CN111592649A - 一种低导热聚酰亚胺泡沫材料及其制备方法 - Google Patents
一种低导热聚酰亚胺泡沫材料及其制备方法 Download PDFInfo
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- CN111592649A CN111592649A CN202010535963.7A CN202010535963A CN111592649A CN 111592649 A CN111592649 A CN 111592649A CN 202010535963 A CN202010535963 A CN 202010535963A CN 111592649 A CN111592649 A CN 111592649A
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- Prior art keywords
- foaming
- polyimide foam
- stirring
- dianhydride
- foam material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 39
- 229920001721 polyimide Polymers 0.000 title claims abstract description 39
- 239000006261 foam material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 75
- 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 42
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000005187 foaming Methods 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000004088 foaming agent Substances 0.000 claims abstract description 17
- 239000012948 isocyanate Substances 0.000 claims abstract description 15
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 229920005862 polyol Polymers 0.000 claims abstract description 10
- 150000003077 polyols Chemical class 0.000 claims abstract description 10
- 238000001723 curing Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002798 polar solvent Substances 0.000 claims abstract description 7
- 239000006260 foam Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- -1 polymethylene isocyanate Polymers 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 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 4
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 4
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 4
- 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 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- UQOQXWZPXFPRBR-UHFFFAOYSA-K bismuth dodecanoate Chemical compound [Bi+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O UQOQXWZPXFPRBR-UHFFFAOYSA-K 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 3
- 229940113116 polyethylene glycol 1000 Drugs 0.000 claims description 3
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- 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 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 3
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 3
- CABKEYSKRKVXQI-UHFFFAOYSA-N 4-methylbenzenesulfonamide urea Chemical compound NC(=O)N.C1(=CC=C(C=C1)S(=O)(=O)N)C CABKEYSKRKVXQI-UHFFFAOYSA-N 0.000 claims description 2
- 102100028175 Abasic site processing protein HMCES Human genes 0.000 claims description 2
- 239000004156 Azodicarbonamide Substances 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- 101001006387 Homo sapiens Abasic site processing protein HMCES Proteins 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 2
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 235000010338 boric acid Nutrition 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- IIPUCUBRDHWANR-UHFFFAOYSA-N 3,4-dimethoxyhexane Chemical compound CCC(OC)C(CC)OC IIPUCUBRDHWANR-UHFFFAOYSA-N 0.000 claims 1
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004604 Blowing Agent Substances 0.000 claims 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims 1
- SKCNNQDRNPQEFU-UHFFFAOYSA-N n'-[3-(dimethylamino)propyl]-n,n,n'-trimethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)CCCN(C)C SKCNNQDRNPQEFU-UHFFFAOYSA-N 0.000 claims 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
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- 239000000047 product Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
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- 230000008569 process Effects 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- 150000004985 diamines Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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Abstract
