CN101812232A - Polyimide foam and preparation method thereof - Google Patents
Polyimide foam and preparation method thereof Download PDFInfo
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- CN101812232A CN101812232A CN 201010144568 CN201010144568A CN101812232A CN 101812232 A CN101812232 A CN 101812232A CN 201010144568 CN201010144568 CN 201010144568 CN 201010144568 A CN201010144568 A CN 201010144568A CN 101812232 A CN101812232 A CN 101812232A
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- foam
- acid
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- polyimide
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- 239000006260 foam Substances 0.000 title claims abstract description 104
- 239000004642 Polyimide Substances 0.000 title claims abstract description 47
- 229920001721 polyimide Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000005187 foaming Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 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 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000002798 polar solvent Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 36
- -1 poly methylene Polymers 0.000 claims description 30
- 239000011148 porous material Substances 0.000 claims description 30
- 239000005056 polyisocyanate Substances 0.000 claims description 26
- 229920001228 polyisocyanate Polymers 0.000 claims description 26
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 18
- 229960004418 trolamine Drugs 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000013543 active substance Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical class CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 claims description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000004984 aromatic diamines Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 claims description 2
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 claims description 2
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 2
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 235000005513 chalcones Nutrition 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- 229960002725 isoflurane Drugs 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 229920000642 polymer Polymers 0.000 abstract description 12
- 239000006261 foam material Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000011157 advanced composite material Substances 0.000 abstract description 3
- 239000004088 foaming agent Substances 0.000 abstract description 3
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- 230000009477 glass transition Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract 2
- 150000002513 isocyanates Chemical class 0.000 abstract 2
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 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 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 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 2
- 238000004500 asepsis Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920007790 polymethacrylimide foam Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Abstract
The invention relates to polyimide foam and a preparation method thereof. The raw materials of the polyimide foam include aromatic dianhydride or aromatic tetracid, isocyanate, polar solvent, composite catalyst, surfactant, foaming agent and other assistants. The preparation method comprises: reacting the aromatic dianhydride or aromatic tetracid with the isocyanate to obtain solution of polyimide foam precursor; adding the foaming agent into the solution of the foam precursor to perform a reaction to obtain a foam intermediate by free foaming; and solidifying and setting the foam intermediate by heat treatment. The method is characterized in that: the polyimide foam prepared by the method has uniform cells, hard texture, low density, a glass-transition temperature of 260 to 305 DEG C, a Shore hardness of 40 to 88 HC and a compression strength of 400 to 700kPa; the preparation process is simple; the cost is low; the foaming process is nontoxic and environmentally-friendly; an innovation is made in high-temperature, light, pressure-resistance, sound-absorbing, noise-reducing and heat-insulating polymer foam materials; and an important support is provided for high-temperature advanced composite material technology.
Description
Technical field
The present invention relates to a kind of polyimide foam and preparation method thereof.
Background technology
Existing polyimide foam material can use down at 400 ℃～500 ℃ in short-term at 250 ℃～300 ℃ following life-time service, is one of thermostability best material in the foam of polymers.The polyimide foam material also has good heat insulation and acoustic absorption performance, excellent dielectric properties, good snappiness and elasticity, and good radiation-resistant property.Therefore, the polyimide foam material is widely used in fields such as aerospace, tactical weapon, electronics, communication and naval vessel as engineering materials.
