CN111363151A - Method for controlling polymerization viscosity of industrial polyamic acid - Google Patents
Method for controlling polymerization viscosity of industrial polyamic acid Download PDFInfo
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- CN111363151A CN111363151A CN202010323925.5A CN202010323925A CN111363151A CN 111363151 A CN111363151 A CN 111363151A CN 202010323925 A CN202010323925 A CN 202010323925A CN 111363151 A CN111363151 A CN 111363151A
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- 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
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
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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
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a method for controlling the polymerization viscosity of industrial polyamic acid, belonging to the fields of light chemical industry and material synthesis. The method comprises the following steps: firstly, preparing a diamine solution; then preparing 3 kinds of dianhydride solutions with different concentrations; and finally adding 3 kinds of dianhydride solutions with different concentrations for 3 times, controlling the reaction to be 3 times, and finally obtaining the dianhydride by the reaction, wherein the polymerization viscosity is controlled to be 5000-20000P. The method realizes the viscosity uniformity and repeatability of the final polymerization stock solution by controlling the monomer concentration, the feeding sequence before and after dissolution, the reaction temperature and the reaction time in different proportioning stages, the reaction stirring speed and the adding speed and the like, and can be used for industrial continuous production.
Description
Technical Field
The invention relates to the fields of light chemical industry and material synthesis, in particular to a method for controlling the polymerization viscosity of industrial polyamic acid.
Technical Field
The polyamic acid is used as a precursor solution of polyimide, and the molecular weight and the uniformity and the stability of the polyamic acid directly influence various indexes of subsequent polyimide materials. The order of addition of the polymerization, the reaction temperature, the rate of addition and the rate of stirring, as well as the reaction time and the concentration of the solution, have a great influence on the molecular weight and the uniformity of the final polymerization. The control of viscosity and uniformity in the polymerization process is particularly important for industrial production. Therefore, the development of industrial polyamide acid polymerization viscosity control has important industrial significance.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for controlling the polymerization viscosity of industrial polyamic acid aiming at the defects of the prior art; the method can effectively realize the viscosity uniformity and repeatability of the final polymerization stock solution, and can be used for industrial continuous production.
The technical problem to be solved by the present invention is achieved by the following technical means. The invention relates to a method for controlling the polymerization viscosity of industrial polyamic acid, which is characterized by comprising the following steps:
(1) diamine solution preparation: adding diamine monomer into solvent, stirring and dissolving, controlling the temperature at-10-30 ℃ and the mass concentration at 5-30%;
(2) preparation of dianhydride solution: respectively adding dianhydride monomers into a solvent, stirring and dispersing at-10-30 ℃ to obtain dianhydride solutions with 3 mass concentrations of 22-30%, 8-15% and 3-7% respectively;
(3) primary reaction: cooling the diamine solution to-10 to-5 ℃, stirring at 50-80rpm, adding a dianhydride solution with the mass concentration of 22-30% into the diamine solution at a certain speed, and controlling the molar ratio of diamine to dianhydride to be 0.5-0.7: 1, controlling the temperature at 10-20 ℃, and stirring for reaction for 2-6 h;
(4) and (3) secondary reaction: reducing the stirring speed to 30-50rpm, adding a dianhydride solution with the mass concentration of 8% -15% into the reaction material after the primary reaction at a certain speed, and controlling the molar ratio of diamine to dianhydride to be 0.7-0.9: 1, controlling the temperature at 20-30 ℃, and stirring for reaction for 2-4 h;
(5) and (3) carrying out three reactions: reducing the stirring speed to 10-20rpm, adding a dianhydride solution with the mass concentration of 3% -7% into the polymerization stock solution obtained by the secondary reaction at a proper speed, controlling the temperature to be 30-60 ℃, and ensuring the molar ratio of diamine to dianhydride to be 0.9-0.998: 1, stirring the mixture for reaction for 2 to 8 hours, and controlling the final polymerization viscosity to be 5000-20000P.
The invention further discloses a method for controlling the polymerization viscosity of industrial polyamic acid, which adopts the following preferable technical scheme: the diamine monomer in the step (1) is selected from one or more of 4, 4-diaminodiphenyl ether ODA, p-phenylenediamine PDA and 4, 4-diaminop-phenylmethane MDA.
