CN101703913A - Method for preparing polyimide microspheres - Google Patents
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- CN101703913A CN101703913A CN200910075811A CN200910075811A CN101703913A CN 101703913 A CN101703913 A CN 101703913A CN 200910075811 A CN200910075811 A CN 200910075811A CN 200910075811 A CN200910075811 A CN 200910075811A CN 101703913 A CN101703913 A CN 101703913A
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Abstract
The invention provides a method for preparing polyimide microspheres. The method comprises: taking non-water inverse emulsion as a reaction system; preparing the non-water inverse emulsion of monomer diamine; adding monomer dianhydride to the emulsion step by step so as to perform reaction and obtain polyamide acid emulsion; and obtaining the polyimide microspheres through a chemical and thermal imidization process. The method takes the non-water inverse emulsion as the system for preparing the polyimide microspheres and allows monomers to react in dispersed-phase droplets, thereby ensuring that the microspheres cannot be crosslinked; the system takes polar and non-polar organic solvents as a dispersed phase and a continuous phase respectively to discard the presence of water phase, so the system applies to the preparation of the polyimide microspheres; the particle size of the microspheres is selected by regulating the ratio of two phases and the consumption of emulsifier; and different dispersed phases can be selected to adapt to different monomers.
Description
Technical field
The present invention relates to a kind of preparation method of polyimide microsphere.Specifically, be in a kind of two organic facies emulsions with non-water, with tetracarboxylic anhydride and diamine compound is monomer, and by the non-water reversed-phase emulsion of polymerization production polyamic acid, the polyamic acid of generation obtains the method for polyimide microsphere through chemical imidization or hot imidization.
Background technology
Polymer microsphere has the advantages such as designability that uniform particle diameter, big, the surperficial absorption property of specific area are strong, aggregate structure is formed, and is having a wide range of applications aspect the fields such as chemical industry, electronics, information and bioengineering.Polyimide microsphere is except that having above-mentioned advantage, also have outstanding hear resistance, superior dielectric properties, solvent resistance, chemicals-resistant corrosivity and radiation resistance, so be widely used in fields such as Aeronautics and Astronautics, electric, mechanical, chemical industry and microelectronics.
Method for preparing microsphere has traditional suspension polymerization, dispersion copolymerization method, precipitation polymerization method, and precipitation polymerization method, self-assembly method etc. again.Suspension polymerization is applicable to the microballoon that preparation is bigger, and particle diameter is usually at the 100-1000 mu m range, but bad dispersibility; Dispersion copolymerization method can replenish the shortcoming of suspension polymerisation, but itself has the inhomogenous deficiency of product particle diameter; The key that precipitation polymerization method prepares microballoon is to select suitable solvent to make monomer be dissolved in wherein, and product is insoluble, thus the difficulty that has caused solvent to select, and this method is difficult to prepare the molecular weight height, the microballoon that particle diameter is big; Reprecipitation method is by object is expelled in the poor solvent, owing to solubility parameter difference, thereby causes the polymer microballoon precipitation, and still, there is weakness crosslinked, bonding in the microballoon of the method preparation, and operability is poor; Self-assembly method is to dress up orderly nanostructured by intermolecular special interaction realization group of molecules, only is suitable for preparing the less microballoon of particle diameter, and the scope of application is restricted.In addition, prepare two acid diesters intermediates by dianhydride in addition, prepare the method for polyimide microsphere afterwards again with diamine reactant.The advantage of this method is that reaction system can exist water, thereby has widened the range of choice of reaction system, but the introducing of two acid diesters has increased the difficulty of technology, is difficult to guarantee high productive rate.
Publication number be CN1246489A's " a kind of polyimide particles preparation method ".This method prepares tetracarboxylic dianhydride and two kinds of solution of diamines respectively, then two kinds of solution is mixed, and separates out polyamic acid particle under ultrasonic agitation, carries out imidization at last and obtains polyimide particles.This method post processing difficulty, the long-chain easy fracture of polyamic acid under ultrasonication, polymer can be degraded, and can cause the fragmentation of particle.
Publication number be US006084000A's " a kind of preparation method of polyimide microsphere of hollow ".This method is that dianhydride is dissolved in the alcohol, synthetic dialkyl-diacid under the condition of methyl alcohol and ether, add diamines then, after in ether, mixing the reaction certain hour, heating steams solvent in rustless steel container, obtain the polyamic acid powder, mechanical crushing is then at high temperature handled and is obtained polyimide microsphere.The particle diameter that this preparation method obtains polyimide microsphere is bigger, and at 100～150 μ m, and microballoon can produce crosslinked in steaming the process of solvent.
