CA2353209A1 - Preparation of polyurethane foams - Google Patents
Preparation of polyurethane foams Download PDFInfo
- Publication number
- CA2353209A1 CA2353209A1 CA002353209A CA2353209A CA2353209A1 CA 2353209 A1 CA2353209 A1 CA 2353209A1 CA 002353209 A CA002353209 A CA 002353209A CA 2353209 A CA2353209 A CA 2353209A CA 2353209 A1 CA2353209 A1 CA 2353209A1
- Authority
- CA
- Canada
- Prior art keywords
- meth
- acrylate
- acrylates
- prepared
- polyisocyanates
- 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.)
- Abandoned
Links
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 23
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 51
- -1 acrylate polyol Chemical class 0.000 claims abstract description 48
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 27
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 20
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 229920000570 polyether Polymers 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 4
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 229920005903 polyol mixture Polymers 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- 229920001567 vinyl ester resin Polymers 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical group N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- HXSACZWWBYWLIS-UHFFFAOYSA-N oxadiazine-4,5,6-trione Chemical compound O=C1ON=NC(=O)C1=O HXSACZWWBYWLIS-UHFFFAOYSA-N 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 238000010348 incorporation Methods 0.000 claims 1
- 239000006260 foam Substances 0.000 description 43
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 150000003077 polyols Chemical class 0.000 description 21
- 150000001298 alcohols Chemical class 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 229920002635 polyurethane Polymers 0.000 description 12
- 239000004814 polyurethane Substances 0.000 description 12
- 229920000058 polyacrylate Polymers 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- 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 5
- 239000004604 Blowing Agent Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 229920005863 Lupranol® Polymers 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229920002266 Pluriol® Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229920005875 Lupranol® 2090 Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000000783 alginic acid Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 229920005873 Lupranol® 2043 Polymers 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- BSRRYOGYBQJAFP-UHFFFAOYSA-N 1,1,1,2,2,3-hexafluorobutane Chemical compound CC(F)C(F)(F)C(F)(F)F BSRRYOGYBQJAFP-UHFFFAOYSA-N 0.000 description 1
- NVSXSBBVEDNGPY-UHFFFAOYSA-N 1,1,1,2,2-pentafluorobutane Chemical compound CCC(F)(F)C(F)(F)F NVSXSBBVEDNGPY-UHFFFAOYSA-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
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 description 1
- VPDXGYUHRGYONQ-UHFFFAOYSA-N 1-isocyanato-1-(3-isocyanatopropyl)cyclohexane Chemical compound O=C=NCCCC1(N=C=O)CCCCC1 VPDXGYUHRGYONQ-UHFFFAOYSA-N 0.000 description 1
- KHXVVWQPIQVNRH-UHFFFAOYSA-N 1-isocyanato-3-(isocyanatomethyl)-1-methylcyclohexane Chemical compound O=C=NC1(C)CCCC(CN=C=O)C1 KHXVVWQPIQVNRH-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- QNIXMCINXVRKGG-UHFFFAOYSA-N 4-ethyl-1-isocyanato-4-(isocyanatomethyl)octane Chemical compound CCCCC(CC)(CN=C=O)CCCN=C=O QNIXMCINXVRKGG-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 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 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 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 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
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 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
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical class CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000008282 halocarbons 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
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 150000002825 nitriles Chemical class 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
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000004383 yellowing 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G2110/0008—Foam properties flexible
-
- 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
-
- 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
- C08G2110/0033—Foam properties having integral skins
-
- 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
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
-
- 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
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
-
- 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
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Polyurethane foams are prepared by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms reactive with isocyanate groups, by a process in which the polyisocyanates a) are aliphatic di- or polyisocyanates and the compounds having at least two hydrogen atoms reactive with isocyanate groups b) contain at least one acrylate polyol.
Description
Preparation of polyurethane foams The present invention relates to a process for the preparation of light-stable polyurethane foams of low density by reacting aliphatic polyisocyanates with compounds having at least two hydrogen atoms reactive with isocyanate groups.
Polyurethane foams have long been known and are widely described in the literature. They are usually prepared by reacting isocyanates with compounds having at least two hydrogen atoms reactive with isocyanate groups. The isocyanates generally used are aromatic di- and polyisocyanates, isomers of tolylene diisocyanate (TDI), isomers of diphenylmethane diisocyanate (MDI) and mixtures of diphenylmethane diisocyanate and polymethylene-polyphenylene polyisocyanates (crude MDI) being of the greatest industrial importance.
However, such polyurethane foams based on aromatic isocyanates tend to yellow under the action of light. This tendency to yellow is troublesome for many'applications. It is known that polyurethanes which are prepared using aliphatic isocyanates are light-stable and exhibit virtually no yellowing at all. However, the disadvantage of using aliphatic isocyanates for the preparation of polyurethane foam is that the foams thus prepared are generally substantially inferior in many respects, in particular in their mechanical properties, to those based on aromatic isocyanates. Particularly because of the insufficient formation of hard and soft phase segments in the foam, important material properties, such as elongation, tensile strength and flexibility, suffer, and aliphatic polyurethane foams are therefore scarely of any industrial importance to date.
WO 98/52987 describes the preparation of lightfast polyurethane foams using aliphatic isocyanates, hydrogenated polydienediols being used as the compound having at least two hydrogen atoms reactive with isocyanate groups. However, such diols are more expensive in comparison with the alcohols usually used. Moreover, these foams exhibit a deterioration in their mechanical properties and become tacky under the action of light.
US-A-3,284,415 describes the preparation of polyurethanes, in particular cellular and foamed polyurethanes, by reacting monomeric diisocyanates or polyisocyanates with compounds having at least two hydrogen atoms reactive with isocyanate groups, copolymers of ethylene and from 4 to 35% by weight alkyl acrylates and/or hydroxyalkyl acrylates being used as compounds having at least two hydrogen atoms reactive with isocyanate groups. These ethylene/acrylate copolymers are used as the sole polyol component, and in particular aromatic di- and polyisocyanates such as tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate or diphenylmethane diisocyanat oligomer are used as diisocyanates. As a result of using the polyethylene acrylates, the mechanical properties of the polyurethanes, in particular the resilience and the impact strength at low temperatures, and the water resistance of the polyurethanes are improved.
DE-C-22 45 710 describes ethylenically unsaturated vinyl chloride copolymers which are liquid at room temperature and can be used as flameproofing agents in rigid polyurethane foams. However, no influence of the copolymers on the mechanical properties of the foams is mentioned.
It is an object of the present invention to provide light-stable polyurethane foams which have good mechanical properites, in particular elongation and tensile strength, and which can be prepared using starting materials customary in polyurethane chemistry.
we have found that this object is achieved, according to the invention, by using aliphatic polyisocyanates and polyacrylate polyols for the preparation of the polyurethane foams.
The present invention accordingly relates to a process for the preparation of polyurethane foams by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms reactive with isocyanate groups, wherein the polyisocyanates a) are aliphatic polyisocyanates and the compounds having at least two hydrogen atoms reactive with isocyanate groups b) contain at least one acrylate polyol.
