CN1138804C - 低热导率闭孔聚氨酯硬发泡材料的生产方法 - Google Patents
低热导率闭孔聚氨酯硬发泡材料的生产方法 Download PDFInfo
- Publication number
- CN1138804C CN1138804C CNB988057948A CN98805794A CN1138804C CN 1138804 C CN1138804 C CN 1138804C CN B988057948 A CNB988057948 A CN B988057948A CN 98805794 A CN98805794 A CN 98805794A CN 1138804 C CN1138804 C CN 1138804C
- Authority
- CN
- China
- Prior art keywords
- rigid polyurethane
- polyurethane foams
- polyethers
- propylene oxide
- production method
- 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.)
- Expired - Lifetime
Links
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 28
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 229920000570 polyether Polymers 0.000 claims abstract description 27
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 11
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 229920000768 polyamine Polymers 0.000 claims abstract description 8
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 6
- 229930006000 Sucrose Natural products 0.000 claims abstract description 6
- 239000005720 sucrose Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 4
- 239000012948 isocyanate Substances 0.000 claims abstract description 3
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 12
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 11
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 8
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 7
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical compound CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- ZMBQZWCDYKGVLW-UHFFFAOYSA-N 1-methylcyclohexa-3,5-diene-1,2-diamine Chemical compound CC1(N)C=CC=CC1N ZMBQZWCDYKGVLW-UHFFFAOYSA-N 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 abstract 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 abstract 1
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000004088 foaming agent Substances 0.000 abstract 1
- 239000000600 sorbitol Substances 0.000 abstract 1
- -1 alkane hydrofluoride Chemical class 0.000 description 23
- 238000009472 formulation Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000006261 foam material Substances 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 4
