AU2011246621B2 - Process for producing rigid polyurethane foams - Google Patents
Process for producing rigid polyurethane foams Download PDFInfo
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- AU2011246621B2 AU2011246621B2 AU2011246621A AU2011246621A AU2011246621B2 AU 2011246621 B2 AU2011246621 B2 AU 2011246621B2 AU 2011246621 A AU2011246621 A AU 2011246621A AU 2011246621 A AU2011246621 A AU 2011246621A AU 2011246621 B2 AU2011246621 B2 AU 2011246621B2
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 229920005830 Polyurethane Foam Polymers 0.000 title description 15
- 239000011496 polyurethane foam Substances 0.000 title description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 51
- 229920000570 polyether Polymers 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001298 alcohols Chemical class 0.000 claims description 30
- 239000004604 Blowing Agent Substances 0.000 claims description 28
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 6
- 229960002887 deanol Drugs 0.000 claims description 5
- 239000012972 dimethylethanolamine Substances 0.000 claims description 5
- AXNUJYHFQHQZBE-UHFFFAOYSA-N toluenediamine group Chemical group C1(=C(C(=CC=C1)N)N)C AXNUJYHFQHQZBE-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 abstract description 31
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 24
- 150000001412 amines Chemical class 0.000 abstract description 21
- 150000004982 aromatic amines Chemical class 0.000 abstract description 16
- 239000004814 polyurethane Substances 0.000 abstract description 10
- 229920002635 polyurethane Polymers 0.000 abstract description 9
- 229920001228 polyisocyanate Polymers 0.000 abstract description 7
- 239000005056 polyisocyanate Substances 0.000 abstract description 7
- 229920005862 polyol Polymers 0.000 description 38
- 150000003077 polyols Chemical class 0.000 description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 25
- 125000002947 alkylene group Chemical group 0.000 description 22
- 239000000203 mixture Substances 0.000 description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 18
- 239000007858 starting material Substances 0.000 description 16
- 239000006260 foam Substances 0.000 description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 13
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 12
- -1 TDA polyols Chemical class 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000004970 Chain extender Substances 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 229930006000 Sucrose Natural products 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- CZSSKBQAJULWPY-UHFFFAOYSA-N 2-undecylsulfanylacetic acid Chemical compound CCCCCCCCCCCSCC(O)=O CZSSKBQAJULWPY-UHFFFAOYSA-N 0.000 description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000002666 chemical blowing agent Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 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 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 1
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 1
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical class CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- HYNDYAQJODYUGF-UHFFFAOYSA-N 1,2,3,4,5,7,8,9-octahydropyrido[1,2-a][1,4]diazepine Chemical compound C1NCCCN2CCCC=C21 HYNDYAQJODYUGF-UHFFFAOYSA-N 0.000 description 1
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 description 1
- QKKSKKMOIOGASY-UHFFFAOYSA-N 2,3-dibromobut-1-ene-1,1-diol Chemical compound CC(Br)C(Br)=C(O)O QKKSKKMOIOGASY-UHFFFAOYSA-N 0.000 description 1
- PTBPTNCGZUOCBK-UHFFFAOYSA-N 2,4,5-trimethyl-1h-imidazole Chemical compound CC1=NC(C)=C(C)N1 PTBPTNCGZUOCBK-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-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
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- XIRDTMSOGDWMOX-UHFFFAOYSA-N 3,4,5,6-tetrabromophthalic acid Chemical compound OC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O XIRDTMSOGDWMOX-UHFFFAOYSA-N 0.000 description 1
- ISPIHWORPMENMZ-UHFFFAOYSA-N 3-(1h-imidazol-2-yl)propan-1-ol Chemical compound OCCCC1=NC=CN1 ISPIHWORPMENMZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XHLKOHSAWQPOFO-UHFFFAOYSA-N 5-phenyl-1h-imidazole Chemical compound N1C=NC=C1C1=CC=CC=C1 XHLKOHSAWQPOFO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Chemical class CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 1
- WOURXYYHORRGQO-UHFFFAOYSA-N Tri(3-chloropropyl) phosphate Chemical compound ClCCCOP(=O)(OCCCCl)OCCCCl WOURXYYHORRGQO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- DIBHLCJAJIKHGB-UHFFFAOYSA-N dec-5-ene Chemical compound [CH2]CCCC=CCCCC DIBHLCJAJIKHGB-UHFFFAOYSA-N 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GUAWMXYQZKVRCW-UHFFFAOYSA-N n,2-dimethylaniline Chemical compound CNC1=CC=CC=C1C GUAWMXYQZKVRCW-UHFFFAOYSA-N 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 125000005270 trialkylamine group Chemical group 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
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000005436 troposphere Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
- C08G18/5027—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups directly linked to carbocyclic groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2627—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aromatic or arylaliphatic amine groups
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2672—Nitrogen or compounds thereof
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
Abstract
The invention relates to a process for producing polyurethanes via reaction of a) polyisocyanates with b) compounds having at least two hydrogen atoms reactive towards isocyanate groups, characterized in that the compounds b) having at least two hydrogen atoms reactive towards isocyanate groups contain at least one polyether alcohol b1) which has been produced via reaction of an aromatic amine b1a) with propylene oxide with use, as catalyst, of an amine b1b) which differs from b1a).