The present invention furthermore relates to polyurethane foams which can be prepared by the process described above.
The present invention furthermore relates to polyol blends containing at least one acrylate polyol and at least one further alcohol, preferably an at least difunctional polyether alcohol or a polyester alcohol.
Polyurethane foams have long been known and are widely described in the literature. They are usually prepared by reacting isocyanates with compounds having at least two hydrogen atoms reactive with isocyanate groups. The isocyanates generally used are aromatic di- and polyisocyanates, isomers of tolylene diisocyanate (TDI), isomers of diphenylmethane diisocyanate (MDI) and mixtures of diphenylmethane diisocyanate and polymethylene-polyphenylene polyisocyanates (crude MDI) being of the greatest industrial importance.
However, such polyurethane foams based on aromatic isocyanates tend to yellow under the action of light. This tendency to yellow is troublesome for many'applications. It is known that polyurethanes which are prepared using aliphatic isocyanates are light-stable and exhibit virtually no yellowing at all. However, the disadvantage of using aliphatic isocyanates for the preparation of polyurethane foam is that the foams thus prepared are generally substantially inferior in many respects, in particular in their mechanical properties, to those based on aromatic isocyanates. Particularly because of the insufficient formation of hard and soft phase segments in the foam, important material properties, such as elongation, tensile strength and flexibility, suffer, and aliphatic polyurethane foams are therefore scarely of any industrial importance to date.
WO 98/52987 describes the preparation of lightfast polyurethane foams using aliphatic isocyanates, hydrogenated polydienediols being used as the compound having at least two hydrogen atoms reactive with isocyanate groups. However, such diols are more expensive in comparison with the alcohols usually used. Moreover, these foams exhibit a deterioration in their mechanical properties and become tacky under the action of light.
US-A-3,284,415 describes the preparation of polyurethanes, in particular cellular and foamed polyurethanes, by reacting monomeric diisocyanates or polyisocyanates with compounds having at least two hydrogen atoms reactive with isocyanate groups, copolymers of ethylene and from 4 to 35% by weight alkyl acrylates and/or hydroxyalkyl acrylates being used as compounds having at least two hydrogen atoms reactive with isocyanate groups. These ethylene/acrylate copolymers are used as the sole polyol component, and in particular aromatic di- and polyisocyanates such as tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate or diphenylmethane diisocyanat oligomer are used as diisocyanates. As a result of using the polyethylene acrylates, the mechanical properties of the polyurethanes, in particular the resilience and the impact strength at low temperatures, and the water resistance of the polyurethanes are improved.
DE-C-22 45 710 describes ethylenically unsaturated vinyl chloride copolymers which are liquid at room temperature and can be used as flameproofing agents in rigid polyurethane foams. However, no influence of the copolymers on the mechanical properties of the foams is mentioned.
It is an object of the present invention to provide light-stable polyurethane foams which have good mechanical properites, in particular elongation and tensile strength, and which can be prepared using starting materials customary in polyurethane chemistry.
we have found that this object is achieved, according to the invention, by using aliphatic polyisocyanates and polyacrylate polyols for the preparation of the polyurethane foams.
The present invention accordingly relates to a process for the preparation of polyurethane foams by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms reactive with isocyanate groups, wherein the polyisocyanates a) are aliphatic polyisocyanates and the compounds having at least two hydrogen atoms reactive with isocyanate groups b) contain at least one acrylate polyol.
The present invention furthermore relates to polyurethane foams which can be prepared by the process described above.
The present invention furthermore relates to polyol blends containing at least one acrylate polyol and at least one further alcohol, preferably an at least difunctional polyether alcohol or a polyester alcohol.
The acrylate polyols used are preferably low molecular weight acrylate polyols, i.e. those whose number average molecular weight is not more than 12 000, preferably not more than 8 000, particularly preferably not more than 6 000, g/mol and not less than 400 g/mol. Below, the terms acrylate polyols and polyacrylate polyols are used synonymously.
The acrylate polyols used according to the invention are prepared by polymerization of hydroxy-functionalized (meth)acrylates, preferably by copolymerization of hydroxy-functionalized (meth)acrylates with (meth)acrylates not having hydroxyl functional groups. Furthermore, they can also be prepared by copolymerization of said acrylate monomers with other aliphatic, ethylenically unsaturated monomers, for example ethene, propene, butene, isobutene, acrylonitrile, acrylamide, acrolein, vinyl esters of carboxylic acids or unsaturated carboxylic acids, such as malefic acid, fumaric acid or crotonic acid or derivatives thereof.
Such copolymerization can be carried out in reactors operated continuously or batchwise, for example kettles, annular gap reactors, Taylor reactors, extruders or tubular reactors.
Reaction conditions which lead to polymers having a low level of impurities are preferably chosen. Thus, in the preparation of the acrylate polyols used according to the invention, polymerization regulators are preferably not used.
In the preparation of the acrylate polyols used according to the invention, polymerization is preferably effected at above 160°C in the absence of polymerization regulators and with very low initiator concentrations. The chosen procedure for the process is preferably such that acrylate polyols having average molar masses (Mn) of not more than about 12 000 g/mol are present at the end of the reaction.
Homopolymers of hydroxyalkyl (meth)acrylates or copolymers of hydroxyalkyl (meth)acrylates with (meth)acrylic monomers having no OH functional groups are preferred. In particular, halogen-free monomers are used in the preparation of the acrylate polyols used according to the invention.
The acrylate polyols used according to the invention are prepared in particular by polymerization of hydroxy-C1- to Ce-alkyl (meth)acrylates, e.g. hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate.
The acrylate polyols used according to the invention are prepared by polymerization of hydroxy-functionalized (meth)acrylates, preferably by copolymerization of hydroxy-functionalized (meth)acrylates with (meth)acrylates not having hydroxyl functional groups. Furthermore, they can also be prepared by copolymerization of said acrylate monomers with other aliphatic, ethylenically unsaturated monomers, for example ethene, propene, butene, isobutene, acrylonitrile, acrylamide, acrolein, vinyl esters of carboxylic acids or unsaturated carboxylic acids, such as malefic acid, fumaric acid or crotonic acid or derivatives thereof.
Such copolymerization can be carried out in reactors operated continuously or batchwise, for example kettles, annular gap reactors, Taylor reactors, extruders or tubular reactors.
Reaction conditions which lead to polymers having a low level of impurities are preferably chosen. Thus, in the preparation of the acrylate polyols used according to the invention, polymerization regulators are preferably not used.
In the preparation of the acrylate polyols used according to the invention, polymerization is preferably effected at above 160°C in the absence of polymerization regulators and with very low initiator concentrations. The chosen procedure for the process is preferably such that acrylate polyols having average molar masses (Mn) of not more than about 12 000 g/mol are present at the end of the reaction.
