CN101402795B - Novel fire resistant polyimide foam and method of producing the same - Google Patents
Novel fire resistant polyimide foam and method of producing the same Download PDFInfo
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- CN101402795B CN101402795B CN2008102268635A CN200810226863A CN101402795B CN 101402795 B CN101402795 B CN 101402795B CN 2008102268635 A CN2008102268635 A CN 2008102268635A CN 200810226863 A CN200810226863 A CN 200810226863A CN 101402795 B CN101402795 B CN 101402795B
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- polyimide foam
- phenylacetylene
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- fire resistant
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- 239000006260 foam Substances 0.000 title claims abstract description 82
- 239000004642 Polyimide Substances 0.000 title claims abstract description 81
- 229920001721 polyimide Polymers 0.000 title claims abstract description 80
- 230000009970 fire resistant effect Effects 0.000 title claims description 22
- 238000000034 method Methods 0.000 title description 15
- 239000002243 precursor Substances 0.000 claims abstract description 59
- 239000000843 powder Substances 0.000 claims abstract description 26
- 150000005690 diesters Chemical class 0.000 claims abstract description 20
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- -1 acetylenyl Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 204
- 239000002253 acid Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 17
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 238000005187 foaming Methods 0.000 claims description 11
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012965 benzophenone Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 2
- 238000009413 insulation Methods 0.000 abstract description 2
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000002981 blocking agent Substances 0.000 abstract 1
- 230000008859 change Effects 0.000 abstract 1
- 230000009467 reduction Effects 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 14
- 238000000227 grinding Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 238000013019 agitation Methods 0.000 description 13
- 239000004305 biphenyl Substances 0.000 description 13
- 238000001816 cooling Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000006261 foam material Substances 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- YKNMIGJJXKBHJE-UHFFFAOYSA-N (3-aminophenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC(N)=C1 YKNMIGJJXKBHJE-UHFFFAOYSA-N 0.000 description 1
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 1
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 description 1
- GCNTZFIIOFTKIY-UHFFFAOYSA-N 4-hydroxypyridine Chemical compound OC1=CC=NC=C1 GCNTZFIIOFTKIY-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920007790 polymethacrylimide foam Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates a novel high temperature resistant polyimide foam and the preparation process thereof is as follows: (1) firstly, 2, 3, 3', 4'-biphenyl tetracarboxylic dianhydride or 2, 3, 3', 4'-biphenyl tetracarboxylic dianhydride and another type of aromatic dianhydride are heated and refluxed in a fatty alcohol solution so as to change the tetracarboxylic dianhydride into diacid diester; (2) in accordance with a certain proportion, the obtained diacid diester is synthesized into a precursor solution with one type or more of aromatic diamine and a blocking agent of acetylenyl benzeneand a certain quantity of foam stabilizer is added into the solution; (3) the solution is heated to remove tiny molecule volatile matter and obtain a polymide precursor powder; and (4) the precursor powder is filled into a mould to be frothed at high temperature and carries out imidization so as to obtain the polyimide foam. The density of the novel high temperature resistant polyimide foam is 10kg/m<3> to 500 kg/m<3> and the vitrified transformation temperature is over 350 DEG C; and the foam is characterized by excellent high temperature resistance, low temperature resistance, mechanical properties and functions of anti flaming, heat insulation or noise reduction.
Description
Technical field
The present invention relates to a kind of novel fire resistant polyimide foam and preparation method thereof.
Background technology
Compare with conventional foam such as polystyrene, polyethylene, polyurethane foams, polyimide foam has excellent flame, outstanding high and low temperature resistance and good dimensional stability.Therefore; the polyimide foam material is as a member of polyimide material family; since the sixties, Dupont company began development; just caused people's extensive concern; and develop rapidly; be widely used in aspects such as aircraft, spacecraft, weaponry, naval vessel and bullet train at present, as indivedual countries used as the electromagnetic window electromagnetic wave transparent material of the impact absorbing pad of spacecraft low temperature tank lagging material, crash helmet, radome and aircraft corridor structured material etc.
The polyimide foam preparation methods is more at present, U.S. Pat 3249561, US3483144, US4305796, US4439381, US4900761, US6235803, US5994418, US4177333, US5234966, US5077318, European patent EP 0376592, Chinese patent CN1528808, CN101113209 etc. have reported that some prepare the method for polyimide foam material, comprise powder foaming, presoma microballoon foaming, slurry foaming, stick with paste foaming, foam melt method, microwave foaming etc.
