CN1528808A - Method for preparing polyimide foam by polyether couple precuror process - Google Patents
Method for preparing polyimide foam by polyether couple precuror process Download PDFInfo
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- CN1528808A CN1528808A CNA031434193A CN03143419A CN1528808A CN 1528808 A CN1528808 A CN 1528808A CN A031434193 A CNA031434193 A CN A031434193A CN 03143419 A CN03143419 A CN 03143419A CN 1528808 A CN1528808 A CN 1528808A
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Abstract
The invention discloses a method to prepare polyimide foam in the course that polyether is coupled with precursor. It makes aromatic dianhydride react with monohydroxy polyether and small molecular alcohol at 60-90 deg.C, to obtain aromatic diacid diester solution, then adds in aromatic diamine and small molecular ether to fully react at 50-80 deg.C, adds in foam stabilizer and strengthener; eliminates superfluous alcohol and small molecular ether to obtain polyether-coupled monomer precursor powder; places the powder in mould, preheats and foams at 70-180 deg.C, and solidifies at high temperature of 200-450 deg.C to obtain the polyimide foam which has closed cell structure and density 0.01-0.5g/cu cm.
Description
Technical field
The present invention relates to the preparation method of polymeric foamed material, relate in particular to the method that a kind of polyethers coupling precursor process prepares polyimide foam.
Background technology
Foam of polymers is because density is low, and light weight is usually used in fields such as thermal insulation, sound insulation, damping.Commonly used to have with polyolefine, urethane and phenolic aldehyde be the first-generation, the s-generation foam of polymers of matter material, but the intensity of these materials, temperature tolerance, physics and chemical stability, non-flame properties etc. can not satisfy the requirement of some special dimensions.Typical polyimide is the polymkeric substance that contains aromatic ring, heterocycle structure, it is the material that has best over-all properties at aspects such as intensity, high temperature resistant/low temperature, insulation, chemically stable, radioprotectives that a class is generally acknowledged, can be used as synthon, tackiness agent, coating-forming agent, film, composite matrix resin and dielectric materials, especially performances such as its outstanding high strength, heatproof and easy processing make aspects such as its metal-metal in fields such as Aeronautics and Astronautics, engineering is bonding, Composite Preparation that the incomparable effect of other polymkeric substance be arranged.Because under the high-lighting of polyimide can keep in the foam materials that with the polyimide is the matter material, polyimide foam is in gradually and rises the stage as having the light material that high strength, high temperature resistant/low temperature, the fire resistive third generation are heat insulation, insulate against sound.
The polyimide foam preparation method has following several:
US 4,241, and 114; 4,273,886; 4,305,796 by heating polyimide oligomers in hot stove or microwave oven, prepare polyimide foam, and the problem of this method is that chainpropagation is carried out simultaneously with foaming, is difficult to the physicals of control foam.
US 4,806, and 573; 4,824,874; 4,830,883 usefulness benzophenone tetracarboxylic dianhydrides, isocyanic ester, furfural prepare polyimide precursor, obtain the foamy structure of perforate, are mainly used in sound absorbent material.
US 3,483, and 144 will be dissolved in the diamines under dicarboxylic anhydride or the tetracarboxylic acid molten state, and the water that utilizes the condensation reaction generation makes flux foaming as whipping agent, the preparation polyimide foam.
US 4,900, and 761; 5,077,183; 5,122,546; 5,298,531 by being dissolved in diamines, dianhydride in the low-molecular-weight alcoholic solvent, adds whipping agent, and imidization forms polyimide foam.In this way, whipping agent can remain in the final froth product.
In the above-mentioned method for preparing polyimide foam, can't provide the polyimide foam of wide density range, it is also wayward to obtain foamy density and even aperture distribution.The foam that the precursor of use isocyanic ester obtains, poor stability, facile hydrolysis and easily decomposition; Open-celled structure content is higher in the foam, causes the infiltration of steam to reduce its heat-proof quality easily, runs into fire and high-temperature shrinkage rate height.Thereby improving unicellular structure content, improving even aperture distribution and maintenance morphological stability etc. is the main direction of the development of polyimide foam material preparation technology.