本发明公开了一种低导热聚酰亚胺泡沫材料及其制备方法；该方法的步骤为：将芳香二酐与极性溶剂混合，在加热条件下溶解后，将低分子量醇加入并持续加热使各组分发生酯化反应得到酯化前驱体溶液；然后将催化剂、发泡剂、表面活性剂、聚合物多元醇、发泡剂加入并使其均匀分散得到发泡白料，最后将异氰酸酯加入白料中，快速搅拌使其均匀分散后再将其放入模具中发泡成型，待其停止发泡后经过加热固化得到聚酰亚胺泡沫材料；本发明方法制备得到的聚酰亚胺泡沫材料具有导热系数低、极限氧指数高、阻燃性好、泡孔大小均匀、密度可控、力学强度高的优点，可广泛应用于航空航天、军用舰船、建筑保温、车辆建造等领域。
Description
技术领域
本发明属于高分子发泡材料技术领域，具体涉及一种低导热聚酰亚胺泡沫材料及其制备方法。
背景技术
聚酰亚胺泡沫材料是一种具有特定化学结构的轻质多孔泡沫塑料，具有保温隔热、耐火、耐高低温、耐辐射、耐腐蚀、低吸湿性、透波、高绝缘、隔音、轻质等性能特点，性能优良。在航空航天、舰船、建筑、汽车、电子电器、机械工业等领域广泛的应用或具有巨大的应用潜力。
目前广泛应用的保温隔热材料主要是岩棉、玻璃棉、膨胀珍珠岩等无机材料和聚氨酯泡沫、聚苯板等有机材料。其中岩棉、玻璃棉保温隔热性能差、吸湿率高、环保性能差、对人体健康有危害。聚氨酯泡沫和聚苯板泡沫阻燃性较差，近年来我国发生过许多次重大火灾，其中相当大的一部分损失都是由于外墙保温材料不合格导致的。而聚酰亚胺泡沫具有高阻燃、环保无毒、烟密度小、低导热性优点，若能够广泛的应用，将会对人民健康安全、国家经济发展做出重要贡献。
中国专利CN101402743A报道了一种通过一步法制备聚酰亚胺泡沫的方法。具体为将一定比例的芳香二酐、催化剂、低分子醇、表面活性剂等原料混合均匀，形成发泡白料，再将发泡黑料异氰酸酯加入，然后通过微波和加热处理得到最终的聚酰亚胺泡沫产品。
中国专利CN101402895A公开了一种耐高温聚酰亚胺泡沫的制备方法，该方法通过将二酐酯化，然后在酯化液中加入二胺来防止产生粉末预聚体，再通过两步法来制备聚酰亚胺泡沫材料。
美国专利US3772216、US4177333、WO2004072032公开了以二酐及其衍生物等为前驱体溶液A，以异氰酸酯溶液为发泡前驱体溶液B，利用混合后室温发泡。高温或微波固化的工艺，制备出低密度阻燃的聚酰亚胺泡沫材料。
美国专利US4923907报道了一种引入无机纳米蛭石对聚酰亚胺泡沫耐热性增强的方法。具体为，将等量的纳米蛭石与聚酰亚胺预聚物混合后放入模具中压实，将模具置于190℃环境下发泡30min，再在260℃下后处理2h，待其温度降至室温后拆模。
目前，聚酰亚胺泡沫的制备工艺分为一步法和二步法，一步法是指将二酐或二酸酯、低分子量醇、催化剂以及其他添加剂在一定溶剂中制成泡沫前体溶液,再与异氰酸酯发生缩合反应，产生小分子气体作为发泡剂而制得PI泡沫，此方法工艺相对简单，生产周期短，但酰亚胺化程度不高；二步法是指将二酐先与二胺反应制备成前驱体粉末,随后将其在一定条件下发泡制备成PI泡沫，该方法可以制备较高密度的泡沫，但工艺较为复杂，且泡沫的缺陷较多；所以，降低生产成本和生产工艺条件，仍是目前聚酰亚胺泡沫材料的研究重点，同时优化其特有的性能也是至关重要的。
发明内容
本发明针对现有技术的不足，提出了一种低导热聚酰亚胺泡沫材料及其制备方法。
具体是通过以下技术方案来实现的：
一种低导热聚酰亚胺泡沫材料，所述低导热聚酰亚胺泡沫材料，按重量份计物料用量为：芳香二酐90-135份、极性溶剂120-160份、低分子量醇20-38份、催化剂1.9-3.5份、发泡剂2.5-16份、表面活性剂4.5-12份、聚合物多元醇8.5-13.5份、异氰酸酯110-162份。
进一步地，所述低导热聚酰亚胺泡沫材料，是先将芳香二酐溶液与低分子量醇加热搅拌形成前驱体酯化液，然后向其中加入催化剂、发泡剂、表面活性剂、聚合物多元醇制得发泡白料，再将发泡白料与异氰酸酯快速混匀，进行充分发泡后，经加热固化，即得。
一种低导热聚酰亚胺泡沫材料的制备方法，包括以下步骤：
1)将芳香二酐与加入极性溶剂中，在加热搅拌至二酐溶解，制得二酐溶液后，将低分子量醇加入二酐溶液中，经加热搅拌反应，生成前驱体酯化液；
2)将前驱体酯化液降至室温后，向其中加入催化剂、发泡剂、表面活性剂、聚合物多元醇并混合均匀，发泡白料；
3)将异氰酸酯加入白料中，快速搅拌使其混合均匀，然后将混合物倒入模具进行发泡；
4)待发泡结束后，将预发泡产物通过烘箱加热固化，得聚酰亚胺泡沫材料。
所述的芳香二酐为3,3`,4,4`-二苯醚四酸酐、3,3`,4,4`-二苯甲酮四羧酸二酐、3,3`,4,4`-联苯基四羧基二酐、均苯四酸二酐、2,3,3`,4`-联苯基四羧基二酐中的一种或几种的混合物。