Description
Process for producing rigid polyurethane foams Description 5 The invention relates to a process for producing rigid polyurethane foams by reacting polyisocyanates with compounds having at least two hydrogen atoms which are reactive toward isocyanate groups in the presence of blowing agents. Rigid polyurethane foams have been known for a long time and are used 10 predominantly for heat and cold insulation, e.g. in refrigeration appliances, in hot water storages, in district heating pipes or in building and construction, for example in sandwich elements. A summary overview of the production and use of rigid foams based on isocyanate may be found, for example, in Kunststoff-Handbuch, volume 7, Polyurethane, 1st edition 1966, edited by Dr. R. Vieweg and Dr. A. H6chtlen, and 2nd 15 edition 1983, edited by Dr. Gunter Oertel, and 3rd edition 1993, edited by Dr. GOnter Oertel, Carl Hanser Verlag, Munich, Vienna. In the past, mostly fluorochloroalkanes (CFCs), preferably trichlorofluoromethane, were used as blowing agents for producing rigid polyurethane foams. However, a 20 disadvantage of these blowing gases is pollution of the environment. As successors to CFCs, use is now mostly made of hydrocarbons, preferably pentanes. Thus, EP-A-421 269 describes the use of cyclopentane and/or cyclohexane, if appropriate in admixture with other hydrocarbons, as blowing agents. 25 However, these blowing agents differ in various ways from the halogenated blowing agents. Thus, they have poorer compatibility with the other constituents of the polyurethane systems. This leads to rapid demixing of the components comprising blowing agent. 30 A further important criterion for the processing of rigid polyurethane foams is the viscosity of the liquid starting materials. This has a direct influence on the flow behavior of the starting components. In addition, very highly viscous components are difficult to pump. 35 For the present purposes, the flowability of the foam is the flow behavior of the reacting mixture of polyisocyanate and the compound having at least two hydrogen atoms which are reactive toward isocyanate groups. The flowability is usually determined by determining the path length which is covered by a defined amount of the reacting 40 mixture. This can be done by introducing the reaction mixture into a flexible hose of plastic film, hereinafter referred to as hose test, or into a standardized elongated mold, for example a Bosch lance, and the length of the molding formed in this way is 2 determined. The flowability plays an important role in the filling of hollow spaces with foam, as occurs, in particular, in the production of refrigeration appliances. A frequently used starting component for the production of rigid polyurethane foams is 5 polyether alcohols which are prepared by addition of alkylene oxides onto aromatic amines. These polyether alcohols reduce the thermal conductivity of the foams and can improve the compatibility with the blowing agents. As aromatic amines, preference is given to using methylenedianiline (MDA), which is usually present in admixture with condensation products thereof having more than two rings (PMDA), and 10 toluenediamine (TDA). In the case of TDA, the ortho isomers, frequently also referred to as vicinal TDA, have the greatest industrial importance. The polyether alcohols prepared using aromatic amines frequently have a very high viscosity. 15 To overcome this disadvantage and to keep the viscosities of such polyols low, it is therefore customary to choose not too high a hydroxyl number for such polyols. The hydroxyl numbers of the polyols are preferably less than 400 mg KOH/g. 20 A further possible way of reducing the viscosity is the concomitant use of ethylene oxide for building up the polyether chain. The hydroxyl number of the polyols can be increased in this way. US 4209609 describes the preparation of TDA polyols in the hydroxyl number range of 25 400-630 mg KOH/g which are prepared by reacting TDA firstly with about 4 mol of ethylene oxide and subsequently with propylene oxide. These TDA polyols display some advantages (e.g. low coefficient of thermal conductivity). Further production processes are described in DE 4232970 Al and US 4562290. The amine-catalyzed preparation of TDA polyols, in which firstly from 2 to 5 mol of ethylene oxide and then 30 propylene oxide are introduced, is described in EP 0318784 B1 and DE 3740634. EP 0318784 B1 and DE 3740634 describe the preparation of polyols based on TDA, in which firstly 2-5 mol of ethylene oxide and then propylene oxide are added onto the TDA, with amines being used as catalysts. 35 Although the ethylene oxide in the chain reduces the viscosity of the polyether alcohols, the compatibility with the hydrocarbons used as blowing agent is adversely affected. In addition, the ethylene oxide in the chain leads to an increase in the hydrophilicity. 40 US 4391728 describes the preparation of low-viscosity TDA polyols by means of KOH catalysis at temperatures above 1400C. Exclusively propylene oxide is used as 3 alkylene oxide. At least 0.8% by weight of alkali metal hydroxide as catalyst is necessary for the reaction. The use of such large amounts of alkali metal hydroxides as catalyst makes a complicated work-up necessary. In addition, the large amount of catalyst can result in not all hydrogen atoms of the TDA reacting, which can lead to problems in the 5 production of the foams. It was an object of the present invention to provide a process for producing rigid polyurethane foams using polyols based on aromatic amines, in particular TDA, which have good compatibility with the hydrocarbons used as blowing agent, a low viscosity of 10 the liquid starting components and good processing and foaming properties. The object has surprisingly been achieved by the use of polyether alcohols which are based on aromatic amines and have been prepared by addition of propylene oxide onto aromatic amines using amines as catalysts. 15 The invention accordingly provides a process for producing polyurethanes, preferably polyurethane foams, in particular rigid polyurethane foams, by reacting a) polyisocyanates with 20 b) compounds having at least two hydrogen atoms which are reactive toward isocyanate groups, wherein the compounds b) having at least two hydrogen atoms which are reactive toward 25 isocyanate groups comprise at least one polyether alcohol b1) which has been prepared by reaction of toluenediamine (TDA) bla) with propylene oxide using dimethylethanol amine b1b) which is different from bla) as catalyst. As aromatic amines b1a) in the preparation of the polyether alcohols b1), it is in principle 30 possible to use all known aromatic amines having at least one, preferably at least two and particularly preferably two amino groups. The amino groups are usually primary amino groups. In a preferred embodiment of the process of the invention, the aromatic amines bla) are 35 selected from the group consisting of aniline, TDA, MDA and PMDA, particularly preferably from the group consisting of TDA and PMDA. In particular, TDA is used. When TDA is used, it is possible to use all isomers either alone or in any mixtures with one another. In particular, it is possible to use 2,4-TDA, 2,6-TDA, mixtures of 2,4-TDA 40 and 2,6-TDA, 2,3-TDA, 3,4-TDA, mixtures of 3,4-TDA and 2,3-TDA and also mixtures of all isomers mentioned.