Summary of the invention
The purpose of this invention is to provide the method that a kind of polyethers coupling precursor process prepares polyimide foam.
Its step is as follows:
1) aromatic dianhydride and monohydroxy polyethers and small molecular alcohol are formed esterification solution, form aromatic diacid two ester solutions;
2) in aromatic diacid two ester solutions, add the aromatic diamines reaction, add small molecules ether, suds-stabilizing agent, reinforcing filler again, remove the polyimide precursor powder that obtains the saloid structure of polyethers link coupled after desolvating;
3) the saloid structure polyimide precursor of polyethers link coupled powder is put into metal or ceramic die, heating makes the precursor powder foaming; The shape of the shape control foam by mould, the add-on by regulating precursor powder and the density of the ratio control foam of mold volumes obtain the polyimide tiny balloon under bigger blowing ratio;
4) imidization under higher temperature, sclerosis obtain polyimide foam or microballoon.
Advantage of the present invention is:
1) terminal hydroxy group of polyethers and two anhydride reactants form ester bond, be not only a kind of and the coupling agent monomer precursor stable bond, and polyethers has long molecular chain, be that two acid diesters and diamines interact, form bigger and stable template in the reaction of monomer precursor, with respect to small molecules ether coupling agent, the polyimide monomer precursor that obtains has better stability and compound with regular structure.
2) existence of polyethers long-chain can further make between the monomer precursor form crosslinked, help forming in the polyimide molecule spacial framework, monomer precursor can be foamed in wide temperature range, the foam that obtains has better stability, has improved the homogeneity in aperture in the polyimide foam.
3) foamable and imidization under negative pressure state, help fully foaming and improve the homogeneity of foaming, can be implemented in imidization and sclerosis under the higher temperature simultaneously, and the decomposition or the charing of polyimide can not take place, help improving the physical strength of polyimide foam.
Embodiment
The method that polyethers coupling precursor process prepares polyimide foam is: at first 1 mole of aromatic dianhydride and the 10-100 mole small molecular alcohol that contains the monohydroxy polyethers are fully reacted down at 60-90 ℃, obtained aromatic diacid two ester solutions in esterification 2-10 hour, in above-mentioned solution, add 1 mole of aromatic diamines, small molecules ether, 50-80 ℃ was reacted 1-6 hour, and obtained homogeneous polyethers link coupled " saloid " structure polyimide precursor solution; In this precursor solution, add suds-stabilizing agent and reinforcing filler, mix, then this mixture heating up drying or spraying drying are removed excessive small molecular alcohol and ether, obtain the polyimide precursor powder of saloid structure.In case of necessity, by grinding and sieve the precursor powder that needing to obtain granularity.
Precursor powder is put into the electrically heated metal die of different structure or the ceramic die of microwave heating, and in 70-180 ℃ of foaming down, 200-450 ℃ following imidization, sclerosis, according to the structure of mould, the demoulding obtains sheet, tubular polyimide foam.According to the density of precursor powder add-on with the ratio control foam of mold volumes.During precursor powder and mold volumes bigger, the demoulding is after fragmentation obtains the polyimide tiny balloon.
Being used for aromatic dianhydride of the present invention is: 1,2,4, and 5-pyromellitic acid dianhydride, 3,3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-the benzophenone tetracarboxylic dianhydride.
Being used for aromatic diamines of the present invention is: Ursol D, 4.
Main body composition-the polyimide of polyimide foam-come from the polycondensation of aromatic dianhydride and aromatic diamines, residues such as the small molecular alcohol in the precursor, polyethers are removed in the imidization process.For guaranteeing that polyimide has the intensity of sufficiently high molecular weight and polyimide foam, when the preparation precursor, the amount of aromatic dianhydride and aromatic diamines with etc. stoichiometry to use be the best.