Along with the further investigation of polyimide foam, and the continuous expansion of the market requirement, existing at present a few countries is with its polyimide foam commercialization.Up to now, main in the world polyimide foam commodity have: SF series polyimide foam, Germany that du pont company is produced
The Rohacell polymethacrylimide foam of company, U.S. Ethyl company produce
Polyetherimide foam, the NASA of series polyimide foam, Switzerland Alcan Airex AG company authorize
The TEEK of Rexfoam series product and NASA exploitation
TMThe series high-performance polyimide foam.The life-time service temperature of these commercial polyimide foams is between 160 ℃～320 ℃.
In view of the requirement of some high-temperature applications, need further to improve the second-order transition temperature of polyimide foam, to satisfy military installations, weaponry and spacecraft etc. to foam materials lightweight, high-strength, high temperature resistant and low temperature resistant requirement.Chinese scholars is being done certain work aspect the raising polyimide foam thermotolerance at present, and has obtained certain effect.U.S. Pat 20020040068, US2003065044 has reported a kind of preparation method of fire resistant polyimide foam, this method is (mainly to be 2 with dianhydride monomer, 3,3 ', 4 '-BPDA) the backflow esterification becomes monoesters or diester in ethanol or methyl alcohol, and in esterification process, add imidization catalyst 1,2 '-methylimidazole, mixture that obtains and Ursol D or 4,4 '-diaminodiphenyl oxide and the reaction of a small amount of 1,3 '-two (3-aminopropyl) tetramethyl-silica alkane obtain the polyimide foam precursor solution, postheating is removed and is desolvated, grinding obtains precursor powder, adopts the microwave heating foaming, finally makes density at 13.5kg/m
3～900kg/m
3Polyimide foam, second-order transition temperature is between 370 ℃～405 ℃.Adopt the HIGH-POWERED MICROWAVES foamable in this method, higher to equipment requirements, increased production cost, simultaneously the poor controllability of foaming process.
U.S. Pat 4978690, US4923907 have reported a kind of by adding the stable on heating method of inorganic nano-particle raising polyimide foam.This method puts it into 400g vermiculite and 400g polyimide prepolymer uniform mixing in the mould then, after the compacting, mould 190.6 ℃ of heating 30min foaming down, is handled 2h down at 260 ℃ then, is cooled to room temperature, and can obtain density is 144kg/m
3The polyimide foam goods.This method is improving the stable on heating while of polyimide foam, has increased the density of polyimide foam, and vermiculite easily mixes inequality with polyimide prepolymer, thereby influences the foamy performance.In addition, Yuan-JyhLeea[Polymer, 2005,46:10056] etc. by using the PEO-POSS template of hydridization, prepared softening temperature between 360 ℃～370 ℃, the temperature of 5wt% thermal weight loss has the polyimide foam of nanoporous between 565 ℃～580 ℃, because formation is nanometer foam, therefore the density of this kind polyimide foam is higher, and this method only is fit to the preparation film article simultaneously.
Chinese patent CN101113209 has reported a kind of preparation method of polysiloxane acid imide foam, and this method adopts situ aggregation method to prepare nanometer SiO
2Micropartical strengthens polyimide foam, and second-order transition temperature has improved 15 ℃～25 ℃, reaches as high as 350 ℃.But this foam still can't satisfy the requirement in some special high temperature fields.
In order to overcome defective of the prior art, the present invention utilizes 2,3,3 ', 4 '-BPDA makes the characteristics that polyimide has good thermoplasticity and high second-order transition temperature, by in polyimide foam presoma building-up process, the phenylacetylene base end-capping reagent of heat cross-linking can take place in introducing, further improve 2,3, the thermotolerance of 3 ', 4 '-BPDA base polyimide foam, its second-order transition temperature can reach more than 450 ℃, and a kind of novel fire resistant polyimide foam of temperature tolerance excellence is provided.
Summary of the invention
The purpose of this invention is to provide polyimide foam of a kind of novel fire resistant and preparation method thereof, promptly, further improve the thermotolerance of polyimide foam by in the building-up process of polyimide foam presoma, introducing the phenylacetylene base end-capping reagent of heat cross-linking type.
