CN110272543B - Preparation method of polyimide foam hollow microspheres - Google Patents
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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- 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
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The invention relates to the field of preparation of polyimide materials, in particular to a preparation method of polyimide foam hollow microspheres. The preparation method of the polyimide foam hollow microsphere adopts low-boiling micromolecules as pore-forming agents, utilizes a spray drying method to prepare the polyimide microsphere, sprays PAA sol at a proper temperature through a spray dryer, generates physical and chemical changes in a short time under the action of hot air flow to form fine liquid hollow microspheres, and solidifies the obtained hollow microspheres; the preparation method is simple and efficient, has high repeatability, reduces the industrialization cost, ensures the high yield of the product, has no pollution, and ensures that the particle size of the prepared polyimide hollow microsphere is about 5-20 mu m.
Description
Technical Field
The invention relates to the field of preparation of polyimide materials, in particular to a preparation method of polyimide foam hollow microspheres.
Background
Polyimides are polymers having imide groups in their molecular structure, and classified according to the types of molecular structural units, they are classified into aliphatic polyimides and aromatic polyimides. Micron-sized materials are attracting more and more attention, and have potential application in the directions of aerospace, photoelectric materials, medical instruments and the like.
The polyimide microspheres have the characteristics of large specific surface area, strong adsorbability and large agglutination of the polymer microspheres, and also have the characteristics of excellent heat resistance, higher mechanical strength, excellent dielectric property and the like of polyimide, so the polyimide microspheres have wider application prospect. The preparation methods of the polyimide microspheres mainly comprise suspension polymerization, a dispersion copolymerization method, a self-assembly method and other preparation methods. The existing method for preparing the microspheres has the characteristics of high energy consumption, complex production process and great pollution.
Disclosure of Invention
The invention aims to provide a preparation method of polyimide foam hollow microspheres, which has the advantages of simple process, low production cost, high preparation efficiency and no pollution, and the particle size of the prepared polyimide hollow microspheres is about 5-20 mu m.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of polyimide foam hollow microspheres comprises the following steps:
(1) at 25-35 ℃, dissolving diamine in a high-boiling point aprotic solvent, and after dissolving the diamine, according to the weight ratio of the diamine to the tetracarboxylic dianhydride of (6-12): (7-16) weighing tetracarboxylic dianhydride, adding the tetracarboxylic dianhydride into a diamine-dispersed high-boiling-point aprotic solvent in a weight ratio of 1:3:6 in batches under the condition of stirring for polymerization to obtain a polyamic acid solution, wherein the solid content of the polyamic acid solution obtained by polymerization is 10-30%;
(2) stirring the polyamic acid solution prepared in the step (1), and adding the low-boiling micromolecules into the polymerized polyamic acid solution in the stirring process to uniformly mix the low-boiling micromolecules and the polyamic acid solution for later use;
(3) putting the uniformly mixed solution in the step (2) into a material barrel for later use;
(4) starting a fan and a heater of the spray dryer, setting the inlet temperature to be 80-150 ℃, the outlet temperature to be 65-85 ℃, setting the rotating speed of the peristaltic pump to be 5-10r/min, and starting the peristaltic pump to be automatic when the outlet air temperature reaches a set value;
(5) after the setting in the step (4) is finished, putting the material barrel containing the uniformly mixed solution in the step (3) into a spray dryer, and preliminarily obtaining polyimide microspheres PI through a spray drying method;
(6) performing high-temperature treatment on the polyimide microspheres PI prepared in the step (5), and performing thermal imidization in a stepped heating mode, wherein the heating process comprises the following steps: raising the temperature from room temperature to 160 ℃ within 8-12min, and keeping the temperature for 1 h; then raising the temperature from 160 ℃ to 208 ℃ to 300 ℃ within 15-18min, preserving the temperature for 1h again, and naturally cooling to room temperature to obtain the polyimide microsphere PII.