Homopolymers of hydroxyalkyl (meth)acrylates or copolymers of hydroxyalkyl (meth)acrylates with (meth)acrylic monomers having no OH functional groups are preferred. In particular, halogen-free monomers are used in the preparation of the acrylate polyols used according to the invention.
The acrylate polyols used according to the invention are prepared in particular by polymerization of hydroxy-C1- to Ce-alkyl (meth)acrylates, e.g. hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate.
Particularly suitable acrylic monomers without OH groups, which, if required, may be used as comonomers are aliphatic monomers containing olefinic double bonds and having a wide range of chemical structures, for example alkenes of 2 to 6 carbon atoms, such as ethene, propene, butene or isobutene, acrylonitrile, acrylamide, acrolein, vinyl esters of carboxylic acids or unsaturated carboxylic acids, such as malefic acid, fumaric acid or crotonic acid or derivatives thereof, and particularly preferably alkyl (meth)acrylates having C1- to Clo-alkyl groups, for example n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-butyl (meth)acrylate, propyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, ethylhexyl (meth)acrylate and/or hexanediol di(meth)acrylate. Said monomers can be used individually or in any desired mixture with one another.
The acrylate polyols used according to the invention are preferably prepared by copolymerization of hydroxy-C1- to Cg-alkyl (meth)acrylates with the (meth)acrylic monomers described above and having OH functional groups, any desired combination of different hydroxyalkyl (meth)acrylates with the (meth)acrylates having no functional groups being possible. Preferably, the OH-containing monomers are used in concentrations of from 5 to 95, particularly preferably from 10 to 80, mol%.
The number-average molar masses (Mn) of the acrylate polyols used according to the invention are particularly preferably not more than 6 000 g/mol, and the average OH functionalities are from 2 to 20 and the OH numbers are from 100 to 500 mg KOH/g. In the case of higher molecular weights and higher functionalities, the acrylate polyols are too viscous or solid and can therefore be processed only with difficulty in polyurethane systems. Moreover, the polyurethanes thus prepared have inadequate mechanical properties owing to the very high crosslinking.
The polyacrylate alcohols are preferably added in an amount of from 0.1 to 50, preferably from 0.5 to 40, particularly preferably from 1 to 30, parts by weight, based on 100 parts by weight of the compounds having at least two hydrogen atoms reactive with isocyanate groups b).
Polyester alcohols and preferably polyether alcohols having a functionality of from 2 to 8, in particular from 2 to 6, preferably from 2 to 4, and an average molecular weight of from 400 to 10 000, preferably from 1 000 to 8 000, g/mol are particularly suitable as compounds having at least two active hydrogen atoms b), which can be used together with the acrylate polyols used according to the invention.
The polyether alcohols can be prepared by known processes, 5 generally by a catalytic addition reaction of alkylene oxides, in particular ethylene oxide and/or propylene oxide, with H-functional initiator substances, or by condensation of tetrahydrofuran. The H-functional initiator substances used in particular are polyfunctional alcohols and/or amines. Water, dihydric alcohols, for example ethylene glycol, propylene glycol or butanediols, trihydric alcohols, for example glycerol or trimethylolpropane, and alcohols having a higher functionality, such as pentaerythritol, sugar alcohols, for example sucrose, glucose or sorbitol, are preferably used. Preferably used amines are aliphatic amines of up to 10 carbon atoms, for example ethylenediamine, diethylenetriamine or propylenediamine, and aminoalcohols, such as ethanolamine or diethanolamine. The alkylene oxides used are preferably ethylene oxide and/or propylene oxide, an ethylene oxide block frequently being added at the chain end in the case of polyether alcohols which are used for the preparation of flexible polyurethane foams. Catalysts used in the addition reaction of the alkylene oxides are in particular basic compounds, potassium hydroxide being of the greatest industrial importance here. If the content of unsaturated components in the polyether alcohols is to be low, multimetal cyanide compounds, i.e. DMC catalysts, may also be used as catalysts.
For specific applications, in particular for increasing the rigidity of the flexible polyurethane foams, polymer-modified polyols may also be used. Such polyols can be prepared, for example, by in situ polymerization of ethylenically unsaturated monomers, preferably styrene and/or acrylonitrile, in polyether alcohols. The polymer-modified polyether alcohols also include polyether alcohols which contain polyurea dispersions and are preferably prepared by reacting amines with isocyanates in polyols.
For the preparation of flexible foams and integral foams, in particular difunctional and/or trifunctional polyether alcohols are used. For the preparation of rigid foams, in particular polyether alcohols which are prepared by addition reaction of alkylene oxides with tetrafunctional initiators or initiators having a higher functionality, such as sugar alcohols or aromatic amines are used.
The acrylate polyols used according to the invention are preferably prepared by copolymerization of hydroxy-C1- to Cg-alkyl (meth)acrylates with the (meth)acrylic monomers described above and having OH functional groups, any desired combination of different hydroxyalkyl (meth)acrylates with the (meth)acrylates having no functional groups being possible. Preferably, the OH-containing monomers are used in concentrations of from 5 to 95, particularly preferably from 10 to 80, mol%.
The number-average molar masses (Mn) of the acrylate polyols used according to the invention are particularly preferably not more than 6 000 g/mol, and the average OH functionalities are from 2 to 20 and the OH numbers are from 100 to 500 mg KOH/g. In the case of higher molecular weights and higher functionalities, the acrylate polyols are too viscous or solid and can therefore be processed only with difficulty in polyurethane systems. Moreover, the polyurethanes thus prepared have inadequate mechanical properties owing to the very high crosslinking.
The polyacrylate alcohols are preferably added in an amount of from 0.1 to 50, preferably from 0.5 to 40, particularly preferably from 1 to 30, parts by weight, based on 100 parts by weight of the compounds having at least two hydrogen atoms reactive with isocyanate groups b).
Polyester alcohols and preferably polyether alcohols having a functionality of from 2 to 8, in particular from 2 to 6, preferably from 2 to 4, and an average molecular weight of from 400 to 10 000, preferably from 1 000 to 8 000, g/mol are particularly suitable as compounds having at least two active hydrogen atoms b), which can be used together with the acrylate polyols used according to the invention.
The polyether alcohols can be prepared by known processes, 5 generally by a catalytic addition reaction of alkylene oxides, in particular ethylene oxide and/or propylene oxide, with H-functional initiator substances, or by condensation of tetrahydrofuran. The H-functional initiator substances used in particular are polyfunctional alcohols and/or amines. Water, dihydric alcohols, for example ethylene glycol, propylene glycol or butanediols, trihydric alcohols, for example glycerol or trimethylolpropane, and alcohols having a higher functionality, such as pentaerythritol, sugar alcohols, for example sucrose, glucose or sorbitol, are preferably used. Preferably used amines are aliphatic amines of up to 10 carbon atoms, for example ethylenediamine, diethylenetriamine or propylenediamine, and aminoalcohols, such as ethanolamine or diethanolamine. The alkylene oxides used are preferably ethylene oxide and/or propylene oxide, an ethylene oxide block frequently being added at the chain end in the case of polyether alcohols which are used for the preparation of flexible polyurethane foams. Catalysts used in the addition reaction of the alkylene oxides are in particular basic compounds, potassium hydroxide being of the greatest industrial importance here. If the content of unsaturated components in the polyether alcohols is to be low, multimetal cyanide compounds, i.e. DMC catalysts, may also be used as catalysts.
