CN109666144B - Method for preparing polyamic acid solution - Google Patents
Method for preparing polyamic acid solution Download PDFInfo
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- CN109666144B CN109666144B CN201710965060.0A CN201710965060A CN109666144B CN 109666144 B CN109666144 B CN 109666144B CN 201710965060 A CN201710965060 A CN 201710965060A CN 109666144 B CN109666144 B CN 109666144B
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- acid solution
- dianhydride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
Abstract
The invention relates to a preparation method of a polyamic acid solution, belongs to the field of preparation of polyamic acid solutions, and mainly solves the problems that in the prior art, the viscosity of the polyamic acid solution is uncontrollable, and polyamic acid lumps are easy to form or the uniformity is poor in the preparation of polyamic acid. The invention adopts a preparation method of a polyamic acid solution, which is characterized in that a dianhydride monomer is added into a diamine solution in a uniform speed manner, and then a tetracarboxylic acid monomer is added to prepare the polyamic acid solution; wherein the amount of dianhydride monomer is less than or equal to the amount of diamine monomer; the technical proposal that the sum of the substances of the dianhydride monomer and the tetracarboxylic acid monomer is equal to the substance of the diamine monomer better solves the problem and can be used for industrial application of preparing the polyamide acid.
Description
Technical Field
The present invention relates to a novel method for preparing a polyamic acid solution, by which a uniform and viscosity-controllable polyamic acid solution can be prepared.
Background
Polyimide has irreplaceable effects in the fields of aerospace, cable packaging, flexible circuit boards, lithium battery diaphragms, separation membranes, high-temperature filtration, microelectronic devices and medical use due to excellent high-temperature resistance, low-temperature resistance, corrosion resistance, irradiation resistance, high strength, high modulus, high dimensional stability, low dielectric constant, no toxicity, self-extinguishing after fire leaving and the like.
The main method for preparing polyimide is to imidize the polyamic acid solution, so preparing a high-quality polyamic acid solution is a prerequisite for obtaining a high-quality polyimide material. Polyamic acids are typically prepared by reacting a dianhydride with a diamine in an aprotic polar solvent at low temperatures. The common polymerization method is to dissolve diamine monomer in aprotic polar solvent, then add dianhydride monomer by one-time feeding or batch feeding, and adjust the relative molecular mass by adding more or less dianhydride monomer or hydrolyzing a part of dianhydride by aqueous solvent.
The preparation of polyamic acid solution by the above polymerization method has the following disadvantages:
1. the dianhydride monomer is fed in one time or batch by times, so that the apparent viscosity of the solution is rapidly increased in a short time, and the system becomes very viscous before the dianhydride is dissolved, so that the mass transfer is difficult and the reaction is difficult to be sufficient, or polyamide acid blocks are formed, and the processing performance is influenced;
2. the method of adding more or less dianhydride monomers is adopted to adjust the relative molecular mass, so that the quantity unequal ratio of dianhydride and diamine substances is caused, the relative molecular mass of polyimide is reduced, and the product performance is influenced;
3. the dianhydride monomers such as pyromellitic dianhydride and the like have strong activity, so that the method for hydrolyzing a part of dianhydride by using an aqueous solvent is difficult to operate, the excessive hydrolysis often causes the low viscosity of the solution, the performance of the product is reduced, and the product is difficult to process.
Disclosure of Invention
Based on the above background art, the technical problem to be solved by the present invention is to provide a method for preparing a polyamic acid solution, which can effectively solve the above problems, obtain a uniform and viscosity-controllable polyamic acid solution, and has the advantages of good solution uniformity, controllable viscosity, and high quality.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a polyamic acid solution is characterized in that a dianhydride monomer is added into a diamine solution at a constant speed, and then a tetracarboxylic acid monomer is added to prepare the polyamic acid solution; wherein the amount of dianhydride monomer is less than or equal to the amount of diamine monomer; the sum of the amounts of the dianhydride monomer and the tetraacid monomer is equal to the amount of the diamine monomer.