The invention further discloses a method for controlling the polymerization viscosity of industrial polyamic acid, which adopts the following preferable technical scheme: the dianhydride monomer in the step (2) is selected from pyromellitic dianhydride PMDA or biphenyl tetracarboxylic dianhydride BPDA.
The invention further discloses a method for controlling the polymerization viscosity of industrial polyamic acid, which adopts the following preferable technical scheme: the solvent is a common solvent, preferably dimethylacetamide (DMAc).
The invention further discloses a method for controlling the polymerization viscosity of industrial polyamic acid, which adopts the following preferable technical scheme: in the preparation of the diamine solution in the step (1), the temperature is controlled to be 20-25 ℃, and the mass concentration of the diamine solution is 22%.
The invention further discloses a method for controlling the polymerization viscosity of industrial polyamic acid, which adopts the following preferable technical scheme: in the preparation of the dianhydride solution in the step (2): the stirring dispersion condition is 20-25 deg.C, and the obtained 3 mass concentration dianhydride solutions are respectively 25%, 10% and 5% in mass concentration.
Compared with the prior art, the invention has the beneficial effects that: the method realizes the viscosity uniformity and repeatability of the final polymerization stock solution by controlling the monomer concentration, the feeding sequence before and after dissolution, the reaction temperature and the reaction time in different proportioning stages, the reaction stirring speed and the adding speed and the like, and can be used for industrial continuous production.
Detailed description of the invention
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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.
Example 1, a method for controlling polymerization viscosity of industrial polyamic acid, comprising the steps of:
(1) diamine solution preparation: adding diamine monomer into solvent, stirring and dissolving, controlling the temperature at-10 ℃ and the mass concentration at 5%;
(2) preparation of dianhydride solution: respectively adding dianhydride monomers into a solvent, stirring and dispersing at-10 ℃ to obtain dianhydride solutions with 3 mass concentrations of 22%, 8% and 3% respectively;
(3) primary reaction: controlling the temperature of the diamine solution at-10 ℃, stirring at 50rpm, adding a dianhydride solution with the mass concentration of 22% into the diamine solution at a certain speed, and controlling the molar ratio of diamine to dianhydride to be 0.5: 1, controlling the temperature at 10 ℃, and stirring for reaction for 2 hours;
(4) and (3) secondary reaction: reducing the stirring speed to 30rpm, adding a dianhydride solution with the mass concentration of 8% into the reaction material after the first reaction at a certain speed, and controlling the molar ratio of diamine to dianhydride to be 0.7: 1, controlling the temperature at 20 ℃, and stirring for reaction for 2 hours;
(5) and (3) carrying out three reactions: and (3) reducing the stirring speed to 10rpm, adding a dianhydride solution with the mass concentration of 3% into the polymerization stock solution obtained by the secondary reaction at a proper speed, controlling the temperature to be 30 ℃, and ensuring the molar ratio of diamine to dianhydride to be 0.9: 1, stirring the reaction for 2h, and controlling the final polymerization viscosity to be 5000-20000P.
The diamine monomer in the step (1) is 4, 4-diaminodiphenyl ether ODA. The dianhydride monomer in the step (2) is pyromellitic dianhydride PMDA. The solvent is dimethylacetamide (DMAc).
Example 2, a method for controlling the polymerization viscosity of industrial polyamic acid, comprising the steps of:
(1) diamine solution preparation: adding a diamine monomer into a solvent, stirring and dissolving, and controlling the temperature at 30 ℃ and the mass concentration at 30%;
(2) preparation of dianhydride solution: respectively adding dianhydride monomers into a solvent, stirring and dispersing at 30 ℃ to obtain dianhydride solutions with 3 mass concentrations, namely 30%, 15% and 7% in mass concentration;
(3) primary reaction: cooling the diamine solution to-5 ℃, stirring at 80rpm, adding a dianhydride solution with the mass concentration of 30% into the diamine solution at a certain speed, and controlling the molar ratio of diamine to dianhydride to be 0.7: 1, controlling the temperature at 20 ℃, and stirring for reaction for 6 hours;
(4) and (3) secondary reaction: reducing the stirring speed to 50rpm, adding a dianhydride solution with the mass concentration of 15% into the reaction material after the first reaction at a certain speed, and controlling the molar ratio of diamine to dianhydride to be 0.9: 1, controlling the temperature at 30 ℃, and stirring for reaction for 4 hours;
(5) and (3) carrying out three reactions: and (3) reducing the stirring speed to 20rpm, adding a dianhydride solution with the mass concentration of 7% into the polymerization stock solution obtained by the secondary reaction at a proper speed, controlling the temperature at 60 ℃, and ensuring that the molar ratio of diamine to dianhydride is 0.998: 1, stirring the mixture for reaction for 8 hours, and controlling the final polymerization viscosity to be 5000-20000P.
