CN101812232B - Polyimide foam and preparation method thereof - Google Patents
Polyimide foam and preparation method thereof Download PDFInfo
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- CN101812232B CN101812232B CN 201010144568 CN201010144568A CN101812232B CN 101812232 B CN101812232 B CN 101812232B CN 201010144568 CN201010144568 CN 201010144568 CN 201010144568 A CN201010144568 A CN 201010144568A CN 101812232 B CN101812232 B CN 101812232B
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- foam
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- polyimide
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- 239000006260 foam Substances 0.000 title claims abstract description 109
- 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 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 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 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 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 9
- 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 35
- 239000011148 porous material Substances 0.000 claims description 29
- -1 poly methylene Polymers 0.000 claims description 28
- 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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group 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 group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000013543 active substance Substances 0.000 claims description 11
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 150000001412 amines Chemical class 0.000 claims description 4
- 230000015572 biosynthetic process Effects 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 group 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
- 150000004984 aromatic diamines Chemical class 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
- 125000002524 organometallic group Chemical group 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
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-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
- 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
- 235000011054 acetic acid Nutrition 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
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-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
- 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
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 229920000642 polymer Polymers 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000006261 foam material Substances 0.000 abstract description 3
- 239000004088 foaming agent Substances 0.000 abstract description 3
- 239000011157 advanced composite material Substances 0.000 abstract description 2
- 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
- 238000003756 stirring Methods 0.000 description 23
- 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
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-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
- 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
- 239000000805 composite resin Substances 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
- 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
- 150000003839 salts Chemical class 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
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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 foams can at 250 ℃～300 ℃ lower life-time service, can 400 ℃～500 ℃ lower uses, be one of thermostability best material in the foam of polymers in short-term.Polyimide foams also has good heat insulation and acoustic absorption performance, good dielectric properties, good snappiness and elasticity, and good radiation-resistant property.Therefore, Polyimide foams is widely used in the fields such as aerospace, tactical weapon, electronics, communication and naval vessel as engineering materials.
The research of Polyimide foams arises from the sixties in 19th century, du pont company has been applied for patent US3249561 in 1966, this patent discloses a kind of polyamic acid solution that at first prepares, then add dewatering agent or dewatering agent/tertiary amine mixture, add the acid can produce gas such as formic acid etc., the acid that add this moment produces CO or CO under the effect of dewatering agent or dewatering agent/tertiary amine mixture again
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 standby foam aperture of this legal system easily to remain in the foam.1969, E.Lavin etc. proposed to adopt ball milled to prepare the method for polyimide foam in patent US3483144.The 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 process and just can obtaining density in 10 minutes is 430kg/m
3The High Strength Polyimide foam.Though the standby polyimide foam of this legal system is without a large amount of whipping agents that adds, the foam density of preparation is larger, and defective is more.The 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.The method at first with aromatic dianhydride and low mass molecule alcohol reaction preparation esterification products, then is mixed with the polyimide precursor powder with esterification products and diamine, and the precursor powder that obtains is foamed in mould makes polyimide foam at last.The standby polyimide foam aperture of this legal system is more even, and density is controlled and temperature tolerance good, but complicated process of preparation, cost is high.
1973, Robert W.Rosser etc. disclosed a kind of preparation method of heat-insulating flame-retardant polyimide foam in patent US3772216.The method in mixed at room temperature and stir, is then 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 small amount of water
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 controlled by the consumption of conditioned reaction temperature and tensio-active agent the density of foam.US Patent No. 5900440 discloses a kind of low density perforate polyimide foam and preparation method thereof.This foam be by the acid of the polyisocyanates that contains at least two functional groups 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 (approximately 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 the method is complex process, CO
2Burst size is wayward and hold.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 within the very short time
2Foaming, the foam percentage of open area is high and sound absorbing capabilities 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 is without obvious second-order transition temperature.
As shown in Table 1, the compressive strength of rigid polyvinyl chloride (PVC) foam, hard polyaminoester (PU) foam and polystyrene (PS) foam is 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 high temperature Advanced Resin-based Composites supporter that becomes uses; The life-time service temperature of Polymethacrylimide (PMI) foam materials is up to 180 ℃, compressive strength and use temperature improve, although substantially satisfy the requirement of carbon-fibre reinforced epoxy resin composite material support, but the 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 greater than 200 ℃, hard, low density polymer porous plastics, 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 materials and use.
