic anhydride was added, and the mixture was kept at room temperature and then stirred for 5 to 6 hours. Again, 1.2 liter of acetic anhydride and 0.3 liter of pyridine were added to the reaction mixture, reacted at 150 ° C. for 5 hours, and then cooled. Distilled water was added to cause precipitation, and the precipitate was washed several times with methanol to obtain 1.55 kg (yield 60%) of diimidedicarboxylic acid [IPDAA] having an isoprene diamine structure.

Further, in a 30 liter reactor equipped with a stirrer, a nitrogen inlet and a condenser, 1.22 kg (10.25 mol) of thionyl chloride was added to 10 liters of NMP while passing nitrogen gas. Cooled to below 5 ° C. After 1 hour, warm to room temperature and prepare 1.55 kg (3 mol) of IPDAA, 1.09, prepared as above.
kg (2 mol) of OBTI and 10 liters of NMP were added to the reaction mixture, and the mixture was reacted at room temperature for 1 hour, then 100 k.
g (5 mol) of diaminodiphenyl ether was added and 2
The mixture was stirred at 5 to 50 ° C for 2 hours. Then, the reaction product was treated in the same manner as in Example 1 to obtain a PAI resin. The intrinsic viscosity measured by dissolving this PAI resin in DMAc was 0.65 dL / g.

Example 6 Using the same reactor as in Example 1, HMPA was used instead of NMP as a reaction solvent to produce a dicarboxylic acid. Also, in a 25 liter reactor equipped with a stirrer and a nitrogen inlet, 1.18 kg (10.0 mol) of thionyl chloride was added to 10 liters of HMPA while passing nitrogen gas and cooled to 5 ° C or lower. did. After 1 hour, the temperature was raised to room temperature and added all at once to the diimidecarboxylic acid reactant prepared as above.
Then, after stirring at 25 ° C. for 1 hour, 0.70 kg (3.
5 mol) of diaminodiphenyl ether, 0.16 kg
Further (1.5 mol) of metaphenylenediamine and 5 liters of HMPA were added and reacted at 7 ° C. for 3 hours. After the reaction, the reaction product was treated in the same manner as in Example 1 to obtain PAI. This PAI was dissolved in DMAc at a concentration of 0.5 g / dL and the intrinsic viscosity measured at 30 ° C. was 0.88 dL / g.

Example 7 A diimidedicarboxylic acid was produced in the same manner as in Example 1 using the same reactor.
In a 25 liter reactor equipped with a stirrer and a nitrogen inlet, 1.22 kg (10.
25 mol) of thionyl chloride and 10 liters of NM
In addition to P, it was cooled to 5 ° C or lower. After 1 hour, the temperature was raised to room temperature and the reactants were added all at once to the reactor containing the diimidodicarboxylic acid prepared above. Then, after stirring at 25 ° C. for 1 hour, 0.70 kg (3.5 mol) of diaminodiphenyl ether, 0.16 kg (1.
5 mol) of metaphenylenediamine and 5 liters of NMP were added all at once, and then 2.79 liters (20 mol) of triethylamine was gradually added to the reaction temperature of 50.
The temperature was maintained below the temperature for 2 hours. After reaction, after cooling,
The reaction product was treated in the same manner as in Example 1 to obtain a polymer. DM of manufactured PAI resin at a concentration of 0.5 g / dL
Intrinsic viscosity measured at 30 ° C by dissolving in Ac is 1.52
It was dL / g.

Example 8 Using the same reactor as in Example 1 and in the same manner as in Example 4, OBTI and BTI, which are diimidedicarboxylic acids, were produced. Then, in a 30 liter reactor equipped with a stirrer, nitrogen inlet and condenser, 1.93 kg (10.1 mol) of tosyl chloride was added to 20 liters of NMP and cooled to below 10 ° C. After 1 hour, the temperature was raised to room temperature and 1.92 kg (3.5 mol) of OBTI prepared as above, 0.68 kg
After adding (1.5 mol) BTI and 10 liters of NMP and stirring at room temperature for 1 hour, continuously 1.28 kg
(22.0 mol) of PO was added and stirred at room temperature. Then, the reaction product was treated in the same manner as in Example 1 to obtain powdered PAI. The intrinsic viscosity of this PAI resin dissolved in DMAc and measured at 30 ° C. was 1.29 dL / g.