The research of polyimide foam material arises from the sixties in 19th century, du pont company has been applied for patent US3249561 in 1966, a kind of polyamic acid solution that at first prepares of this patent disclosure, add dewatering agent or dewatering agent/tertiary amine mixture then, add the acid can produce gas such as formic acid etc. again, the acid that add this moment produces CO or CO under the effect of dewatering agent or dewatering agent/tertiary amine mixture
2Foaming, the imidization curing molding obtains the method for polyimide foam under the final high temperature.But, adopt the inhomogeneous and chemical foaming agent of the foam aperture of this method preparation to remain in the foam easily.1969, E.Lavin etc. proposed to adopt the method for Prepared by Ball Milling polyimide foam in patent US3483144.This method is made volatile content with the benzophenone tetracarboxylic acid of equivalent ratio and mphenylenediamine and is at least 6.1% mixture, and then mixture being placed 300 ℃ baking oven to handle and just can obtaining density in 10 minutes is 430kg/m
3The high strength polyimide foam.Though the polyimide foam of this method preparation does not have a large amount of whipping agents that adds, the foam density of preparation is bigger, and defective is more.People such as Garson P.Shulman disclose a kind of method that adopts the powder foaming to prepare polyimide foam in patent US4647596, US4656198 and US4670478.This method at first with aromatic dianhydride and low mass molecule alcohol prepared in reaction esterification products, is mixed with the polyimide precursor powder with esterification products and diamine then, and the precursor powder that obtains is foamed in mould makes polyimide foam at last.The polyimide foam aperture of this method preparation is more even, and controllable density and temperature tolerance are good, but complicated process of preparation, the cost height.
1973, Robert W.Rosser etc. disclosed a kind of preparation method of heat-insulating flame-retardant polyimide foam in patent US3772216.This method in mixed at room temperature and stir, is put into baking oven for heating to 110 ℃～330 ℃ reaction 1 hour～2 hours, the CO that utilizes original position to produce with polyisocyanates, dianhydride, catalyzer, silane surface active agent and a spot of water then
2Gas foaming has prepared a kind of density at 16kg/m
3～96kg/m
3In the scope, has the polyimide foam of good heat-insulating flame-retardant performance.This method can be come the density of control foam by the consumption of conditioned reaction temperature and tensio-active agent.U.S. Pat 5900440 discloses a kind of low density perforate polyimide foam and preparation method thereof.This foam be by the acid of polyisocyanates that contains two functional groups at least and two functional groups and the mixture of acid anhydride (wherein in the polyisocyanates-ratio of NCO and acid anhydride base and carboxyl summation between 0.9～1.1) tertiary amine catalyst, tensio-active agent, and the condition that exists of solvent under react.Reaction process was divided into for two to three steps usually, and reactant is (about 150 ℃) hybrid reaction at first at low temperatures, as the CO of reaction generation
2When burst size was the 1wt%～8wt% of reaction-ure mixture, termination reaction also shifted out mixture from reaction vessel, wear into fine powder after the cooling, at last powder is heated further reaction and emit CO under 225 ℃～260 ℃ high temperature
2Foaming obtains density at 1.602kg/m
3～6.408kg/m
3Low density perforate polyimide foam in the scope.The defective of this method is a complex process, CO
2Wayward and the assurance of burst size.Chinese patent CN101402743A discloses and a kind of aromatic dianhydride and/or aromatic esters, low mass molecule alcohol, catalyzer and tensio-active agent has been mixed in proportion, and forms foam precursors solution in polar solvent; Then foam precursors solution is stirred rapidly with isocyanic ester in proportion, treat to pour into when solution begins to turn white in the preprepared mould, free foaming obtains foam intermediate; And through microwave radiation or/and baking oven for heating is solidified the method obtain polyimide foam.Because this method is mainly utilized aromatic dianhydride and/or aromatic esters and isocyanic ester rapid hybrid reaction and produce CO in the very short time
2Foaming, foam percentage of open area height and sound absorbing capabilities are good, but defective is many, and matter is soft, mechanical property is very poor, shore hardness is 2.5HC only, limited its as structural material applications in high-end fields such as aerospace.
At present, the foam as the interlayer composite material core mainly contains Polymethacrylimide (PMI) foam, rigid polyvinyl chloride (PVC) foam, hard polyaminoester (PU) foam, polystyrene (PS) foam.Table 1 compares the performance of these several porous plastics.
The performance of several porous plastics of table 1
| The foam kind | Density/kg.m -3 | Compressive strength/kPa | Second-order transition temperature/℃ | The life-time service temperature/℃ |
| The PMI foam | ??110 | ??3000 | ??～ * | ??≤180 |
| The hard PVC foam | ??45 | ??180 | ??82 | ??≤60 |
| Hard PU foam | ??40 | ??410 | ??130 | ??≤120 |
| The PS foam | ??51 | ??360 | ??105 | ??≤75 |
* polymethacrylimide foam does not have obvious second-order transition temperature.
