TWI379851B - - Google Patents

Description

IX. Description of the Invention [Technical Field According to the Invention] A conventional polyimine film is a two-component polycondensate. The present invention is derived from pyromellitic dianhydride (hereinafter referred to as PMDA), 4,4'-diaminodiphenyl ether (hereinafter referred to as DADE), biphenyltetracarboxylic dianhydride (hereinafter, referred to as BPDA), and Solvent-soluble super-heat-resistant polyimine which is formed by the four components of 2,4-diaminotoluene (hereinafter referred to as DAT). Instead of BPDA, benzophenone tetracarboxylic dianhydride (called BTDA) is used, and similarly, a solvent-soluble super heat-resistant polyimide can be produced. Further, in place of DAT, 3,5-diaminobenzoic acid (hereinafter referred to as DABz) can be used to form a solvent-soluble polyimine. [Prior Art] Polyimide film of super heat resistant resin was manufactured by DuPont in 1960 and is called KAPTON. It is made up of pyromellitic dianhydride (called PMDA) and 1,4-diaminodiphenyl. It is composed of ether (called DADE). It is characterized by a glass transition temperature (Tg) of 420 ° C and a thermal decomposition initiation temperature (Tm) of 500 ° C or higher. It is widely used as a polymer for electrical insulation, mechanical strength, and chemical resistance. Materials for vehicles, electronic and electrical parts, materials for semiconductors, etc. (Non-Patent Document 1: polyimides; D. Wilson, HD Steinberger, RM Morgenrother; Blackie, New York (1 990)) 〇1 9 80, by Ube The company's polyimine film "Upilex" is composed of biphenyltetracarboxylic dianhydride (called BPDA) and 1,4-~1379851 aminobenzene, Tg>500 °C, Tm>550 °C Heat resistant film (Non-Patent Document 1). » To date, no heat-resistant polythene film has been produced for KAP TON and Up ilex. A tetracarboxylic dianhydride which is substituted for PMDA or BPDA is not developed for the polyimide which is poorly soluble in a solvent. KAPTON and Upilex are difficult to dissolve in an organic solvent, and are polymerized at a low temperature in an anhydrous solvent to synthesize polyamic acid, followed by casting and heating of φ to produce a polyimide film. Polylysine is easily decomposed by water and has poor preservation stability. When the other component is added to the polyamic acid, the exchange reaction proceeds rapidly, and it becomes a random copolymer, which is difficult to reform. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] It is known that a tetracarboxylic dianhydride and an aromatic diamine are directly formed into a polyimine by heating and polycondensing Φ in an organic polar solvent (Patent Document 1: H. Itatani) , USP 5,202, 4 1 1 (1 993), USP 6,627,307 B 1 (2003), USP 6,890,626 B 1 (1 995 )). Toluenesulfonic acid was used as a catalyst (Patent Document 2: A. Berger, USP 4,0 1, 1,297 (1979), USP 4,3 5 9,5 72 (1 9 83 )). However, in the case of synthesizing polyimine in the presence of an acid catalyst, the presence of a catalyst in the film causes deterioration, so separation of the polyimide and the catalyst is required. The polyimine copolymer formed by PMDA and DADE is tried in a solution of the solvent-difficult-5-soluble PMDA-DADE-BPDA-DAT 4 component of the polyamidene copolymer in solution, using acid catalyst sequential The reaction was synthesized, but a solvent-soluble polyimine copolymer was not obtained. Using a novel three-stage polycondensation step, a solvent-soluble 4 component polyimine (a polyimine formed by PMDA-DADE-BPDA-DAT) was synthesized via a specific quinone oligo oligomer intermediate. . The first stage of the polycondensation reaction is: a reaction of 1 mol of B PDA with 2 mol of DADE (containing 6 benzene ring components) as a quinone imine oligomer, the second stage reaction is: make 4 mo The PMDA of the ear is reacted with 2 moles of DAT (containing 6 benzene ring components) to synthesize an intermediate (referred to as 6,6-polyimine oligomer). The step of terminating the polycondensation is carried out by finally adding the remaining components. That is, the gist of the present invention is as follows. (i) (BPDA) : (DADE) : (PMDA) : (DAT) Mohr than 2: 2: m: m (here, m is an integer of 3, 4 or 5.)

(ii) ( BTDA ) : (DADE) : (PMDA) : ( DAT ) molar ratio 2:2:111:111 (here, 111 is an integer of 3, 4 or 5 °) Determine the end of the reaction. It was not observed at the thermal decomposition onset temperature 50 (TC or higher, and the glass transition temperature was at 430 ° C. Instead of DAT, DABz was used to form a solvent-soluble polyimine of the 4-component system (the above (i) Or (ii) change). After thermal decomposition, the amount starts to decrease near 43 °C, and the thermal decomposition start temperature rises to 540 ° C. 1379851 [Means for solving the problem] In the solvent-soluble polyimine For the synthesis, it is first necessary to develop a novel catalyst. It has been developed in a polycondensation reaction and used as a catalyst, and the development of a catalyst that will disappear at the end of the reaction (Patent Document 3: Y. Oie, H. Itatani, USP 5) , 5 02,1 42 (1 996)). Develop a catalyst that utilizes lactone equilibrium. A mixture of valerolactone and pyridine or 7-valerolactone and N-methylmorpholine becomes [acid] in the presence of water [ Alkali], profit φ is used to remove water from this system to become the balance between [lactone] and [base] (Formula 1). [Number 1] 0-valerolactone] + [deep] + [water] [acid] + [Alkali] - A small amount of r-valerolactone and pyridine or r-valerolactone and N-methylmorpholine were added to the reaction system, and heated at 180 ° C to carry out the oxime imidization reaction. The resulting [water] produces [acid] + [base]·, and promotes the oxime imidization reaction. By the addition of toluene in the reaction system, the water formed in the reaction is azeotroped by toluene and discharged outside the system. When the hydrazine imidization reaction is completed, the reaction system is nearly anhydrous, and [acid] + [base] _ becomes [r-valerolactone] and [pyridine] and is discharged outside the system. Moreover, a high-purity polyfluorene can be obtained. Amine copolymer. The solvent-soluble polyimine produces a multi-component block copolymerized polyimine by making the polycondensation reaction a hydrazine reaction. The acid dianhydride is Αι ' A2, which makes the fragrance When the group diamine is B!, B2, the following formula is formed: [2] A2 X B 2 Α, + Β, — (A, -ΒΛη -^ 1379851 The four components are block copolymerized polyimine. The 4-component block copolymerization of PMDA and DADE is carried out after the above reaction, and the solvent-soluble polyimine is not obtained. PMDA-DADE-PMDA component and DADE-PMDA-DADE component It is difficult to dissolve in a solvent. However, it is necessary to synthesize a block copolymerized polyimine without this poorly soluble component. In the novel polycondensation reaction, a non-oxime polycondensation reaction is developed. A polycondensation reaction is added to the three-stage addition of a specific component. As a result, the solvent-soluble polyimine of the PMDA-DADE-BPDA-DAT component is successfully synthesized. [Invention effect] [6,6 - Use of polyamidene copolymer] 6,6-polyimine copolymer is a solvent-soluble polyimine resin, which has good storage stability. It is coated on a metal surface to form a composite material, or used for a copper substrate. Etc. The modified polyimine can be used as an electrodeposition or an adhesive. It can be cast and heated to form a film, and it can be widely used as a super-heat-resistant film for electronic, electrical parts, aircraft materials for transportation, semiconductors, etc., and can be manufactured with high-performance, low-cost products. Features, can be used for medical materials, building materials, high-temperature materials for household use (such as iron bottom, inner wall of the oven 'microwave oven wall), TeflonTM replacement -8 - 1379851