Comparative Example 1 A diimidedicarboxylic acid mixture was prepared in the same manner as in Example 1 using the same reactor, and 20 liters of NMP, 0.70 kg ( 3.5 mol) of diaminodiphenyl ether and 0.16 kg (1.5 mol) of metaphenylenediamine were added and reacted at room temperature for 3 hours, then the reaction product was treated as in Example 1 to obtain the desired PAI. I couldn't.

Comparative Example 2 A diimidedicarboxylic acid mixture was produced by the same reactor and method as in Example 1.
In another reactor of 25 liters, while passing nitrogen gas, 1.78 kg (15.0 mol) of thionyl chloride and 10 liters of NMP were mixed, cooled to 5 ° C or lower, and after 1 hour, The temperature was raised to room temperature and added to the reactor containing the diimidedicarboxylic acid mixture prepared as above at once with stirring. Thereafter, the reaction mixture was treated in the same manner as in Example 1, but the desired PAI resin could not be obtained.

Comparative Example 3 A PAI resin was manufactured by repeating the process of Example 1 except that N, N'-dimethylformamide (DMF) was used as a solvent. PA obtained
The intrinsic viscosity of I resin dissolved in DMAc at a concentration of 0.5 g / dL was 0.09 dL / g.

[Comparative Example 4] Using the same reactor as in Example 1 and by the same method as in Example 4, OBTI and BTI, which are diimide dicarboxylic acids, were separated. And, in a 30 liter reactor equipped with a stirrer, a nitrogen inlet and a condenser, under a nitrogen gas atmosphere, 1.22 kg (10.25
(Mol) thionyl chloride was added to 10 liters of NMP and cooled to 5 ° C or lower. After 1 hour, the temperature was raised to room temperature, and 1.72 kg (3.5
Mol) OBTI, 0.68 kg (1.5 mol) BTI
Then, 10 liter of NMP was added and the mixture was stirred at room temperature for 30 minutes. Subsequently, 0.7 kg (3.5 mol) of diaminodiphenyl ether, 0.16 kg (1.5 mol) of metaphenylenediamine and 1.25 L of NMP were added, and the mixture was stirred at 150 ° C. for 2 hours. Then, the reaction product was treated in the same manner as in Example 1 to obtain a PAI powder.
The intrinsic viscosity measured by dissolving this PAI powder in DMAc was 0.35 dL / g.

Table 1 shows the polymerization conditions and physical properties of the produced PAI.
Organized into According to the present invention, as shown in Table 1, P
It is possible to obtain a high-molecular polymer having an AI viscosity of 0.60 dL / g or more, which can be easily formed into a film. When the tensile strength was measured, the value was 1
It showed a considerably excellent mechanical strength of about 205 to 1438 kg / cm ² .

Further, in order to evaluate the thermal characteristics of the manufactured PAI resin, in the present invention, TGA (thermogravimetric) is used.
analysis) and DSC (differential scanning cal)
ori-meter) was used to measure the thermal stability and the glass transition temperature. As shown in Table 1, PAI measured by DSC
The glass transition temperature of the resin was in the range of 260 to 285 ° C., and showed a value similar to the glass transition temperature of toluron, which is a typical commercialized PAI resin.

