GB1586019A - Polyol composition - Google Patents
Polyol composition Download PDFInfo
- Publication number
- GB1586019A GB1586019A GB16548/78A GB1654878A GB1586019A GB 1586019 A GB1586019 A GB 1586019A GB 16548/78 A GB16548/78 A GB 16548/78A GB 1654878 A GB1654878 A GB 1654878A GB 1586019 A GB1586019 A GB 1586019A
- Authority
- GB
- United Kingdom
- Prior art keywords
- composition
- polyol
- amine
- dextrose
- halogenated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims description 104
- 229920005862 polyol Polymers 0.000 title claims description 84
- 150000003077 polyols Chemical class 0.000 title claims description 83
- 239000003054 catalyst Substances 0.000 claims description 54
- 150000001412 amines Chemical class 0.000 claims description 45
- 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 claims description 26
- 239000008121 dextrose Substances 0.000 claims description 26
- 229960001031 glucose Drugs 0.000 claims description 26
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 23
- 239000011496 polyurethane foam Substances 0.000 claims description 23
- 125000002947 alkylene group Chemical group 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229920000570 polyether Polymers 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- -1 alkyl tertiary amine Chemical class 0.000 claims description 18
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 16
- 229930006000 Sucrose Natural products 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 16
- 239000005720 sucrose Substances 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 11
- 150000004985 diamines Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229960002887 deanol Drugs 0.000 claims description 7
- 239000012972 dimethylethanolamine Substances 0.000 claims description 7
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical group CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- CYYDNXCYDWWSPS-UHFFFAOYSA-N 2-(2,2,2-trichloroethyl)oxirane Chemical group ClC(Cl)(Cl)CC1CO1 CYYDNXCYDWWSPS-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- 239000004604 Blowing Agent Substances 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 claims description 2
- BIHLHMHULOMJLI-UHFFFAOYSA-N 3-[bis(2-hydroxyethyl)amino]propan-1-ol Chemical compound OCCCN(CCO)CCO BIHLHMHULOMJLI-UHFFFAOYSA-N 0.000 claims description 2
- ITBPIKUGMIZTJR-UHFFFAOYSA-N [bis(hydroxymethyl)amino]methanol Chemical compound OCN(CO)CO ITBPIKUGMIZTJR-UHFFFAOYSA-N 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical group OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 2
- 229940029284 trichlorofluoromethane Drugs 0.000 claims description 2
- 125000005263 alkylenediamine group Chemical group 0.000 claims 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims 2
- VEAZEPMQWHPHAG-UHFFFAOYSA-N n,n,n',n'-tetramethylbutane-1,4-diamine Chemical group CN(C)CCCCN(C)C VEAZEPMQWHPHAG-UHFFFAOYSA-N 0.000 claims 2
- OSNSWKAZFASRNG-WNFIKIDCSA-N (2s,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol;hydrate Chemical compound O.OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O OSNSWKAZFASRNG-WNFIKIDCSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 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 20
- 238000006243 chemical reaction Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 150000005846 sugar alcohols Polymers 0.000 description 11
- 239000006260 foam Substances 0.000 description 10
- 230000032683 aging Effects 0.000 description 9
- 230000000903 blocking effect Effects 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 230000000153 supplemental effect Effects 0.000 description 6
- 150000003512 tertiary amines Chemical class 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- 239000006071 cream Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- GEEGPFGTMRWCID-UHFFFAOYSA-N 1-n,1-n,1-n',1-n'-tetramethylbutane-1,1-diamine Chemical compound CCCC(N(C)C)N(C)C GEEGPFGTMRWCID-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- YEICNIAYNWWXNZ-UHFFFAOYSA-N C(=O)OCCCCCCN(C)C Chemical compound C(=O)OCCCCCCN(C)C YEICNIAYNWWXNZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- DAMFDFKOXMYOTN-UHFFFAOYSA-N cyclohexyl(dimethyl)azanium;formate Chemical compound OC=O.CN(C)C1CCCCC1 DAMFDFKOXMYOTN-UHFFFAOYSA-N 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002924 oxiranes Chemical group 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- HOVAGTYPODGVJG-UVSYOFPXSA-N (3s,5r)-2-(hydroxymethyl)-6-methoxyoxane-3,4,5-triol Chemical compound COC1OC(CO)[C@@H](O)C(O)[C@H]1O HOVAGTYPODGVJG-UVSYOFPXSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-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
