CN110272543A - A kind of polyimide foam hollow microsphere preparation method - Google Patents
A kind of polyimide foam hollow microsphere preparation method Download PDFInfo
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- CN110272543A CN110272543A CN201910537470.4A CN201910537470A CN110272543A CN 110272543 A CN110272543 A CN 110272543A CN 201910537470 A CN201910537470 A CN 201910537470A CN 110272543 A CN110272543 A CN 110272543A
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- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- 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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G73/1046—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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- 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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- 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
- C08G73/1075—Partially aromatic polyimides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/122—Pulverisation by spraying
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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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
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The present invention relates to the preparation field of polyimide material, especially a kind of polyimide foam hollow microsphere preparation method.A kind of polyimide foam hollow microsphere preparation method of the invention, pore-foaming agent is done using low boiling small molecule, polyimide microsphere is prepared using spray drying process, PAA colloidal sol is ejected by spray dryer at a proper temperature, physical and chemical changes occur in the short time under stream of hot air effect, form tiny liquid tiny balloon, the tiny balloon solidified；The preparation method is simple and efficient, and repeatability is high, while reducing industrialization cost, also ensures the high yield of product, pollution-free, the polyimides hollow microsphere partial size of preparation is about 5-20 μm.
Description
Technical field
The present invention relates to the preparation fields of polyimide material, especially a kind of polyimide foam hollow microsphere preparation side
Method.
Background technique
Polyimides refers to the quasi polymer in molecular structure containing imide group, not according to molecular structure unit
Same type is classified, then can be divided into lard type polyimides and aroma type polyimides.Micron order material increasingly causes people
Extensive concern, have potential application on the directions such as aerospace, photoelectric material and medical device.
Polyimide microsphere is due to both having polymer microballoon large specific surface area, strong adsorption and the big spy of agglutination
Property, and the features such as show the outstanding heat resistance of polyimides, higher mechanical strength, excellent dielectric properties, therefore it is poly-
Acid imide microballoon has more wide application prospect.And for the preparation method of polyimide microsphere mainly have suspension polymerisation,
The preparation methods such as the legal, self-assembly method of dispersion copolymerization.The current method for preparing microballoon is high there are energy consumption and production technology is complicated, dirty
Contaminate big feature.
Summary of the invention
The purpose of the present invention is to provide a kind of polyimide foam hollow microsphere preparation method, simple process is produced into
This is low, preparation efficiency is high, pollution-free, preparation polyimides hollow microsphere partial size is about 5-20 μm.
The technical scheme adopted by the invention to solve the technical problem is that:
A kind of polyimide foam hollow microsphere preparation method, includes the following steps:
(1) at 25-35 DEG C, diamines is dissolved in the sprotic solvent of higher boiling, after diamines dissolution, according to diamines and four
Carboxylic acid dianhydride weight ratio is (6-12): (7-16) weighs tetracarboxylic dianhydride, and in the case of stirring, weight ratio 1:3:6 is in batches
Tetracarboxylic dianhydride is added in the sprotic solvent of higher boiling for be dispersed with diamines and is polymerize, polymerization obtains polyamic acid
Solution, the solid content that polymerization obtains polyamic acid solution is 10-30%；
(2) low boiling small molecule is added to the polyamides having polymerize in whipping process by polyamic acid solution made from whipping step (1)
In amino acid solution, it is uniformly mixed low boiling small molecule with polyamic acid solution, it is spare；
(3) solution being uniformly mixed in step (2) is put into material barrel, it is spare;
(4) start the blower and heater of spray dryer, inlet temperature is set as 80-150 DEG C, and outlet temperature is set as 65-
85 DEG C, the revolving speed of peristaltic pump is set as 5-10r/min, and when leaving air temp reaches setting value, it is automatic to open peristaltic pump；
(5) after step (4) is provided with, the material for filling uniformly mixed solution of step (3) is put into spray dryer
Bucket, polyimide microsphere PI is tentatively obtained by spray drying process；
(6) polyimide microsphere PI obtained in step (5) is subjected to high-temperature process, heat is carried out using stepped heating mode
Imidization, wherein temperature-rise period are as follows: be raised to 120-160 DEG C from room temperature in 8-12min, keep the temperature 1h；Then in 15-18min from
120-160 DEG C is warming up to 208-300 DEG C, keeps the temperature 1h again, is naturally cooling to room temperature to get polyimide microsphere P II.