4 2,3-TDA and 3,4-TDA are frequently also referred to as ortho-TDA or vicinal TDA. The TDA can be exclusively vicinal TDA. In a particularly preferred embodiment of the process of the invention, the TDA comprises at least 90% by weight, particularly preferably at least 95% by weight and in particular at least 99% by weight, in each case 5 based on the weight of the TDA, of vicinal TDA. As alkylene oxide, preference is given to use exclusively propylene oxide. For individual applications, it can be advantageous to use a small amount of ethylene oxide in addition. To avoid the disadvantages indicated above, the proportion of ethylene 10 oxide should not exceed 10% by weight. The content of ethylene oxide is, in this embodiment, preferably in the range from greater than zero to 10% by weight, particularly preferably from greater than zero to 5% by weight and in particular from greater than zero to 2% by weight, in each case on the weight of the alkylene oxides b). 15 As catalysts for preparing the polyether alcohols b1), use is made of, as described, of amines bib). It goes without saying that the amines bib) used as catalysts are not the above-described aromatic amines bla) used as starter substance. In the following, the term starter substance refers to the compounds which have hydrogen atoms which are 20 reactive toward alkylene oxides. For the purposes of the present invention, amines bib) are all substitution products of ammonia in which at least one hydrogen atom has been replaced by alkyl and/or aryl radicals. 25 In an embodiment of the invention, the amines bib) are aliphatic amines. The aliphatic amines can comprise primary, secondary or tertiary amino groups. Among aliphatic amines, particular preference is given to tertiary amines such as trialkylamines or dimethylalkylamines. Amino alcohols also count as amines. 30 In a further embodiment of the invention, the amine bib) is an aromatic amine different from bia), for example dimethylaniline. In an embodiment of the process of the invention, the amines b1b) can be aromatic 35 heterocyclic compounds having at least one nitrogen atom, preferably at least two nitrogen atoms, in the ring. The amines bi b) used as catalyst are preferably selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, N,N'-dimethylethanolamine, 40 N,N'-dimethylcyclohexylamine, dimethylethylamine, dimethylbutylamine, N,N' dimethylaniline, 4-dimethylaminopyridine, N,N'-dimethylbenzylamine, pyridine, imidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, 5- 5 methylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 1 hydroxypropylimidazole, 2,4,5-trimethylimidazole, 2-ethylimidazole, 2-ethyl-4 methylimidazole, N-phenylimidazole, 2-phenylimidazole, 4-phenylimidazole, guanidine, alkylated guanidines, 1,1,3,3-tetramethylguanidine, 7-methyl-1,5,7 5 triazabicyclo[4.4.0]dec-5-ene, 1,5-diazobicyclo[4.3.0]-non-5-ene, 1,5 diazabicyclo[5.4.0]undec-7-ene. The amines bi b) can be used either alone or in any mixtures with one another. 10 In a preferred embodiment of the invention, the catalyst bib) is dimethylethanolamine. In a preferred embodiment of the invention, the catalyst b1b) is an imidazole, particularly preferably imidazole. 15 The amine bib) is preferably used in an amount of 0.1-1.0% by mass, based on the weight of all starting components for the preparation of the polyether alcohol b1). This amount is particularly preferred when aliphatic amines are used. The heterocyclic compounds, in particular the imidazoles, are preferably used in an 20 amount of from 0.01 to 0.5% by mass based on the weight of all starting components for the preparation of the polyether alcohol. The amines bib) used as catalyst for preparing the polyether alcohols b1) can be added at the beginning of the reaction. The catalyst bi b) can be added before the 25 addition of the alkylene oxides or, less preferably, simultaneously with the commencement of introduction of the alkylene oxides. In a particularly preferred embodiment of the invention, it is possible for the addition reaction of the alkylene oxides to proceed in the absence of a catalyst at the beginning 30 of the reaction and for the catalyst to be added during the reaction. In this embodiment, the addition of the catalyst preferably takes place after introduction of up to 3.4 mol of propylene oxide per mol of aromatic amine a), particularly preferably up to 3.0 mol of propylene oxide per mol of aromatic amine bla). 35 The reaction of the amines with the alkylene oxide is carried out by customary processes which are described, for example, in EP 318 784. As described, the catalyst bib) can be added before the reaction, simultaneously with the commencement of introduction of the alkylene oxides or during the reaction. The starter mixture can be stripped, for example at a pressure of 0.01-1 bar and a temperature of 25-1500C, 40 before introduction of the alkylene oxides.