Preferably, the diamine is one or two of 4, 4-diaminodiphenyl ether, propane diamine and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane; the tetracarboxylic dianhydride is one or more of 1,2,4, 5-pyromellitic dianhydride, 3 ', 4, 4' - -benzophenone tetracarboxylic dianhydride, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride or 4, 4' -oxydiphthalic anhydride.
Preferably, the high-boiling point aprotic solvent is one or more of dimethylformamide, N-methylpyrrolidone and dimethylacetamide.
Preferably, the weight portion of the high-boiling point aprotic solvent is 70-200 parts.
Preferably, the low-boiling-point small molecule is one or more of carbon disulfide, anhydrous methanol, acetone and lithium chloride.
Preferably, the weight part of the low-boiling-point micromolecules is 18-22 parts.
The invention has the beneficial effects that: compared with the prior art, the preparation method of the hollow polyimide foam microspheres adopts low-boiling micromolecules as pore-forming agents, polyimide microspheres are prepared by a spray drying method, PAA sol is sprayed out through a spray dryer at a proper temperature, physical and chemical changes are generated in a short time under the action of hot air flow, fine liquid hollow microspheres are formed, and the obtained hollow microspheres are solidified; the preparation method is simple and efficient, has high repeatability, reduces the industrialization cost, ensures the high yield of the product, has no pollution, and ensures that the particle size of the prepared polyimide hollow microsphere is about 5-20 mu m.
Detailed Description
Example 1
A preparation method of polyimide foam hollow microspheres is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving 10g of 4, 4-diaminodiphenyl ether in 190g of high-boiling-point aprotic solvent dimethylacetamide at 25-35 ℃, after dissolving 4, 4-diaminodiphenyl ether, weighing 11.118g of 1,2,4, 5-pyromellitic dianhydride, adding 1,2,4, 5-pyromellitic dianhydride into the high-boiling-point aprotic solvent dimethylacetamide in which the 4, 4-diaminodiphenyl ether is dispersed in batches according to the weight ratio of 1:3:6 under the condition of stirring, polymerizing, and obtaining a polyamic acid solution;
(2) stirring the polyamic acid solution prepared in the step (1), and adding 19g of low-boiling micromolecule anhydrous methanol into the polymerized polyamic acid solution in the stirring process to uniformly mix the low-boiling micromolecule anhydrous methanol with the polyamic acid solution for later use;
(3) putting the uniformly mixed solution in the step (2) into a material barrel for later use;
(4) starting a fan and a heater of the spray dryer, setting the inlet temperature to be 100 ℃, the outlet temperature to be 70 ℃, setting the rotating speed of the peristaltic pump to be 8r/min, and starting the peristaltic pump to automatically control when the outlet air temperature reaches a set value;
(5) after the setting in the step (4) is finished, putting the material barrel containing the uniformly mixed solution in the step (3) into a spray dryer, and preliminarily preparing a polyimide microsphere PI through the spray dryer;
(6) performing high-temperature treatment on the polyimide microspheres PI prepared in the step (5), and performing thermal imidization in a stepped heating mode, wherein the heating process comprises the following steps: raising the temperature from room temperature to 140 ℃ within 10min, and keeping the temperature for 1 h; then heating to 300 ℃ from 140 ℃ within 16min, preserving the heat for 1h again, and naturally cooling to room temperature to obtain the polyimide microsphere PII.
The average particle size of the polyimide microsphere PII prepared in the embodiment is 5.2 μm through detection.