所述的极性溶剂为二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二氯甲烷、甲醇、乙醇、二苯醚、环己烷、丙酮、四氢呋喃、甲苯、二甲苯、石油醚、异丙醚中的一种或几种的混合物。
所述的催化剂为辛酸亚锡、二月桂酸二丁基锡、月桂酸铋、钯、三乙烯二胺、三亚乙基二胺、二亚乙基三胺、乙二胺、三乙醇胺、五甲基二乙烯三胺、二甲基环己胺、双(二甲氮丙基)甲胺、一缩二丙二醇、四甲基乙二胺等中的一种或几种的复合物。
所述的发泡剂为水、正戊烷、正己烷、正庚烷、石油醚、二氯三氟甲烷、丙酮、乙醇、碳酸钙、碳酸镁、碳酸氢钠、偶氮二甲酸钡、偶氮二甲酰胺、硼酸、苯甲酸、对甲苯磺酰胺基脲、二氧杂环乙烷、1,2-二乙氧基乙烷、二乙烷基乙二醇基二甲醚、四氢呋喃、三乙胺等中的一种或几种。
所述的表面活性剂为十二烷基磺酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、硬脂酸、十六烷基三甲基溴化铵、烷基聚氧乙烯醚、DC12、DC01、DC193、DC6070、DC5950、op-10、Span-80、Span-60、Triton x-100、有机硅AK8808、有机硅AK8805、有机硅AK8803等中的一种或几种。
所述的聚合物多元醇为聚乙烯醇、聚乙二醇200、聚乙二醇400、聚乙二醇600、聚乙二醇1000、聚乙二醇2000等中的一种或几种。
所述的异氰酸酯为二苯甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、赖氨酸二异氰酸酯、多苯基多亚甲基异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或几种。
所述的烘箱加热采取梯度升温、固定温度中任一种，其加热时间为0.5h-35h。
所述梯度升温是以30℃-100℃为初始温度，以3℃/min-20℃/min的速率升温至180℃-320℃后，保温。
所述固定温度，其温度取值范围为110℃-300℃。
所述混合采取机械搅拌、磁力搅拌中任一种。
所述机械搅拌，其搅拌速率为300rpm-2600rpm，搅拌时间为6s-30min。
所述磁力搅拌，其搅拌速率为100rpm-1250rpm，搅拌时间为10min-2h。
所述加热采取水浴加热、油浴加热、超声油浴加热中任一种。
所述加热，其温度为30℃-140℃，时间为5min-2h。
有益效果：
采用本发明得到的聚酰亚胺泡沫材料具有泡孔大小均匀、大尺寸外形完整性较好、密度可控、导热系数低、极限氧指数高、阻燃性好等优点。
本方法无须使用微波处理，降低了设备投入和能耗，且无副反应，发泡效果优，过程操作简单。
本发明通过控制搅拌速率和加热温度，使得反应充分，将二酐与醇类物质进行酯化，再通过催化剂、发泡剂、表面活性剂、聚合物多元醇，使得前驱体酯化异构化，并利用反应中自身产生的小分子和发泡剂的作用，在升温过程中生成核点以及泡孔生长。本发明通过加入催化剂和表面活性剂，使得前驱体酯化液体系不稳定，进而形成大量泡核，在形成泡核之后加入异氰酸酯，配合加热和搅拌作用，使得气体迅速解析，扩散进入泡核，有助于气泡快速生长。
具体实施方式
下面对本发明的具体实施方式作进一步详细的说明，但本发明并不局限于这些实施方式，任何在本实施例基本精神上的改进或代替，仍属于本发明权利要求所要求保护的范围。
实施例1
1)将3,3`,4,4`-联苯基四羧基二酐90g加入盛有四氢呋喃120g的反应釜中，在105℃下搅拌30min使二酐充分溶解，搅拌方式为磁力搅拌，搅拌速率为400r/min，制得二酐溶液；将甲醇20g缓慢加入至二酐溶液中，保持温度为60℃搅拌使其反应1h生成前驱体酯化液，搅拌方式为磁力搅拌，搅拌速率为550r/min；
2)将前驱体酯化液降至室温后，将由辛酸亚锡0.8g、三乙醇胺0.8g、四甲基乙二胺1.1g组成的催化剂、由水3.3g和对甲苯磺酰胺基脲2.5g组成的复合发泡剂、9.0g DC5950、8.6g聚乙二醇400依次加入至前驱体酯化液中，并搅拌10min使其混合均匀制得发泡白料，搅拌方式为机械搅拌，搅拌速率为830r/min；
3)将多苯基多亚甲基异氰酸酯110g加入白料中，并快速搅拌11s使其混合均匀，然后将混合物倒入模具中使其发泡成型，搅拌方式为机械搅拌，搅拌速率为1300r/min；
4)待发泡结束后，将预发泡产物通过烘箱加热固化，烘箱温度为70℃、90℃、110℃、150℃各1h，180℃保持5h，升温速率为5℃/min，得聚酰亚胺泡沫材料。
实施例2