In the above technical solution, the preparation method of the polyamic acid solution preferably specifically includes the following steps:
(1) dissolving a diamine monomer in an aprotic polar solvent;
(2) adding a required amount of dianhydride monomer into the diamine solution obtained in the step (1) at a constant speed;
(3) after the dianhydride monomer is dissolved in the step (2), adding a tetracarboxylic acid monomer, so that the total amount of the dianhydride monomer and the tetracarboxylic acid monomer is equal to the amount of the diamine monomer;
(4) and (4) dissolving the tetra-acid monomer in the step (3), and then carrying out polymerization reaction to obtain the polyamic acid solution.
In the above technical solution, the diamine monomer in step (1) is preferably one or more of diphenyl ether diamine and p-phenylenediamine.
In the above technical solution, the aprotic polar solvent in step (1) is preferably at least one of N, N dimethylformamide, N dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide.
In the technical scheme, the uniform speed in the step (2) is 0.1 g/min-100 g/min, and the preferable charging time of the dianhydride monomer is not less than 0.5 hour.
In the above technical scheme, the dianhydride monomer in step (2) is one or more than two of pyromellitic dianhydride, biphenyl dianhydride, benzophenone dianhydride, and diphenyl ether dianhydride.
In the technical scheme, the ratio of the amount of the dianhydride monomer to the amount of the diamine monomer in the step (2) is 95-100%.
In the above technical scheme, the tetraacid monomer in step (3) is one or more than two of pyromellitic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid.
In the technical scheme, the initial temperature of the polymerization reaction is controlled to be-10-40 ℃, and the temperature is kept constant in the polymerization process (namely the dianhydride monomer adding and dissolving process).
In the technical scheme, the stirring speed of the polymerization reaction is controlled to be 30-400 r/min.
Compared with the prior art, the invention has the following purposes and effects:
1. the dianhydride monomer is added in a continuous and uniform-speed feeding manner, so that the phenomenon that the apparent viscosity of the solution is rapidly increased in a short time is avoided, the mass transfer effect is improved, the reaction is fully performed, and the uniformity of the solution is improved, so that the subsequent processing is facilitated;
2. the method of adding the tetracid monomer is adopted, so that equivalent weight of dianhydride and diamine is kept, and excessive viscosity is avoided, thus not only ensuring the processability of the solution, but also ensuring the performance of the product;
3. the preparation method of the polyamic acid solution provided by the invention is simple in process and strong in operability, and can be used for preparing the high-quality polyamic acid solution with the required viscosity and good uniformity.
The method controls the feeding speed of the dianhydride monomer to ensure that the reaction is more sufficient, thereby obtaining the uniform and high-quality polyamic acid solution. In addition, the method can control the relative molecular mass of the polyamic acid solution by controlling the amount of the dianhydride monomer, and can also keep the equivalent weight of the dianhydride and the diamine by the tetracarboxylic acid monomer, thereby obtaining the polyamic acid solution with ideal viscosity. The polyamic acid solution has the advantages of uniform system, moderate viscosity and easy processing, and does not cause the reduction of the relative molecular mass of the final product polyimide due to equivalent weight of dianhydride, diamine and the like, thereby affecting the performance of the polyimide. The polyamic acid solution prepared by the method has wide application prospect in the fields of polyimide film, polyimide fiber manufacturing and the like.
By adopting the technical scheme of the invention, the viscosity of the polyamic acid solution is controllable, the uniformity is good, no polyamic acid block is formed, the polyamic acid solution passes through a 2-micron glass fiber filter membrane, and the filter membrane is free from foreign matter under the irradiation of an ultraviolet fluorescent lamp, so that a good technical effect is obtained.
Detailed Description
The present invention is further illustrated by the following examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the invention.