Publication number be CN101089030A's " a kind of preparation method of polyimide microsphere ", this method is the monomer diamines to be dissolved in have in the molten organic solvent of dispersant, again the monomer dianhydride is added in batches, the preparation polyamic acid solution; Obtain polyimide solution through chemical imidization; The aqueous solution of dispersant is dropwise joined in the solution of the good polyimides of above-mentioned imidization, separate out solid particle, centrifugal filtration, washing, oven dry obtains polyimide microsphere.This preparation method's weak point is that process is difficult to control when dripping the aqueous solution of dispersant, is difficult to guarantee the dispersiveness of polyimide microsphere and the uniform particle diameter of microballoon.
Based on above-mentioned the deficiencies in the prior art, the invention provides a kind of non-water reversed-phase emulsion is reaction system, with diamines, dianhydride is monomer, prepares the method for polyimide microsphere through two step imidizations. and this method technology is simple, and the range of choice of monomer is very big. and the inventive method is still for appearing in the newspapers.
Summary of the invention
Serious based on existing polyimide microsphere preparation method microspheres prepared particle diameter heterogeneity, crosslinked phenomenon, the breakable deficiency of microballoon, it is simple to the invention provides a kind of technology, with low cost, the preparation method of the polyimide microsphere of microspherulite diameter homogeneous and favorable dispersibility.
A kind of method for preparing polyimide microsphere of the present invention, be as reaction system with non-water reversed-phase emulsion, the non-water reversed-phase emulsion that at first prepares the monomer diamines, the monomer dianhydride is progressively added react in this emulsion then and obtain the polyamic acid emulsion, after chemistry and hot imidization process obtain polyimide microsphere;
Described non-water reversed-phase emulsion system is to be continuous phase with the non-polar organic solvent, is decentralized photo with the polar organic solvent, is emulsifying agent with the composite anion surfactant of high molecular surfactant;
The continuous phase in the described non-water reversed-phase emulsion system and the volume ratio of decentralized photo are 8: 1～1: 1; The emulsifying agent mass fraction is 3%～8% in the non-water reversed-phase emulsion;
Wherein, the mass ratio of high molecular surfactant and anion surfactant is 1: 1～4: 1;
The solid content of reaction system is 8%～40%.
The present invention is above-mentioned to prepare in the method for polyimide microsphere, and the preparation method of described polyamic acid emulsion at first is dissolved in diamine monomer the polarity decentralized photo; Then compounded surfactant is scattered in non-polar organic solvent, and mixes with the solution of diamine monomer; Progressively dianhydride monomer is added mixed solution at last, reacted 4～6 hours, obtain the non-water reversed-phase emulsion of polyamic acid.
Described chemistry and hot imidization process are pyridine/acetic anhydride to be joined the non-water reversed-phase emulsion of polyamic acid in 1: 1 in molar ratio, and chemical imidization is more than 2 hours, and polyimide microsphere begins to separate out, and through centrifugal, oven dry obtains Powdered polyimide microsphere; Again with polyimide microsphere 280 ℃ of following hot imidizations 2 hours, obtain imidization polyimide microsphere completely.
Described non-polar organic solvent is benzinum, atoleine, kerosene, benzene, n-hexane or cyclohexane.
Described polar organic solvent is oxolane, methyl alcohol, N, dinethylformamide, n-hexane, N, N-dimethylacetylamide, N-methyl pyrrolidone or methyl-sulfoxide.
Described high molecular surfactant is Pluronic block polymer: L64, L121, P123, F68, F127; Polyhydric alcohol polymer: pentaerythritol fatty ester, dehydration xylitol fatty acid ester or sorbitan fatty acid ester.
Described anion surfactant is dodecyl sodium sulfate SDS, sulphation natrium ricinoleicum, cycloalkanes sodium sulphate or neopelex (ABS-Na).
The polyimide microsphere particle diameter of described preparation is distributed in 5～15 microns, and the Tg temperature range is at 450 ℃～620 ℃.
