CN101113209B - Polysiloxane acid imide foam and method for preparing same - Google Patents
Polysiloxane acid imide foam and method for preparing same Download PDFInfo
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- CN101113209B CN101113209B CN2007101191684A CN200710119168A CN101113209B CN 101113209 B CN101113209 B CN 101113209B CN 2007101191684 A CN2007101191684 A CN 2007101191684A CN 200710119168 A CN200710119168 A CN 200710119168A CN 101113209 B CN101113209 B CN 101113209B
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- polysiloxane
- acid imide
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- -1 Polysiloxane Polymers 0.000 title claims abstract description 118
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 100
- 239000002253 acid Substances 0.000 title claims abstract description 90
- 239000006260 foam Substances 0.000 title claims abstract description 53
- 150000003949 imides Chemical class 0.000 title claims description 77
- 238000000034 method Methods 0.000 title description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 48
- 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 21
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- 150000003384 small molecules Chemical class 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 3
- 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 claims description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 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 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 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
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 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
- 239000004642 Polyimide Substances 0.000 abstract description 38
- 229920001721 polyimide Polymers 0.000 abstract description 38
- 239000006261 foam material Substances 0.000 abstract description 9
- 238000009413 insulation Methods 0.000 abstract description 4
- 230000009477 glass transition Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002981 blocking agent Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000003039 volatile agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- 238000003756 stirring Methods 0.000 description 32
- 238000005187 foaming Methods 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 20
- 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 16
- 239000003795 chemical substances by application Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 150000004985 diamines Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 4
- 206010000269 abscess Diseases 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 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 3
- 239000000178 monomer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920006259 thermoplastic polyimide Polymers 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- AGKRHAILCPYNFH-DUQSFWPASA-N 7,7-dimethyl-5,8-Eicosadienoic Acid Chemical compound CCCCCCCCCCC\C=C/C(C)(C)\C=C/CCCC(O)=O AGKRHAILCPYNFH-DUQSFWPASA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000005401 siloxanyl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Abstract
The invention relates to polysiloxane-imide foam and a preparation method thereof. The polysiloxane-imide foam is made by the steps: one or more than one sort of aromatic dianhydride is composed with one or more than one sort of aromatic diamine according to a certain proportion to get polyimide acid solution, then certain content of silicon-containing blocking agent, polysiloxane precursor and foam stabilizer are added sequentially, then the mixture is heated to remove small molecule volatiles so as to obtain polysiloxane precursor powder, then the powder is filled in a mould and frothed at high temperature to make soft elastic, semi-rigid and rigid polysiloxane-imide foam materials with a density of 0.01g/cm3-1.0g/cm3 and a glass transition temperature of 280 DEGC -350 DEG C. The polysiloxane-imide foam materials of the invention have good performances of high temperature resistance, low temperature resistance, flame retardancy, heat insulation and noise reduction and mechanical properties.
Description
Technical field
The present invention relates to a kind of polysiloxane acid imide foam and preparation method thereof.
Background technology
Polysiloxane acid imide foam of the present invention is a kind of foam by the preparation of polysiloxane polyimide, belongs to this special engineering plastics of polyimide.
Polyimide is a class excellent combination property, the exsertile macromolecular material of thermotolerance, in field widespread uses such as Aeronautics and Astronautics, microelectronics, nanometer, liquid crystal, separatory membrane, laser.Polyimide-type materials goods kind is numerous, mainly comprises: moulding resin/part, film, fiber, prepreg/matrix material, coating, tackiness agent and soft, rigid foam etc.
The polyimide foam structured material not only kept polyimide resistance toheat, flame retardant properties, anti-naked light, be not fuming, not halogen-containing and consume performance such as ozone; Also have good gentle elasticity of foam materials and heat insulation, sound-proofing properties simultaneously.Easy to use, the environmental friendliness of polyimide foam as heat insulation, noise reduction, fire retardant material, is widely used.