[ example 1 ]
24.0288g (120mmol) diphenyletherdiamine (ODA) were dissolved in 304ml N, N-dimethylacetamide (DMAc) at 25 ℃ N2Stirring under protection, adding 26.0174g (119.28mmol) of pyromellitic dianhydride (PMDA) at the speed of 0.5g/min after the PMDA is completely dissolved, adding 0.1830g (0.72mmol) of pyromellitic acid into the system after the PMDA is completely dissolved, and continuing to carry out N reaction at 25 DEG C2Stirring for 1h under protection at the stirring speed of 250rpm to obtain uniform pale yellow transparent viscous polyamic acid solutionAnd (4) liquid. The polyamic acid solution was tested at 25 ℃ and a shear rate of 1s-1The apparent viscosity under the condition is 290Pa · s, and the intrinsic viscosity is 2.18 dL/g; after passing through a 2 μm glass fiber filter membrane, the filter membrane was free from foreign matter under irradiation of an ultraviolet fluorescent lamp.
[ example 2 ]
20.024g (100mmol) diphenyletherdiamine (ODA) were dissolved in 253ml of N, N-dimethylacetamide (DMAc) at 0 ℃ N2Stirring under protection, after completely dissolving, adding 21.5939g (99mmol) of pyromellitic dianhydride (PMDA) at the speed of 0.1g/min, adding 0.2542g (1mmol) of pyromellitic acid into the system after the PMDA is completely dissolved, and continuing to perform N reaction at the temperature of 0 ℃ after the addition is finished2Stirring for 1h under protection at the stirring speed of 200rpm to obtain a uniform light yellow transparent viscous polyamic acid solution. The polyamic acid solution was tested at 25 ℃ and a shear rate of 1s-1The apparent viscosity under the condition is 210Pa · s, and the intrinsic viscosity is 2.04 dL/g; after passing through a 2 μm glass fiber filter membrane, the filter membrane was free from foreign matter under irradiation of an ultraviolet fluorescent lamp.
[ example 3 ]
24.0288g (120mmol) diphenyletherdiamine (ODA) were dissolved in 302ml N, N-Dimethylformamide (DMF) at 20 ℃ N2Stirring under protection, adding 26.0174g (119.28mmol) of pyromellitic dianhydride (PMDA) at the speed of 1g/min after the PMDA is completely dissolved, adding 0.1830g (0.72mmol) of pyromellitic acid into the system after the PMDA is completely dissolved, and continuing to perform N reaction at 20 ℃ after the addition is finished2Stirring for 1h under protection at the stirring speed of 400rpm to obtain a uniform light yellow transparent viscous polyamic acid solution. The polyamic acid solution was tested at 25 ℃ and a shear rate of 1s-1The apparent viscosity under the condition is 70Pa · s, and the intrinsic viscosity is 1.90 dL/g; after passing through a 2 μm glass fiber filter membrane, the filter membrane was free from foreign matter under irradiation of an ultraviolet fluorescent lamp.
[ example 4 ]
24.0288g (120mmol) diphenyletherdiamine (ODA) were dissolved in 277ml N-methylpyrrolidone (DMF) at-10 ℃ N2Stirring under protection, adding 26.0174g (1 g/min) after complete dissolution19.28mmol) of pyromellitic dianhydride (PMDA), 0.1830g (0.72mmol) of pyromellitic acid is added into the system after the PMDA is completely dissolved, and the temperature is kept at-10 ℃ N after the addition is finished2Stirring for 1h under protection at the stirring speed of 200rpm to obtain a uniform light yellow transparent viscous polyamic acid solution. The polyamic acid solution was tested at 25 ℃ and a shear rate of 1s-1The apparent viscosity under the condition is 68Pa · s, and the intrinsic viscosity is 1.91 dL/g; after passing through a 2 μm glass fiber filter membrane, the filter membrane was free from foreign matter under irradiation of an ultraviolet fluorescent lamp.