6 The aromatic amines bla) used as starter substance can, in a preferred embodiment of the invention, be used as sole starter substance. In a further embodiment of the invention, the aromatic amines bi a) can be used in 5 combination with other compounds b1c) having at least two hydrogen atoms which are reactive toward isocyanate groups. The compounds b1c) are preferably alcohols or amino alcohols different from bib) and having a molecular weight of 40-400 g/mol, in particular 60-120 g/mol, and from 1 to 8, preferably 2 or 3, hydroxyl groups. The compounds b1c) will hereinafter also be referred to as costarters. 10 The compound bi c) is preferably selected from the group consisting of water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol and triethanolamine. The compounds mentioned can also be used in the form of their reaction products with alkylene oxides having a molecular weight of up to 800 g/mol. 15 The compounds of b1c) are preferably used in an amount of from 0.1 to 20% by weight, based on the weight of the starter compounds. The addition reaction of the alkylene oxides is preferably carried out at a temperature in 20 the range from 90 to 150 0 C and a pressure of from 0.1 to 8 bar. The introduction of the alkylene oxides is usually followed by an after-reaction phase to achieve very complete reaction of the alkylene oxides. The crude polyether alcohol obtained in this way is freed of unreacted alkylene oxide and volatile compounds by distillation, preferably under reduced pressure. 25 The polyether alcohols prepared by the process of the invention preferably have a hydroxyl number in the range from 200 to 800 mg KOH/g, particularly preferably from 350 to 500 mg KOH/g and in particular from 350 to 450 mg KOH/g. 30 Owing to their low viscosity, the polyurethane systems produced using the polyether alcohols b1) have good processability, in particular a good flowability. They are readily compatible with blowing agents, in particular blowing agents based on hydrocarbons, and have a good storage stability. The compatibility with the isocyanate 35 component is also increased. The demolding time for the foams was surprisingly also shorter. The reaction of the amines, in particular TDA, with the alkylene oxides is quantitative and virtually no free amine is present in the polyether alcohols b1). 40 As regards the starting materials used for the process of the invention, the following details may be provided: 7 Possible organic polyisocyanates a) are preferably aromatic polyfunctional isocyanates. Specific examples are: tolylene 2,4- and 2,6-diisocyanate (TDI) and the corresponding 5 isomer mixtures, diphenylmethane 4,4'-, 2,4'- and 2,2'-diisocyanate (MDI) and the corresponding isomer mixtures, mixtures of diphenylmethane 4,4'- and 2,4' diisocyanates and, in the production of rigid polyurethane foams, in particular mixtures of diphenylmethane 4,4'-, 2,4'- and 2,2'-diisocyanates and polyphenylpolymethylene polyisocyanates (crude MDI). 10 The polyether alcohols b1) are usually used in admixture with other compounds having at least two hydrogen atoms which are reactive toward isocyanate groups. As compounds which have at least two hydrogen atoms which are reactive toward 15 isocyanate and can be used together with the polyether alcohols bi) used according to the invention, use is made of, in particular, polyether alcohols and/or polyester alcohols having OH numbers in the range from 100 to 1200 mg KOH/g. The polyester alcohols used together with the polyether alcohols b1) are usually 20 prepared by condensation of polyfunctional alcohols, preferably diols, having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms, with polyfunctional carboxylic acids having from 2 to 12 carbon atoms, for example succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid and preferably phthalic acid, isophthalic acid, terephthalic acid and the 25 isomeric naphthalenedicarboxylic acids. The polyether alcohols used together with the polyether alcohols bi) used according to the invention usually have a functionality in the range from 2 to 8, in particular from 3 to 8. 30 In particular, polyether alcohols prepared by known methods, for example by anionic polymerization of alkylene oxides in the presence of catalysts, preferably alkali metal hydroxides or amines, are used in addition to the polyether alcohols b1). 35 As alkylene oxides, use is usually made of ethylene oxide, propylene oxide and/or butylene oxide, preferably ethylene oxide and/or butylene oxide and in particular pure 1,2-propylene oxide. Starter molecules used are, in particular, compounds having at least 2, preferably from 40 3 to 8, hydroxyl groups or having at least two primary amino groups in the molecule.