As far back as 1966, du pont company has just been reported the method for preparing the polyimide bubble in its patent US3249561, this method is at first prepared polyamic acid solution, in solution, add dewatering agent or dewatering agent/tertiary amine mixture then, in solution, add the acid to produce gas such as formic acid etc. again, produce CO or CO
2Gas foaming is made this solution that curing molding can obtain the polyimide foam material in one deck wet film or the direct injection progressive die chamber at last.But the inhomogeneous and chemical foaming agent of the foam abscess of this method preparation remains in the foam easily.
U.S. Pat 3483144 adopts the Prepared by Ball Milling polyimide foam.Dianhydride is generated the water foaming by two amine solvent end reactions and forms foam under the ball milling molten state.It is inhomogeneous that this legal system is equipped with the foamy abscess, and be approximately 0.43 gram per centimeter because the less water that produces in the reaction only can prepare density
3The high-density polyimide foam.
US4305796,4439381,4822537 replaces electrically heated or baking oven for heating to prepare polyimide foam by the microwave foaming technique, its foaming and imidization speed are fast, the efficient height, but the foam defective is more, density unevenness is even, and the product properties of different batches also exists than big difference.
EP0376592 has introduced a kind of method of thermoplastic polyimide extrusion foaming.Thermoplastic polyimide is melt extruded at 380 ℃-410 ℃, and by adding whipping agent or foaming in the decompression cooling of mouth mould place, processing condition are than difficult control, and the foamy abscess is inhomogeneous.
US4900761,507183,5122546,5298531 is dissolved in dianhydride earlier and obtains two acid diesters (DADA) in the alcohol, add preparation polyimide precursor solutions such as diamines, whipping agent then, in the imidization process, make polyimide precursor solution be processed into polyimide foam by discharging water and alcohol (R-OH).Whipping agent can cause foam to produce non-homogeneous vesicular structure as an independent subject in this method, simultaneously can residual whipping agent on cell wall.
US6180746, US6133330A1 are with dianhydride esterification in the solution of small molecular alcohol and ether, make dianhydride be transformed into DADA, while and small molecules ether form hydrogen bond, adding diamines afterwards reacts and obtains polyimide salt shape solution, oven dry is pulverized, and high temperature prepares frangible microballoon of polyimide and polyimide foam then.
CN1528808A is with dianhydride esterification in the solution of small molecular alcohol and monohydroxy polyethers, make dianhydride be transformed into DADA, hydroxyl with polyethers interacts simultaneously, adding diamines afterwards reacts and obtains polyimide salt shape solution, oven dry is pulverized, and high temperature prepares frangible microballoon of polyimide and polyimide foam then.
Better in the aforesaid method with the polyimide foam over-all properties of the synthetic preparation of two acid diesters intermediates, but the preparation intermediate is wayward, by product is more, and may generate three esters or four esters etc. can the final foaming properties of influence, and this legal system to be equipped with the polyimide foam molecular weight lower.
The present invention directly reacts aromatic diamines and aromatic dianhydride in solvent, avoided the process of synthetic two acid diesters intermediates.Polysiloxane is introduced the resistance to elevated temperatures that can improve polyimide foam in the polyimide molecule chain, improve foamy body simultaneously, thereby obtain the high-temperature-resistant high polyimide foam; Can replace polyurethane foam, satisfy military installations and weaponry, improve the reliability of military installations and the fighting capacity of weaponry foam materials lightweight, high-strength, high temperature resistant and low temperature resistant requirement.
Preparation method about polysiloxane acid imide roughly is divided into following several:
The synthetic earlier polysiloxane that contains diamino, then with two anhydride reactants, the preparation polysiloxane acid imide.Disclosed by a the polysiloxane acid imide of ω-two amido organopolysiloxane and two ether dianhydrides (DEDA) preparation among the US3847867.US4051163, US4030948 have made polysiloxane acid imide mainly as electric appliance paint with dianhydride and diamino polysiloxane.
The synthetic earlier dianhydride that contains siloxanes, then with diamine reactant, the preparation polysiloxane acid imide has made siliceous dianhydride and has contained the siloxanes dianhydride as far back as the J.R.PRATT of University of Mississippi in 1973, can be used for preparing polysiloxane acid imide (documents and materials).The Lv Hong of China Shandong University boats in 1999 etc. have also made and have contained the siloxanes dianhydride, but productive rate is lower, the difficulty of purifying.