As shown in Table 1, rigid polyvinyl chloride (PVC) foam, hard polyaminoester (PU) foam and polystyrene (PS) foamy compressive strength are higher, but second-order transition temperature is all less than 130 ℃, the life-time service temperature is lower than≤and 120 ℃, can not make high temperature sound absorption or acoustic damping materials uses, also be difficult to use as the carbon-fibre reinforced epoxy resin composite material support, the more impossible advanced polymer matrix composites supporter of high temperature that becomes uses; The life-time service temperature of Polymethacrylimide (PMI) foam materials is up to 180 ℃, compressive strength and use temperature improve, though satisfy the requirement of carbon-fibre reinforced epoxy resin composite material support substantially, but thermal deformation in the opposing moulding process or creep ability are low, and its foam rate of closed hole almost 100%, sound absorbing capabilities is poor.Therefore, be badly in need of exploitation second-order transition temperature and life-time service temperature, make it both can make the high temperature sound-absorbing material and use, also can make high temperature advanced composite material moulding supporter or sandwich material and use greater than 200 ℃, hard, low density polymer porous plastics.
Summary of the invention
The object of the present invention is to provide a kind of life-time service temperature greater than 200 ℃, hard, low density, the aperture is even, and compression performance and sound absorbing capabilities are good, and preparation technology is simple, cost is low, polyimide foam of foaming process asepsis environment-protecting and preparation method thereof.
Be above-mentioned purpose, the present invention proposes a kind of polyimide foam and preparation method thereof, and raw materials used is aromatic dianhydride or fragrant tetracid, isocyanic ester, polar solvent, composite catalyst, tensio-active agent, pore forming material, and other auxiliary agent.It is characterized in that:
(a) the first step, this preparation method are included under composite catalyst and the tensio-active agent existence condition, and aromatic dianhydride or fragrant tetracid and isocyanic ester are mixed in proportion, and formation polyimide, the CO of generation are reacted in heating in polar solvent
2Gas is partly overflowed, and obtains foam precursors solution.Each amounts of components is in weight part, and proportioning is as follows:
0～100 part of aromatic dianhydride
0～100 part of aromatic esters
95～200 parts of isocyanic ester
100～300 parts of polar solvents
0.01～10 part of composite catalyst
0.5～10 part in tensio-active agent
5～30 parts of pore forming materials
0～10 part of other auxiliary agent
(b) in second step, this preparation method comprises described foam precursors solution is cooled to 10 ℃～50 ℃; Pore forming material added in the foam precursors solution react, stirred rapidly 0.05 minute～2 minutes, poured in the mould of preheating free foaming into 1 minute～10 minutes, form foam intermediate;
(c) the 3rd step, this preparation method comprises described foam intermediate room temperature placement 0.5 hour～12 hours; Last being heating and curing in 150 ℃～250 ℃ vacuum drying oven finalized the design 2 hours～10 hours, obtained the hard low density polyimide foam of abundant imidization.
Described aromatic dianhydride or fragrant tetracid have following structure:
Wherein A is
X is
Described isocyanic ester is 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate, in phenylene vulcabond, naphthyl vulcabond, hexamethylene vulcabond, poly methylene poly phenyl poly isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate or the isoflurane chalcone diisocyanate one or both.
Described polar solvent is hexamethylphosphoramide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), N-pyridine oxide, N, a kind of in dinethylformamide or the diethylene glycol dimethyl ether.
Described composite catalyst is trolamine, N, N-dimethylethanolamine, N, N '-lutidine, dimethyl benzylamine, N, in N-dimethyl hexadecylamine, triethylenediamine, N-ethylmorpholine, two (dimethyl amido ethyls) and the triethylamine organic amine catalyzer a kind of respectively with stannous octoate, dibutyl tin laurate, dibutyltin diacetate, two toxilic acid dibutyl tins and mercaptan dibutyl tin organo-metallic salt catalyzer in a kind of mixture.
