CN104072770B - A kind of foaming fluorinated polyimide and foam preparation processes thereof - Google Patents
A kind of foaming fluorinated polyimide and foam preparation processes thereof Download PDFInfo
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Abstract
The invention discloses a kind of foaming fluorinated polyimide and foam preparation processes thereof, belong to polyimide foam and foam preparation field thereof, wherein foam the preparation method of fluorinated polyimide, comprises the following steps successively: in reactor, add the fluorinated diamine being dissolved in organic solvent, fluorine-containing dianhydride and end-capping reagent; Reaction solution heats up, and adds organic bases and stirs; Reaction solution decompression dehydration.Foaming fluorinated polyimide prepared by aforementioned preparation process, the preparation method of further fluorinated polyimide foam, by the fluorinated polyimide of aforementioned preparation through microwave setting foaming, fluorinated polyimide foam is made in ambient cure.Foam precursors solution excellent storage stability prepared by the present invention, adapt to pour into a mould, spray, the complete processing such as to extrude.The foam made has that density is light and rate of moisture absorption is extremely low, do not need interpolation plasticized modifier, and polyimide foam toughness is better.
Description
Technical field
The invention belongs to polyimide foam and foam preparation field thereof.
Background technology
Polyimide is the polymkeric substance that a kind of thermotolerance is fabulous, has good mechanics and electrical property and radiation hardness and corrosion resistance nature, is widely used in the fields such as aerospace, military affairs, electronics.The polyimide material of foamy structure not only maintains the heatproof of unmodified resin excellence, the performance such as fire-retardant, also there is outstanding wave transparent characteristic and the over-all properties such as light, the flexible resilience of quality is good, easy to use, therefore in military equipment, have extremely important purposes.Compared with the material such as polystyrene foam, polyvinyl chloride foam, polyurethane foam accounting for leading market status in early days, in fire-retardant, it has special excellent victory energy, and it is lightweight, rigidity is large, good stability of the dimension, resistance to chemical attack, good heat resistance, difficult combustion, from putting out, low smog, flame resistant penetrates, meet fire without unrestrained thing, moderate; Therefore be the ideal insulated heat lagging material of the industries such as electronics, building, petrochemical complex, aerospace, attract widespread attention.At present, polyimide foam has become one of kind with fastest developing speed in porous plastics, and consumption constantly increases, and range of application constantly expands, and research and development is all quite active both at home and abroad.
Polyimide foam is divided into hard polyimide and soft polyimide, and such as hard polyimide many employings benzophenone tetracarboxylic dianhydride, diamine and whipping agent form through foaming.And some soft thermoplastic polyimide foam uses thermoplastic polyimide powder to add whipping agent in high temperature foaming to form, the equal Uniform of abscess and the less stable of technique; The resistance to elevated temperatures of foam is also poor.And some polyimide foams directly use the esterification solution of two acid anhydride and isocyanate reaction slaking to obtain, the mechanical property of foam is poor.
A kind of novel fire resistant polyimide foam disclosed in CN101402795A, it is also by by two acid anhydride esterification, and the method adding active diamine in solution, to produce powder performed polymer, produces polyimide foam by two-step approach, and this foam is rigid foam, density is 100-500kg/m
3, be not suitable for low-density foam production.
CN101402743A is disclosed a kind of to be mixed in proportion reaction in polar solvent to be formed foam precursors solution by aromatic dianhydride and/or aromatic esters, low mass molecule alcohol, catalyzer, tensio-active agent, precursor solution and isocyanic ester react in mould, free foaming forms foam intermediate, again through microwave radiation or/and baking oven for heating solidification after obtain solid polyimide foam, solvent low mass molecule alcohol residual in reaction and whipping agent tolylene diisocyanate etc. reduce the fire-retardant of foam and temperature tolerance, later stage needs hot setting energy consumption to increase, and uses limited.
Because existing polyimide foam density is all greater than 5kg/m
3, aperture is comparatively large, and rate of moisture absorption is higher.Polyimide foam enbrittles greatly, intensity and toughness is poor, the shortcoming of high opening rate, in use easily comes off, and easily falls slag when boring cuts.In addition, bigger than normal for the polyimide resin free monomers content foamed, cause polyimide foam body smell large, in processing and application process, all can cause certain influence to environment and human body.In addition, polyimide foam percentage of open area is higher, easily absorbs water.These shortcomings all limit the application of polyimide foam.Therefore, many countries have all carried out about can the correlative study of polyimide foam modification in the world.