1)将均苯四酸二酐135g加入盛有N,N-二甲基甲酰胺160g的反应釜中，在90℃下搅拌45min使二酐充分溶解，制得二酐溶液，搅拌方式为磁力搅拌，搅拌速率为1100r/min；将丙醇38g缓慢加入至二酐溶液中，保持温度为72℃搅拌使其反应0.8h生成前驱体酯化液，搅拌方式为磁力搅拌，搅拌速率为660r/min；
2)将前驱体酯化液降至室温后，将由1.1g二月桂酸二丁基锡、1.2g五甲基二乙烯三胺、0.8g三亚乙基二胺组成的复合催化剂、由7.8g碳酸镁、6.9g正己烷组成的复合发泡剂、6.2g Span-60、5.8g AK8803、8.6g聚乙二醇1000依次加入至前驱体酯化液中，并搅拌15min使其混合均匀制得发泡白料，搅拌方式为机械搅拌，搅拌速率为780r/min；
3)将异佛尔酮二异氰酸酯162g加入白料中，并快速搅拌16s使其混合均匀，然后将混合物倒入模具中使其发泡成型，搅拌方式为机械搅拌，搅拌速率为1050r/min；
4)待发泡结束后，将预发泡产物通过烘箱加热固化，烘箱温度为70℃、100℃、130℃各1h，180℃保持8h，升温速率为2℃/min，得聚酰亚胺泡沫材料。
实施例3
1)将3,3`,4,4`-二苯甲酮四羧酸二酐120g加入盛有二氯甲烷135g的反应釜中，在125℃下搅拌25min使二酐充分溶解，制得二酐溶液，搅拌方式为磁力搅拌，搅拌速率为800r/min；将乙二醇36g缓慢加入至二酐溶液中，保持温度为82℃搅拌使其反应1.5h生成前驱体酯化液，搅拌方式为磁力搅拌，搅拌速率为710r/min；
2)将前驱体酯化液降至室温后，向其中依次加入4.6g Triton x-100、6.8gAK8805、10.2g聚乙二醇600、由4.5g石油醚、7.8g二氧杂环乙烷组成的复合发泡剂、由0.8g月桂酸铋、0.6g三乙烯二胺、2.1g三亚乙基二胺组成的复合催化剂，并搅拌1h使其混合均匀得到发泡白料，搅拌方式为机械搅拌，搅拌速率为900r/min；
3)将2,4-甲苯二异氰酸酯134g加入白料中，并快速搅拌9s使其混合均匀，然后将混合物倒入模具中使其发泡成型，搅拌方式为机械搅拌，搅拌速率为1500r/min；
4)待发泡结束后，将预发泡产物通过烘箱加热固化，烘箱温度为90℃、130℃各1h，180℃保持6h，升温速率为10℃/min，得聚酰亚胺泡沫材料。
实施例4
1)将2,3,3`,4`-联苯基四羧基二酐120g加入盛有丙酮150g的反应釜中，在130℃下搅拌1h使二酐充分溶解，制得二酐溶液，搅拌方式为机械搅拌，搅拌速率为400r/min；将异丙醇28g缓慢加入至二酐溶液中，保持温度为90℃搅拌使其反应2h生成前驱体酯化液，搅拌方式为磁力搅拌，搅拌速率为1000r/min；
2)将前驱体酯化液降至室温后，向其中依次加入4.6g DC193、10.2g聚乙二醇600、由3.6g正戊烷、4.1g1,2-二乙氧基乙烷组成的复合发泡剂、由1.3g二月桂酸二丁基锡、0.8g三乙醇胺、0.8g一缩二丙二醇混合而成的复合催化剂，并搅拌2h使其混合均匀得到发泡白料，搅拌方式为机械搅拌，搅拌速率为880r/min；
3)将含有二苯甲烷二异氰酸酯85g、六亚甲基二异氰酸酯62g的混合物加入白料中，并快速搅拌15s使其混合均匀，然后将混合物倒入模具中使其发泡成型，搅拌方式为机械搅拌，搅拌速率为1100r/min；
4)待发泡结束后，将预发泡产物通过烘箱加热固化，烘箱温度为180℃，保持12h，升温速率为10℃/min，得到最终产物聚酰亚胺泡沫材料。
实施例5
1)将3,3`,4,4`-二苯醚四酸酐61g、2,3,3`,4`-联苯基四羧基二酐46g加入盛有N,N-二甲基乙酰胺155g的反应釜中，在118下搅拌36min使二酐充分溶解，制得二酐溶液，搅拌方式为机械搅拌，搅拌速率为760r/min；将乙醇15g、异丙醇21g一次性加入至二酐溶液中，保持温度为125℃搅拌使其反应55min生成前驱体酯化液，搅拌方式为磁力搅拌，搅拌速率为1320r/min；
2)在酯化液降至室温后，将3.2g DC01、4.1g十六烷基三甲基溴化铵、13.2份聚乙二醇200、由3.3g正庚烷、5.8g水、6.9g碳酸氢钠组成的复合发泡剂、由0.9g辛酸亚锡、1.1g乙二胺、0.6g二甲基环己胺组成的复合催化剂依次加入降温后的前驱体酯化液中，并搅拌1.2h使其混合均匀得到发泡白料，搅拌方式为机械搅拌，搅拌速率为700r/min；
3)将2,6-甲苯二异氰酸酯77g、二环己基甲烷二异氰酸酯69g加入白料中，并快速搅拌10s使其混合均匀，然后将混合物倒入模具中使其发泡成型，搅拌方式为机械搅拌，搅拌速率为1350r/min；