The diamine monomer in the step (1) is 4, 4-diamino-p-phenylmethane MDA. The dianhydride monomer in the step (2) is biphenyl tetracarboxylic dianhydride BPDA. The solvent is dimethylacetamide (DMAc).
Example 3, a method for controlling the polymerization viscosity of industrial polyamic acid, comprising the steps of:
(1) diamine solution preparation: adding a diamine monomer into a solvent, stirring and dissolving, and controlling the temperature at 20 ℃ and the mass concentration at 22%;
(2) preparation of dianhydride solution: respectively adding dianhydride monomers into a solvent, stirring and dispersing at 20 ℃ to obtain dianhydride solutions with 3 mass concentrations, namely dianhydride solutions with 25%, 10% and 5% mass concentrations;
(3) primary reaction: cooling the diamine solution to-8 ℃, stirring at 65rpm, adding a dianhydride solution with the mass concentration of 25% into the diamine solution at a certain speed, and controlling the molar ratio of diamine to dianhydride to be 0.6: 1, controlling the temperature at 15 ℃, and stirring for reaction for 4 hours;
(4) and (3) secondary reaction: reducing the stirring speed to 30-50rpm, adding a dianhydride solution with the mass concentration of 10% into the reaction material after the primary reaction at a certain speed, and controlling the molar ratio of diamine to dianhydride to be 0.8: 1, controlling the temperature at 25 ℃, and stirring for reaction for 3 hours;
(5) and (3) carrying out three reactions: and (3) reducing the stirring speed to 15rpm, adding a dianhydride solution with the mass concentration of 5% into the polymerization stock solution obtained by the secondary reaction at a proper speed, controlling the temperature at 50 ℃, and ensuring that the molar ratio of diamine to dianhydride is 0.998: 1, stirring the mixture for reaction for 5 hours, and controlling the final polymerization viscosity to be 5000-20000P.
The diamine monomer in the step (1) is 4, 4-diaminodiphenyl ether ODA, p-phenylenediamine PDA or 4, 4-diaminop-phenylmethane MDA. The dianhydride monomer in the step (2) is pyromellitic dianhydride PMDA or biphenyl tetracarboxylic dianhydride BPDA. The solvent is dimethylacetamide (DMAc).
Claims (6)
1. A method for controlling the polymerization viscosity of industrial polyamic acid is characterized by comprising the following steps:
(1) diamine solution preparation: adding diamine monomer into solvent, stirring and dissolving, controlling the temperature at-10-30 ℃ and the mass concentration at 5-30%;
(2) preparation of dianhydride solution: respectively adding dianhydride monomers into a solvent, stirring and dispersing at-10-30 ℃ to obtain dianhydride solutions with 3 mass concentrations of 22-30%, 8-15% and 3-7% respectively;
(3) primary reaction: cooling the diamine solution to-10 to-5 ℃, stirring at 50-80rpm, adding a dianhydride solution with the mass concentration of 22-30% into the diamine solution at a certain speed, and controlling the molar ratio of diamine to dianhydride to be 0.5-0.7: 1, controlling the temperature at 10-20 ℃, and stirring for reaction for 2-6 h;
(4) and (3) secondary reaction: reducing the stirring speed to 30-50rpm, adding a dianhydride solution with the mass concentration of 8% -15% into the reaction material after the primary reaction at a certain speed, and controlling the molar ratio of diamine to dianhydride to be 0.7-0.9: 1, controlling the temperature at 20-30 ℃, and stirring for reaction for 2-4 h;
(5) and (3) carrying out three reactions: reducing the stirring speed to 10-20rpm, adding a dianhydride solution with the mass concentration of 3% -7% into the polymerization stock solution obtained by the secondary reaction at a proper speed, controlling the temperature to be 30-60 ℃, and ensuring the molar ratio of diamine to dianhydride to be 0.9-0.998: 1, stirring the mixture for reaction for 2 to 8 hours, and controlling the final polymerization viscosity to be 5000-20000P.