Described tensio-active agent is a kind of in PEG-12 polydimethylsiloxane (DC-193) and the AK series organic silicone oil.
Described pore forming material is one or both in formic acid, acetate, oxalic acid, propionic acid, butanic acid, Succinic Acid, phenylformic acid, salicylic acid, phenylpropionic acid, phthalic acid, furancarboxylic acid, maleic acid, α-Nai Yisuan, water, methyl alcohol, ethanol, propyl alcohol, Virahol or the propyl carbinol.
Described other auxiliary agent comprises at least a following material that is selected from: ethylene glycol, butyleneglycol, glycol ether, low-molecular-weight polyethylene glycol, glycerol, dihydroxyphenyl propane, aromatic diamines and 1,1-two chloro-1-fluoroethanes, difluoro monochlorethane, 1,1,1,3,3-pentafluoropropane, 1,1-C2H4F2 C2H4F2, Skellysolve A, pentamethylene and sherwood oil.
Cardinal principle of the present invention is to utilize raw material aromatic dianhydride or fragrant tetracid to be dissolved in the polar solvent, reacts the formation polyimide, the CO of generation with the isocyanic ester thorough mixing and under 60 ℃～120 ℃
2Gas is partly overflowed, obtain the bigger foam precursors solution of viscosity, be cooled to 10 ℃～50 ℃ then, with pore forming material and the rapid hybrid reaction of foam precursors solution, produce a large amount of whipping agent free foamings and obtain the polyimide foam intermediate, by the typing that in vacuum drying oven, is heating and curing, finally obtain the hard low density polyimide foam of abundant imidization.In hybrid resin, add tensio-active agent in order to stable bubble hole; Add amine and organo-metallic salt composite catalyst in order to quicken and to coordinate transfer reaction and foamable reaction; Add pore forming material in order to produce a large amount of whipping agent foaming.
(a) the first step
(b) second step
Also can add a kind of in ethylene glycol, butyleneglycol, glycol ether, low-molecular-weight polyethylene glycol, glycerol, dihydroxyphenyl propane or the aromatic diamine in the present invention prescription, so that forming with the isocyano with the isocyanic ester pre-polymerization is the performed polymer of end group, improve reactive behavior.Also can add 1 in the present invention prescription, 1-two chloro-1-fluoroethanes, difluoro monochlorethane, 1,1,1,3,3-pentafluoropropane, 1, in 1-C2H4F2 C2H4F2, Skellysolve A, pentamethylene or the sherwood oil one or both so that reduce the density of foams.
The present invention has following difference and advantage:
(1) foam materials life-time service temperature height, hardness is big, density is low, compressive strength is big, sound absorbing capabilities is good;
(2) the foams aperture is even, does not have to collapse bubble and steep, split bubble and the incomplete defective of material imidization;
(3) preparation technology is simple, need not specific equipment;
(4) compare with the polyimide foam of diamine preparation with traditional binary acid anhydride, adopt the polyimide foam of binary acid anhydride and isocyanic ester preparation cheap;
(5) foaming process asepsis environment-protecting;
(6) resulting product stable performance of the present invention, Application Areas is wide.
Embodiment:
The present invention can be further understood by the following examples, but content of the present invention can not be limited.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
1,2,4,100 parts of 5-pyromellitic dianhydrides
130 parts of poly methylene poly phenyl poly isocyanates
N, 150 parts of dinethylformamides
0.50 part of trolamine
0.50 part of stannous octoate
2.50 parts of DC-193
6 parts of pore forming materials
With 1,2,4,5-pyromellitic dianhydride and N, the dinethylformamide solvent joins in the container and fully stirs, and treats 1,2,4,5-pyromellitic dianhydride powder all after the dissolving, adds poly methylene poly phenyl poly isocyanate, trolamine, stannous octoate, DC-193, and 60 ℃～90 ℃ temperature range internal reactions 0.3 hour～2 hours, be cooled to 30 ℃ then, obtain the bigger foam precursors solution of viscosity; Add pore forming material, stir fast, treat to pour in the preprepared mould after solution begins to turn white, free foaming 5 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, solidified 2 hours down at 240 ℃, the cooling back demoulding obtains the solid polyimide foam.
