US20050124711A1 - Polyurethane foam - Google Patents
Polyurethane foam Download PDFInfo
- Publication number
- US20050124711A1 US20050124711A1 US10/505,148 US50514805A US2005124711A1 US 20050124711 A1 US20050124711 A1 US 20050124711A1 US 50514805 A US50514805 A US 50514805A US 2005124711 A1 US2005124711 A1 US 2005124711A1
- Authority
- US
- United States
- Prior art keywords
- foam
- range
- polyester
- dimer fatty
- acid
- 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 description 36
- 239000011496 polyurethane foam Substances 0.000 title claims description 36
- 239000000539 dimer Substances 0.000 claims abstract description 52
- 229920000728 polyester Polymers 0.000 claims abstract description 48
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 27
- 239000000194 fatty acid Substances 0.000 claims abstract description 27
- 229930195729 fatty acid Natural products 0.000 claims abstract description 27
- 150000002009 diols Chemical class 0.000 claims abstract description 26
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 26
- 239000006260 foam Substances 0.000 claims abstract description 25
- 239000004970 Chain extender Substances 0.000 claims abstract description 19
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 16
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 30
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 20
- 230000007062 hydrolysis Effects 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 235000011037 adipic acid Nutrition 0.000 claims description 10
- 239000001361 adipic acid Substances 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 13
- 239000004814 polyurethane Substances 0.000 abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 12
- 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 11
- 239000000203 mixture Substances 0.000 description 10
- -1 polyoxypropylene Polymers 0.000 description 10
- 239000012948 isocyanate Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 229920005862 polyol Polymers 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 5
- 239000004604 Blowing Agent Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- PGYPOBZJRVSMDS-UHFFFAOYSA-N loperamide hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(C=1C=CC=CC=1)(C(=O)N(C)C)CCN(CC1)CCC1(O)C1=CC=C(Cl)C=C1 PGYPOBZJRVSMDS-UHFFFAOYSA-N 0.000 description 3
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229920003054 adipate polyester Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-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
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- FQAMAOOEZDRHHB-UHFFFAOYSA-N 1,2,2-trichloro-1,1-difluoroethane Chemical compound FC(F)(Cl)C(Cl)Cl FQAMAOOEZDRHHB-UHFFFAOYSA-N 0.000 description 1
- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-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
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 1
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 1
- QJGNSTCICFBACB-UHFFFAOYSA-N 2-octylpropanedioic acid Chemical compound CCCCCCCCC(C(O)=O)C(O)=O QJGNSTCICFBACB-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- NBPOOCGXISZKSX-UHFFFAOYSA-N 6-methylheptyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)CCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NBPOOCGXISZKSX-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- KYXHKHDZJSDWEF-LHLOQNFPSA-N CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 Chemical compound CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 KYXHKHDZJSDWEF-LHLOQNFPSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 244000061944 Helianthus giganteus Species 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000008121 dextrose Substances 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
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- YSFZWUJOBANROZ-UHFFFAOYSA-N heptylmalonic acid Chemical compound CCCCCCCC(C(O)=O)C(O)=O YSFZWUJOBANROZ-UHFFFAOYSA-N 0.000 description 1
- SAMYCKUDTNLASP-UHFFFAOYSA-N hexane-2,2-diol Chemical compound CCCCC(C)(O)O SAMYCKUDTNLASP-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 1
- 235000021281 monounsaturated fatty acids Nutrition 0.000 description 1
- QBYNWJVTTUAPCT-UHFFFAOYSA-N n,n'-bis(2-chlorophenyl)methanediamine Chemical compound ClC1=CC=CC=C1NCNC1=CC=CC=C1Cl QBYNWJVTTUAPCT-UHFFFAOYSA-N 0.000 description 1
- MQXZIFFLHHSLOY-UHFFFAOYSA-N n,n'-dipropyl-n,n'-bis(2-propylphenyl)methanediamine Chemical compound C=1C=CC=C(CCC)C=1N(CCC)CN(CCC)C1=CC=CC=C1CCC MQXZIFFLHHSLOY-UHFFFAOYSA-N 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 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 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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
- C08G18/42—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
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
- A43B13/18—Resilient soles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy 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
- 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
-
- 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
- C08G2120/00—Compositions for reaction injection moulding processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
Definitions
- the present invention relates to a microcellular polyurethane foam, a process of making the foam, and in particular to the use thereof in shoe soles.
- Polyurethanes are extremely versatile materials and have been used in a wide variety of applications such as foam insulation, car seats and abrasion resistant coatings. Polyurethanes are used in a wide variety of forms, for example non-cellular materials such as elastomers; and cellular materials such as low density flexible foams, high density flexible foams, and microcellular foams. Microcellular foams have been used for energy absorbing bumper mountings and auxiliary suspension units for wheels, and in particular in shoe soles.
- Microcellular polyurethane foams used in shoe soles require a wide range of properties such as resistance and durability in actual use, combined with high flexibility, optimal impact resilience, low weight, high thermal insulation and cushioning. There is a need for microcellular polyurethane foams to provide an improvement in one or more of the aforementioned properties.
- known shoe soling materials tend to have insufficient flexibility on repeated flexing at low temperature (due to strain hardening), and hydrolytic instability.
- EP-0795572-A is directed to the use of a polyester polyol, derived from terephthalic acid and adipic acid, to produce polyurethane foam for shoe soles.
- U.S. Pat. No. 5,856,372 is directed to a microcellular polyurethane shoe sole component formed from isocyanate-terminated prepolymers derived from polyoxypropylene diols.
- microcellular polyurethane foam which reduces or substantially overcomes at least one of the aforementioned problems.
- the present invention provides a microcellular polyurethane foam obtainable by reacting a polyisocyanate, a polyester formed from a dimer fatty acid and/or dimer fatty diol, and a chain extender.
- the invention also provides a process for preparing a microcellular polyurethane foam which comprises (i) reacting a polyisocyanate with a polyester formed from a dimer fatty acid and/or dimer fatty diol, to form an isocyanate-terminated prepolymer, and (ii) reacting the prepolymer with a chain extender.
- the invention further provides an isocyanate-terminated prepolymer which is the reaction product of a polyisocyanate and a polyester which is the reaction product of dimer fatty acid, adipic acid and diethylene glycol.
- the invention still further provides a shoe sole comprising a microcellular polyurethane foam obtainable by reacting a polyisocyanate, a polyester formed from a dimer fatty acid and/or dimer fatty diol, and a chain extender.
- the polyester used in the present invention is formed from, ie comprises the reaction product of, at least one dimer fatty acid and/or dimer fatty diol and/or equivalent thereof.
- Polyester is normally produced in a condensation reaction between at least one polycarboxylic acid and at least one polyol.
- Dicarboxylic acids and diols are preferred.
- the preferred dicarboxylic acid component of the polyester used in the present invention preferably comprises at least one dimer fatty acid.
- dimer fatty acid is well known in the art and refers to the dimerisation product of mono- or polyunsaturated fatty acids and/or esters thereof.
- Preferred dimer fatty acids are dimers of C 10 to C 30 , more preferably C 12 to C 24 , particularly C 14 to C 22 , and especially C 18 alkyl chains.
- Suitable dimer fatty acids include the dimerisation products of oleic acid, linoleic acid, linolenic acid, palmitoleic acid, and elaidic acid.
