CN103172861A - Polyimide particle containing aliphatic chain structure and application thereof - Google Patents

Polyimide particle containing aliphatic chain structure and application thereof Download PDF

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CN103172861A
CN103172861A CN2013101320267A CN201310132026A CN103172861A CN 103172861 A CN103172861 A CN 103172861A CN 2013101320267 A CN2013101320267 A CN 2013101320267A CN 201310132026 A CN201310132026 A CN 201310132026A CN 103172861 A CN103172861 A CN 103172861A
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particulate
chain structure
fatty chain
polyimide
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CN103172861B (en
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张艺
方伟镇
许家瑞
刘四委
池振国
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Sun Yat Sen University
National Sun Yat Sen University
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Abstract

The invention discloses a polyimide particle containing an aliphatic chain structure and an application thereof. The copolyimide particle prepared by adopting aliphatic diamine, aromatic diamine and various dianhydrides as raw materials has the characteristics of high crystallinity, stability in property, large specific area, regular structure, and the like; the preparation method of the polyimide particle has the advantages of simple process, high yield and good repetitiveness, thereby being suitable for industrial production; and the prepared polyimide particle containing the aliphatic chain structure, which is disclosed by the invention, can be applied to preparing a micro-electronic product, a liquid crystal display or a carbon material with a high graphitization degree, and the like.

Description

A kind of medlin particulate of fatty chain structure and application thereof
Technical field
The present invention relates to material science, particularly a kind of medlin particulate of fatty chain structure and application thereof.
Technical background
Polyimide is one of macromolecular material that temperature classification is the highest in the practical application of industry up to now, have simultaneously higher physical strength, good dielectric properties, nontoxicity, chemical resistance corrosion and radiation resistance, be widely used in the fields such as Aeronautics and Astronautics, electric, mechanical, chemical industry, microelectronics.It uses form varied, comprises Kapton, polyimide insulative paint, polyimide photosensitivity coating, polyimide electrophoretic paint, polyimide binder, polyimide powder, particulate, polyimide formed body etc.
Medlin particulate is due to existing polyimide, shows again that the polymer particles specific surface area is large, adsorptivity reaches by force the characteristics such as agglutination is large, has broad application prospects.For example, be used for support of the catalyst, have wear-resisting, anti-solvent and the good characteristic such as high temperature resistant, and particle diameter be controlled; For separating of purifying, selectivity is good, anti-solvent, dimensional stabilizing; Be used for pharmaceutical carrier, stability is high, and is good with the cytolemma consistency, can reach the effect of slowly-releasing, target by certain blocking agent.Therefore, the exploitation of medlin particulate becomes important component part and the study hotspot of polyimide research gradually.
Summary of the invention
The object of the present invention is to provide a kind of medlin particulate of fatty chain structure, the characteristics such as it has, and degree of crystallinity is high, stable performance, specific surface area are high, compound with regular structure.
Another object of the present invention is to provide the application of medlin particulate in microelectronic, liquid-crystal display, carbon material preparation of above-mentioned fatty chain structure.
The object of the present invention is achieved like this: a kind of medlin particulate of fatty chain structure is characterized in that its general formula of molecular structure is:
Figure BDA00003054662300011
In formula:
(1) n=2～12, the ratio of X and Y are (99～1): (1～99);
(2) Ar 1, Ar 2Be respectively and be selected from one or more in the following structural formula group and Ar 1, Ar 2Can be identical or different:
Figure BDA00003054662300021
Wherein, R 1～R 24Be respectively hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms and be 1～4 alkyl or allyl group; R 25Be selected from one or more in following radicals:
Figure BDA00003054662300022
R wherein 26Any in the following structural formula group:
Wherein, R 27～R 121Be respectively hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms and be 1～4 alkyl or allyl group.
(3) Ar 3Be respectively and be selected from any of following structural formula:
Figure BDA00003054662300031
Wherein, R 122～R 280Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms and be 1～4 alkyl or allyl group; R 281Be selected from a kind of in following radicals:
Figure BDA00003054662300032
Wherein, R 282～R 303Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms and be 1～4 alkyl or allyl group; R 304Be selected from a kind of in following radicals:
Figure BDA00003054662300033
Wherein, R 305～R 376Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms and be 1～4 alkyl or allyl group.