- 238000012644 addition polymerization Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 125000005702 oxyalkylene group Chemical group 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000001408 fungistatic effect Effects 0.000 description 2
- 239000011796 hollow space material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000005437 stratosphere Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- CXIGIYYQHHRBJC-UHFFFAOYSA-N 1,1,1,4,4,4-hexafluorobutane Chemical compound FC(F)(F)CCC(F)(F)F CXIGIYYQHHRBJC-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- OHKOAJUTRVTYSW-UHFFFAOYSA-N 2-[(2-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC=C1CC1=CC=CC=C1N OHKOAJUTRVTYSW-UHFFFAOYSA-N 0.000 description 1
- UTNMPUFESIRPQP-UHFFFAOYSA-N 2-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1N UTNMPUFESIRPQP-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- BRKHZWFIIVVNTA-UHFFFAOYSA-N 4-cyclohexylmorpholine Chemical compound C1CCCCC1N1CCOCC1 BRKHZWFIIVVNTA-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- GTJVPLGQFHDOAC-UHFFFAOYSA-N C(C(=O)O)(=O)O.C(CCCCCCC)[Sn]CCCCCCCC Chemical compound C(C(=O)O)(=O)O.C(CCCCCCC)[Sn]CCCCCCCC GTJVPLGQFHDOAC-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000002650 habitual effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexamethylene diamine Natural products NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FJIKWRGCXUCUIG-UHFFFAOYSA-N lormetazepam Chemical compound N=1C(O)C(=O)N(C)C2=CC=C(Cl)C=C2C=1C1=CC=CC=C1Cl FJIKWRGCXUCUIG-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 description 1
- NXHXNTAEDQTBLD-UHFFFAOYSA-N n,n-dimethyl-3-(triazinan-1-yl)propan-1-amine Chemical class CN(C)CCCN1CCCNN1 NXHXNTAEDQTBLD-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- ADRDEXBBJTUCND-UHFFFAOYSA-N pyrrolizidine Chemical compound C1CCN2CCCC21 ADRDEXBBJTUCND-UHFFFAOYSA-N 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 239000010458 rotten stone Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 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 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