Example 2
A preparation method of polyimide foam hollow microspheres is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving 4, 4-diaminodiphenyl ether and 2.754 g of propylene diamine in 71g of high-boiling-point aprotic solvent dimethylacetamide at the temperature of 25-35 ℃, dissolving 4, 4-diaminodiphenyl ether and propylene diamine, weighing 11.118g of 1,2,4, 5-pyromellitic dianhydride, adding 1,2,4, 5-pyromellitic dianhydride to the high-boiling-point aprotic solvent dimethylacetamide in which the 4, 4-diaminodiphenyl ether and the propylene diamine are dispersed in batches according to the weight ratio of 1:3:6 under the condition of stirring, polymerizing, and obtaining a polyamic acid solution;
(2) stirring the polyamic acid solution prepared in the step (1), and adding 19g of low-boiling micromolecule anhydrous methanol into the polymerized polyamic acid solution in the stirring process to uniformly mix the low-boiling micromolecule anhydrous methanol with the polyamic acid solution for later use;
(3) putting the uniformly mixed solution in the step (2) into a material barrel for later use;
(4) starting a fan and a heater of the spray dryer, setting the inlet temperature to be 80 ℃, the outlet temperature to be 65 ℃, setting the rotating speed of the peristaltic pump to be 6r/min, and starting the peristaltic pump to automatically control when the outlet air temperature reaches a set value;
(5) after the setting in the step (4) is finished, putting the material barrel containing the uniformly mixed solution in the step (3) into a spray dryer, and preliminarily preparing a polyimide microsphere PI through the spray dryer;
(6) performing high-temperature treatment on the polyimide microspheres PI prepared in the step (5), and performing thermal imidization in a stepped heating mode, wherein the heating process comprises the following steps: heating from room temperature to 120 ℃ within 8min, and keeping the temperature for 1 h; then heating to 260 ℃ from 120 ℃ within 15min, preserving the heat for 1h again, and naturally cooling to room temperature to obtain the polyimide microsphere PII.
The average particle size of the polyimide microsphere PII prepared in the embodiment is 8.6 μm through detection.
Example 3
A preparation method of polyimide foam hollow microspheres is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving 4, 4-diaminodiphenyl ether 10g in dimethylacetamide 230g with high boiling point and aprotic solvent at 25-35 ℃, dissolving 4, 4-diaminodiphenyl ether, weighing 15.511g of 4,4 '-oxydiphthalic anhydride, adding 4, 4' -oxydiphthalic anhydride into dimethylacetamide with high boiling point and aprotic solvent dispersed with 4, 4-diaminodiphenyl ether in a weight ratio of 1:3:6 in batches under stirring, polymerizing to obtain polyamic acid solution;
(2) stirring the polyamic acid solution prepared in the step (1), and adding 19g of low-boiling small molecular acetone into the polymerized polyamic acid solution in the stirring process to uniformly mix the low-boiling small molecular acetone and the polyamic acid solution for later use;
(3) putting the uniformly mixed solution in the step (2) into a material barrel for later use;
(4) starting a fan and a heater of the spray dryer, setting the inlet temperature to be 140 ℃, the outlet temperature to be 85 ℃, setting the rotating speed of the peristaltic pump to be 10r/min, and starting the peristaltic pump to automatically control when the outlet air temperature reaches a set value;
(5) after the setting in the step (4) is finished, putting the material barrel containing the uniformly mixed solution in the step (3) into a spray dryer, and preliminarily preparing a polyimide microsphere PI through the spray dryer;
(6) performing high-temperature treatment on the polyimide microspheres PI prepared in the step (5), and performing thermal imidization in a stepped heating mode, wherein the heating process comprises the following steps: heating from room temperature to 160 ℃ within 12min, and keeping the temperature for 1 h; then heating to 300 ℃ from 160 ℃ within 18min, preserving the heat for 1h again, and naturally cooling to room temperature to obtain the polyimide microsphere PII.
The average particle size of the polyimide microsphere PII prepared in the embodiment is 16.8 μm through detection.