Adopt the effect of monohydroxy polyethers to have two, one among the present invention, be used as the template of monomer precursor, the 2nd, improve the stability of foaming.Said monohydroxy polyethers comprises monohydroxy end group polyethylene oxide, poly(propylene oxide), comprises that molecular weight is that polyethylene oxide, the molecular weight of 200-5000 is the poly(propylene oxide) of 500-10000, and consumption is the 1-20% of polyimide.
The effect that is used for small molecular alcohol of the present invention has three, one, forms the aromatic diacid diester with the aromatic dianhydride reaction, and the 2nd, as one of solvent for preparing polyethers coupling monomer precursor, the 3rd, as main foaming agent.Said small molecular alcohol molecular formula is: ROH, wherein R be carbon number in the straight chained alkyl below 5, branched-chain alkyl or cycloalkyl, comprise methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, primary isoamyl alcohol and furfuryl alcohol.Preferred methyl alcohol and the ethanol of using most preferably uses methyl alcohol.
The small molecules ether that uses among the present invention is second solvent, second coupling agent and second whipping agent.Said small molecules ether comprises tetrahydrofuran (THF), ring amyl ether, 1,2-glycol dimethyl ether, methyl ethyl ether.
The suds-stabilizing agent that is used for the present invention is a polysiloxane, and effect is stability, micropore size and the distributing homogeneity that further improves foaming.The consumption of suds-stabilizing agent is the 1-6% of aromatic dianhydride and aromatic diamines gross weight.Preferred 2.5-3%.
The effect that is used for reinforcing filler of the present invention is to improve the foamy physical strength.Said reinforcing filler comprises polyimide fiber, glass fibre, carbon fiber; Add-on is the 0.5-20% of polyimide, and the adding mode is directly to add in the dry preceding precursor solution.
Except that adopting small molecular alcohol, small molecules ether to do the whipping agent, no longer add other physics, chemical foaming agent in the inventive method.
Following embodiment is done more detailed description to the present invention, but described embodiment is not construed as limiting the invention.
Embodiment 1
1) preparation of precursor
With 21.8 gram (0.1 moles) 1,2,4, the 5-pyromellitic acid dianhydride joins in 250 milliliters of reactors that agitator, temperature control meter, prolong be housed, adding in this reactor and containing 4.5 gram molecular weights is 1200 monohydroxy poly(propylene oxide), 100 gram methanol mixture, and 70-75 ℃ of reflux continues reaction 4 hours to the clear back of solution becomes, in this solution, add 20 gram tetrahydrofuran (THF)s then, stirred 1 hour down at 65-70 ℃.Solution is chilled to below 50 ℃, adds 20.1 gram (0.1 mole) 4,55-60 ℃ of following stirring reaction 4 hours, in reaction mixture, add 1.5 gram polysiloxane then, stirred 2 hours under the room temperature, obtain the saloid precursor solution of homogeneous polyimide.This solution is added excessive small molecular alcohol of heat extraction and small molecules ether in 70 ℃, be cooled to room temperature, wear into fine powder, obtain the saloid precursor powder of polyimide.
2) foaming and sclerosis
Mould: tubulose, inside cavity are of a size of 2.0 centimetres of internal diameters, 4.0 centimetres of external diameters, 15.0 centimetres of length; Material is the stainless steel that has ventilative micropore.
The saloid precursor powder of the polyimide that obtains 15.3 grams are placed above-mentioned stainless steel mould, state pressure be under the negative pressure of 25-50 centimeter mercury column in energising heat, controlled temperature is 100 ℃, keeps 50 minutes, again in 230 ℃ of constant temperature 50 minutes.Mould is taken out, put into 350 ℃ of hot stove heating 60 minutes.After the cooling, open mould, obtain the piped polyimide foam.
