CA2797528C - Process for producing rigid polyurethane foams - Google Patents
Process for producing rigid polyurethane foams Download PDFInfo
- Publication number
- CA2797528C CA2797528C CA2797528A CA2797528A CA2797528C CA 2797528 C CA2797528 C CA 2797528C CA 2797528 A CA2797528 A CA 2797528A CA 2797528 A CA2797528 A CA 2797528A CA 2797528 C CA2797528 C CA 2797528C
- Authority
- CA
- Canada
- Prior art keywords
- process according
- polyester alcohol
- prepared
- weight
- koh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims description 30
- 230000008569 process Effects 0.000 title claims description 30
- 239000011496 polyurethane foam Substances 0.000 title claims description 24
- 229920005830 Polyurethane Foam Polymers 0.000 title claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 33
- 229920000728 polyester Polymers 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 14
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 239000000306 component Substances 0.000 claims description 42
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 27
- 229920000570 polyether Polymers 0.000 claims description 26
- 239000004604 Blowing Agent Substances 0.000 claims description 22
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 19
- 229930195729 fatty acid Natural products 0.000 claims description 19
- 239000000194 fatty acid Substances 0.000 claims description 19
- 150000004665 fatty acids Chemical class 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 239000003063 flame retardant Substances 0.000 claims description 15
- -1 aromatic carboxylic acids Chemical class 0.000 claims description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 125000004437 phosphorous atom Chemical group 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000006260 foam Substances 0.000 abstract description 27
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000004814 polyurethane Substances 0.000 abstract description 5
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 57
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 33
- 150000001298 alcohols Chemical class 0.000 description 26
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 21
- 229920005862 polyol Polymers 0.000 description 18
- 150000003077 polyols Chemical class 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 235000019256 formaldehyde Nutrition 0.000 description 11
- 229960004279 formaldehyde Drugs 0.000 description 11
- 239000007858 starting material Substances 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 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 8
- 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 8
- 150000001412 amines Chemical class 0.000 description 8
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 8
- 239000000600 sorbitol Substances 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 150000001735 carboxylic acids Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 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 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 229930006000 Sucrose Natural products 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000005720 sucrose Substances 0.000 description 6
- 229940113165 trimethylolpropane Drugs 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 235000021313 oleic acid Nutrition 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 229920000582 polyisocyanurate Polymers 0.000 description 5
- 239000011495 polyisocyanurate Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- 239000004872 foam stabilizing agent Substances 0.000 description 4
- 238000007373 indentation Methods 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 4
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229940093476 ethylene glycol Drugs 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229960004063 propylene glycol Drugs 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 description 2
- YWDFOLFVOVCBIU-UHFFFAOYSA-N 1-dimethoxyphosphorylpropane Chemical compound CCCP(=O)(OC)OC YWDFOLFVOVCBIU-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- 206010059837 Adhesion Diseases 0.000 description 2
- 229930188104 Alkylresorcinol Natural products 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- 239000004971 Cross linker Substances 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
- 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000002666 chemical blowing agent Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 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
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920005903 polyol mixture Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 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 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- GWHCXVQVJPWHRF-KTKRTIGZSA-N (15Z)-tetracosenoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-KTKRTIGZSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-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
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- DMUPYMORYHFFCT-UHFFFAOYSA-N 1,2,3,3,3-pentafluoroprop-1-ene Chemical compound FC=C(F)C(F)(F)F DMUPYMORYHFFCT-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- PIFPCDRPHCQLSJ-WYIJOVFWSA-N 4,8,12,15,19-Docosapentaenoic acid Chemical compound CC\C=C\CC\C=C\C\C=C\CC\C=C\CC\C=C\CCC(O)=O PIFPCDRPHCQLSJ-WYIJOVFWSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- YWWVWXASSLXJHU-UHFFFAOYSA-N 9E-tetradecenoic acid Natural products CCCCC=CCCCCCCCC(O)=O YWWVWXASSLXJHU-UHFFFAOYSA-N 0.000 description 1
- 235000019489 Almond oil Nutrition 0.000 description 1
- 235000000832 Ayote Nutrition 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PIFPCDRPHCQLSJ-UHFFFAOYSA-N Clupanodonic acid Natural products CCC=CCCC=CCC=CCCC=CCCC=CCCC(O)=O PIFPCDRPHCQLSJ-UHFFFAOYSA-N 0.000 description 1
- 240000004244 Cucurbita moschata Species 0.000 description 1
- 235000009854 Cucurbita moschata Nutrition 0.000 description 1
- 235000009804 Cucurbita pepo subsp pepo Nutrition 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
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- CNVZJPUDSLNTQU-SEYXRHQNSA-N petroselinic acid Chemical compound CCCCCCCCCCC\C=C/CCCCC(O)=O CNVZJPUDSLNTQU-SEYXRHQNSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
-
- 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
- C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
-
- 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
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a method for producing polyurethane rigid foams by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms that are reactive with isocyanate groups in the presence of c) expanding agents, characterized in that the compounds having at least two hydrogen atoms that are reactive with isocyanate groups contain b) at least one aromatic polyester alcohol bi), at least one polyester alcohol bii) having a functionality of 4 to 8 and a hydroxyl number ranging between 300 and 600 mgKOH/gh.
Description
Process for producing rigid polyurethane foams Description .. The invention relates to a process for producing rigid polyurethane foams by reacting polyisocyanates with b) compounds having at least two hydrogen atoms which are re-active toward isocyanate groups.
Rigid polyurethane foams have been known for a long time and are used predominant-ly 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 polyurethane foams may be found, for example, in Kunststoff¨Handbuch, Volume 7, Polyurethane 1st edition 1966, edited by Dr. R. Vieweg and Dr. A. Hochtlen, 2nd edition 1983, edited by Dr.
Gunter Oertel, and 3rd edition 1993, edited by Dr. Gunter Oertel, Carl Hanser Verlag, Munich, Vienna.
They are usually produced by reacting polyisocyanates with compounds having at least two hydrogen atoms which are reactive toward isocyanate groups in the presence of catalysts, blowing agents and auxiliaries and/or additives.
Important requirements which rigid polyurethane foams have to meet are a low thermal conductivity, good flowability, satisfactory adhesion of the foam to the covering layers and good mechanical properties.
A further requirement which rigid polyurethane foams have to meet is good burning behavior. This is of great importance in, in particular, applications in the building sector, particularly in the case of composite elements comprising metallic covering layers and a core composed of polyurethane or polyisocyanurate foam. The term polyisocyanurate foam usually refers to a foam which comprises not only urethane groups but also iso-cyanurate groups. In the following, the term rigid polyurethane foam can also encom-pass polyisocyanurate foam.
Polyisocyanurate foams in particular frequently display unsatisfactory adhesion to the metallic covering layers. To remedy this deficiency, a bonding agent is usually applied between the covering layer and the foam, as described, for example, in WO
99/00559.
WO 2005090432 describes a process for producing rigid polyurethane foams produced using a mixture of a polyester alcohol based on an aromatic carboxylic acid and at least one polyether alcohol based on aromatic amines. The use of the polyester alco-hols is said to reduce the thermal conductivity of the foam and improve the compatibil-ity with the blowing agent. The foams produced by this process are preferably used in refrigeration appliances.
Rigid polyurethane foams have been known for a long time and are used predominant-ly 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 polyurethane foams may be found, for example, in Kunststoff¨Handbuch, Volume 7, Polyurethane 1st edition 1966, edited by Dr. R. Vieweg and Dr. A. Hochtlen, 2nd edition 1983, edited by Dr.
Gunter Oertel, and 3rd edition 1993, edited by Dr. Gunter Oertel, Carl Hanser Verlag, Munich, Vienna.