[ example 5 ]
2002.4g (10mol) of diphenyletherdiamine (ODA) were dissolved in 23.75kg of N, N-dimethylacetamide (DMAc) at 40 ℃ N2Stirring under protection, after complete dissolution, adding 2137.6g (9.8mol) of pyromellitic dianhydride (PMDA) at the speed of 100g/min, adding 50.83g (0.2mol) of pyromellitic acid into the system after the PMDA is completely dissolved, and continuing to carry out N reaction at 40 ℃ after the addition is finished2Stirring for 1h under protection, and stirring speed is 50rpm, thus obtaining the homogeneous light yellow transparent viscous polyamic acid solution. The polyamic acid solution was tested at 25 ℃ and a shear rate of 1s-1The apparent viscosity under the condition is 88Pa · s, and the intrinsic viscosity is 1.94 dL/g; after passing through a 2 μm glass fiber filter membrane, the filter membrane was free from foreign matter under irradiation of an ultraviolet fluorescent lamp.
[ example 6 ]
12.0144g (60mmol) diphenyletherdiamine (ODA) and 6.4884g (60mmol) p-phenylenediamine (p-PDA) were dissolved in 306g dimethyl sulfoxide (DMSO) at 20 ℃ N2Stirring under protection, after complete dissolution, adding 34.2472g (116.4mmol) of biphenyl dianhydride (BPDA) at the speed of 2g/min, adding 1.1889g (3.6mmol) of biphenyltetracarboxylic acid into the system after the BPDA is completely dissolved, and continuing to add at 20 ℃ N after the addition is finished2Stirring for 1h under protection at a stirring speed of 250rpm to obtain a uniform brown polyamic acid solution. The polyamic acid solution was tested at 25 ℃ and a shear rate of 1s-1The apparent viscosity under the condition is 16.1Pa · s, and the intrinsic viscosity is 0.71 dL/g; after passing through a 2 μm glass fiber filter membrane, the filter membrane was free from foreign matter under irradiation of an ultraviolet fluorescent lamp.
[ example 7 ]
20.024g (100mmol) diphenyletherdiamine (ODA) were dissolved in 316ml N, N-dimethylacetamide (DMAc) at 10 ℃ N2Stirring under protection, adding 31.9008g (99mmol) of benzophenone dianhydride (BTDA) at the speed of 0.5g/min after completely dissolving, adding 0.3583g (1mmol) of benzophenone tetracarboxylic acid into the system after completely dissolving the BTDA, and continuing to add the benzophenone tetracarboxylic acid at the temperature of 10 ℃ N after finishing adding2Stirring is carried out for 1h under protection, and the stirring speed is 250rpm, so that a uniform light yellow transparent polyamic acid solution is obtained. The polyamic acid solution was tested at 25 ℃ and a shear rate of 1s-1The apparent viscosity under the condition is 62Pa · s, and the intrinsic viscosity is 1.54 dL/g; after passing through a 2 μm glass fiber filter membrane, the filter membrane was free from foreign matter under irradiation of an ultraviolet fluorescent lamp.
[ example 8 ]
20.024g (100mmol) diphenyletherdiamine (ODA) were dissolved in 254ml of N, N-dimethylacetamide (DMAc) at 0 ℃ N2Stirring under protection, after completely dissolving, adding 20.7214g (95mmol) of pyromellitic dianhydride (PMDA) at the speed of 1g/min, adding 1.2710g (5mmol) of pyromellitic acid into the system after PMDA is completely dissolved, and continuing to perform N reaction at the temperature of 0 ℃ after the addition is finished2Stirring for 1h under protection at the stirring speed of 200rpm to obtain a uniform light yellow transparent viscous polyamic acid solution. The polyamic acid solution was tested at 25 ℃ and a shear rate of 1s-1The apparent viscosity under the condition is 110Pa · s, and the intrinsic viscosity is 1.12 dL/g; after passing through a 2 μm glass fiber filter membrane, the filter membrane was free from foreign matter under irradiation of an ultraviolet fluorescent lamp.