The method improving polyimide foam toughness is generally adopt to add toughening component in polyimide resin foaming process, although adding of various toughening component improves to the toughness of foam, but reduces the performances such as the flame retardant resistance of polyimide foam.Adding of a large amount of toughening component also can affect foam microtexture, and make foamed open cell rate, aperture increase, thermal conductivity increases, thus has influence on the heat-proof quality of foam.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, a kind of high-foaming fluorinated polyimide is proposed, and the preparation method of this foaming fluorinated polyimide and foam thereof, the foam precursors solution excellent storage stability of preparation, adapt to pour into a mould, spray, the complete processing such as to extrude.Process route is short, and technique is simple, and gel time is short, ambient cure after microwave foaming, there will not be to split steep and steep, subside and the halfway defect of material imidization, and preparation cost is low; Adopt this fluorinated polyimide to utilize solvent to foam, need not foam supplementary additive, and the foam made has that density is light and rate of moisture absorption is extremely low, do not need interpolation plasticized modifier, and polyimide foam toughness is better.
The object of the invention is realized by following technical proposals:
Foam the preparation method of fluorinated polyimide, comprises the following steps successively:
A, in reactor, add the fluorinated diamine being dissolved in organic solvent, fluorine-containing dianhydride and end-capping reagent, mol ratio is fluorinated diamine: fluorine-containing dianhydride: end-capping reagent=1:1:0.1, at 5 ~ 10 DEG C, and stirring reaction 5 ~ 8 hours;
In b, step a, reaction solution is warming up to 10 ~ 20 DEG C, and adding organic bases, to be stirred to pH value be 6.0 ~ 8.0;
The reaction solution decompression dehydration of c, step b, at 50 ~ 60 DEG C, viscosity is 5000 ~ 6000mPa.s.
As selection, described step c is specially: the reaction solution of step b is stopped dehydration at vacuum tightness 0.080 ~ 0.082MPa, 50 ~ 60 DEG C of water-bath decompression dehydrations to during viscosity 5000 ~ 6000mPa.s.
As selection, described fluorinated diamine is selected from the one in two (3-amino-4-hydroxylphenyl) HFC-236fa of 2,2'-, two (trifluoromethyl) biphenyl of 3,3'-diamino-5,5'-, 4,4'-diamino octafluoro base biphenyl.
As selection, described fluorine-containing dianhydride is selected from the one in 4,4'-(hexafluoro isopropyl) two O-phthalic acid dianhydride, Isosorbide-5-Nitrae-bis-(trifluoromethyl)-2,3,5,6-benzene tertacarbonic acid's dianhydride, Isosorbide-5-Nitrae-difluoro pyromellitic acid anhydride.
As selection, described end-capping reagent is selected from the one in 4-phenylacetylene base phthalic anhydride aniline, Tetra hydro Phthalic anhydride, 4-phenylacetylene base aniline, 5-norbornylene-2,3-dicarboxylic anhydride.
As selection, described organic bases is selected from the one of 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene, 1,5-diazabicylo [5.4.0] 11 carbon-5-alkene.
As selection, described organic solvent is selected from the one in DMF (DMF), N,N-DIMETHYLACETAMIDE (DMAC).
The present invention also provides the foaming fluorinated polyimide prepared with aforementioned foaming fluorinated polyimide preparation method: in this fluorinated polyimide, water-content is for 0 ~ 10wt%, organic solvent content is 10 ~ 15wt%, gel time is 80 ~ 400s, and solid content is 75 ~ 85wt%.
The present invention also provides the preparation method preparing fluorinated polyimide foam with aforementioned foaming fluorinated polyimide preparation method: foamed through microwave by fluorinated polyimide prepared by aforementioned foaming fluorinated polyimide preparation method, fluorinated polyimide foam is made in ambient cure.
The main scheme of aforementioned the present invention and each further selection scheme thereof can independent assortment to form multiple scheme; be the present invention can adopt and claimed scheme: as the present invention; each selection can select arbitrary combination with other; those skilled in the art can understand there is multiple combination according to prior art and common practise after understanding the present invention program; be the claimed technical scheme of the present invention, do not do exhaustive at this.