The main ingredient of fire resistant polyimide foam of the present invention comprises: (1) one or more aromatic dianhydride A; (2) a kind of or more than one aromatic diamines B; (3) a kind of or more than one phenylacetylene base end-capping reagents C; (4) choose any one kind of them or more than one suds-stabilizing agents.
Wherein, the A component is 2,3, and 3 ', 4 '-BPDA (α-BPDA); Perhaps 2,3,3 ', 4 '-BPDA and another aromatic dianhydride D, the D component is selected from: 3,3 ', 4, and 4 '-BPDA (s-BPDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (s-BTDA), 2,3 ', 3,4 '-benzophenone tetracarboxylic dianhydride (α-BTDA), bisphenol A-type phenyl ether dianhydride (BPADA), 1,2,4,5-pyromellitic acid dianhydride (PMDA), or its mixture.
The B component comprises: Ursol D (p-PDA), mphenylenediamine (m-PDA), 4,4 '-diaminodiphenyl oxide (4,4 '-ODA), 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), 4,4 '-diaminobenzophenone (4,4 '-DABP), 3,4 '-diaminobenzophenone (3,4 '-DABP) or its mixture.
The C component comprises: 4-phenylacetylene phthalic anhydride, 3-phenylacetylene phthalic anhydride, 3-(3-phenylacetylene phenolic group) phthalic anhydride, 4-phenylacetylene aniline, 3-phenylacetylene aniline, 4-styryl-3-Trifluoro methyl benzeneamine, 3-(3-phenylacetylene phenolic group) aniline, 3-amino-4 '-phenylacetylene base benzophenone, 4-amino-4 '-phenylacetylene base benzophenone or its mixture.
Described suds-stabilizing agent comprises: polymethyl siloxane, polydimethylsiloxane, polyether-modified polysiloxane, organosilicon glycol copolymer, vinyl polysiloxane, polyoxyethylene groups ethers non-ionic type fluorocarbon surfactant, water-soluble polyoxyethylene base class non-ionic type fluorocarbon surfactant and cationic fluorochemical tensio-active agent.
The typical preparation method of novel fire resistant polyimide foam provided by the present invention is as follows:
(1), forms the alcoholic solution of two acid diesters, and when the backflow esterification, add the imide reaction catalyzer with component A (m mole) 70 ℃ of reflux in Fatty Alcohol(C12-C14 and C12-C18);
(2) fatty alcohol solution of B component (n mole), end-capping reagent C (x mole) and optional suds-stabilizing agent are joined the alcoholic solution of above-mentioned (1) described two acid diesters that are cooled to room temperature, reacted 6 hours～24 hours, and prepared the polyimide foam precursor solution;
(3) with the polyimide foam precursor solution described in above-mentioned (2) at 35 ℃～100 ℃ internal heating, remove most of small molecules volatile matter, obtain the polyimide foam precursor powder;
(4) the polyimide foam precursor powder described in above-mentioned (3) is filled in the mould, room temperature rises to 300 ℃～450 ℃, and fire resistant polyimide foam is prepared in foaming, imidization, curing cross-linked 0.5 hour～2 hours.
Among the component A of the present invention 2,3,3 ', (α-BPDA) mol ratio with aromatic dianhydride D is 0/100～50/50 to 4 '-BPDA, preferred 0/100～30/70, the mol ratio of described component A and B component is m/n=0.5/1.0～1.0/0.5, preferred 0.9/1.0～1.0/0.9, and m/n ≠ 1.0/1.0, the mole number x=2 (m-n) of described end-capping reagent C when n (m＞) or 2 (n-m) (when n＞m) mole, the addition of described suds-stabilizing agent is 0～5wt% of polyimide foam precursor solution, preferred 0.5wt%～2wt%.
Fatty Alcohol(C12-C14 and C12-C18) described in step (1) and (2) comprises: methyl alcohol, ethanol, n-propyl alcohol, Virahol and butanols.
Imidization reaction catalyzer of the present invention comprises: 1,2-methylimidazole, 2-ethyl-4-methylimidazole, benzoglyoxaline, isoquinoline 99.9 and substituted pyridines, the pyridine of wherein said replacement can be the 2-picoline, the 3-picoline, the 3-pyridone, 4-pyridone or 4,6-lutidine etc.
The solid content of polyimide precursor solution of the present invention is 8wt%～50wt%, preferred 10wt%～30wt%.