Further, FIG. 1 attached shows the TGA curve of toluron and the PAI resin of Example 3 which is one of the PAI resins produced. 80 of PAI produced by the present invention
The residual weight at 0 ° C. was 52.5% and the 10% weight loss temperature was about 480 ° C., showing excellent thermal stability comparable to that of toluron. The molecular weight (number average molecular weight, weight average molecular weight, dispersity) of the produced PAI was measured under the following conditions. The value is a value calculated based on polystyrene: Detector: SP 8450 Varible UV detector (280 nm) Column: Tosoh TSK gel G6000H _XL- GMH _XL- G2500H
_XL solvent: DMF / 0.03M LiBr / 1 vol% T
HF flow rate: 0.5 ml / min Standard: polystyrene In order to evaluate the melt processability of the produced PAI, the melt viscosity of the resin was measured by the RDS (Rheometrics Dynamic Spectrometer) method in the present invention. The results are shown in the attached FIGS. 2 and 3. The measurement conditions are as follows. A sample obtained by molding a powdered PAI resin into a parallel plate (diameter 25 mm, thickness 2 mm) by a hot press is used. After heating up to 330 ° C., the frequency is 0.1 at isothermal condition. ~ 50
The melt viscosity was measured while changing at 0 rad / s. At this time, the stress was a constant value of 10%. In order to observe the change in melt viscosity with increasing temperature, samples having the same shape as above were measured in the temperature range of 300 to 370 ° C. As a result, the melt viscosity was lower than or equivalent to that of toluron under the same conditions, and good processing characteristics were shown.

[0050]

[Table 1]

Note) ODA: 4,4'-diaminodiphenyl ether m-PDA: metaphenylenediamine TC: thionyl chloride NMP: N-methylpyrrolidone TMA: trimylic anhydride IPDA: isophoronediamine

[Brief description of drawings]

1 is a TGA curve of a PAI resin prepared according to the present invention.

FIG. 2 is a diagram showing a comparison of melt viscosity curves of a PAI resin produced according to the present invention and an existing toluron resin.

FIG. 3 is a graph showing a comparison of changes in melt viscosity with respect to temperature of a PAI resin produced according to the present invention and an existing toluron resin.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Lee Mie 155 Shinseong-dong, Yuseong-gu, Daejeon, Republic of Korea (72) Inventor Chen Wenli 464-1 Tamin-dong, Yuseong-gu, Daejeon, Republic of Korea Expo Apartment 302-1402

Claims (5)

[Claims] 1. An aromatic tricarboxylic acid and a diamine are subjected to a condensation reaction to produce a diimidedicarboxylic acid, and then an intermediate is formed by using an acyl halogenating agent as a catalyst, and then the intermediate is directly polymerized with the diamine. A method for producing a polyamide-imide resin, which comprises reacting to produce a polyamide-imide resin having a high molecular weight. 2. A catalyst selected from organic or inorganic acyl halogenating agents such as thionyl chloride, paratoluenesulfonyl chloride, sulfuryl chloride, cyanuryl chloride and phosphorus trichloride is used. The method for producing a polyamide-imide resin according to 1. 3. The catalyst is 17 based on moles of monomer.
The method for producing a polyamide-imide resin according to claim 1, wherein the method is used in an amount of 0 to 230 mol%. 4. The polymerization reaction is carried out at a reactant concentration of 5 to 50% by weight and a temperature of 0 to 100 ° C. for 0.5 to 10 hours to obtain an intrinsic viscosity (solvent: DMAc, temperature: 30 ° C., concentration: 0.5).
The method for producing a polyamide-imide resin according to claim 1, wherein the polyamide-imide resin has a g / dL of 0.1 to 2.5 dL / g. 5. A reaction solvent, which is a polar solvent that forms a complex with an acyl halogenating agent at 0 to 10 ° C. to facilitate acylation, and is N-methylpyrrolidone, N-methylimidazole, or N-ethylpyrrolidone. , N-phenylpiperidone, N-methylcaprolactam, N, N'-ethylenedipyrrolidone, hexamethylphosphoric triamide, N-ethylalphapyridone, N, N'-dimethylacetamide and N, N'-dimethylpropionamide. The method for producing a polyamide-imide resin according to claim 1, wherein one selected from the group consisting of: