CN112321829B - Method for aqueous phase synthesis of polyamide-imide resin - Google Patents
Method for aqueous phase synthesis of polyamide-imide resin Download PDFInfo
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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Abstract
The invention relates to a method for aqueous phase synthesis of polyamide-imide resin, comprising the following steps: respectively or mixing the trimellitic acid and diamine compounds and then carrying out grain size refinement treatment on the raw materials; mixing the trimellitic acid subjected to the particle size refinement treatment, diamine compounds and water, performing deoxidation and nitrogen filling treatment under stirring, performing a first program pressure control and temperature rise reaction, and performing constant temperature reaction for 1-4 h after reaching a set first temperature; keeping the pressure, carrying out a second temperature programming reaction, and carrying out a constant temperature reaction for 4-10 h after reaching a set second temperature to obtain the polyamide-imide resin. The invention adopts aqueous phase and low pressure polymerization, does not use catalyst and organic solvent, and the PAI resin prepared has better performance.
Description
Technical Field
The invention relates to the technical field of high polymer material synthesis, in particular to a method for synthesizing polyamide-imide resin by using a water phase.
Background
Polyamide-imide (abbreviated as PAI) resins are polymers having a regular alternating arrangement of imide rings and amide bonds. It is a non-crystalline high temperature resistant engineering thermoplastic resin, and has heat resistant aromatic hetero imine group and flexible amide group in the molecule. PAI has good dimensional stability and creep resistance, excellent heat resistance, radiation resistance, dielectric property, mechanical property and chemical stability, is an engineering material with excellent performance, and has wide application in the fields of aviation, aerospace, transportation, chemical equipment, electronic industry and the like.
PAI is generally synthesized by the following methods: (1) diisocyanate method: diisocyanate and trimellitic anhydride (TMA) are used as main raw materials for preparation; (2) aromatic tetracarboxylic anhydride method: reacting an aromatic tetracarboxylic dianhydride represented by pyromellitic dianhydride (PMDA) with an aromatic diamine containing an amide group; (3) an acid chloride method: trimellitic anhydride (TMA) and derivatives thereof are reacted with aromatic diamines or derivatives to form amic acids, which are heated to lose one water molecule and form imine-group-containing compounds.
However, the above-mentioned preparation methods are all synthesized in an organic solvent, and polar aprotic solvents such as N, N-dimethylacetamide, N-methylpyrrolidone, and N-methylformamide are generally used as the organic solvent. It can be coated to form a film, an adhesive, or to form a thermoset article. In the processes, the organic solvent is generally removed by evaporation, so that the reaction cost is high, the reaction period is long, the environmental pollution is great, the residual high-boiling-point organic solvent in the product is not easy to remove, and the method consumes time and energy. When the solid-liquid separation of the resin is finished after the synthesis, a large amount of low-boiling-point high-volatility organic solvent is needed to participate in the precipitation, and the toxicity characteristic of the chemical structure of the high-boiling-point solvent causes great damage to the environment and the human nervous system. Therefore, in order to ensure safe production and environmental friendliness in the synthetic production process, large equipment, time, personnel and capital investment are required.
Therefore, there is an urgent need to develop a PAI liquid phase synthesis method which does not use organic solvents.
