CN115895253A - High-temperature-resistant flame-retardant polyimide foam material and preparation method thereof - Google Patents
High-temperature-resistant flame-retardant polyimide foam material and preparation method thereof Download PDFInfo
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- CN115895253A CN115895253A CN202211056729.1A CN202211056729A CN115895253A CN 115895253 A CN115895253 A CN 115895253A CN 202211056729 A CN202211056729 A CN 202211056729A CN 115895253 A CN115895253 A CN 115895253A
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- diisocyanate
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 107
- 229920001721 polyimide Polymers 0.000 title claims abstract description 107
- 239000006261 foam material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims description 13
- 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 title description 23
- 239000003063 flame retardant Substances 0.000 title description 23
- 239000006260 foam Substances 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000012948 isocyanate Substances 0.000 claims abstract description 25
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 23
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- 239000004088 foaming agent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 54
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 42
- 238000005187 foaming Methods 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 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 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 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 14
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 14
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 claims description 14
- 229940099364 dichlorofluoromethane Drugs 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000009775 high-speed stirring Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 12
- 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 10
- 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 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000004604 Blowing Agent Substances 0.000 claims description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 8
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 7
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 claims description 7
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 7
- PRIUALOJYOZZOJ-UHFFFAOYSA-L 2-ethylhexyl 2-[dibutyl-[2-(2-ethylhexoxy)-2-oxoethyl]sulfanylstannyl]sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS[Sn](CCCC)(CCCC)SCC(=O)OCC(CC)CCCC PRIUALOJYOZZOJ-UHFFFAOYSA-L 0.000 claims description 7
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 7
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 7
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 claims description 7
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- -1 polymethylene Polymers 0.000 claims description 7
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 7
- 229940096992 potassium oleate Drugs 0.000 claims description 7
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 7
- SXWZSWLBMCNOPC-UHFFFAOYSA-M potassium;6-methylheptanoate Chemical compound [K+].CC(C)CCCCC([O-])=O SXWZSWLBMCNOPC-UHFFFAOYSA-M 0.000 claims description 7
- 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 7
- LTOVZUHVYHATET-UHFFFAOYSA-N 1,2-diisocyanatoethylcyclohexane Chemical compound O=C=NCC(N=C=O)C1CCCCC1 LTOVZUHVYHATET-UHFFFAOYSA-N 0.000 claims description 6
- DDPRYTUJYNYJKV-UHFFFAOYSA-N 1,4-diethylpiperazine Chemical compound CCN1CCN(CC)CC1 DDPRYTUJYNYJKV-UHFFFAOYSA-N 0.000 claims description 6
- BBNWETAONXSJGQ-UHFFFAOYSA-N 1-(1,2-diisocyanatoethyl)-2,3,4,5-tetramethylbenzene Chemical compound CC1=CC(C(CN=C=O)N=C=O)=C(C)C(C)=C1C BBNWETAONXSJGQ-UHFFFAOYSA-N 0.000 claims description 6
- SSDCYACDOZSOHT-UHFFFAOYSA-N C(CCCCN=C=O)N=C=O.C(=O)OC Chemical compound C(CCCCN=C=O)N=C=O.C(=O)OC SSDCYACDOZSOHT-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- VCDRAONLIPOEFL-UHFFFAOYSA-N 4-n-[4-(4-anilinoanilino)phenyl]benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC(C=C1)=CC=C1NC(C=C1)=CC=C1NC1=CC=CC=C1 VCDRAONLIPOEFL-UHFFFAOYSA-N 0.000 claims description 5
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 claims description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000168 pyrrolyl group Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 22
- 239000001301 oxygen Substances 0.000 abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 abstract description 22
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 abstract description 11
- 230000006872 improvement Effects 0.000 abstract description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract 2
- 238000001723 curing Methods 0.000 description 25
- 239000011148 porous material Substances 0.000 description 12
- 238000003908 quality control method Methods 0.000 description 10
- 238000007493 shaping process Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- CJIJXIFQYOPWTF-UHFFFAOYSA-N 7-hydroxycoumarin Natural products O1C(=O)C=CC2=CC(O)=CC=C21 CJIJXIFQYOPWTF-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 description 3
- HFTAFOQKODTIJY-UHFFFAOYSA-N umbelliferone Natural products Cc1cc2C=CC(=O)Oc2cc1OCC=CC(C)(C)O HFTAFOQKODTIJY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GNDLGOZYDSQVAK-UHFFFAOYSA-N 2,7-diisocyanato-2,7-dimethyloctane Chemical compound O=C=NC(C)(C)CCCCC(C)(C)N=C=O GNDLGOZYDSQVAK-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GKGXKPRVOZNVPQ-UHFFFAOYSA-N diisocyanatomethylcyclohexane Chemical compound O=C=NC(N=C=O)C1CCCCC1 GKGXKPRVOZNVPQ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Abstract
The invention provides a polyimide foam material, which comprises, by mass, 15-60 parts of a umbellate polyamic acid precursor, 15-60 parts of isocyanate, 10-40 parts of a solvent, 2-8 parts of a foaming agent, 5-12 parts of a foam stabilizer and 0.5-5 parts of a catalyst. The invention uses the pyrrole polyamic acid precursor prepared by PMDA and tetraphenylamine to react with isocyanate groups, foam and realize the introduction of a trapezoidal polyimide structure into foam through an imidization process, and the introduced trapezoidal polyimide rigid structure has obvious improvement on oxygen index and mechanical property. The foam material prepared by the invention has the advantages of high oxygen index, high temperature resistance and the like.
Description
Technical Field
The invention belongs to the technical field of high-temperature-resistant flame-retardant polyimide foam materials, relates to a polyimide foam material and a preparation method thereof, and particularly relates to a high-temperature-resistant flame-retardant polyimide foam material and a preparation method thereof.
Background
The polyimide is a polymer containing an imide ring structure on a chain link of a main chain, can be divided into three types of aliphatic polyimide, semi-aromatic polyimide and aromatic polyimide according to the chemical structure of a repeating unit, can be divided into a cross-linking type and a non-cross-linking type according to the interaction force between chains, is an organic high polymer material with the best known comprehensive performance, and has a simple structure shown as a formula I.