[ example 9 ]
20.024g (100mmol) diphenyletherdiamine (ODA) were dissolved in 253ml of N, N-dimethylacetamide (DMAc) at 0 ℃ N2Stirring under protection, after completely dissolving, adding 20.9395g (96mmol) of pyromellitic dianhydride (PMDA) at the speed of 1g/min, adding 1.0168g (4mmol) of pyromellitic acid into the system after the PMDA is completely dissolved, and continuing to perform N reaction at the temperature of 0 ℃ after the addition is finished2Stirring for 1h under protection at a stirring speed of 30rpm to obtain a uniform pale yellow transparent viscous polyamic acid solution. The polyamic acid solution was tested inAt 25 ℃ and a shear rate of 1s-1The apparent viscosity under the condition is 102Pa · s, and the intrinsic viscosity is 1.05 dL/g; after passing through a 2 μm glass fiber filter membrane, the filter membrane was free from foreign matter under irradiation of an ultraviolet fluorescent lamp.
[ example 10 ]
20.024g (100mmol) diphenyletherdiamine (ODA) were dissolved in 309ml N, N-dimethylacetamide (DMAc) at 0 ℃ N2Stirring under protection, dissolving completely, adding 31.021g (100mmol) diphenyl ether dianhydride (ODPA) at 0.5g/min, and continuing to add at 0 deg.C N2Stirring for 1h under protection at the stirring speed of 200rpm to obtain a uniform light yellow transparent viscous polyamic acid solution. The polyamic acid solution was tested at 25 ℃ and a shear rate of 1s-1The apparent viscosity under the condition is 115Pa · s, and the intrinsic viscosity is 1.54 dL/g; after passing through a 2 μm glass fiber filter membrane, the filter membrane was free from foreign matter under irradiation of an ultraviolet fluorescent lamp.
[ COMPARATIVE EXAMPLE 1 ]
24.0288g (120mmol) diphenyletherdiamine (ODA) were dissolved in 304ml N, N-dimethylacetamide (DMAc) at 25 ℃ N2Stirring under protection, dissolving completely, adding 26.0174g (119.28mmol) of pyromellitic dianhydride (PMDA) at 25 deg.C in one portion, and adding N2Stirring under protection, dissolving completely, adding 0.1830g (0.72mmol) of pyromellitic acid once again, and continuing to add N at 25 deg.C2Stirring for 1h under protection, wherein the stirring speed is 250rpm, and the mass transfer effect of the solution is not ideal, so that the obtained polyamic acid solution is not uniform. The polyamic acid solution was tested at 25 ℃ and a shear rate of 1s-1The apparent viscosity under the conditions was 183 pas and the intrinsic viscosity was 1.58 dL/g.
[ COMPARATIVE EXAMPLE 2 ]
20.024g (100mmol) diphenyletherdiamine (ODA) were dissolved in 253ml of N, N-dimethylacetamide (DMAc) at 0 ℃ N2Stirring under protection, dissolving completely, adding 21.812g (100mmol) of pyromellitic dianhydride (PMDA) at one time, and continuing to add at 0 deg.C N2Stirring for 2h under protection, stirring speed of 200rpm, violent solution heat release, out-of-control viscosity, unsatisfactory mass transfer effect, and non-uniform polyamic acid solutionHomogenizing gel. The solution is in a gel state, the apparent viscosity is difficult to measure, the intrinsic viscosity is 3.12dL/g, and the subsequent processing and molding are difficult to perform due to the excessive viscosity.
[ COMPARATIVE EXAMPLE 3 ]
20.024g (100mmol) diphenyletherdiamine (ODA) were dissolved in 309ml N, N-dimethylacetamide (DMAc) at 0 ℃ N2Stirring under protection, dissolving completely, adding 31.021g (100mmol) diphenyl ether dianhydride (ODPA) four times, adding for 20min, and continuing at 0 deg.C N2Stirring for 2h under protection at a stirring speed of 200rpm, wherein the mass transfer effect is not ideal after the last feeding, and the obtained polyamic acid solution is not uniform. The polyamic acid solution was tested at 25 ℃ and a shear rate of 1s-1The apparent viscosity under the conditions was 97 pas and the intrinsic viscosity was 1.29 dL/g.