For specific applications, in particular for increasing the rigidity of the flexible polyurethane foams, polymer-modified polyols may also be used. Such polyols can be prepared, for example, by in situ polymerization of ethylenically unsaturated monomers, preferably styrene and/or acrylonitrile, in polyether alcohols. The polymer-modified polyether alcohols also include polyether alcohols which contain polyurea dispersions and are preferably prepared by reacting amines with isocyanates in polyols.
For the preparation of flexible foams and integral foams, in particular difunctional and/or trifunctional polyether alcohols are used. For the preparation of rigid foams, in particular polyether alcohols which are prepared by addition reaction of alkylene oxides with tetrafunctional initiators or initiators having a higher functionality, such as sugar alcohols or aromatic amines are used.
Di- and/or trifunctional polyether alcohols which have primary hydroxyl groups, in particular those having an ethylene oxide block at the chain end or those which are based only on ethylene oxide, are preferably used for the preparation of flexible foams by the novel process.
The compounds having at least two active hydrogen atoms also include the chain extenders and crosslinking agents which, if required, may be concomitantly used. Preferably used chain IO extenders and crosslinking agents are difunctional and trifunctional alcohols having molecular weights of less than 400, in particular from 60 to 150, g/mol. Examples are ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, glycerol and trimethylolpropane. Diamines, too, can be used as crosslinking agents. If chain extenders and crosslinking agents are used, their amount is preferably up to 5% by weight, based on the weight of the compounds having at least two active hydrogen atoms.
The polyisocyanates used may be the conventional and known (cyclo)aliphatc di-, tri- and polyisocyanates. Examples of (cyclo)aliphatic di- or triisocyanates are tetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), isophorone diisocyanate (IPDI), 2-methylpentamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene 1,6-diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane, isocyanatopropylcyclohexyl isocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, lysine ester isocyanates, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, 4-isocyanato-methyloctamethylene 1,8-diisocyanate and mixtures thereof.
Hexamethylene 1,6-diisocyanate, isophorone diisocyanate, bis(4-isocyanatocyclohexyl)methane or mixtures of the isocyanates are preferably used.
Oligoisocyanates or polyisocyanates prepared from the monomeric isocyanates, in particular based on HDI and IPDI, are preferably used together with or in place of the monomeric isocyanates.
These oligoisocyanates or polyisocyanates can be prepared from said di- or triisocyanates or mixtures thereof by linkage by means of urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine, oxadiazinetrione or iminooxadiazinedione structures. Urethane, allophanate, uretdione, biuret or isocyanurate-containing polymers of HDI or IPDI are preferably used here, the use of allophanate, biuret or isocyanurate-containing polymers based on HDI being particularly preferred.
For carrying out the novel process, further starting materials, in particular catalysts, blowing agents and assistants and/or additives can be concomitantly used, about which the following may be stated specifically:
The catalysts used for the preparation of the novel polyurethane foams are the conventional and known polyurethane formation catalysts, for example organic tin compounds, such as tin diacetate, tin dioctanoate or dialkyltin diluarate, and/or strongly basic amines, such as triethylamine, pentamethyl-diethylenetriamine, tetramethyldiaminoethyl ether, imidazoles or preferably triethylenediamine. The catalysts are used preferably in an amount of from 0.01 to 5, especially from 0.05 to 2, % by weight.
A preferably used blowing agent for the preparation of the polyurethane foams is water, which reacts with the isocyanate groups with liberation of carbon dioxide. Physically acting blowing agents, for example carbon dioxide, hydrocarbons, such as n-pentane, isopentane, cyclopentane or cyclohexane, or halogenated hydrocarbons, such as tetrafluoroethane, pentafluoropropane, heptafluoropropane, pentafluorobutane, hexafluorobutane or dichloromonofluoroethane, can also be used together with or in place of water. The amount of the physical blowing agent is preferably from 1 to 15, in particular from 1 to 10, % by weight and the amount of water is preferably from 0.5 to 10, in particular from 1 to 5, % by weight.
The assistants and/or additives used are, for example, surfactants, foam stabilizers, cell regulators, external and internal lubricants, fillers, flameproofing agents, pigments, hydrolysis stabilizers and fungistatic and bacteriostatic substances.
In the industrial preparation of polyurethane foams, it is usual to combine the compounds having at least two active hydrogen atoms b) and the further starting materials and assistants and/or additives before the reaction to give a polyol component.
Further information about the starting materials used can be found, for example, in Kunststoffhandbuch, volume 7, Polyurethane, edited by Gunter Oertel, Carl-Hanser-Verlag, Munich, 3rd edition 1993.
For the preparation of the novel polyurethanes, the organic polyisocyanates a) are reacted with the compounds having at least two active hydrogen atoms b) and said blowing agents, catalysts and assistants and/or additives (polyol component), the acrylate polyols used according to the invention preferably being added to the polyol component.
In the preparation of the novel polyurethanes, isocyanate and polyol components are combined in an amount such that the ratio of the number of equivalents of isocyanate groups to the sum of the active hydrogen atoms is from 0.6:1 to 1:1.4, preferably from 0.7:1 to 1:1.20.
The preparation of the polyurethane foams is preferably carried out by the one-shot process, for example with the aid of the high pressure or low pressure technique. The foams can be prepared in open or closed metallic molds or by the continuous application of the reaction mixture to belt lines for the production of foam slabs.
It is particularly advantageous to employ the two-component process in which, as stated above, a polyol component and an isocyanate component are prepared and are foamed. The components are preferably mixed at from 15 to 120°C, preferably from 20 to 80°C, and introduced into the mold or onto the belt line. The temperature in the mold is generally from 15 to 120°C, preferably from 30 to 80°C. If acrylate polyols having a viscosity above 10 000 mPas, measured at 23°C, are used, it is advantageous to predilute the acrylate with a low-viscosity OH component of the polyol mixture at about 50°C and only thereafter to add it to the polyol mixture.
The acrylate polyols used according to the invention permit the preparation of resilient and viscoelastic flexible foams having low densities and excellent mechanical properties, for example very good flexibility, elongation and tensile strength and excellent aging resistance (compression set after autoclave aging).
According to the invention, it is also possible to prepare integral foams and rigid foams which, in addition to having very good mechanical properties, are distinguished from the prior art especially by the excellent aging resistance in the presence of moisture and heat and the light stability of the foams.
The examples which follow illustrate the invention.
The polyacrylate polyols shown in table 1 were used.