- the dimerisation products of the unsaturated fatty acid mixtures obtained in the hydrolysis of natural fats and oils, e.g. sunflower oil, soybean oil, olive oil, rapeseed oil, cottonseed oil and tall oil, may also be used. Hydrogenated, for example by using a nickel catalyst, dimer fatty acids may also be employed.
- dimerisation usually results in varying amounts of oligomeric fatty acids (so-called “trimer”) and residues of monomeric fatty acids (so-called “monomer”), or esters thereof, being present.
- the amount of monomer can, for example, be reduced by distillation.
- Suitable dimer fatty acids have a dicarboxylic (or dimer) content of greater than 60%, preferably greater than 75%, more preferably in the range from 80 to 96%, particularly 85 to 92%, and especially 87 to 89% by weight.
- the trimer content is suitably less than 40%, preferably in the range from 2 to 25%, more preferably 5 to 15%, particularly 7 to 13%, and especially 9 to 11% by weight.
- the monomer content is preferably less than 10%, more preferably in the range from 0.2 to 5%, particularly 0.5 to 3%, and especially 1 to 2% by weight. All of the above % by weight values are based on the total weight of trimer, dimer and monomer present.
- the dicarboxylic acid component of the polyester preferably also comprises non-dimeric dicarboxylic acids (hereinafter referred to as non-dimeric acids).
- the non-dimeric acids may be aliphatic or aromatic (such as phthalic acid, isophthalic acid and terephthalic acid), and include dicarboxylic acids and the esters, preferably alkyl esters, thereof, preferably linear dicarboxylic acids having terminal carboxyl groups having a carbon chain in the range from 2 to 20, more preferably 6 to 12 carbon atoms, such as adipic acid, glutaric acid, succinic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, heptane dicarboxylic acid, octane dicarboxylic acid, nonane dicarboxylic acid, decane dicarboxylic acid, undecane dicarboxylic acid, dodecane dicarboxylic acid and higher homologs thereof.
- a monomeric dicarboxylic acid anhydride such as phthalic anhydride, may also be employed as the or as part of the non-dimeric acid component.
- the polyester is preferably formed from dimer fatty acids to non-dimer acids present at a ratio in the range from 10 to 100:0 to 90%, more preferably 30 to 70:30 to 70%, particularly 40 to 60:40 to 60%, and especially 45 to 55:45 to 55% by weight of the total dicarboxylic acids.
- the polyol component of the polyester used in the present invention suitably has a molecular weight in the range from 50 to 650, preferably 60 to 250, more preferably 70 to 200, and particularly 100 to 150.
- the polyol component may comprise polyols such as pentaerythritol, triols such as glycerol and trimethylolpropane, and preferably diols.
- Suitable diols include straight chain aliphatic diols such as ethylene glycol, diethylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, branched diols such as neopentyl glycol, 3-methyl pentane glycol, 1,2-propylene glycol, and cyclic diols such as 1,4-bis(hydroxymethyl)cyclohexane and (1,4-cyclohexane-dimethanol).
- Diethylene glycol is a particularly preferred diol.
- the polyol component may also comprise a dimer fatty diol.
- Dimer fatty acids are mentioned above in relation to the dicarboxylic acid component, and dimer fatty diols can be produced by hydrogenation of the corresponding dimer fatty acid.
- the same preferences above for the dimer fatty acid apply to the corresponding dimer fatty diol component of the polyester.
- the polyester is preferably formed from dicarboxylic acid to diol starting materials at a molar ratio in the range from 1:1.0 to 5.0, more preferably 1:1.05 to 3.0, particularly 1:1.1 to 2.0, and especially 1:1.2 to 1.4.
- the diol is preferably present in molar excess so as to obtain a polyester terminated at both ends with OH groups.
- the polyester is formed from dimer fatty acid, adipic acid, and diethylene glycol, preferably at a weight ratio in the range from 0.3 to 0.7:0.3 to 0.7:1.0 to 3.0, more preferably 0.4 to 0.6:0.4 to 0.6:1.1 to 2.0, particularly 0.45 to 0.55:0.45 to 0.55:1.2 to 1.4, and especially approximately 0.5:0.5:1.3.
- the polyester preferably has a molecular weight number average in the range from 1,000 to 5,000, more preferably 1,700 to 3,000, particularly 1,800 to 2,500, and especially 1,900 to 2,200.
- the polyester preferably has a glass transition temperature (Tg) value (measured as described herein) in the range from ⁇ 60 to 0° C., more preferably ⁇ 50 to ⁇ 5° C., particularly ⁇ 40 to ⁇ 10° C., and especially ⁇ 35 to ⁇ 15° C.
- Tg glass transition temperature
- the polyester preferably has a hydroxyl value (measured as described herein) in the range from 10 to 100, more preferably 30 to 80, particularly 40 to 70, and especially 50 to 60 mgKOH/g.
- the polyester preferably has an acid value (measured as described herein) of less than 2, more preferably less than 1.7, particularly less than 1.3, and especially less than 1.0.
- the polyisocyanate component is preferably at least one isocyanate which has a functionality of at least 2, and may be an aliphatic isocyanate such as hexamethylene 1,6-diisocyanate, but more preferably is an aromatic isocyanate such as tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylenepolyphenyl diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 3,3-dichloro-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, or modified compounds thereof such as
- the polyisocyanate monomers can be used alone or as mixtures thereof.
- 4,4′-diphenylmethane diisocyanate (MDI) is used alone, or more preferably a mixture of MDI and a uretonimine-modified 4,4′-diphenylmethane diisocyanate (modified MDI) is employed.
- At least one of the aforementioned polyisocyanates is reacted with at least one of the aforementioned polyesters, to form a prepolymer.
- the ratio of polyisocyanate to polyester starting materials which are mixed together to react to form the prepolymer is preferably in the range from 20 to 80:20 to 80%, more preferably 35 to 75:25 to 65%, particularly 45 to 70:30 to 55%, and especially 55 to 65:35 to 45% by weight.
- the polyisocyanate is preferably used in molar excess relative to OH group content of the polyester, so as to obtain a reaction mixture containing isocyanate-terminated prepolymer and sufficient unreacted polyisocyanate, such that later addition of the chain extender can result in reaction to form the polyurethane foam, without the requirement for adding further polyisocyanate.
- the prepolymer reaction mixture preferably has an isocyanate content (measured as described herein) in the range from 5 to 30%, more preferably 15 to 23%, particularly 17 to 20%, and especially 18 to 19% NCO.
- the chain extender component used to form the polyurethane suitably comprises a low molecular compound having 2 or more active hydrogen groups, for example polyols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butylene glycol, 1,5-pentylene glycol, methylpentanediol, 1,6-hexylene glycol, neopentyl glycol, trimethylolpropane, hydroquinone ether alkoxylate, resorcinol ether alkoxylate, glycerol, pentaerythritol, diglycerol, and dextrose; aliphatic polyhydric amines such as ethylenediamine, hexamethylenediamine, and isophorone diamine; aromatic polyhydric amines such as methylene-bis(2-chloroaniline), methylenebis(dipropylaniline), diethyltoluenediamine, trimethylene glycol di-p-amin
- the chain extender is a polyol, more preferably a diol, particularly having an aliphatic linear carbon chain comprising in the range from 1 to 10, and especially 3 to 5 carbon atoms.