一种以多元醇与多异氰酸酯为原料并采用发泡剂和任选的发泡助剂生产聚氨酯硬发泡材料的方法，其特征在于，该聚氨酯硬发泡材料通过以下成分的反应获得：A.多元醇组分，它包含(1)40～80wt%以蔗糖或山梨醇为基础、分子量为300～800的聚环氧乙烷/环氧丙烷聚醚，(2)3～40wt%以芳族单-、二-或多胺为基础、分子量为300～800的聚环氧乙烷/环氧丙烷聚醚，(3)3～40wt%以脂族单-、二-或多胺为基础、分子量为200～800的聚环氧乙烷/环氧丙烷聚醚，(4)3～40wt%分子量为500～1500的线型聚环氧乙烷/环氧丙烷聚醚，(5)任选的包含至少2个能与异氰酸酯起反应的氢原子、分子量为150～12，500g/mol的其他化合物，(6)催化剂，(7)水，(8)发泡剂，选自链烷、环烷、氢氯氟烃、氢氟烃，以及(9)任选的辅助剂材料和/或添加剂，与B.有机和/或改性的有机多异氰酸酯，具有20～48wt%的NCO含量。
Description
由于其热导率低，聚氨酯硬发泡材料被广泛应用于工业设施、罐区及管线以及造船和建筑工业中的冷藏及冷冻设备的绝缘。有关聚氨酯硬发泡材料的生产及其应用的综述刊载在《塑料手册》，第7卷(聚氨酯)，第二版中1983，Gunter Oertel博士主编(Carl Hanser出版社，慕尼黑)。
基本闭孔的聚氨酯硬发泡材料的热导率在很大程度上取决于所使用的发泡剂和泡孔气体的种类。全卤化氯氟烃(CFC)已证明特别适合此种用途，尤其是三氯氟甲烷(R11)，具有特别低的热导率。这些物质为化学惰性和无毒的。然而，由于具有高度稳定性，全卤化氨氟烃会进入同温层，由于它们含有氯，会促使存在于同温层中臭氧的破坏。(Molina，Rowland，《自然界》249(1974)810)。
作为氯氟烃的替代物，已建议采用氢氟链烷，如R141b(二氯氟乙烷)作为发泡剂(US 5 272 183)。
还有人建议使用仍旧含有至少1个碳-氢键的部分氟化烃(氢氟链烷)作为发泡剂(EP 344 537、US 4 931 482)。此类化合物不含氯原子，故其ODP值(臭氧耗蚀能力)为0(相比之下，R11的ODP值为1)。这类物质的典型代表例如是1，1，1，4，4，4-六氟丁烷(R356)和1，1，1，3，3-五氟丙烷(245fa)。
另外，从EP 0 421 269中又得知环戊烷或环戊烷与其他链烷如异丁烷、正丁烷或异戊烷的混合物作为发泡剂的应用。
根据所用发泡剂的情况，还需对多元醇配制物实施改性，以便获得大致相当的低热导率聚氨酯硬发泡材料。因此，希望在使用不同发泡剂体系时，所使用的多元醇配制物能生产出热导率相近的硬发泡材料，同时不必改变配方或改变发泡配方所要求的机械设备参数，因为，这种改变对于成本都是不利的。
据此，本发明的目的是找到一种生产低热导率闭孔聚氨酯硬发泡材料的方法，用此种方法，即使当使用不同发泡剂体系时仍可获得具有类似低热导率的聚氨酯硬发泡材料。
现已令人惊奇地发现一种多元醇配制物，它可以采用上面提到的所有用于替代氯氟烃的物质，特别是以环戊烷、环戊烷/异丁烷混合物、环戊烷/异戊烷混合物、R141b和R245fa进行发泡，总是可以使获得的聚氨酯硬发泡材料具有类似的低热导率及出色的综合性能，且该产品特别适合用于冷藏和冷冻设备的绝缘。这特别有利于此种配制物的加工者，因为，出于法律的原因而不得不改变发泡剂时，不需要对机械设备做相应的调整，且不需改变原料，故而可以迅速和符合成本效益地改变发泡剂。
本发明涉及一种以多元醇与多异氰酸酯为原料并采用发泡剂和任选的发泡助剂生产低热导率闭孔聚氨酯硬发泡材料的方法，其特征在于，该聚氨酯硬发泡材料通过以下成分的反应获得：
A.多元醇组分，它包含
(1)40～80wt％以蔗糖或山梨醇为基础、分子量为300～800的聚环氧乙烷/环氧丙烷聚醚，
(2)3～40wt％以芳族单-、二-或多胺为基础、分子量为300～800的聚环氧乙烷/环氧丙烷聚醚，
(3)3～40wt％以脂族单-、二-或多胺为基础、分子量为200～800的聚环氧乙烷/环氧丙烷聚醚，
(4)3～40wt％分子量为500～1500的线型聚环氧乙烷/环氧丙烷聚醚，
(5)任选的包含至少2个能与异氰酸酯起反应的氢原子、分子量为150～12,500g/mol的其他化合物，
(6)催化剂，
(7)水，
(8)发泡剂，选自链烷、环烷、氢氯氟烃、氢氟烃，以及
(9)任选的辅助剂材料和/或添加剂，与
B.多异氰酸酯，任选为改性的，具有20～48wt％的NCO含量。
可用于本发明的多元醇配制物包含分子量为300～800g/mol、含至少2个能与异氰酸酯起反应的氢原子的化合物。它们可通过诸如环氧乙烷、环氧丙烷、氧化丁烯、氧化十二碳烯或氧化苯乙烯之类的氧化烯，优选环氧丙烷或环氧乙烷，与初始化合物之间的加成聚合来制备。诸如蔗糖和山梨醇之类的多羟基醇以及这类醇与水、甘油、丙二醇、乙二醇或二甘醇的混合物，作为起始化合物使用。通过使用按照本发明的这些多元醇，可获得通常所要求的聚氨酯硬发泡材料的机械性能。
按照本发明使用的多元醇配制物另外还包含至少1种分子量为300～800g/mol且包含至少2个能与异氰酸酯起反应的氢原子的化合物。这些化合物是通过--诸如环氧乙烷、环氧丙烷、氧化丁烯、氧化十二碳烯或氧化苯乙烯之类的氧化烯，优选环氧丙烷或环氧乙烷，与芳族单-、二-或多胺，如苯胺、苯二胺、二氨基甲苯(2，3-二氨基甲苯、3，4-二氨基甲苯、2，4-二氨基甲苯、2，5-二氨基甲苯、2，6-二氨基甲苯或这些异构体的混合物)、2，2’-二氨基二苯甲烷、2，4’-二氨基二苯甲烷、4，4’-二氨基二苯甲烷或这些异构体的混合物--之间的加成聚合获得的。