They are usually produced by reacting polyisocyanates with compounds having at least two hydrogen atoms which are reactive toward isocyanate groups in the presence of catalysts, blowing agents and auxiliaries and/or additives.
Important requirements which rigid polyurethane foams have to meet are a low thermal conductivity, good flowability, satisfactory adhesion of the foam to the covering layers and good mechanical properties.
A further requirement which rigid polyurethane foams have to meet is good burning behavior. This is of great importance in, in particular, applications in the building sector, particularly in the case of composite elements comprising metallic covering layers and a core composed of polyurethane or polyisocyanurate foam. The term polyisocyanurate foam usually refers to a foam which comprises not only urethane groups but also iso-cyanurate groups. In the following, the term rigid polyurethane foam can also encom-pass polyisocyanurate foam.
Polyisocyanurate foams in particular frequently display unsatisfactory adhesion to the metallic covering layers. To remedy this deficiency, a bonding agent is usually applied between the covering layer and the foam, as described, for example, in WO
99/00559.
WO 2005090432 describes a process for producing rigid polyurethane foams produced using a mixture of a polyester alcohol based on an aromatic carboxylic acid and at least one polyether alcohol based on aromatic amines. The use of the polyester alco-hols is said to reduce the thermal conductivity of the foam and improve the compatibil-ity with the blowing agent. The foams produced by this process are preferably used in refrigeration appliances.
2 A further challenge which is always present in the use of rigid polyurethane foams is improving the flame resistance of the foams. Flame retardants are usually added to the foam for this purpose. The addition of the flame retardants can alter the mechanical properties and the processing properties of the foams. Furthermore, it is desirable to restrict the use of flame retardants, in particular those based on halogens, especially bromine, in the production of rigid polyurethane foams.
A further ongoing requirement is to improve the adhesion of the foams to the covering layers, in particular to reduce or completely avoid the use of bonding agents.
It was therefore an object of the invention to develop a process for producing rigid pol-yurethane foams which have good mechanical properties, good adhesion to covering layers and good flame resistance, have good compatibility with blowing agents and flame retardants and are readily processable.
The object has surprisingly been able to be achieved by a process for producing rigid polyurethane foams by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms which are reactive toward isocya-nate groups in the presence of c) blowing agents, wherein the compounds b) having at least two hydrogen atoms which are reactive to-ward isocyanate groups comprise at least one aromatic polyester alcohol bi), at least one polyether alcohol bii) having a functionality of from 4 to 8 and a hydroxyl number in the range from 300 to 600 mg KOH/g.
2a The invention accordingly provides a process for producing rigid polyurethane foams by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms which are reactive toward isocya-nate groups in the presence of c) blowing agents, wherein the compounds b) having at least two hydrogen atoms which are reactive to-ward isocyanate groups comprise at least one aromatic polyester alcohol bi), at least one polyether alcohol bii) having a functionality of from 4 to 8 and a hydroxyl number in the range from 300 to 600 mg KOH/g.
The invention accordingly provides a process for producing rigid polyurethane foams by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms which are reactive toward isocyanate groups in the presence of c) blowing agents, in the presence of flame retardants d), wherein the com-pounds b) having at least two hydrogen atoms which are reactive toward isocyanate groups comprise - at least one aromatic polyester alcohol bi) prepared using at least one fatty acid, - at least one polyether alcohol bii) having a functionality of from 4 to 8 and a hydroxyl number in the range from 300 to 600 mg KOH/g, and -at least one polyether alcohol biii) having a functionality of from 2 to 4 and a hydroxyl number in the range from 100 to < 300 mg KOH/g, where the weight ratio of the com-ponent bi) to the sum of the components bii) and biii) is less than 4 and greater than 0.15.
The invention accordingly provides a rigid polyurethane foam produced according to the processes herein described.
The hydroxyl number is determined in accordance with DIN 53240.
The hydroxyl number of the component b) is preferably at least 175 mg KOH/g, in par-ticular at least 225 mg KOH/g.
A further ongoing requirement is to improve the adhesion of the foams to the covering layers, in particular to reduce or completely avoid the use of bonding agents.
It was therefore an object of the invention to develop a process for producing rigid pol-yurethane foams which have good mechanical properties, good adhesion to covering layers and good flame resistance, have good compatibility with blowing agents and flame retardants and are readily processable.
The object has surprisingly been able to be achieved by a process for producing rigid polyurethane foams by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms which are reactive toward isocya-nate groups in the presence of c) blowing agents, wherein the compounds b) having at least two hydrogen atoms which are reactive to-ward isocyanate groups comprise at least one aromatic polyester alcohol bi), at least one polyether alcohol bii) having a functionality of from 4 to 8 and a hydroxyl number in the range from 300 to 600 mg KOH/g.
2a The invention accordingly provides a process for producing rigid polyurethane foams by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms which are reactive toward isocya-nate groups in the presence of c) blowing agents, wherein the compounds b) having at least two hydrogen atoms which are reactive to-ward isocyanate groups comprise at least one aromatic polyester alcohol bi), at least one polyether alcohol bii) having a functionality of from 4 to 8 and a hydroxyl number in the range from 300 to 600 mg KOH/g.
The invention accordingly provides a process for producing rigid polyurethane foams by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms which are reactive toward isocyanate groups in the presence of c) blowing agents, in the presence of flame retardants d), wherein the com-pounds b) having at least two hydrogen atoms which are reactive toward isocyanate groups comprise - at least one aromatic polyester alcohol bi) prepared using at least one fatty acid, - at least one polyether alcohol bii) having a functionality of from 4 to 8 and a hydroxyl number in the range from 300 to 600 mg KOH/g, and -at least one polyether alcohol biii) having a functionality of from 2 to 4 and a hydroxyl number in the range from 100 to < 300 mg KOH/g, where the weight ratio of the com-ponent bi) to the sum of the components bii) and biii) is less than 4 and greater than 0.15.
The invention accordingly provides a rigid polyurethane foam produced according to the processes herein described.
The hydroxyl number is determined in accordance with DIN 53240.
The hydroxyl number of the component b) is preferably at least 175 mg KOH/g, in par-ticular at least 225 mg KOH/g.
3 Furthermore, the hydroxyl number of the component b) is preferably not more than 325 mg KOH/g, particularly preferably not more than 300 mg KOH/g, in particular not more than 290 mg KOH/g.
The polyester alcohol bi) preferably has a functionality of 2-3 and a hydroxyl number of from 200 to 300 mg KOH/g.
The polyester alcohol bi) is usually prepared by reacting carboxylic acids and/or deriva-tives thereof, in particular esters and anhydrides, with alcohols. The carboxylic acids and/or the alcohols, preferably both, are polyfunctional.
In an embodiment of the invention, the polyester alcohol bi) is prepared using at least one fatty acid or a fatty acid derivative, preferably a fatty acid.
The fatty acids can comprise hydroxyl groups. Furthermore, the fatty acids can com-prise double bonds.
In an embodiment of the invention, the fatty acid does not comprise any hydroxyl groups. In a further embodiment of the invention, the fatty acid does not comprise any double bonds.
The average fatty acid content of the component b) is preferably greater than 1% by weight, more preferably greater than 2.5% by weight, more preferably greater than 4%
by weight and particularly preferably greater than 5% by weight, based on the weight of the components b) and d).
The average fatty acid content of the component b) is preferably less than 30%
by weight, more preferably less than 20% by weight, based on the total weight of the components b) and d).
The fatty acid or fatty acid derivative is preferably a fatty acid or fatty acid derivative based on renewable raw materials, selected from the group consisting of castor oil,
The polyester alcohol bi) preferably has a functionality of 2-3 and a hydroxyl number of from 200 to 300 mg KOH/g.
The polyester alcohol bi) is usually prepared by reacting carboxylic acids and/or deriva-tives thereof, in particular esters and anhydrides, with alcohols. The carboxylic acids and/or the alcohols, preferably both, are polyfunctional.