The polyimide foam is a light porous material, and has the properties of light weight, excellent high and low temperature resistance, heat insulation, sound absorption, noise reduction, flame retardance, insulation and the like. The high-performance polyimide foam can resist 250-300 ℃ for a long time and 400-500 ℃ for a short time, and is one of the materials with the best heat stability in organic polymers. The high-performance polyimide foam material can resist extremely low temperature and does not generate brittle fracture in liquid helium at the temperature of-269 ℃. Just because the polyimide foam material has the advantages, in recent years, the polyimide foam material is known as one of new materials which are most hopeful to solve the core scientific and technical problems in the 21 st century, and has wide application prospect and great commercial value in many high and new technical fields such as aerospace, ships, electronics, new energy, rail transit and the like.
With the continuous complexity and rigor of downstream application scenes, the requirements for polyimide foam, particularly temperature resistance and flame retardance, are increasing day by day. Polyimide foam prepared by a solution method of an isocyanate route has certain defects in flame retardance and temperature resistance.
Therefore, how to further improve the flame retardant and temperature resistance of the polyimide foam material prepared by the solution method of the isocyanate route, and further widen the application depth and the application range of the polyimide foam material has important significance, and is one of the focuses of wide attention of a plurality of research and development type production enterprises in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polyimide foam material and a preparation method thereof, particularly a high temperature resistant and flame retardant polyimide foam material. The polyimide foam material provided by the invention has a specific rigid trapezoidal structure, the structure has high rigidity, and simultaneously can effectively improve the glass transition temperature and the oxygen index, and improve the temperature resistance and the oxygen index while ensuring the mechanical property, so that the polyimide foam material becomes a new generation of high-performance polyimide foam; and the process is simple and easy to control, and is favorable for realizing industrial continuous production.
The invention provides a polyimide foam material which comprises the following raw materials in parts by weight:
preferably, the umber polyamic acid precursor is obtained by reacting aromatic dianhydride and aromatic tetramine in a solvent;
the aromatic dianhydride comprises pyromellitic dianhydride;
the aromatic tetraamine comprises tetraaniline;
the tetraphenylamine comprises 1,2,4,5-tetraaniline.
Preferably, the adding amount of the aromatic dianhydride is 10 to 20 parts by weight;
the adding amount of the aromatic tetramine is 5-10 parts by weight;
the reaction temperature is 25-120 ℃;
the reaction time is 2-24 h;
the number average molecular weight of the umber polyamic acid precursor is 2000-10000.
Preferably, the solvent comprises one or more of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide;
the isocyanate comprises one or more of toluene diisocyanate, 4,4' -diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate, 1,5-naphthalene diisocyanate, 3,3' -dimethoxy-4,4 ' -diphenyl diisocyanate, tetramethylphenyl dimethylene diisocyanate, isophorone diisocyanate, methylcyclohexane diisocyanate, cyclohexyldimethylene diisocyanate, hexamethylene diisocyanate, and methyl formate pentamethylene diisocyanate;
the blowing agent comprises one or more of dichlorotrifluoroethane, dichloromonofluoromethane, acetone, water, methanol, ethanol, and 2-butoxyethanol;
the foam stabilizer comprises one or more of DC193, DC197, DC5000, DC5598, L560, L580, AK8805, SF8427, KY-6035, HK-314, GT-320, B4900, B8123 and B8002.
Preferably, the catalyst comprises a metal catalyst and/or an amine catalyst;
the metal catalyst comprises one or more of stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin mercaptide, potassium isooctanoate, potassium oleate, cobalt isooctanoate and cobalt neodecanoate;
the amine catalyst comprises one or more of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenetetramine, triethylamine, N, N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, N, N '-diethylpiperazine, triethanolamine and N, N' -dimethylpyridine.
Preferably, the polyimide foam material is a polyimide foam material with a trapezoidal umber structure;
the trapezoid is specifically a trapezoid rigid structure.
The invention also provides a preparation method of the polyimide foam material, which comprises the following steps:
1) Reacting aromatic dianhydride and aromatic tetramine in a solvent to obtain a solution of a umbelliferone polyamic acid precursor;
2) Mixing the solution of the umber polyamic acid precursor, the catalyst, the foaming agent and the foam stabilizer again to obtain a mixed solution;
3) And finally mixing the mixed solution obtained in the step with isocyanate, performing free foaming molding in a mold, and performing pre-curing and imidization to obtain the polyimide foam material.
Preferably, the reaction temperature is 25-120 ℃;
the reaction time is 2-24 h;
the time for mixing again is 1-10 min;
the final mixing means includes high speed mixing.
Preferably, the mould comprises an open foaming mould;
the rotating speed of the high-speed stirring and mixing is 800-3000 r/min;
the high-speed stirring and mixing time is 10-40 s;
the free foaming time is 5-30 min;
the setting temperature in the pre-curing process is 200-250 ℃.
Preferably, the pre-curing means comprises microwave and/or oven heating;
the microwave pre-curing time is 20-50 min;
the microwave power stage gradient of microwave pre-curing is set to be 200-800W;
the imidization mode comprises microwave and/or oven heating;
the imidization temperature is 250-300 ℃;
the imidization time is 3-5 h.
The invention provides a polyimide foam material, which comprises, by mass, 15-60 parts of a umbellate polyamic acid precursor, 15-60 parts of isocyanate, 10-40 parts of a solvent, 2-8 parts of a foaming agent, 5-12 parts of a foam stabilizer and 0.5-5 parts of a catalyst. Compared with the prior art, the invention aims at the defects of the polyimide foam prepared by the existing solution method adopting an isocyanate route in the aspects of flame retardance and temperature resistance, and researches prove that although corresponding improvement is carried out on the polyimide foam in the industry, the performance of the polyimide foam is improved by the traditional micromolecule addition type or reaction type flame retardant, the flame retardant performance can be improved, but the problems of serious migration, powder falling and mechanical property reduction of the flame retardant exist, the invention has great influence on the performance of the foam in the subsequent use process, and the traditional addition type flame retardant is used as disclosed in the patent 201510103241.3
80 and->
82, the oxygen index is only improved to about 30, and the flame-retardant efficiency is low. Therefore, the invention considers that the preparation of the polyimide foam material with high temperature resistance and high oxygen index by adjusting the structure of the reaction monomer and the precursor through chemical reaction is a necessary trend for the continuous development of the polyimide foam material, and is also the research direction of the invention.