另外，本发明所使用的多元醇配制物包含至少1种分子量为200～800g/mol且包含至少2个能与异氰酸酯起反应的氢原子的化合物，它们是通过--诸如环氧乙烷、环氧丙烷、氧化丁烯、氧化十二碳烯或氧化苯乙烯之类的氧化烯，优选环氧丙烷或环氧乙烷，与脂族单-、二-或多胺，如乙二胺、乙二胺的低聚物(如，二亚乙基三胺、三亚乙基四胺或五亚乙基六胺)、乙醇胺、二乙醇胺、三乙醇胺、N-甲基-或N-乙基二乙醇胺、1，3-丙二胺、1，3-或1，4-丁二胺或者1，2-、1，3-、1，4-、1，5-或1，6-六亚甲基二胺--之间的加成聚合获得的。
本发明的多元醇配制物还包含分子量为500～1500g/mol且包含至少2个能与异氰酸酯起反应的氢原子的化合物。这些化合物是通过--诸如环氧乙烷、环氧丙烷、氧化丁烯、氧化十二碳烯或氧化苯乙烯之类的氧化烯，优选环氧丙烷或环氧乙烷，与诸如水、丙二醇、乙二醇或二甘醇之类的起始化合物--之间的加成聚合获得的。
聚氨酯化学中惯用的催化剂可用于本发明的方法中。此类型的催化剂的例子包括：三亚乙基二胺、N，N-二甲基环己胺、四亚甲基二胺、1-甲基-4-二甲氨乙基哌嗪、三乙胺、三丁胺、二甲基苄胺、N，N’，N”-三(二甲氨丙基)-六氢三嗪、二甲氨丙基甲酰胺、N，N，N’，N”-四甲基乙二胺、N，N，N’，N”-四甲基丁二胺、四甲基己二胺、五甲基二亚乙基三胺、四甲基二氨基乙基醚、二甲基哌嗪、1，2-二甲基咪唑、1-氮杂-双环-(3，3，0)-辛烷、双-(二甲氨丙基)-脲、N-甲基吗啉、N-乙基吗啉、N-环己基吗啉、2，3-二甲基-3，4，5，6-四氢嘧啶、三乙醇胺、二乙醇胺、三异丙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、二甲基乙醇胺、醋酸锡(II)、辛酸锡(II)、乙基己酸锡(II)、月桂酸锡(II)、二乙酸二丁基锡、二月桂酸 二丁基锡、马来酸二丁基锡、二乙酸二辛基锡、三-(N，N-二甲氨丙基)-s-六氢三嗪、氢氧化四甲铵、醋酸钠、醋酸钾、氢氧化钠，或者它们的混合物或类似的催化剂。
用于本发明方法的多元醇配制物包含0.5～7.0重量份，优选1.0～3.0重量份水，每100重量份多元醇组分A。
用于本发明的发泡剂选自链烷，特别是包含4～5个碳原子的那些，如异戊烷、正戊烷、正丁烷、异丁烷、2，2-二甲基丁烷，或者环烷，特别是环戊烷或环己烷，或者氢氯氟烃，优选R141b(二氯氟乙烷)或者氢氟烃，优选R 245fa，乃至它们的混合物。
异氰酸酯组分的例子包括芳族多异氰酸酯，如W.Siefken在《Justus Liebigs Annalen der Chemie》562，pp.75～136中所描述的那些，例如具有如下通式的，
Q(NCO)n
其中
n代表2～4，优选2，以及
Q代表C2～C18-，优选C6～C10-脂族烃基、C4～C15-，优选C5～C10-环脂族烃基，或者C8～C15-，优选C8～C13-芳烃基，例如描述于DE-OS 2832 253，PP.10～11中的那些多异氰酸酯。
一般地，易于从市场上获得的多异氰酸酯是特别优选的，如甲苯2，4-及2，6-二异氰酸酯及这些异构体的任意混合物(“TDI”)、聚苯基聚亚甲基多异氰酸酯，例如，通过苯胺-甲醛缩合，随后经光气化制备的那些(“粗MDI”)，以及包含碳化二亚胺基团、氨基甲酸酯基团、脲基甲酸酯基团、异氰尿酸酯基团、脲基团或缩二脲基团的“改性多异氰酸酯”。由甲苯2，4-及2，6-二异氰酸酯或由4，4’和/或2，4’-二苯甲烷二异氰酸酯衍生的改性多异氰酸酯是特别优选的。
由所述异氰酸酯与包含至少1个羟基基团的有机化合物生成的预聚物也可使用，例如，可使用分子量为60～1400且包含1～4个羟基基团的多元醇或聚酯成分。
石蜡或脂肪醇或二甲基聚硅氧烷，乃至颜料或着色剂、抗老化或耐天候效应的稳定剂、增塑剂及具有防霉及抑菌效果的物质，也可配合使用，同样，也可使用填料，如硫酸钡、硅土、碳黑或增白剂。
表面活性添加剂及泡孔稳定剂，乃至泡孔调节剂、反应阻滞剂、稳定剂、阻燃剂、着色剂及填料，以及具有防霉和抑菌效果的物质的其他例子，以及使用方法细节和这些调节剂的作用模式，描述于《塑料手册》，卷VII，Vieweg及Hochtlen主编，Carl Hanser出版社，慕尼黑1966，例如，pp.121～205中，以及第二版1983，G.Oertel主编(Carl Hanser出版社)。
为了生产泡沫体，按照本发明在封闭的模具中进行发泡。在此程序的实施过程中，反应混合物被引入到模具中。合适的模具材料包括金属，如铝，或者塑料，如环氧树脂。反应混合物在模具中发泡并成形为模塑件。在模具中的发泡可按照使模塑件表面形成微孔结构的方式实施。然而，也可按照使模塑件具有实体的表层和微孔芯部的方式实施。在所提到的第一种情况下，本发明的程序包括向模具中引入足以使成形的发泡材料刚好充满该模具的可发泡反应混合物。后一种情况的程序包括将多于使模具内部充满泡沫体所需数量的可发泡反应混合物引入到模具中。因此，在后一种情况下，采用“超进料”。此类型的程序可从US 3 178 490及US 3 182 104中得知。
本发明方法优选用于冷藏和冷冻设备的空心空间内的发泡。发泡材料当然也可通过本领域技术人员熟知的块料发泡或双向输送(double conveying)法来生产。