The medlin particulate of fatty chain structure of the present invention has degree of crystallinity high, the characteristics such as stable performance, specific surface area are high, compound with regular structure, and also its preparation technology is simple, and productive rate is high, good reproducibility, thereby be suitable for industrial production.The medlin particulate of the fatty chain structure of the present invention is applied to microelectronic, as the dielectric layer with good thermal stability; Be applied to the interval insulant of liquid-crystal display; Effective presoma and catalysis, encapsulation, controllable release and filler etc. as the carbon material for preparing high degree of graphitization.
Description of drawings
Fig. 1 is X-ray powder diffraction (XRD) figure of the polyimide of the embodiment 1 fatty chain structure of preparation gained.
Fig. 2 is scanning electron microscope (SEM) figure of the polyimide of the embodiment 1 fatty chain structure of preparation gained.
Fig. 3 is X-ray powder diffraction (XRD) figure of the polyimide of the embodiment 2 fatty chain structures of preparation gained.
Fig. 4 is scanning electron microscope (SEM) figure of the polyimide of the embodiment 2 fatty chain structures of preparation gained.
Fig. 5 is X-ray powder diffraction (XRD) figure of the polyimide of the embodiment 3 fatty chain structures of preparation gained.
Fig. 6 is scanning electron microscope (SEM) figure of the polyimide of the embodiment 3 fatty chain structures of preparation gained.
Fig. 7 is X-ray powder diffraction (XRD) figure of the polyimide of the embodiment 4 fatty chain structures of preparation gained.
Fig. 8 is scanning electron microscope (SEM) figure of the polyimide of the embodiment 4 fatty chain structures of preparation gained.
Fig. 9 is X-ray powder diffraction (XRD) figure of the polyimide of the embodiment 5 fatty chain structures of preparation gained.
Figure 10 is scanning electron microscope (SEM) figure of the polyimide of the embodiment 5 fatty chain structures of preparation gained.
Figure 11 is X-ray powder diffraction (XRD) figure of the polyimide of the embodiment 6 fatty chain structures of preparation gained.
Figure 12 is scanning electron microscope (SEM) figure of the polyimide of the embodiment 6 fatty chain structures of preparation gained.
Figure 13 is X-ray powder diffraction (XRD) figure of the polyimide of the embodiment 7 fatty chain structures of preparation gained.
Figure 14 is scanning electron microscope (SEM) figure of the polyimide of the embodiment 7 fatty chain structures of preparation gained.
Figure 15 is X-ray powder diffraction (XRD) figure of the polyimide of the embodiment 8 fatty chain structures of preparation gained.
Figure 16 is scanning electron microscope (SEM) figure of the polyimide of the embodiment 8 fatty chain structures of preparation gained.
Figure 17 is X-ray powder diffraction (XRD) figure of the polyimide of the embodiment 9 fatty chain structures of preparation gained.
Figure 18 is scanning electron microscope (SEM) figure of the polyimide of the embodiment 9 fatty chain structures of preparation gained.
Embodiment
The present invention is a kind of medlin particulate of fatty chain structure, and its general formula of molecular structure is:
In formula: n=2～12, the ratio of X and Y are (99～1): (1～99); Ar 1, Ar 2Be respectively and be selected from one or more in the following structural formula group and Ar 1And Ar 2Can be identical or different:
Figure BDA00003054662300052
Wherein, R 1～R 24Be respectively hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms are 1～4 alkyl or allyl group; R 25Be selected from one or more in following radicals:
—CO—、—O—、—S—、—SO 2—、—CH 2—、—C(CH 3) 2—、—C(CF 3) 2—、—O—R 26—O—
R wherein 26Any in the following structural formula group:
Figure BDA00003054662300053
Wherein, R 27～R 121Be respectively hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms and be 1～4 alkyl or allyl group.
Ar 3Be respectively and be selected from any of following structural formula:
Figure BDA00003054662300061
Wherein, R 122～R 280Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms and be 1～4 alkyl or allyl group; R 281Be selected from a kind of in following radicals:
Figure BDA00003054662300062
Wherein, R 282～R 303Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms and be 1～4 alkyl or allyl group; R 304Be selected from a kind of in following radicals:
Figure BDA00003054662300063
Wherein, R 305～R 376Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms and be 1～4 alkyl or allyl group.
During preparation, with dianhydride monomer and excessive Fatty Alcohol(C12-C14 and C12-C18) hybrid reaction under catalyst action, obtain ester-acid derivative; Then institute acquisition ester-acid derivative and diamine monomer are mixed in polar non-proton organic solvent, in 130-200 ℃ of stirring reaction 6～48h, obtain medlin particulate through separation, washing, drying.The medlin particulate of the above-mentioned fatty chain structure that makes can be applicable to microelectronic, as the dielectric layer with good thermal stability; Also can be applicable to the interval insulant of liquid-crystal display; Perhaps for the preparation of effective presoma and catalysis, encapsulation, controllable release and the filler etc. of the carbon material of high degree of graphitization.