Based on the above, the invention designs a polyimide foam material with a specific structure and composition, and the foam material is prepared from a PAA acid precursor containing a umber structure by an isocyanate solution method. According to the invention, the precursor reacts with isocyanate groups, foaming is carried out, and a trapezoidal polyimide structure is introduced into the foam through an imidization process, so that the introduced trapezoidal polyimide rigid structure has obvious improvement on the oxygen index and the mechanical property, and the foam material prepared by the method has the advantages of high oxygen index, high temperature resistance and the like.
The precursor with the umbellate structure has a rigid trapezoidal structure, and the structure has high rigidity and can effectively improve the glass transition temperature and the oxygen index. The PAA acid with the structure is reacted with isocyanate, and the structure is effectively introduced into a polyimide foam framework through forming, sizing and imidization retaining ring reaction, so that the temperature resistance and the oxygen index can be improved while the mechanical property is ensured, and a new generation of high-performance polyimide foam is prepared. The flame retardant and heat-resistant composite material is introduced into a polyimide foam framework, so that the flame retardant and heat-resistant performances are greatly improved.
The experimental result shows that the density of the polyimide foam material prepared by the invention is about 10kg/m 3 The tensile strength is about 50-71 kPa, and the composite material has good mechanical properties. The oxygen index is about 34-40%, the 5% thermal weight loss temperature is about 350-420 ℃, and the oxygen index is excellentFlame retardant and heat resistant properties.
Drawings
Fig. 1 is a schematic diagram of a synthesis route and a structure of a umbellate pore structure provided by the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs purity requirements that are conventional in the analytical grade or polyimide foam preparation art.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides a polyimide foam material which comprises the following raw materials in parts by weight:
in the present invention, the amount of the umber polyamic acid precursor added is 15 to 60 parts by weight, may be 25 to 50 parts by weight, and is preferably 35 to 40 parts by weight.
In the present invention, the isocyanate may be added in an amount of 15 to 60 parts by weight, 25 to 50 parts by weight, and preferably 35 to 40 parts by weight.
In the present invention, the solvent may be added in an amount of 10 to 40 parts by weight, 16 to 34 parts by weight, and preferably 22 to 26 parts by weight.
In the present invention, the amount of the blowing agent added is 2 to 8 parts by weight, and may be 3 to 6 parts by weight, and preferably 4 to 5 parts by weight.
In the present invention, the amount of the foam stabilizer to be added may be from 5 to 12 parts by weight, preferably from 6 to 11 parts by weight, more preferably from 7 to 10 parts by weight, and still more preferably from 8 to 9 parts by weight.
In the present invention, the catalyst may be added in an amount of 0.5 to 5 parts by weight, 1 to 4 parts by weight, and preferably 2 to 3 parts by weight.
In the present invention, the umber polyamic acid precursor is preferably obtained by reacting an aromatic dianhydride and an aromatic tetraamine in a solvent. Wherein, the precursor is polyamic acid (PAA acid) precursor with a umber structure.
In the present invention, the aromatic dianhydride preferably comprises pyromellitic dianhydride.
In the present invention, the aromatic tetraamine preferably includes tetraaniline.
In the present invention, the tetraphenylamine preferably comprises 1,2,4,5-tetraaniline.
In the present invention, the aromatic dianhydride is added in an amount of preferably 10 to 20 parts by weight, more preferably 12 to 19, and still more preferably 15 to 18.
In the present invention, the amount of the aromatic tetraamine added is preferably 5 to 10 parts by weight, more preferably 6 to 9 parts by weight, and still more preferably 7 to 8 parts by weight;
in the present invention, the number average molecular weight of the umber polyamic acid precursor is preferably 2000 to 10000, more preferably 3000 to 9000, more preferably 4000 to 8000, and more preferably 5000 to 7000.
Referring to fig. 1, fig. 1 is a schematic diagram of a synthesis route and a structure of a umber structure provided by the present invention.
In the invention, the umber polyamic acid precursor preferably contains a structure shown as a formula (I):
wherein n is the degree of polymerization.
In the present invention, the temperature of the reaction is preferably 25 to 120 ℃, more preferably 45 to 100 ℃, and more preferably 65 to 80 ℃.
In the present invention, the reaction time is preferably 2 to 24 hours, more preferably 6 to 20 hours, and still more preferably 10 to 16 hours.
In the present invention, the solvent preferably includes one or more of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide, and more preferably N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, or dimethylsulfoxide.
In the present invention, the isocyanate preferably includes one or more of toluene diisocyanate, 4,4 '-diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate, 1,5-naphthalene diisocyanate, 3,3' -dimethoxy-4,4 '-diphenyl diisocyanate, tetramethylphenyl dimethylene diisocyanate, isophorone diisocyanate, methylcyclohexane diisocyanate, cyclohexyl dimethylene diisocyanate, hexamethylene diisocyanate, and methyl formate pentamethylene diisocyanate, and more preferably toluene diisocyanate, 4,4' -diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate, 1,5-naphthalene diisocyanate, 3,3 '-dimethoxy-4,4' -diphenyl diisocyanate, tetramethylphenyl dimethylene diisocyanate, isophorone diisocyanate, methylcyclohexane diisocyanate, cyclohexyl dimethylene diisocyanate, hexamethylene diisocyanate, or methyl formate pentamethylene diisocyanate.
In the present invention, the blowing agent preferably comprises one or more of dichlorotrifluoroethane, dichloromonofluoromethane, acetone, water, methanol, ethanol and 2-butoxyethanol, more preferably dichlorotrifluoroethane, dichloromonofluoromethane, acetone, water, methanol, ethanol or 2-butoxyethanol.
In the present invention, the foam stabilizer is preferably one or more of DC193, DC197, DC5000, DC5598, L560, L580, AK8805, SF8427, KY-6035, HK-314, GT-320, B4900, B8123 and B8002, more preferably DC193, DC197, DC5000, DC5598, L560, L580, AK 5, SF8427, KY-6035, HK-314, GT-320, B4900, B8123 or B8002.
In the present invention, the catalyst preferably includes a metal catalyst and/or an amine catalyst, more preferably a metal catalyst or an amine catalyst.
In the present invention, the metal catalyst preferably comprises one or more of stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin mercaptide, potassium isooctanoate, potassium oleate, cobalt isooctanoate and cobalt neodecanoate, and more preferably stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin mercaptide, potassium isooctanoate, potassium oleate, cobalt isooctanoate or cobalt neodecanoate.