Preferably, the diamines is 4,4- diaminodiphenyl ether, propane diamine, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl]
One or both of propane；The tetracarboxylic dianhydride is 1,2,4,5- pyromellitic acid anhydride, 3,3 ', 4,4 ' --- benzophenone
Tetracid dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides or 4, one of double phthalic anhydrides of 4'- oxygen or multiple combinations.
Preferably, the sprotic solvent of the higher boiling is dimethylformamide, N-Methyl pyrrolidone, dimethyl second
One of amide or multiple combinations.
Preferably, the parts by weight of the sprotic solvent of the higher boiling are 70-200 parts.
Preferably, the low boiling point small molecule is one of carbon disulfide, anhydrous methanol, acetone, lithium chloride or a variety of
Combination.
Preferably, the parts by weight of the low boiling point small molecule are 18-22 parts.
The beneficial effects of the present invention are: compared with prior art, a kind of polyimide foam hollow microsphere system of the invention
Preparation Method does pore-foaming agent using low boiling small molecule, prepares polyimide microsphere using spray drying process, PAA colloidal sol is appropriate
At a temperature of ejected by spray dryer, physical and chemical changes occur in the short time under stream of hot air effect, are formed
Tiny liquid tiny balloon, the tiny balloon solidified；The preparation method is simple and efficient, and repeatability is high, reduces industry chemical conversion
This while, also ensures the high yield of product, pollution-free, and the polyimides hollow microsphere partial size of preparation is about 5-20 μm.
Specific embodiment
Embodiment 1
A kind of polyimide foam hollow microsphere preparation method, characterized by the following steps:
(1) at 25-35 DEG C, by 10g4,4- diaminodiphenyl ether is dissolved in the sprotic solvent dimethyl second of 190g higher boiling
In amide, after the dissolution of 4,4- diaminodiphenyl ethers, 1,2,4,5- pyromellitic acid anhydride 11.118g are weighed, in the feelings of stirring
Under condition, 1,2,4,5- pyromellitic acid anhydride is added in batches by weight 1:3:6 and is dispersed with 4,4- diaminodiphenyl ether
The sprotic solvent dimethyl acetamide of higher boiling in polymerize, polymerization obtain polyamic acid solution；
(2) 19g low boiling small molecule anhydrous methanol is added in whipping process by polyamic acid solution made from whipping step (1)
In the polyamic acid solution having polymerize, it is uniformly mixed low boiling small molecule anhydrous methanol with polyamic acid solution, it is spare；
(3) solution being uniformly mixed in step (2) is put into material barrel, it is spare；
(4) start the blower and heater of spray dryer, inlet temperature is set as 100 DEG C, and outlet temperature is set as 70 DEG C, compacted
The revolving speed of dynamic pump is set as 8r/min, and when leaving air temp reaches setting value, it is automatic to open peristaltic pump；
(5) after step (4) is provided with, the material for filling uniformly mixed solution of step (3) is put into spray dryer
Polyimide microsphere PI is tentatively made by spray dryer in bucket；
(6) polyimide microsphere PI obtained in step (5) is subjected to high-temperature process, heat is carried out using stepped heating mode
Imidization, wherein temperature-rise period are as follows: be raised to 140 DEG C from room temperature in 10min, keep the temperature 1h；Then it heats up in 16min from 140 DEG C
To 300 DEG C, 1h is kept the temperature again, is naturally cooling to room temperature to get polyimide microsphere P II.
Through detecting, II mean particle size of polyimide microsphere P made from the present embodiment is 5.2 μm.