Below in conjunction with specific embodiment, the present invention is further set forth; it is important to point out that following examples can not be interpreted as the restriction to the invention protection domain; the person skilled in the art in this field to some nonessential improvement and adjustment that the present invention makes, must belong to protection scope of the present invention according to the foregoing invention content.
Embodiment 1
By 3,3`, 4,4-benzophenone tetracarboxylic dianhydride (BTDA), Ursol D (PDA) and Putriscine (DBA) preparation copolyimide particulate.
With 3.2223g(10mmol) BTDA adds in the 100ml there-necked flask, and add 50ml ethanol and 1.5ml triethylamine, and be heated to 120 ℃ and carry out the first step reaction, after reaction 1h, unnecessary ethanol distillation out, stay the sticking ester-acid derivative of tool; Then adding respectively 0.8651g(8mmol) PDA, 0.1763g (2mmol) DBA and 42.64g weight ratio be the vapor of mixture solvent that N-Methyl pyrrolidone (NMP) and the orthodichlorobenzene (o-DCB) of 4:1 forms, be heated to 150 ℃, stir, finish reaction after reaction 24h, suction filtration, obtain medlin particulate, be placed in dry 24h under 200 ℃ of vacuum drying ovens.5% thermal weight loss temperature of this copolyimide particulate is 503.9 ℃, and the BET specific surface area is 58m 2g -1, the X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 1-2.
Embodiment 2
By 3,3`, 4,4-benzophenone tetracarboxylic dianhydride (BTDA), 4,4 '-diaminodiphenyl oxide (ODA) and Putriscine (DBA) preparation copolyimide particulate.
With 3.2223g(10mmol) BTDA adds in the 100ml there-necked flask, and add 50ml ethanol and 1.5ml triethylamine, and be heated to 120 ℃ and carry out the first step reaction, after reaction 1h, unnecessary ethanol distillation out, stay the sticking ester-acid derivative of tool; Then adding respectively 1.4017g(7mmol) ODA, 0.2645g (3mmol) DBA and 48.89g weight ratio be the vapor of mixture solvent that N-Methyl pyrrolidone (NMP) and the orthodichlorobenzene (o-DCB) of 4:1 forms, be heated to 150 ℃, stir, finish reaction after reaction 24h, suction filtration, obtain medlin particulate, be placed in dry 24h under 200 ℃ of vacuum drying ovens.5% thermal weight loss temperature (N of this copolyimide particulate 2Atmosphere) be 505.0 ℃, the BET specific surface area is 62m 2g -1, the X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 3-4.
Embodiment 3
By 3,3`, 4,4-benzophenone tetracarboxylic dianhydride (BTDA), 4,4 '-diaminobenzene anilide (DABA) and Putriscine (DBA) preparation copolyimide particulate.
With 3.2223g(10mmol) BTDA adds in the 100ml there-necked flask, and add 50ml ethanol and 1.5ml triethylamine, and be heated to 120 ℃ and carry out the first step reaction, after reaction 1h, unnecessary ethanol distillation out, stay the sticking ester-acid derivative of tool; Then adding respectively 1.5908g(7mmol) DABA, 0.2645g (3mmol) DBA and 50.78g weight ratio be the vapor of mixture solvent that N-Methyl pyrrolidone (NMP) and the orthodichlorobenzene (o-DCB) of 4:1 forms, be heated to 150 ℃, stir, finish reaction after reaction 24h, suction filtration, obtain medlin particulate, be placed in dry 24h under 200 ℃ of vacuum drying ovens.5% thermal weight loss temperature of this copolyimide particulate is 495.2 ℃, and the BET specific surface area is 82m 2g -1, the X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 5-6.
Embodiment 4
By 4,4 '-Biphenyl Ether dianhydride (OPDA), Ursol D (PDA) and Putriscine (DBA) preparation copolyimide particulate.