4)待发泡结束后，将预发泡产物通过烘箱加热固化，烘箱温度为80℃、120℃、160各2h，180℃保持4h，升温速率为15℃/min，得到最终产物聚酰亚胺泡沫材料。
所述生产工艺制备得到的聚酰亚胺泡沫材料，其主要性能参数如下所示：
表6聚酰亚胺泡沫材料主要性能参数
以上所述的实施例是对本发明的研究方案、工艺技术和积极效益做出了详细说明，应理解的是以上所述仅为本发明的具体实施例，并不限制本发明，凡在本发明的原则范围之内所做出的任何改进，均在本发明的保护范围之内。
Claims (10)
1.一种低导热聚酰亚胺泡沫材料，其特征在于，所述低导热聚酰亚胺泡沫材料，按重量份计物料用量为：芳香二酐90-135份、极性溶剂120-160份、低分子量醇20-38份、催化剂1.9-3.5份、发泡剂2.5-16份、表面活性剂4.5-12份、聚合物多元醇8.5-13.5份、异氰酸酯110-162份。
2.如权利要求1所述低导热聚酰亚胺泡沫材料，其特征在于，所述低导热聚酰亚胺泡沫材料，是先将芳香二酐溶液与低分子量醇加热搅拌形成前驱体酯化液，然后向其中加入催化剂、发泡剂、表面活性剂、聚合物多元醇制得发泡白料，再将发泡白料与异氰酸酯快速混匀，进行充分发泡后，经加热固化，即得。
3.如权利要求1或2所述低导热聚酰亚胺泡沫材料的制备方法，其特征在于，包括以下步骤：
1)将芳香二酐与加入极性溶剂中，在加热搅拌至二酐溶解，制得二酐溶液后，将低分子量醇加入二酐溶液中，经加热搅拌反应，生成前驱体酯化液；
2)将前驱体酯化液降至室温后，向其中加入催化剂、发泡剂、表面活性剂、聚合物多元醇并混合均匀，发泡白料；
3)将异氰酸酯加入白料中，快速搅拌使其混合均匀，然后将混合物倒入模具进行发泡；
4)待发泡结束后，将预发泡产物通过烘箱加热固化，得聚酰亚胺泡沫材料。
4.如权利要求3所述低导热聚酰亚胺泡沫材料的制备方法，其特征在于，所述的芳香二酐为3,3`,4,4`-二苯醚四酸酐、3,3`,4,4`-二苯甲酮四羧酸二酐、3,3`,4,4`-联苯基四羧基二酐、均苯四酸二酐、2,3,3`,4`-联苯基四羧基二酐中的一种或几种的混合物。
5.如权利要求3所述低导热聚酰亚胺泡沫材料的制备方法，其特征在于，所述的极性溶剂为二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二氯甲烷、甲醇、乙醇、二苯醚、环己烷、丙酮、四氢呋喃、甲苯、二甲苯、石油醚、异丙醚中的一种或几种的混合物。
6.如权利要求3所述低导热聚酰亚胺泡沫材料的制备方法，其特征在于，所述的催化剂为辛酸亚锡、二月桂酸二丁基锡、月桂酸铋、钯、三乙烯二胺、三亚乙基二胺、二亚乙基三胺、乙二胺、三乙醇胺、五甲基二乙烯三胺、二甲基环己胺、双(二甲氮丙基)甲胺、一缩二丙二醇、四甲基乙二胺等中的一种或几种的复合物。
7.如权利要求3所述低导热聚酰亚胺泡沫材料的制备方法，其特征在于，所述的发泡剂为水、正戊烷、正己烷、正庚烷、石油醚、二氯三氟甲烷、丙酮、乙醇、碳酸钙、碳酸镁、碳酸氢钠、偶氮二甲酸钡、偶氮二甲酰胺、硼酸、苯甲酸、对甲苯磺酰胺基脲、二氧杂环乙烷、1,2-二乙氧基乙烷、二乙烷基乙二醇基二甲醚、四氢呋喃、三乙胺等中的一种或几种。
8.如权利要求3所述低导热聚酰亚胺泡沫材料的制备方法，其特征在于，所述的表面活性剂为十二烷基磺酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、硬脂酸、十六烷基三甲基溴化铵、烷基聚氧乙烯醚、DC12、DC01、DC193、DC6070、DC5950、op-10、Span-80、Span-60、Triton x-100、有机硅AK8808、有机硅AK8805、有机硅AK8803等中的一种或几种。
9.如权利要求3所述低导热聚酰亚胺泡沫材料的制备方法，其特征在于，所述的聚合物多元醇为聚乙烯醇、聚乙二醇200、聚乙二醇400、聚乙二醇600、聚乙二醇1000、聚乙二醇2000等中的一种或几种。
10.如权利要求3所述低导热聚酰亚胺泡沫材料的制备方法，其特征在于，所述的异氰酸酯为二苯甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、赖氨酸二异氰酸酯、多苯基多亚甲基异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯中的一种或几种。
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Application publication date: 20200828 |