Embodiment 2
A kind of polyimide foam hollow microsphere preparation method, characterized by the following steps:
(1) at 25-35 DEG C, by 5.1g4, it is sprotic that 4- diaminodiphenyl ether and 2.754 propane diamine are dissolved in 71g higher boiling
In solvent dimethyl acetamide, after 4,4- diaminodiphenyl ethers and propane diamine dissolution, 1,2,4,5- Pyromellitic Acids two are weighed
1,2,4,5- pyromellitic acid anhydride is added to point by weight 1:3:6 by acid anhydride 11.118g in batches in the case of stirring
It dissipates to have in the sprotic solvent dimethyl acetamide of the higher boiling of 4,4- diaminodiphenyl ether and propane diamine and be polymerize, is polymerize
Obtain polyamic acid solution；
(2) 19g low boiling small molecule anhydrous methanol is added in whipping process by polyamic acid solution made from whipping step (1)
In the polyamic acid solution having polymerize, it is uniformly mixed low boiling small molecule anhydrous methanol with polyamic acid solution, it is spare；
(3) solution being uniformly mixed in step (2) is put into material barrel, it is spare；
(4) start the blower and heater of spray dryer, inlet temperature is set as 80 DEG C, and outlet temperature is set as 65 DEG C, compacted
The revolving speed of dynamic pump is set as 6r/min, and when leaving air temp reaches setting value, it is automatic to open peristaltic pump；
(5) after step (4) is provided with, the material for filling uniformly mixed solution of step (3) is put into spray dryer
Polyimide microsphere PI is tentatively made by spray dryer in bucket；
(6) polyimide microsphere PI obtained in step (5) is subjected to high-temperature process, heat is carried out using stepped heating mode
Imidization, wherein temperature-rise period are as follows: be raised to 120 DEG C from room temperature in 8min, keep the temperature 1h；Then it heats up in 15min from 120 DEG C
To 260 DEG C, 1h is kept the temperature again, is naturally cooling to room temperature to get polyimide microsphere P II.
Through detecting, II mean particle size of polyimide microsphere P made from the present embodiment is 8.6 μm.
Embodiment 3
A kind of polyimide foam hollow microsphere preparation method, characterized by the following steps:
(1) at 25-35 DEG C, by 10g4,4- diaminodiphenyl ether is dissolved in the sprotic solvent dimethyl second of 230g higher boiling
In amide, after the dissolution of 4,4- diaminodiphenyl ethers, the double phthalic anhydride 15.511g of 4,4'- oxygen are weighed, the case where stirring
Under, the double phthalic anhydrides of 4,4'- oxygen are added to are dispersed with the high boiling of 4,4- diaminodiphenyl ether in batches by weight ratio 1:3:6
It is polymerize in the sprotic solvent dimethyl acetamide of point, polymerization obtains polyamic acid solution；
(2) 19g low boiling small molecule acetone is added to polymerization in whipping process by polyamic acid solution made from whipping step (1)
In good polyamic acid solution, it is uniformly mixed low boiling small molecule acetone with polyamic acid solution, it is spare；
(3) solution being uniformly mixed in step (2) is put into material barrel, it is spare；
(4) start the blower and heater of spray dryer, inlet temperature is set as 140 DEG C, and outlet temperature is set as 85 DEG C, compacted
The revolving speed of dynamic pump is set as 10r/min, and when leaving air temp reaches setting value, it is automatic to open peristaltic pump；
(5) after step (4) is provided with, the material for filling uniformly mixed solution of step (3) is put into spray dryer
Polyimide microsphere PI is tentatively made by spray dryer in bucket；
(6) polyimide microsphere PI obtained in step (5) is subjected to high-temperature process, heat is carried out using stepped heating mode
Imidization, wherein temperature-rise period are as follows: be raised to 160 DEG C from room temperature in 12min, keep the temperature 1h；Then it heats up in 18min from 160 DEG C
To 300 DEG C, 1h is kept the temperature again, is naturally cooling to room temperature to get polyimide microsphere P II.
Through detecting, II mean particle size of polyimide microsphere P made from the present embodiment is 16.8 μm.
Embodiment 4
A kind of polyimide foam hollow microsphere preparation method, characterized by the following steps:
(1) at 25-35 DEG C, by 5.1g4, it is sprotic that 4- diaminodiphenyl ether and 2.754 propane diamine are dissolved in 71g higher boiling
In solvent N-methyl pyrilidone, after 4,4- diaminodiphenyl ethers and propane diamine dissolution, 1,2,4,5- Pyromellitic Acids are weighed
1,2,4,5- pyromellitic acid anhydride is added to point by dianhydride 11.118g, in the case of stirring, weight ratio 1:3:6 in batches
It dissipates to have in the sprotic solvent N-methyl pyrilidone of the higher boiling of 4,4- diaminodiphenyl ether and propane diamine and be polymerize, gathered
Conjunction obtains polyamic acid solution；
(2) 19g low boiling small molecule lithium chloride is added in whipping process poly- by polyamic acid solution made from whipping step (1)
In the polyamic acid solution got togather, it is uniformly mixed low boiling small molecule lithium chloride with polyamic acid solution, it is spare；
(3) solution being uniformly mixed in step (2) is put into material barrel, it is spare；
(4) start the blower and heater of spray dryer, inlet temperature is set as 100 DEG C, and outlet temperature is set as 70 DEG C, compacted
The revolving speed of dynamic pump is set as 7r/min, and when leaving air temp reaches setting value, it is automatic to open peristaltic pump；
(5) after step (4) is provided with, the material for filling uniformly mixed solution of step (3) is put into spray dryer
Polyimide microsphere PI is tentatively made by spray dryer in bucket；
(6) polyimide microsphere PI obtained in step (5) is subjected to high-temperature process, heat is carried out using stepped heating mode
Imidization, wherein temperature-rise period are as follows: be raised to 140 DEG C from room temperature in 10min, keep the temperature 1h；Then it heats up in 16min from 140 DEG C
To 300 DEG C, 1h is kept the temperature again, is naturally cooling to room temperature to get polyimide microsphere P II.