Aforesaid method all needs to prepare the dianhydride or the diamine monomer of siliceous or siloxanes segment, the step complexity, and cost height, and the easy hydrolysis of monomer of preparation influence the performance of polyimide.These class methods are used for preparing electronics more and microelectronic product sticks with glue agent and packaged material.
Human dianhydride and diamines such as Taiwan National Chiao Tung University MEI-HUI TSAI and the synthetic low-molecular-weight polyimide acid solution of monoamine that contains siloxanes add the hybrid film of polyimide that siloxanes has made similar polysilsesquioxane hydridization then.This method has been avoided the preparation of siliceous or siloxanyl monomers to a certain extent, but this method is difficult to prepare massive material and foam materials.
The present invention utilizes siliceous end-capping reagent that polyimide acid is carried out end-blocking, add the polysiloxane presoma afterwards, in-situ polymerization is introduced polysiloxane in the polyimide molecule chain, and prepares the polyimide precursor powder, foam then and solidify, obtain polysiloxane acid imide foam.
Summary of the invention
The main ingredient of polysiloxane acid imide foam material of the present invention comprises: (1) more than one aromatic diamines, (2) more than one aromatic dianhydride, (3) more than one siliceous end-capping reagents, (4) more than one polysiloxane presomas, (5) more than one suds-stabilizing agents.
Being used for aromatic dianhydride of the present invention comprises: 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), bisphenol A-type two ether dianhydrides (BPADA), 3,3 ', 4,4 '-BPDA (BPDA), 1,2,4, more than one of 5-pyromellitic acid dianhydride (PMDA).
Being used for aromatic diamines of the present invention comprises: 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), 4,4 '-diaminodiphenyl oxide (4,4 '-ODA), 4,4 '-diaminobenzophenone (4,4 '-DABP), 3,4 '-diaminobenzophenone (3,4 '-DABP), 3,3 '-diaminobenzophenone (3,3 '-DABP), dihydroxyphenyl propane phenyl ether diamines (BAPP) more than one.
Being used for siliceous end-capping reagent of the present invention comprises: N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan or γ-aminopropyl methyl dimethoxysilane.
Being used for polysiloxane presoma of the present invention comprises: methyl silicate, tetraethoxy, silicic acid propyl ester, methyltrimethoxy silane, Union carbide A-162 or phenyl triethoxysilane.
Being used for suds-stabilizing agent of the present invention comprises: polymethyl siloxane, polydimethylsiloxane, polyether-modified polysiloxane, vinyl polysiloxane etc.
The typical operational procedure of preparation polysiloxane acid imide foam material of the present invention is as follows:
1) more than one aromatic dianhydride x mole and more than one aromatic diamines y mole reacted in the mixed solvent of small molecules ether and small molecular alcohol 2 hours～20 hours, added siliceous end-capping reagent m mole then, reacted after 2 hours～10 hours; Add polysiloxane presoma n mole again, react after 2 hours～10 hours, forming solid content is the polysiloxane acid imide acid solution of 8%wt～45%wt; The x/y=1.0/1.0～1.0/0.50 here, m=2 (x-y) mole, m/n=1: 0.1～1: 20.
2) add suds-stabilizing agent in above-mentioned polysiloxane acid imide acid solution, addition is the 0.008%wt～0.30%wt of polysiloxane acid imide acid solution.
3) add heat extraction small molecules volatile matter, obtain the polysiloxane acid imide precursor powder.
4) at 100 ℃～180 ℃ the pre-frothing of polysiloxane acid imide precursor powder is become microballoon.
5) polysiloxane acid imide precursor powder or microballoon are put into mould, form polysiloxane acid imide foam at 250 ℃～400 ℃ imidizations.
Advantage of the present invention is:
1) diamines and dianhydride are directly reacted, without other intermediate conversions, simple to operate, cost is lower.
2) can adopt copolyimide as the polyimide foam main body.
3) polysiloxane presoma and siliceous end-capping reagent reaction combines closely and good dispersion with polyimide.