The present inventor is after furtheing investigate the key factor of the polyimide foam affecting polyimide foam body foam performance, foam structure and pore size, using the research of raw material polyimide as focus, determining can the synthesis technique of foaming fluorinated polyimide of PhastGel, core achieves to control polyimide key index by adjustment polyimide raw material and synthesis condition, reaches the object accurately preparing the polyimide foam body of diverse microcosmic appearance.
Compared with prior art, the present invention is by controlling specific synthetic technological condition, make described the fluorinated polyimide of PhastGel can have high foaming and curing activity, avoid adding whipping agent in foaming process, thus keep the excellent heatproof of fluorinated polyimide, the performance such as fire-retardant.Simultaneously, adopt fluorine-containing raw material, the existence of fluorine element makes foam have extremely low rate of moisture absorption, density foam is low, microporous structure rule, the fine and smooth densification of abscess, outstanding wave transparent characteristic and the superperformance such as light, the flexible resilience of quality is good, easy to use, simultaneously again without the need to adding any plasticized modifier.In synthetic technological condition, as the proportionlity of reactant and temperature of reaction and time, guarantee that sufficient reacting completes, decrease product free monomers; Preferred diamines, dianhydride and end-capping reagent, and the mol ratio between three, more be conducive to the complete of fluorinated polyimide reaction, make in the fluorinated polyimide obtained containing lower residual monomer, to be conducive in the generation of follow-up polyimide foam foaming early stage steadily and sufficient nucleation, the hole gauge of foam is then tiny.In reaction, control ph is 6.0 ~ 8.0, while guarantee product storage period, controls product acid, is conducive to the PhastGel in follow-up foaming process, makes final foams aperture tiny.Final obtained fluorinated polyimide has following characteristics: water-content is 0 ~ 10wt%; Organic solvent content is 10 ~ 15wt%; Gel time is 80 ~ 400s; Solid content is 75 ~ 85wt%.Such fluorinated polyimide has the characteristic of PhastGel, can be cured by normal temperature again, simultaneously because free monomer is few, so smell is little, little on the impact of environment and human body.
Owing to using the high-foaming fluorinated polyimide of energy PhastGel to make foam, causing the density of this fluorinated polyimide foam lower is 3-4kg/m
3, the microporous structure rule of foam, the fine and smooth densification of abscess.Because aperture is little, the toughness of fluorinated polyimide foam is better, does not fall slag.
Beneficial effect of the present invention: the foam precursors solution excellent storage stability of preparation, adapt to pour into a mould, spray, the complete processing such as to extrude.Process route is short, and technique is simple, and gel time is short, ambient cure after microwave foaming, there will not be to split steep and steep, subside and the halfway defect of material imidization, and preparation cost is low; Adopt this fluorinated polyimide to utilize solvent to foam, need not foam supplementary additive, and the foam made has that density is light and rate of moisture absorption is extremely low, do not need interpolation plasticized modifier, and polyimide foam toughness is better.
Embodiment
Following non-limiting examples is for illustration of the present invention.
Embodiment 1:
Add successively by proportioning in the there-necked flask that mechanical stirring, thermometer, reflux exchanger are housed and be dissolved in N, 2 of N'-dimethyl formamide (DMF), two (3-amino-4-hydroxylphenyl) the HFC-236fa 36.6g (0.1mol) of 2'-, 4,4'-(hexafluoro isopropyl) two O-phthalic acid dianhydride 44.4g (0.1mol) and end-capping reagent 5-norbornylene-2,3-dicarboxylic anhydride 1.6g (0.01mol), stir lower liquid circulation and maintain reaction 10 DEG C of internal condensation reactions, about 5 hours total condensation reaction used times; System is warming up to 20 DEG C, adds organic bases 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU) and be neutralized to pH value 6.5; Solution system is stopped dehydration at vacuum tightness 0.080MPa, 60 DEG C of water-bath decompression dehydrations to during viscosity 5000mPa.s, and be cooled to 50 DEG C of dischargings, obtain fluorinated polyimide A, its performance index are listed in table 1.
By 100 weight part fluorinated polyimide A lower foaming fast in 10 minutes under 700W microwave condition, and carry out after fixing 2 hours in room temperature placement, prepare fluorinated polyimide foams A-F, gained foam article is soft, the equal Uniform of structure, abscess is fine and smooth, apparent density 3.32kg/m
3, foam index is listed in table 2.