Disclosure of Invention
In order to solve the technical problems of high reaction cost, great environmental pollution, difficult removal of residual high-boiling-point organic solvent in a product, time consumption and energy consumption caused by using an organic solvent in the PAI synthesis process, the method for synthesizing the polyamide-imide resin by the aqueous phase is provided. The method directly adopts trimellitic acid and diamine compounds as polymerization reaction monomers, adopts a water phase and low pressure method for polymerization, does not use a catalyst, abandons the use of a high boiling point solvent as a reaction medium and a large amount of low boiling point and high volatility organic solvents for precipitation, and the prepared PAI resin has good performance.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for aqueous phase synthesis of polyamide-imide resin comprising the steps of:
(1) Respectively or mixing the trimellitic acid and diamine compounds and then carrying out grain size refinement treatment on the raw materials; after the particle size is thinned, the water solubility of raw material monomers can be increased, and the probability and the speed of a synthesis reaction are further increased;
(2) Mixing the trimellitic acid subjected to the particle size refinement treatment, diamine compounds and water, performing deoxidation and nitrogen filling treatment under stirring, performing a first program pressure control and temperature rise reaction, and performing constant temperature reaction for 1-4 h after reaching a set first temperature;
keeping the pressure, carrying out a second temperature programming reaction, reacting at constant temperature for 4-10 h after reaching a set second temperature, cooling, separating a product from water to obtain the polyamide-imide resin, and recycling the separated water. The first pressure-programmed temperature-rising reaction is carried out at a lower temperature, and mainly prevents the monomer from being oxidized; the second temperature programmed reaction is carried out at a higher temperature than the first temperature programmed reaction, in order to reach the activation energy of the synthesis reaction, the temperature is raised to be more than 100 ℃, water is boiled, the pressure in a reaction device is increased, and the pressure needs to be controlled in the reaction process.
Further, one scheme is as follows: the first program pressure control heating reaction is to set the first temperature to be 100-150 ℃ and control the pressure to be-0.1-1.5 Mpa to carry out heating reaction; and the second temperature programming reaction is to set a second temperature to be 150-250 ℃ for continuous temperature programming reaction, separate out the wet prepolymer from water after the second temperature programming reaction is finished, wash and dry the wet prepolymer to obtain an intermediate polymer, and then heat, dehydrate and cyclize the intermediate polymer to obtain the polyamide-imide resin.
Still further, the washing process is: and adding boiling water into the wet prepolymer for dispersing, washing and separating, and stopping the washing process after the pH value of the washing water is more than 4 after repeated operation.
Still further, the drying process is: and drying the wet prepolymer at a temperature lower than 150 ℃ for at least more than 10h, and turning over the wet prepolymer in the drying process. The stirring is to volatilize water as soon as possible, reduce the surface hardening of the prepolymer and improve the effect of cyclized imine.
Still further, the heating dehydration and cyclization process is to dehydrate for 1 to 5 hours at the temperature of 200 to 250 ℃.
Further, another scheme is as follows: the first program pressure control heating reaction is to set the first temperature at 100-150 ℃ and control the pressure at-0.1-1.5 Mpa to carry out heating reaction; and the second temperature programming reaction is to set a second temperature to be 250-280 ℃ for continuous temperature programming reaction, and after the second temperature programming reaction is finished, a product can be separated from water and is dried at a temperature not higher than 120 ℃ to obtain the polyamide-imide resin.
Further, the diamine compound in the step (1) is one or more of m-phenylenediamine, p-phenylenediamine, diphenyl ether diamine, sulfonyl diphenylamine, methylene diphenylamine and bis (aminophenoxy) benzene.
Further, the particle size refining treatment in the step (1) is dry grinding and/or wet grinding to obtain particles with the particle size of 5-50 microns; the mixing temperature in the step (2) is lower than 150 ℃, and the stirring speed is 30-200 rpm.
Furthermore, the temperature of the particle size refining treatment is-196 ℃ to 100 ℃, and the time is 5min to 20min. The pulverization can adopt one or more modes of jet mill pulverization, micro-jet dispersion, a ball mill and an emulsifying machine.
Further, in the step (1), the molar ratio of the p-trimellitic acid to the diamine compound is (0.9-1) to 1; the weight ratio of the total weight of the trimellitic acid and the diamine compound to the added water in the step (2) is 1 (5-20).
The beneficial technical effects are as follows: the method adopts trimellitic acid and diamine compounds as polymerization monomers, takes water as a reaction solvent, and polymerizes into a prepolymer and then PAI in low pressure under the condition of no catalyst; in the invention, water is used as a solvent, and conventional raw materials such as anhydride and isocyanate can react with the water, so that trimellitic acid is directly used as a reaction monomer.