In an embodiment of the invention, the polyester alcohol bi) is prepared using at least one fatty acid or a fatty acid derivative, preferably a fatty acid.
The fatty acids can comprise hydroxyl groups. Furthermore, the fatty acids can com-prise double bonds.
In an embodiment of the invention, the fatty acid does not comprise any hydroxyl groups. In a further embodiment of the invention, the fatty acid does not comprise any double bonds.
The average fatty acid content of the component b) is preferably greater than 1% by weight, more preferably greater than 2.5% by weight, more preferably greater than 4%
by weight and particularly preferably greater than 5% by weight, based on the weight of the components b) and d).
The average fatty acid content of the component b) is preferably less than 30%
by weight, more preferably less than 20% by weight, based on the total weight of the components b) and d).
The fatty acid or fatty acid derivative is preferably a fatty acid or fatty acid derivative based on renewable raw materials, selected from the group consisting of castor oil,
4 polyhydroxy fatty acids, ricinoleic acid, hydroxyl-modified oils, grapeseed oil, black cumin oil, pumpkin kernel oil, borage seed oil, soybean oil, wheatgerm oil, rapeseed oil, sunflower oil, peanut oil, apricot kernel oil, pistacchio oil, almond oil, olive oil, macada-mia nut oil, avocado oil, sea buckthorn oil, sesame oil, hemp oil, hazelnut oil, primrose oil, wild rose oil, safflower oil, walnut oil, hydroxyl-modified fatty acids and fatty acid esters based on myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, petroselic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, steridonic acid, arachidonic acid, timnodonic acid, clupanodonic acid and cervonic acid.
Preference is given to using oleic acid as fatty acid.
As described above, the polyester alcohol bi) is prepared using aromatic carboxylic acids or anhydrides thereof. In particular, these are selected from the group consisting of terephthalic acid, phthalic acid and phthalic anhydride.
In an embodiment of the invention, the polyester alcohol bi) is prepared using esters of aromatic carboxylic acids. In particular, these are selected from the group consisting of polyethylene terephthalate and dimethyl terephthalate. The polyethylene terephthalate can be a recycling product, in particular from the recycling of beverage bottles.
The polyester alcohol bi) is particularly preferably obtained using mixtures of carboxylic acids and derivatives thereof which comprise at least 50% by weight, based on the weight of the carboxylic acids, of terephthalic acid. In a further preferred embodiment of the invention, exclusively terephthalic acid is used as carboxylic acid.
Apart from the abovementioned carboxylic acids and derivatives thereof, it is also pos-sible to use other known polyfunctional carboxylic acids, for example aliphatic carbox-ylic acids such as adipic acid or succinic acid. However, the content of these should be below 50% by weight, based on the weight of the carboxylic acids.
As alcohols for preparing the polyester alcohols bi), use is usually made of bifunctional alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene gly-col, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol and alkoxylates thereof, in particular ethoxylates thereof. In particular, the aliphatic diol is diethylene glycol.
In an embodiment of the invention, the polyester alcohol bi) has a content of compo-nents having a functionality of > 2.9 of at least 200 mmol/kg of polyester alcohol, pref-erably at least 400 mmol/kg, particularly preferably at least 600 mmol/kg, especially at least 800 mmol/kg and in particular at least 1000 mmol/kg of polyester alcohol. Particu-lar preference is given to the hydroxyl-comprising components used in the esterifica-tion. These are preferably more than bifunctional alcohols, higher-functional polyols selected from the group consisting of glycerol, alkoxylated glycerol, trimethylolpropane, alkoxylated trimethylolpropane, pentaerythritol and alkoxylated pentaerythritol.
In a further preferred embodiment of the invention, the component b) additionally corn-
Preference is given to using oleic acid as fatty acid.
As described above, the polyester alcohol bi) is prepared using aromatic carboxylic acids or anhydrides thereof. In particular, these are selected from the group consisting of terephthalic acid, phthalic acid and phthalic anhydride.
In an embodiment of the invention, the polyester alcohol bi) is prepared using esters of aromatic carboxylic acids. In particular, these are selected from the group consisting of polyethylene terephthalate and dimethyl terephthalate. The polyethylene terephthalate can be a recycling product, in particular from the recycling of beverage bottles.
The polyester alcohol bi) is particularly preferably obtained using mixtures of carboxylic acids and derivatives thereof which comprise at least 50% by weight, based on the weight of the carboxylic acids, of terephthalic acid. In a further preferred embodiment of the invention, exclusively terephthalic acid is used as carboxylic acid.
Apart from the abovementioned carboxylic acids and derivatives thereof, it is also pos-sible to use other known polyfunctional carboxylic acids, for example aliphatic carbox-ylic acids such as adipic acid or succinic acid. However, the content of these should be below 50% by weight, based on the weight of the carboxylic acids.
As alcohols for preparing the polyester alcohols bi), use is usually made of bifunctional alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene gly-col, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol and alkoxylates thereof, in particular ethoxylates thereof. In particular, the aliphatic diol is diethylene glycol.
In an embodiment of the invention, the polyester alcohol bi) has a content of compo-nents having a functionality of > 2.9 of at least 200 mmol/kg of polyester alcohol, pref-erably at least 400 mmol/kg, particularly preferably at least 600 mmol/kg, especially at least 800 mmol/kg and in particular at least 1000 mmol/kg of polyester alcohol. Particu-lar preference is given to the hydroxyl-comprising components used in the esterifica-tion. These are preferably more than bifunctional alcohols, higher-functional polyols selected from the group consisting of glycerol, alkoxylated glycerol, trimethylolpropane, alkoxylated trimethylolpropane, pentaerythritol and alkoxylated pentaerythritol.
In a further preferred embodiment of the invention, the component b) additionally corn-
5 prises at least one polyether alcohol biii) having a functionality of from 2 to 4 and a hy-droxyl number in the range from 100 to < 300 mg KOH/g.
The polyether alcohols bii) and biii) are usually prepared by addition of alkylene oxides onto H-functional starter substances. This process is generally known and is routine for the preparation of such products.
As starter substances, it is possible to use alcohols or amines. As amines, it is possible to use aliphatic amines such as ethylenediamine. In another embodiment of the inven-tion, aromatic amines, in particular toluenediamine (TDA) or mixtures of diphenylme-thanediamine and polyphenylenepolymethylenepolyamines can be used. The compo-nent b) preferably comprises not more than 65% by weight, more preferably not more than 40% by weight, in each case based on the weight of the component a), of poly-ether alcohols based on aromatic amines.
.. In a particularly preferred embodiment of the invention, the component b) does not comprise any polyether alcohols based on aliphatic or aromatic amines.
Thus, polyfunctional alcohols are preferred as H-functional starter substances for the preparation of the polyether alcohols bii) and biii).
These are, in particular, 2- to 8-functional alcohols. Examples are glycols such as eth-ylene glycol or propylene glycol, glycerol, trimethylolpropane, pentaerythritol and also sugar alcohols such as sucrose or sorbitol. Mixtures of alcohols with one another are also possible. The solid starter substances such as sucrose and sorbitol, in particular, are frequently mixed with liquid starter substances such as glycols or glycerol.
2- to 3-functional alcohols, in particular glycerol or trimethylolpropane, are preferably used for preparing the polyols biii). To increase the functionality, higher-functional alco-hols can also be added in small amounts.
To prepare the polyols bii), preference is given to using mixtures of high-functionality alcohols and the abovementioned alcohols which are liquid at room temperature, in particular glycerol. As high-functionality alcohols, preference is given to using sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols such as oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols, formaldehyde and dialkanolamines and also melamine.
Par-ticular preference is given to sugar alcohols, in particular sucrose or sorbitol.