Embodiment 2
1) preparation of precursor
With embodiment 1
2) foaming and sclerosis
Mould: rectangular parallelepiped, cavity size are 5.0 centimetres of 8.0 cm x, 8.0 cm x, and material is a permeable-gas ceramics.
With saloid precursor powder 0.3 gram of the polyimide that obtains, put into above-mentioned ceramic die after the grinding.It is 25 centimeter mercury column subnormal ambients that mould is put into pressure, heats 30 minutes down at 1 kilowatt earlier with microwave oven, again with 2 kilowatts of heating 50 minutes.After the cooling, open mould, promptly obtain polyimide microsphere.
Embodiment 3
1) preparation of precursor
With 29.4 gram (0.1 moles) 3,3 ', 4,4 '-BPDA joins in 250 milliliters of reactors that agitator, temperature control meter, prolong be housed, adding in this reactor and containing 5 gram molecular weights is 2000 monohydroxy polyethylene oxide, 110 gram methanol mixture, and 70-75 ℃ of following reflux continues reaction 4 hours to the clear back of solution becomes, in this solution, add 20 gram tetrahydrofuran (THF)s then, stirred 1 hour at 65-70 ℃.Solution is chilled to below 50 ℃, adds 20.1 gram (0.1 mole) 4, in 55-60 ℃ of reaction 3 hours, in reaction mixture, add 1.5 gram polysiloxane then, stirred 1 hour under the room temperature, obtain the saloid precursor solution of homogeneous polyimide.This solution is removed excessive small molecular alcohol and small molecules ether in 60 ℃ of spraying dryings, obtain the saloid precursor powder of polyimide.
2) foaming and sclerosis
Mould: cavity size is 2.0 centimetres of 8.0 cm x, 8.0 cm x, and material is a permeable-gas ceramics.
In above-mentioned ceramic die, put into saloid precursor powder 22.7 grams of polyimide, place microwave oven to heat on mould, earlier with 1 kilowatt of heating 120 minutes, again with 2 kilowatts of heating 90 minutes.After the cooling, mould is put into 400 ℃ of hot stove heating 60 minutes, can obtain flaky polyimide foam.
Embodiment 4
1) preparation of precursor
With embodiment 3
2) foaming and sclerosis
Mould is with embodiment 2
With saloid precursor powder 65 grams of polyimide, put into embodiment 2 described ceramic dies.At pressure is under the negative pressure of 25-50 centimeter mercury column, with the microwave oven heating, earlier with 1 kilowatt of heating 30 minutes, again with 2 kilowatts of heating 50 minutes.Again with mould 350 ℃ of constant temperature 90 minutes, can arrive blocky polyimide foam.
Embodiment 5
1) preparation of precursor
With 32.2 gram (0.1 moles) 3,3 ', 4,4 '-the benzophenone tetracarboxylic dianhydride joins in 250 milliliters of reactors that agitator, temperature control meter, prolong be housed, adding in this reactor and containing 4.5 gram molecular weights is 1200 monohydroxy poly(propylene oxide), 100 gram methanol mixture, and 70-75 ℃ of following reflux continues reaction 4 hours to the clear back of solution becomes, in this solution, add 20 gram tetrahydrofuran (THF)s then, stirred 1 hour at 65-70 ℃.Solution is chilled to below 50 ℃, adds 10.8 gram (0.1 mole) Ursol D,, in reaction mixture, add 1.5 gram polysiloxane then, stirred 2 hours under the room temperature, obtain the saloid precursor solution of homogeneous polyimide 55-60 ℃ of reaction 3 hours.Add short glass fiber 2.1 grams in this solution, the back that stirs adds excessive small molecular alcohol of heat extraction and small molecules ether in 70 ℃, is cooled to room temperature, wears into fine powder, obtains the saloid precursor powder of polyimide.