8 As starter molecules having at least 2, preferably from 3 to 8, hydroxyl groups in the molecule, preference is given to using trimethylolpropane, glycerol, pentaerythritol, castor oil, sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols such as oligomeric condensation products of phenol and 5 formaldehyde, and Mannich condensates of phenols, formaldehydes and dialkanolamines, and also melamine. The starter substances can be used individually or in the form of mixtures. The polyether alcohols have a functionality of preferably from 3 to 8 and hydroxyl 10 numbers of preferably from 100 mg KOH/g to 1200 mg KOH/g and in particular from 120 mg KOH/g to 570 mg KOH/g. The use of bifunctional polyols, for example polyethylene glycols and/or polypropylene glycols, having a molecular weight in the range from 500 to 1500 in the polyol 15 component enables the viscosity of the polyol component to be adjusted. The proportion of polyether alcohols b1) in the component b) is preferably at least 5% by weight, particularly preferably at least 10% by weight, in particular at least 20% by weight, and not more than 60% by weight, preferably not more than 40% by weight and 20 in particular not more than 30% by weight. In a preferred embodiment of the process of the invention, the component b) comprises a polyether alcohol b2) having a hydroxyl number in the range from 350 to 600 mg KOH/g and a functionality in the range from 4 to 8 in addition to the polyether alcohol 25 b1). The polyether alcohol b2) is preferably prepared by addition of propylene oxide onto a starter substance comprising at least one sugar. As sugar, preference is given to using sucrose and/or sorbitol, preferably sucrose. The starter substance usually additionally comprises at least one alcohol which is liquid at room temperature, preferably an alcohol selected from the group consisting of ethylene glycol, propylene 30 glycol and glycerol, in particular glycerol. The preparation of the polyether alcohol b2) is usually carried out in the presence of a basic catalyst, usually an alkali metal hydroxide, or an amine. In a preferred embodiment of the invention, an amine as described above in the group bib) is used as catalyst. When a polyether alcohol b2) is used, it is preferably present in an amount of 50-60% by weight, based on the 35 component b). In a further preferred embodiment of the process of the invention, the component b) comprises a polyether alcohol b3) having a functionality of from 2 to 3 and a hydroxyl number in the range from 100 to 300 mg KOH/g. The polyether alcohol b3) is 40 preferably prepared by addition of alkylene oxides onto diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and/or onto glycerol, 9 trimethylolpropane or TDA. When a polyether alcohol b3) is used, it is preferably present in an amount of from 10 to 30% by weight, based on the component b). In a particularly preferred embodiment of the invention, the component b) comprises at 5 least one polyether alcohol b2) and at least one polyether alcohol b3) in the amounts indicated above in addition to the polyether alcohol b1). In a further preferred embodiment of the process of the invention, the component b) comprises at least one polyester alcohol b4). This preferably has a hydroxyl number in 10 the range from 200 to 350 mg KOH/g and a functionality of from 2 to 3. The polyester alcohol b4) is preferably prepared using aromatic carboxylic acids such as phthalic acid, terephthalic acid or phthalic anhydride. In an embodiment of the process of the invention, the polyester alcohol b4) is prepared using polyalkylene terephthalates. The polyester alcohol b4) is preferably used in an amount of from 20 to 40% by weight, 15 based on the component b). The component b) usually comprises the polyether alcohols b2) and/or b3) or at least one polyester alcohol b4) in addition to the polyether alcohol b1). 20 The compounds b) having at least two hydrogen atoms which are reactive toward isocyanate also include the chain extenders and crosslinkers which may be concomitantly used. The rigid polyurethane foams can be produced with or without concomitant use of chain extenders and/or crosslinkers. The addition of bifunctional chain extenders, trifunctional and higher-functionality crosslinkers or, if appropriate, 25 mixtures thereof can prove to be advantageous for modifying the mechanical properties. As chain extenders and/or crosslinkers, preference is given to using alkanolamines and in particular diols and/or triols having molecular weights of less than 400, preferably from 60 to 300. 30 Chain extenders, crosslinkers or mixtures thereof are advantageously used in an amount of from 1 to 20% by weight, preferably from 2 to 5% by weight, based on the polyol component. In an embodiment of the invention, propylene carbonate is used, in particular in an 35 amount of from 0 to 3 parts by weight, based on the component b). A description of this class of compounds may be found, for example, in WO 9502620. In this way, it is possible, inter alia, to adjust the viscosity of the component b). The production of the polyurethane foams is usually carried out in the presence of 40 blowing agents c). Here, a distinction is made between chemical blowing agents which react with at least one of the starting components, preferably the polyisocyanate a), to 10 liberate the blowing gas, and physical blowing agents which are inert toward the starting components for polyurethane production. As chemical blowing agent, preference is given to using water which reacts with 5 isocyanate groups to eliminate carbon dioxide. A further frequently used physical blowing agent is formic acid. In combination with or in place of chemical blowing agents, physical blowing agents can also be used. These are, as described, compounds which are inert toward the 10 starting components and are usually liquid at room temperature and vaporize under the conditions of the urethane reaction. The boiling point of these compounds is preferably below 50*C. The physical blowing agents also include compounds which are gaseous at room temperature and are introduced under pressure into the starting components or are dissolved therein, for example carbon dioxide, low-boiling alkanes and 15 fluoroalkanes. The physical blowing agents are usually selected from the group consisting of alkanes and cycloalkanes having at least 4 carbon atoms, dialkyl ethers, esters, ketones, acetals, fluoroalkanes having from 1 to 8 carbon atoms and tetraalkylsilanes having 20 from 1 to 3 carbon atoms in the alkyl chain, in particular tetramethylsilane. In a preferred embodiment of the invention, the blowing agents are hydrocarbons. The blowing agents are particularly preferably selected from the group consisting of alkane and cycloalkanes having at least 4 carbon atoms. In particular, pentanes, preferably 25 isopentane and cyclopentane, are used. When the rigid foams are used as insulation in refrigeration appliances, cyclopentane is preferred. The hydrocarbons can be used in admixture with water. Examples which may be mentioned are propane, n-butane, isobutane and cyclobutane, 30 n-pentane, isopentane and cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl formate, acetone and also fluoroalkanes which are degraded in the troposphere and therefore do not damage the ozone layer, e.g. trifluoromethane, difluoromethane, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3 pentafluoropropane, 1,1,1,2-tetrafluoroethane, difluoroethane and 1,1,1,2,3,3,3 35 heptafluoropropane and also perfluoroalkanes such as C3F8, C4F10, C5F12, C6F14, and C7F1 6. Particular preference is given to pentanes, in particular cyclopentane. The physical blowing agents mentioned can be used either alone or in any combinations with one another. 40 Furthermore, hydrofluoroolefins such as 1,3,3,3-tetrafluoropropene or hydrochlorofluoroolefins such as 1-chloro-3,3,3-trifluoropropene can be used as blowing agents. Such blowing agents are described, for example, in WO 2009/048826.