- Preferred diols include ethylene glycol, propylene glycol, 1,4-butylene glycol, and 1,5-pentylene glycol. 1,4-butylene glycol is particularly preferred.
- At least one of the aforementioned polyesters is added together with the chain extender to react with the prepolymer in order to form the polyurethane.
- the molar ratio of chain extender to polyester employed is preferably in the range from 1 to 10:1, more preferably 1.5 to 8:1, particularly 2 to 5:1, and especially 2.5 to 4:1.
- the polyester employed may be the same as or different to the polyester used to form the prepolymer.
- non-dimer (acid or diol) containing polyester may also be employed in forming the microcellular polyurethane foam, in addition to the dimer fatty (acid and/or diol) containing polyesters described herein.
- Suitable non-dimer containing materials include polyesters derived from adipic acid and common diols such as ethylene glycol, diethylene glycol, 1,4-butylene glycol, or speciality glycols and other special ingredients, eg caprolactone.
- the microcellular polyurethane foam is formed from dimer-containing polyester to non-dimer containing polyester (both used as the polyester and/or in isocyanate-terminated prepolymer form) preferably at a ratio in the range from 10 to 95:5 to 90, more preferably 30 to 90:10 to 70, particularly 40 to 80:20 to 60, and especially 50 to 70:30 to 50% by weight.
- the dimer fatty acid and/or dimer fatty diol content of the polyurethane foam is preferably in the range from 5 to 50%, more preferably 8 to 40%, particularly 12 to 30%, and especially 15 to 20% by weight.
- the chain extender composition may optionally contain other additives such as blowing agents, urethane promoting catalysts, surfactants, stabilizers and pigments.
- Suitable blowing agents include water, and fluorocarbons such as trichlorofluoromethane, dichlorodifluoromethane and trichlorodifluoroethane.
- the blowing agents may be used alone or as mixtures thereof.
- urethane catalysts include tertiary amines such as triethylamine, 1,4-diazabicyclo[2.2.2.]octane (DABCO), N-methylmorpholine, N-ethylmorpholine, N,N,N′,N′-tetramethylhexamethylenediamine, 1,2-dimethylimidazol; and tin compounds such as tin(II)acetate, tin(II)octanoate, tin(II)laurate, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin diacetate and dibutyltin dichloride.
- the catalysts may be used alone or as mixtures thereof.
- Suitable surfactants include silicone surfactants such as dimethylpolysiloxane, polyoxyalkylene polyol-modified dimethylpolysiloxane and alkylene glycol-modified dimethylpolysiloxane; and anionic surfactants such as fatty acid salts, sulfuric acid ester salts, phosphoric acid ester salts and sulfonates.
- stabilizers examples include hindered phenol radical scavengers such as dibutylhydroxytoluene, pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; antioxidants such as phosphorous acid compounds such as triphenylphosphite, triethylphosphite and triphenylphosphine; ultraviolet absorbing agents such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole and a condensation product of methyl-3-[3-t-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate and polyethylene glycol.
- Suitable pigments include inorganic pigments such as transition metal salts; organic pigments such as azo compounds; and carbon powder.
- the microcellular polyurethane foam according to the present invention may be produced by efficiently mixing the prepolymer with a chain extender composition, preferably in an injection moulding polyurethane machine.
- the chain extender composition is preferably prepared by simple pre-mixing of, for example, the chain extender, polyester and other additives (such as blowing agent, and/or urethane catalyst, and/or surfactant).
- the NCO/OH ratio employed is preferably in the range from 1 to 1.2:1, more preferably 1 to 1.1:1, and particularly 1 to 1.03:1.
- the microcellular polyurethane foam according to the present invention is suitably defined as an elastomer of cellular structure containing mostly closed cells which are difficult to see with the naked eye (cell size of the order of approximately less than 0.1 mm).
- the foam preferably has a density (measured as described herein) in the range from 0.2 to 0.9, more preferably 0.25 to 0.7, particularly 0.3 to 0.6, and especially 0.35 to 0.5 gcm ⁇ 3 .
- the microcellular polyurethane foam preferably has a hardness (measured as described herein) in the range from 10 to 70, more preferably 20 to 60, particularly 25 to 55, and especially 30 to 50 Shore A.
- the microcellular polyurethane foam suitably has a tensile strength (measured as described herein) of greater than 20, preferably greater than 30, more preferably in the range from 35 to 80, particularly 40 to 75, and especially 50 to 70 kgcm ⁇ 2 .
- the elongation at break (measured as described herein) of the microcellular polyurethane foam is suitably greater than 150%, preferably greater than 200%, more preferably greater than 250%, particularly in the range from 300 to 550% and especially 350 to 400%.
- the tear strength (measured as described herein) of the microcellular polyurethane foam is preferably greater than 1.2, more preferably in the range from 1.6 to 6, particularly 2 to 5, and especially 2.5 to 4 kNm ⁇ 1 .
- the impact resilience (measured as described herein) of the microcellular polyurethane foam is suitably less than 45%, preferably in the range from 10 to 35%, more preferably 15 to 30%, particularly 18 to 27%, and especially 20 to 25%.
- a particular advantage of the microcellular polyurethane foam according to the present invention is that it is resistant to hydrolysis.
- the foam after being subjected to hydrolysis for 2 weeks, as described under test procedures herein suitably has a tensile strength and/or elongation at break, within the respective preferred values given above.
- the foam suitably retains at least 40%, preferably at least 60%, more preferably at least 80%, particularly at least 90%, and especially at least 100% of its initial tensile strength and/or initial elongation at break properties, after being subjected to hydrolysis for 2 weeks.
- the microcellular polyurethane foam preferably retains at least 20%, more preferably at least 30%, particularly at least 40%, and especially at least 50% of its initial tensile strength properties, after being subjected to hydrolysis for 4 weeks.
- the foam preferably has a tensile strength of greater than 10, more preferably in the range from 15 to 45, particularly 20 to 40, and especially 25 to 35 kgcm ⁇ 2 after being subjected to hydrolysis for 4 weeks.
- the foam also suitably retains at least 30%, preferably at least 50%, more preferably at least 70%, particularly at least 85%, and especially at least 95% of its initial elongation at break properties after being subjected to hydrolysis for 4 weeks.
- the foam suitably has an elongation at break of greater than 100%, preferably greater than 150%, more preferably greater than 200%, particularly in the range from 250 to 450% and especially 300 to 400% after being subjected to hydrolysis for 4 weeks.
- the microcellular polyurethane foam according to the present invention is suitable for use, inter alia, as shock absorbers/“spring aids” for automotive suspension, tyres (energy absorbing wheels for buggies, trollies) and technical parts (car seat components), and is particularly suitable for use in shoes.
- the foam can be used in dual density outsoles, single density boots, single density casual/formal, single density sandals, single density insoles, and especially in dual and single density midsoles.
- Tg glass transition temperature
- the hydroxyl value is defined as the number of mg of potassium hydroxide equivalent to the hydroxyl content of 1 g of sample, and was measured by acetylation followed by hydrolysation of excess acetic anhydride. The acetic acid formed was subsequently titrated with an ethanolic potassium hydroxide solution.