Advantage of the present invention has:
(1) polyimide foam presoma preparation technology is simple;
(2) have 2,3 of unsymmetrical structure by employing, 3 ', 4 '-BPDA when guaranteeing high second-order transition temperature, improves the thermoplasticity of polyimide, reduces melt viscosity, thereby increases foaming power.
(3) by introducing the phenylacetylene base end-capping reagent of heat cross-linking type, in imidization, heat cross-linking takes place, further improve the foamy thermotolerance, and can come the thermotolerance of control foam by the consumption of regulating end-capping reagent.
Fire resistant polyimide foam of the present invention has excellent high-and low-temperature resistance, fire-retardant, heat insulation, anti-acoustic capability, and its density is 10kg/m
3～500kg/m
3Second-order transition temperature is more than 350 ℃; can reach more than 450 ℃; can be used in aircraft, aircraft, weaponry, submarine, naval vessel, automobile or the radar, as the electromagnetic window electromagnetic wave transparent material of the impact absorbing pad of spacecraft low temperature tank lagging material, crash helmet, radome and aircraft corridor structured material etc.
Embodiment
Present invention is described by the following examples; and only be applicable to further specifying to invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can do some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1
In the single port bottle, 5.884g (0.02mol) α-BPDA is joined in the 36g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, (methanol solution of α-BPDE) is cooled to room temperature with it to 3 ', 4 '-biphenyl acid diester then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the α-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours～8 hours down, add 0.773g (0.004mol) 4-phenylacetylene aniline (4-PEA) end-blocking, react after 3 hours～4 hours, add the 0.086g polymethyl siloxane, and add 16.421g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution in 1 hour～2 hours, 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.
The above-mentioned precursor powder of 1.3g is put into the high-temperature resistant micropore air-permeable mould, and mould is a cubic, and cavity dimension is 50mm * 50mm * 13mm, mould is put into high-temperature heater, after room temperature rises to 360 ℃, be incubated 1 hour, obtain fire resistant polyimide foam after the cooling.
Embodiment 2
The precursor powder that makes among the 2.6g embodiment 1 is put into the high-temperature resistant micropore air-permeable mould, and mould is a cubic, and cavity dimension is 50mm * 50mm * 13mm, mould is put into high-temperature heater, after room temperature rises to 360 ℃, be incubated 1 hour, obtain fire resistant polyimide foam after the cooling.
Embodiment 3
The precursor powder that makes among the 5.2g embodiment 1 is put into the high-temperature resistant micropore air-permeable mould, and mould is a cubic, and cavity dimension is 50mm * 50mm * 13mm, mould is put into high-temperature heater, after room temperature rises to 360 ℃, be incubated 1 hour, obtain fire resistant polyimide foam after the cooling.
Embodiment 4
The precursor powder that makes among the 2.6g embodiment 1 is put into the high-temperature resistant micropore air-permeable mould, and mould is a cubic, and cavity dimension is 50mm * 50mm * 13mm, mould is put into high-temperature heater, after room temperature rises to 390 ℃, be incubated 1 hour, obtain fire resistant polyimide foam after the cooling.
Embodiment 5
The precursor powder that makes among the 2.6g embodiment 1 is put into the high-temperature resistant micropore air-permeable mould, and mould is a cubic, and cavity dimension is 50mm * 50mm * 13mm, mould is put into high-temperature heater, after room temperature rises to 420 ℃, be incubated 1 hour, obtain fire resistant polyimide foam after the cooling.