Embodiment 2
3,3 ', 4,80 parts of 4 '-benzophenone tetracarboxylic dianhydrides
109 parts of poly methylene poly phenyl poly isocyanates
N, 210 parts of dinethylformamides
0.35 part of triethylamine
0.35 part of stannous octoate
8,805 1 parts of AK
5 parts of pore forming materials
With 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and N, the dinethylformamide solvent joins in the container and fully stirs, and treats 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride powder adds poly methylene poly phenyl poly isocyanate, triethylamine, stannous octoate, AK 8805 after all dissolving, and reacts 1 hour～2 hours down at 90 ℃, be cooled to 30 ℃ then, obtain the bigger foam precursors solution of viscosity; Add pore forming material, stir fast, treat to pour in the preprepared mould after solution begins to turn white, free foaming 10 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, solidified 3 hours down at 250 ℃, the cooling back demoulding obtains the solid polyimide foam.
Embodiment 3
1,2,4,45 parts of 5-pyromellitic dianhydrides
3,3 ', 4,65 parts of 4 '-benzophenone tetracarboxylic dianhydrides
180 parts of poly methylene poly phenyl poly isocyanates
210 parts of N,N-dimethylacetamide
0.40 part of trolamine
0.40 part of dibutyl tin laurate
8,805 2 parts of AK
4 parts of pore forming materials
With 1,2,4,5-pyromellitic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and N, the N-dimethylacetamide solvent joins in the container and fully stirs, and treats 1,2,4,5-pyromellitic dianhydride and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride powder adds poly methylene poly phenyl poly isocyanate, trolamine, dibutyl tin laurate, AK 8805 after all dissolving, and under 90 ℃, reacted 1 hour～2 hours, be cooled to 30 ℃ then, obtain the bigger foam precursors solution of viscosity; Add pore forming material, stir fast, treat to pour in the preprepared mould after solution begins to turn white, free foaming 8 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, solidified 3 hours down at 250 ℃, the cooling back demoulding obtains the solid polyimide foam.
Embodiment 4
3,3 ', 4,65 parts of 4 '-benzophenone tetracarboxylic dianhydrides
4,13 parts of 4 '-diphenylmethanediisocyanates
90 parts of poly methylene poly phenyl poly isocyanates
145 parts of N,N-dimethylacetamide
0.30 part of trolamine
0.30 part of dibutyl tin laurate
2 parts of DC-193
1,2.5 parts of 4-butyleneglycols
6.5 parts of pore forming materials
With 4,4 '-diphenylmethanediisocyanate and poly methylene poly phenyl poly isocyanate are invested in the container and stir, slowly add 1 then, the 4-butyleneglycol, make it and 4, the abundant pre-polymerization of 4 '-diphenylmethanediisocyanate and poly methylene poly phenyl poly isocyanate was reacted 5 minutes～30 minutes after the thing clarification to be mixed again, and obtaining with the isocyano is the performed polymer of end group; To be dissolved in N then, in the N-N,N-DIMETHYLACETAMIDE 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride solution slowly joins in the performed polymer and stirs, add trolamine, dibutyl tin laurate, DC-193 again, and be cooled to 35 ℃ after 0.5 hour～1 hour, obtain foam precursors solution in reaction under 70 ℃; Add pore forming material, stir fast, treat to pour in the preprepared mould after solution begins to turn white, free foaming 7 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, solidified 3 hours down at 200 ℃, the cooling back demoulding obtains the solid polyimide foam.