- the acid value is defined as the number of mg of potassium hydroxide required to neutralise the free fatty acids in 1 g of sample, and was measured by direct titration with a standard potassium hydroxide solution.
- the isocyanate value is defined as the weight % content of isocyanate in the sample and was determined by reacting with excess dibutylamine, and back titrating with hydrochloric acid.
- Samples were aged by placing dumbells of the material in a climate chamber at 70° C. and >98% relative humidity for periods of 2 and 4 weeks.
- the tensile strength and elongation at break of the “aged” samples were determined as above and the values compared to the original figures (on percentage retention terms).
- a chain extender composition was prepared by mixing the following components in the following ratio: Polyester prepared in (a) 100 DABCO DC193 silicone surfactant (ex Air Products) 0.4 1,4-butylene glycol (dry) 12 DABCO crystal (triethylene diamine, ex Air Products) 0.5 Distilled water 0.5
- the resulting polyurethane foam had the following properties, measured as described above;
- the polyurethane foam was subjected to hydrolysis conditions for 2 weeks and 4 weeks as described above, and the following properties were remeasured;
- the resulting polyurethane foam had the following properties, measured as described above;
- the polyurethane foam was subjected to hydrolysis conditions for 2 weeks and 4 weeks as described above, and the following properties were remeasured;
- the resulting adipate derived polyurethane foam had the following properties, measured as described above;
- the polyurethane foam was subjected to hydrolysis conditions for 2 weeks and 4 weeks as described above, and the following properties were remeasured;
- Example 2 This is a comparative example not according to the invention.
- the procedure according to Example 1 was repeated except that the starting materials were adipate polyester (Desmophen 2000 MZ, ex Bayer (468 g)), flake pure MDI (ex Bayer (640.4 g)) and modified MDI (Suprasec 2021, ex Huntsman Polyurethanes (123.1 g)).
- the starting materials were adipate polyester (Desmophen 2000 MZ, ex Bayer (468 g)), flake pure MDI (ex Bayer (640.4 g)) and modified MDI (Suprasec 2021, ex Huntsman Polyurethanes (123.1 g)).
- the resulting adipate derived polyurethane foam was subjected to hydrolysis conditions for 4 weeks as described above, and the following properties were measured;
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Abstract
Description
- The present invention relates to a microcellular polyurethane foam, a process of making the foam, and in particular to the use thereof in shoe soles.
- Polyurethanes are extremely versatile materials and have been used in a wide variety of applications such as foam insulation, car seats and abrasion resistant coatings. Polyurethanes are used in a wide variety of forms, for example non-cellular materials such as elastomers; and cellular materials such as low density flexible foams, high density flexible foams, and microcellular foams. Microcellular foams have been used for energy absorbing bumper mountings and auxiliary suspension units for wheels, and in particular in shoe soles.
- Microcellular polyurethane foams used in shoe soles require a wide range of properties such as resistance and durability in actual use, combined with high flexibility, optimal impact resilience, low weight, high thermal insulation and cushioning. There is a need for microcellular polyurethane foams to provide an improvement in one or more of the aforementioned properties. In particular, known shoe soling materials tend to have insufficient flexibility on repeated flexing at low temperature (due to strain hardening), and hydrolytic instability.
- EP-0795572-A is directed to the use of a polyester polyol, derived from terephthalic acid and adipic acid, to produce polyurethane foam for shoe soles.
- U.S. Pat. No. 5,856,372 is directed to a microcellular polyurethane shoe sole component formed from isocyanate-terminated prepolymers derived from polyoxypropylene diols.
- We have now surprisingly discovered a microcellular polyurethane foam which reduces or substantially overcomes at least one of the aforementioned problems.
- Accordingly, the present invention provides a microcellular polyurethane foam obtainable by reacting a polyisocyanate, a polyester formed from a dimer fatty acid and/or dimer fatty diol, and a chain extender.
- The invention also provides a process for preparing a microcellular polyurethane foam which comprises (i) reacting a polyisocyanate with a polyester formed from a dimer fatty acid and/or dimer fatty diol, to form an isocyanate-terminated prepolymer, and (ii) reacting the prepolymer with a chain extender.
- The invention further provides an isocyanate-terminated prepolymer which is the reaction product of a polyisocyanate and a polyester which is the reaction product of dimer fatty acid, adipic acid and diethylene glycol.
- The invention still further provides a shoe sole comprising a microcellular polyurethane foam obtainable by reacting a polyisocyanate, a polyester formed from a dimer fatty acid and/or dimer fatty diol, and a chain extender.
- The polyester used in the present invention is formed from, ie comprises the reaction product of, at least one dimer fatty acid and/or dimer fatty diol and/or equivalent thereof. Polyester is normally produced in a condensation reaction between at least one polycarboxylic acid and at least one polyol. Dicarboxylic acids and diols are preferred. The preferred dicarboxylic acid component of the polyester used in the present invention preferably comprises at least one dimer fatty acid.
- The term dimer fatty acid is well known in the art and refers to the dimerisation product of mono- or polyunsaturated fatty acids and/or esters thereof. Preferred dimer fatty acids are dimers of C10 to C30, more preferably C12 to C24, particularly C14 to C22, and especially C18 alkyl chains. Suitable dimer fatty acids include the dimerisation products of oleic acid, linoleic acid, linolenic acid, palmitoleic acid, and elaidic acid. The dimerisation products of the unsaturated fatty acid mixtures obtained in the hydrolysis of natural fats and oils, e.g. sunflower oil, soybean oil, olive oil, rapeseed oil, cottonseed oil and tall oil, may also be used. Hydrogenated, for example by using a nickel catalyst, dimer fatty acids may also be employed.
- In addition to the dimer fatty acids, dimerisation usually results in varying amounts of oligomeric fatty acids (so-called “trimer”) and residues of monomeric fatty acids (so-called “monomer”), or esters thereof, being present. The amount of monomer can, for example, be reduced by distillation. Suitable dimer fatty acids have a dicarboxylic (or dimer) content of greater than 60%, preferably greater than 75%, more preferably in the range from 80 to 96%, particularly 85 to 92%, and especially 87 to 89% by weight. The trimer content is suitably less than 40%, preferably in the range from 2 to 25%, more preferably 5 to 15%, particularly 7 to 13%, and especially 9 to 11% by weight. The monomer content is preferably less than 10%, more preferably in the range from 0.2 to 5%, particularly 0.5 to 3%, and especially 1 to 2% by weight. All of the above % by weight values are based on the total weight of trimer, dimer and monomer present.
- The dicarboxylic acid component of the polyester preferably also comprises non-dimeric dicarboxylic acids (hereinafter referred to as non-dimeric acids). The non-dimeric acids may be aliphatic or aromatic (such as phthalic acid, isophthalic acid and terephthalic acid), and include dicarboxylic acids and the esters, preferably alkyl esters, thereof, preferably linear dicarboxylic acids having terminal carboxyl groups having a carbon chain in the range from 2 to 20, more preferably 6 to 12 carbon atoms, such as adipic acid, glutaric acid, succinic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, heptane dicarboxylic acid, octane dicarboxylic acid, nonane dicarboxylic acid, decane dicarboxylic acid, undecane dicarboxylic acid, dodecane dicarboxylic acid and higher homologs thereof. Adipic acid is particularly preferred.