Through detecting, II mean particle size of polyimide microsphere P made from the present embodiment is 10.6 μm.
Embodiment 5
A kind of polyimide foam hollow microsphere preparation method, characterized by the following steps:
(1) at 25-35 DEG C, by 10g2, it is lazy that bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2- are dissolved in 160g higher boiling proton
Property solvent dimethylformamide in, after 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane dissolutions, weigh 3,3 ', 4,
4 ' --- benzophenone tetracid dianhydride 7.86g, in the case of stirring, weight ratio 1:3:6 is in batches by 3,3 ', 4,4 ' --- benzophenone
Tetracid dianhydride is added to the sprotic solvent two of higher boiling for being dispersed with bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2,2-
It is polymerize in methylformamide, polymerization obtains polyamic acid solution；
(2) 19g low boiling small molecule carbon disulfide is added in whipping process by polyamic acid solution made from whipping step (1)
In the polyamic acid solution having polymerize, it is uniformly mixed low boiling small molecule carbon disulfide with polyamic acid solution, it is spare；
(3) solution being uniformly mixed in step (2) is put into material barrel, it is spare；
(4) start the blower and heater of spray dryer, inlet temperature is set as 100 DEG C, and outlet temperature is set as 70 DEG C, compacted
The revolving speed of dynamic pump is set as 8r/min, and when leaving air temp reaches setting value, it is automatic to open peristaltic pump；
(5) after step (4) is provided with, the material for filling uniformly mixed solution of step (3) is put into spray dryer
Polyimide microsphere PI is tentatively made by spray dryer in bucket；
(6) polyimide microsphere PI obtained in step (5) is subjected to high-temperature process, heat is carried out using stepped heating mode
Imidization, wherein temperature-rise period are as follows: be raised to 140 DEG C from room temperature in 10min, keep the temperature 1h；Then it heats up in 16min from 140 DEG C
To 300 DEG C, 1h is kept the temperature again, is naturally cooling to room temperature to get polyimide microsphere P II.
Through detecting, II mean particle size of polyimide microsphere P made from the present embodiment is 12.5 μm.
Comparative example 1
Comparative example 1 and the method for embodiment 1 are essentially identical, and difference is: in step (1), in the case of stirring, by weight
1,2,4,5- pyromellitic acid anhydride is added to the higher boiling proton for being dispersed with 4,4- diaminodiphenyl ether in batches than 1:1:1
It is polymerize in inert solvent dimethyl acetamide, polymerization obtains polyamic acid solution
Through detecting, II mean particle size of polyimide microsphere P made from the present embodiment is 32.4 μm.
Comparative example 2
The method of more than 2 embodiment 1 of comparative example is essentially identical, and difference is: in step (4), inlet temperature is set as 160 DEG C,
Outlet temperature is set as 90 DEG C.
Through detecting, II mean particle size of polyimide microsphere P made from the present embodiment is 30.2 μm.
Above-mentioned specific embodiment is only specific case of the invention, and scope of patent protection of the invention includes but is not limited to
The product form and style of above-mentioned specific embodiment, any claims of the present invention and any technical field of meeting
The appropriate changes or modifications that those of ordinary skill does it, all shall fall within the protection scope of the present invention.