[Best Mode for Carrying Out the Invention] The quantitative relationship of the polyimine of a combination of aPMDA + bBPDA + cDADE + dDAT (a, b, c 'd is a molar number) is set as follows: [Number 3] a + b = c + d 谟 ears) Consider the difficulty of obtaining materials, product cost, etc., and set the following conditions: [4] a(PMDA) d(DAT) 1 a(PMDA) ^ b(BPDA) ^ ' c (DADE) 51, d (DAT) in a solution of an organic polar solvent (N-methylpyrrolidone, dimethylacetamide, cyclobutylhydrazine, dimethylformate), adding pentane vinegar and pyridine or r - Valentate and N-methylmorpholine, the formation reaction of the polyimine containing the above four components is discussed. The results of the polycondensation reaction of the three-stage addition or the polyimine synthesis method of the primary polycondensate showing a specific composition can be carried out to obtain a solvent-soluble polyimine. (BPDA) : ( DADE ) : ( PMDA ) : ( DAT ) The molar ratio 2:2:111:111 (here, 111 is an integer of 3, 4 or 5). 1-1.( BPDA ) : (DADE) : (PMDA) : ( DAT ) Mohr ratio 2: 2: 4: 4 polyimine aspect 1789851 The first stage of the polycondensation reaction is 2 mol DADE and 1 Mo

BPDA is heated at 180 ° C in an organic polar solvent in the presence of an acid catalyst to carry out a ruthenium iodide reaction to form a soluble oligomer of the diamine at both terminals (Formula 5). The water formed in the reaction is azeotropically discharged to the outside of the system via toluene. [Number 5] 2DADE + BPDA — (DADE — B PDA — DADE) oligomer

The second stage of the reaction was followed by the addition of 4 moles of PMDA and 2 moles of DAT. An oligomer of both ends of PMDA (Formula 6) was produced. [Number 6]

4PMDA+2DAT (DADE-BPDA-DADE) oligomer -► [(PMDA-DAT-PMDA) (DADE-BPDA-DADE) (PMDA-DAT-PMDA)] oligomers

This time, the intermediate was added to the remaining mixture (BPDA + 2DAT), stirred, and heated to 180 ° C to carry out a polycondensation reaction to synthesize a solvent-soluble polyimine copolymer (Formula 7). [Number 7] [primary product] (DAT-BPDA - DAT)] n polyimine primary oligomer in the first stage reaction and the second stage reaction - respectively, a component containing 6 benzene rings Reaction (Formula 8) ° -10- 1379851 [Number 8] (BPDA+2DADE) + (4 PMDA+2DAT) - Primary Intermediate Oligomer - A component containing 6 benzene rings containing 6 benzene rings (called 6,6*醯imino oligomer) The number of benzene rings contained in the component added by the reaction in the first stage and the second stage is 6, respectively, which is distinguished from other polyimine products, and is called 6 , 6-polyimine. 1-2. ( BPDA ) : (DADE) : (PMDA ) : (DAT) Mohr than 2: 2: 5: 5 in the first stage, the second stage of the reaction, 6 The 6-quinone imine fragment is added to the third stage (BPDA + PMDA + 3DAT) component, and heated and stirred to obtain a solvent-soluble polyimine copolymer. That is, the first stage of the reaction is to carry out the reaction of the (BPDA + 2DADE) component in an organic solvent in the presence of a catalyst at 180 ° C for 1 hour. φ Next, in the second stage of the reaction, the (4PMDA + 2DAT) component is added at room temperature and stirred to form a 6,6-quinone imine fragment; (BPDA + 2DADE) (4PMDA + 2DAT) is added to this solution ( The BPDA + PMDA + 3DAT) component was heated and stirred at 180 ° C to obtain a solvent-soluble polyimine copolymer. 1-3. ( BPDA ) : ( DADE ) : ( PMDA ) : (DAT) Mohr than 2: 2: 3: 3 Polyimine Aspect -11 - 1379851 Three-stage addition reaction for PMDA Part of it is replaced by the reaction of BPDA. In the first-stage reaction, the (BPDA + 2DADE) component was reacted in an organic solvent at 180 ° C for 1 hour to form a quinone imine oligomer. The second stage reaction is the addition of (3PMDA + BPDA + 2DAT) component, which is stirred at room temperature to form a quinone imine fragment (Equation 9): [9] (BPDA+2DADE) (3PMDA + BPDA+2DAT): (醢Imine fragment)

DAT was added to this liquid, and the copolymer of polyimine was obtained by heating and stirring at 180 °C. The product is of the following formula: [10] (BPDA + 2DADE) (3PMDA + BPDA + 2DAT) (DAT) The embodiment is a variant such as the sub-type: # [数11] (BPDA+2DADEH3 PMD A + BP DA) (3 DAT) In this way, (BPDA): (DADE) : (PMDA ) : (DAT ) Mohr ratio 2: 2: m: m (here, m is an integer of 3, 4 or 5 Poly)imine copolymer. As shown in the polyethylenimine physical property table, a part of the polyimide liquid is cast on a glass plate, and heated at 90 ° C for 1 hour, 2 1 0 ° C for 1 hour by an infrared heater. After the polyimide film was subjected to thermal analysis. -12- 1379851 It was not observed in the measurement field of the thermal decomposition onset temperature of 5 〇〇 * t or more and the glass transition temperature to 430 C. II. (BPDA) : (DADE) : (PMDA) : (DAT) Polyimine synthesis of 2:2:111:111 (here, 111 is an integer of 3, 4 or 5) In the reaction, the substituted BPDA uses benzophenone tetracarboxylic dianhydride (φ BTDA) to form a solvent-soluble polyimine of the same composition. Also 艮[3' (BTDA) : (DADE) : (PMDA) : (DAT) of the molar ratio 2: 2: m: m (here, m is an integer of 3, 4 or 5) Imine. As a result of the thermal analysis of this polyimine, the Tm was 500 ° C or more, and the range of Tg to 43 0 ° C was not observed. In place of BPDA, the polybendimimine of BTDA is used, and its Mw (weight average molecular weight) / MN (number average molecular weight) ratio is large, and it is considered that one g ^ ^ g φ is crosslinked. It can be used as a copper substrate or a composite polyimide material having excellent adhesion: a diaminotoluene having the following structure:

And 3,5-diamino benzoic acid having the following structure: -13- 1379851 [Chemical 2]

All are derivatives of 1,3-phenylenediamine. Further, the physical properties of the copolymerized polyimine in the case where a part of the diaminotoluene was substituted with the 3,5-diaminobenzoic acid was examined. III. (PMDA-DADE-BPDA-DAT) and the use of 3,5-diaminobenzoic acid (DABz) instead of DAT in the synthesis of polyimine (PMDA-DADE-BTDA-DAT) system (PMDA) In the synthesis reaction of -DADE-BPDA-DAT) and (PMDA-DADE-BTDA-DAT)-based polyimine, 3,5-diaminobenzoic acid (DABz) can be used instead of DAT. The experimental procedure is the same. As shown in the examples, there are various methods such as substituting the DAT of the second stage with DABz or replacing the DAT of the third stage with DABz. The DABz-containing (PMDA-DADE-BPDA-DABz) system and the (PMDA-DADE-BTDA-DABz)-based polyimine copolymer were analyzed by thermal analysis, and a decrease was observed near 440 to 45 °C. It is considered to have a decarbonation reaction. As a result, the Tm becomes as high as 530 to 550 °C. The polyimine copolymer of this system can be converted into a polyimide film by cationic electrodeposition. It is also excellent in nature and can also be used as a composite material. 1379851 IV. (PMDA-DADE-BPDA-DAT), (PMDA-DADE-BTDA-DAT), (PMDA-DADE-BPDA-DABz), (PMDA-DADE-BTDA-DABz) The molecular weight measurement and thermal analysis (TG-DTA measurement) of the amine copolymer by GPC are shown in Table 1. The results of the determination of dimethylformamide as a developing solution in the GPC measurement of the polybendimimine copolymer containing DABz The molecular weight could not be determined. When the methyl group of the diaminotoluene is ortho to the amino group to form a polyamidene bond, molecular distortion occurs. As a result, the resonance effect of the polyimine is hindered, and the instability is further increased. The thermal decomposition onset temperature is around 500 °C, which is mainly thought to be caused by the factor of DAT. By making the portion of DAT a DABz, the carboxylic acid group becomes far away from the amine group, which does not cause stereoscopic distortion of the polyimide. Therefore, it is stabilized by the resonance effect. Further reduction can be seen in the vicinity of 450 ° C, which is considered to be due to the carboxyl group. However, it is considered to be an upi lex type structure, which shows a high thermal decomposition start temperature. -15- 1379851

Thermal analysis of mu 4 component in polyimine (measured by TG-DTA) and determination of molecular weight (GPC) Polyphosphoramine (TG-DTA) (DSC) GPC measurement - subsurface Tm Ta Mw Μκ. mw/mn Example 1 (BPDA): (DADE): (PMDA): (DAT)=2:2:4: 4 512. 5t: None 101.430 33.470 3.03 Example 2 (BPDA): (DADE): (PMDA): (DAT) =2:2:5: 5 506. 6t: None 66. 900 10.300 6.5 Reference Example 1 (BPDA): (DADE): (PMDA): (DAT)=2:Z:3: 3 510. 7t: No implementation Example 4 (BTDA): (DADE): (PMDA): (DAT) = 2:2:4: 4 509. 5Ό No 117. 800 12.300 9.6 Example 5 (BTDA): (DADE): (PMDA): ( DAT)=2:2:5: 5 506. 6X: None 85.800 6.770 12.7 Example 6 (BTDA): (DADE): (PMDA) :(DAT)=2:2:3: 3 505. 7*C None 288. 400 97.000 29.7 Example 7 (BPDA): (DADE): (PMDA): (DABz): (DAT) = 2:2:4:2:2 450*C 544. 4*C No Example 8 ( BPDA): (DADE): (PMDA): (DAT): (DABz) = 2:2:4:2:2 4451 534. 5\: None Example 9 (BPDA): (DADE): (PMDA): (DAT): (PMDA): (DABz) = 2:2:4:3:1:2 458. 3= 553.61 None Example 10 (BTDA): (DADE): (PMDA): (DABz): (DAT ) =2:2:4:2:2 445X: 536. 3*C No comparison of the characteristics of 6,6-polyimine film and PMDA-DADE film. (A) Characteristics of 6,6-polyimine A-1 is a copolymer of PMDA-DADE-BPDA-DAT, PMD A-DADE-BTDA-DAT (substituted DAT, DAB z ) and soluble in solvent - 16- 1379851 A-2 is directly subjected to hydrazine imidization by dehydration-polycondensation reaction with an acid catalyst. A-3 was synthesized by a 6,6-imine fragment synthesized by a three-stage polycondensation reaction. A-4 can be reacted in a 0.1% aqueous solvent, and the molecular weight of GPC is determined to determine the end point of the reaction, and the reproducibility is high. The film of A-5 with a quinone imine copolymer is at a lower temperature and at a higher speed. The film was not observed at Tm > 500 ° C and Tg to 430 ° C. A-6 can be modified by changing parts of the ingredients. The A-7 polyimine copolymer has a long-term stability at room temperature and excellent storage stability. (B) PMDA-DADE Polyimine B-1 is a two-component system of the PMDA-DADE system and is hardly soluble in solvents. The pro-lysine of the precursor is synthesized by addition polymerization of B-2 in an anhydrous solvent at a low temperature. B-3 produces a polyimine by a heating dehydration reaction of polyamic acid. Polylysine is easily decomposed in water. B-4 was reacted in an anhydrous solvent. The polyglycine was unable to determine the molecular weight due to the exchange reaction. The end point of the reaction is determined by the viscosity. The B-5 film is produced by a combination of desolvation and dehydration, and the film formation speed is slower at a higher temperature. The film was Tm > 500 ° C, Tg = 420 ° C. B-6 changes the part of the component, and it becomes difficult to become a copolymer by the exchange reaction. -17- 1379851 B-7 polyaminic acid solution has poor storage stability, and the storage period for freezing is 1 to 2 months. [Embodiment] Hereinafter, the present invention will be described by way of examples, in place of PMDA-DADE-BPDA-DAT copolymer, PMDA-DADE-BTDA-DAT copolymer and DAT, DABz-6,6-polyimine Copolymer. The invention is not limited to the embodiments. The copolymers were analyzed by machine. The molecular weight and molecular weight distribution measurement was carried out by diluting a portion of the polyimide solution as shown in the examples with dimethylformaldehyde and measuring by high-speed liquid chromatography (GPC; HLC-8 120GPCC (Tosoh)). The number average molecular weight (Mn), the weight average molecular weight (Mw), and Mw/Mn are shown. For thermal analysis, the polyimine solution was cast and measured at 90 ° C for 1 hour and 2 1 0 ° C for 1 hour using a dried film. The thermal decomposition initiation temperature (Tm) was measured using (TGA-GTA) Thermo Plus Tg 8120 (Nippon Electric Co., Ltd.) at a temperature increase rate of 10 ° C / l and a temperature increase to 600 ° C. The glass transition temperature (Tg) was performed using a DSCPerkin Elmer PYRIS Diameter DSC. The temperature was raised to 400 °C in l〇t:/l minutes, air-cooled, and the temperature was raised at 1 〇 ° C / 1 minute, and the temperature was raised to 430 ° C. [Example 1] -18- 1379851 (BPDA) : (DADE) : (PMDA ) : (DAT) Mohr ratio 2: 2: 4: 4 Polyimine was produced in a stainless steel type In the glass separable three-necked flask of the agitator, a small ball cooling tube equipped with a moisture separation trap was provided. The flask was immersed in an oil bath while passing nitrogen gas, and heated and stirred.