In the present invention, the amine-based catalyst preferably includes N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N ' -tetramethylalkylenetetramine, triethylamine, N, N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, N, N ' -diethylpiperazine, triethanolamine and N, one or more of N, N-dimethyl pyridine, more preferably N, N-dimethyl cyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N ' -tetramethylalkylenetetramine, triethylamine, N, N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, N, N ' -diethylpiperazine, triethanolamine or N, N ' -dimethyl pyridine.
In the present invention, the polyimide foam is preferably a polyimide foam having a trapezoidal umber structure. More specifically, the trapezoid is preferably a trapezoid rigid structure.
In the present invention, the pore size of the polyimide foam is preferably 100nm to 100. Mu.m, more preferably 1 μm to 10 μm, and still more preferably 5 μm to 6 μm.
In the present invention, in the polyimide foam, the proportion of pores having a pore diameter of 100nm to 1000nm to the entire pores is preferably 20% to 30%, more preferably 22% to 28%, and still more preferably 24% to 26%.
In the present invention, in the polyimide foam, the proportion of pores having a pore diameter of 1000nm to 10 μm to the entire pores is preferably 10% to 30%, more preferably 14% to 26%, and still more preferably 18% to 22%.
In the present invention, in the polyimide foam, the proportion of the pores having a pore diameter of 10 to 100 μm to the entire pores is preferably 40 to 70%, more preferably 45 to 65%, and still more preferably 50 to 60%.
The invention is an integral and refined technical scheme, better ensures the specific structure of the polyimide foam material, and further improves the high-temperature resistance and the flame-retardant property of the polyimide foam material on the basis of ensuring the original property, and the high-temperature-resistant and flame-retardant polyimide foam material can specifically comprise the following components:
a polyimide foam material comprises the following raw materials:
specifically, after the adopted precursor forms foam, a 'trapezoidal' umbellate structure can be formed through a 'buckle' reaction.
Specifically, the aromatic dianhydride used for preparing the precursor is pyromellitic dianhydride, and 1,2,4,5-tetraphenylamine is tetraaniline.
Specifically, the isocyanate includes one or more of toluene diisocyanate, 4,4' -diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate, 1,5-naphthalene diisocyanate, 3,3' -dimethoxy-4,4 ' -diphenyl diisocyanate, tetramethylphenyl dimethylene diisocyanate, isophorone diisocyanate, methylcyclohexane diisocyanate, cyclohexyldimethylene diisocyanate, hexamethylene diisocyanate, and methyl formate pentamethylene diisocyanate.
Specifically, the solvent includes one or more of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide.
Specifically, the blowing agent comprises one or more of dichlorotrifluoroethane, dichloromonofluoromethane, acetone, water, methanol, ethanol, and 2-butoxyethanol.
Specifically, the foam stabilizer comprises one or more of DC193, DC197, DC5000, DC5598, L560, L580, AK8805, SF8427, KY-6035, HK-314, GT-320, B4900, B8123 and B8002.
Specifically, the catalyst comprises a metal catalyst and/or an amine catalyst.
Specifically, the metal catalyst is one or more of stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin mercaptide, potassium isooctanoate, potassium oleate, cobalt isooctanoate and cobalt neodecanoate.
Specifically, the amine catalyst comprises one or more of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine, triethylamine, N, N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, N, N '-diethylpiperazine, triethanolamine and N, N' -dimethylpyridine.
Further:
the amount of the umbellate precursor is 15-60 parts by weight, preferably 40-55 parts by weight, and more preferably 45-50 parts by weight. The structure of the precursor of the umber is PMDA and tetraphenylamine, and the related molecular weight can be adjusted and controlled through the reaction time and the reaction temperature.
The isocyanate of the present invention is added in an amount of 15 to 60 parts by weight, preferably 30 to 50 parts by weight, and more preferably 35 to 40 parts by weight. The specific choice of the isocyanate is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to actual production conditions, application requirements and quality control, and the invention is preferably to ensure the structure of the main molecular chain of the material, and the isocyanate preferably includes one or more of toluene diisocyanate, 4,4 '-diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate, 1,5-naphthalene diisocyanate, 3,3' -dimethoxy-3534 '-diphenyl diisocyanate, tetramethylphenyl dimethylene diisocyanate, isophorone diisocyanate, methylcyclohexane diisocyanate, cyclohexyl dimethylene diisocyanate, hexamethylene diisocyanate and methyl formate pentamethylene diisocyanate, and more preferably Toluene Diisocyanate (TDI), 4,4' -diphenylmethane diisocyanate (MDI), polyphenyl polymethylene polyisocyanate (PAPI), 1,5-Naphthalene Diisocyanate (NDI), 3,3 '-dimethoxy-3432' -diphenylmethane diisocyanate (vdi), tetramethylhexamethylene diisocyanate (HDI), or cyclohexylmethylene diisocyanate (HDI).
The solvent of the present invention is added in an amount of 10 to 40 parts by weight, preferably 15 to 25 parts by weight, more preferably 15 to 23 parts by weight, and still more preferably 20 to 23 parts by weight. The specific choice of the solvent is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to actual production conditions, application requirements and quality control, and the solvent preferably includes one or more of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, and more preferably N, N '-Dimethylformamide (DMF), N' -Dimethylacetamide (DMAC), N-methylpyrrolidone (NMP) or dimethyl sulfoxide (DMSO), in order to better ensure the structure of the main molecular chain of the material.
The amount of the blowing agent of the present invention is 2 to 8 parts by weight, preferably 3 to 7 parts by weight, and more preferably 4 to 6 parts by weight. The specific selection of the blowing agent is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to actual production conditions, application requirements and quality control, and the blowing agent preferably comprises one or more of dichlorotrifluoroethane, dichloromonofluoromethane, acetone, water, methanol, ethanol and 2-butoxyethanol, and more preferably dichlorotrifluoroethane, dichloromonofluoromethane, acetone, water, methanol, acetic anhydride, ethanol or 2-butoxyethanol.
The amount of the foam stabilizer of the present invention is 5 to 12 parts by weight, preferably 6.5 to 11 parts by weight, more preferably 7 to 10 parts by weight, and still more preferably 8 to 9 parts by weight. The invention is in principle not particularly limited to the specific selection of the foam stabilizer, which may be selected and adjusted by the skilled person in view of the actual production conditions, application requirements and quality control, and which is preferably to ensure the structure of the host molecular chain of the material, the foam stabilizer preferably comprises one or more of DC193, DC197, DC5000, DC5598, L560, L580, AK8805, SF8427, KY-6035, HK-314, GT-320, B4900, B8123 and B8002, more preferably DC193, DC197, DC5000, DC5598, L560, L580, AK8805, SF8427, KY-6035, HK-314, GT-320, B4900, B8123 or B8002.
The catalyst of the present invention is added in an amount of 0.5 to 5 parts by weight, preferably 0.5 to 4.5 parts by weight, more preferably 1 to 4 parts by weight, and still more preferably 2 to 3 parts by weight. The catalyst preferably comprises a metal catalyst and/or an amine catalyst, more preferably a metal catalyst or an amine catalyst. Among them, the amine catalyst according to the present invention preferably includes N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N ' -tetramethylalkylenediamine, triethylamine, N, N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, N, N ' -diethylpiperazine, triethanolamine and N, one or more of N ' -dimethylpyridine, more preferably N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N ' -tetramethylalkylenediamine, triethylamine, N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, N ' -diethylpiperazine, triethanolamine or N, N ' -dimethylpyridine. The metal catalyst preferably comprises one or more of stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin mercaptide, potassium isooctanoate, potassium oleate, cobalt isooctanoate and cobalt neodecanoate, more preferably stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin mercaptide, potassium isooctanoate, potassium oleate, cobalt isooctanoate or cobalt neodecanoate.
The invention provides a preparation method of a polyimide foam material, which comprises the following steps:
1) Reacting aromatic dianhydride and aromatic tetramine in a solvent to obtain a solution of a umbelliferone polyamic acid precursor;
2) Mixing the solution of the umber polyamic acid precursor, the catalyst, the foaming agent and the foam stabilizer again to obtain a mixed solution;
3) And finally mixing the mixed solution obtained in the step with isocyanate, performing free foaming molding in a mold, and then performing pre-curing and imidization to obtain the polyimide foam material.
Firstly, reacting aromatic dianhydride and aromatic tetramine in a solvent to obtain a solution of a umbelliferone polyamic acid precursor.
In the present invention, the temperature of the reaction is preferably 25 to 120 ℃, more preferably 45 to 100 ℃, and more preferably 65 to 80 ℃.
In the present invention, the reaction time is preferably 2 to 24 hours, more preferably 7 to 19 hours, and still more preferably 12 to 14 hours.
The mixed solution is obtained by mixing the solution of the umber polyamic acid precursor, the catalyst, the foaming agent and the foam stabilizer again.
In the present invention, the time for the remixing is preferably 1 to 10min, more preferably 3 to 8min, and still more preferably 5 to 6min.
In the present invention, the means of the final mixing preferably comprises high-speed stirring mixing.
Finally, the mixed solution obtained in the step and isocyanate are mixed, are subjected to free foaming molding in a mold, and are subjected to pre-curing and imidization to obtain the polyimide foam material.
In the present invention, the mold preferably comprises an open foaming mold.
In the present invention, the rotation speed of the high-speed stirring and mixing is preferably 800 to 3000r/min, more preferably 1300 to 2500r/min, and still more preferably 1800 to 2000r/min.
In the present invention, the time for the high-speed stirring and mixing is preferably 10 to 40 seconds, more preferably 16 to 34 seconds, and still more preferably 22 to 28 seconds.
In the present invention, the time for the free foaming is preferably 5 to 30min, more preferably 10 to 25min, and still more preferably 15 to 20min.
In the present invention, the temperature for setting in the pre-curing process is preferably 200 to 250 ℃, more preferably 210 to 240 ℃, and more preferably 220 to 230 ℃.
In the present invention, the pre-curing means preferably comprises microwave and/or oven heating, more preferably microwave or oven heating.
In the present invention, the microwave pre-curing time is preferably 20 to 50min, more preferably 25 to 45min, and still more preferably 30 to 40min.
In the present invention, the microwave power step gradient of the microwave pre-curing is set to preferably 200 to 800W, more preferably 300 to 700W, and still more preferably 400 to 600W.
In the present invention, the imidization means preferably comprises microwave and/or oven heating, more preferably microwave or oven heating.
In the present invention, the temperature of the imidization is preferably 250 to 300 ℃, more preferably 260 to 290 ℃, and more preferably 270 to 280 ℃.
In the present invention, the imidization time is preferably 3 to 5 hours, more preferably 3.4 to 4.6 hours, and still more preferably 3.8 to 4.2 hours.
The invention is a complete and refined integral technical scheme, better ensures the specific structure of the polyimide foam material, further improves the high temperature resistance and the flame retardant property of the polyimide foam material on the basis of ensuring the original property, and the preparation method of the high temperature resistant and flame retardant polyimide foam material can specifically comprise the following steps:
1) Reacting aromatic dianhydride and tetraphenylamine in a solvent to obtain a PAA acid foaming precursor solution;
2) Mixing the foaming precursor solution, the catalyst, the foaming agent and the foam stabilizer obtained in the step again to obtain a mixed solution;
3) And finally mixing the mixed solution obtained in the step with isocyanate, then carrying out free foaming molding in a mold, and then carrying out shaping, molding and imidization of a 'snap ring' to obtain the polyimide foam material containing the 'trapezoidal rigid structure'.
Specifically, the reaction temperature is 25-120 ℃.
Specifically, the reaction time is 2-24 h.
Specifically, the time for remixing is 1-10 min.
Specifically, the final mixing mode comprises high-speed stirring and mixing.
Specifically, the mold comprises an open type foaming mold.
Specifically, the rotating speed of the high-speed stirring and mixing is 800-3000 r/min,
specifically, the time for high-speed stirring and mixing is 10-40 s.
Specifically, the free foaming time is 5-30 min.
Specifically, the forming, shaping and imidizing modes comprise microwave and oven heating.
Specifically, the microwave pre-curing time is 20-50 min.
Specifically, the microwave power step gradient of the microwave preforming is set to be 200-8000W.
Specifically, the temperature step gradient of the setting is set to be 200-250 ℃.
Specifically, the temperature of the imidization and 'snap ring' stage is 220-300 ℃.
Specifically, the post-curing time is 3-5 h.
In the present invention, the pre-curing process includes a setting process and a molding process.
In the present invention, the imidization process includes a dehydration ring-closing (buckle) process.