- A monomeric dicarboxylic acid anhydride, such as phthalic anhydride, may also be employed as the or as part of the non-dimeric acid component.
- The polyester is preferably formed from dimer fatty acids to non-dimer acids present at a ratio in the range from 10 to 100:0 to 90%, more preferably 30 to 70:30 to 70%, particularly 40 to 60:40 to 60%, and especially 45 to 55:45 to 55% by weight of the total dicarboxylic acids.
- The polyol component of the polyester used in the present invention suitably has a molecular weight in the range from 50 to 650, preferably 60 to 250, more preferably 70 to 200, and particularly 100 to 150. The polyol component may comprise polyols such as pentaerythritol, triols such as glycerol and trimethylolpropane, and preferably diols. Suitable diols include straight chain aliphatic diols such as ethylene glycol, diethylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, branched diols such as neopentyl glycol, 3-methyl pentane glycol, 1,2-propylene glycol, and cyclic diols such as 1,4-bis(hydroxymethyl)cyclohexane and (1,4-cyclohexane-dimethanol). Diethylene glycol is a particularly preferred diol.
- The polyol component may also comprise a dimer fatty diol. Dimer fatty acids are mentioned above in relation to the dicarboxylic acid component, and dimer fatty diols can be produced by hydrogenation of the corresponding dimer fatty acid. The same preferences above for the dimer fatty acid apply to the corresponding dimer fatty diol component of the polyester.
- The polyester is preferably formed from dicarboxylic acid to diol starting materials at a molar ratio in the range from 1:1.0 to 5.0, more preferably 1:1.05 to 3.0, particularly 1:1.1 to 2.0, and especially 1:1.2 to 1.4. Thus, the diol is preferably present in molar excess so as to obtain a polyester terminated at both ends with OH groups.
- In a preferred embodiment, the polyester is formed from dimer fatty acid, adipic acid, and diethylene glycol, preferably at a weight ratio in the range from 0.3 to 0.7:0.3 to 0.7:1.0 to 3.0, more preferably 0.4 to 0.6:0.4 to 0.6:1.1 to 2.0, particularly 0.45 to 0.55:0.45 to 0.55:1.2 to 1.4, and especially approximately 0.5:0.5:1.3.
- The polyester preferably has a molecular weight number average in the range from 1,000 to 5,000, more preferably 1,700 to 3,000, particularly 1,800 to 2,500, and especially 1,900 to 2,200.
- The polyester preferably has a glass transition temperature (Tg) value (measured as described herein) in the range from −60 to 0° C., more preferably −50 to −5° C., particularly −40 to −10° C., and especially −35 to −15° C.
- The polyester preferably has a hydroxyl value (measured as described herein) in the range from 10 to 100, more preferably 30 to 80, particularly 40 to 70, and especially 50 to 60 mgKOH/g. In addition, the polyester preferably has an acid value (measured as described herein) of less than 2, more preferably less than 1.7, particularly less than 1.3, and especially less than 1.0.
- The polyisocyanate component is preferably at least one isocyanate which has a functionality of at least 2, and may be an aliphatic isocyanate such as hexamethylene 1,6-diisocyanate, but more preferably is an aromatic isocyanate such as tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylenepolyphenyl diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 3,3-dichloro-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, or modified compounds thereof such as uretonimine-modified compounds thereof. The polyisocyanate monomers can be used alone or as mixtures thereof. In a preferred embodiment, 4,4′-diphenylmethane diisocyanate (MDI) is used alone, or more preferably a mixture of MDI and a uretonimine-modified 4,4′-diphenylmethane diisocyanate (modified MDI) is employed.
- In one embodiment of the invention, at least one of the aforementioned polyisocyanates is reacted with at least one of the aforementioned polyesters, to form a prepolymer. The ratio of polyisocyanate to polyester starting materials which are mixed together to react to form the prepolymer is preferably in the range from 20 to 80:20 to 80%, more preferably 35 to 75:25 to 65%, particularly 45 to 70:30 to 55%, and especially 55 to 65:35 to 45% by weight. The polyisocyanate is preferably used in molar excess relative to OH group content of the polyester, so as to obtain a reaction mixture containing isocyanate-terminated prepolymer and sufficient unreacted polyisocyanate, such that later addition of the chain extender can result in reaction to form the polyurethane foam, without the requirement for adding further polyisocyanate.
- The prepolymer reaction mixture preferably has an isocyanate content (measured as described herein) in the range from 5 to 30%, more preferably 15 to 23%, particularly 17 to 20%, and especially 18 to 19% NCO.
- The chain extender component used to form the polyurethane suitably comprises a low molecular compound having 2 or more active hydrogen groups, for example polyols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butylene glycol, 1,5-pentylene glycol, methylpentanediol, 1,6-hexylene glycol, neopentyl glycol, trimethylolpropane, hydroquinone ether alkoxylate, resorcinol ether alkoxylate, glycerol, pentaerythritol, diglycerol, and dextrose; aliphatic polyhydric amines such as ethylenediamine, hexamethylenediamine, and isophorone diamine; aromatic polyhydric amines such as methylene-bis(2-chloroaniline), methylenebis(dipropylaniline), diethyltoluenediamine, trimethylene glycol di-p-aminobenzoate; alkanolamines such as diethanolamine, triethanolamine and diisopropanolamine.
- In a preferred embodiment of the invention, the chain extender is a polyol, more preferably a diol, particularly having an aliphatic linear carbon chain comprising in the range from 1 to 10, and especially 3 to 5 carbon atoms. Preferred diols include ethylene glycol, propylene glycol, 1,4-butylene glycol, and 1,5-pentylene glycol. 1,4-butylene glycol is particularly preferred.
- In a particularly preferred embodiment of the invention, at least one of the aforementioned polyesters is added together with the chain extender to react with the prepolymer in order to form the polyurethane. The molar ratio of chain extender to polyester employed is preferably in the range from 1 to 10:1, more preferably 1.5 to 8:1, particularly 2 to 5:1, and especially 2.5 to 4:1. The polyester employed may be the same as or different to the polyester used to form the prepolymer.
- In one embodiment of the invention, non-dimer (acid or diol) containing polyester, may also be employed in forming the microcellular polyurethane foam, in addition to the dimer fatty (acid and/or diol) containing polyesters described herein. Suitable non-dimer containing materials include polyesters derived from adipic acid and common diols such as ethylene glycol, diethylene glycol, 1,4-butylene glycol, or speciality glycols and other special ingredients, eg caprolactone.
- When the optional non-dimer containing polyester is present, the microcellular polyurethane foam is formed from dimer-containing polyester to non-dimer containing polyester (both used as the polyester and/or in isocyanate-terminated prepolymer form) preferably at a ratio in the range from 10 to 95:5 to 90, more preferably 30 to 90:10 to 70, particularly 40 to 80:20 to 60, and especially 50 to 70:30 to 50% by weight.
- The dimer fatty acid and/or dimer fatty diol content of the polyurethane foam is preferably in the range from 5 to 50%, more preferably 8 to 40%, particularly 12 to 30%, and especially 15 to 20% by weight.
- In the present invention, the chain extender composition may optionally contain other additives such as blowing agents, urethane promoting catalysts, surfactants, stabilizers and pigments.