The polyether alcohols bii) and biii) are usually prepared by addition of alkylene oxides onto H-functional starter substances. This process is generally known and is routine for the preparation of such products.
As starter substances, it is possible to use alcohols or amines. As amines, it is possible to use aliphatic amines such as ethylenediamine. In another embodiment of the inven-tion, aromatic amines, in particular toluenediamine (TDA) or mixtures of diphenylme-thanediamine and polyphenylenepolymethylenepolyamines can be used. The compo-nent b) preferably comprises not more than 65% by weight, more preferably not more than 40% by weight, in each case based on the weight of the component a), of poly-ether alcohols based on aromatic amines.
.. In a particularly preferred embodiment of the invention, the component b) does not comprise any polyether alcohols based on aliphatic or aromatic amines.
Thus, polyfunctional alcohols are preferred as H-functional starter substances for the preparation of the polyether alcohols bii) and biii).
These are, in particular, 2- to 8-functional alcohols. Examples are glycols such as eth-ylene glycol or propylene glycol, glycerol, trimethylolpropane, pentaerythritol and also sugar alcohols such as sucrose or sorbitol. Mixtures of alcohols with one another are also possible. The solid starter substances such as sucrose and sorbitol, in particular, are frequently mixed with liquid starter substances such as glycols or glycerol.
2- to 3-functional alcohols, in particular glycerol or trimethylolpropane, are preferably used for preparing the polyols biii). To increase the functionality, higher-functional alco-hols can also be added in small amounts.
To prepare the polyols bii), preference is given to using mixtures of high-functionality alcohols and the abovementioned alcohols which are liquid at room temperature, in particular glycerol. As high-functionality alcohols, preference is given to using sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols such as oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols, formaldehyde and dialkanolamines and also melamine.
Par-ticular preference is given to sugar alcohols, in particular sucrose or sorbitol.
6 It has been found that the use of sorbitol-initiated polyether alcohols brings advantages in the processing and the properties of the foams. Thus, better curing and improved compressive strength are obtained.
As alkylene oxides, preference is given to using ethylene oxide, propylene oxide or mixtures of these compounds. Particular preference is given to using pure propylene oxide.
The addition of the alkylene oxides onto the starter substance is preferably carried out in the presence of catalysts. Basic compounds are usually used as catalysts, with the oxides and in particular the hydroxides of alkali metals or alkaline earth metals having attained the greatest industrial importance. Potassium hydroxide is usually used as catalyst.
In one embodiment of the invention, amines are used as catalysts for preparing the polyether alcohols bii) and bill), in particular the polyether alcohols bii).
These are pref-erably amines having at least one tertiary amino group, imidazoles, guanidines or de-rivatives thereof. These amine catalysts preferably have at least one group which is reactive toward alkylene oxides, for example a primary or secondary amino group or, particularly preferably, a hydroxyl group. These catalysts are particularly preferably amino alcohols such as dimethylethanolamine. Such catalysts are used particularly when starter substances comprising sucrose are employed.
In a preferred embodiment of the invention, the weight ratio of the component bi) to the sum of the components bii) and biii) is less than 4.
Furthermore, the weight ratio of the component bi) to the sum of the components bii) and biii) is preferably greater than 0.15.
As blowing agents, it is possible to use chemical and physical blowing agents.
Chemi-cal blowing agents are compounds which react with isocyanate groups to eliminate gases, in particular carbon dioxide or carbon dioxide and carbon monoxide.
These are usually water and/or formic acid, preferably water.
In place of or in combination with the chemical blowing agents, it is also possible to use physical blowing agents. These are compounds which are inert toward the starting components and are usually liquid at room temperature and vaporize under the condi-tions of the urethane reaction. The boiling point of these compounds is preferably be-low 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
As alkylene oxides, preference is given to using ethylene oxide, propylene oxide or mixtures of these compounds. Particular preference is given to using pure propylene oxide.
The addition of the alkylene oxides onto the starter substance is preferably carried out in the presence of catalysts. Basic compounds are usually used as catalysts, with the oxides and in particular the hydroxides of alkali metals or alkaline earth metals having attained the greatest industrial importance. Potassium hydroxide is usually used as catalyst.
In one embodiment of the invention, amines are used as catalysts for preparing the polyether alcohols bii) and bill), in particular the polyether alcohols bii).
These are pref-erably amines having at least one tertiary amino group, imidazoles, guanidines or de-rivatives thereof. These amine catalysts preferably have at least one group which is reactive toward alkylene oxides, for example a primary or secondary amino group or, particularly preferably, a hydroxyl group. These catalysts are particularly preferably amino alcohols such as dimethylethanolamine. Such catalysts are used particularly when starter substances comprising sucrose are employed.
In a preferred embodiment of the invention, the weight ratio of the component bi) to the sum of the components bii) and biii) is less than 4.
Furthermore, the weight ratio of the component bi) to the sum of the components bii) and biii) is preferably greater than 0.15.
As blowing agents, it is possible to use chemical and physical blowing agents.
Chemi-cal blowing agents are compounds which react with isocyanate groups to eliminate gases, in particular carbon dioxide or carbon dioxide and carbon monoxide.
These are usually water and/or formic acid, preferably water.
In place of or in combination with the chemical blowing agents, it is also possible to use physical blowing agents. These are compounds which are inert toward the starting components and are usually liquid at room temperature and vaporize under the condi-tions of the urethane reaction. The boiling point of these compounds is preferably be-low 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
7 are dissolved therein, for example carbon dioxide, low-boiling alkanes and fluoroal-kanes.
The blowing agents are usually selected from the group consisting of water, formic ac-.. id, 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 from 1 to 3 carbon atoms in the alkyl chain, in particular tetramethylsilane.
Mention may be made by way of example of propane, n-butane, isobutane and cyclo-butane, n-pentane, isopentane and cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl formate, acetone and also fluoroalkanes which can be degraded in the troposphere and therefore do not damage the ozone layer, e.g.
trifluoromethane, difluoromethane, 1,3,3,3-pentafluoropropene, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,3-pentafluoropropene, 1-chloro-3,3,3-trifluoropropene, difluoroethane and heptafluoro-propane. The physical blowing agents mentioned can be used either alone or in any combinations with one another.
Particularly preferred physical blowing agents are fluoroalkanes and/or hydrocarbons.
The blowing agent component c) is usually used in an amount of from 2 to 45%
by weight, preferably from 2 to 30% by weight, particularly preferably from 2 to 20% by weight, based on the total weight of the components b) to e).
In a preferred embodiment, the blowing agent mixture c) comprises exclusively hydro-carbons as physical blowing agent. Particularly preferred hydrocarbons are n-pentane, cyclopentane, isopentane and mixtures of the isomers. In particular, a mixture of n-pentane and isopentane is used as physical blowing agent c).
In a preferred embodiment of the invention, a flame retardant d) is additionally used.
The flame retardant d) is preferably used in an amount of from 10 to 55% by weight, based on the total weight of the components b) and d).
The flame retardant d) can comprise hydrogen atoms which are reactive toward isocy-anate groups. In a preferred embodiment of the invention, the flame retardant does not comprise any hydrogen atoms which are reactive toward isocyanate groups.
Preference is given to using flame retardants d) which comprise at least one phospho-rus atom in the molecule.
They can preferably be the products characterized in more detail below.
The blowing agents are usually selected from the group consisting of water, formic ac-.. id, 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 from 1 to 3 carbon atoms in the alkyl chain, in particular tetramethylsilane.
Mention may be made by way of example of propane, n-butane, isobutane and cyclo-butane, n-pentane, isopentane and cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl formate, acetone and also fluoroalkanes which can be degraded in the troposphere and therefore do not damage the ozone layer, e.g.
trifluoromethane, difluoromethane, 1,3,3,3-pentafluoropropene, 1,1,1,3,3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,3-pentafluoropropene, 1-chloro-3,3,3-trifluoropropene, difluoroethane and heptafluoro-propane. The physical blowing agents mentioned can be used either alone or in any combinations with one another.