The present invention is prepared that polyimide foam has excellent high temperature resistant, low temperature resistant, fire-retardant, heat insulation, anti-acoustic capability and good mechanical performance, and foam is gentle elasticity or semi-rigid or inflexible polysiloxane acid imide foam, and its density is 0.01 gram per centimeter
3～1.0 gram per centimeters
3, its second-order transition temperature is 280 ℃～350 ℃, the foam shape that makes can be that tabular, column, round barrel shape, special-shaped transverse section tubbiness, radar are hood-like etc.
Embodiment
Present invention is described by the following examples; and only be applicable to and further specify of the present 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
About ODPA/4, the preparation of 4 '-ODA system foamy.
1) preparation of polysiloxane acid imide foam presoma
In being furnished with three neck reaction flasks of agitator, with 392 gram (y=1.96mol) 4,4 '-ODA is dissolved in the mixed solvent of 2400 gram tetrahydrofuran (THF)s and 800 gram methyl alcohol, stirring is all dissolved solid, in this solution, add 620 gram (x=2.00mol) ODPA then, stirring below 30 ℃ adds 18.0 gram γ-An Bingjisanyiyangjiguiwans and carries out end-blocking after 10 hours～12 hours, continue to stir 3 hours～5 hours to reacting completely, add 30.0 gram tetraethoxy reactions 3 hours～4 hours again, add 30.0 gram polymethyl siloxanes at last and stir 1 hour～2 hours one-tenth uniform solution, this solution is pulverized after 8 hours～24 hours 70 ℃ of oven dry is the polysiloxane acid imide precursor powder.
2) foaming of polysiloxane acid imide presoma and imidization
These powder 300 grams are become frangible microballoon 140 ℃ of pre-frothing, at last this microballoon is put into the high-temperature resistant micropore air-permeable mould, mould is a cubic, cavity dimension is 500mm * 500mm * 13mm, mould is put into 250 ℃ of heating of high-temperature heater 1 hour, 300 ℃ were heated 1 hour, and cooling promptly gets polysiloxane acid imide foam.
Embodiment 2
About ODPA/4, the preparation of 4 '-ODA system foamy.
1) preparation of polysiloxane acid imide foam presoma
The preparation method of polysiloxane acid imide foam presoma is with embodiment 1.
2) foaming of polysiloxane acid imide presoma and imidization
These powder 500 grams are become frangible microballoon 140 ℃ of pre-frothing, at last this microballoon is put into the high-temperature resistant micropore air-permeable mould, mould is a cubic, cavity dimension is 500mm * 500mm * 13mm, mould is put into 250 ℃ of heating of high-temperature heater 1 hour, 300 ℃ were heated 1 hour, and cooling promptly gets polysiloxane acid imide foam.
Embodiment 3
About ODPA/4, the preparation of 4 '-ODA system foamy.
1) preparation of polysiloxane acid imide foam presoma
The preparation method of polysiloxane acid imide foam presoma is with embodiment 1
2) foaming of polysiloxane acid imide presoma and imidization
These powder 1000 grams are become frangible microballoon 140 ℃ of pre-frothing, at last this microballoon is put into the high-temperature resistant micropore air-permeable mould, mould is a cubic, cavity dimension is 500mm * 500mm * 13mm, mould is put into 250 ℃ of heating of high-temperature heater 1 hour, 300 ℃ were heated 1 hour, and cooling promptly gets polysiloxane acid imide foam.
Embodiment 4
About ODPA/4, the preparation of 4 '-ODA system foamy.
1) preparation of polysiloxane acid imide presoma
In being furnished with three neck reaction flasks of agitator, with 196 grams 4,4 '-ODA (y=0.98) is dissolved in the mixed solvent of 1600 gram tetrahydrofuran (THF)s and 400 gram methyl alcohol, stirring is all dissolved solid, in this solution, add 310 gram ODPA (x=0.1mol) then, stirring below 30 ℃ adds 9.0 gram γ-An Bingjisanyiyangjiguiwans and carries out end-blocking after 10 hours～12 hours, continue to stir 3 hours～5 hours to reacting completely, add 45 gram tetraethoxy reactions 3～4 hours again, add 15 gram polymethyl siloxanes at last and stir 1 hour～2 hours one-tenth uniform solution, this solution is pulverized after 6 hours～24 hours 70 ℃ of oven dry is the polysiloxane acid imide presoma.