Further:
the preparation method of the polyimide foam material can also comprise the following steps:
(1) Dissolving PMDA and tetraphenylamine in a solvent, heating to 80-120 ℃, and reacting for 3-5 h until the solution is clear and transparent;
(2) Cooling the solution to room temperature, adding a catalyst, a foaming agent and a foam stabilizer, and uniformly mixing;
(3) Stirring the solution and isocyanate at a high speed of 800-3000 rpm, uniformly mixing, injecting into a mold for 10-40 s, and foaming at room temperature;
(4) And then carrying out microwave treatment on the foam, molding in an oven, shaping, imidizing and retaining ring to finally prepare the polyimide foam material.
In the above polyimide foam material of the present invention, the selection and proportion of the raw materials and the preferred range thereof are preferably consistent with those of the above polyimide foam material, and are not described herein again. In the present invention, the parts by weight and the mass percentages are only different in terms of expressions and the same in essential meanings, and those skilled in the art can understand the correct meanings based on the general knowledge and can uniquely determine the same.
Firstly, PMDA, tetraaniline and a solvent are reacted to obtain a foaming precursor solution.
The reaction mode and parameters are not particularly limited in principle, and those skilled in the art can select and adjust the reaction mode and parameters according to actual production conditions, application requirements and quality control, and the reaction temperature is preferably room temperature to 120 ℃, more preferably 35 to 120 ℃, more preferably 40 to 120 ℃, and more preferably 80 to 120 ℃ in order to better ensure the structure of the main molecular chain of the material. The reaction time is preferably 3 to 5 hours, more preferably 3.2 to 4.8 hours, more preferably 3.5 to 4.5 hours, and more preferably 3.8 to 4.2 hours.
In the present invention, the foaming precursor solution obtained in the above step, the catalyst, the foaming agent, and the foam stabilizer are mixed again to obtain a mixed solution.
The invention is in principle not restricted to the manner and parameters of the remixing, which can be selected and adjusted by the skilled person according to the actual production situation, application requirements and quality control, and the remixing time is preferably 1-10 min, more preferably 3-8 min, and more preferably 5-7 min.
Finally, mixing the mixed solution obtained in the step with isocyanate, performing free foaming molding in a mold, and performing pre-curing and post-curing to obtain the polyimide foam material.
The invention is in principle not particularly limited with respect to the manner and parameters of the final mixing. The rotation speed of the high-speed stirring and mixing is preferably 800 to 3000r/min, more preferably 1300 to 2500r/min, and more preferably 1800 to 2000r/min. The time for the high-speed stirring and mixing is preferably 10 to 40 seconds, more preferably 15 to 35 seconds, and still more preferably 20 to 30 seconds.
The invention is in principle not particularly restricted to the specific choice of the mould, which preferably comprises an open-cell foaming mould, and which can be selected and adjusted by the person skilled in the art according to the actual production situation, application requirements and quality control.
The parameters of the free foaming process are not particularly limited in principle, and those skilled in the art can select and adjust the parameters according to actual production conditions, application requirements and quality control, and the time of the free foaming process is preferably 5 to 30min, more preferably 10 to 25min, and still more preferably 15 to 20min.
The invention is in principle not particularly restricted to the manner and parameters of said pre-curing, which can be selected and adjusted by the person skilled in the art according to the actual production situation, application requirements and quality control, while having a lower density and better heat and mechanical properties, preferably including microwave pre-curing, more preferably gradient pre-curing. The microwave pre-curing time is preferably 20-50 min, more preferably 25-45 min, and more preferably 30-40 min. The microwave power step gradient setting of the microwave pre-curing is preferably 200 to 8000W, more preferably 500 to 3000W, more preferably 1000 to 3000W, and specifically may be any two or more gradient settings of 1200 to 1500W.
The invention is in principle not particularly limited in the manner and parameters of the shaping, and the skilled person can select and adjust the shaping stage time according to the actual production situation, application requirements and quality control, and the shaping stage time is preferably 3 to 5 hours, more preferably 3.2 to 4.8 hours, more preferably 3.5 to 4.5 hours, and more preferably 4 hours. The temperature step gradient setting of the shaping is preferably 200-250 ℃, and more preferably 230 ℃. The imidization and retaining ring time is preferably 3-5 h, more preferably 3.2-4.8 h, and more preferably 3.5h, and the temperature step gradient of imidization and retaining ring is preferably set to 250-300 ℃, and more preferably 260 ℃.
The invention provides a high-temperature-resistant and flame-retardant polyimide foam material and a preparation method thereof. The polyimide foam material with a specific structure and composition is prepared from a PAA acid precursor containing a umber structure by an isocyanate solution method. According to the invention, the precursor reacts with isocyanate groups, foaming is carried out, and the introduction of a trapezoidal polyimide structure into foam is realized through an imidization process, and the introduced trapezoidal polyimide rigid structure has obvious improvement on oxygen index and mechanical property, so that the foam material prepared by the invention has the advantages of high oxygen index, high temperature resistance and the like.
The precursor with the umbellate structure has a rigid trapezoidal structure, and the structure has high rigidity and can effectively improve the glass transition temperature and the oxygen index. The PAA acid with the structure is reacted with isocyanate, and the structure is effectively introduced into a polyimide foam framework through forming, sizing and imidization retaining ring reaction, so that the temperature resistance and the oxygen index can be improved while the mechanical property is ensured, and a new generation of high-performance polyimide foam is prepared. The flame retardant and heat-resistant composite material is introduced into a polyimide foam framework, so that the flame retardant and heat-resistant performances are greatly improved.
The experimental result shows that the density of the polyimide foam material prepared by the invention is about 10kg/m 3 The tensile strength is about 50-71 kPa, and the composite material has good mechanical properties. The oxygen index is about 34-40%, the 5% thermal weight loss temperature is about 350-420 ℃, and the flame retardant and heat resistant performance is excellent.
For further illustration of the present invention, a polyimide foam and a method for preparing the same according to the present invention will be described in detail with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
The polyimide foam prepared by the invention is subjected to related performance tests in the following way, and the specific process is as follows:
the prepared polyimide foam is cut into cubic blocks, and the apparent density of the polyimide foam is calculated by measuring the mass and the volume of the polyimide foam.
The invention adopts a thermal weight loss analysis tester, and is measured in N 2 Under the atmosphere, the thermal weight loss condition of the polyimide foam prepared by the invention is measured at the heating rate of 10 ℃/min.
The oxygen index of the polyimide foam prepared by the invention is measured by adopting an oxygen index measuring instrument and taking GB/T2406.2-2009 as a test standard.