2) foaming and sclerosis
Mould is with embodiment 2
Taking by weighing saloid precursor powder 35.5 grams of polyimide, put into embodiment 2 described ceramic dies, is under the negative pressure of 25-50 centimeter mercury column at pressure, with the microwave oven heating, earlier with 1 kilowatt of heating 30 minutes, again with 2 kilowatts of heating 50 minutes.Again with mould 350 ℃ of constant temperature 90 minutes, can arrive blocky polyimide foam.
Embodiment 6
1) preparation of precursor
With 29.4 gram (0.1 moles) 3,3 ', 4,4 '-BPDA joins in 250 milliliters of reactors that agitator, temperature control centimetre meter, prolong be housed, adding in this reactor and containing 5 gram molecular weights is 2500 monohydroxy poly(propylene oxide)s, 110 gram methanol mixture, and 70-75 ℃ of following reflux continues reaction 4 hours to the clear back of solution becomes, in this solution, add 20 gram tetrahydrofuran (THF)s then, be that 65-70 ℃ was stirred 1 hour down.Solution is chilled to below 50 ℃, adds 20.1 gram (0.1 mole) 4, be 55-60 ℃ of following stirring reaction 3 hours, in reaction mixture, add 1.5 gram polysiloxane then, stirred 1 hour under the room temperature, obtain the saloid precursor solution of homogeneous polyimide.Add 2.1 gram carbon fibers in this solution, the back that stirs obtains the saloid precursor powder of polyimide in 70 ℃ of spraying dryings.
2) foaming and sclerosis
Mould: cavity size is 2.0 centimetres of 8.0 cm x, 8.0 cm x, and material is the stainless steel of the ventilative micropore of band.
The saloid precursor powder of polyimide 36.5 grams are placed above-mentioned stainless steel mould, the energising heating, controlled temperature is 100 ℃ and kept 120 minutes, again in 250 ℃ of constant temperature 60 minutes, 350 ℃ of constant temperature 50 minutes.After the cooling, open mould, obtain blocky polyimide foam.
Embodiment 7
1) preparation of precursor
With embodiment 6
2) foaming and sclerosis
Mould is with embodiment 1
The saloid precursor powder of 45 gram polyimide is placed stainless steel mould, the energising heating.Controlled temperature is 100 ℃ and kept 120 minutes, again in 250 ℃ of constant temperature 60 minutes, and 350 ℃ of constant temperature 50 minutes.After the cooling, open mould, obtain the piped polyimide foam.
Embodiment 8
1) preparation of precursor
With 21.8 gram (0.1 moles) 1,2,4, the 5-pyromellitic acid dianhydride joins in 250 milliliters of reactors that agitator, temperature control meter, prolong be housed, adding in this reactor and containing 4.5 gram molecular weights is 2000 monohydroxy polyethylene oxides, 100 gram methanol mixture, and 70-75 ℃ of following reflux continues reaction 4 hours to the clear back of solution becomes, in this solution, add 20 gram tetrahydrofuran (THF)s then, stirred 1 hour down at 165-70 ℃.Solution is chilled to 50 ℃, adds 10.8 gram (0.1 mole) Ursol D, be 60-65 ℃ of following stirring reaction 5 hours, in reaction mixture, add 1.0 gram polysiloxane then, stirred 2 hours under the room temperature, obtain the saloid precursor solution of homogeneous polyimide.In solution, add polyimide fiber 2.0 grams, this mixture 70 ℃ of heating, is removed excessive small molecular alcohol and small molecules ether, be cooled to room temperature, wear into fine powder, obtain the saloid precursor powder of polyimide.
2) foaming and sclerosis
Mould is with embodiment 2
Take by weighing the saloid precursor powder of 60 gram polyimide, put into embodiment 2 described ceramic dies.Place microwave oven to heat on mould, earlier with 1 kilowatt of heating 120 minutes, again with 2 kilowatts of heating 90 minutes.After the cooling, mould is put into 400 ℃ of hot stove heating 60 minutes, can obtain blocky polyimide foam.