- YHWDZWQQFQKTRM-UHFFFAOYSA-N 2-(1,1,2,2,2-pentachloroethyl)oxirane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)C1CO1 YHWDZWQQFQKTRM-UHFFFAOYSA-N 0.000 description 1
- PGHUWHFEKCZJFY-UHFFFAOYSA-N 2-(2,2,2-tribromoethyl)oxirane Chemical compound BrC(Br)(Br)CC1CO1 PGHUWHFEKCZJFY-UHFFFAOYSA-N 0.000 description 1
- HHRCGNUPQWUPFY-UHFFFAOYSA-N 2-(dibromomethyl)oxirane Chemical compound BrC(Br)C1CO1 HHRCGNUPQWUPFY-UHFFFAOYSA-N 0.000 description 1
- FQYGHYRJXOSDIN-UHFFFAOYSA-N 2-(dichloromethyl)-3-(trichloromethyl)oxirane Chemical compound ClC(Cl)C1OC1C(Cl)(Cl)Cl FQYGHYRJXOSDIN-UHFFFAOYSA-N 0.000 description 1
- DIYZRTRTCGAIKG-UHFFFAOYSA-N 2-(dichloromethyl)oxirane Chemical compound ClC(Cl)C1CO1 DIYZRTRTCGAIKG-UHFFFAOYSA-N 0.000 description 1
- VFEXYZINKMLLAK-UHFFFAOYSA-N 2-(trichloromethyl)oxirane Chemical compound ClC(Cl)(Cl)C1CO1 VFEXYZINKMLLAK-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- KOVQQOMROOKART-UHFFFAOYSA-N 2-[2-hydroxyethyl(methyl)amino]propan-1-ol Chemical compound OCC(C)N(C)CCO KOVQQOMROOKART-UHFFFAOYSA-N 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N 2-methylpropane-1,2-diol Chemical compound CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- ISPIHWORPMENMZ-UHFFFAOYSA-N 3-(1h-imidazol-2-yl)propan-1-ol Chemical compound OCCCC1=NC=CN1 ISPIHWORPMENMZ-UHFFFAOYSA-N 0.000 description 1
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FURHUTPHAISBMI-UHFFFAOYSA-N hexane-1,1-diol;oxepan-2-one Chemical compound CCCCCC(O)O.O=C1CCCCCO1 FURHUTPHAISBMI-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
- 229960000367 inositol Drugs 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 1
- KHLCTMQBMINUNT-UHFFFAOYSA-N octadecane-1,12-diol Chemical compound CCCCCCC(O)CCCCCCCCCCCO KHLCTMQBMINUNT-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical class C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002984 plastic foam Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OMMLUKLXGSRPHK-UHFFFAOYSA-N tetramethylbutane Chemical compound CC(C)(C)C(C)(C)C OMMLUKLXGSRPHK-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000004448 titration Methods 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
- 150000004072 triols 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
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5006—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
(54) POLYOL COMPOSITION
(71) We, OLIN CORPORATION, a body corporate organized and existing under the laws of the State of Virginia, United States of America, of 275 Winchester
Avenue, New Haven, Connecticut 06511, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by theS föllowing statement: This invention relates to the stabilization of amines used as catalysts in a halogenated polyol composition, for the production of polyurethane foam.
Polyurethane foam is generally prepared by reacting an organic polyisocyanate with a polyol in the presence of a foaming agent and a reaction catalyst. Although a variety of catalysts have been disclosed in the art for promoting this type of reaction, the most widely and successfully used catalysts are the aliphatic and cycloaliphatic amines including mixtures thereof with selected metal salts such as stannous octoate.
These preferred amine catalysts have an activity profile which results in favorable foam processing characteristics.
Catalyst compositions for polyurethane foam have heretofore been disclosed in the art which include salts of certain amines and acids. For example, U.S. Patent 3,372,130 to Chess et al shows a catalyst consisting of a tertiary amine and phosphoric acid used to control the rate of foam rise. U.C. Patent No. 3,706,687 to Rudzki describes a foam catalyst consisting of a mixture of an aliphatic tertiary amine and a tertiary amine salt of an alkylarylsulfonic acid. In U.S. Patent No. 3,728,291 to
Carroll et al., a triethylene diamine diformate salt is employed in combination with hydroxylpropyl imidazole as a catalyst composition for polyurethane foam. None of these patents, however, are directed to a stabilized amine-catalyzed polyurethane foam composition comprising a halogenated polyol.