2) foaming of polysiloxane acid imide presoma and imidization
Foaming of polysiloxane acid imide presoma and imidization method are with embodiment 1.
Embodiment 5
About ODPA/4, the preparation of 4 '-ODA system foamy.
1) preparation of polysiloxane acid imide presoma
In being furnished with three neck reaction flasks of agitator, with 190 grams 4,4 '-ODA (y=0.95mol) is dissolved in the mixed solvent of 1600 gram tetrahydrofuran (THF)s and 400 gram methyl alcohol, stirring is all dissolved solid, in this solution, add 310 gram ODPA (x=0.1mol) then, stirring below 30 ℃ adds 22.0 gram γ-An Bingjisanyiyangjiguiwans and carries out end-blocking after 10 hours～12 hours, continue to stir 3 hours～5 hours to reacting completely, add 90.0 gram tetraethoxy reactions 3 hours～4 hours again, add 15.0 gram polymethyl siloxanes at last and stir 1 hour～2 hours one-tenth uniform solution, this solution is pulverized after 6 hours～24 hours 70 ℃ of oven dry is the polysiloxane acid imide presoma.
2) foaming of polysiloxane acid imide presoma and imidization
Foaming of polysiloxane acid imide presoma and imidization method are with embodiment 1.
Embodiment 6
About ODPA/4, the preparation of 4 '-ODA system foamy.
1) preparation of polysiloxane acid imide presoma
The preparation method of polysiloxane acid imide presoma is with embodiment 1.
2) foaming of polysiloxane acid imide presoma and imidization
These powder 35.0 grams are become frangible microballoon 140 ℃ of pre-frothing, at last this microballoon is put into the high-temperature resistant micropore air-permeable mould, mold shape is coniform, circular cone cavity dimension bottom surface internal diameter is 100mm, external diameter is 120mm, and height is 100mm, and mould is put into high-temperature heater 250 ℃ of heating 1 hour, 300 ℃ were heated 1 hour, and cooling promptly gets polysiloxane acid imide foam.
Embodiment 7
About ODPA/3, the preparation of 4 '-ODA system foamy.
1) preparation of polysiloxane acid imide presoma
In being furnished with three neck reaction flasks of agitator, with 196 grams 3,4 '-ODA (y=0.98) is dissolved in the mixed solvent of 1600 gram tetrahydrofuran (THF)s and 400 gram methyl alcohol, stirring is all dissolved solid, in this solution, add 310 gram ODPA (x=1.0mol) then, stirring below 30 ℃ adds 9.0 gram γ-An Bingjisanyiyangjiguiwans and carries out end-blocking after 10 hours～12 hours, continue to stir 3 hours～5 hours to reacting completely, add 15.0 gram tetraethoxys reactions 3 hours～4 hours again, add 15.0 gram polymethyl siloxanes at last and stir to become uniform solution that this solution is pulverized after 6 hours～24 hours 70 ℃ of oven dry in 1 hour～2 hours to be the polysiloxane acid imide presoma.
2) foaming of polysiloxane acid imide presoma and imidization
Foaming of polysiloxane acid imide presoma and imidization method are with embodiment 1.
Embodiment 8
About BTDA/3, the preparation of 4 '-ODA system foamy.
1) preparation of polysiloxane acid imide presoma
In being furnished with three neck reaction flasks of agitator, with 196 grams 3,4 '-ODA (y=0.98) is dissolved in the mixed solvent of 1600 gram tetrahydrofuran (THF)s and 400 gram methyl alcohol, stirring is all dissolved solid, in this solution, add 322 gram BTDA (x=1.0mol) then, stirring below 30 ℃ adds 9.0 gram γ-An Bingjisanyiyangjiguiwans and carries out end-blocking after 10 hours～12 hours, continue to stir 3 hours～5 hours to reacting completely, add 15.0 gram tetraethoxy reactions 3 hours～4 hours again, add 15.0 gram polymethyl siloxanes at last and stir 1 hour～2 hours one-tenth uniform solution, this solution is pulverized after 6 hours～24 hours 70 ℃ of oven dry is the polysiloxane acid imide presoma.