3,4,3',4'-biphenyltetracarboxylic dianhydride (hereinafter referred to as BPDA) 5.88 g (20 mmol), 4,4'-diaminodiphenyl hydrazine (hereinafter referred to as DADE) 8.01 g (40 mmol), r_valerolactone 1.5 g (15 mmol), pyridine 3.5 g (44 mmol), N-methylpyrrolidone (hereinafter referred to as NMP) 150 g, toluene 45 g added to 3 Detachable flask. While passing nitrogen, the mixture was heated and stirred for 1 hour at a temperature of 180 ° C and a temperature of 180 ° rpm. 20 ml of water-toluene fraction was removed.

The air was cooled and stirred at 1 hour and 1 80 rpm. Then add pyromellitic dianhydride (hereinafter referred to as PMDA) 17.45g (80 millimoles), then add diaminotoluene (hereinafter referred to as DAT) 4.8 8g (40 millimoles), then add NMP25 0g, at room temperature The nitrogen side was stirred at 180 rpm for 20 minutes. Next, BPDA 5.88 g (20 mmol), DAT 4.88 g (40 mmol), NMP 120 g, and toluene 30 g were added, and the mixture was stirred at 230 rpm for 30 minutes, and then immersed in an oil bath at 180 ° C and stirred at 180 rpm. The toluene 20 ml» was removed and the reaction was carried out at 5 hours, 10 minutes, 180 ° C, and 180 rpm to obtain a 10% by weight solution of a polyimine solution. One part of the reaction solution was diluted with dimethylformamide, and the molecular weight and the distribution of -19 - 1379851 were measured by high-speed liquid chromatography (Tosoh HL (8120 GPC)). The polyethylene was obtained by a number average molecular weight (?π) of 33.470, a weight average molecular weight (Mw) of 101.430, an average molecular weight of lanthanum of 178.642, and Mw/Mn of 3.03. A partially dried polyimine film was taken, and the thermal decomposition initiation temperature (Tm) was measured by a thermoelectric analyzer Thermo Plus Tg 8 120 at a temperature rise rate of 〇 ° C / l, and the temperature was raised to 600 ° C. The Tm is 512.5 °C. The glass transition temperature (Tg) was determined using a Perkin Elmer Pyrid Diameter DSC. The temperature was raised to 400 ° C at a temperature increase rate of 10 ° C / l minutes. After that, the air was cooled and then heated to 430 °C at 10 °C / 1 minute. Tg was not observed. [Example 2] (BPDA): (DADE): (PMDA): (DAT) molar ratio 2: 2: 5: 5 Polyimine was produced in the same manner as in Example 1 to synthesize the above poly Yttrium amine copolymer.

BPDA 2.9 g (10 mmol), DADE 4.00 g (20 mmol), r-valerolactone 1.5 g, pyridine 2.8 g, NMP 100 g, and toluene 35 g were added. In a nitrogen stream, the mixture was stirred at a temperature of 180 ° at a bath temperature of 1 hour and 1 rpm. After removing the simmering oil bath for 30 minutes, air cooling was carried out, and 8.37 g (40 mM) of PMDA and 2.44 § (20 mM) of pentylene were added, followed by the addition of 75 g of NMP, followed by stirring at room temperature for 20 minutes. Add PMDA2.1 8g (10 millimolar), BPDA 2.94g (10 millimolar), DAT3.66g (30 millimolar), and add NMP72g. Take 1 80. (:, 1 80 rpp was heated and stirred in a nitrogen stream for 4 hours and 30 minutes. Measured by -20 - 1379851 The molecular weight of GPC of 10% concentration of polyimine solution. Μη 1 0.3 00 ' M w6 6 · 9 0 0, M w/Mη = 6.5. Thermal analysis was performed. Tm was 506.6 ° C. Although Tg was measured to 430 ° C, it was not observed. [Reference Example 1] (BPDA ) : (DADE) : (PMDA) : (DAT) Production of Polyimine with 2:2:3:3 Mohr Ratio φ System The same procedure as in Example 1 was carried out to synthesize the above copolymer. Add BPDA 5.88 g (20 mmol) , DADE 8 · 0 0 g (40 mAh), 7 • valerolactone 1.58, pyridine 3. (^, \1^? 15 (^, toluene 30g in the reactor. The temperature of the bath is 180 ° C The rotation number was 180 rpm for 1 hour, heating and stirring. After air cooling for 30 minutes, PMDA13_10g (60 millimolar) and NMP100g were added, and after stirring at 180 rpm at room temperature, BPDA 5.88g (20 millimolar) and DAT7 were added. .32g (6〇φ mmol) and NMP1 12g. After stirring at room temperature for 30 minutes, the mixture was heated at 180 ° C and 180 rpm for 4 hours and 35 minutes, and stirred to obtain a 10% concentration of the above polyimine solution. . The reaction solution was diluted with dimethylformamide to carry out GPC measurement, but the molecular weight could not be measured. Thermal analysis was carried out, and the thermal decomposition initiation temperature (Tm) was 510.7 ° C. The Tg was measured by DSC to 430 ° C. 'But Tg cannot be observed. [Example 4] -21 - 1379851 (BTDA) : (DADE) : (PMDA ) : (DAT) Molybdenum 2: 2: 4: 4 polyimine copolymer The production was carried out in the same manner as in Example 1. Instead of BPDA, benzophenonetetracarboxylic dianhydride (BTDA) was used. In a glass separable 3-necked flask equipped with a stainless steel crucible stirrer, water was provided. The small ball cooling tube of the trap was separated, and the flask was immersed in an oil bath while passing nitrogen gas, and then heated and stirred.