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) 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 a kind of in hexamethylphosphoramide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), N-pyridine oxide, DMF 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, acetic acid, oxalic acid, propionic acid, butanic acid, Succinic Acid, phenylformic acid, salicylic acid, phenylpropionic acid, phthalic acid, furancarboxylic acid, maleic acid, α-naphthaleneacetic acid, 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, difluoromono-chloroethane, 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, fully mixes to be incorporated under 60 ℃～120 ℃ with isocyanic ester and reacts the formation polyimide, the CO of generation
2Gas is partly overflowed, obtain the larger foam precursors solution of viscosity, then be cooled to 10 ℃～50 ℃, 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 accelerate 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, in order to the performed polymer of isocyanic ester pre-polymerization formation take isocyano as end group, improve reactive behavior.Also can add 1,1-, two chloro-1-fluoroethanes, difluoromono-chloroethane, 1,1,1,3 in the present invention prescription, 3-pentafluoropropane, 1, in 1-C2H4F2 C2H4F2, Skellysolve A, pentamethylene or the sherwood oil one or both, in order to reduce the density of foams.
The present invention has following difference and advantage:
(1) foam materials life-time service temperature is high, hardness is large, density is low, compressive strength is large, sound absorbing capabilities is good;
(2) the foams aperture is even, steeps and steep, split bubble and the incomplete defective of material imidization without collapsing;
(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
100 parts of 1,2,4,5-pyromellitic dianhydrides
130 parts of poly methylene poly phenyl poly isocyanates
150 parts of DMFs
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, then be cooled to 30 ℃, obtain the larger foam precursors solution of viscosity; Add pore forming material, rapid stirring is poured into after solution begins to turn white in the preprepared mould, and free foaming 5 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, 240 ℃ of lower curing 2 hours, the demoulding obtains the solid polyimide foam after the cooling.
Embodiment 2
3,3 ', 4,80 parts of 4 '-benzophenone tetracarboxylic dianhydrides
109 parts of poly methylene poly phenyl poly isocyanates
210 parts of DMFs
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 90 ℃ of lower reactions 1 hour～2 hours, then be cooled to 30 ℃, obtain the larger foam precursors solution of viscosity; Add pore forming material, rapid stirring is poured into after solution begins to turn white in the preprepared mould, and free foaming 10 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, 250 ℃ of lower curing 3 hours, the demoulding obtains the solid polyimide foam after the cooling.
Embodiment 3
45 parts of 1,2,4,5-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 90 ℃ of lower reactions 1 hour～2 hours, then be cooled to 30 ℃, obtain the larger foam precursors solution of viscosity; Add pore forming material, rapid stirring is poured into after solution begins to turn white in the preprepared mould, and free foaming 8 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, 250 ℃ of lower curing 3 hours, the demoulding obtains the solid polyimide foam after the cooling.
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
2.5 parts of BDOs
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, then slowly add 1, 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, obtained the performed polymer take isocyano as end group; Then will be dissolved in N, in the N-N,N-DIMETHYLACETAMIDE 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride solution slowly joins in the performed polymer and stirs, add again trolamine, dibutyl tin laurate, DC-193, and be cooled to 35 ℃ 70 ℃ of lower reactions after 0.5 hour～1 hour, obtain foam precursors solution; Add pore forming material, rapid stirring is poured into after solution begins to turn white in the preprepared mould, and free foaming 7 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, 200 ℃ of lower curing 3 hours, the demoulding after the cooling obtains the solid polyimide foam.
Embodiment 5
30 parts of 1,2,4,5-pyromellitic dianhydrides
3,3 ', 4,30 parts of 4 '-phenyl ether tetracarboxylic dianhydrides
100 parts of poly methylene poly phenyl poly isocyanates
85 parts of DMFs
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, then slowly add 4,4 '-diaminodiphenyl oxide, make it and the abundant pre-polymerization of poly methylene poly phenyl poly isocyanate, after the thing clarification to be mixed, reacted again 5 minutes～30 minutes, obtain the performed polymer take isocyano as end group; Then will be dissolved in N, 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 larger foam precursors solution of viscosity; Add pore forming material, rapid stirring is poured into after solution begins to turn white in the preprepared mould, and free foaming 2 minutes～5 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, 230 ℃ of lower curing 2.5 hours, the demoulding after the cooling obtains the solid polyimide foam.
Embodiment 6
30 parts of 1,2,4,5-pyromellitic dianhydrides
3,3 ', 4,30 parts of 4 '-phenyl ether tetracarboxylic dianhydrides
100 parts of poly methylene poly phenyl poly isocyanates
210 parts of DMFs
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 60 ℃～100 ℃ temperature range internal reactions 1.5 hours, then be cooled to 38 ℃, obtain foam precursors solution; Add pore forming material and pentamethylene, rapid stirring is even, pours into after solution begins to turn white in the mould of preheating, and free foaming 10 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, 230 ℃ of lower curing 3 hours, the demoulding after the cooling 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
120 parts of DMFs
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, then slowly add glycerol, 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 end group; Then will be dissolved in 3,3 ' in the DMF 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, rapid stirring is even, pours into after solution begins to turn white in the mould of preheating, and free foaming 5 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, 210 ℃ of lower curing 2 hours, the demoulding after the cooling obtains the solid polyimide foam.