Table 1: Polyacrylate polyols Composition Number of the Polyacrylate average PolydispersityOH number monomers No. (mol%) molar mass (MW/M") (mg KOH/g) M~, mol 1 719 1.63 299 75 : 25 ~A / BA
2 25:75 1889 4.79 121 1 751 2.16 241 50 : 50 2 160 2.22 241 SO : 50 1476 4.46 241 50:47:3 HDDA
1 289 2.52 241 50:47:3 HEMA: 2-hydroxyethyl methacrylate BA: n-butyl acrylate HEA: 2-hydroxyethyl acrylate HDDA: hexanediol diacrylate EHA: 2-ethylhexyl acrylate Examples 1 to 7, flexible foams First, a polyol component was prepared from the compounds stated in table 2. 100 parts by weight of the polyol component and the amount in parts by weight, likewise stated in table 2, of the isocyanate component were heated to 60°C separately from one another, combined at this temperature,.homogenized by means of a stirrer and introduced into a mold heated to 60°C, open at the top and having the dimensions 40 x 40 x 40 cm. The foam formed was then cured at room temperature (23°C) for 24 hours.
The characteristic data of the foams are recorded in table 3.
Table 2: Components for the preparation of the novel foams, in parts by weight Example 1 2 3 4 5 ~~ ' ~ ~ 7 5 Polyol component Lupranol'~ 204332.0 28.5 25.5 31.0 23.2 27.7 17.2 Lupranol 2090 55.0 55.0 55.0 55.0 55.0 55.0 55.0 Pluriol E 400 5.0 5.0 5.0 S.0 5.0 5.0 10.0 Glycerol 1.0 3.0 2.0 1.0 2.0 1.0 2.0 1,4-Butanediol - - 0.5 2.0 0.5 Ethanolamine - - _ _ _ 1.0 -Polyacrylate (No.) (1) (2) (2) (3) (5) (6) (3) from tab. 1, 5.0 5.0 10.0 5.0 10.0 5.0 10,0 parts by weight DBTL 0.5 1.0 1.0 0.5 0.3 0.3 0.3 1 Water 1.5 2.5 1.5 2.5 4.0 3.0 5.0 Polyisocyanate ponent com Basonat P LR 77.4 46.0 68.7 87.3 135.3 53.6 164.0 Basonat HI100 - 46.0 - - - 53.6 -FlexibleFlexibleFlexibleFlexibleFlexibleFlexibleFlexible Foam type foam, foam, foam, foam, foam, foam, foam, visco-visco- visco-resilientresilientresilientresilientelasticelasticelastic Table 3: Characteristic data of the flexible foams Example 1 2 3 4 5 6 7 Density (kg/m') 135.975.1 131.168.2 51.0 70.0 40.0 (according to DIN EN
ISO 845) Tensile strength (kPa) 44.7 72.5 35.6 33.1 62.9 69.2 55.0 (according to DIN 53571) Elongation (%) (according to DIN 53571)90 82 76 112 118 88 126 Compressive strength (kPa) at 40%
7,66 5.69 6.37 2.24 n.d. 5.13 n.d.
(according to DIN EN
ISO 3386) Compression set, 70C, 50% compression, 22 h 0 0.1 0 0.5 0.2 0 0.7 loading (%) 3 5 (according to DIN 53572) IZ
Example 8, comparative experiment:
aliphatic flexible foam without addition of a polyacrylate Example (Comparison)8 Polyol component Lupranol 2043 31.0 Lupranol 2090 55.0 Pluriol E 400 5.0 Glycerol 1.0 1~4-Butanediol -Ethanolamine -Polyacrylate (No.)-from tab. 1, parts by weight DBTL 2.0 Water 2.5 Polyisocyanate ponent com Basonat P LR 8926 81.6 Basonat HI100 -The composition of comparative example 8 corresponded to that of novel example 4, but no acrylate was used here. The lack of an acrylate led to a substantial retardation of the reaction, and the DBTL catalysis therefore had to be adapted. The resulting foam was very flexible and remained tacky for a long time. After storage for 12 hours, the foam exhibited extreme shrinkage and no mechanical investigations could therefore be carried out.
Examples 9 to 11, integral foams, Example 12 rigid foam First, a polyol component was prepared from the compounds stated in table 4. 100 parts by weight of this polyol component and the amount in parts by weight, likewise stated in table 4, of isocyanate component were heated to 60°C separately from one another, combined at this temperature and homogenized by means of a stirrer. The integral foam formulations were introduced into a closed mold heated to 60°C and having the dimensions 20 x 20 x 4 cm. The resulting integral foam was.then cured at room temperature (23°C).
The rigid foam formulation was introduced into an unheated mold open at the top and having the dimensions 40 x 40 x 40 cm. The resulting rigid foam was then cured at room temperature (23°C).
Table 4: Components for the preparation of novel integral foams, in parts by weight Foam No. 9 1D 11 12 Pol yol ponent com Lupranol 2043 28.2 2 8.0 30.4 -Lupranol 2090 55.0 55.0 55.0 -Lupranol 2042 - - - 72.2 Pluriol E 400 5.0 5.0 5.0 S.0 1 Glycerol 1.0 1.0 - -1,4-Butanediol - - 2.0 -TMP - - 2.0 -Ethylene glycol- - - 10.0 Polyacrylate (3) 10.0 . ~ (4) 5.0 (3) 10.0 (No.) (3) from tab. 1, 10.0 parts by Weight DBTL 0.3 0.5 0.3 0.3 Water 0.5 0.5 0.3 2.5 Polyisocyanate component Basonat P LR 19.5 19.5 21.5 -Basonat HI 100 - - 21.~ 135.4 Foam type integral integral integral rigid foam foam foam foam Density (kg/m 530 353 X04 122 ) Definition of the starting materials:
Basonat~ I 100: polyisocyanate obtained from hexamethylene H
diisocyanate (HDI), NCO content = 22.0% by weight Basonat~ LR 8926:polyisocyanate P obtained from HDI, NCO
content = 19.0% by weight Lupranol~2090: polyoxypropylenepolyoxyethylenetriol, hydroxyl number 28 mg KOH/g Lupranol~ 2043: polyoxypropylenepolyoxyethylenediol, hydroxyl number 29 mg KOH/g Lupranol~ 2042: polyoxypropylenepolyoxyethylenetriol, hydroxyl number 27 mg KOH/g Pluriol~ 400: polyoxyethylenediol, hydroxyl number E
280 mg KOH/g TMP: trimethylolpropane DBTL: dibutyltin dilaurate ~: Registered trademark of BASF Aktiengesellschaft
The compounds having at least two active hydrogen atoms also include the chain extenders and crosslinking agents which, if required, may be concomitantly used. Preferably used chain IO extenders and crosslinking agents are difunctional and trifunctional alcohols having molecular weights of less than 400, in particular from 60 to 150, g/mol. Examples are ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, glycerol and trimethylolpropane. Diamines, too, can be used as crosslinking agents. If chain extenders and crosslinking agents are used, their amount is preferably up to 5% by weight, based on the weight of the compounds having at least two active hydrogen atoms.