BTDA 6.44 g (20 mmol), DADE 8.0 g (40 mM), r-valerolactone l-8 g, pyridine 3.2 g 'NPM 150 g, and toluene 52 g were added. After stirring at room temperature for 3 G minutes at 180 rpm, the reactor was placed in an oil bath, and heated and stirred at 180 ° C and 180 rpm for 1 hour. After removing the oil bath and air cooling for 30 minutes, PMDA 17.44 g (80 mmol), DAT 44.88 g (40 mmol), and NMP 100 g were added, and after stirring for 15 minutes, BTDA6.44 g (20 m) was added with stirring. Moer), 〇八丁4.88 giant (40 millimoles), and further added NMP103g. The mixture was heated and stirred at 180 ° C, 180 rpm, 3 hours and 20 minutes to obtain a 12% concentration of the polyimine solution. The molecular weight in terms of polystyrene was Mn 1 2,300 'Mw 1 17.800 Mw/Mn = 9.6 by GPC measurement. By thermal analysis by TG-GTA, the thermal decomposition initiation temperature (Tm) was 509.5 °C, and the DSC was measured to 430 °C, and Tg was not observed. [Example 5] (BTDA) ·· (DADE): (PMDA): (DAT) Mo Erbi•22-1379851 Series 2: 2: 5: 5 Polyimine copolymer production and Example 4 Do the same. Add BTDA 3.22g (10 millimolar) and DADE 4.00g (20 millimolar) to a separable 3-neck flask.

7-valerolactone 9. 9 g, pyridine 1.8 g, NMP 80 g, toluene 30 g. The mixture was stirred at room temperature for 30 minutes in a stream of nitrogen. Next, the reactor was immersed in an oil bath and heated and stirred at 180 ° C, 180 rpm for 1 hour in a nitrogen stream. After removing the oil bath, after air cooling for 20 minutes, add PMDA 8.72g (40 millimolar), DAT2.44g (20 millimolar), NMPlOOg' at room temperature for 30 minutes, then add BTDA3.22g (10 millimolar). Ear), PMDA2.18g (l〇mole), DAT3.66g (30 mmol) and NMP67g, heated at 18 CTC, stirred at 180 rpm for 4 hours and 30 minutes to obtain a concentration of 1% by weight of polyimine Solution. A part of the reaction liquid was taken, and the molecular weight in terms of polystyrene was measured. The number average molecular weight (Mn) was 6.770, and the weight average molecular weight (Mw) was 85.800 MW/Mn of 12.7. The thermal analysis results were carried out, and the thermal decomposition starting temperature was 506.6 °C. Although the temperature was measured by DSC to 430 °C, the glass transition temperature (Tg) was not observed. [Example 6] (BTDA): (DADE): (PMDA): (DAT) Mohr ratio 2: 2: 3: 3 Polyimine copolymer production The same procedure as in Example 4 was carried out. Add BTDA6.44 (20 mAh), D AD E 8.0 0 g (4 〇 mA -23- 1379851

Ear), 7-valerolactone 1.5 g, pyridine 3.0 g, NMP 150 g, and toluene 30 g in a 3-neck flask. After stirring at room temperature for 30 minutes at 180 rpm, the mixture was heated and stirred at 180 ° C and 180 rpm for 1 hour. 20 ml of toluene was removed. After air cooling for 25 minutes, PMDA13.10g (60 millimolar), NMP100g was added, and stirred at room temperature for 25 minutes, adding BTDA6.44g (20 millimolar), DAT7_32g (60 millimolar), NMP122g, The mixture was heated at 600 ° C and 180 rpm for 4 hours and 35 minutes. A 10% strength polyimine solution was obtained. A part of the reaction solution was taken, and the molecular weight was measured by GPC. The number average molecular weight (^) is 97.000, and the weight average molecular weight (Mw) is 2 8 8.400.

Mw/Mn was 29.8. Thermal analysis of the polyimide film was carried out, and the thermal decomposition initiation temperature was 5 05.7 °C. Although the glass transition temperature was measured to 430 ° C, it was not observed.

[Embodiment 7]

(BPDA) : (DADE) : (PMDA ) : ( DABz ) : ( DAT ) Mohr than 2: 2: 4: 2: 2 Polyimine copolymer is manufactured to replace DAT, part of which becomes DABz To synthesize a polyamidene copolymer. The operation was carried out in the same manner as in the first embodiment. BPDA 2.94 g (10 mmol), DADE 4.0 g (20 mmol), r-valerolactone 〇.9 g, pyridine 1.8 g, NMP 100 g, toluene 3 〇g were added to the reactor. The mixture was heated at 1,800 ° C and 180 rpm for 1 hour. • 24- 1379851 After stirring for 30 minutes at room temperature, add 8.77 g (40 mmol) of PMDA and stir at 200 rpm for 30 minutes at room temperature. Then add DABz 3.04 g (20 mmol), NMP 83 g, at 180 rpm. Stir for 1 hour. Next, add BPDA 2.94g (10 millimolar), DAT2.44g (20 millimolar), add NMP34g, toluene 20g, stir at room temperature for 30 minutes, and then in an oil bath, 18 (TC, 180 rpm, 4 The reaction was carried out for 30 minutes, and a 10% concentration of the polyimine solution was obtained. Although the molecular weight was measured in the sample diluted with the DMF solution, the corresponding absorption could not be obtained. The film thermal analysis was carried out. Thermal analysis was carried out via TGA-GTA. L〇°C/l minutes, the temperature was raised to 600 ° C. The decrease in weight at 450 ° C was confirmed. The thermal decomposition onset temperature (Tm ) was 544.4 ° C » [Example 8] (BPDA ) : ( DADE ) ( PMDA : ( DAT ): ( DABz) Mohr ratio 2: 2: 4: 2: 2 Polyimine copolymer was produced in the same manner as in Example 7. BPDA 2.94 g was added to the reactor ( 10 mM), DADE 4.0g (20 mM), r_valerolactone 9.9g, pyridine 1.8g, NMP100g, toluene 30g. After stirring at room temperature, it is heated in an oil bath. At 180 ° C, 1 hour at 180 rpm, heating, stirring, air cooling for 30 minutes. Add PMDA 4.82g (40 millimoles), DAT2.44g (20 millimoles) 'NMP83g, stirred at 180 rpm for 1 hour. Then, -25-1379851 was added to BPDA 2.94g (10 mM), DABz 3.04g (20 3 ), NMP34g, and stirred at room temperature for 30 minutes. The film was heated and stirred at 180 ° C and 180 rpm for 3 hours and 30 minutes. The 10% concentration of the polyimine solution. Although the GPC measurement was attempted, the molecular weight could not be measured. The thermal analysis of the film was carried out because of the TG-GTA. Thermal analysis, there was a decrease at 445 ° C. The thermal decomposition onset temperature (Τ^) was 539.5 ° C. Although it was measured by DSC to 43 ° C, Tg was not observed [Example 9] (BPDA): (DADE : (PMDA ) : ( DABz ): ( ) The molar ratio of 2: 2: 5: 2: 3 is prepared in the same manner as in Example 7. In the reactor, BPDA 2.94g (10 millimolar DADE 4.0g (20 millimolar), r-valerolactone 1.5g, pyridine 2, φ NMP100g, toluene 35g. After stirring at room temperature, in an oil bath 180 ° C, 180 rpm, The mixture was heated and stirred for 1 hour, and air-cooling port PMDA 8.73 g (40 mmol), DABz 3.04 g (20 m), and NMP 75 g were stirred at room temperature for 20 minutes. Next, PMDA 2.18 g (10 mmol), BPDA 2.94 g (10 mM DAT 3.66 g (30 mmol) and NMP 77 g were stirred at room temperature for 20 hours at 180 ° C and 180 rpm for 15 hours. After heating for a minute, a solution of a concentration of 1% by weight of polyimine was obtained. The molecular weight could not be determined by GPC measurement. It was confirmed by DAT in a molar bath, 8 g, and the middle was added to the molars. 26- 1379851 The measurement of TG-GTA was carried out at 100 ° C for 1 ° C / l minutes. It was confirmed that there was a decrease at 45 8.3 ° C, and the thermal decomposition initiation temperature (Tm) was 5 53_6 ° C. DS Through DSC, the measurement was carried out until 43 ° C. However, Tg was not observed. [Embodiment 10]