11 When hydrocarbons are used as blowing agents, preference is given to using polyether alcohols b1), b2) and, if appropriate, b3) in the component b). When polyester alcohols b4) are used in the component b), preference is given to 5 using halogenated blowing agents. The production of the polyurethanes can, if necessary, be carried out in the presence of catalysts, flame retardants and customary auxiliaries and/or additives. 10 As catalysts, use is made of, in particular, compounds which strongly accelerate the reaction of the isocyanate groups with the groups which are reactive toward isocyanate groups. Such catalysts are strongly basic amines such as secondary aliphatic amines, 15 imidazoles, amidines and also alkanolamines or organic metal compounds, in particular organic tin compounds. When isocyanurate groups are also to be incorporated into the rigid polyurethane foam, specific catalysts are required for this purpose. As isocyanurate catalysts, use is 20 usually made of metal carboxylates, in particular potassium acetate and solutions thereof. The catalysts can, depending on requirements, be used either alone or in any mixtures with one another. 25 The process of the invention can, if necessary, be carried out in the presence of flame retardants and customary auxiliaries and/or additives. As flame retardants, it is possible to use organic phosphoric esters and/or phosphonic 30 esters. Preference is given to using compounds which are unreactive toward isocyanate groups. Chlorine-comprising phosphoric esters are also among the preferred compounds. Typical representatives of this group of flame retardants are triethyl phosphate, 35 diphenyl cresyl phosphate, tris(chloropropyl) phosphate and diethyl ethanephosphonate. In addition, it is also possible to use bromine-comprising flame retardants. As bromine comprising flame retardants, preference is given to using compounds which have 40 groups which are reactive toward the isocyanate group. Such compounds are esters of tetrabromophthalic acid with aliphatic diols and alkoxylation products of 12 dibromobutenediol. Compounds derived from the group of brominated neopentyl compounds comprising OH groups can also be employed. As auxiliaries and/or additives, use is made of the materials known per se for this 5 purpose, for example surface-active substances, foam stabilizers, cell regulators, fillers, pigments, dyes, flame retardants, hydrolysis inhibitors, antistatics, fungistatic and bacteriostatic agents. Further details regarding the starting compounds used may be found, for example, in 10 Kunststoffhandbuch, volume 7 "Polyurethane", edited by Ginter Oertel, Carl-Hanser Verlag Munich, 3rd edition, 1993. The invention is illustrated by the following examples. 15 Methods: Viscosity determination: The viscosity of the polyols was, unless indicated otherwise, determined at 250C in 20 accordance with DIN EN ISO 3219 by means of a Rheotec RC 20 rotational viscometer using the spindle CC 25 DIN (spindle diameter: 12.5 mm; internal diameter of the measuring cylinder: 13.56 mm) at a shear rate of 50 1/s Measurement of the hydroxyl number: 25 The hydroxyl numbers were determined in accordance with DIN 53240. Thermal conductivity: 30 The thermal conductivity was determined using a heat flow measurement plate instrument Hesto A50 at an average temperature of 23 0 C. To produce the test specimens, the polyurethane reaction mixture was introduced into a mold having the dimensions 2000 x 200 x 50 mm (15% overfilling) and removed from the mold after 5 minutes. After storage for 24 hours under standard conditions of temperature and 35 humidity, a plurality of foam cuboids (positions 10, 900 and 1700 mm based on the start of the lance) having dimensions of 200 x 200 x 50 mm were cut from the middle. The upper side and underside were subsequently removed so that test specimens having dimensions of 200 x 200 x 30 mm were obtained. 40 Compressive strength: 13 The compressive strength was determined in accordance with DIN 53421 / DIN EN ISo 604. Determination of the pentane solubility: 5 To determine the pentane solubility, the polyol component is mixed with the amount of blowing agent indicated in the examples (Vollrath stirrer, 1500 revolutions per minute, 2 minutes stirring time) and introduced into a screw-cap bottle, and the bottle is closed. After all gas bubbles have escaped, the clarity of the sample is firstly checked at room 10 temperature. If the sample is clear, it is subsequently cooled in steps of 10C in a waterbath and checked for clarity 30 minutes after the set temperature has been reached. Determination of the demolding behavior: 15 The demolding behavior was determined by measuring the post-expansion of foam bodies produced using a box mold having the dimensions 700 x 400 x 90 mm as a function of the demolding time and the overpacking (0, corresponds to the ratio of overall foam density/minimum fill density). The post-expansion was determined by 20 measuring the height of the foam cuboids after 24 hours. Preparation of the polyether alcohols: Polyol 1: 25 A 30 I pressure reactor provided with stirrer, jacket heating and cooling, metering facilities for solid and liquid substances and alkylene oxides and also facilities for making inert with nitrogen and a vacuum system was heated to 800C and made inert a number of times. 