The preparation method of the above-mentioned proposition of the present invention compares the advantage and the good effect that are had with prior preparation method, with the system of non-water reversed-phase emulsion as the preparation polyimide microsphere, monomer reacts in dispersed phase drop, and it is crosslinked to have guaranteed that microballoon does not take place; System is decentralized photo and continuous phase with polarity, non-polar organic solvent respectively, thereby abandons the existence of water, makes this system be applicable to the preparation of polyimide microsphere; The consumption of ratio, emulsifying agent by the regulation and control two-phase is realized the selection to microspherulite diameter; And can select different decentralized photos to adapt to different monomers. in the preparation process not needs add precipitating reagent or mechanical lapping, process conditions are simplified. preparation method's of the present invention advantage and good effect also are: (1) has good monodispersity, in preparation process, through the chemical imidization polyimide microsphere that can progressively settle out; (2) microspherulite diameter distribution homogeneous; (3) monomer is applied widely; (4) with low cost, technology is simple.
The present invention tests with the Britain Mastersizer of Ma Erwen company 2000 micron granularity analyzers by the average grain diameter of the prepared polyimide microsphere of above-mentioned preparation method; The thermal weight loss temperature is measured with German Netzsch hour thermogravimetric analyzer Sta409C.Product by scanning electron microscopic observation as shown in Figure 1, 2.
Description of drawings
Fig. 1 is the sem photograph of the prepared polyimide microsphere of the embodiment of the invention 1
Fig. 2 is the sem photograph of the embodiment of the invention 2 prepared polyimide microspheres
The specific embodiment
Followingly illustrate embodiments of the present invention and embodiment, but this area professional is according to the technological process of the present invention of explanation detail knowledge.
The specific embodiment:
The present invention is a monomer with diamines and dianhydride, and its reaction equation and processing step are as follows:
Wherein: Ar:
Deng.
B:
Deng.
Processing step:
The first step: select the solvent in the claim 5 to make decentralized photo, prepare two amine aqueous solutions.Wherein, diamines can be selected following at least a: 4, and 4-diaminodiphenyl ether (ODA), 4,4-MDA (DDM), 1, two (4-amino-benzene oxygen) benzene (TPE) of 4-, p-phenylenediamine (PPD) (PPD), neighbour-phenylenediamine, m-phenylenediamine, 3, the 4-diaminodiphenyl ether, 3, the 3-DADPS; The fats diamines, as 1,2-diaminourea methane, 1,4-DACH or tetra-methylenedimine etc.
Second step: the solvent of selecting claim 4 is as continuous phase, proportioning by claim 1 adds continuous phase with high molecular surfactant in the claim 6,7 and anion surfactant, and the back that is uniformly dispersed is mixed with two amine aqueous solutions of first step preparation and stirred.
The 3rd step: under stirring action, dianhydride is added in batches in the system of second step preparation, reaction is more than 4 hours.Used tetracarboxylic anhydride can be 3,3-biphenyl tetracarboxylic dianhydride, hexafluorodianhydride (6FDA) (6FDA), 4,4-BPDA, pyromellitic acid dianhydride (PMDA), naphthalene-1,2,4,5-tetracarboxylic dianhydride, 1, two (2, the 3-dicarboxylic acids phenoxy group) benzene dianhydrides of 4-, butane-1,2,3,4-tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride or heterocycle tetracarboxylic dianhydride.
The 4th step: question response finishes, and directly quantitative pyridine/acetic anhydride (mol ratio: 1: 1) is added in the 3rd step gained emulsion system and carries out chemical imidization, 2～4 hours time.When chemical imidization finished, polyimide microsphere can settle out through centrifugal.
The 5th step: the gained solution centrifugal separation of the 4th step is obtained the product polyimide microsphere, product is dried.Constant temperature carries out hot imidization in tube furnace at last, and condition is: 1～3 hour, and 280 ℃～330 ℃.
Embodiment one
Select N, dinethylformamide (DMF) is a decentralized photo, and atoleine is a continuous phase; With P123, dodecyl sodium sulfate (SDS) is emulsifying agent; 4,4-diaminodiphenyl ether (ODA), pyromellitic acid dianhydride (PMDA) is a monomer.By first kind of solution: ODA/DMF=1.0g/10ml of above-mentioned first step preparation, place the 500ml three-neck flask; By second step preparation, second kind of solution: P123, SDS (mass ratio: 1: 1)/atoleine=2g/40ml, atoleine and DMF volume ratio=4: 1.Mix 2 two kinds of solution in three-neck flask, be stirred to evenly.Logical nitrogen protection progressively adds PMDA=1.2g.Reacted 5 hours, and added pyridine/acetic anhydride and carry out chemical imidization.After 2 hours the solution centrifugal separation is obtained product, obtain the solid polyimide microsphere after the drying.At last in tube furnace under 280 ℃ of conditions, constant temperature 3 hours.Product average grain diameter 12.4 μ m, 550 ℃ of Tg temperature.