Embodiment 5
1,2,4,30 parts of 5-pyromellitic dianhydrides
3,3 ', 4,30 parts of 4 '-phenyl ether tetracarboxylic dianhydrides
100 parts of poly methylene poly phenyl poly isocyanates
N, 85 parts of dinethylformamides
0.30 part of trolamine
0.30 part of stannous octoate
1 part of DC-193
4,35 parts of 4 '-diaminodiphenyl oxides
5 parts of pore forming materials
Poly methylene poly phenyl poly isocyanate is invested in the container stirs, slowly add 4 then, 4 '-diaminodiphenyl oxide, make it and the abundant pre-polymerization of poly methylene poly phenyl poly isocyanate, after the thing clarification to be mixed, reacted 5 minutes～30 minutes, obtaining with the isocyano is the performed polymer of end group again; To be dissolved in N then, in the dinethylformamide 1,2,4,5-pyromellitic dianhydride and 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride solution slowly joins in the performed polymer and stirs, and adds trolamine, stannous octoate, DC-193 again, and after reacting 0.8 hour under 80 ℃, be cooled to 25 ℃, obtain the bigger foam precursors solution of viscosity; Add pore forming material, stir fast, treat to pour in the preprepared mould after solution begins to turn white, free foaming 2 minutes～5 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, solidified 2.5 hours down at 230 ℃, the cooling back demoulding obtains the solid polyimide foam.
Embodiment 6
1,2,4,30 parts of 5-pyromellitic dianhydrides
3,3 ', 4,30 parts of 4 '-phenyl ether tetracarboxylic dianhydrides
100 parts of poly methylene poly phenyl poly isocyanates
N, 210 parts of dinethylformamides
0.50 part of trolamine
0.50 part of stannous octoate
8,805 1 parts of AK
5.5 parts of pore forming materials
2 parts of pentamethylene
With 1,2,4,5-pyromellitic dianhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride, and N, the dinethylformamide solvent stirs in container, treats 1,2,4,5-pyromellitic dianhydride and 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride adds poly methylene poly phenyl poly isocyanate, trolamine, stannous octoate, AK 8805 after all dissolving, and, be cooled to 38 ℃ then 60 ℃～100 ℃ temperature range internal reactions 1.5 hours, obtain foam precursors solution; Add pore forming material and pentamethylene, stir fast, treat to pour in the mould of preheating after solution begins to turn white, free foaming 10 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, solidified 3 hours down at 230 ℃, the cooling back demoulding obtains the solid polyimide foam.
Embodiment 7
3,3 ', 4,60 parts of 4 '-phenyl ether tetracarboxylic dianhydrides
130 parts of poly methylene poly phenyl poly isocyanates
N, 120 parts of dinethylformamides
0.30 part of trolamine
0.30 part of stannous octoate
8,805 2 parts of AK
2.5 parts of glycerol
3.5 parts of pore forming materials
2 parts of Skellysolve As
Poly methylene poly phenyl poly isocyanate is invested in the container stirs, slowly add glycerol then, make it and the abundant pre-polymerization of poly methylene poly phenyl poly isocyanate, after the thing clarification to be mixed, reacted again 20 minutes, obtain the performed polymer that isocyano is an end group; To be dissolved in N then, 3,3 ' in the dinethylformamide solvent, 4,4 '-phenyl ether tetracarboxylic dianhydride slowly joins in the performed polymer and stirs, and adds trolamine, stannous octoate, AK 8805 again, and after reacting 1 hour under 90 ℃, be cooled to 25 ℃, obtain foam precursors solution; Add pore forming material and Skellysolve A, stir fast, treat to pour in the mould of preheating after solution begins to turn white, free foaming 5 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, solidified 2 hours down at 210 ℃, the cooling back demoulding obtains the solid polyimide foam.