Particularly preferred physical blowing agents are fluoroalkanes and/or hydrocarbons.
The blowing agent component c) is usually used in an amount of from 2 to 45%
by weight, preferably from 2 to 30% by weight, particularly preferably from 2 to 20% by weight, based on the total weight of the components b) to e).
In a preferred embodiment, the blowing agent mixture c) comprises exclusively hydro-carbons as physical blowing agent. Particularly preferred hydrocarbons are n-pentane, cyclopentane, isopentane and mixtures of the isomers. In particular, a mixture of n-pentane and isopentane is used as physical blowing agent c).
In a preferred embodiment of the invention, a flame retardant d) is additionally used.
The flame retardant d) is preferably used in an amount of from 10 to 55% by weight, based on the total weight of the components b) and d).
The flame retardant d) can comprise hydrogen atoms which are reactive toward isocy-anate groups. In a preferred embodiment of the invention, the flame retardant does not comprise any hydrogen atoms which are reactive toward isocyanate groups.
Preference is given to using flame retardants d) which comprise at least one phospho-rus atom in the molecule.
They can preferably be the products characterized in more detail below.
8 A preferred group comprises phosphorus-comprising compounds having a molecular weight of less than 400 g/mol, especially less than 300 g/mol, preferably less than 200 g/mol and particularly preferably in the range from 150 to 190 g/mol, and less than 4 phosphorus atoms, especially less than 3 phosphorus atoms, more especially less than 2 phosphorus atoms and in particular 1 phosphorus atom, in the molecule.
Prefer-ence is given to phosphonates and/or phosphates. Particular preference is given to using phosphates and phosphonates selected from the group consisting of diethyl ethanephosphonate (DEEP), dimethyl propylphosphonate (DMPP) and triethyl phos-phate (TEP), particularly preferably from the group consisting of diethyl ethane phos-phonate (DEEP) and triethyl phosphate (TEP) and in particular diethyl ethanephospho-nate (DEEP). These compounds are preferably used in an amount of from 5 to 40%
by weight, based on the sum of the masses of b) and d).
A further preferred group of phosphorus-comprising compounds comprises compounds of this type having a molecular weight of greater than 300 g/mol. These preferably have at least one phosphorus atom in the molecule. Preference is given to phosphonates and/or phosphates, especially phosphates. Preference is given to using diphenyl cresyl phosphate (DPC) and/or triphenyl phosphate, in particular diphenyl cresyl phosphate.
These compounds are preferably used in an amount of from 10 to 30% by weight, based on the sum of the masses of b) and d).
As regards the other compounds used for the process of the invention, the following details may be provided:
As polyisocyanates a), use is made of the customary aliphatic, cycloaliphatic and in particular aromatic diisocyanates and/or polyisocyanates. Preference is given to using tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and in particular mix-tures of diphenylmethane diisocyanate and polyphenylenepolymethylene polyisocya-nates (crude MDI). The isocyanates can also be modified, for example by incorporation of uretdione, carbamate, isocyanurate, carbodiimide, allophanate and in particular ure-thane groups.
In particular, crude MDI is used for producing rigid polyurethane foams.
In the prior art, it is customary, if appropriate, to incorporate isocyanurate groups into the polyisocyanate. The formation of isocyanurate groups leads to an improvement in the flame resistance of the foams. The isocyanurate groups are preferably formed by addition of specific catalysts during the reaction to produce the foam.
Furthermore, the component b) can optionally comprise chain extenders and/or cross-linkers. Chain extenders and/or crosslinkers used are, in particular, bifunctional or tri-
Prefer-ence is given to phosphonates and/or phosphates. Particular preference is given to using phosphates and phosphonates selected from the group consisting of diethyl ethanephosphonate (DEEP), dimethyl propylphosphonate (DMPP) and triethyl phos-phate (TEP), particularly preferably from the group consisting of diethyl ethane phos-phonate (DEEP) and triethyl phosphate (TEP) and in particular diethyl ethanephospho-nate (DEEP). These compounds are preferably used in an amount of from 5 to 40%
by weight, based on the sum of the masses of b) and d).
A further preferred group of phosphorus-comprising compounds comprises compounds of this type having a molecular weight of greater than 300 g/mol. These preferably have at least one phosphorus atom in the molecule. Preference is given to phosphonates and/or phosphates, especially phosphates. Preference is given to using diphenyl cresyl phosphate (DPC) and/or triphenyl phosphate, in particular diphenyl cresyl phosphate.
These compounds are preferably used in an amount of from 10 to 30% by weight, based on the sum of the masses of b) and d).
As regards the other compounds used for the process of the invention, the following details may be provided:
As polyisocyanates a), use is made of the customary aliphatic, cycloaliphatic and in particular aromatic diisocyanates and/or polyisocyanates. Preference is given to using tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and in particular mix-tures of diphenylmethane diisocyanate and polyphenylenepolymethylene polyisocya-nates (crude MDI). The isocyanates can also be modified, for example by incorporation of uretdione, carbamate, isocyanurate, carbodiimide, allophanate and in particular ure-thane groups.
In particular, crude MDI is used for producing rigid polyurethane foams.
In the prior art, it is customary, if appropriate, to incorporate isocyanurate groups into the polyisocyanate. The formation of isocyanurate groups leads to an improvement in the flame resistance of the foams. The isocyanurate groups are preferably formed by addition of specific catalysts during the reaction to produce the foam.
Furthermore, the component b) can optionally comprise chain extenders and/or cross-linkers. Chain extenders and/or crosslinkers used are, in particular, bifunctional or tri-
9 functional amines and alcohols, in particular diols and/or triols having molecular weights of less than 400, preferably from 60 to 300.
In addition to the components a) to d), the customary catalysts, foam stabilizers and auxiliaries and/or additives can be used.
As catalysts, preference is given to using tertiary amines, tin catalysts or alkali metal salts. It is also possible to allow the reactions to proceed without catalysis. In this case, the catalytic activity of amine-initiated polyols is exploited. Catalysts which catalyze the formation of isocyanurate groups include carboxylates of alkali metals.
Foam stabilizers are substances which promote the formation of a regular cell structure during foam formation.
Examples which may be mentioned are: silicone-comprising foam stabilizers such as siloxane-oxyalkylene copolymers and other organopolysiloxanes. Also alkoxylation products of fatty alcohols, oxo alcohols, fatty amines, alkylphenols, dialkylphenols, al-kylcresols, alkylresorcinol, naphthol, alkylnaphthol, naphthylamine, aniline, alkylaniline, toluidene, bisphenol A, alkylated bisphenol A, polyvinyl alcohol and also further alkoxy-lation products of condensation products of formaldehyde and alkylphenols, formalde-hyde and dialkylphenols, formaldehyde and alkylcresols, formaldehyde and alkylresor-cinol, formaldehyde and aniline, formaldehyde and toluidene, formaldehyde and naph-thol, formaldehyde and alkylnaphthol and also formaldehyde and bisphenol A. As alkoxylation reagents, it is possible to use, for example, ethylene oxide, propylene ox-ide, polyTHF and higher homologues.
Further details regarding the abovementioned and further starting materials may be found in the specialist literature, for example Kunststoffhandbuch, Volume VII, Polyure-thane, Carl Hanser Verlag, Munich, Vienna, 1st, 2nd and 3rd editions 1966, 1983 and 1993.
To produce the rigid polyurethane foams, the polyisocyanates a) and the components b) to d) and also the other compounds used for the production of the polyurethanes are reacted in such amounts that the isocyanate index of the foam is from 90 to 350, pref-erably from 100 to 250, more preferably from 110 to 200 and especially from 120 to 200, and in particular from 160 to 200.