Example 1
(1) Dissolving 18 parts of PMDA and 8 parts of tetraphenylamine in 25 parts of DMF, heating to 80 ℃, and reacting for 3 hours until the solution is clear and transparent;
(2) Cooling the solution to room temperature, adding 0.05 part of dibutyltin dilaurate, 0.08 part of triethylamine, 0.11 part of N-methylmorpholine, 1.8 parts of water, 0.5 part of dichlorofluoromethane, 1.6 parts of DC193 and 0.8 part of B4900, and uniformly mixing;
(3) Stirring the solution and 40 parts of PAPI at a high speed of 1000rpm, uniformly mixing, injecting into a mold, mixing for 15s, and foaming at room temperature;
(4) And then, carrying out microwave treatment and pre-curing on the foam, wherein the microwave power is 300W, the microwave treatment and pre-curing time is 30min, the temperature is continuously increased to 220 ℃ in the shaping process, the time is 3h, and the temperature is increased to 260 ℃ in the imidization and buckling process, so that the polyimide foam material can be prepared.
Example 2
(1) Dissolving 18 parts of PMDA and 6 parts of tetraphenylamine in 20 parts of DMF, heating to 80 ℃, and reacting for 3 hours until the solution is clear and transparent;
(2) Cooling the solution to room temperature, adding 0.05 part of dibutyltin dilaurate, 0.08 part of triethylamine, 0.11 part of N-methylmorpholine, 1.8 parts of water, 0.5 part of dichlorofluoromethane, 1.6 parts of DC193 and 0.8 part of B4900, and uniformly mixing;
(3) Stirring the solution and 35 parts of TDI at a high speed of 1000rpm, uniformly mixing, injecting into a mold, mixing for 25s, and foaming at room temperature;
(4) And (3) continuously heating to 220 ℃ in the shaping process for 3 hours, and heating to 280 ℃ in the imidization and retaining ring process for 3 hours to prepare the polyimide foam material.
Example 3
(1) Dissolving 15 parts of PMDA and 8 parts of tetraphenylamine in 25 parts of DMF, stirring, heating to 45 ℃, adding 1.5 parts of methanol, continuously heating to 80 ℃, and reacting for 3 hours until the solution is clear and transparent;
(2) Cooling the solution to room temperature, adding 0.05 part of dibutyltin dilaurate, 0.08 part of triethylamine, 0.11 part of N-methylmorpholine, 1.8 parts of water, 0.5 part of dichlorofluoromethane, 1.6 parts of DC193 and 0.8 part of B4900, and uniformly mixing;
(3) Stirring the solution and 40 parts of MDI at a high speed of 1000rpm, uniformly mixing, injecting into a mold, mixing for 15s, and foaming and molding at room temperature;
(4) And then, carrying out microwave treatment and pre-curing on the foam, wherein the microwave power is 300W, the microwave treatment and pre-curing time is 30min, the setting temperature is 200 ℃, the microwave treatment and pre-curing time is 3h, and the temperature is raised to 280 ℃ in the amination and retaining ring process for 4h to prepare the polyimide foam material.
Example 4
(1) Dissolving 15 parts of PMDA and 8 parts of tetraphenylamine in 25 parts of DMF, heating to 90 ℃, and reacting for 3 hours until the solution is clear and transparent;
(2) Cooling the solution to room temperature, adding 0.05 part of dibutyltin dilaurate, 0.08 part of triethylamine, 0.11 part of N-methylmorpholine, 1.8 parts of water, 0.5 part of dichlorofluoromethane, 1.6 parts of DC193 and 0.8 part of B4900, and uniformly mixing;
(3) Stirring the solution and 40 parts of isopapai at a high speed of 1000rpm, uniformly mixing, injecting into a mold, mixing for 15s, and foaming and molding at room temperature;
(4) And then carrying out heat treatment setting at 210 ℃ for 3h, carrying out imidization and ring buckling, and heating to 260 ℃ for 3h to obtain the polyimide foam material.
Example 5
(1) Dissolving 17 parts of PMDA and 8 parts of tetraphenylamine in 25 parts of DMF, heating to 100 ℃, and reacting for 3 hours until the solution is clear and transparent;
(2) Cooling the solution to room temperature, adding 0.05 part of dibutyltin dilaurate, 0.08 part of triethylamine, 0.11 part of N-methylmorpholine, 1.8 parts of water, 0.5 part of dichlorofluoromethane, 1.6 parts of DC193 and 0.8 part of B4900, and uniformly mixing;
(3) Stirring the solution and 40 parts of MDI at a high speed of 1000rpm, uniformly mixing, injecting into a mold, mixing for 15s, and foaming and molding at room temperature;
(4) And then carrying out heat treatment setting at the temperature of 210 ℃ for 3 hours, carrying out imidization and buckling processes, heating to 280 ℃ for 3.5 hours, and thus obtaining the polyimide foam material.
Example 6
(1) Dissolving 15 parts of PMDA and 8 parts of tetraphenylamine in 25 parts of DMF, heating to 80 ℃, and reacting for 3 hours until the solution is clear and transparent;
(2) Cooling the solution to room temperature, adding 0.05 part of dibutyltin dilaurate, 0.08 part of triethylamine, 0.11 part of N-methylmorpholine, 1.8 parts of water, 0.5 part of dichlorofluoromethane, 1.6 parts of DC193 and 0.8 part of B4900, and uniformly mixing;
(3) Stirring the solution and 40 parts of TDI at a high speed of 1000rpm, uniformly mixing, injecting into a mold, mixing for 15s, and foaming at room temperature;
(4) And (3) heating to 220 ℃ in the shaping process for 3 hours, and heating to 260 ℃ in the imidization and retaining ring process for 4 hours to prepare the polyimide foam material.
Comparative example 1
(1) Dissolving 15 parts of PMDA and 8 parts of BTDA in 25 parts of DMF, stirring, heating to 45 ℃, adding 1.5 parts of methanol, continuously heating to 80 ℃, and reacting for 3 hours until the solution is clear and transparent;
(2) Cooling the solution to room temperature, adding 0.05 part of dibutyltin dilaurate, 0.08 part of triethylamine, 0.11 part of N-methylmorpholine, 1.8 parts of water, 0.5 part of dichlorofluoromethane, 1.6 parts of DC193 and 0.8 part of B4900, and uniformly mixing;
(3) Stirring the solution and 40 parts of isocyanate at a high speed of 1000rpm, uniformly mixing, injecting into a mold, mixing for 15s, and foaming at room temperature;
(4) And then, carrying out microwave treatment on the foam for pre-curing with the microwave power of 300W for 30min, and carrying out heat treatment and curing at the temperature of 200 ℃ for 3h to prepare the polyimide foam material.