Embodiment 8
1,2,4,60 parts of 5-pyromellitic dianhydrides
130 parts of poly methylene poly phenyl poly isocyanates
N, 120 parts of dinethylformamides
0.30 part of trolamine
0.30 part of stannous octoate
8,805 2 parts of AK
54 parts of Polyethylene Glycol-600s
4.5 parts of pore forming materials
1,2 parts of 1-two chloro-1-fluoroethanes
Poly methylene poly phenyl poly isocyanate is invested in the container stirs, slowly add Polyethylene Glycol-600 then, make it and the abundant pre-polymerization of poly methylene poly phenyl poly isocyanate, after the thing clarification to be mixed, reacted again 20 minutes, obtain with the isocyano is the performed polymer of end group, to be dissolved in N then, in the dinethylformamide solvent 1,2,4,5-Pyromellitic Acid anhydride solution slowly joins in the performed polymer and stirs, add trolamine, stannous octoate, AK 8805 again, and be cooled to 35 ℃ after 1 hour, obtain foam precursors solution in reaction under 78 ℃; Add pore forming material and 1,1-two chloro-1-fluoroethanes stir fast, treat to pour in the mould of preheating after solution begins to turn white, and free foaming 1 minute～4 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, solidified 2 hours down at 250 ℃, the cooling back demoulding obtains the solid polyimide foam.
Embodiment 9
1,2,4,85 parts of 5-pyromellitic dianhydrides
3,3 ', 4,35 parts of 4 '-benzophenone tetracarboxylic dianhydrides
175 parts of poly methylene poly phenyl poly isocyanates
200 parts of N,N-dimethylacetamide
0.30 part of trolamine
0.50 part of dibutyl tin laurate
8,805 1.5 parts of AK
3.8 parts of pore forming materials
With 1,2,4,5-pyromellitic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and N, the N-dimethylacetamide solvent joins in the container and fully stirs, and treats 1,2,4,5-pyromellitic dianhydride and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride powder adds poly methylene poly phenyl poly isocyanate, trolamine, dibutyl tin laurate, AK 8805 after all dissolving, and under 110 ℃, reacted 2 hours, be cooled to 25 ℃ then, obtain the bigger foam precursors solution of viscosity; Add pore forming material, stir fast, treat to pour in the preprepared mould after solution begins to turn white, free foaming 10 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, solidified 3 hours down at 250 ℃, the cooling back demoulding obtains the solid polyimide foam.
Density, mean pore size, compressive strength, second-order transition temperature, hardness and average sound absorption coefficient by the foregoing description 1 to embodiment 9 gained hard low density polyimide foam are illustrated in the table 2.
The polyimide foam fundamental property of table 2 embodiment preparation
| Example/sample number | Density/kgm -3 | Mean pore size/μ m | Compressive strength/kPa | Glass transition temperature Tg/℃ | Hardness * */HC | Average sound absorption coefficient ***(125～4000Hz) |
| ??1 | ??83.0 | ??557 | ??400 | ??285.3 | ??38.3 | ??0.44 |
| ??2 | ??130.0 | ??509 | ??700 | ??276.7 | ??88.4 | ??0.42 |
| ??3 | ??85.8 | ??550 | ??540 | ??280.0 | ??75.0 | ??0.43 |
| ??4 | ??67.0 | ??534 | ??360 | ??272.6 | ??68.0 | ??0.44 |
| ??5 | ??89.5 | ??518 | ??630 | ??281.4 | ??72.0 | ??0.42 |
| ??6 | ??125.4 | ??450 | ??680 | ??274.4 | ??83.5 | ??0.40 |
| ??7 | ??124.5 | ??493 | ??650 | ??269.4 | ??81.7 | ??0.39 |
| ??8 | ??87.7 | ??540 | ??580 | ??285.3 | ??76.2 | ??0.42 |
| ??9 | ??130.0 | ??502 | ??550 | ??305 | ??88.1 | ??0.45 |
* shore hardness testing standard: ASTM D2240-05 " Standard Test Method for Rubber Property-DurometerHardness " promptly " measures the test method of rubber hardness " with sclerometer.
* *Average sound absorption coefficient: adopt the standing-wave-tube method test.