Embodiment 6
In the single port bottle, 5.884g (0.02mol) α-BPDA is joined in the 30g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, (methanol solution of α-BPDE) is cooled to room temperature with it to 3 ', 4 '-biphenyl acid diester then.1.946g (0.018mol) mphenylenediamine (m-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the α-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours～8 hours down, add 0.773g (0.004mol) 4-phenylacetylene aniline (4-PEA) end-blocking, react after 3 hours～4 hours, add the 0.086g polymethyl siloxane, and add 21.589g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution in 1 hour～2 hours, 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 7
In the single port bottle, 5.884g (0.02mol) α-BPDA is joined in the 36g methyl alcohol, add the 0.359g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, (methanol solution of α-BPDE) is cooled to room temperature with it to 3 ', 4 '-biphenyl acid diester then.With 3.604g (0.018mol) 4,4 '-diaminodiphenyl oxide (4,4 '-ODA) is dissolved in the 35g methyl alcohol, add in the methanol solution of the α-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours～8 hours down, add 0.773g (0.004mol) 4-phenylacetylene aniline (4-PEA) end-blocking, react after 3 hours～4 hours, add the 0.103g polymethyl siloxane, and add 21.349g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continues reaction and obtains precursor solution, 70 ℃ of oven dry subsequently in 1 hour～2 hours, grinding obtains the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 8
In the single port bottle, 5.884g (0.02mol) α-BPDA is joined in the 36g methyl alcohol, add the 0.33g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, (methanol solution of α-BPDE) is cooled to room temperature with it to 3 ', 4 '-biphenyl acid diester then.1.622g (0.015mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the α-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours～8 hours down, add 1.932g (0.01mol) 4-phenylacetylene aniline (4-PEA) end-blocking, react after 3 hours～4 hours, add the 0.094g polymethyl siloxane, and add 28.942g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution in 1 hour～2 hours, 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 9
In the single port bottle, 5.884g (0.02mol) α-BPDA is joined in the 36g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, (methanol solution of α-BPDE) is cooled to room temperature with it to 3 ', 4 '-biphenyl acid diester then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the α-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours～8 hours down, add 0.773g (0.004mol) 3-phenylacetylene aniline (3-PEA) end-blocking, react after 3 hours～4 hours, add the 0.086g polymethyl siloxane, and add 16.421g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution in 1 hour～2 hours, 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 10
In the single port bottle, 5.296g (0.018mol) α-BPDA and 0.993g (0.004mol) 3-phenylacetylene phthalic anhydride (3-PEPA) are joined in the 40g methyl alcohol, add the 0.296g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h, obtain 2,3,3 ', (methanol solution of α-BPDE) and 3-phenylacetylene benzene methyl (3-PEPE) is cooled to room temperature with it to 4 '-biphenyl acid diester then.2.163g (0.02mol) Ursol D (p-PDA) is dissolved in the 25g methyl alcohol, add in the methanol solution of the α-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours～8 hours down, add the 0.084g polymethyl siloxane, and add 11.068g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continues reaction and obtains precursor solution in 1 hour～2 hours, and 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 11
In the single port bottle, 5.296g (0.018mol) α-BPDA and 0.993g (0.004mol) 4-phenylacetylene phthalic anhydride (4-PEPA) are joined in the 40g methyl alcohol, add the 0.296g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h, obtain 2,3,3 ', (methanol solution of α-BPDE) and 4-phenylacetylene benzene methyl (4-PEPE) is cooled to room temperature with it to 4 '-biphenyl acid diester then.2.163g (0.02mol) Ursol D (p-PDA) is dissolved in the 25g methyl alcohol, add in the methanol solution of the α-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours～8 hours down, add the 0.084g polymethyl siloxane, and add 11.068g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continues reaction and obtains precursor solution in 1 hour～2 hours, and 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 12
In the single port bottle, 5.884g (0.02mol) α-BPDA is joined in the 36g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, (methanol solution of α-BPDE) is cooled to room temperature with it to 3 ', 4 '-biphenyl acid diester then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the α-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours～8 hours down, add 1.045g (0.004mol) 4-styryl-3-Trifluoro methyl benzeneamine (3-FPA) end-blocking, react after 3 hours～4 hours, add the 0.086g polymethyl siloxane, and add 16.421g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution, 70 ℃ of oven dry subsequently in 1 hour～2 hours, grinding obtains the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 13