Embodiment 2:
Add successively by proportioning in the there-necked flask that mechanical stirring, thermometer, reflux exchanger are housed and be dissolved in N, 3 of N'-dimethyl formamide (DMF), 3'-diamino-5, two (trifluoromethyl) biphenyl 32.0g (0.1mol) of 5'-, 1, two (trifluoromethyl)-2 of 4-, 3,5,6-benzene tertacarbonic acid dianhydride 46.5g (0.1mol) and end-capping reagent 5-norbornylene-2,3-dicarboxylic anhydride 1.6g (0.01mol), stirs lower liquid circulation and maintains reaction 10 DEG C of internal condensation reactions, about 8 hours total condensation reaction used times; System is warming up to 20 DEG C, adds organic bases 1,5-diazabicylo [5.4.0] 11 carbon-5-alkene (DBN) and be neutralized to pH value 7.0; Resin system is stopped dehydration at vacuum tightness 0.082MPa, 50 DEG C of water-bath decompression dehydrations to during viscosity 6000mPa.s, and be cooled to 50 DEG C of dischargings, obtain fluorinated polyimide B, its performance index are listed in table 1.
By 100 weight part fluorinated polyimide B lower foaming fast in 10 minutes under 700W microwave condition, and carry out after fixing in room temperature placement, prepare fluorinated polyimide foams B-F, gained foam article is soft, the equal Uniform of structure, and abscess is fine and smooth, apparent density 3.61kg/m
3, foam index is listed in table 2.
Embodiment 3:
Add successively by proportioning in the there-necked flask that mechanical stirring, thermometer, reflux exchanger are housed and be dissolved in N, 2 of N'-dimethyl formamide (DMF), two (3-amino-4-hydroxylphenyl) the HFC-236fa 36.6g (0.1mol) of 2'-, 1,4-difluoro pyromellitic acid anhydride 42.7g (0.1mol) and end-capping reagent 5-norbornylene-2,3-dicarboxylic anhydride 1.6g (0.01mol), stir lower liquid circulation and maintain reaction 10 DEG C of internal condensation reactions, about 6.5 hours total condensation reaction used times; System is warming up to 20 DEG C, adds organic bases 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU) and be neutralized to pH value 6.5; Resin system is stopped dehydration at vacuum tightness 0.081MPa, 60 DEG C of water-bath decompression dehydrations to during viscosity 5800mPa.s, and be cooled to 50 DEG C of dischargings, obtain fluorinated polyimide C, its performance index are listed in table 1.
By 100 weight part fluorinated polyimide C fast lower foaming in 10 minutes under 700W microwave condition, and place in room temperature and within 2 hours, carry out after fixing, prepare fluorinated polyimide foams C-F, gained foam article is soft, the equal Uniform of structure, abscess is fine and smooth, apparent density 3.72kg/m
3, foam index is listed in table 2.
Comparative example 1:
Reaction times was less than 5 hours: add successively by proportioning in the there-necked flask that mechanical stirring, thermometer, reflux exchanger are housed and be dissolved in N, 2 of N'-dimethyl formamide (DMF), two (3-amino-4-hydroxylphenyl) the HFC-236fa 36.6g (0.1mol) of 2'-, 4,4'-(hexafluoro isopropyl) two O-phthalic acid dianhydride 44.4g (0.1mol) and end-capping reagent 5-norbornylene-2,3-dicarboxylic anhydride 1.6g (0.01mol), stir lower liquid circulation and maintain reaction 10 DEG C of internal condensation reactions, about 3.5 hours total condensation reaction used times; System is warming up to 20 DEG C, adds organic bases 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU) and be neutralized to pH value 6.5; Solution system is stopped dehydration at vacuum tightness 0.08MPa, 60 DEG C of water-bath decompression dehydrations to during viscosity 5000mPa.s, and be cooled to 50 DEG C of dischargings, obtain fluorinated polyimide D, its performance index are listed in table 1.
By 100 weight part polyimide A lower foaming fast in 10 minutes under 700W microwave condition, and carry out after fixing 2 hours in room temperature placement, prepare fluorinated polyimide foams D-F, apparent density 5.09kg/m
3, foam index lists in table 2.Because polycondensation reaction time is not enough, comparative example 1 fluorinated polyimide D free monomer content is high, and gel is slow, and foam D-F density is bigger than normal.