The polyisocyanates used may be the conventional and known (cyclo)aliphatc di-, tri- and polyisocyanates. Examples of (cyclo)aliphatic di- or triisocyanates are tetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), isophorone diisocyanate (IPDI), 2-methylpentamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene 1,6-diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane, isocyanatopropylcyclohexyl isocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, lysine ester isocyanates, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, 4-isocyanato-methyloctamethylene 1,8-diisocyanate and mixtures thereof.
Hexamethylene 1,6-diisocyanate, isophorone diisocyanate, bis(4-isocyanatocyclohexyl)methane or mixtures of the isocyanates are preferably used.
Oligoisocyanates or polyisocyanates prepared from the monomeric isocyanates, in particular based on HDI and IPDI, are preferably used together with or in place of the monomeric isocyanates.
These oligoisocyanates or polyisocyanates can be prepared from said di- or triisocyanates or mixtures thereof by linkage by means of urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine, oxadiazinetrione or iminooxadiazinedione structures. Urethane, allophanate, uretdione, biuret or isocyanurate-containing polymers of HDI or IPDI are preferably used here, the use of allophanate, biuret or isocyanurate-containing polymers based on HDI being particularly preferred.
For carrying out the novel process, further starting materials, in particular catalysts, blowing agents and assistants and/or additives can be concomitantly used, about which the following may be stated specifically:
The catalysts used for the preparation of the novel polyurethane foams are the conventional and known polyurethane formation catalysts, for example organic tin compounds, such as tin diacetate, tin dioctanoate or dialkyltin diluarate, and/or strongly basic amines, such as triethylamine, pentamethyl-diethylenetriamine, tetramethyldiaminoethyl ether, imidazoles or preferably triethylenediamine. The catalysts are used preferably in an amount of from 0.01 to 5, especially from 0.05 to 2, % by weight.
A preferably used blowing agent for the preparation of the polyurethane foams is water, which reacts with the isocyanate groups with liberation of carbon dioxide. Physically acting blowing agents, for example carbon dioxide, hydrocarbons, such as n-pentane, isopentane, cyclopentane or cyclohexane, or halogenated hydrocarbons, such as tetrafluoroethane, pentafluoropropane, heptafluoropropane, pentafluorobutane, hexafluorobutane or dichloromonofluoroethane, can also be used together with or in place of water. The amount of the physical blowing agent is preferably from 1 to 15, in particular from 1 to 10, % by weight and the amount of water is preferably from 0.5 to 10, in particular from 1 to 5, % by weight.
The assistants and/or additives used are, for example, surfactants, foam stabilizers, cell regulators, external and internal lubricants, fillers, flameproofing agents, pigments, hydrolysis stabilizers and fungistatic and bacteriostatic substances.
In the industrial preparation of polyurethane foams, it is usual to combine the compounds having at least two active hydrogen atoms b) and the further starting materials and assistants and/or additives before the reaction to give a polyol component.
Further information about the starting materials used can be found, for example, in Kunststoffhandbuch, volume 7, Polyurethane, edited by Gunter Oertel, Carl-Hanser-Verlag, Munich, 3rd edition 1993.
For the preparation of the novel polyurethanes, the organic polyisocyanates a) are reacted with the compounds having at least two active hydrogen atoms b) and said blowing agents, catalysts and assistants and/or additives (polyol component), the acrylate polyols used according to the invention preferably being added to the polyol component.
In the preparation of the novel polyurethanes, isocyanate and polyol components are combined in an amount such that the ratio of the number of equivalents of isocyanate groups to the sum of the active hydrogen atoms is from 0.6:1 to 1:1.4, preferably from 0.7:1 to 1:1.20.
The preparation of the polyurethane foams is preferably carried out by the one-shot process, for example with the aid of the high pressure or low pressure technique. The foams can be prepared in open or closed metallic molds or by the continuous application of the reaction mixture to belt lines for the production of foam slabs.
It is particularly advantageous to employ the two-component process in which, as stated above, a polyol component and an isocyanate component are prepared and are foamed. The components are preferably mixed at from 15 to 120°C, preferably from 20 to 80°C, and introduced into the mold or onto the belt line. The temperature in the mold is generally from 15 to 120°C, preferably from 30 to 80°C. If acrylate polyols having a viscosity above 10 000 mPas, measured at 23°C, are used, it is advantageous to predilute the acrylate with a low-viscosity OH component of the polyol mixture at about 50°C and only thereafter to add it to the polyol mixture.
The acrylate polyols used according to the invention permit the preparation of resilient and viscoelastic flexible foams having low densities and excellent mechanical properties, for example very good flexibility, elongation and tensile strength and excellent aging resistance (compression set after autoclave aging).
According to the invention, it is also possible to prepare integral foams and rigid foams which, in addition to having very good mechanical properties, are distinguished from the prior art especially by the excellent aging resistance in the presence of moisture and heat and the light stability of the foams.
The examples which follow illustrate the invention.
The polyacrylate polyols shown in table 1 were used.
Table 1: Polyacrylate polyols Composition Number of the Polyacrylate average PolydispersityOH number monomers No. (mol%) molar mass (MW/M") (mg KOH/g) M~, mol 1 719 1.63 299 75 : 25 ~A / BA
2 25:75 1889 4.79 121 1 751 2.16 241 50 : 50 2 160 2.22 241 SO : 50 1476 4.46 241 50:47:3 HDDA
1 289 2.52 241 50:47:3 HEMA: 2-hydroxyethyl methacrylate BA: n-butyl acrylate HEA: 2-hydroxyethyl acrylate HDDA: hexanediol diacrylate EHA: 2-ethylhexyl acrylate Examples 1 to 7, flexible foams First, a polyol component was prepared from the compounds stated in table 2. 100 parts by weight of the polyol component and the amount in parts by weight, likewise stated in table 2, of the isocyanate component were heated to 60°C separately from one another, combined at this temperature,.homogenized by means of a stirrer and introduced into a mold heated to 60°C, open at the top and having the dimensions 40 x 40 x 40 cm. The foam formed was then cured at room temperature (23°C) for 24 hours.
The characteristic data of the foams are recorded in table 3.
Table 2: Components for the preparation of the novel foams, in parts by weight Example 1 2 3 4 5 ~~ ' ~ ~ 7 5 Polyol component Lupranol'~ 204332.0 28.5 25.5 31.0 23.2 27.7 17.2 Lupranol 2090 55.0 55.0 55.0 55.0 55.0 55.0 55.0 Pluriol E 400 5.0 5.0 5.0 S.0 5.0 5.0 10.0 Glycerol 1.0 3.0 2.0 1.0 2.0 1.0 2.0 1,4-Butanediol - - 0.5 2.0 0.5 Ethanolamine - - _ _ _ 1.0 -Polyacrylate (No.) (1) (2) (2) (3) (5) (6) (3) from tab. 1, 5.0 5.0 10.0 5.0 10.0 5.0 10,0 parts by weight DBTL 0.5 1.0 1.0 0.5 0.3 0.3 0.3 1 Water 1.5 2.5 1.5 2.5 4.0 3.0 5.0 Polyisocyanate ponent com Basonat P LR 77.4 46.0 68.7 87.3 135.3 53.6 164.0 Basonat HI100 - 46.0 - - - 53.6 -FlexibleFlexibleFlexibleFlexibleFlexibleFlexibleFlexible Foam type foam, foam, foam, foam, foam, foam, foam, visco-visco- visco-resilientresilientresilientresilientelasticelasticelastic Table 3: Characteristic data of the flexible foams Example 1 2 3 4 5 6 7 Density (kg/m') 135.975.1 131.168.2 51.0 70.0 40.0 (according to DIN EN
ISO 845) Tensile strength (kPa) 44.7 72.5 35.6 33.1 62.9 69.2 55.0 (according to DIN 53571) Elongation (%) (according to DIN 53571)90 82 76 112 118 88 126 Compressive strength (kPa) at 40%
7,66 5.69 6.37 2.24 n.d. 5.13 n.d.