In the single port bottle, 5.884g (0.02mol) α-BPDA is joined in the 36g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, (methanol solution of α-BPDE) is cooled to room temperature with it to 3 ', 4 '-biphenyl acid diester then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the α-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours～8 hours down, add 1.141g (0.004mol) 3-(3-phenylacetylene phenolic group) aniline (PEPOA) end-blocking, react after 3 hours～4 hours, add the 0.086g polymethyl siloxane, and add 16.421g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution, 70 ℃ of oven dry subsequently in 1 hour～2 hours, grinding obtains the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 14
In the single port bottle, 5.884g (0.02mol) α-BPDA is joined in the 36g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, (methanol solution of α-BPDE) is cooled to room temperature with it to 3 ', 4 '-biphenyl acid diester then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the α-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours～8 hours down, adding 1.189g (0.004mol) 3-amino-4 '-phenylacetylene base benzophenone (3A4 ' PEB) end-blocking, react after 3 hours～4 hours, add the 0.086g polymethyl siloxane, and add 16.421g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution, 70 ℃ of oven dry subsequently in 1 hour～2 hours, grinding obtains the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 15
In the single port bottle, 5.884g (0.02mol) α-BPDA is joined in the 36g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, (methanol solution of α-BPDE) is cooled to room temperature with it to 3 ', 4 '-biphenyl acid diester then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the α-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours～8 hours down, adding 1.189g (0.004mol) 4-amino-4 '-phenylacetylene base benzophenone (4A4 ' PEB) end-blocking, react after 3 hours～4 hours, add the 0.086g polymethyl siloxane, and add 16.421g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution, 70 ℃ of oven dry subsequently in 1 hour～2 hours, grinding obtains the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 16
In the single port bottle, with 4.708g (0.016mol) α-BPDA and 1.289g (0.004mol) 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (s-BTDA) joins in the 40g methyl alcohol, add the 0.3g 2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, (methanol solution of α-BPDE) is cooled to room temperature with it to 3 ', 4 '-biphenyl acid diester then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 20g methyl alcohol, add in the methanol solution of the α-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours～8 hours down, add 0.773g (0.004mol) 4-phenylacetylene aniline (4-PEA) end-blocking, react after 3 hours～4 hours, add the 0.087g polymethyl siloxane, and add 18.444g methyl alcohol, the solid content of adjusting precursor solution is 10wt%, continue reaction and obtained precursor solution in 1 hour～2 hours, 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Embodiment 17
In the single port bottle, 5.884g (0.02mol) α-BPDA is joined in the 15g methyl alcohol, add 0.3g2-ethyl-4-methylimidazole subsequently, 70 ℃ of reflux 2h obtain 2,3, (methanol solution of α-BPDE) is cooled to room temperature with it to 3 ', 4 '-biphenyl acid diester then.1.946g (0.018mol) Ursol D (p-PDA) is dissolved in the 15g methyl alcohol, add in the methanol solution of the α-BPDE that is cooled to room temperature, the magnetic agitation effect is reacted after 6 hours～8 hours down, add 0.773g (0.004mol) 4-phenylacetylene aniline (4-PEA) end-blocking, react after 3 hours～4 hours, add the 0.086g polymethyl siloxane, and add 4.412g methyl alcohol, the solid content of adjusting precursor solution is 20wt%, continue reaction and obtained precursor solution in 1 hour～2 hours, 70 ℃ of oven dry, grindings subsequently obtain the polyimide foam precursor powder.All the other are with embodiment 5.
Density and second-order transition temperature by the foregoing description 1 to embodiment 17 gained polyimide foam are illustrated in the table 1.
The proportioning and the foamy second-order transition temperature (Tg) of table 1 preparation fire resistant polyimide foam
Claims (4)
1. fire resistant polyimide foam, it is characterized in that: described fire resistant polyimide foam comprises aromatic dianhydride A component, aromatic diamines B component and end-capping reagent C, wherein, the A component is by 2,3,3 ', 4 '-BPDA or 2,3, the mixture of 3 ', 4 '-BPDA and another aromatic dianhydride D is formed; The B component is selected from Ursol D, mphenylenediamine, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminobenzophenone, 3, a kind of or its mixture in 4 '-diaminobenzophenone; C is the phenylacetylene base end-capping reagent, is selected from a kind of in 4-phenylacetylene phthalic anhydride, 3-phenylacetylene phthalic anhydride, 3-(3-phenylacetylene phenolic group) phthalic anhydride 4-phenylacetylene aniline, 3-phenylacetylene aniline, 4-styryl-3-Trifluoro methyl benzeneamine, 3-(3-phenylacetylene phenolic group) aniline, 3-amino-4 '-phenylacetylene base benzophenone, 4-amino-the 4 '-phenylacetylene base benzophenone; D is selected from 3, and 3 ', 4,4 '-BPDA, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3 ', 3,4 '-benzophenone tetracarboxylic dianhydride, bisphenol A-type phenyl ether dianhydride, 1,2,4, a kind of in the 5-pyromellitic acid dianhydride, the density of described fire resistant polyimide foam is at 10kg/m
3～500kg/m
3, second-order transition temperature is more than 350 ℃.