(BTDA) : (DADE) (PMDA) : ( D ABz ) (DAT ) Mohr Ratio 2: 2: 4: 2: 2 Polyimine Copolymer Production Substituting BPDA with Benzophenone Tetracarboxylate Acid dianhydride (BTDA) ' was operated in the same manner as in Example 7. To the reactor, BTDA (6.44 g (20 mmol), DADE 8.0 g (40 mmol), r·valerolactone 1.8 g, pyridine 3.6 g, NMP 150 g, and toluene 35 g were added. After stirring at room temperature, the mixture was heated and stirred at 180 ° C and 180 rPm for 1 hour. After 30 minutes of air cooling and stirring, 'PMDA17.44g (80 millimolar), DABz6.48g (40 millimolar), and NMP13 1g were added and stirred at room temperature for 30 minutes. Then, add BTDA6.44g (20 millimolar), DAT4.88g (40 millimolar), NMP100g, heat and stir at 180 °C, 180rPm for 3 hours and 25 minutes to obtain 丨〇% concentration of polyimine. Solution. Molecular weight determination cannot be performed. Perform a thermal analysis. TGA-GTA measurement was carried out up to 600 °C. Confirm the reduction at 445 °C. The thermal decomposition start temperature (Tm) is 5 36.3 °C °. The measurement by DSC proceeds to the bucket "^" but the Tg is not observed. -27- 1379851

To. The present invention can utilize the characteristics of a new manufacturing step, a high-performance polymer, and a low-cost product, and has a wide range of applications, and can be used as a substitute for a high-temperature member for medical materials, construction materials, household products, and TeflonTM. -28-

Claims (1)