Example 4
A preparation method of polyimide foam hollow microspheres is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving 4, 4-diaminodiphenyl ether and 2.754 g of propylene diamine in 71g of high-boiling-point aprotic solvent N-methylpyrrolidone at 25-35 ℃, dissolving 4, 4-diaminodiphenyl ether and propylene diamine, weighing 11.118g of 1,2,4, 5-pyromellitic dianhydride, adding 1,2,4, 5-pyromellitic dianhydride to the high-boiling-point aprotic solvent N-methylpyrrolidone in which 4, 4-diaminodiphenyl ether and propylene diamine are dispersed in batches at a weight ratio of 1:3:6 under stirring, polymerizing, and obtaining a polyamic acid solution;
(2) stirring the polyamic acid solution prepared in the step (1), and adding 19g of low-boiling micromolecule lithium chloride into the polymerized polyamic acid solution in the stirring process to uniformly mix the low-boiling micromolecule lithium chloride with the polyamic acid solution for later use;
(3) putting the uniformly mixed solution in the step (2) into a material barrel for later use;
(4) starting a fan and a heater of the spray dryer, setting the inlet temperature to be 100 ℃, the outlet temperature to be 70 ℃, setting the rotating speed of the peristaltic pump to be 7r/min, and starting the peristaltic pump to automatically control when the outlet air temperature reaches a set value;
(5) after the setting in the step (4) is finished, putting the material barrel containing the uniformly mixed solution in the step (3) into a spray dryer, and preliminarily preparing a polyimide microsphere PI through the spray dryer;
(6) performing high-temperature treatment on the polyimide microspheres PI prepared in the step (5), and performing thermal imidization in a stepped heating mode, wherein the heating process comprises the following steps: raising the temperature from room temperature to 140 ℃ within 10min, and keeping the temperature for 1 h; then heating to 300 ℃ from 140 ℃ within 16min, preserving the heat for 1h again, and naturally cooling to room temperature to obtain the polyimide microsphere PII.
The average particle size of the polyimide microsphere PII prepared in the embodiment is 10.6 μm through detection.
Example 5
A preparation method of polyimide foam hollow microspheres is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving 10g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane in 160g of high-boiling-point aprotic solvent dimethylformamide at the temperature of 25-35 ℃, dissolving 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, weighing 7.86g of 3,3 ', 4, 4' - -benzophenone tetracarboxylic dianhydride, adding 3,3 ', 4, 4' - -benzophenone tetracarboxylic dianhydride into the high-boiling-point aprotic solvent dimethylformamide in which the 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane is dispersed in batches with the weight ratio of 1:3:6 under stirring, and polymerizing to obtain a polyamide acid solution;
(2) stirring the polyamic acid solution prepared in the step (1), and adding 19g of low-boiling small-molecule carbon disulfide into the polymerized polyamic acid solution in the stirring process to uniformly mix the low-boiling small-molecule carbon disulfide with the polyamic acid solution for later use;
(3) putting the uniformly mixed solution in the step (2) into a material barrel for later use;
(4) starting a fan and a heater of the spray dryer, setting the inlet temperature to be 100 ℃, the outlet temperature to be 70 ℃, setting the rotating speed of the peristaltic pump to be 8r/min, and starting the peristaltic pump to automatically control when the outlet air temperature reaches a set value;
(5) after the setting in the step (4) is finished, putting the material barrel containing the uniformly mixed solution in the step (3) into a spray dryer, and preliminarily preparing a polyimide microsphere PI through the spray dryer;
(6) performing high-temperature treatment on the polyimide microspheres PI prepared in the step (5), and performing thermal imidization in a stepped heating mode, wherein the heating process comprises the following steps: raising the temperature from room temperature to 140 ℃ within 10min, and keeping the temperature for 1 h; then heating to 300 ℃ from 140 ℃ within 16min, preserving the heat for 1h again, and naturally cooling to room temperature to obtain the polyimide microsphere PII.
The average particle size of the polyimide microsphere PII prepared in the embodiment is 12.5 μm through detection.
Comparative example 1
Comparative example 1 is essentially the same as example 1 except that: in the step (1), under the condition of stirring, 1,2,4, 5-pyromellitic dianhydride is added into dimethyl acetamide, which is a high-boiling-point aprotic solvent and is dispersed with 4, 4-diaminodiphenyl ether, in batches according to the weight ratio of 1:1:1 for polymerization, and the polyamide acid solution is obtained through polymerization.
The average particle size of the polyimide microsphere PII prepared in the embodiment is 32.4 μm through detection.