Claims (6)
1. a kind of polyimide foam hollow microsphere preparation method, characterized by the following steps:
At 25-35 DEG C, diamines is dissolved in the sprotic solvent of higher boiling, after diamines dissolution, according to diamines and tetracarboxylic acid
Acid dianhydride weight ratio is (6-12): (7-16) weighs tetracarboxylic dianhydride, and in the case of stirring, weight ratio 1:3:6 in batches will
Tetracarboxylic dianhydride, which is added in the sprotic solvent of higher boiling for be dispersed with diamines, to be polymerize, and it is molten that polymerization obtains polyamic acid
Liquid；
Low boiling small molecule is added to the polyamide having polymerize in whipping process by polyamic acid solution made from whipping step (1)
In acid solution, it is uniformly mixed low boiling small molecule with polyamic acid solution, it is spare；
The solution being uniformly mixed in step (2) is put into material barrel, it is spare;
Start the blower and heater of spray dryer, inlet temperature is set as 80-150 DEG C, and outlet temperature is set as 65-85
DEG C, the revolving speed of peristaltic pump is set as 5-10r/min, and when leaving air temp reaches setting value, it is automatic to open peristaltic pump；
After step (4) is provided with, the material barrel for filling uniformly mixed solution of step (3) is put into spray dryer,
Polyimide microsphere PI is tentatively obtained by spray drying process；
Polyimide microsphere PI obtained in step (5) is subjected to high-temperature process, it is sub- to carry out heat using stepped heating mode
Amination, wherein temperature-rise period are as follows: be raised to 120-160 DEG C from room temperature in 8-12min, keep the temperature 1h；Then in 15-18min from
120-160 DEG C is warming up to 208-300 DEG C, keeps the temperature 1h again, is naturally cooling to room temperature to get polyimide microsphere P II.
2. a kind of polyimide foam hollow microsphere preparation method according to claim 1, it is characterised in that: the diamines
For one or both of bis- [4- (4- amino-benzene oxygen) phenyl] propane of 4,4- diaminodiphenyl ether, propane diamine, 2,2-；It is described
Tetracarboxylic dianhydride is 1,2,4,5- pyromellitic acid anhydride, 3,3 ', 4,4 ' --- benzophenone tetracid dianhydride, 3,3 ', 4,4 '-biphenyl
Tetracarboxylic acid dianhydride or 4, one of double phthalic anhydrides of 4'- oxygen or multiple combinations.
3. a kind of polyimide foam hollow microsphere preparation method according to claim 1, it is characterised in that: described high boiling
The sprotic solvent of point is one of dimethylformamide, N-Methyl pyrrolidone, dimethyl acetamide or multiple combinations.
4. a kind of polyimide foam hollow microsphere preparation method according to claim 3, it is characterised in that: described high boiling
The parts by weight of the sprotic solvent of point are 70-200 parts.
5. a kind of polyimide foam hollow microsphere preparation method according to claim 1, it is characterised in that: the low boiling
Point small molecule is one of carbon disulfide, anhydrous methanol, acetone, lithium chloride or multiple combinations.
6. a kind of polyimide foam hollow microsphere preparation method according to claim 5, it is characterised in that: the low boiling
The parts by weight of point small molecule are 18-22 parts.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5910558A (en) * | 1993-01-08 | 1999-06-08 | Basf Aktiengesellschaft | Micropowders |
| CN101089030A (en) * | 2007-06-18 | 2007-12-19 | 南京工业大学 | Prepn process of polyimide microsphere |
| CN101463135A (en) * | 2009-01-13 | 2009-06-24 | 吉林大学 | Preparation of water-dispersion polyamic acid particle |
| CN102585221A (en) * | 2011-12-23 | 2012-07-18 | 太原理工大学 | Preparation method of porous polyimide microspheres |
-
2019
- 2019-06-20 CN CN201910537470.4A patent/CN110272543B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5910558A (en) * | 1993-01-08 | 1999-06-08 | Basf Aktiengesellschaft | Micropowders |
| CN101089030A (en) * | 2007-06-18 | 2007-12-19 | 南京工业大学 | Prepn process of polyimide microsphere |
| CN101463135A (en) * | 2009-01-13 | 2009-06-24 | 吉林大学 | Preparation of water-dispersion polyamic acid particle |
| CN102585221A (en) * | 2011-12-23 | 2012-07-18 | 太原理工大学 | Preparation method of porous polyimide microspheres |
Non-Patent Citations (2)
| Title |
|---|
| 井晶: "聚酰亚胺及聚酰胺酸微纳米颗粒的制备及研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
| 张晓霞: "聚酰亚胺微球制备的工艺条件优化和采用小分子致孔剂致孔的初步探讨", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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