- Suitable blowing agents include water, and fluorocarbons such as trichlorofluoromethane, dichlorodifluoromethane and trichlorodifluoroethane. The blowing agents may be used alone or as mixtures thereof.
- Examples of urethane catalysts include tertiary amines such as triethylamine, 1,4-diazabicyclo[2.2.2.]octane (DABCO), N-methylmorpholine, N-ethylmorpholine, N,N,N′,N′-tetramethylhexamethylenediamine, 1,2-dimethylimidazol; and tin compounds such as tin(II)acetate, tin(II)octanoate, tin(II)laurate, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin diacetate and dibutyltin dichloride. The catalysts may be used alone or as mixtures thereof.
- Suitable surfactants include silicone surfactants such as dimethylpolysiloxane, polyoxyalkylene polyol-modified dimethylpolysiloxane and alkylene glycol-modified dimethylpolysiloxane; and anionic surfactants such as fatty acid salts, sulfuric acid ester salts, phosphoric acid ester salts and sulfonates.
- Examples of the stabilizers include hindered phenol radical scavengers such as dibutylhydroxytoluene, pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; antioxidants such as phosphorous acid compounds such as triphenylphosphite, triethylphosphite and triphenylphosphine; ultraviolet absorbing agents such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole and a condensation product of methyl-3-[3-t-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate and polyethylene glycol. Suitable pigments include inorganic pigments such as transition metal salts; organic pigments such as azo compounds; and carbon powder.
- The microcellular polyurethane foam according to the present invention may be produced by efficiently mixing the prepolymer with a chain extender composition, preferably in an injection moulding polyurethane machine. The chain extender composition is preferably prepared by simple pre-mixing of, for example, the chain extender, polyester and other additives (such as blowing agent, and/or urethane catalyst, and/or surfactant). In the polyurethane synthesis, the NCO/OH ratio employed is preferably in the range from 1 to 1.2:1, more preferably 1 to 1.1:1, and particularly 1 to 1.03:1.
- The microcellular polyurethane foam according to the present invention is suitably defined as an elastomer of cellular structure containing mostly closed cells which are difficult to see with the naked eye (cell size of the order of approximately less than 0.1 mm). The foam preferably has a density (measured as described herein) in the range from 0.2 to 0.9, more preferably 0.25 to 0.7, particularly 0.3 to 0.6, and especially 0.35 to 0.5 gcm−3.
- The microcellular polyurethane foam preferably has a hardness (measured as described herein) in the range from 10 to 70, more preferably 20 to 60, particularly 25 to 55, and especially 30 to 50 Shore A.
- The microcellular polyurethane foam suitably has a tensile strength (measured as described herein) of greater than 20, preferably greater than 30, more preferably in the range from 35 to 80, particularly 40 to 75, and especially 50 to 70 kgcm−2.
- The elongation at break (measured as described herein) of the microcellular polyurethane foam is suitably greater than 150%, preferably greater than 200%, more preferably greater than 250%, particularly in the range from 300 to 550% and especially 350 to 400%.
- The tear strength (measured as described herein) of the microcellular polyurethane foam is preferably greater than 1.2, more preferably in the range from 1.6 to 6, particularly 2 to 5, and especially 2.5 to 4 kNm−1.
- The impact resilience (measured as described herein) of the microcellular polyurethane foam is suitably less than 45%, preferably in the range from 10 to 35%, more preferably 15 to 30%, particularly 18 to 27%, and especially 20 to 25%.
- A particular advantage of the microcellular polyurethane foam according to the present invention is that it is resistant to hydrolysis. Thus, the foam after being subjected to hydrolysis for 2 weeks, as described under test procedures herein, suitably has a tensile strength and/or elongation at break, within the respective preferred values given above. The foam suitably retains at least 40%, preferably at least 60%, more preferably at least 80%, particularly at least 90%, and especially at least 100% of its initial tensile strength and/or initial elongation at break properties, after being subjected to hydrolysis for 2 weeks.
- In addition, the microcellular polyurethane foam preferably retains at least 20%, more preferably at least 30%, particularly at least 40%, and especially at least 50% of its initial tensile strength properties, after being subjected to hydrolysis for 4 weeks. The foam preferably has a tensile strength of greater than 10, more preferably in the range from 15 to 45, particularly 20 to 40, and especially 25 to 35 kgcm−2 after being subjected to hydrolysis for 4 weeks. The foam also suitably retains at least 30%, preferably at least 50%, more preferably at least 70%, particularly at least 85%, and especially at least 95% of its initial elongation at break properties after being subjected to hydrolysis for 4 weeks. The foam suitably has an elongation at break of greater than 100%, preferably greater than 150%, more preferably greater than 200%, particularly in the range from 250 to 450% and especially 300 to 400% after being subjected to hydrolysis for 4 weeks.
- The microcellular polyurethane foam according to the present invention is suitable for use, inter alia, as shock absorbers/“spring aids” for automotive suspension, tyres (energy absorbing wheels for buggies, trollies) and technical parts (car seat components), and is particularly suitable for use in shoes. The foam can be used in dual density outsoles, single density boots, single density casual/formal, single density sandals, single density insoles, and especially in dual and single density midsoles.
- The invention is illustrated by the following non-limiting examples.
- In this specification the following test methods have been used.
- (a) For Polyester and Prepolymer
- (i) The glass transition temperature (Tg) was measured by Differential Scanning Calorimetry (DSC) at a scan rate of 20° C./minute using a Mettler DSC30.
- (ii) Molecular weight number average was determined by end group analysis.
- (iii) The hydroxyl value is defined as the number of mg of potassium hydroxide equivalent to the hydroxyl content of 1 g of sample, and was measured by acetylation followed by hydrolysation of excess acetic anhydride. The acetic acid formed was subsequently titrated with an ethanolic potassium hydroxide solution.
- (iv) The acid value is defined as the number of mg of potassium hydroxide required to neutralise the free fatty acids in 1 g of sample, and was measured by direct titration with a standard potassium hydroxide solution.
- (v) The isocyanate value is defined as the weight % content of isocyanate in the sample and was determined by reacting with excess dibutylamine, and back titrating with hydrochloric acid.
- (b) For Microcellular Polyurethane Foam
- (i) Density
- Determined by measuring the mass and volume of the specimen (to within 1% accuracy) and calculating density (=mass/volume).
- (ii) Hardness
- Measured using a Shore A meter on a 10 mm thick sample. Mean value of 10 readings calculated.
- (iii) Tensile Strength
- Determined according to ISO 37/DIN 53504 using a Z82B29 sample die.
- (iv) Elongation at Break
- Measured according to ISO 37/DIN 53504 using a Z82B29 sample die.
- (v) Tear Strength
- Determined using a procedure analogous to ASTM D3574 test F, except that the sample used was 100×25×10 mm with a 40 mm cut in the centre of the 25×10 mm face, parallel to the 25×100 mm face. The crosshead speed was 200 mm/min. The maximum load from the start of tearing over a 20 mm tear was recorded, and the tear strength calculated by dividing by the thickness (25 mm).
- (vi) Impact Resilience
- Measured according to ASTM D3574 (falling ball rebound test).
- (vii) Hydrolysis
- Samples were aged by placing dumbells of the material in a climate chamber at 70° C. and >98% relative humidity for periods of 2 and 4 weeks. The tensile strength and elongation at break of the “aged” samples were determined as above and the values compared to the original figures (on percentage retention terms).