Comparative example 2
Comparative example 2 the process of the rest of example 1 is substantially the same, with the difference that: in the step (4), the inlet temperature is set to 160 ℃ and the outlet temperature is set to 90 ℃.
The average particle size of the polyimide microsphere PII prepared in the embodiment is 30.2 μm through detection.
The above embodiments are only specific examples of the present invention, and the protection scope of the present invention includes but is not limited to the product forms and styles of the above embodiments, and any suitable changes or modifications made by those skilled in the art according to the claims of the present invention shall fall within the protection scope of the present invention.
Claims (6)
1. A preparation method of polyimide foam hollow microspheres is characterized by comprising the following steps: the method comprises the following steps:
(1) at 25-35 ℃, dissolving diamine in a high-boiling point aprotic solvent, and after dissolving the diamine, according to the weight ratio of the diamine to the tetracarboxylic dianhydride of (6-12): (7-16) weighing tetracarboxylic dianhydride, adding the tetracarboxylic dianhydride into a high-boiling-point aprotic solvent in which diamine is dispersed in batches with a weight ratio of 1:3:6 under the condition of stirring, and polymerizing to obtain a polyamic acid solution;
(2) stirring the polyamic acid solution prepared in the step (1), and adding the low-boiling micromolecules into the polymerized polyamic acid solution in the stirring process to uniformly mix the low-boiling micromolecules and the polyamic acid solution for later use;
(3) putting the uniformly mixed solution in the step (2) into a material barrel for later use;
(4) starting a fan and a heater of the spray dryer, setting the inlet temperature to be 80-150 ℃, the outlet temperature to be 65-85 ℃, setting the rotating speed of the peristaltic pump to be 5-10r/min, and starting the peristaltic pump to be automatic when the outlet air temperature reaches a set value;
(5) after the setting in the step (4) is finished, putting the material barrel containing the uniformly mixed solution in the step (3) into a spray dryer, and preliminarily obtaining polyimide microspheres PI through a spray drying method;
(6) performing high-temperature treatment on the polyimide microspheres PI prepared in the step (5), and performing thermal imidization in a stepped heating mode, wherein the heating process comprises the following steps: raising the temperature from room temperature to 160 ℃ within 8-12min, and keeping the temperature for 1 h; then raising the temperature from 160 ℃ to 208 ℃ to 300 ℃ within 15-18min, preserving the temperature for 1h again, and naturally cooling to room temperature to obtain the polyimide microsphere PII.
2. The method for preparing hollow microspheres of polyimide foam according to claim 1, wherein the method comprises the following steps: the diamine is one or two of 4, 4-diaminodiphenyl ether, propane diamine and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane; the tetracarboxylic dianhydride is one or more of 1,2,4, 5-pyromellitic dianhydride, 3 ', 4, 4' - -benzophenone tetracarboxylic dianhydride, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride or 4, 4' -oxydiphthalic anhydride.
3. The method for preparing hollow microspheres of polyimide foam according to claim 1, wherein the method comprises the following steps: the high-boiling point aprotic solvent is one or a combination of more of dimethylformamide, N-methylpyrrolidone and dimethylacetamide.
4. The method for preparing hollow microspheres of polyimide foam according to claim 3, wherein the method comprises the following steps: the weight portion of the high-boiling point aprotic solvent is 70-200 portions.
5. The method for preparing hollow microspheres of polyimide foam according to claim 1, wherein the method comprises the following steps: the low-boiling-point micromolecules are one or a combination of carbon disulfide, anhydrous methanol, acetone and lithium chloride.
6. The method for preparing hollow microspheres of polyimide foam according to claim 5, wherein the method comprises the following steps: the weight portion of the low-boiling-point micromolecules is 18-22.
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| CN201910537470.4A CN110272543B (en) | 2019-06-20 | 2019-06-20 | Preparation method of polyimide foam hollow microspheres |
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| CN101463135A (en) * | 2009-01-13 | 2009-06-24 | 吉林大学 | Preparation of water-dispersion polyamic acid particle |
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