[ COMPARATIVE EXAMPLE 4 ]
30.04kg (150mol) of diphenyletherdiamine (ODA) were dissolved in 328.00kg of N, N-dimethylacetamide (DMAc) at 30 ℃ under reduced pressure2Stirring under protection, after complete dissolution, adding 31.74kg (145.5mol) of pyromellitic dianhydride (PMDA), and stirring for 3h to obtain a polyamic acid prepolymer solution. 0.98kg (4.5mol) of pyromellitic dianhydride was dissolved in 27.00kg of dimethyl sulfoxide (DMSO) to prepare a dianhydride solution. Adding the polyamic acid prepolymer solution and the dianhydride solution into a kettle at a certain speed, mixing and stirring to obtain the final polyamic acid solution which is an opaque viscous solution. The polyamic acid solution was tested to have an apparent viscosity of 289 Pa.s, a number average molecular weight of 186000, and a molecular weight distribution of 1.79 at 25 deg.C, and after passing through a 2 μm glass fiber filter, the filter was exposed to ultraviolet fluorescent light to provide white foreign matter.
Claims (8)
1. A method for producing a polyamic acid solution, characterized by comprising the steps of,
(1) dissolving a diamine monomer in an aprotic polar solvent;
(2) adding a required amount of dianhydride monomer into the diamine solution obtained in the step (1) at a constant speed for polymerization, wherein the amount of the dianhydride monomer is less than or equal to that of the diamine monomer;
(3) after the dianhydride monomer is dissolved in the step (2), adding a tetracarboxylic acid monomer, so that the total amount of the dianhydride monomer and the tetracarboxylic acid monomer is equal to the amount of the diamine monomer;
(4) dissolving the tetra-acid monomer in the step (3) to obtain a polyamic acid solution;
in the step (3), the tetraacid monomer is one or more than two of pyromellitic acid, biphenyltetracarboxylic acid and benzophenone tetracarboxylic acid.
2. The method for preparing a polyamic acid solution according to claim 1, wherein the diamine monomer in step (1) is one or more of diphenyl ether diamine and p-phenylenediamine.
3. The method for producing a polyamic acid solution according to claim 1, wherein said aprotic polar solvent in step (1) is at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide.
4. The method for preparing a polyamic acid solution according to claim 1, wherein the uniform speed in step (2) is 0.1g/min to 100 g/min.
5. The method for preparing a polyamic acid solution according to claim 1, wherein said dianhydride monomer in step (2) is one or more of pyromellitic dianhydride, biphenyl dianhydride, benzophenone dianhydride, and diphenyl ether dianhydride.
6. The method for preparing polyamic acid solution according to claim 1, wherein the ratio of the amount of dianhydride monomer to diamine monomer species in step (2) is 95% to 100%.
7. The method for producing a polyamic acid solution according to claim 1, wherein the polymerization initiation temperature is controlled to be-10 to 40%oC in dianhydrideThe temperature was kept constant during the monomer addition and dissolution.
8. The method for producing a polyamic acid solution according to claim 1, wherein a polymerization stirring speed is controlled to 30 to 400 r/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024019360A1 (en) * | 2022-07-22 | 2024-01-25 | 피아이첨단소재 주식회사 | Polyamic acid composition |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0053927A1 (en) * | 1980-12-05 | 1982-06-16 | E.I. Du Pont De Nemours And Company | Polyimide manufacture |
| CN105622936A (en) * | 2014-10-27 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation method for polyamide acid solution |
| CN106589370A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Polyamic acid composition, preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0053927A1 (en) * | 1980-12-05 | 1982-06-16 | E.I. Du Pont De Nemours And Company | Polyimide manufacture |
| CN105622936A (en) * | 2014-10-27 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation method for polyamide acid solution |
| CN106589370A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Polyamic acid composition, preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024019360A1 (en) * | 2022-07-22 | 2024-01-25 | 피아이첨단소재 주식회사 | Polyamic acid composition |
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