With 3.1022g(10mmol) OPDA adds in the 100ml there-necked flask, and add 50ml ethanol and 1.5ml triethylamine, and be heated to 120 ℃ and carry out the first step reaction, after reaction 1h, unnecessary ethanol distillation out, stay the sticking ester-acid derivative of tool; Then adding respectively 0.9733g(9mmol) PDA, 0.0888g (1mmol) DBA and 41.64g weight ratio be the vapor of mixture solvent that N-Methyl pyrrolidone (NMP) and the orthodichlorobenzene (o-DCB) of 4:1 forms, be heated to 150 ℃, stir, finish reaction after reaction 24h, suction filtration, obtain medlin particulate, be placed in dry 24h under 200 ℃ of vacuum drying ovens.5% thermal weight loss temperature of this copolyimide particulate is 536.3 ℃, and the BET specific surface area is 32m 2g -1, the X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 7-8.
Embodiment 5
By 4,4 '-Biphenyl Ether dianhydride (OPDA), 4,4 '-benzidine (BZD) and Putriscine (DBA) preparation copolyimide particulate.
With 3.1022g(10mmol) OPDA adds in the 100ml there-necked flask, and add 50ml ethanol and 1.5ml triethylamine, and be heated to 120 ℃ and carry out the first step reaction, after reaction 1h, unnecessary ethanol distillation out, stay the sticking ester-acid derivative of tool; Then adding respectively 1.2897g(7mmol) BZD, 0.2645g (3mmol) DBA and 46.56g weight ratio be the vapor of mixture solvent that N-Methyl pyrrolidone (NMP) and the orthodichlorobenzene (o-DCB) of 4:1 forms, be heated to 150 ℃, stir, finish reaction after reaction 24h, suction filtration, obtain medlin particulate, be placed in dry 24h under 200 ℃ of vacuum drying ovens.5% thermal weight loss temperature of this copolyimide particulate is 518.4 ℃, and the BET specific surface area is 41m 2g -1, the X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 9-10.
Embodiment 6
By 4,4 '-Biphenyl Ether dianhydride (OPDA), 4,4 '-diaminobenzene anilide (DABA) and Putriscine (DBA) preparation copolyimide particulate.
With 3.1022g(10mmol) OPDA adds in the 100ml there-necked flask, and add 50ml ethanol and 1.5ml triethylamine, and be heated to 120 ℃ and carry out the first step reaction, after reaction 1h, unnecessary ethanol distillation out, stay the sticking ester-acid derivative of tool; Then adding respectively 1.5908g(7mmol) DABA, 0.2645g (3mmol) DBA and 49.58g weight ratio be the vapor of mixture solvent that N-Methyl pyrrolidone (NMP) and the orthodichlorobenzene (o-DCB) of 4:1 forms, be heated to 150 ℃, stir, finish reaction after reaction 24h, suction filtration, obtain medlin particulate, be placed in dry 24h under 200 ℃ of vacuum drying ovens.5% thermal weight loss temperature of this copolyimide particulate is 504.3 ℃, and the BET specific surface area is 17m 2g -1, the X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 11-12.
Embodiment 7
By pyromellitic acid anhydride (PMDA), Ursol D (PDA) and Putriscine (DBA) preparation copolyimide particulate.
With 2.1812g(10mmol) PMDA adds in the 100ml there-necked flask, and add 50ml ethanol and 1.5ml triethylamine, and be heated to 120 ℃ and carry out the first step reaction, after reaction 1h, unnecessary ethanol distillation out, stay the sticking ester-acid derivative of tool; Then adding respectively 0.7570g(7mmol) PDA, 0.2645g (3mmol) DBA and 32.03g weight ratio be the vapor of mixture solvent that N-Methyl pyrrolidone (NMP) and the orthodichlorobenzene (o-DCB) of 4:1 forms, be heated to 150 ℃, stir, finish reaction after reaction 24h, suction filtration, obtain medlin particulate, be placed in dry 24h under 200 ℃ of vacuum drying ovens.5% thermal weight loss temperature of this copolyimide particulate is 510.1 ℃, and the BET specific surface area is 122m 2g -1, the X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 13-14.
Embodiment 8
By pyromellitic acid anhydride (PMDA), 4,4 '-diaminodiphenyl oxide (ODA) and Putriscine (DBA) preparation copolyimide particulate.
With 2.1812g(10mmol) PMDA adds in the 100ml there-necked flask, and add 50ml ethanol and 1.5ml triethylamine, and be heated to 120 ℃ and carry out the first step reaction, after reaction 1h, unnecessary ethanol distillation out, stay the sticking ester-acid derivative of tool; Then adding respectively 1.4017g(7mmol) ODA, 0.2645g (3mmol) DBA and 38.47g weight ratio be the vapor of mixture solvent that N-Methyl pyrrolidone (NMP) and the orthodichlorobenzene (o-DCB) of 4:1 forms, be heated to 150 ℃, stir, finish reaction after reaction 24h, suction filtration, obtain medlin particulate, be placed in dry 24h under 200 ℃ of vacuum drying ovens.5% thermal weight loss temperature of this copolyimide particulate is 487.5 ℃, and the BET specific surface area is 90m 2g -1, the X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 15-16.