- All the above tests were performed after the foam samples had been conditioned for a minimum of 24 hours, undeflected and undistorted at 23° C. and 50% relative humidity.
- (a) 902 g of adipic acid, 902 g of PRIPOL 1017 (trade mark, ex Uniqema (dimer acid)) and 1051 g of diethylene glycol were reacted at 225° C. in the presence of 50 ppm of tetrabutyl titanate catalyst. On completion of the reaction, the excess diethylene glycol was removed in vacuo and the dimerate polyester product was purified by filtration. Hydroxyl value was found by titration to be 54 mg KOH/g.
- (b) 586 g of the polyester produced above was placed in a flask and dried by heating for 2 hours at 120° C. and 50 mbar. 860 g of flake pure MDI (ex Bayer) was added at a temperature of 50 to 60° C. over 1 hour period at atmospheric pressure. 161 g of modified MDI (Suprasec 2021, ex Huntsman Polyurethanes) was then added, and the reaction was heated at 55° C. for a further hour, and then at 85° C. for a further two hours. The product was discharged and stored at 50° C. The prepolymer material was found to have an isocyanate content of 18.5% NCO.
- (c) A chain extender composition was prepared by mixing the following components in the following ratio:
Polyester prepared in (a) 100 DABCO DC193 silicone surfactant (ex Air Products) 0.4 1,4-butylene glycol (dry) 12 DABCO crystal (triethylene diamine, ex Air Products) 0.5 Distilled water 0.5 - (d) The prepolymer (prepared in (b)) and the chain extender composition (prepared in (c)) were mixed using an injection moulding polyurethane machine, with an isocyanate index of 100 to 103, and a mixing temperature of 35 to 45° C. The cream time was 5 to 10 seconds. The mould was coated in silicone release agent and was at a temperature of 65° C. A polyurethane foam sheet of 150×150 mm was yielded (step mould resulted in 4 mm thick and 10 mm thick sections). The foam was demoulded after 8 minutes.
- The resulting polyurethane foam had the following properties, measured as described above;
- (i) The density (of 10 mm thick section) was 0.37 gcm−2,
- (ii) The hardness was 35 Shore A,
- (iii) The tensile strength was 33.9 kgcm−2 (the modulus at 100% was 15 kgcm−2),
- (iv) The elongation at break was 300%, and
- (v) The tear strength was 2.2 kNm−1.
- The polyurethane foam was subjected to hydrolysis conditions for 2 weeks and 4 weeks as described above, and the following properties were remeasured;
- Two Weeks—
-
- (i) The tensile strength was 30.9 kgcm−2 (=91% retention of initial value), and
- (ii) The elongation at break was 253% (=84% retention of initial value).
Four Weeks— - (i) The tensile strength was 14.6 kgcm−2 (=43% retention of initial value), and
- (ii) The elongation at break was 122% (=41% retention of initial value).
- (a) The procedure according to Example 1(a) was used except that the starting materials were 879 g of adipic acid, 879 g of dimer acid (containing 88% by weight dimer and 10% by weight trimer) were reacted with 1042 g of diethylene glycol. Hydroxyl value of the resultant polyester was 54 mg KOH/g.
- (b) The procedure according to Example 1(b) was employed except that 706 g of the polyester produced above was reacted with 960 g of flake pure MDI (ex Bayer) and 185 g of modified MDI (Desmodur CD, ex Bayer). The prepolymer material had an isocyanate content of 18.5% NCO.
- (c) The procedure according to Example 1(c) was employed except that polyester produced in Example 2(a) above was used.
- (d) The procedure according to Example 1(d) was employed except that materials produced in Example 2(b) and (c) above were used.
- The resulting polyurethane foam had the following properties, measured as described above;
- (i) The density (of 10 mm thick section) was 0.48 gcm−2,
- (ii) The hardness was 46 Shore A,
- (iii) The tensile strength was 74 kgcm−2 (the modulus at 100% was 27 kgcm−2),
- (iv) The elongation at break was 341%,
- (v) The tear strength was 2.5 kNm−1, and
- (vi) The impact resilience was 25%.
- The polyurethane foam was subjected to hydrolysis conditions for 2 weeks and 4 weeks as described above, and the following properties were remeasured;
- Two Weeks—
-
- (i) The tensile strength was 70 kgcm−2 (=95% retention of initial value), and
- (ii) The elongation at break was 397% (=16% increase over initial value).
Four Weeks— - (i) The tensile strength was 33 kgcm−2 (=45% retention of initial value), and
- (ii) The elongation at break was 339% (=99% retention of initial value).
- This is a comparative example not according to the invention. The procedure according to Example 1 was repeated except that Daltorez P716 (adipate polyester, ex Huntsman Polyurethanes) was used as polyester, and Suprasec 2980 (polyester modified MDI, ex Huntsman Polyurethanes) was used as the as prepolymer.
- The resulting adipate derived polyurethane foam had the following properties, measured as described above;
- (i) The density (of 10 mm thick section) was 0.42 gcm−2,
- (ii) The hardness was 38 Shore A,
- (iii) The tensile strength was 60 kgcm−2 (the modulus at 100% was 16 kgcm−2),
- (iv) The elongation at break was 516%,
- (v) The tear strength was 4.1 kNm−1, and
- (vi) The impact resilience was 37%.
- The polyurethane foam was subjected to hydrolysis conditions for 2 weeks and 4 weeks as described above, and the following properties were remeasured;
- Two Weeks—
-
- (i) The tensile strength was 11 kgcm−2 (=18% retention of initial value), and
- (ii) The elongation at break was 104% (=20% retention of initial value).
Four Weeks— - (i) The tensile strength was 0 kgcm−2 (=0% retention of initial value), and
- (ii) The elongation at break was 0% (=0% retention of initial value).
- This is a comparative example not according to the invention. The procedure according to Example 1 was repeated except that the starting materials were adipate polyester (Desmophen 2000 MZ, ex Bayer (468 g)), flake pure MDI (ex Bayer (640.4 g)) and modified MDI (Suprasec 2021, ex Huntsman Polyurethanes (123.1 g)).
- The resulting adipate derived polyurethane foam was subjected to hydrolysis conditions for 4 weeks as described above, and the following properties were measured;
- (i) The tensile strength was 6 kgcm−2, and
- (ii) The elongation at break was 42%.
- The above examples illustrate the improved properties of a microcellular polyurethane foam according to the present invention.