The method adopts water as a reaction medium, abandons a high-boiling point solvent as the reaction medium and uses a large amount of low-boiling point high-volatility organic solvents for precipitation, the whole synthesis and post-treatment process is environment-friendly, no three wastes are discharged, and the synthesis medium pure water has low cost and can be recycled; the PAI synthesis method using water as a medium has the total time of synthesizing and post-treating the product by organic solvent phase which is 1/3 or even shorter than the total time of synthesizing and post-treating the product, greatly reduces the labor cost and the time cost, and does not involve any organic solvent or other organic solvents, thereby not harming the health of technical personnel.
The method has high utilization rate of raw materials, the PAI yield can reach more than 95 percent, the viscosity-average molecular weight distribution of the synthesized PAI polymer is balanced, and the quality is stable; the PAI resin prepared by the invention is yellow or brown yellow solid powder, does not generate black impurities after being processed at the high temperature of 380 ℃ for 1 to 4 hours, and has stable product quality.
The water-phase synthesis of the polyamide-imide resin provided by the invention is a new method between a melt polycondensation method and a solution polycondensation method, and is a completely environment-friendly polyamide-imide synthesis method with a green chemical concept. In the whole synthesis reaction process, water is used as a solvent and a reaction medium, raw materials are crushed and refined, and the reaction under the conditions of low pressure, stirring and temperature rise generates excellent mixing performance, controllable multiphase flow and combinability, so that the energy and momentum transfer method under the original particle size of the raw materials is changed, the activation energy and collision probability among monomer molecules participating in the reaction are greatly activated, the complete of the relatively sufficient reaction between solid/liquid and homogeneous phase interfaces in a safe environment is ensured, and the PAI polymer with high yield and good performance is obtained. The whole reaction process does not involve organic solvent, and does not need catalyst, and the water solution of solid-liquid separation after reaction can be directly recycled, thereby avoiding the pollution to the environment and making up the deficiency of the solution polymerization method; due to the existence of water and pressure, the reaction temperature is reduced, the decomposition of monomers and polymers is avoided, the reaction is stable and easy to control, the process procedures are less, the time consumption is short, the energy consumption is low, and the overall cost is reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
It should be noted that the terms "first" and "second" are used to limit the temperature of the temperature rise, and are only used for the purpose of distinguishing the temperature change in the reaction in this step, and unless otherwise stated, the terms do not have any special meaning, and therefore, should not be construed as limiting the scope of the present invention.
The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards; if no corresponding national standard exists, the method is carried out according to the universal international standard or the standard requirement set by related enterprises.
Example 1
A method for aqueous phase synthesis of polyamide-imide resin, comprising the steps of:
(1) Weighing raw material monomers (210 g) of trimellitic acid and diphenyl ether diamine (220 g) required by the reaction, and respectively carrying out particle size refinement treatment until the particle size is less than or equal to 20 mu m; the particle size refining treatment is micronization in a solid state by adopting a jet mill pulverizer under the condition that compressed nitrogen is introduced for treatment for 20min at normal temperature; the size reduction of the raw material monomer is the result of high-speed collision between the particles of the raw material monomer under the action of high-speed gas flow;
(2) Weighing the amount of water required in the reaction process according to the weighed total mass of the monomers, and weighing the amount of water (4300 g) according to the proportion of the total mass of the monomers to the mass of water = 1;
putting trimellitic acid subjected to particle size refinement treatment, diphenyl ether diamine and weighed water into a reaction device, mixing at normal temperature at the rotating speed of 150rpm, vacuumizing to-0.1 MPa under the stirring state, introducing nitrogen, setting a first temperature to be 130 ℃ to perform a first program pressure control heating reaction, increasing the pressure in the reaction device due to the fact that the water is heated to boiling in the heating process, controlling the pressure in the reaction device to be 1.5MPa through the introduced nitrogen, and performing constant temperature reaction for 2 hours after the set first temperature of 130 ℃ is reached;
keeping the pressure at 1.5Mpa, setting a second temperature of 220 ℃ to perform a second temperature programming reaction, continuing the reaction, reaching the set second temperature of 220 ℃ and then performing a constant temperature reaction for 6 hours to complete the pre-polymerization reaction of the raw material monomers, and separating out the prepolymer from water; removing temperature control, cooling to below 100 ℃, separating water from the reaction equipment, separating wet prepolymer from water, washing and drying to obtain an intervening polymer, and recycling the separated water;
wherein the washing process comprises the following steps: adding boiling water into the obtained wet prepolymer for dispersing, stirring and washing, separating water and materials, repeating the operation for multiple times until the pH value of the washing water is =7, and stopping the washing process;
wherein the drying process comprises the following steps: the obtained wet prepolymer is turned over and dried at the temperature of 120 ℃, and after 12 hours (the mass difference of the prepolymer weighed before and after being less than 0.001g can be regarded as a dry product), an intervening polymer is obtained; determination of prepolymer: the dried prepolymer is a bright golden yellow substance, a small amount of material is taken and put into a DMAC solvent to be stirred at 30 ℃, and the prepolymer is successfully prepared if the prepolymer is dissolved;
(3) Dehydrating and cyclizing the prepolymer at 220 ℃ for 3h, and taking out the prepolymer after the temperature is reduced to normal temperature to obtain polyamide-imide resin (423.3 g); judgment of Polyamide-imide resin: the material is bright golden yellow, a small amount of the material is taken and put into DMAC solvent to be stirred at 30 ℃, and the polyamide-imide resin is successfully prepared if the material cannot be dissolved.