2. fire resistant polyimide foam as claimed in claim 1 is characterized in that: the mol ratio m/n=0.5/1.0～1.0/0.5 of described aromatic dianhydride A component and aromatic diamines B component, and m/n ≠ 1.0/1.0; When m＞n, the mole number x=2 (m-n) of described end-capping reagent C; When n＞m, the mole number x=2 (n-m) of described end-capping reagent C.
3. the preparation method of claim 1 and 2 each described fire resistant polyimide foams is characterized in that: may further comprise the steps:
(1), forms the alcoholic solution of two acid diesters, and when the backflow esterification, add the imide reaction catalyzer with aromatic dianhydride A component reflux in the Fatty Alcohol(C12-C14 and C12-C18) solvent;
(2) fatty alcohol solution, end-capping reagent C and the suds-stabilizing agent of aromatic diamines B component joined the alcoholic solution of above-mentioned (1) described two acid diesters that are cooled to room temperature, reacted 6 hours～24 hours, prepare the polyimide foam precursor solution;
(3) with the polyimide foam precursor solution described in above-mentioned (2) at 35 ℃～100 ℃ internal heating, remove the small molecules volatile matter, obtain the polyimide foam precursor powder;
(4) the polyimide foam precursor powder described in above-mentioned (3) is filled in the mould, inserts in the oven heat, room temperature rises to 300 ℃～450 ℃, and fire resistant polyimide foam is prepared in foaming, imidization, curing cross-linked 0.5 hour～2 hours.
4. preparation method as claimed in claim 3, it is characterized in that: described Fatty Alcohol(C12-C14 and C12-C18) solvent is selected from a kind of in methyl alcohol, ethanol, n-propyl alcohol, Virahol and the butanols, the imidization reaction catalyzer is selected from 1,2-methylimidazole, 2-ethyl-4-methylimidazole, benzoglyoxaline, isoquinoline 99.9 or substituted pyridines, suds-stabilizing agent are selected from polymethyl siloxane, polydimethylsiloxane, polyether-modified polysiloxane, organosilicon glycol copolymer, vinyl polysiloxane, polyoxyethylene groups ethers non-ionic type fluorocarbon surfactant, cationic fluorochemical tensio-active agent.
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| CN102634020B (en) * | 2011-09-19 | 2013-09-11 | 京东方科技集团股份有限公司 | Prepolymer, oriented film, preparation method for oriented film, and liquid crystal display device |
| CN102604094A (en) * | 2012-01-11 | 2012-07-25 | 复旦大学 | Crosslinking fluorine-containing polyimide and synthesis method thereof |
| 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 |
| CN103012793A (en) * | 2012-12-28 | 2013-04-03 | 青岛海洋新材料科技有限公司 | Novel mould-pressing polyimide foamed plastic and preparation method thereof |
| CN104072770B (en) * | 2014-06-30 | 2016-04-20 | 自贡中天胜新材料科技有限公司 | A kind of foaming fluorinated polyimide and foam preparation processes thereof |
| CN104231269B (en) * | 2014-10-14 | 2018-04-10 | 中国科学院长春应用化学研究所 | A kind of polyimides and preparation method thereof and polyimide molding powder |
| US10448541B2 (en) * | 2015-11-19 | 2019-10-15 | Boyd Corporation | Densified foam for thermal insulation in electronic devices |
| CN108017786A (en) * | 2017-12-24 | 2018-05-11 | 桂林理工大学 | The method that Kapton is prepared using benzophenone tetracarboxylic dianhydride |
| CN108395535A (en) * | 2018-04-03 | 2018-08-14 | 上海市合成树脂研究所有限公司 | A kind of imido preparation method of hot polymerization for laminated product |
| CN109535714A (en) * | 2018-11-20 | 2019-03-29 | 北京航空航天大学 | A kind of polyimides composite foam material resistant to high temperature and preparation method thereof |
| 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 |
| CN112175335B (en) * | 2020-10-29 | 2021-04-20 | 吉林化工学院 | Ablation-resistant aerospace material and preparation method thereof |
| CN115651339A (en) * | 2022-11-05 | 2023-01-31 | 浙江中科恒泰新材料科技有限公司 | PMI foaming method by using dihydric alcohol |
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| EP1167427A1 (en) * | 2000-06-28 | 2002-01-02 | Ube Industries, Ltd. | Aromatic polyimide foam |
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| EP1167427A1 (en) * | 2000-06-28 | 2002-01-02 | Ube Industries, Ltd. | Aromatic polyimide foam |
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