The rigid polyurethane foams can be produced batchwise or continuously with the aid of known processes, for example by means of the double belt process.
Particular pref-.. erence is given to processing of the rigid polyurethane foams according to the invention by means of a continuous double belt.
It has been found to be particularly advantageous to employ the two-component pro-cess and combine the compounds having at least two hydrogen atoms which are reac-tive toward isocyanate groups with the blowing agents, foam stabilizers and flame re-tardants and also the optional catalysts and auxiliaries and/or additives to form a polyol 5 component and react this with the polyisocyanates or mixtures of the polyisocyanates and optionally blowing agents, also referred to as isocyanate component.
The rigid polyurethane foams of the invention have good mechanical and processing properties. They adhere very well to the surface of the substrates.
Furthermore, they
In addition to the components a) to d), the customary catalysts, foam stabilizers and auxiliaries and/or additives can be used.
As catalysts, preference is given to using tertiary amines, tin catalysts or alkali metal salts. It is also possible to allow the reactions to proceed without catalysis. In this case, the catalytic activity of amine-initiated polyols is exploited. Catalysts which catalyze the formation of isocyanurate groups include carboxylates of alkali metals.
Foam stabilizers are substances which promote the formation of a regular cell structure during foam formation.
Examples which may be mentioned are: silicone-comprising foam stabilizers such as siloxane-oxyalkylene copolymers and other organopolysiloxanes. Also alkoxylation products of fatty alcohols, oxo alcohols, fatty amines, alkylphenols, dialkylphenols, al-kylcresols, alkylresorcinol, naphthol, alkylnaphthol, naphthylamine, aniline, alkylaniline, toluidene, bisphenol A, alkylated bisphenol A, polyvinyl alcohol and also further alkoxy-lation products of condensation products of formaldehyde and alkylphenols, formalde-hyde and dialkylphenols, formaldehyde and alkylcresols, formaldehyde and alkylresor-cinol, formaldehyde and aniline, formaldehyde and toluidene, formaldehyde and naph-thol, formaldehyde and alkylnaphthol and also formaldehyde and bisphenol A. As alkoxylation reagents, it is possible to use, for example, ethylene oxide, propylene ox-ide, polyTHF and higher homologues.
Further details regarding the abovementioned and further starting materials may be found in the specialist literature, for example Kunststoffhandbuch, Volume VII, Polyure-thane, Carl Hanser Verlag, Munich, Vienna, 1st, 2nd and 3rd editions 1966, 1983 and 1993.
To produce the rigid polyurethane foams, the polyisocyanates a) and the components b) to d) and also the other compounds used for the production of the polyurethanes are reacted in such amounts that the isocyanate index of the foam is from 90 to 350, pref-erably from 100 to 250, more preferably from 110 to 200 and especially from 120 to 200, and in particular from 160 to 200.
The rigid polyurethane foams can be produced batchwise or continuously with the aid of known processes, for example by means of the double belt process.
Particular pref-.. erence is given to processing of the rigid polyurethane foams according to the invention by means of a continuous double belt.
It has been found to be particularly advantageous to employ the two-component pro-cess and combine the compounds having at least two hydrogen atoms which are reac-tive toward isocyanate groups with the blowing agents, foam stabilizers and flame re-tardants and also the optional catalysts and auxiliaries and/or additives to form a polyol 5 component and react this with the polyisocyanates or mixtures of the polyisocyanates and optionally blowing agents, also referred to as isocyanate component.
The rigid polyurethane foams of the invention have good mechanical and processing properties. They adhere very well to the surface of the substrates.
Furthermore, they
10 have good flame resistance.
The invention is illustrated by the following examples.
Starting materials Polyesterol 1: Esterification product of phthalic anhydride, diethylene glycol and mo-noethylene glycol having a hydroxyl functionality of 2.0 and a hydroxyl number of 240 mg KOH/g Polyesterol 2: Esterification product of terephthalic acid, diethylene glycol, trime-thylolpropane and oleic acid having a hydroxyl functionality of 2.3 and a hydroxyl num-ber of 245 mg KOH/g Polyetherol 1: Polyether polyol having a hydroxyl number of 490 mg KOH/g, prepared by polyaddition of propylene oxide onto a sucrose/glycerol mixture as starter molecule Polyetherol 2: Polyether polyol having a hydroxyl number of 490 mg KOH/g, prepared by polyaddition of propylene oxide onto a 72% strength aqueous sorbitol solution as starter molecule Polyetherol 3: Polyether polyol having a hydroxyl number of 160 mg KOH/g, prepared by polyaddition of propylene oxide onto trimethylolpropane Polyetherol 4: Polyether polyol prepared by polyaddition of ethylene oxide onto eth-ylene glycol and having a hydroxyl functionality of 2 and a hydroxyl number of 190 mg KOH/g Polyetherol 5: Polyether polyol prepared by polyaddition of propylene oxide onto pro-pylene glycol and having a hydroxyl functionality of 2 and a hydroxyl number of 104 mg KOH/g TCPP: tris-2-chloroisopropyl phosphate =
The invention is illustrated by the following examples.
Starting materials Polyesterol 1: Esterification product of phthalic anhydride, diethylene glycol and mo-noethylene glycol having a hydroxyl functionality of 2.0 and a hydroxyl number of 240 mg KOH/g Polyesterol 2: Esterification product of terephthalic acid, diethylene glycol, trime-thylolpropane and oleic acid having a hydroxyl functionality of 2.3 and a hydroxyl num-ber of 245 mg KOH/g Polyetherol 1: Polyether polyol having a hydroxyl number of 490 mg KOH/g, prepared by polyaddition of propylene oxide onto a sucrose/glycerol mixture as starter molecule Polyetherol 2: Polyether polyol having a hydroxyl number of 490 mg KOH/g, prepared by polyaddition of propylene oxide onto a 72% strength aqueous sorbitol solution as starter molecule Polyetherol 3: Polyether polyol having a hydroxyl number of 160 mg KOH/g, prepared by polyaddition of propylene oxide onto trimethylolpropane Polyetherol 4: Polyether polyol prepared by polyaddition of ethylene oxide onto eth-ylene glycol and having a hydroxyl functionality of 2 and a hydroxyl number of 190 mg KOH/g Polyetherol 5: Polyether polyol prepared by polyaddition of propylene oxide onto pro-pylene glycol and having a hydroxyl functionality of 2 and a hydroxyl number of 104 mg KOH/g TCPP: tris-2-chloroisopropyl phosphate =
11 Stabilizer: Niax Silicone L 6635 (silicone-comprising stabilizer) from Momentive B component Polymeric MDI (Lupranat M50) having an NCO content of 31% and a viscosity of 500 mPas at 25 C.
Additives DMCHA Dimethylcyclohexylamine Catalyst 2: 47% strength potassium acetate solution in 95% strength monoethylene glycol Water 5.5 parts of an n-pentane/isopentane mixture in a ratio of 80:20 Measurement methods:
Curing Curing was determined by means of the indentation test. For this purpose, a steel in-denter having a hemispherical end having a radius of 10 mm was pressed by means of a tensile/compressive testing machine to a depth of 10 mm into the foam body formed at times of 2.5, 3, 4, 5, 6 and 7 minutes after mixing of the components in a polystyrene cup. The maximum force in N required for this is a measure of the curing of the foam.
As a measure of the brittleness of the rigid polyisocyanurate foam, the time at which the surface of the rigid foam had visible fracture zones during the indentation test was determined.
Flame resistance The flame height was measured in accordance with EN ISO 11925-2.
The hydroxyl numbers were determined in accordance with DIN 53240.