2) foaming of polysiloxane acid imide presoma and imidization
Foaming of polysiloxane acid imide presoma and imidization method are with embodiment 1.
Embodiment 9
About BTDA/4, the preparation of 4 '-ODA system foamy.
1) preparation of polysiloxane acid imide presoma
In being furnished with three neck reaction flasks of agitator, with 196 grams 4,4 '-ODA (y=0.98mol) is dissolved in the mixed solvent of 1600 gram tetrahydrofuran (THF)s and 400 gram methyl alcohol, stirring is all dissolved solid, in this solution, add 322 gram BTDA (x=1.0mol) then, stirring below 30 ℃ adds 9.0 gram γ-An Bingjisanyiyangjiguiwans and carries out end-blocking after 10 hours～12 hours, continue to stir 3 hours～5 hours to reacting completely, add 15.0 gram tetraethoxy reactions 3 hours～4 hours again, add 15.0 gram polymethyl siloxanes at last and stir 1 hour～2 hours one-tenth uniform solution, this solution is pulverized after 6 hours～24 hours 70 ℃ of oven dry is the polysiloxane acid imide presoma.
2) foaming of polysiloxane acid imide presoma and imidization
Foaming of polysiloxane acid imide presoma and imidization method are with embodiment 1.
Embodiment 10
About ODPA/PMDA/4, the preparation of 4 '-ODA system foamy.
1) preparation of polysiloxane polyimide precursor
In being furnished with three neck reaction flasks of agitator, with 196 gram (y=0.98mol) 4,4 '-ODA is dissolved in the mixed solvent of 1600 gram tetrahydrofuran (THF)s and 400 gram methyl alcohol, stirs solid is all dissolved, and adds 290 gram (x then in this solution successively
1=0.90mol) ODPA and 22 restrains (x
2=0.10mol) PMDA, stirring below 30 ℃ adds 9.0 gram γ-An Bingjisanyiyangjiguiwans and carries out end-blocking after 10 hours～12 hours, continue to stir 3 hours～5 hours to reacting completely, add 15.0 gram tetraethoxy reactions 3 hours～4 hours again, add 15.0 gram polymethyl siloxanes at last and stir 1 hour～2 hours one-tenth uniform solution, this solution is pulverized after 6 hours～24 hours 70 ℃ of oven dry is the polysiloxane polyimide precursor.
2) foaming of polysiloxane acid imide presoma and imidization
Foaming of polysiloxane acid imide presoma and imidization method are with example 1.
Embodiment 11
About ODPA/4,4 '-ODA/4, the preparation of 4 '-DABP system foamy.
1) preparation of polysiloxane acid imide presoma
In being furnished with three neck reaction flasks of agitator, with 98 gram (y
1=0.49mol) 4,4 '-ODA, 104 grams 4,4 '-DABP (y
2=0.49mol) be dissolved in the mixed solvent of 1600 gram tetrahydrofuran (THF)s and 400 gram methyl alcohol, stirring is all dissolved solid, in this solution, add 310 gram (1.0mol) ODPA then, stirring below 30 ℃ adds 9.0 gram γ-An Bingjisanyiyangjiguiwans and carries out end-blocking after 10 hours～12 hours, continue to stir 3 hours～5 hours to reacting completely, add 15.0 gram tetraethoxy reactions 3 hours～4 hours again, add 15.0 gram polymethyl siloxanes at last and stir 1 hour～2 hours one-tenth uniform solution, this solution is pulverized after 6 hours～24 hours 70 ℃ of oven dry is the polysiloxane polyimide precursor.
2) foaming of polysiloxane acid imide presoma and imidization
Foaming of polysiloxane acid imide presoma and imidization method are with example 1.
Be illustrated in the table 1 by above-mentioned example 1 to embodiment 11 gained foamy density and second-order transition temperature.