Comparative example 2:
Amine acid anhydride mol ratio is on the low side: add successively by proportioning in the there-necked flask that mechanical stirring, thermometer, reflux exchanger are housed and be dissolved in N, 3 of N'-dimethyl formamide (DMF), 3'-diamino-5, two (trifluoromethyl) biphenyl 38.4g (0.12mol) of 5'-, 1, two (trifluoromethyl)-2 of 4-, 3,5,6-benzene tertacarbonic acid dianhydride 46.5g (0.1mol) and end-capping reagent 5-norbornylene-2,3-dicarboxylic anhydride 1.6g (0.01mol), stirs lower liquid circulation and maintains reaction 10 DEG C of internal condensation reactions, about 8 hours total condensation reaction used times; System is warming up to 20 DEG C, adds organic bases and be neutralized to pH value 6.5; Resin system is stopped dehydration at vacuum tightness 0.082MPa, 50 DEG C of water-bath decompression dehydrations to during viscosity 6000mPa.s, and be cooled to 50 DEG C of dischargings, obtain fluorinated polyimide E, its performance index are listed in table 1.
By 100 weight part fluorinated polyimide B lower foaming fast in 10 minutes under 700W microwave condition, and carry out after fixing 2 hours in room temperature placement, prepare fluorinated polyimide foams E-F, apparent density 4.96kg/m
3, foam index is listed in table 2.
Because amine acid anhydride mol ratio is on the low side, comparative example 2 fluorinated polyimide E free amine content is high, and during foaming, thermal discharge is large in earlier stage, is unfavorable for nucleation, and foam cell is thick, and fragility is large.
Comparative example 3:
With insufficient in resin: add successively by proportioning in the there-necked flask that mechanical stirring, thermometer, reflux exchanger are housed and be dissolved in N, 2 of N'-dimethyl formamide (DMF), two (3-amino-4-hydroxylphenyl) the HFC-236fa 36.6g (0.1mol) of 2'-, 1,4-difluoro pyromellitic acid anhydride 42.7g (0.1mol) and end-capping reagent 5-norbornylene-2,3-dicarboxylic anhydride 1.6g (0.01mol), stir lower liquid circulation and maintain reaction 10 DEG C of internal condensation reactions, about 6.5 hours total condensation reaction used times; System is warming up to 20 DEG C, adds organic bases 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU) and be neutralized to pH value 8.6; Resin system is stopped dehydration at vacuum tightness 0.081MPa, 60 DEG C of water-bath decompression dehydrations to during viscosity 5600mPa.s, and be cooled to 30 DEG C of dischargings, obtain polyimide F, its performance index are listed in table 1.
By 100 weight part fluorinated polyimide F lower foaming fast in 10 minutes under 700W microwave condition, and carry out after fixing 2 hours in room temperature placement, prepare fluorinated polyimide foams F-F, apparent density 5.70kg/m
3, foam index is listed in table 2.
Because reaction solution degree of neutralization is inadequate, comparative example 3 fluorinated polyimide F foaming activity is low, and foams F-F aperture is large.
Table 1
Table 2
| Polyimide foam | A-F | B-F | C-F | D-F | E-F | F-F |
| Apparent density/kg/m 3 | 3.32 | 3.61 | 3.72 | 5.09 | 4.96 | 5.70 |
| Mean pore size/μm | 55.36 | 50.07 | 56.09 | 101.11 | 134.6 | 87.30 |
| Line ball intensity (50%, KPa) 6 | 7.957 | 7.308 | 7.544 | 4.639 | 5.15 | 4.66 |
| Thermal conductivity (mk) | 0.037 | 0.037 | 0.038 | 0.039 | 0.040 | 0.039 |
| Rate of moisture absorption (%) | 0.42 | 0.38 | 0.41 | 2.35 | 3.15 | 2.13 |
| Tensile strength (KPa) | 85.33 | 83.45 | 82.36 | 63.02 | 51.406 | 49.33 |
As shown in table 1: comparative example 1 reaction times, because polycondensation reaction time is not enough, comparative example 1 fluorinated polyimide D free monomer content was high, and gel is slow, and foam D-F aperture is large less than 5 hours.Comparative example 2 amine acid anhydride mol ratio is on the low side, and fluorinated polyimide E free phenol content is high, and during foaming, thermal discharge is large in earlier stage, is unfavorable for nucleation, and foam cell is thick, and fragility is large.With insufficient in comparative example 3 reaction solution, fluorinated polyimide F foaming activity is low, and foams F-F aperture is large.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. foam the preparation method of fluorinated polyimide, it is characterized in that comprising the following steps successively:
A, in reactor, add the fluorinated diamine being dissolved in organic solvent, fluorine-containing dianhydride and end-capping reagent, mol ratio is fluorinated diamine: fluorine-containing dianhydride: end-capping reagent=1:1:0.1, at 5 ~ 10 DEG C, and stirring reaction 5 ~ 8 hours;
In b, step a, reaction solution is warming up to 10 ~ 20 DEG C, and adding organic bases, to be stirred to pH value be 6.0 ~ 8.0;
The reaction solution decompression dehydration of c, step b, at 50 ~ 60 DEG C, viscosity is 5000 ~ 6000mPa.s.