Embodiment two
Select N, dinethylformamide (DMF) is a decentralized photo, and atoleine is a continuous phase; With F127, neopelex (ABS-Na) is emulsifying agent; P-phenylenediamine (PPD) (PPD), hexafluorodianhydride (6FDA) (6FDA) is a monomer.By first kind of solution: PPD/DMF=0.5g/10ml of above-mentioned first step preparation, place 500 three-neck flasks; By second step preparation, second kind of solution: P123, ABS-Na (mass ratio: 2: 1)/atoleine=2g/40ml, atoleine and DMF volume ratio=5: 1.Under function composite by electromagnetic stirring, mix 2 two kinds of solution in three-neck flask, be stirred to evenly.Logical nitrogen protection is by progressively adding 6FDA=0.745g.Reacted 5 hours, and added pyridine/acetic anhydride and carry out chemical imidization.After 3 hours solution centrifugal is separated, and obtain solid polyimides product after the drying.At last in tube furnace under 300 ℃ of conditions, constant temperature 2 hours.Product average grain diameter 10 μ m, 530 ℃ of Tg temperature.
Embodiment three
Selection methyl alcohol is decentralized photo, and cyclohexane is a continuous phase; With pentaerythritol fatty ester, cycloalkanes sodium sulphate is emulsifying agent; 4,4-diaminodiphenyl ether (ODA), pyromellitic acid dianhydride (PMDA) is a monomer. prepare first kind of solution by the above-mentioned first step: ODA/ methyl alcohol=0.5g/10ml; Prepare second kind of solution by second step: pentaerythritol fatty ester, cycloalkanes sodium sulphate (mass ratio: 1: 1)/cyclohexane=2g/40ml, cyclohexane and methyl alcohol volume ratio=3: 2. under function composite by electromagnetic stirring, mix first, second two kinds of solution, be stirred to evenly. by progressively adding PMDA=0.545g. reaction 5 hours, adding pyridine/acetic anhydride carries out after chemical imidization .4 hour solution centrifugal being separated, and obtain solid polyimides product after the drying. constant temperature 1 hour under 330 ℃ of conditions in tube furnace at last. product average grain diameter 9 μ m, 500 ℃ of Tg temperature.
Embodiment four
Select N, dinethylformamide (DMF) is a decentralized photo, and atoleine is a continuous phase; With dehydration xylitol fatty acid ester, dodecyl sodium sulfate (SDS) is emulsifying agent; 4,4-diaminodiphenyl ether (ODA), pyromellitic acid dianhydride (PMDA) is a monomer.By first kind of solution: ODA/DMF=0.5g/10ml of above-mentioned first step preparation, place 500 three-neck flasks; Prepare second kind of solution by second step: dehydration xylitol fatty acid ester, SDS (mass ratio: 4: 1)/atoleine=2g/40ml, atoleine and DMF volume ratio=6: 1.Under function composite by electromagnetic stirring, mix 2 two kinds of solution in three-neck flask, be stirred to evenly, by progressively adding PMDA=0.545g.Reacted 5 hours, and added pyridine/acetic anhydride and carry out chemical imidization.After 3 hours the solution centrifugal separation is obtained product, obtain the solid polyimide microsphere after the drying.At last in tube furnace under 300 ℃ of conditions, constant temperature 2 hours.Product average grain diameter 13 μ m, 510 ℃ of Tg temperature.
Embodiment five
Selecting N-methyl pyrrolidone (NMP) is decentralized photo, and benzene is continuous phase; With sorbitan fatty acid ester, sulphation natrium ricinoleicum is emulsifying agent; 4,4-MDA (DDM), pyromellitic acid dianhydride (PMDA) is a monomer.By first kind of solution: DDM/NMP=0.5g/10ml of above-mentioned first step preparation, place 500 three-neck flasks; Prepare second kind of solution by second step: sorbitan fatty acid ester, sulphation natrium ricinoleicum (mass ratio: 2: 1)/atoleine=2g/40ml, atoleine and NMP volume ratio=6: 1.Under function composite by electromagnetic stirring, mix 2 two kinds of solution in three-neck flask, be stirred to evenly, logical nitrogen protection progressively adds PMDA=0.545g.Reacted 5 hours, and added pyridine/acetic anhydride and carry out chemical imidization.After 4 hours the solution centrifugal separation is obtained product, obtain the solid polyimide microsphere after the drying.Constant temperature 1 hour under 330 ℃ of conditions in tube furnace at last.Product average grain diameter 8 μ m, 490 ℃ of Tg temperature.