Adhesion:
The adhesion was determined by means of a peel adhesion test. For this purpose, a test specimen was produced in a closed box mold which had the dimensions 200 mm x 200 mm x 200 mm and whose temperature could be controlled. The test specimen is produced in such away that the foam has a degree of compaction of 1.15 0.3.
In addition, an aluminum-coated paper is placed in the bottom before foaming.
After 5 minutes, the test specimen is removed from the mold. After storage for 24 hours, the aluminum paper on the underside is cut with parallel cuts with the aid of a template.
The parallel strip is pulled off to a distance of about 3 cm and clamped in a testing de-vice in a Zwick tensile testing machine. The tensile testing machine then pulls the foil strip off at a uniform speed of 100 mm/min. A force transducer is integrated into the
Additives DMCHA Dimethylcyclohexylamine Catalyst 2: 47% strength potassium acetate solution in 95% strength monoethylene glycol Water 5.5 parts of an n-pentane/isopentane mixture in a ratio of 80:20 Measurement methods:
Curing Curing was determined by means of the indentation test. For this purpose, a steel in-denter having a hemispherical end having a radius of 10 mm was pressed by means of a tensile/compressive testing machine to a depth of 10 mm into the foam body formed at times of 2.5, 3, 4, 5, 6 and 7 minutes after mixing of the components in a polystyrene cup. The maximum force in N required for this is a measure of the curing of the foam.
As a measure of the brittleness of the rigid polyisocyanurate foam, the time at which the surface of the rigid foam had visible fracture zones during the indentation test was determined.
Flame resistance The flame height was measured in accordance with EN ISO 11925-2.
The hydroxyl numbers were determined in accordance with DIN 53240.
Adhesion:
The adhesion was determined by means of a peel adhesion test. For this purpose, a test specimen was produced in a closed box mold which had the dimensions 200 mm x 200 mm x 200 mm and whose temperature could be controlled. The test specimen is produced in such away that the foam has a degree of compaction of 1.15 0.3.
In addition, an aluminum-coated paper is placed in the bottom before foaming.
After 5 minutes, the test specimen is removed from the mold. After storage for 24 hours, the aluminum paper on the underside is cut with parallel cuts with the aid of a template.
The parallel strip is pulled off to a distance of about 3 cm and clamped in a testing de-vice in a Zwick tensile testing machine. The tensile testing machine then pulls the foil strip off at a uniform speed of 100 mm/min. A force transducer is integrated into the
12 tensile apparatus to measure the force required for pulling off the foil and thus the peel adhesion value.
The peel adhesion values indicated below are the arithmetic mean of 2 independent repeat tests.
Flexural strength:
The flexural strength was determined by means of a 3-point bending test using a meth-od based on DIN 53423. Three test specimens having the dimensions 120 mm x 25 mm x 20 mm are sawn from a foam cube having an edge length of 20 cm. In the bend-ing test, the test specimen is positioned on two supports having a spacing of 100 mm and a single force F is applied in the middle. As measurement results, the flexure and also the force at fracture or at 20 mm flexure are determined. The flexural strength is calculated therefrom as the ratio of bending moment in the middle of the test specimen at fracture and the resistance moment of its cross section.
Production of the rigid polyurethane foams The isocyanates and the components which are reactive toward isocyanate were foamed together with the blowing agents, catalysts and all further additives at a con-stant molar ratio of OH to NCO functions of 100:153 +/- 6. A constant fiber time of 49 +/- 1 seconds was in each case set by varying the amount of DMCHA and an overall foam density of 38.5 +/- 1 WI was in each case set by varying the amount of water. The amount of catalyst 2 was kept constant at 1.5% by weight and that of pentane was kept constant at 5.5% by weight, based on 100% by weight of the mixture of the polyester alcohols and polyether alcohols and the flame retardant and stabilizer and also 0.5 part of water.
The peel adhesion values indicated below are the arithmetic mean of 2 independent repeat tests.
Flexural strength:
The flexural strength was determined by means of a 3-point bending test using a meth-od based on DIN 53423. Three test specimens having the dimensions 120 mm x 25 mm x 20 mm are sawn from a foam cube having an edge length of 20 cm. In the bend-ing test, the test specimen is positioned on two supports having a spacing of 100 mm and a single force F is applied in the middle. As measurement results, the flexure and also the force at fracture or at 20 mm flexure are determined. The flexural strength is calculated therefrom as the ratio of bending moment in the middle of the test specimen at fracture and the resistance moment of its cross section.
Production of the rigid polyurethane foams The isocyanates and the components which are reactive toward isocyanate were foamed together with the blowing agents, catalysts and all further additives at a con-stant molar ratio of OH to NCO functions of 100:153 +/- 6. A constant fiber time of 49 +/- 1 seconds was in each case set by varying the amount of DMCHA and an overall foam density of 38.5 +/- 1 WI was in each case set by varying the amount of water. The amount of catalyst 2 was kept constant at 1.5% by weight and that of pentane was kept constant at 5.5% by weight, based on 100% by weight of the mixture of the polyester alcohols and polyether alcohols and the flame retardant and stabilizer and also 0.5 part of water.
13 Table 1: Effect of an excessively high hydroxyl number of the polyol mixture Example 1 Comparative example 1 Polyesterol 2 39 16 Polyetherol 1 27.5 50.5 Polyetherol 4 5.5 5.5 Polyetherol 5 Water 0.5 0.5 Stabilizer 2.5 2.5 Polyol OHN 271 328 B2 determination [cm]
value 11 15 2nd value 9 16 3rd value 10 15 ¨4th value 11 16 B2 mean [cm] 10.25 15.5 Table 1 shows that excessively high OH numbers of the polyol component have an adverse effect on the flame resistance.
Table 2: Effect of an excessively low hydroxyl number of the polyol mixture or the ab-sence of a polyether alcohol bii) Comparative Comparative Comparative Example 1 example 2 example 3 example 4 Polyesterol 2 39 , 39 72 66.5 Polyetherol 1 27.5 Polyetherol 4 5.5 5.5 5.5 , Polyetherol 5 27.5 Water 0.5 0.5 0.5 0.5 , Stabilizer 2.5 2.5 2.5 2.5 Polyol OHN 271 165 208 204
value 11 15 2nd value 9 16 3rd value 10 15 ¨4th value 11 16 B2 mean [cm] 10.25 15.5 Table 1 shows that excessively high OH numbers of the polyol component have an adverse effect on the flame resistance.
Table 2: Effect of an excessively low hydroxyl number of the polyol mixture or the ab-sence of a polyether alcohol bii) Comparative Comparative Comparative Example 1 example 2 example 3 example 4 Polyesterol 2 39 , 39 72 66.5 Polyetherol 1 27.5 Polyetherol 4 5.5 5.5 5.5 , Polyetherol 5 27.5 Water 0.5 0.5 0.5 0.5 , Stabilizer 2.5 2.5 2.5 2.5 Polyol OHN 271 165 208 204
14 Indentation test [N]
2.5 min 47 19 30 34 3 min 61 , 23 38 43 4 min 80 30 55 58 min 97 37 67 69 6 min 108 42 73 82 7 min 119 46 84 88 Peel adhe-sion [N] 9.4 5.8 5.2 3.8 Table 2 shows that excessively low OH numbers of the polyol component or the ab-sence of the polyether alcohol bii) have an adverse effect on the peel adhesion and curing.
Table 3: Effect of the use of a polyether alcohol having a low functionality and a low hydroxyl number Example 1 Example 5 Polyesterol 2 39 39 Polyetherol 1 27.5 33 Polyetherol 3 Polyetherol 4 5.5 Polyetherol 5 Water 0.5 0.5 Stabilizer 2.5 2.5 Polyol OHN 271 288 B2 determina-tion [cm]
1stva1ue 11 12 2nd value 9 13 3rd value 10 12 41h value 11 14 B2 mean [cm] 10.25 12.75 Peel adhesion [N] 9.4 8.7 Table 3 shows that the use of a low-functionality polyether having a low hydroxyl num-ber in the polyol component improves the fire resistance and peel adhesion of the foam.