1379851 X. Patent application scope 1. A heat-resistant polyimine copolymer, which is composed of biphenyltetracarboxylic dianhydride (BPDA), 4,4'-diaminodiphenyl ether (DADE), and benzene. A heat-resistant polyimide polymer copolymer of tetracarboxylic acid dianhydride (PMDA) and 2,4-diaminotoluene (DAT), which is soluble in an organic polar solvent, and is characterized in that both ends of the BPDA are formed. The first stage of the oligomer of DADE' is followed by the addition of PMDA and DAT to make the second stage of the ruthenium imine oligomer having both ends of PMDA and the third stage of the enthalpy condensation of DAT added. And the glass transition temperature is above 43 0 °C. 2 · The heat-resistant polyimine copolymer described in the first paragraph of the patent application 'BPDA' : (DADE) : (PMDA) : (DAT ) Mohiel series 2: 2: m: m (at Thus, m is an integer of 3, 4 or 5). 3. A method for producing a heat-resistant polyimine copolymer which is soluble in an organic polar solvent, which is characterized by: (Ο 联 biphenyltetracarboxylic acid II Anhydride (1 molar equivalent) and 4,4,---decyl-based acid (DADE) (2 旲 equivalent) in the presence of a catalyst in an organic polar solvent at 160 to 200. a first stage of generating an oligomer of DADE at both ends, (b) adding pyromellitic dianhydride (PMDA) (3 molar equivalents), biphenyltetracarboxylic dianhydride (1 molar equivalent), 2, 4-diaminotoluene (2 molar equivalents), followed by stirring and dissolving to obtain a second stage of the quinone imine oligomer having PMDA at both ends, and (c) adding 2,4-diamine Base toluene (1 molar equivalent) -29- 1379851 The third stage of synthesizing a solvent-soluble polyimine copolymer after heating and polycondensation. 4_ A heat-resistant polyazide soluble in an organic polar solvent The amine copolymer' is characterized by a composition formula: {(PMDA-DAT-BPDA)( DADE-BPDA-DADE) ( PMDA - DAT - PMDA ) - DAT } n. 5. Heat-resistant in organic polar solvent A method for producing a polyimine copolymer characterized by: (a) making biphenyltetracarboxylic dianhydride (1 molar equivalent) and 44, diaminodiphenyl ether (DADE) (2 Mo Ear equivalent) The first stage of the reaction at 160~200 °C in the presence of a catalyst in an organic polar solvent to form an oligomer of both ends DADE, (b) the addition of pyromellitic dianhydride (PMDA) ( 4 molar equivalents) and 2,4-diaminotoluene (2 molar equivalents), followed by stirring to dissolve 'the second stage of the quinone imine oligomers having PMD A at both ends, and (c) Adding biphenyltetracarboxylic dianhydride (1 molar equivalent) and 2,4-diaminotoluene (2 molar equivalent), heating and polycondensing to synthesize a third soluble solvent-soluble polyimine copolymer The composition of the stage 6. A heat-resistant polyimine copolymer soluble in an organic polar solvent, characterized by a composition formula: {(PMDA-DAT-PMDA) (DADE-BPDA-DA DE)(PMDA-DAT-PMDA)(DAT-BPDA-DAT)}n 7. A method for producing a heat-resistant polyimide pigment copolymer soluble in an organic polar solvent, characterized by: (a) The presence of biphenyl tetracarboxylic dianhydride (1 molar equivalent) and 4,4'--30-1379851 diaminodiphenyl ether (DADE) (2 molar equivalents) in an organic polar solvent The reaction is carried out at 160 to 2001 to form the first stage of the oligomer of the two ends DADE, (b) the addition of pyromellitic dianhydride (PmdA) (4 mole equivalent) and 2,4-diaminotoluene ( 2 molar equivalents), followed by stirring to dissolve 'the second stage of the quinone imine oligomer having both ends of PMDA, and (c) adding biphenyltetracarboxylic dianhydride (1 molar equivalent), both Pyromellitic dianhydride (1 molar equivalent) and 2,4-diaminotoluene (3 mole equivalent) are formed by heating, polycondensing, and synthesizing a solvent-soluble polyimine copolymer. 8_- a heat-resistant polyimine copolymer soluble in an organic polar solvent, characterized by a composition formula: {(PMDA-DAT-PMDA)(DADE-BPDA-DADE)(PMDA-DAT-PMDA) (DAT -PMDA-DAT-BPDA-DAT)} „9. The manufacturing method of claim 3, 5 or 7, wherein in the above polycondensation reaction, N-methylpyrrolidone, cyclobutane, and dimethyl are used. Ethyl acetamide or dimethylformamide as a solvent, a small amount of 7-valerolactone and pyridine, or 7-valerolactone and N-methylmorpholine as a catalyst, heated at 160~200 ° C, After stirring, toluene is added to the solvent, and the formed water is azeotropically removed by toluene to form a solvent-soluble polyimine copolymer. 10. A heat-resistant polyimine copolymer characterized by Benzophenone tetracarboxylic dianhydride (BTDA), 4,4'-diaminodiphenyl ether (DADE -31 - 1379851), pyromellitic dianhydride (PMDA) and 2,4-diamine The heat-resistant polyimine copolymer which is soluble in the organic polar solvent formed by the four components of toluene (DAT) is the first stage of the formation of the oligomer of DTD at the end of BTD A. The addition of PMDA and DAT results in the second stage of the second stage of the polycondensation of DAM with both PMD A and the third stage of the polycondensation of DAT. 11. Heat resistance according to item 10 of the patent application Polyimine copolymer, wherein (BTDA) : (DADE) : (PMDA) : (DAT) Mohr than 2: 2: m: m (here, m is an integer of 3, 4 or 5 p 12 A method for producing a heat-resistant polyimine copolymer which is soluble in an organic polar solvent, characterized by: (a) benzophenone tetracarboxylic dianhydride (1 molar equivalent) and 4, 4 '-Diaminodiphenyl ether (DADE) (2 molar equivalent) in the presence of a catalyst in an organic polar solvent at 160 to 200. (: The reaction is carried out to form the first of the two end DADE oligomers Stage, (b) adding pyromellitic dianhydride (PMDA) (3 molar equivalents), benzophenone tetracarboxylic dianhydride (1 molar equivalent), 2,4-diaminotoluene (2 moles) Equivalent), stirring, dissolving, making the second stage of the quinone imine oligomer which is PMDA at both ends, and (c) adding 2,4-diaminotoluene (1 molar equivalent), heating, After polycondensation The third phase of the solvent-soluble polyimine copolymer is formed. 13. A heat-resistant polyimine copolymer soluble in an organic polar solvent, characterized by a composition formula: {( PMDA-DAT-BTDA) -32- 1379851 (DADE-BTDA-DADE)(PMDA-DAT-PMDA)(DAT)}n. A method for producing a heat-resistant polyimine copolymer which is soluble in an organic polar solvent, characterized by: ' (a) benzophenone tetracarboxylic dianhydride (1 molar equivalent) and 4, 4'-Diaminodiphenyl ether (DAde) (2 molar equivalent) is reacted at 160 to 200 ° C in the presence of a catalyst in an organic polar solvent to form the first of the oligomers at both ends of DADE In the stage, φ (b) is added with pyromellitic dianhydride (PMDA) (4 molar equivalent) and 2,4-diaminotoluene (2 molar equivalent), and then stirred and dissolved to make PMDA at both ends. The second stage of the quinone imine oligomer, and (C) adding benzophenone tetracarboxylic dianhydride (1 molar equivalent) and 2,4-diaminotoluene (2 mole equivalent), heating The third stage of the synthesis of the solvent-soluble polyimine copolymer after polycondensation constitutes 〇φ 15. a heat-resistant polyimine copolymer which is soluble in an organic polar solvent, and has the characteristics Composition: {(PMDA-DAT-PMDA)(DADE·BTDA-DADE)(PMDA-DAT-PMDA)(DAT-BTDA-DAT)}n. 16. A process for producing a heat-resistant polyimine copolymer which is soluble in an organic polar solvent, characterized by: (a) benzophenone tetracarboxylic dianhydride (1 molar equivalent) and 4, 4'-Diaminodiphenyl ether (DADE) (2 molar equivalent) is reacted in an organic polar solvent in the presence of a catalyst at 160 to 200 ° C to form the first of the oligomers at both ends of DADE. Stage, -33- 1379851 (b) Add pyromellitic dianhydride (PMDA) (4 molar equivalent) and 2,4-diaminotoluene (2 molar equivalent), stir and dissolve to make two a second stage of the quinone imine oligomer having a terminal end of PMDA, and (c) adding benzophenone tetracarboxylic dianhydride (1 molar equivalent), pyromellitic dianhydride (1 molar equivalent), and 2 4-Diaminotoluene (3 mole equivalent), which is composed of a third stage of synthesizing a solvent-soluble polyimine copolymer after heating and polycondensation. 