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/588,622 US8067479B2 (en) | 2002-02-19 | 2009-10-21 | Polyurethane foam |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB0203881.8A GB0203881D0 (en) | 2002-02-19 | 2002-02-19 | Polyurethane foam |
GB0203881.8 | 2002-02-19 | ||
PCT/GB2003/000599 WO2003070801A1 (en) | 2002-02-19 | 2003-02-10 | Polyurethane foam |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/588,622 Continuation US8067479B2 (en) | 2002-02-19 | 2009-10-21 | Polyurethane foam |
Publications (1)
Publication Number | Publication Date |
---|---|
US20050124711A1 true US20050124711A1 (en) | 2005-06-09 |
Family
ID=9931350
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/505,148 Abandoned US20050124711A1 (en) | 2002-02-19 | 2003-02-10 | Polyurethane foam |
US12/588,622 Expired - Fee Related US8067479B2 (en) | 2002-02-19 | 2009-10-21 | Polyurethane foam |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/588,622 Expired - Fee Related US8067479B2 (en) | 2002-02-19 | 2009-10-21 | Polyurethane foam |
Country Status (9)
Country | Link |
---|---|
US (2) | US20050124711A1 (en) |
EP (1) | EP1476485B1 (en) |
KR (1) | KR100991057B1 (en) |
CN (1) | CN100556927C (en) |
AU (1) | AU2003207310A1 (en) |
GB (1) | GB0203881D0 (en) |
MX (1) | MXPA04008002A (en) |
TW (1) | TWI312349B (en) |
WO (1) | WO2003070801A1 (en) |
Cited By (10)
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US20070108416A1 (en) * | 2003-12-25 | 2007-05-17 | Ihara Chemical Industry Co., Ltd. | Method for inhibiting the discoloration of methylenebisaniline compounds |
US20100130632A1 (en) * | 2006-12-29 | 2010-05-27 | Speas Eric Scott Rick | Closed Cell Foams Comprising Urethane Elastomers |
WO2010111069A2 (en) | 2009-03-24 | 2010-09-30 | Dow Global Technologies Inc. | Natural oil polyols in elastomers for tires |
WO2010114695A1 (en) | 2009-04-01 | 2010-10-07 | Dow Global Technologies Inc. | Storage-stable polyol compositions for producing rigid polyisocyanurate foam |
US20110039968A1 (en) * | 2008-04-17 | 2011-02-17 | Dow Global Technologies Inc. | Polyurethane elastomers from renewable resources |
WO2011112829A1 (en) | 2010-03-12 | 2011-09-15 | Dow Global Technologies Llc | Gels and soft polyurethane elastomers made with natural oil based polyols |
WO2011112813A1 (en) | 2010-03-12 | 2011-09-15 | Dow Global Technologies Llc | Elastomer binding materials made with natural oil based polyols |
WO2012135625A1 (en) * | 2011-03-31 | 2012-10-04 | Dow Global Technologies Llc | Hydrophobic polyester polycarbonate polyols for use in polyurethane applications |
EP2746309A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | Hydrolysis resistant polyurethane mouldings made from polyester polyurethane |
EP2818489A1 (en) | 2013-06-28 | 2014-12-31 | Basf Se | Hydrolysis resistant PUR molded parts |
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EP1911781A1 (en) * | 2006-10-12 | 2008-04-16 | Arizona Chemical Company | Oil absorbing foam |
CN101066920B (en) * | 2007-04-29 | 2010-10-06 | 中国林业科学研究院林产化学工业研究所 | Fatty polyol dimer and its preparation process and application in foamed polyurethane plastic |
EP2239287A1 (en) * | 2009-04-08 | 2010-10-13 | Recticel | Process for preparing a flexible polyurethane foam |
WO2011163598A1 (en) * | 2010-06-25 | 2011-12-29 | Aetrex Worldwide, Inc. | Shoe with conforming upper |
CN102344542A (en) * | 2010-08-02 | 2012-02-08 | 拜耳材料科技(中国)有限公司 | Reaction system for preparing microporous polyurethane foam, microporous polyurethane foam, and purpose of microporous polyurethane foam |
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US20170174818A1 (en) * | 2014-03-26 | 2017-06-22 | Lubrizol Advanced Materials, Inc. | Polyurethane foams and method for producing same |
EP3947507A1 (en) | 2019-04-05 | 2022-02-09 | Sika Technology AG | Dimer fatty acid-polyester diol-based polymer, containing isocyanate groups |
US10934385B1 (en) * | 2020-09-09 | 2021-03-02 | Evoco Ltd. | Polyurethane elastomers, bio-additive foam compositions |
US11905359B2 (en) * | 2020-09-09 | 2024-02-20 | Evoco Limited | Polyurethane elastomers, bio-additive compositions |
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- 2003-02-10 AU AU2003207310A patent/AU2003207310A1/en not_active Abandoned
- 2003-02-10 US US10/505,148 patent/US20050124711A1/en not_active Abandoned
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US7632424B2 (en) * | 2003-12-25 | 2009-12-15 | Ihara Chemical Industry Co., Ltd. | Method for inhibiting the discoloration of methylenebisaniline compounds |
US20070108416A1 (en) * | 2003-12-25 | 2007-05-17 | Ihara Chemical Industry Co., Ltd. | Method for inhibiting the discoloration of methylenebisaniline compounds |
US20100130632A1 (en) * | 2006-12-29 | 2010-05-27 | Speas Eric Scott Rick | Closed Cell Foams Comprising Urethane Elastomers |
US20110039968A1 (en) * | 2008-04-17 | 2011-02-17 | Dow Global Technologies Inc. | Polyurethane elastomers from renewable resources |
CN102066446A (en) * | 2008-04-17 | 2011-05-18 | 陶氏环球技术公司 | Polyurethane elastomers from renewable resources |
US8598247B2 (en) * | 2008-04-17 | 2013-12-03 | Dow Global Technologies Llc | Polyurethane elastomers from renewable resources |
US20120018066A1 (en) * | 2009-03-24 | 2012-01-26 | Dow Global Technologies Inc. | Natural oil polyols in elastomers for tires |
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WO2011112813A1 (en) | 2010-03-12 | 2011-09-15 | Dow Global Technologies Llc | Elastomer binding materials made with natural oil based polyols |
WO2011112829A1 (en) | 2010-03-12 | 2011-09-15 | Dow Global Technologies Llc | Gels and soft polyurethane elastomers made with natural oil based polyols |
WO2012135625A1 (en) * | 2011-03-31 | 2012-10-04 | Dow Global Technologies Llc | Hydrophobic polyester polycarbonate polyols for use in polyurethane applications |
CN103562251A (en) * | 2011-03-31 | 2014-02-05 | 陶氏环球技术有限责任公司 | Hydrophobic polyester polycarbonate polyols for use in polyurethane applications |
EP2746309A1 (en) | 2012-12-19 | 2014-06-25 | Basf Se | Hydrolysis resistant polyurethane mouldings made from polyester polyurethane |
WO2014095438A1 (en) | 2012-12-19 | 2014-06-26 | Basf Se | Hydrolysis-resistant polyurethane moulded articles made of polyester polyurethane |
EP2818489A1 (en) | 2013-06-28 | 2014-12-31 | Basf Se | Hydrolysis resistant PUR molded parts |
Also Published As
Publication number | Publication date |
---|---|
CN100556927C (en) | 2009-11-04 |
KR100991057B1 (en) | 2010-10-29 |
EP1476485A1 (en) | 2004-11-17 |
EP1476485B1 (en) | 2016-08-31 |
WO2003070801A1 (en) | 2003-08-28 |
GB0203881D0 (en) | 2002-04-03 |
TW200303321A (en) | 2003-09-01 |
AU2003207310A1 (en) | 2003-09-09 |
KR20040083529A (en) | 2004-10-02 |
US8067479B2 (en) | 2011-11-29 |
US20100112333A1 (en) | 2010-05-06 |
CN1633452A (en) | 2005-06-29 |
MXPA04008002A (en) | 2005-05-16 |
TWI312349B (en) | 2009-07-21 |
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