5.47 kg of vic-toluenediamine were introduced into the reactor and 30 the stirrer was started. The temperature was subsequently increased to 1380C and a mixture of 3.61 kg of ethylene oxide and 2.77 kg of propylene oxide (2.9 mol of alkylene oxide per mole of TDA) was introduced. After a reaction time of 2 hours, the temperature was reduced to 100*C and 88 g of 48% strength aqueous KOH were added. The temperature was increased to 1380C and the intermediate was reacted 35 with a further 12.26 kg of propylene oxide. The after-reaction proceeded for 2 hours at 1380C. The mixture was stripped with nitrogen for 20 minutes. 2.5% of water was subsequently added and the mixture was neutralized with phosphoric acid. The water was stripped out under reduced pressure and the product was filtered at 800C. This gave 22.9 kg of product having the following properties: 40 Hydroxyl number 396 mg KOH/g Viscosity (25 0C) 13772 mPas 14 Polyol 2: The reactor described in example 1 was heated to 80*C and made inert a number of 5 times. 5.65 kg of vic-toluenediamine were introduced into the reactor and the stirrer was started. The temperature was subsequently increased to 1380C and 7.50 kg of propylene oxide (2.8 mol of propylene oxide per mol of TDA) were introduced. After a reaction time of 2 hours, the temperature was reduced to 100 C and 91 g of 48% strength aqueous KOH were added. The temperature was increased to 138*C and the 10 intermediate was reacted with a further 11.74 kg of propylene oxide. The after-reaction proceeded for 2 hours at 1380C. The mixture was stripped with nitrogen for 20 minutes. 2.5% of water was subsequently added and the mixture was neutralized with phosphoric acid. The water was stripped out under reduced pressure and the product was filtered at 80*C. This gave 22.7 kg of product having the following properties: 15 Hydroxyl number 371 mg KOH/g Viscosity (250C) 42359 mPas Polyol 3: 20 The reactor described in example 1 was heated to 80*C and made inert a number of times. 6.2 kg of vic-toluenediamine were introduced into the reactor and the stirred was started. The temperature was subsequently increased to 1380C and 8.26 kg of propylene oxide (2.8 mol of propylene oxide per mol of TDA) were introduced. After a 25 reaction time of 2 hours, the temperature was reduced to 100*C and 220 g of dimethylethanolamine were added. The temperature was increased to 950C and the intermediate was reacted with a further 12.07 kg of propylene oxide. The after-reaction proceeded for 2 hours at 950C. The mixture was stripped by means of nitrogen for 20 minutes. This gave 23.6 kg of product having the following properties: 30 Hydroxyl nymber 404 mg KOH/g Viscosity (250C) 14600 mPas Table 1: Comparison of the viscosities of polyols based on TDA 35 OH number Viscosity [mg KOH/g] [mPas@25 0 C] Polyol 1 396 13772 Polyol 2 371 42359 Polyol 3 401 14600 15 A comparison of the polyol viscosities obtained shows that polyol 3 according to the invention has, despite a higher OH number, a significantly lower viscosity than polyol 2 which is not according to the invention and has been prepared by means of KOH catalysis. The viscosity is of the same order of magnitude as that obtained for the 5 polyol 1 which is not according to the invention and has corresponding proportions of ethylene oxide units. Production of the rigid polyurethane foams: 10 Starting materials: Polyol 1: from example 1 Polyol 2: from example 2 Polyol 3: from example 3 15 Polyol 4: polyetherol based on sucrose, glycerol and propylene oxide, KOH catalyzed, functionality = 5.1, hydroxyl number = 450 mg KOH/g Polyol 5: polyetherol based on vic-TDA, ethylene oxide and propylene oxide, hydroxyl number = 160 mg KOH/g, KOH-catalyzed Polyol 6: dipropylene glycol 20 Stabilizer: Tegostab B 8491 (silicone stabilizer from Evonik) Catalyst 1: dimethylcyclohexylamine (DMCHA) Catalyst 2: pentamethyldiethylenetriamine (PMDETA) Catalyst 3: Lupragen N600 (BASF) Isocyanate: polymeric MDI (Lupranat@ M20) 16 Machine foaming: A polyol component was produced from the raw materials indicated. The polyol component was mixed with the amount of the indicated isocyanate required to achieve 5 an isocyanate index of 110 by means of a high-pressure Puromat® PU 30/80 IQ (Elastogran GmbH) at a discharge rate of 250 g/sec. The reaction mixture was injected into temperature- controlled molds having dimensions of 2000 mm x 200 mm x 50 mm or 400 mm x 700 mm x 90 mm and allowed to foam there. The overpacking was 15%. 10 The starting materials used, the production properties and the mechanical properties of the foams are shown in table 2. Table 2: Overview of machine experiments (C = comparative experiment) Tabelle 2: Obersicht Maschinenversuche (V = Vergleichsversuch) 1c) 2 Polyol component [pbw] ...... .. .. . - -- 2 2---- - Clyt - 22 PolI 4 54 Pyol 5 1515 Stabilizer,- Z8 e, Catalysi0, 05 .aa s ....... 0.8 0,8 Cataat 30,4 0A4 water 2,6 Cyclopentane _ _13 ------- 3--- d socyvanate Compone nt. paet@156 156 Creamraf s]- ....... Fiberltimes 40 41 Pefondensity IY~23 23 Cloud point of polyol component ['01 10 5 viscosity of polyol component [mPas@25*C] 6600 7400 flow factor mWas@25q 1 13 1.3 Lambda fmW/m 19, Com pressive strength [Nminim Post-oxansioni%I 4min. 3.4 2,4 5min. 2,3 1.5 7min. 1,0 0,3 overallfoam densityqL7' 35,2 35,9 Foam.densityofcorer/Lj 31,7 32 15 Example 1 is a comparative example. The system in example 2 (according to the invention) comprising a polyether alcohol based on TDA and propylene oxide using dimethylethanolamine as catalyst has significantly improved demolding properties which 20 are reflected in a lower post-expansion. Furthermore, the compatibility with the blowing agent is improved, as reflected in a lower cloud point.