The polyamide-imide resin of this example has the structure shown in formula I above, and the yield is 97.7wt%.
The intrinsic viscosity of the polyamide-imide resin of formula I of this example was measured to be 0.8dL/g; the polyamide-imide resin of the formula I of this example was subjected to Differential Scanning Calorimetry (DSC) to have a glass transition temperature of 276 ℃.
The polyamide-imide resin of formula I prepared according to the process of the present invention has an intrinsic viscosity of 0.2dL/g to 1dL/g and a glass transition temperature (Tg) of 270 ℃ to 285 ℃.
Example 2
A method for aqueous phase synthesis of polyamide-imide resin comprising the steps of:
the structure of the polyamide-imide resin of this example is shown in formula II:
(1) Weighing raw material monomers of p-trimellitic acid (210 g) and p-phenylenediamine (120 g) required by the reaction, and carrying out particle size refinement treatment until the particle size is less than or equal to 10 mu m; the particle size refinement treatment is to adopt a jet mill pulverizer to inject compressed nitrogen for treatment for 20min at normal temperature to carry out micronization in a solid state, then weigh the amount of water (shown in step 2) required in the reaction process, mix the micronized para-trimellitic acid and the p-phenylenediamine, and place the mixture in an emulsifying machine for emulsification to obtain an emulsified mixed solution;
(2) Weighing the amount of water required in the reaction process according to the weighed total mass of the monomers, and weighing the amount of water (about 3000 g) according to the ratio of the total mass of the monomers to the mass of water = 1;
introducing nitrogen into the emulsified mixed solution of the trimellitic acid and the p-phenylenediamine which are subjected to particle size refinement at the rotating speed of 200rpm, setting a first temperature of 100 ℃ to perform a first program pressure control and temperature rise reaction, controlling the pressure in the reaction process to be 1.0Mpa by adjusting the nitrogen flow rate, and performing constant temperature reaction for 4 hours after the set first temperature of 100 ℃ is reached;
keeping the pressure at 1.0Mpa, setting a second temperature of 160 ℃ to perform a second temperature programming reaction, and after the set second temperature of 160 ℃ is reached, performing a constant temperature reaction for 8 hours to complete the pre-polycondensation reaction of the raw material monomers, and separating out the prepolymer from water; removing temperature control, cooling to below 100 ℃, separating water from the reaction equipment, separating wet prepolymer from water, washing and drying to obtain an intervening polymer, and recycling the separated water;
wherein the washing process comprises the following steps: adding boiling water into the obtained wet prepolymer for dispersing, stirring and washing, separating water and materials, repeating the operation for multiple times until the pH value of the washing water is =7, and stopping the washing process;
wherein the drying process comprises the following steps: the obtained wet prepolymer is turned over and dried at the temperature of 100 ℃, and an intervening polymer is obtained after 14 hours (the mass difference of the prepolymer weighed before and after being less than 0.001g can be regarded as a dry product); determination of prepolymer: the dried prepolymer is a bright golden yellow substance, a small amount of taken materials are put into a DMAC solvent to be stirred at the temperature of 30 ℃, and the prepolymer is successfully prepared after being dissolved;
(3) Carrying out high-temperature dehydration cyclization on the prepolymer at the temperature of 200 ℃ for 4h, and taking out the prepolymer after cooling to the normal temperature to obtain polyamide-imide resin (324.1 g); judgment of Polyamide-imide resin: the material is bright golden yellow, a small amount of the material is taken and put into a DMAC solvent to be stirred at 30 ℃, and if the material cannot be dissolved, the polyamide-imide resin is successfully prepared.