(according to DIN EN
ISO 3386) Compression set, 70C, 50% compression, 22 h 0 0.1 0 0.5 0.2 0 0.7 loading (%) 3 5 (according to DIN 53572) IZ
Example 8, comparative experiment:
aliphatic flexible foam without addition of a polyacrylate Example (Comparison)8 Polyol component Lupranol 2043 31.0 Lupranol 2090 55.0 Pluriol E 400 5.0 Glycerol 1.0 1~4-Butanediol -Ethanolamine -Polyacrylate (No.)-from tab. 1, parts by weight DBTL 2.0 Water 2.5 Polyisocyanate ponent com Basonat P LR 8926 81.6 Basonat HI100 -The composition of comparative example 8 corresponded to that of novel example 4, but no acrylate was used here. The lack of an acrylate led to a substantial retardation of the reaction, and the DBTL catalysis therefore had to be adapted. The resulting foam was very flexible and remained tacky for a long time. After storage for 12 hours, the foam exhibited extreme shrinkage and no mechanical investigations could therefore be carried out.
Examples 9 to 11, integral foams, Example 12 rigid foam First, a polyol component was prepared from the compounds stated in table 4. 100 parts by weight of this polyol component and the amount in parts by weight, likewise stated in table 4, of isocyanate component were heated to 60°C separately from one another, combined at this temperature and homogenized by means of a stirrer. The integral foam formulations were introduced into a closed mold heated to 60°C and having the dimensions 20 x 20 x 4 cm. The resulting integral foam was.then cured at room temperature (23°C).
The rigid foam formulation was introduced into an unheated mold open at the top and having the dimensions 40 x 40 x 40 cm. The resulting rigid foam was then cured at room temperature (23°C).
Table 4: Components for the preparation of novel integral foams, in parts by weight Foam No. 9 1D 11 12 Pol yol ponent com Lupranol 2043 28.2 2 8.0 30.4 -Lupranol 2090 55.0 55.0 55.0 -Lupranol 2042 - - - 72.2 Pluriol E 400 5.0 5.0 5.0 S.0 1 Glycerol 1.0 1.0 - -1,4-Butanediol - - 2.0 -TMP - - 2.0 -Ethylene glycol- - - 10.0 Polyacrylate (3) 10.0 . ~ (4) 5.0 (3) 10.0 (No.) (3) from tab. 1, 10.0 parts by Weight DBTL 0.3 0.5 0.3 0.3 Water 0.5 0.5 0.3 2.5 Polyisocyanate component Basonat P LR 19.5 19.5 21.5 -Basonat HI 100 - - 21.~ 135.4 Foam type integral integral integral rigid foam foam foam foam Density (kg/m 530 353 X04 122 ) Definition of the starting materials:
Basonat~ I 100: polyisocyanate obtained from hexamethylene H
diisocyanate (HDI), NCO content = 22.0% by weight Basonat~ LR 8926:polyisocyanate P obtained from HDI, NCO
content = 19.0% by weight Lupranol~2090: polyoxypropylenepolyoxyethylenetriol, hydroxyl number 28 mg KOH/g Lupranol~ 2043: polyoxypropylenepolyoxyethylenediol, hydroxyl number 29 mg KOH/g Lupranol~ 2042: polyoxypropylenepolyoxyethylenetriol, hydroxyl number 27 mg KOH/g Pluriol~ 400: polyoxyethylenediol, hydroxyl number E
280 mg KOH/g TMP: trimethylolpropane DBTL: dibutyltin dilaurate ~: Registered trademark of BASF Aktiengesellschaft
Claims (14)
1. A process for the preparation of polyurethane foams by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms reactive with isocyanate groups, wherein the polyisocyanates a) are aliphatic di- or polyisocyanates and the compounds having at least two hydrogen atoms reactive with isocyanate groups b) contain at least one acrylate polyol.
2. A process as claimed in claim 1, wherein the acrylate polyols have a molecular weight Mn of not more than 12 000 g/mol.
3. A process as claimed in claim 1, wherein the acrylate polyols are prepared by polymerization of hydroxy-functionalized (meth)acrylates.
4. A process as claimed in claim 1, wherein the acrylate polyols are prepared by copolymerization of hydroxy-functionalized (meth)acrylates with aliphatic monomers having no hydroxyl functional groups and containing olefinic double bonds.
5. A process as claimed in claim 1, wherein the acrylate polyols are prepared by copolymerization of hydroxy-functionalized (meth)acrylates with ethene, propene, butene, isobutene, acrylonitrile, acrylamide, acrolein, vinyl esters of carboxylic acids or unsaturated carboxylic acids, for example malefic acid, fumaric acid or crotonic acid or derivatives thereof.
6. A process as claimed in claim 1, wherein the acrylate polyols are prepared by copolymerization of hydroxy-functionalized (meth)acrylates with (meth)acrylates having no hydroxyl functional groups.
7. A process as claimed in claim 1, wherein the acrylate polyols are prepared by polymerization of hydroxy-C1- to C8-alkyl (meth)acrylates.
8. A process as claimed in claim 1, wherein the acrylate polyols are prepared by copolymerization of hydroxy-C1- to C8-alkyl (meth)acrylates with alkyl (meth)acrylates having C1- to C10-alkyl groups.
9. A process as claimed in claim 1, wherein the compounds having at least two hydrogen atoms reactive with isocyanate groups b) contain at least one acrylate polyol and at least one polyether alcohol or polyester alcohol.
10. A process as claimed in claim 1, wherein the acrylate polyols are used in an amount of from 0.1 to 50 parts by weight, based on 100 parts by weight of the compounds having at least two hydrogen atoms reactive with isocyanate groups b).
11. A process as claimed in claim 1, wherein the polyisocyanates a) used are hexamethylene 1,6-diisocyanate, isophorone diisocyanate, bis(4-isocyanatocyclohexyl)methane or mixtures of said isocyanates.
12. A process as claimed in claim 1, wherein the polyisocyanates a) were modified by incorporation of urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine, oxadiazinetrione or iminooxadiazinedione structures.