16a Comprises/comprising and grammatical variations thereof when used in this specification are to be taken to specify the presence of stated features, integers, steps or components or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.
Claims (7)
- 2. The process according to claim 1, wherein the toluenediamine (TDA) b1a) 15 comprises at least 90% by weight, based on the weight of the TDA, of vicinal TDA.
- 3. The process according to claim 1 or claim 2, wherein the dimethylethanol amine b1b) is used in an amount of 0.1-1.0% by mass based on the weight of all starting components for the preparation of the polyether alcohol b1).
- 4. The process according to any one of claims 1 to 3, wherein the polyether alcohols 20 b1) have a hydroxyl number in the range from 200 to 800 mg KOH/g.
- 5. The process according to any one of claims 1 to 4, wherein the component b) comprises at least one further compound having at least two hydrogen atoms which are reactive toward isocyanate groups in addition to the polyether alcohol b1). 18
- 6. The process according to any one of claims 1 to 5, wherein the component b) comprises at least one polyether alcohol b2) having a hydroxyl number in the range from 350 to 600 mg KOH/g and a functionality in the range from 4 to 8 in addition to the polyether alcohol b1). 5 7. The process according to any one of claims I to 6, wherein the component b) comprises at least one polyether alcohol b3) having a functionality of from 2 to 3 and a hydroxyl number in the range from 100 to 300 mg KOH/g in addition to the polyether alcohol b1).
- 8. The process according to any one of claims 1 to 7, wherein the component b) 10 comprises at least one polyester alcohol b4 having a hydroxyl number in the range from 200 to 350 mg KOH/g and a functionality of from 2 to 3 in addition to the polyether alcohol b1).
- 9. The process according to any one of claims 1 to 8, wherein the reaction is carried out in the presence of blowing agents c). 15 10. The process according to any one of claims 1 to 9, wherein hydrocarbons are used as blowing agents c).
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US20130261206A1 (en) * | 2012-04-03 | 2013-10-03 | Basf Se | Process for the continuous production of polyetherols |
US10946562B2 (en) | 2015-10-19 | 2021-03-16 | Basf Se | Sandwich structure including a VIP and method for producing the same |
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US20120235070A1 (en) | 2011-03-18 | 2012-09-20 | Basf Se | Process for producing flame-retardant porous materials based on polyurea |
US9188384B2 (en) | 2011-03-31 | 2015-11-17 | Basf Se | Dynamically evacuable devices comprising organic aerogels or xerogels |
HUE027583T2 (en) * | 2011-04-15 | 2016-10-28 | Basf Se | Process for producing rigid polyurethane foams |
US9403963B2 (en) | 2011-08-23 | 2016-08-02 | Basf Se | Particle-comprising polyether alcohols |
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JP2017508118A (en) | 2014-02-06 | 2017-03-23 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Thermal insulation assembly for storage container and method for its preparation |
CN110461897B (en) * | 2017-03-27 | 2022-05-10 | 巴斯夫欧洲公司 | Polyol component and use thereof for producing rigid polyurethane foams |
PL4031609T3 (en) | 2019-09-19 | 2024-02-26 | Basf Se | Enhancement of long-term properties of closed-cell rigid polyurethane foams |
US20220397334A1 (en) | 2019-09-27 | 2022-12-15 | Basf Se | Foam separator for polyurethane foams |
CN114829441A (en) | 2019-12-17 | 2022-07-29 | 巴斯夫欧洲公司 | Foaming process for preparing elastic insulation products |
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US20130261206A1 (en) * | 2012-04-03 | 2013-10-03 | Basf Se | Process for the continuous production of polyetherols |
US10946562B2 (en) | 2015-10-19 | 2021-03-16 | Basf Se | Sandwich structure including a VIP and method for producing the same |
Also Published As
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SG184861A1 (en) | 2012-11-29 |
HUE025768T2 (en) | 2016-04-28 |
KR20130093001A (en) | 2013-08-21 |
ES2536501T3 (en) | 2015-05-26 |
EP2563833B1 (en) | 2015-02-25 |
EA201291036A1 (en) | 2013-06-28 |
MX2012012401A (en) | 2012-11-29 |
CN102858832B (en) | 2015-08-05 |
WO2011134856A1 (en) | 2011-11-03 |
JP2013528677A (en) | 2013-07-11 |
KR101878503B1 (en) | 2018-07-13 |
JP5823496B2 (en) | 2015-11-25 |
PL2563833T3 (en) | 2015-07-31 |
EP2563833A1 (en) | 2013-03-06 |
ZA201208780B (en) | 2014-01-29 |
CN102858832A (en) | 2013-01-02 |
BR112012027196B1 (en) | 2020-02-04 |
EA022900B1 (en) | 2016-03-31 |
BR112012027196A2 (en) | 2016-07-19 |
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