The structure of the polyamide-imide resin of this example is shown in formula II, and the yield is 98.2wt%.
The intrinsic viscosity of the polyamide-imide resin of formula II of this example was measured to be 0.7dL/g; the polyamide-imide resin of the present example represented by the formula II was subjected to Differential Scanning Calorimetry (DSC) and had a glass transition temperature of 297 ℃.
The intrinsic viscosity of the polyamide-imide resin shown in the formula II prepared by the method is 0.6 dL/g-0.8 dL/g; the glass transition temperature (Tg) is from 290 ℃ to 310 ℃.
Example 3
The preparation process of the polyamide-imide resin of this example is the same as that of example 1, except that the diamine compound is m-phenylenediamine, the temperature of the second temperature programming reaction in the step (2) is 270 ℃ and the reaction time is 10 hours, and after the second temperature programming reaction is finished, the product can be separated from water and dried at 120 ℃ for 3 hours to obtain the polyamide-imide resin.
The yield of the polyamide-imide resin of this example was 97.4wt%.
The polyamide-imide resin of this example was tested for intrinsic viscosity and the product of this example was found to have an intrinsic viscosity of 0.4dL/g; the polyamide-imide resin of this example was subjected to Differential Scanning Calorimetry (DSC) to have a glass transition temperature of 250 ℃.
The intrinsic viscosity of the polyamide-imide resin of this example prepared according to the process of the present invention is 0.3dL/g to 0.5dL/g; the glass transition temperature (Tg) is 240 ℃ to 260 ℃.
Other performance data for the polyamide imide resin products of example 1, example 2, and example 3 are shown in Table 1.
TABLE 1 Property data for Polyamide-imide resin products of example 1, example 2 and example 3
| Example 1 | Example 2 | Example 3 | |
| Tensile Strength (MPa) | 164 | 190 | 175 |
| Elongation at Break (%) | 18％ | 14％ | 15％ |
| Glass transition temperature (. Degree. C.) | 276 | 297 | 250 |
In the above examples, the glass transition temperature and the intrinsic viscosity can be used to determine that the obtained product is a polyamide-imide resin with a corresponding structure. The polyamide-imide resin prepared by the method has better mechanical property.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (4)
1. The method for synthesizing the polyamide-imide resin in the water phase is characterized by comprising the following steps:
(1) Respectively or after mixing trimellitic acid and diamine compounds, carrying out grain size refinement treatment on the raw materials; the molar ratio of the trimellitic acid to the diamine compound is (0.9-1): 1;
the particle size refinement treatment is dry grinding and/or wet grinding to obtain particle size of 5-50 μm; the temperature of the particle size refining treatment is-196 ℃ to 100 ℃, and the time is 5min to 20min;
(2) Mixing trimellitic acid subjected to particle size refinement treatment, diamine compounds and water at a temperature lower than 150 ℃, wherein the weight ratio of the total weight of trimellitic acid and diamine compounds to the weight of added water is 1 (5-20), performing deoxidation and nitrogen filling treatment under the stirring of 30-200 rpm, performing a first program pressure-control heating reaction, and performing constant-temperature reaction for 1-4 h after reaching a set first temperature;
keeping the pressure, carrying out a second temperature programming reaction, reacting at constant temperature for 4-10 h after reaching a set second temperature, and separating a product from water after cooling to obtain the polyamide-imide resin;
the first program pressure control heating reaction is to set the first temperature at 100-150 ℃ and control the pressure at-0.1-1.5 Mpa to carry out heating reaction; the second temperature programming reaction is to set a second temperature to be 150-250 ℃ for continuous temperature programming reaction, separate a wet prepolymer from water after the second temperature programming reaction is finished, wash the wet prepolymer, dry the wet prepolymer to obtain an intermediate polymer, and then subject the intermediate polymer to heating dehydration cyclization, wherein the heating dehydration cyclization is performed at 200-250 ℃ for 1-5 h to obtain the polyamide-imide resin;
or, the first program-controlled pressure-raising reaction is carried out at a first temperature of 100-150 ℃ and a controlled pressure of-0.1-1.5 MPa; and the second temperature programming reaction is to set a second temperature to be 250-280 ℃ for continuous temperature programming reaction, and after the second temperature programming reaction is finished, a product can be separated from water and is dried at a temperature not higher than 120 ℃ to obtain the polyamide-imide resin.