Claims (8)
1. polyimide foam and preparation method thereof, raw materials used is aromatic dianhydride or fragrant tetracid, isocyanic ester, polar solvent, composite catalyst, tensio-active agent, pore forming material, and other auxiliary agent.It is characterized in that:
(a) the first step, this preparation method are included under composite catalyst and the tensio-active agent existence condition, and aromatic dianhydride or fragrant tetracid and isocyanic ester are mixed in proportion, and formation polyimide, the CO of generation are reacted in heating in polar solvent
2Gas is partly overflowed, and obtains foam precursors solution.Each amounts of components is in weight part, and proportioning is as follows:
0～100 part of aromatic dianhydride
0～100 part of fragrance tetracid
95～200 parts of isocyanic ester
100～300 parts of polar solvents
0.01～10 part of composite catalyst
0.5～10 part in tensio-active agent
5～30 parts of pore forming materials
0～10 part of other auxiliary agent
(b) second step, this preparation method comprises described foam precursors solution is cooled to 10 ℃～50 ℃, pore forming material is added in the foam precursors solution react, and stirs rapidly 0.05 minute～2 minutes, pour in the mould of preheating free foaming into 1 minute～10 minutes, and formed foam intermediate.
(c) the 3rd step, this preparation method comprises described foam intermediate room temperature placement 0.5 hour～12 hours, last being heating and curing in 150 ℃～250 ℃ vacuum drying oven finalized the design 2 hours～10 hours, obtained the hard low density polyimide foam of abundant imidization.
2. the described method of claim 1 is characterized in that, aromatic dianhydride wherein or fragrant tetracid have following structure:
Wherein A is
X is
3. the described method of claim 1, it is characterized in that, isocyanic ester wherein is 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate, in phenylene vulcabond, naphthyl vulcabond, hexamethylene vulcabond, poly methylene poly phenyl poly isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate or the isoflurane chalcone diisocyanate one or both.
4. the described method of claim 1, it is characterized in that, polar solvent wherein is hexamethylphosphoramide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), N-pyridine oxide, N, a kind of in dinethylformamide or the diethylene glycol dimethyl ether.
5. the described method of claim 1, it is characterized in that, composite catalyst wherein is trolamine, N, N-dimethylethanolamine, N, N '-lutidine, dimethyl benzylamine, N, in N-dimethyl hexadecylamine, triethylenediamine, N-ethylmorpholine, two (dimethyl amido ethyls) and the triethylamine organic amine catalyzer a kind of respectively with stannous octoate, dibutyl tin laurate, dibutyltin diacetate, two toxilic acid dibutyl tins and mercaptan dibutyl tin organo-metallic salt catalyzer in a kind of mixture.
6. the described method of claim 1 is characterized in that, tensio-active agent wherein is a kind of in PEG-12 polydimethylsiloxane (DC-193) and the AK series organic silicone oil.
7. the described method of claim 1, it is characterized in that pore forming material wherein is one or both in formic acid, acetate, oxalic acid, propionic acid, butanic acid, Succinic Acid, phenylformic acid, salicylic acid, phenylpropionic acid, phthalic acid, furancarboxylic acid, maleic acid, α-Nai Yisuan, water, methyl alcohol, ethanol, propyl alcohol, Virahol or the propyl carbinol.
8. the described method of claim 1, it is characterized in that, other auxiliary agent wherein comprises at least a following material that is selected from: ethylene glycol, butyleneglycol, glycol ether, low-molecular-weight polyethylene glycol, glycerol, dihydroxyphenyl propane, aromatic diamines and 1,1-two chloro-1-fluoroethanes, difluoro monochlorethane, 1,1,1,3,3-pentafluoropropane, 1,1-C2H4F2 C2H4F2, Skellysolve A, pentamethylene and sherwood oil.
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| CN108017786A (en) * | 2017-12-24 | 2018-05-11 | 桂林理工大学 | The method that Kapton is prepared using benzophenone tetracarboxylic dianhydride |
| CN109810251A (en) * | 2019-01-15 | 2019-05-28 | 哈尔滨工程大学 | A kind of preparation method of high-performance rigid polyimides heat insulation and acoustic absorption foam |
| CN114854009A (en) * | 2022-05-13 | 2022-08-05 | 华中科技大学 | Polyimide foam and preparation method thereof |
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