Example 7
Examples 1-6 are polyimide foams prepared using the formulations and processes of the present invention, and comparative example 1 is a polyimide foam prepared using conventional means.
The performance tests of the polyimide foams of the examples and comparative examples are shown in Table 1.
The foam density test standard is GB/T6343-2009, the tensile strength test standard is GB/T6344-2008, the oxygen index test standard is GB/T2406.2-2009, and the 5% thermal weight loss temperature test standard is GB/T27761-2011.
Results are shown in Table 1, and Table 1 shows the results of the property tests of the polyimide foams prepared in the examples of the present invention and the comparative examples.
TABLE 1
As can be seen from Table 1, the density of the polyimide foam prepared by the present invention is about 10kg/m 3 The tensile strength is about 50-71 kPa, and the composite material has good mechanical properties. The oxygen index is about 34-40%, the 5% thermal weight loss temperature is about 350-420 ℃, and the flame retardant and heat resistant performance is excellent. Examples 1-6 all have temperature resistance and oxygen index in comparison to comparative example 1 of conventional polyimide foamThe improvement is obvious.
While the present invention has been described in detail with respect to a high temperature resistant, flame retardant polyimide foam and a method of making the same, the principles and embodiments of the present invention are described herein using specific examples, which are included to facilitate an understanding of the process and its core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The polyimide foam material is characterized by comprising the following raw materials in parts by mass:
2. the polyimide foam material of claim 1, wherein the umber polyamic acid precursor is obtained by reacting aromatic dianhydride and aromatic tetramine in a solvent;
the aromatic dianhydride comprises pyromellitic dianhydride;
the aromatic tetraamine comprises tetraaniline;
the tetraphenylamine comprises 1,2,4,5-tetraaniline.
3. The polyimide foam material according to claim 2, wherein the aromatic dianhydride is added in an amount of 10 to 20 parts by weight;
the adding amount of the aromatic tetramine is 5-10 parts by weight;
the reaction temperature is 25-120 ℃;
the reaction time is 2-24 h;
the number average molecular weight of the umber polyamic acid precursor is 2000-10000.
4. The polyimide foam of claim 1, wherein the solvent comprises one or more of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide;
the isocyanate comprises one or more of toluene diisocyanate, 4,4' -diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate, 1,5-naphthalene diisocyanate, 3,3' -dimethoxy-4,4 ' -diphenyl diisocyanate, tetramethylphenyl dimethylene diisocyanate, isophorone diisocyanate, methylcyclohexane diisocyanate, cyclohexyldimethylene diisocyanate, hexamethylene diisocyanate, and methyl formate pentamethylene diisocyanate;
the blowing agent comprises one or more of dichlorotrifluoroethane, dichloromonofluoromethane, acetone, water, methanol, ethanol, and 2-butoxyethanol;
the foam stabilizer comprises one or more of DC193, DC197, DC5000, DC5598, L560, L580, AK8805, SF8427, KY-6035, HK-314, GT-320, B4900, B8123 and B8002.
5. The polyimide foam of claim 1, wherein the catalyst comprises a metal catalyst and/or an amine catalyst;
the metal catalyst comprises one or more of stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin mercaptide, potassium isooctanoate, potassium oleate, cobalt isooctanoate and cobalt neodecanoate;
the amine catalyst comprises one or more of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenetetramine, triethylamine, N, N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, N, N '-diethylpiperazine, triethanolamine and N, N' -dimethylpyridine.
6. The polyimide foam material according to claim 1, wherein the polyimide foam material is a polyimide foam material having a trapezoidal-shaped pyrrole structure;
the trapezoid is specifically a trapezoid rigid structure.
7. The preparation method of the polyimide foam material is characterized by comprising the following steps:
1) Reacting aromatic dianhydride with aromatic tetramine in a solvent to obtain a solution of a umbellate polyamic acid precursor;
2) Mixing the solution of the umber polyamic acid precursor, the catalyst, the foaming agent and the foam stabilizer again to obtain a mixed solution;
3) And finally mixing the mixed solution obtained in the step with isocyanate, performing free foaming molding in a mold, and performing pre-curing and imidization to obtain the polyimide foam material.
8. The method of claim 7, wherein the reaction temperature is 25 to 120 ℃;
the reaction time is 2-24 h;
the time for mixing again is 1-10 min;
the final mixing mode comprises high-speed stirring and mixing.
9. The method of manufacturing of claim 7, wherein the mold comprises an open-cell foaming mold;
the rotating speed of the high-speed stirring and mixing is 800-3000 r/min;
the high-speed stirring and mixing time is 10-40 s;
the free foaming time is 5-30 min;
the setting temperature in the pre-curing process is 200-250 ℃.
10. The method of claim 7, wherein the pre-curing means comprises microwave and/or oven heating;
the microwave pre-curing time is 20-50 min;
the microwave power step gradient of microwave precuring is set to be 200-800W;
the imidization mode comprises microwave and/or oven heating;
the imidization temperature is 250-300 ℃;
the imidization time is 3-5 h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS495217B1 (en) * | 1969-03-04 | 1974-02-06 | ||
| CN103113581A (en) * | 2012-11-05 | 2013-05-22 | 哈尔滨工程大学 | Polyamide acid and polyphenyl-oxazine ketone imide with thermosetting property and preparation method thereof |
| CN109880145A (en) * | 2019-03-07 | 2019-06-14 | 中国科学院长春应用化学研究所 | A kind of fire-retardant Polyimide foams of low smell and preparation method thereof |
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- 2022-08-31 CN CN202211056729.1A patent/CN115895253A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS495217B1 (en) * | 1969-03-04 | 1974-02-06 | ||
| CN103113581A (en) * | 2012-11-05 | 2013-05-22 | 哈尔滨工程大学 | Polyamide acid and polyphenyl-oxazine ketone imide with thermosetting property and preparation method thereof |
| CN109880145A (en) * | 2019-03-07 | 2019-06-14 | 中国科学院长春应用化学研究所 | A kind of fire-retardant Polyimide foams of low smell and preparation method thereof |
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