2. The method for aqueous phase synthesis of polyamide-imide resin as claimed in claim 1 wherein the washing process is: and adding boiling water into the wet prepolymer for dispersing, washing and separating, and stopping the washing process after the pH value of the washing water is more than 4 after repeated operation.
3. The method for aqueous phase synthesis of polyamide-imide resin as claimed in claim 1 wherein the drying process is: and drying the wet prepolymer at a temperature lower than 150 ℃ for at least more than 10h, and turning over the wet prepolymer in the drying process.
4. The method for aqueous synthesis of polyamide-imide resin as claimed in any one of claims 1 to 3 wherein the diamine compound in step (1) is one or more of m-phenylenediamine, p-phenylenediamine, diphenyl ether diamine, sulfonyldiphenylamine, methylenediphenylamine, bis (aminophenoxy) benzene.
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| JPS5714622A (en) * | 1980-06-30 | 1982-01-25 | Toray Ind Inc | Production of polyamideimide resin |
| CN102099398A (en) * | 2008-06-12 | 2011-06-15 | 罗地亚管理公司 | Process for preparing a polyamideimide, a polyamideimide and composition comprising this polyamideimide |
| CN102532545A (en) * | 2011-12-29 | 2012-07-04 | 东莞市信诺橡塑工业有限公司 | Long-carbon-chain semi-aromatic polyamide imide and synthetic method thereof |
| CN104098772A (en) * | 2014-07-29 | 2014-10-15 | 上海华谊（集团）公司 | Novel polyamide-imide preparation method |
| JP2017186560A (en) * | 2016-04-05 | 2017-10-12 | ユニチカ株式会社 | Polyamide-imide precursor solution |
| JP2020012104A (en) * | 2018-07-05 | 2020-01-23 | ユニチカ株式会社 | Production method of polyamide-imide resin |
| CN111072963A (en) * | 2019-12-27 | 2020-04-28 | 江门市优巨新材料有限公司 | Method for synthesizing polyimide in aqueous phase |
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2020
- 2020-10-29 CN CN202011184708.9A patent/CN112321829B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5714622A (en) * | 1980-06-30 | 1982-01-25 | Toray Ind Inc | Production of polyamideimide resin |
| CN102099398A (en) * | 2008-06-12 | 2011-06-15 | 罗地亚管理公司 | Process for preparing a polyamideimide, a polyamideimide and composition comprising this polyamideimide |
| CN102532545A (en) * | 2011-12-29 | 2012-07-04 | 东莞市信诺橡塑工业有限公司 | Long-carbon-chain semi-aromatic polyamide imide and synthetic method thereof |
| CN104098772A (en) * | 2014-07-29 | 2014-10-15 | 上海华谊（集团）公司 | Novel polyamide-imide preparation method |
| JP2017186560A (en) * | 2016-04-05 | 2017-10-12 | ユニチカ株式会社 | Polyamide-imide precursor solution |
| JP2020012104A (en) * | 2018-07-05 | 2020-01-23 | ユニチカ株式会社 | Production method of polyamide-imide resin |
| CN111072963A (en) * | 2019-12-27 | 2020-04-28 | 江门市优巨新材料有限公司 | Method for synthesizing polyimide in aqueous phase |
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