Embodiment six
Selection methyl alcohol is decentralized photo, and kerosene is continuous phase; With L121, dodecyl sodium sulfate (SDS) is emulsifying agent; 4,4-diaminodiphenyl ether (ODA), pyromellitic acid dianhydride (PMDA) is a monomer.Prepare first kind of solution by the above-mentioned first step: DDM/ methyl alcohol=0.5g/10ml places 500 three-neck flasks; By second step preparation, second kind of solution: L121, SDS (mass ratio: 3: 2)/benzene=2g/40ml, kerosene and methyl alcohol volume ratio=3: 1.Under function composite by electromagnetic stirring, mix 2 two kinds of solution in three-neck flask, be stirred to evenly.Logical nitrogen protection progressively adds PMDA=0.545g.Reacted 5 hours, and added pyridine/acetic anhydride and carry out chemical imidization.After 3 hours the solution centrifugal separation is obtained product, obtain the solid polyimide microsphere after the drying.At last in tube furnace under 300 ℃ of conditions, constant temperature 2 hours.Product average grain diameter 11.7 μ m, 570 ℃ of Tg temperature.
Embodiment seven
The selection methyl-sulfoxide is a decentralized photo, and n-hexane is a continuous phase; With L64, dodecyl sodium sulfate (SDS) is emulsifying agent; 4,4-diaminodiphenyl ether (ODA), naphthalene-1,2,4,5-tetracarboxylic dianhydride are monomer. prepare first kind of solution by the above-mentioned first step: DDM/ methyl alcohol=0.38g/10ml places 500 three-neck flasks; By second kind of solution: L64 of second step preparation; SDS (mass ratio: 4: 1)/benzene=2g/40ml; n-hexane and methyl-sulfoxide volume ratio=3: 1. under function composite by electromagnetic stirring; mix 2 two kinds of solution in three-neck flask; be stirred to evenly. logical nitrogen protection; progressively add naphthalene-1; 2; 4; 5-tetracarboxylic dianhydride=0.54g. reacted 5 hours; adding pyridine/acetic anhydride carries out after chemical imidization .4 hour the solution centrifugal separation being obtained product; obtain the solid polyimide microsphere after the drying. at last in tube furnace under 330 ℃ of conditions, constant temperature 1 hour. product average grain diameter 12.5 μ m, 570 ℃ of Tg temperature.
Embodiment eight
The selection methyl-sulfoxide is a decentralized photo, and benzene is continuous phase; With F68, neopelex (ABS-Na) is emulsifying agent; 4,4-diaminodiphenyl ether (ODA), naphthalene-1,2,4,5-tetracarboxylic dianhydride are monomer.Prepare first kind of solution by the above-mentioned first step: DDM/ methyl alcohol=0.38g/10ml places 500 three-neck flasks; By second step preparation, second kind of solution: F68, ABS-Na (mass ratio: 2: 1)/benzene=2g/40ml, benzene and methyl-sulfoxide volume ratio=1: 1.Under function composite by electromagnetic stirring, mix 2 two kinds of solution in three-neck flask, be stirred to evenly.Logical nitrogen protection progressively adds naphthalene-1,2,4,5-tetracarboxylic dianhydride=0.54g.Reacted 5 hours, and added pyridine/acetic anhydride and carry out chemical imidization.After 3 hours the solution centrifugal separation is obtained product, obtain the solid polyimide microsphere after the drying.At last in tube furnace under 300 ℃ of conditions, constant temperature 2 hours.Product average grain diameter 11.5 μ m, 450 ℃ of Tg temperature.
Embodiment nine
Selecting oxolane (THF) is decentralized photo, and cyclohexane is a continuous phase; With F68, neopelex (ABS-Na) is emulsifying agent; 4,4-diaminodiphenyl ether (ODA), naphthalene-1,2,4,5-tetracarboxylic dianhydride are monomer.By first kind of solution: DDM/THF=0.38g/10ml of above-mentioned first step preparation, place 500 beakers; By second step preparation, second kind of solution: F68, ABS-Na (mass ratio: 2: 1)/benzene=2g/40ml, benzene and methyl-sulfoxide volume ratio=1: 1.Under function composite by electromagnetic stirring, mix 2 two kinds of solution in three-neck flask, be stirred to evenly, progressively add naphthalene-1,2,4,5-tetracarboxylic dianhydride=0.54g.Reacted 5 hours, and added pyridine/acetic anhydride and carry out chemical imidization.After 2 hours the solution centrifugal separation is obtained product, obtain the solid polyimide microsphere after the drying.At last in tube furnace under 280 ℃ of conditions, constant temperature 3 hours.Product average grain diameter 11 μ m, 470 ℃ of Tg temperature.