Table one. polyimide foam structures of samples and performance
| The embodiment sample number | Apparent density (g/cm 3) | Mean pore size (mm) | Voidage (%) | Rate of closed hole (%) | Limiting oxygen index(LOI) (%) | 25 ℃ of thermal conductivitys (W/Km) | 25 ℃ of ultimate compression strength (MPa) |
| ????1 | ??0.09 | ????0.5 | ??13 | ????60 | ????50 | ????0.038 | ????8 |
| ????2 | ??- | ????0.8 | ??- | ????- | ????- | ????- | ????- |
| ????3 | ??0.15 | ????0.3 | ??15 | ????51 | ????48 | ????0.039 | ????10 |
| ????4 | ??0.07 | ????0.5 | ??8 | ????55 | ????46 | ????0.037 | ????83 |
| ????5 | ??0.09 | ????0.4 | ??11 | ????70 | ????48 | ????0.040 | ????22 |
| ????6 | ??0.25 | ????0.3 | ??22 | ????72 | ????50 | ????0.041 | ????35 |
| ????7 | ??0.31 | ????0.3 | ??25 | ????60 | ????48 | ????0.040 | ????30 |
| ????8 | ??0.14 | ????0.2 | ??17 | ????68 | ????51 | ????0.041 | ????25 |
Claims (7)
1. a polyethers coupling precursor process prepares the method for polyimide foam, and its feature is as follows:
1) aromatic dianhydride and monohydroxy polyethers, small molecular alcohol are formed esterification solution, form aromatic diacid two ester solutions;
2) add aromatic diamines, small molecules ether, suds-stabilizing agent, reinforcing filler in aromatic diacid two ester solutions, excessive solvent is removed in heating, obtains the saloid structure polyimide precursor of polyethers link coupled powder;
3) the polyimide precursor powder is put into mould, heating makes the precursor powder foaming;
4) imidization under higher temperature, sclerosis form polyimide foam.
2. a kind of polyethers coupling precursor process according to claim 1 prepares the method for polyimide foam, and it specifically is characterised in that:
At first 1 mole of aromatic dianhydride and monohydroxy polyethers, 10-100 mole small molecular alcohol are fully reacted at 60-90 ℃, obtain aromatic diacid two ester solutions; Add 1 mole of aromatic diamines and fully stir, add small molecules ether again, 50-80 ℃ of reaction obtains homogeneous polyethers link coupled polyimide precursor solution; In this solution, add suds-stabilizing agent and reinforcing filler, mix; The precursor mixture heat drying or the spraying drying that will contain suds-stabilizing agent and reinforcing filler are removed excessive small molecular alcohol and ether, obtain the saloid structure precursor powder of polyethers link coupled; Precursor powder is placed mould, and with electrically heated or microwave heating, in 70-180 ℃ of foaming down, 200-450 ℃ following imidization, sclerosis, the demoulding obtains polyimide foam.
3. a kind of polyethers coupling precursor process according to claim 1 prepares the method for polyimide foam, and it is characterized in that: said aromatic dianhydride is: 1,2,4,5-pyromellitic acid dianhydride, 3,3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-the benzophenone tetracarboxylic dianhydride.
4. a kind of polyethers coupling precursor process according to claim 1 prepares the method for polyimide foam, and it is characterized in that: said aromatic diamines is: Ursol D, 4.
5. a kind of polyethers coupling precursor process according to claim 1 prepares the method for polyimide foam, it is characterized in that: said monohydroxy polyethers is meant that molecular weight is that polyethylene oxide, the molecular weight of 200-5000 is the poly(propylene oxide) of 500-10000.
6. a kind of polyethers coupling precursor process according to claim 1 prepares the method for polyimide foam, and it is characterized in that: said polyimide foam comprises sheet, piped polyimide foam and polyimide tiny balloon.