13. A polyurethane foam, which can be prepared as claimed in any of claims 1 to 12.
14. A polyol mixture for the preparation of polyurethane foams, containing at least one acrylate polyol and at least one polyether alcohol and/or one polyester alcohol.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10035400.9 | 2000-07-19 | ||
DE10035400A DE10035400A1 (en) | 2000-07-19 | 2000-07-19 | Process for the production of polyurethane foams |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2353209A1 true CA2353209A1 (en) | 2002-01-19 |
Family
ID=7649641
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002353209A Abandoned CA2353209A1 (en) | 2000-07-19 | 2001-07-18 | Preparation of polyurethane foams |
Country Status (8)
Country | Link |
---|---|
US (1) | US6696505B2 (en) |
EP (1) | EP1174452B1 (en) |
JP (1) | JP2002069148A (en) |
KR (1) | KR100777531B1 (en) |
AT (1) | ATE301146T1 (en) |
CA (1) | CA2353209A1 (en) |
DE (2) | DE10035400A1 (en) |
DK (1) | DK1174452T3 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10035400A1 (en) * | 2000-07-19 | 2002-01-31 | Basf Ag | Process for the production of polyurethane foams |
DE10110553A1 (en) * | 2001-03-05 | 2002-09-12 | Basf Ag | Process for the production of flexible polyurethane foams |
DE10226414A1 (en) * | 2002-06-13 | 2003-12-24 | Basf Ag | Process for the production of polyurethane foams |
US6734220B2 (en) | 2002-08-27 | 2004-05-11 | Foamex L.P. | Fine cell, high density viscoelastic polyurethane foams |
US6653363B1 (en) | 2002-12-04 | 2003-11-25 | Foamex, L.P. | Low energy-loss, high firmness, temperature sensitive polyurethane foams |
US7855240B2 (en) * | 2003-08-20 | 2010-12-21 | Basf Corporation | Formulated resin component for use in spray-in-place foam system to produce a low density polyurethane foam |
DE10352100A1 (en) * | 2003-11-04 | 2005-06-02 | Basf Ag | Polyurethane foams containing acrylate polyols |
KR101609116B1 (en) | 2014-04-25 | 2016-04-05 | 주식회사 빅스 | Low-density urethane foam composition used biomass resources |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE634494A (en) * | 1962-07-05 | |||
US3284415A (en) | 1964-09-04 | 1966-11-08 | Dow Chemical Co | Polyurethane from ethylene-hydroxyalkyl acrylate copolymers |
US3770810A (en) | 1971-10-28 | 1973-11-06 | Air Prod & Chem | Liquid halo-vinylic copolymers having hydroxyl functionality |
CA1145881A (en) * | 1980-11-17 | 1983-05-03 | Som N. Khanna | Interpolymers of polyurethanes and addition polymerizable monomers |
JPS59168020A (en) * | 1983-03-15 | 1984-09-21 | Toyoda Gosei Co Ltd | Nonyellowing semirigid polyurethane foam |
DE3501857A1 (en) * | 1985-01-22 | 1986-07-24 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING NEW POLYISOCYANATE PREPARATIONS, THE PREPARATIONS AVAILABLE AFTER THE METHOD AND THEIR USE IN THE PRODUCTION OF PLASTICS BY THE ISOCYANATE POLYADDITION METHOD |
KR0159915B1 (en) * | 1994-10-07 | 1999-01-15 | 윌리엄 에프. 마쉬 | Process for the preparation of rigid polyurethane foam |
BR9809668A (en) | 1997-05-23 | 2000-07-11 | Sheel Internationale Reseach M | Polyurethane foams |
DE19741257A1 (en) * | 1997-09-19 | 1999-03-25 | Basf Ag | Process for the production of polyurethane foams |
DE10035400A1 (en) * | 2000-07-19 | 2002-01-31 | Basf Ag | Process for the production of polyurethane foams |
-
2000
- 2000-07-19 DE DE10035400A patent/DE10035400A1/en not_active Withdrawn
-
2001
- 2001-06-21 AT AT01115061T patent/ATE301146T1/en not_active IP Right Cessation
- 2001-06-21 EP EP01115061A patent/EP1174452B1/en not_active Expired - Lifetime
- 2001-06-21 DE DE50106946T patent/DE50106946D1/en not_active Expired - Lifetime
- 2001-06-21 DK DK01115061T patent/DK1174452T3/en active
- 2001-07-18 KR KR1020010043086A patent/KR100777531B1/en not_active IP Right Cessation
- 2001-07-18 JP JP2001218450A patent/JP2002069148A/en not_active Withdrawn
- 2001-07-18 CA CA002353209A patent/CA2353209A1/en not_active Abandoned
- 2001-07-18 US US09/908,404 patent/US6696505B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
KR100777531B1 (en) | 2007-11-20 |
US20020035165A1 (en) | 2002-03-21 |
EP1174452B1 (en) | 2005-08-03 |
JP2002069148A (en) | 2002-03-08 |
EP1174452A1 (en) | 2002-01-23 |
ATE301146T1 (en) | 2005-08-15 |
DK1174452T3 (en) | 2005-09-26 |
US6696505B2 (en) | 2004-02-24 |
DE10035400A1 (en) | 2002-01-31 |
KR20020008059A (en) | 2002-01-29 |
DE50106946D1 (en) | 2005-09-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1006133B2 (en) | Polyurethane foam, process for producing the same, and foam forming composition | |
US5840781A (en) | Polyether polyols, polyol formulation containing them and their use in the production of hard polyurethane foams | |
CN102858835A (en) | Method for producing rigid foam synthetic resin | |
WO2008062794A1 (en) | Method for producing hard polyurethane foam | |
WO2008062792A1 (en) | Method for producing hard polyurethane foam | |
MXPA04003978A (en) | Flexible moldings of foamed polyurethane and their use. | |
US6696505B2 (en) | Preparation of polyurethane foams | |
US9238704B2 (en) | Polyether polyurethanes exhibiting enhanced slip resistance under wet conditions | |
JP6872536B2 (en) | Highly elastic polyurethane foam made of high functional value, high equivalent polyol, mainly having a secondary hydroxyl group | |
US20050176838A1 (en) | Method for the production of polyurethane foam materials | |
EP2513182B1 (en) | Polyurethane foam with soft surface touch | |
JPS6040119A (en) | Novel system for polyurethane manufacture | |
US20010023263A1 (en) | Production of polyurethane foams | |
US20040102538A1 (en) | Method of producing flexible polyurethane foams | |
RU2765788C2 (en) | Polyol compositions | |
JP3665621B2 (en) | Method for producing rigid polyurethane foam | |
CN109937220B (en) | Polyurethane foam having sufficient hardness and good flexibility | |
JP3885851B2 (en) | Method for producing flexible polyurethane foam | |
KR20220023311A (en) | Production of polyurethane foam | |
JP2022514469A (en) | Hybrid foam formulation | |
WO2004020496A1 (en) | Polyol combination | |
JP2005139468A (en) | Method for producing rigid polyurethane foam |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
FZDE | Discontinued |