Embodiment ten
Select N, dinethylformamide (DMF) is a decentralized photo, and n-hexane is a continuous phase; With F127, neopelex (ABS-Na) is emulsifying agent; P-phenylenediamine (PPD) (PPD), pyromellitic acid dianhydride (PMDA) is a monomer.By first kind of solution: PPD/DMF=0.5g/10ml of above-mentioned first step preparation, place 500 three-neck flasks; By second step preparation, second kind of solution: P123, ABS-Na (mass ratio: 1: 1)/atoleine=2g/40ml, atoleine and DMF volume ratio=5: 1.Under function composite by electromagnetic stirring, mix 2 two kinds of solution in three-neck flask, be stirred to evenly, progressively add 6FDA=0.745g.Reacted 5 hours, and added pyridine/acetic anhydride and carry out chemical imidization.After 4 hours solution centrifugal is separated, and obtain solid polyimides product after the drying.At last in tube furnace under 330 ℃ of conditions, constant temperature 1 hour.Product average grain diameter 10 μ m, 530 ℃ of Tg temperature.
Claims (10)
1. method for preparing polyimide microsphere, this method is as reaction system with non-water reversed-phase emulsion, the non-water reversed-phase emulsion that at first prepares the monomer diamines, the monomer dianhydride is progressively added react in this emulsion then and obtain the polyamic acid emulsion, after chemistry and hot imidization process obtain polyimide microsphere;
Described non-water reversed-phase emulsion system is to be continuous phase with the non-polar organic solvent, is decentralized photo with the polar organic solvent, is emulsifying agent with the composite anion surfactant of high molecular surfactant;
The continuous phase in the described non-water reversed-phase emulsion system and the volume ratio of decentralized photo are 8: 1～1: 1; The emulsifying agent mass fraction is 3%～8% in the non-water reversed-phase emulsion;
Wherein, the mass ratio of high molecular surfactant and anion surfactant is 1: 1～4: 1;
The solid content of reaction system is 8%～40%.
2. claim 1 is described, and the preparation method of its polyamic acid emulsion at first is dissolved in diamine monomer the polarity decentralized photo; Then compounded surfactant is scattered in non-polar organic solvent, and mixes with the solution of diamine monomer; Progressively dianhydride monomer is added mixed solution at last, reacted 4～6 hours, obtain the non-water reversed-phase emulsion of polyamic acid.
3. claim 1 is described, and its chemistry and hot imidization process are pyridine/acetic anhydride to be joined the non-water reversed-phase emulsion of polyamic acid in 1: 1 in molar ratio, and chemical imidization is more than 2 hours, polyimide microsphere begins to separate out, through centrifugal, oven dry obtains Powdered polyimide microsphere; The polyimide microsphere that obtains 280 ℃ of following hot imidizations 2 hours, is obtained imidization polyimide microsphere completely.
4. claim 1 is described, and its non-polar organic solvent is: benzinum, atoleine, kerosene, benzene, n-hexane or cyclohexane.
5. claim 1 is described, and its polar organic solvent is oxolane, methyl alcohol, N, dinethylformamide, N, N-dimethylacetylamide, N-methyl pyrrolidone or methyl-sulfoxide.
6. claim 1 is described, and its high molecular surfactant is Pluronic block polymer or polyhydric alcohol polymer.
7. claim 6 is described, and its Pluronic block polymer is L64, L121, P123, F68 or F127;
8. claim 6 is described, and its polyhydric alcohol polymer is pentaerythritol fatty ester, dehydration xylitol fatty acid ester or sorbitan fatty acid ester.
9. claim 1 is described, and its anion surfactant is dodecyl sodium sulfate SDS, sulphation natrium ricinoleicum, cycloalkanes sodium sulphate or neopelex ABS-Na.
10. claim 1 is described, and its polyimide microsphere particle diameter is 5～15 μ m, and the Tg temperature range is at 450 ℃～620 ℃.
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