Embodiment 9
By pyromellitic acid anhydride (PMDA), 4,4 '-diaminodiphenyl sulfide (SDA) and Putriscine (DBA) preparation copolyimide particulate.
With 2.1812g(10mmol) PMDA adds in the 100ml there-necked flask, and add 50ml ethanol and 1.5ml triethylamine, and be heated to 120 ℃ and carry out the first step reaction, after reaction 1h, unnecessary ethanol distillation out, stay the sticking ester-acid derivative of tool; Then adding respectively 1.5141g(7mmol) SDA, 0.2645g (3mmol) DBA and 39.60g weight ratio be the vapor of mixture solvent that N-Methyl pyrrolidone (NMP) and the orthodichlorobenzene (o-DCB) of 4:1 forms, be heated to 150 ℃, stir, finish reaction after reaction 24h, suction filtration, obtain medlin particulate, be placed in dry 24h under 200 ℃ of vacuum drying ovens.5% thermal weight loss temperature of this copolyimide particulate is 507.6 ℃, and the BET specific surface area is 116m 2g -1, the X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 17-18.

Claims (4)

1. the medlin particulate of a fatty chain structure is characterized in that general formula of molecular structure is:
Figure FDA00003054662200011
In formula:
(1) n=2～12, the ratio of X and Y are (99～1): (1～99);
(2) Ar 1, Ar 2Be respectively and be selected from one or more in the following structural formula group and Ar 1, Ar 2Can be identical or different:
Figure FDA00003054662200012
Wherein, R 1～R 24Be respectively hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms and be 1～4 alkyl or allyl group; R 25Be selected from one or more in following radicals:
-CO-、-O-、-S-、-SO 2-、-CH 2-、-C(CH 3) 2-、-C(CF 3) 2-、-O-R 26-O-
R wherein 26Any in the following structural formula group:
Figure FDA00003054662200013
Wherein, R 27～R 121Be respectively hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms and be 1～4 alkyl or allyl group.
(3) Ar3 is selected from any in following structural formula:
Figure FDA00003054662200021
Wherein, R 122～R 280Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms are 1～4 alkyl or allyl group; R 281Be selected from a kind of in following radicals:
Figure FDA00003054662200022
-CONH-、-CO-、-O-、-S-、-S-S-、-SO 2-、-CH 2-、-C(CH 3) 2-、-C(CF 3) 2-、-O-R 304-O-
Wherein, R 282～R 303Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms and be 1～4 alkyl or allyl group; R 304Be selected from a kind of in following radicals:
Figure FDA00003054662200031
Wherein, R 305～R 376Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonatoms and be 1～4 alkyl or allyl group.
2. the medlin particulate of fatty chain structure claimed in claim 1 is in the application of preparation microelectronic product.
3. the medlin particulate of fatty chain structure claimed in claim 1 is in the application of preparation liquid-crystal display.
4. the medlin particulate of fatty chain structure claimed in claim 1 is in effective presoma of preparation carbon material and the application of catalysis, encapsulation, controllable release and filler.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6057379A (en) * 1998-07-25 2000-05-02 Korea Research Institute Of Chemical Technology Method of preparing polyimide foam with excellent flexibility properties
CN101089030A (en) * 2007-06-18 2007-12-19 南京工业大学 Prepn process of polyimide microsphere
CN101230136A (en) * 2007-01-22 2008-07-30 东丽纤维研究所（中国）有限公司 Polyimide microparticle and preparation method thereof
CN102690415A (en) * 2012-06-05 2012-09-26 中国科学院化学研究所 Polyimide microspheres and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6057379A (en) * 1998-07-25 2000-05-02 Korea Research Institute Of Chemical Technology Method of preparing polyimide foam with excellent flexibility properties
CN101230136A (en) * 2007-01-22 2008-07-30 东丽纤维研究所（中国）有限公司 Polyimide microparticle and preparation method thereof
CN101089030A (en) * 2007-06-18 2007-12-19 南京工业大学 Prepn process of polyimide microsphere
CN102690415A (en) * 2012-06-05 2012-09-26 中国科学院化学研究所 Polyimide microspheres and preparation method and application thereof

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