可采用本发明方法获得的硬发泡材料可用于建筑业和用于长期加热的管道或容器的绝缘。
本发明还涉及按照本发明生产的硬发泡材料作为复合元件中间层的应用以及用于家用冰箱壳体空心空间内的发泡。
下面的实施例用于说明本发明但不构成对本发明范围的限制。
实施例
所使用的原料：
多元醇A：以蔗糖/甘油为基础的分子量为550的聚环氧丙烷/环氧乙烷聚醚
多元醇B：以2，3-和2，4-二氨基甲苯为基础的分子量为560的聚环氧丙烷/环氧乙烷聚醚
多元醇C：以乙二胺为基础的分子量为540的聚环氧丙烷聚醚
多元醇D：以丙二醇为基础的分子量为900的聚环氧丙烷聚醚
由聚醚A～D按50∶25∶15∶10(重量)的比例制备按照本发明的混合物。该混合物按照下表中给出的配方在Hennecke供应的HK 270-高压机器中在20℃被加工成形为聚氨酯硬发泡材料。
催化剂：二甲基环己胺(拜尔公司，Leverkusen)
硅氧烷稳定剂：市售硅氧烷稳定剂，由Goldschmidt公司，Essen，提供
环戊烷：由Erdlchemie，Dormagen，提供
异丁烷：由Linde公司提供
异戊烷：由埃克森公司提供
R141b：由Solvay公司提供
R245fa：由联合信号公司提供
异氰酸酯：“聚合MDI”Desmodur44V20(拜尔公司，Leverkusen)。
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | |
| 多元醇混合物 | 100 | 100 | 100 | 100 | 100 |
| 硅氧烷稳定剂 | 2 | 2 | 2 | 2 | 2 |
| 催化剂 | |||||
| 环戊烷 | 14 | ||||
| 环戊烷/异丁烷(80∶20) | 14 | ||||
| 环戊烷/异戊烷(80∶20) | 14 | ||||
| R141b | 31 | ||||
| R245fa | 28 | ||||
| 异氰酸酯 | 142 | 142 | 142 | 142 | 142 |
| 表层表观密度(kg/m3) | 22.0 | 21.6 | 21.0 | 21.8 | 24 |
| 芯部表观密度(kg/m3) | 32.6 | 31.5 | 31.0 | 31.4 | 32 |
| 热导率，按DIN 52616-77(mW/mK) | 20.6 | 21.4 | 21.6 | 18.5 | 19.9 |
| 压缩强度，按DIN 52421-84(MPa) | 0.15 | 0.15 | 0.15 | 0.13 | 0.16 |
| 尺寸稳定性，按照DIN 53431-77，3h，-30℃；尺寸变化％ | 0 | 0 | 0 | 0 | 0 |
实施例1～5显示，当按照本发明的多元醇配制物采用各种市售发泡剂进行发泡时，所获得的硬发泡材料一概表现出符合实际要求的优异性能。这些性能的获得又伴随着本领域技术人员可以看出的低芯部表观密度。
Claims (12)
1.一种以多元醇与多异氰酸酯为原料并采用发泡剂和任选的发泡助剂生产聚氨酯硬发泡材料的方法，其特征在于，该聚氨酯硬发泡材料通过以下成分的反应获得：
A.多元醇组分，它包含
(1)40～80wt％以蔗糖或山梨醇为基础、分子量为300～800的聚环氧乙烷/环氧丙烷聚醚，
(2)3～40wt％以芳族单-、二-或多胺为基础、分子量为300～800的聚环氧乙烷/环氧丙烷聚醚，
(3)3～40wt％以脂族单-、二-或多胺为基础、分子量为200～800的聚环氧乙烷/环氧丙烷聚醚，
(4)3～40wt％分子量为500～1500的线型聚环氧乙烷/环氧丙烷聚醚，
(5)任选的包含至少2个能与异氰酸酯起反应的氢原子、分子量为150～12,500g/mol的其他化合物，
(6)催化剂，
(7)水，
(8)发泡剂，选自链烷、环烷、氢氯氟烃、氢氟烃，以及
(9)任选的辅助剂材料和/或添加剂，与
B.有机和/或改性的有机多异氰酸酯，具有20～48wt％的NCO含量。
2.权利要求1的聚氨酯硬发泡材料的生产方法，其特征在于，组分(1)是在蔗糖上开始的聚醚，该聚醚主要由70～100wt％1，2-环氧丙烷和0～30wt％环氧乙烷组成。
3.权利要求1的聚氨酯硬发泡材料的生产方法，其特征在于，组分(2)是在邻甲苯二胺上开始的聚醚，该聚醚主要由70～100wt％1，2-环氧丙烷和0～30wt％环氧乙烷组成。
4.权利要求1的聚氨酯硬发泡材料的生产方法，其特征在于，组分(3)是在乙二胺上开始的聚醚，该聚醚主要由50～100wt％1，2-环氧丙烷和0～50wt％环氧乙烷组成。
5.权利要求1的聚氨酯硬发泡材料的生产方法，其特征在于，组分(1)是在山梨醇上开始的聚醚，该聚醚主要由70～100wt％1，2-环氧丙烷和0～30wt％环氧乙烷组成。
6.权利要求1的聚氨酯硬发泡材料的生产方法，其特征在于，组分(4)是在丙二醇上开始的聚醚，该聚醚主要由70～100wt％1，2-环氧丙烷和0～30wt％环氧乙烷组成。
7.权利要求1～6中任何一项的聚氨酯硬发泡材料的生产方法，其特征在于，水用量为0.5～7.0重量份每100重量份多元醇组分A.
8.权利要求1～6中任何一项的聚氨酯硬发泡材料的生产方法，其特征在于，环戊烷和/或环己烷被当作发泡剂(8)使用。