17. A heat-resistant polyimine copolymer soluble in an organic polar solvent, characterized by a composition formula: {(PMDA-DAT-PMDA)(DADE-BTDA-DADE)(PMDA-DAT-PMDA) ( DAT-PMDA-DAT-BTDA-DAT)}n. 1 8 · a heat-resistant polyimine copolymer characterized by only pyromellitic dianhydride (PMDA), 4,4'-diaminodiphenyl ether (DADE), biphenyltetracarboxylic acid The heat resistance of dianhydride (8?0) and 3,5-diaminobenzoic acid (0.82) and 2,4-diaminotoluene (DAT) are soluble in organic polar solvents The polyamidene copolymer is the first stage of the formation of an oligomer of DADE at both ends of BPDA, and then, by adding PMDA to DAT or DABz, it becomes a quinone imine oligomer having both ends thereof as PMDA. The second stage and the reaction product of the third stage of the polycondensation of DAT or DABz are added, and the glass transition temperature is above 40 °C. 1 9 · A heat-resistant polyimine copolymer as claimed in Article 18 of the patent application, wherein (BPDA): (DADE) : (PMDA) : (in total of (DABz) and (DABz) molecules) Ratio 2: 2: m: m ( -34 - 1379851 where m is an integer of 3, 4 or 5). 20. A method for producing a heat-resistant polyimine copolymer which is soluble in an organic polar solvent, characterized by: (a) a biphenyltetracarboxylic dianhydride (丨 molar equivalent) and 4, 4' _ Diaminodiphenyl ether (DADE) (2 molar equivalent) in an organic polar solvent, reacted at 160 to 200 ° C in the presence of a catalyst to form the first stage of the oligomer of both ends DADE, (b) Adding pyromellitic dianhydride (PMDA) (4 molar equivalent) and 3,5-diaminobenzoic acid (2 molar equivalents), stirring and dissolving, so that both ends are PMD A The second stage of the quinone imine oligomer, and (c) the addition of biphenyltetracarboxylic dianhydride (1 molar equivalent) and 2,4-diaminotoluene (2 mole equivalent)' for heating, polycondensation It is composed of a third stage of synthesizing a solvent-soluble polyimine copolymer. 21_- a heat-resistant polyimine copolymer soluble in an organic polar solvent, characterized by a composition formula: {(PMDA-DABz-PMDA)(DADE-BPDA-DADE)(PMDA-DABz-PMDA)(DAT -BPDA-DAT)}ne 2 2. A method for producing a heat-resistant polyimine copolymer which is soluble in an organic polar solvent, which is characterized by: (a) a biphenyltetracarboxylic dianhydride (1 Mo) The ear equivalent) is reacted with 4,4,-diaminodiphenyl ether (DADE) (2 molar equivalent) in an organic polar solvent in the presence of a catalyst at 160 to 200 ° C to form a DADE at both ends. In the first stage of the oligomer, (b) adding pyromellitic dianhydride (pMDA) (4 molars -35 - 1379851) and 2,4-diaminotoluene (2 molar equivalents) followed by stirring The second stage of dissolving 'make the quinone imine oligomers with PMDA at both ends, and (c) adding biphenyltetracarboxylic dianhydride (1 molar equivalent) and 3,5-diamino benzoin The acid (2 molar equivalent) is composed of a third stage in which a solvent-soluble polyimine copolymer is synthesized by heating and polycondensation. 23_ — a heat-resistant polyimine copolymer φ substance soluble in an organic polar solvent, characterized by a composition formula: {(pmda-dat-pmda)(dade-BPDA-DADE)(PMDA-DAT-PMDA)( DABz-BPDA-DABz)}n. 24. A method for producing a heat-resistant polyimine copolymer which is soluble in an organic polar solvent, characterized by: (a) biphenyltetracarboxylic dianhydride (BPDA) (1 molar equivalent) and 4 4'-Diaminodiphenyl ether (DADE) (2 molar equivalent) is reacted in an organic polar solvent at 160 to 200 ° C in the presence of a catalyst to form an oligomer of both ends of DADE. In one stage, • (b) adding pyromellitic dianhydride (PMDA) (4 molar equivalents) and 3,5-di-based benzoic acid (2 molar equivalents), stirring, 'dissolving, making two The second stage of the quinone imine oligomer having a terminal end of PMDA, and (c) the addition of biphenyltetracarboxylic dianhydride (1 molar equivalent), pyromellitic dianhydride (1 molar equivalent), and 2,4 -Diaminotoluene (3 mole equivalent) is composed of a third stage in which a solvent-soluble polyimine copolymer is synthesized by heating and polycondensation. 25_- a heat-resistant polyimine copolymer-36- 1379851 soluble in an organic polar solvent, characterized by a composition formula: {(pmda-dabz-pmda) (DADE-BPDA-DADE) (PMDA-DABz- PMDA)(DAT-PMDA-DAT-BPDA-DAT)}„ · ' 26. A heat-resistant polyimine copolymer characterized by pyromellitic dianhydride (PMDA), 4,4'- Diaminodiphenyl ether (DADE), benzophenone tetracarboxylic dianhydride (BTDA), 2,4-diaminotoluene (DAT) and 3,5-diaminobenzoic acid (DABz) 5 The heat-resistant polyimine copolymer which is soluble in the φ organic polar solvent is the first stage of the formation of the oligomer of DADE at both ends of BTDA, and then is added by adding PMDA with DAT or DABz. The second stage of the ruthenium imine oligomer of PMDA and the reaction product of the third stage of the polycondensation of DAT or j) ABz are added, and the glass transition temperature is 43 (TC or more. 27. Patent application Ref. No. 26, heat-resistant polyimine copolymer 'where (BTDA) : (DADE) : (PMDA) : (total of (DAT ) and (DABz) molecules) Mohs ratio 2: 2: m : m( φ here, m is 3, 4 or An integer of 5). A method for producing a heat-resistant polyimide intermediate copolymer soluble in an organic polar solvent, characterized by: (a) benzophenone tetracarboxylic dianhydride (1 molar equivalent) And reacting with 4'4-amino-benyl ether (DADE) (2 molar equivalent) in the presence of a catalyst in an organic polar solvent at 160 to 200 t to form an oligomer of both ends of DADE In one stage, b) fragrant '^ shoulder amino acid tetramethyl benzene is added to add IT acid amount when the ear is 3 after solution and dissolution), the amount, when the ear is stirred 4 into -37- 1379851 to become the two ends The second stage of the quinone imine oligomer of pyromellitic dianhydride, and (C) the addition of benzophenone tetracarboxylic dianhydride (1 molar equivalent) and 2,4-diaminotoluene (2) Mohr equivalent), which is formed by the third stage of synthesizing a solvent-soluble polyimine copolymer after heating and polycondensation. 29. A heat-resistant polyimine copolymer copolymerizable in an organic polar solvent The 'characteristic' has a composition formula: {(PMDA-DABz-PMDA)(DADE-BTDA-DADE)(PMDA-DABz-PMDA)(DAT-BTDA-DAT)}n. 30. Heat polyimide film, characterized in that the system range patent application 14 5 or the heat resistance of the polyimide according to the method of the copolymer made by casting, and heated to more than 2 5 0 ° C is generated. 31. A heat-resistant polyimide film characterized in that the heat-resistant polyimide polymer produced by the method of claim 22 or 28 is cast and heated to 250 ° C or higher. And generated. A heat-resistant polyimide film characterized in that the heat-resistant polyimide polymer produced by the method of claim 22, 24 or 28 is cast and heated to 250. (The above-mentioned heat-resistant polyimide film which is used as a material for electrodeposition or a material for subsequent use. -38-