Embodiment 8
60 parts of 1,2,4,5-pyromellitic dianhydrides
130 parts of poly methylene poly phenyl poly isocyanates
120 parts of DMFs
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
2 parts of 1,1-, two chloro-1-fluoroethanes
Poly methylene poly phenyl poly isocyanate is invested in the container stirs, then slowly add Polyethylene Glycol-600, 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 take isocyano as end group, then will be dissolved in N, in the dinethylformamide solvent 1,2,4,5-Pyromellitic Acid anhydride solution slowly joins in the performed polymer and stirs, add again trolamine, stannous octoate, AK 8805, and be cooled to 35 ℃ 78 ℃ of lower reactions after 1 hour, obtain foam precursors solution; Add pore forming material and 1,1-, two chloro-1-fluoroethanes, rapid stirring is even, pours into after solution begins to turn white in the mould of preheating, and free foaming 1 minute～4 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, 250 ℃ of lower curing 2 hours, the demoulding after the cooling obtains the solid polyimide foam.
Embodiment 9
85 parts of 1,2,4,5-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 110 ℃ of lower reactions 2 hours, then be cooled to 25 ℃, obtain the larger foam precursors solution of viscosity; Add pore forming material, rapid stirring is poured into after solution begins to turn white in the preprepared mould, and free foaming 10 minutes obtains foam intermediate; Then foam intermediate is put into vacuum drying oven, 250 ℃ of lower curing 3 hours, the demoulding obtains the solid polyimide foam after the cooling.
Density, mean pore size, compressive strength, second-order transition temperature, hardness and average sound absorption coefficient by above-described embodiment 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 " namely " measures the test method of rubber hardness " with sclerometer.
* *Average sound absorption coefficient: adopt the standing-wave-tube method test.
Claims (5)
1. the preparation method of a polyimide foam, 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, each amounts of components is as follows in weight part:
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;
(b) second step, this preparation method comprises described foam precursors solution is cooled to 10 ℃～50 ℃, pore forming material and other auxiliary agent added in the foam precursors solution react, stirred 0.05 minute～2 minutes rapidly, 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;
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 pore forming material is one or both in formic acid, acetic acid, oxalic acid, propionic acid, butanic acid, Succinic Acid, phenylformic acid, salicylic acid, phenylpropionic acid, phthalic acid, furancarboxylic acid, maleic acid, α-naphthaleneacetic acid, water, methyl alcohol, ethanol, propyl alcohol, Virahol or the propyl carbinol;
Described composite catalyst is a kind of mixture in a kind of and organo-metallic salt catalyzer in the organic amine catalyzer;
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, difluoromono-chloroethane, 1,1,1,3,3-pentafluoropropane, 1,1-C2H4F2 C2H4F2, Skellysolve A, pentamethylene and sherwood oil.
2. method claimed in claim 1 is characterized in that, aromatic dianhydride wherein or fragrant tetracid have following structure:
Wherein A is
X is
3. method claimed in claim 1, it is characterized in that, polar solvent wherein is a kind of in hexamethylphosphoramide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), N-pyridine oxide, DMF or the diethylene glycol dimethyl ether.
4. method claimed in claim 1, it is characterized in that, the organic amine catalyzer is trolamine, N, N-dimethylethanolamine, N, N '-lutidine, dimethyl benzylamine, N, N-dimethyl hexadecylamine, triethylenediamine, N-ethylmorpholine, two (dimethyl amido ethyls) or triethylamine; Organo-metallic salt catalyzer is stannous octoate, dibutyl tin laurate, dibutyltin diacetate, two toxilic acid dibutyl tins or mercaptan dibutyl tin.
5. method claimed in 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.
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| CN114854009B (en) * | 2022-05-13 | 2023-05-30 | 华中科技大学 | Polyimide foam and preparation method thereof |
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| US4177333A (en) * | 1978-02-24 | 1979-12-04 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Catalysts for polyimide foams from aromatic isocyanates and aromatic dianhydrides |
| US5153234A (en) * | 1990-07-12 | 1992-10-06 | Lenzing Aktiengesellschaft | Flame-retardant, high-temperature resistant foams of polyimides |
| CN101402743A (en) * | 2008-11-25 | 2009-04-08 | 北京市射线应用研究中心 | Polyimide foam and method of producing the same |
-
2010
- 2010-04-09 CN CN 201010144568 patent/CN101812232B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4177333A (en) * | 1978-02-24 | 1979-12-04 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Catalysts for polyimide foams from aromatic isocyanates and aromatic dianhydrides |
| US5153234A (en) * | 1990-07-12 | 1992-10-06 | Lenzing Aktiengesellschaft | Flame-retardant, high-temperature resistant foams of polyimides |
| CN101402743A (en) * | 2008-11-25 | 2009-04-08 | 北京市射线应用研究中心 | Polyimide foam and method of producing the same |
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|---|---|
| CN101812232A (en) | 2010-08-25 |
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