Table 4: Effect of the use of an oleic acid-based polyester alcohol Example 2 Example 6 Polyesterol 1 39.5 Polyesterol 2 , 39 Polyetherol 1 22.5 27.5 Polyetherol 3 5 5 Polyetherol 4 5.5 Water 0.5 0.5 Stabilizer 2.5 2.5 B2 determi-nation [cm]
1s, value 12 12 2nd value 12 13 3rd value 10 13 4th value 11 12 B2 mean 11.25 12.5 Peel adhe-sion [N] 9.3 5.9 Table 4 shows that the use of an oleic acid-based ester significantly improves the ad-hesion. Furthermore, this table shows that the use of a terephthalic acid-based ester 10 significantly improves the burning behavior.
Table 5: Effect of the use of a sorbitol-initiated polyether alcohol Example 1 according to the invention Comparative example 7 Polyesterol 2 39 39 Polyetherol 1 27.5 Polyetherol 2 27.5 Polyetherol 4 5.5 5.5 Water 0.5 0.5 Stabilizer 2.5 2.5 Polyol OHN 271 271 Indentation test [N]
2.5 min 47 50 3 min 61 65 4 min 80 84 min 97 99 6 min 108 115 7 min 119 116 Flexural strength [N/mm2] 0.17 0.21 Table 5 shows that the use of a sorbitol-initiated polyether alcohol in the polyol compo-nent improves the curing and the flexural strength.
2.5 min 47 19 30 34 3 min 61 , 23 38 43 4 min 80 30 55 58 min 97 37 67 69 6 min 108 42 73 82 7 min 119 46 84 88 Peel adhe-sion [N] 9.4 5.8 5.2 3.8 Table 2 shows that excessively low OH numbers of the polyol component or the ab-sence of the polyether alcohol bii) have an adverse effect on the peel adhesion and curing.
Table 3: Effect of the use of a polyether alcohol having a low functionality and a low hydroxyl number Example 1 Example 5 Polyesterol 2 39 39 Polyetherol 1 27.5 33 Polyetherol 3 Polyetherol 4 5.5 Polyetherol 5 Water 0.5 0.5 Stabilizer 2.5 2.5 Polyol OHN 271 288 B2 determina-tion [cm]
1stva1ue 11 12 2nd value 9 13 3rd value 10 12 41h value 11 14 B2 mean [cm] 10.25 12.75 Peel adhesion [N] 9.4 8.7 Table 3 shows that the use of a low-functionality polyether having a low hydroxyl num-ber in the polyol component improves the fire resistance and peel adhesion of the foam.
Table 4: Effect of the use of an oleic acid-based polyester alcohol Example 2 Example 6 Polyesterol 1 39.5 Polyesterol 2 , 39 Polyetherol 1 22.5 27.5 Polyetherol 3 5 5 Polyetherol 4 5.5 Water 0.5 0.5 Stabilizer 2.5 2.5 B2 determi-nation [cm]
1s, value 12 12 2nd value 12 13 3rd value 10 13 4th value 11 12 B2 mean 11.25 12.5 Peel adhe-sion [N] 9.3 5.9 Table 4 shows that the use of an oleic acid-based ester significantly improves the ad-hesion. Furthermore, this table shows that the use of a terephthalic acid-based ester 10 significantly improves the burning behavior.
Table 5: Effect of the use of a sorbitol-initiated polyether alcohol Example 1 according to the invention Comparative example 7 Polyesterol 2 39 39 Polyetherol 1 27.5 Polyetherol 2 27.5 Polyetherol 4 5.5 5.5 Water 0.5 0.5 Stabilizer 2.5 2.5 Polyol OHN 271 271 Indentation test [N]
2.5 min 47 50 3 min 61 65 4 min 80 84 min 97 99 6 min 108 115 7 min 119 116 Flexural strength [N/mm2] 0.17 0.21 Table 5 shows that the use of a sorbitol-initiated polyether alcohol in the polyol compo-nent improves the curing and the flexural strength.
Claims (16)
1. A process for producing rigid polyurethane foams by reacting a) polyisocyanates with b) compounds having at least two hydrogen atoms which are reactive toward isocyanate groups in the presence of c) blowing agents, in the presence of flame retardants d), wherein the compounds b) having at least two hydrogen atoms which are reactive toward isocyanate groups comprise - at least one aromatic polyester alcohol bi) prepared using at least one fatty acid, - at least one polyether alcohol bii) having a functionality of from 4 to 8 and a hydroxyl number in the range from 300 to 600 mg KOH/g, and - at least one polyether alcohol biii) having a functionality of from 2 to 4 and a hydroxyl number in the range from 100 to < 300 mg KOH/g, where the weight ratio of the component bi) to the sum of the components bii) and biii) is less than 4 and greater than 0.15.
2. The process according to claim 1, wherein the hydroxyl number of the compo-nent b) is at least 175 mg KOH/g.
3. The process according to claim 1, wherein the hydroxyl number of the compo-nent b) is not more than 325 mg KOH/g.
4. The process according to claim 1, wherein the polyester alcohol bi) has a func-tionality of from 2 to 3 and a hydroxyl number of from 200 to 300 mg KOH/g.
5. The process according to claim 1, wherein the polyester alcohol bi) is prepared using aromatic carboxylic acids or anhydrides thereof.
6. The process according to claim 1, wherein the polyester alcohol bi) is prepared using aromatic carboxylic acids or anhydrides thereof selected from the group consisting of terephthalic acid, phthalic acid and phthalic anhydride.
7. The process according to claim 1, wherein the polyester alcohol bi) is prepared using esters of aromatic carboxylic acids.
8. The process according to claim 1, wherein the polyester alcohol bi) is prepared using esters of aromatic carboxylic acids selected from the group consisting of polyethylene terephthalate and dimethyl terephthalate.
9. The process according to claim 6, wherein the polyester alcohol bi) is prepared using exclusively terephthalic acid.
10. The process according to claim 5, wherein the polyester alcohol bi) is prepared using at least 50% by weight, based on the weight of the carboxylic acid used, of terephthalic acid.
11. The process according to claim 1, wherein the polyester alcohol bi) comprises a content of components having a functionality of 2.9 of at least 200 mmol/kg of polyester alcohol.
12. The process according to claim 1, wherein hydrocarbons are used as blowing agents c).
13. The process according to claim 1, wherein the flame retardant d) is used in an amount of from 10 to 55% by weight, based on the weight of the sum of the components b) and d).
14. The process according to claim 1, wherein the flame retardant does not com-prise any groups which are reactive toward isocyanate groups.
15. The process according to claim 1, wherein the flame retardant comprises phos-phorus atoms in the molecule.
16. A rigid polyurethane foam produced according to any one of claims 1 to 15.
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CN105367742B (en) * | 2015-12-10 | 2018-04-24 | 上海东大聚氨酯有限公司 | Combined polyether, polyurethane foam and its preparation method and application |
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US11091652B2 (en) | 2017-01-25 | 2021-08-17 | Basf Se | Cold flexible polyurethane formulation |
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US5648019A (en) * | 1995-11-01 | 1997-07-15 | Basf Corporation | Three component polyol blend for use in insulating rigid polyurethane foams |
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JP2000264945A (en) | 1999-03-16 | 2000-09-26 | Toyo Tire & Rubber Co Ltd | Production of polyurethane foam modified with isocyanurate |
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US7601761B2 (en) * | 2007-02-26 | 2009-10-13 | Bayer Materialscience Llc | Rigid polyurethane foams with increased heat performance |
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