Table 1 preparation polysiloxane acid imide foam material mixture ratio and multicellular glass transition temperature
| Example/sample number | End-capping reagent/2 (x-y) mol | Polysiloxane presoma/mol | Density/gcm -3 | Glass transition temperature Tg/℃ |
| 1 | 0.08 | 0.14 | 0.080 | 295 |
| 2 | 0.08 | 0.14 | 0.111 | 295 |
| 3 | 0.08 | 0.14 | 0.243 | 295 |
| 4 | 0.04 | 0.21 | 0.081 | 301 |
| 5 | 0.10 | 0.42 | 0.083 | 305 |
| 6 | 0.04 | 0.07 | 0.080 | 295 |
| 7 | 0.04 | 0.07 | 0.081 | 260 |
| 8 | 0.04 | 0.07 | 0.079 | 272 |
| 9 | 0.04 | 0.07 | 0.083 | 315 |
| 10 | 0.04 | 0.07 | 0.085 | 318 |
| 11 | 0.04 | 0.07 | 0.084 | 313 |
Claims (7)
1. the preparation method of a polysiloxane acid imide foam, its feature is as follows:
1) more than one aromatic dianhydride x mole and more than one aromatic diamines y mole reacted in the mixed solvent of small molecules ether and small molecular alcohol 2 hours～20 hours, added siliceous end-capping reagent m mole then, reacted after 2 hours～10 hours; Add polysiloxane presoma n mole again, react after 2 hours～10 hours, forming solid content is the polysiloxane acid imide acid solution of 8%wt～45%wt, the x/y=1.0/1.0～1.0/0.50 here, m=2 (x-y) mole, m/n=1: 0.1～1: 20.
2) add suds-stabilizing agent in above-mentioned polysiloxane acid imide acid solution, its addition is the 0.008%wt～0.30%wt of polysiloxane acid imide acid solution.
3) add heat extraction small molecules volatile matter, obtain the polysiloxane acid imide precursor powder;
4) at 100 ℃～180 ℃ the pre-frothing of polysiloxane acid imide precursor powder is become microballoon;
5) microballoon of step 4 is put into mould, form polysiloxane acid imide foam at 250 ℃～400 ℃ imidizations.
2. the preparation method of a kind of polysiloxane acid imide foam according to claim 1, it is characterized in that: described aromatic dianhydride is: 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, bisphenol A-type two ether dianhydrides, 3,3 ', 4,4 '-BPDA, 1,2,4, more than one of 5-pyromellitic acid dianhydride.
3. the preparation method of a kind of polysiloxane acid imide foam according to claim 1, it is characterized in that: described aromatic diamines is: 3, and 4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl oxide, 4,4 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, more than one of dihydroxyphenyl propane phenyl ether diamines.
4. the preparation method of polysiloxane acid imide foam according to claim 1, described siliceous end-capping reagent is: N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan or γ-aminopropyl methyl dimethoxysilane.
5. the preparation method of polysiloxane acid imide foam according to claim 1, described polysiloxane presoma is: methyl silicate, tetraethoxy, silicic acid propyl ester, methyltrimethoxy silane, Union carbide A-162 or phenyl triethoxysilane.
6. the preparation method of polysiloxane acid imide foam according to claim 1, described suds-stabilizing agent is: polymethyl siloxane, polydimethylsiloxane, polyether-modified polysiloxane or vinyl polysiloxane.
7. the preparation method of a kind of polysiloxane acid imide foam according to claim 1 is characterized in that: described foam is gentle elasticity or semi-rigid or inflexible polysiloxane acid imide foam, and foamy density is 0.01 gram per centimeter
3～1.0 gram per centimeters
3, second-order transition temperature is 280 ℃～350 ℃.
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| CN101407594B (en) * | 2008-11-25 | 2012-03-21 | 北京市射线应用研究中心 | Modified polyimides foam and preparation thereof |
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| CN107189436B (en) * | 2017-07-20 | 2019-12-27 | 中国科学院长春应用化学研究所 | Polyimide nano foam and preparation method thereof |
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