2. the preparation method of foaming fluorinated polyimide as claimed in claim 1, is characterized in that: described step c is specially: the reaction solution of step b is stopped dehydration at vacuum tightness 0.080 ~ 0.082MPa, 50 ~ 60 DEG C of water-bath decompression dehydrations to during viscosity 5000 ~ 6000mPa.s.
3. the preparation method of foaming fluorinated polyimide as claimed in claim 1 or 2, it is characterized in that: described fluorinated diamine is selected from 2, two (3-amino-4-hydroxylphenyl) HFC-236fa, 3 of 2'-, 3'-diamino-5, one in two (trifluoromethyl) biphenyl of 5'-, 4,4'-diamino octafluoro base biphenyl.
4. the preparation method of foaming fluorinated polyimide as claimed in claim 1 or 2, it is characterized in that: described fluorine-containing dianhydride is selected from 4,4'-(hexafluoro isopropyl) two O-phthalic acid dianhydride, 1, two (trifluoromethyl)-2 of 4-, 3, one in 5,6-benzene tertacarbonic acid dianhydride, Isosorbide-5-Nitrae-difluoro pyromellitic acid anhydride.
5. the preparation method of foaming fluorinated polyimide as claimed in claim 1 or 2, is characterized in that: described end-capping reagent is selected from the one in Tetra hydro Phthalic anhydride, 4-phenylacetylene base aniline, 5-norbornylene-2,3-dicarboxylic anhydride.
6. the preparation method of foaming fluorinated polyimide as claimed in claim 1 or 2, is characterized in that: described organic bases is 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene.
7. the preparation method of foaming fluorinated polyimide as claimed in claim 1 or 2, is characterized in that: described organic solvent is selected from the one in DMF, N,N-DIMETHYLACETAMIDE.
8. foaming fluorinated polyimide prepared by the foaming fluorinated polyimide preparation method described in a claim 1 or 2, it is characterized in that: in this fluorinated polyimide, water-content is 0 ~ 10wt%, organic solvent content is 10 ~ 15wt%, gel time is 80 ~ 400s, and solid content is 75 ~ 85wt%.
9. a preparation method for fluorinated polyimide foam, is characterized in that: by fluorinated polyimide described in claim 8 through microwave setting foaming, fluorinated polyimide foam is made in ambient cure.
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| CN115028835A (en) * | 2021-03-03 | 2022-09-09 | 中国科学院大连化学物理研究所 | Hydrophobic polyimide foam and preparation method thereof |
| CN113072699B (en) * | 2021-03-09 | 2022-03-01 | 东莞市华盈新材料有限公司 | Low-hygroscopicity PA10T and synthesis method thereof |
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| CN101058639A (en) * | 2006-04-19 | 2007-10-24 | 中国科学院化学研究所 | Fluorine-containing polyimide basal body resin and preparation method thereof |
| CN101062980A (en) * | 2006-04-28 | 2007-10-31 | 中国科学院化学研究所 | Fluorine-containing thermoplastic polyimide polymer and preparation method thereof |
| CN101402795A (en) * | 2008-11-19 | 2009-04-08 | 北京航空航天大学 | Novel fire resistant polyimide foam and method of producing the same |
| CN102775789A (en) * | 2012-08-15 | 2012-11-14 | 自贡天龙化工有限公司 | Thermosetting compound fluorine-containing polyimide resin and preparation method thereof |
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