9.权利要求1～6中任何一项的聚氨酯硬发泡材料的生产方法，其特征在于，混合物正-和/或异戊烷和/或环戊烷和/或环己烷被当作发泡剂(8)使用。
10.权利要求1～6中任何一项的聚氨酯硬发泡材料的生产方法，其特征在于，环戊烷与正丁烷和/或异丁烷和/或2，2-二甲基丁烷的混合物被当作发泡剂(8)使用。
11.权利要求1～6中任何一项的聚氨酯硬发泡材料的生产方法，其特征在于，正-和/或异戊烷被当作发泡剂(8)使用。
12.权利要求1～6中任何一项的聚氨酯硬发泡材料的生产方法，其特征在于，1，1，1-二氯氟乙烷(R 141b)或1，1，1，3，3-五氟丙烷(R245fa)被当作发泡剂(8)使用。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19723193.4 | 1997-06-03 | ||
| DE19723193A DE19723193A1 (de) | 1997-06-03 | 1997-06-03 | Verfahren zur Herstellung von geschlossenzelligen Polyurethan-Hartschaumstoffen mit geringer Wärmeleitfähigkeit |
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| Publication Number | Publication Date |
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| CN1259149A CN1259149A (zh) | 2000-07-05 |
| CN1138804C true CN1138804C (zh) | 2004-02-18 |
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| US (1) | US6306920B1 (zh) |
| EP (1) | EP0991686B1 (zh) |
| JP (1) | JP4761591B2 (zh) |
| CN (1) | CN1138804C (zh) |
| AT (1) | ATE211749T1 (zh) |
| AU (1) | AU7915098A (zh) |
| BR (1) | BR9809930B1 (zh) |
| CA (1) | CA2292510C (zh) |
| DE (2) | DE19723193A1 (zh) |
| DK (1) | DK0991686T3 (zh) |
| ES (1) | ES2171029T3 (zh) |
| HK (1) | HK1029355A1 (zh) |
| PT (1) | PT991686E (zh) |
| RU (1) | RU2222549C2 (zh) |
| SI (1) | SI0991686T1 (zh) |
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| US7691913B2 (en) * | 2003-11-03 | 2010-04-06 | Dow Global Technologies, Inc. | Rigid polyurethane foam based on toluene diamine-initiated polyols |
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| DE102004048728A1 (de) * | 2004-10-05 | 2006-04-06 | Basf Ag | Verfahren zur Herstellung von Polyurethan-Hartschaumstoffen |
| KR20140043830A (ko) | 2005-11-14 | 2014-04-10 | 다우 글로벌 테크놀로지스 엘엘씨 | 향상된 열 전도성을 갖는 강성 폴리우레탄 발포체의 성형 방법 |
| JP5189254B2 (ja) * | 2006-06-13 | 2013-04-24 | アキレス株式会社 | 発泡樹脂断熱材 |
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| JP5172861B2 (ja) * | 2007-01-30 | 2013-03-27 | ダウ グローバル テクノロジーズ エルエルシー | アミン開始ポリオール及びアミン開始ポリオールから作製される硬質ポリウレタンフォーム |
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| WO2010111021A1 (en) * | 2009-03-24 | 2010-09-30 | Dow Global Technologies Inc. | Production of rigid polyurethane foams and the use thereof |