2. The method for controlling the polymerization viscosity of industrial polyamic acid according to claim 1, wherein: the diamine monomer in the step (1) is selected from one or more of 4, 4-diaminodiphenyl ether ODA, p-phenylenediamine PDA and 4, 4-diaminop-phenylmethane MDA.
3. The method for controlling the polymerization viscosity of industrial polyamic acid according to claim 1, wherein the dianhydride monomer in the step (2) is selected from pyromellitic dianhydride PMDA or biphenyl tetracarboxylic dianhydride BPDA.
4. The method for controlling the polymerization viscosity of industrial polyamic acid according to claim 1, wherein the solvent is dimethylacetamide (DMAc).
5. The method for controlling polymerization viscosity of polyamic acid in industry according to any one of claims 1 to 4, wherein the temperature is controlled at 20 ℃ to 25 ℃ in the preparation of the diamine solution in the step (1), and the mass concentration of the diamine solution is 22%.
6. The method for controlling the polymerization viscosity of industrial polyamic acid according to any one of claims 1 to 4, wherein in the preparation of the dianhydride solution of step (2): the stirring dispersion condition is 20-25 deg.C, and the obtained 3 mass concentration dianhydride solutions are respectively 25%, 10% and 5% in mass concentration.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010323925.5A CN111363151A (en) | 2020-04-22 | 2020-04-22 | Method for controlling polymerization viscosity of industrial polyamic acid |
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| CN202010323925.5A CN111363151A (en) | 2020-04-22 | 2020-04-22 | Method for controlling polymerization viscosity of industrial polyamic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111808285A (en) * | 2020-07-15 | 2020-10-23 | 南通博联材料科技有限公司 | Method for preparing low-viscosity and controllable-solid-content polyamic acid composition |
| CN114534523A (en) * | 2022-03-10 | 2022-05-27 | 迈得医疗工业设备股份有限公司 | Hemodialysis membrane and preparation method and application thereof |
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| US4487911A (en) * | 1979-07-23 | 1984-12-11 | The P. D. George Company | Stable polyamic acids |
| WO2010131442A1 (en) * | 2009-05-12 | 2010-11-18 | 株式会社カネカ | Process for producing polyamic acid solution, and polyimide film |
| CN104114644A (en) * | 2011-12-27 | 2014-10-22 | 可隆工业株式会社 | Polyamic acid solution |
| CN105461926A (en) * | 2016-01-29 | 2016-04-06 | 黑龙江省科学院石油化学研究院 | Environment-friendly stable polyamide acid solution and preparation method thereof |
| CN106810693A (en) * | 2015-12-02 | 2017-06-09 | 株洲时代新材料科技股份有限公司 | Polyamic acid solution, polyamic acid composition and Kapton |
| CN107286653A (en) * | 2017-07-17 | 2017-10-24 | 安徽国风塑业股份有限公司 | A kind of preparation method of high-performance low thermal expansion coefficient polyimide film |
-
2020
- 2020-04-22 CN CN202010323925.5A patent/CN111363151A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4487911A (en) * | 1979-07-23 | 1984-12-11 | The P. D. George Company | Stable polyamic acids |
| WO2010131442A1 (en) * | 2009-05-12 | 2010-11-18 | 株式会社カネカ | Process for producing polyamic acid solution, and polyimide film |
| CN104114644A (en) * | 2011-12-27 | 2014-10-22 | 可隆工业株式会社 | Polyamic acid solution |
| CN106810693A (en) * | 2015-12-02 | 2017-06-09 | 株洲时代新材料科技股份有限公司 | Polyamic acid solution, polyamic acid composition and Kapton |
| CN105461926A (en) * | 2016-01-29 | 2016-04-06 | 黑龙江省科学院石油化学研究院 | Environment-friendly stable polyamide acid solution and preparation method thereof |
| CN107286653A (en) * | 2017-07-17 | 2017-10-24 | 安徽国风塑业股份有限公司 | A kind of preparation method of high-performance low thermal expansion coefficient polyimide film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111808285A (en) * | 2020-07-15 | 2020-10-23 | 南通博联材料科技有限公司 | Method for preparing low-viscosity and controllable-solid-content polyamic acid composition |
| CN114534523A (en) * | 2022-03-10 | 2022-05-27 | 迈得医疗工业设备股份有限公司 | Hemodialysis membrane and preparation method and application thereof |
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