7. a kind of polyethers coupling precursor process according to claim 1 prepares the method for polyimide foam, it is characterized in that: foaming, the imidization under normal pressure or condition of negative pressure of said foaming, imidization process.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03143419 CN1215107C (en) | 2003-09-27 | 2003-09-27 | Method for preparing polyimide foam by polyether couple precuror process |
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| CN 03143419 CN1215107C (en) | 2003-09-27 | 2003-09-27 | Method for preparing polyimide foam by polyether couple precuror process |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113209B (en) * | 2007-07-17 | 2010-08-25 | 北京航空航天大学 | Polysiloxane acid imide foam and method for preparing same |
| CN102618034A (en) * | 2012-03-24 | 2012-08-01 | 青岛海洋新材料科技有限公司 | Method for preparing polyether amine modified isocyanate group polyimide foam |
| CN102838745A (en) * | 2012-09-19 | 2012-12-26 | 中国科学院长春应用化学研究所 | Preparation method of polyimide foam |
| CN102850569A (en) * | 2012-09-20 | 2013-01-02 | 中国科学院长春应用化学研究所 | Preparation method of polyimide foam |
| CN103275319A (en) * | 2013-06-14 | 2013-09-04 | 中国科学院长春应用化学研究所 | Polyimide foam plastic and preparation method thereof |
| CN105308098A (en) * | 2014-05-28 | 2016-02-03 | 常州天晟新材料股份有限公司 | Method for continuously preparing solvent-free open-cell and closed-cell polyimide foam |
| CN106280447A (en) * | 2016-08-15 | 2017-01-04 | 瑞安市智造科技有限公司 | A kind of high resiliency antidetonation Polyimide foams and preparation method thereof |
| CN110028668A (en) * | 2019-04-25 | 2019-07-19 | 航天材料及工艺研究所 | A kind of preparation method of hard polyimide foaming material |
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| CN101402743B (en) * | 2008-11-25 | 2011-02-02 | 北京市射线应用研究中心 | Polyimide foam and method of producing the same |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113209B (en) * | 2007-07-17 | 2010-08-25 | 北京航空航天大学 | Polysiloxane acid imide foam and method for preparing same |
| CN102618034A (en) * | 2012-03-24 | 2012-08-01 | 青岛海洋新材料科技有限公司 | Method for preparing polyether amine modified isocyanate group polyimide foam |
| CN102618034B (en) * | 2012-03-24 | 2015-07-15 | 青岛海洋新材料科技有限公司 | Method for preparing polyether amine modified isocyanate group polyimide foam |
| CN102838745A (en) * | 2012-09-19 | 2012-12-26 | 中国科学院长春应用化学研究所 | Preparation method of polyimide foam |
| CN102838745B (en) * | 2012-09-19 | 2014-11-26 | 中国科学院长春应用化学研究所 | Preparation method of polyimide foam |
| CN102850569A (en) * | 2012-09-20 | 2013-01-02 | 中国科学院长春应用化学研究所 | Preparation method of polyimide foam |
| CN102850569B (en) * | 2012-09-20 | 2014-05-21 | 中国科学院长春应用化学研究所 | Preparation method of polyimide foam |
| CN103275319A (en) * | 2013-06-14 | 2013-09-04 | 中国科学院长春应用化学研究所 | Polyimide foam plastic and preparation method thereof |
| CN105308098A (en) * | 2014-05-28 | 2016-02-03 | 常州天晟新材料股份有限公司 | Method for continuously preparing solvent-free open-cell and closed-cell polyimide foam |
| CN106280447A (en) * | 2016-08-15 | 2017-01-04 | 瑞安市智造科技有限公司 | A kind of high resiliency antidetonation Polyimide foams and preparation method thereof |
| CN110028668A (en) * | 2019-04-25 | 2019-07-19 | 航天材料及工艺研究所 | A kind of preparation method of hard polyimide foaming material |
| CN110028668B (en) * | 2019-04-25 | 2021-08-10 | 航天材料及工艺研究所 | Preparation method of hard polyimide foam material |
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| Publication number | Publication date |
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| CN1215107C (en) | 2005-08-17 |
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