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| RU2611493C2 (ru) * | 2011-08-01 | 2017-02-27 | Басф Се | Вспениваемые гидрофторолефинами/водой системы для жестких пеноматериалов |
| JP6893522B2 (ja) * | 2016-05-20 | 2021-06-23 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | ポリウレタンフォームおよびそれを含むポリウレタン複合材 |
| CN107163219A (zh) * | 2017-05-19 | 2017-09-15 | 美的集团股份有限公司 | 聚氨酯泡沫的发泡配方、制备方法和聚氨酯泡沫保温材料 |
| CN107903366B (zh) * | 2017-11-14 | 2019-08-30 | 美的集团股份有限公司 | 用于聚氨酯发泡的催化剂、聚氨酯发泡组合物及其发泡方法与应用 |
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-
1997
- 1997-06-03 DE DE19723193A patent/DE19723193A1/de not_active Withdrawn
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1998
- 1998-05-22 DK DK98929365T patent/DK0991686T3/da active
- 1998-05-22 US US09/424,093 patent/US6306920B1/en not_active Expired - Lifetime
- 1998-05-22 WO PCT/EP1998/003039 patent/WO1998055528A1/de active IP Right Grant
- 1998-05-22 TR TR1999/03017T patent/TR199903017T2/xx unknown
- 1998-05-22 BR BRPI9809930-2A patent/BR9809930B1/pt not_active IP Right Cessation
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- 1998-05-22 EP EP98929365A patent/EP0991686B1/de not_active Expired - Lifetime
- 1998-05-22 SI SI9830080T patent/SI0991686T1/xx unknown
- 1998-05-22 DE DE59802846T patent/DE59802846D1/de not_active Expired - Lifetime
- 1998-05-22 CA CA002292510A patent/CA2292510C/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| DE19723193A1 (de) | 1998-12-10 |
| ES2171029T3 (es) | 2002-08-16 |
| JP2002502455A (ja) | 2002-01-22 |
| CA2292510A1 (en) | 1998-12-10 |
| EP0991686B1 (de) | 2002-01-09 |
| TR199903017T2 (xx) | 2000-05-22 |
| BR9809930A (pt) | 2000-08-01 |
| DK0991686T3 (da) | 2002-04-22 |
| JP4761591B2 (ja) | 2011-08-31 |
| BR9809930B1 (pt) | 2008-11-18 |
| HK1029355A1 (en) | 2001-03-30 |
| SI0991686T1 (en) | 2002-04-30 |
| AU7915098A (en) | 1998-12-21 |
| CA2292510C (en) | 2007-09-18 |
| DE59802846D1 (de) | 2002-02-28 |
| CN1259149A (zh) | 2000-07-05 |
| US6306920B1 (en) | 2001-10-23 |
| EP0991686A1 (de) | 2000-04-12 |
| WO1998055528A1 (de) | 1998-12-10 |
| ATE211749T1 (de) | 2002-01-15 |
| RU2222549C2 (ru) | 2004-01-27 |
| PT991686E (pt) | 2002-06-28 |
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