Polyurethanes derived from halogenated polyols exhibit varying degrees of resistance to burning; and, in view of the increasing demand for flame retardant polyurethane foam, numerous halogenated polyol compositions have been developed for use by the polyurethane industry. Illustrative of these are polyether polyols which contain two or more halogens substituted on an aliphatic carbon atom within the polyol molecule. See, for example, U.S. Patent Nos. 3,402,169 and 3,726,855.
It has recently been discovered that halogenated polyols, such as those referred to above, exert a detrimental effect on the catalytic stability of amine catalysts. Thus, when brought in contact with such polyols, the amines become catalytically less active, the reduction in activity becoming more pronounced on prolonged contact. This phenomenon, the chemical nature of which is not yet fully understood, manifests itself particularly in those applications wherein the amine catalyst is preparatorily blended in with the halogenated polyol and the blend is stored or shipped as such for eventual use in polyurethane foam production.
It has now been found that amine-catalyzed, halogenated polyol compoositions can be stabilized against catalyst degradation during storage by blocking the amine catalyst with an acid. Accordingly, pursuant to the invention, there is provided a catalytically stable polyol composition for use in the production of polyurethane
foam, comprising a halogenated polyol and an acid-blocked amine catalyst.
As used in the specification and claims herein, the term "halogenated polyol" is
intended to encompass any polyol containing at least one halogen atom substituted on
an aliphatic carbon atom in the polyol molecule, the halogen being chlorine, bromine,
or a mixture thereof. These polyols usually have 28 hydroxy groups and include
polyether polyols, polyester polyols and mixtures thereof. However, the polyester
polyols, including mixtures of halogenated and halogen-free polyether polyols, are preferred.
The polyether polyols include the halogenated oxyalkylated polyols. These may
be prepared by a method generally well known in the art wherein a polyhydroxy com
pound is condensed, optionally in the presence of an oxyalkylation catalyst, with a halo
genated alkylene oxide or a mixture of halogenated and halogen-free alkylene oxides
using random or step-wise addition. U.S. Patent No. 3,402,169, issued September
17, 1969, to D. R. Jackson, provides a detailed description of this method.
In preparing the halogenated polyether polyols, polyhydroxy compound (including
mixtures of such compounds and alkylene oxide condensates thereof) may be employed
which contains 2-8 hydroxy groups and is suitable for reaction with an alkylene oxide
to form a polyether. Thus, a wide range of polyhydroxy compounds is contemplated
for use in preparing the halogenated polyether polyols. For illustration, the polyhydroxy
compounds include ethylene glycol, propylene glycol, isobutylene glycol, 2,3-butanediol,
1,4-dihydroxy-2-butane, 1,4-dihydroxycyclohexane, 2-butyue- 1,4-diol, 1,12-dihydroxy
octadecane, glycerin, trimethylolpropane, sorbitol, mannitol, inositol, erythritol,
pentaerythritol, sucrose, dextrose, methyl glucoside, 1,4-dimethylolbenzene, glycerin,
monochlorohydrin, diglycerol, methyl ether of glycerin, mixtures thereof, and conden
sates thereof with alkylene oxide, e.g., ethylene oxide, propylene oxide and butylene oxide.
The polyhydroxy compounds also include, as a preferred group, the carbohydrate-based materials, particularly dextrose- and sucrose-based materials. As used in the specification and claims herein, the term "dextrose-based material" means one of the following: a mixture of dextrose and water, an oxyalkylated mixture of dextrose and water, a mixture of dextrose and an aliphatic polyhydric alcohol, an oxyalkylated mixture of dextrose and an aliphatic polyhydric alcohol, a mixture of dextrose, water, and an aliphatic polyhydric alcohol, or an oxyalkylated mixture of dextrose, water and an aliphatic polyhydric - alcohol. The dextrose may be anhydrous such as d-glucose or hydrous such as a-d-glucose monohydrate. By the same taken, the term "sucrose-based material" means one of the following: a mixture of sucrose and water, an oxyalkylated mixture of sucrose and water, a mixture of sucrose and an aliphatic polyhydric alcohol,
an oxyalkylated mixture of sucrose and an aliphatic polyhydric alcohol, a mixture of
sucrose, water, and an aliphatic polyhydric alcohol, or an oxyalkylated mixture of
sucrose, water, and an aliphatic polyhydric alcohol. Illustrative aliphatic polyhydric
alcohols which may be used in preparing the dextrose- and sucrose-based materials
include, for example, the aliphatic diols and triols such as ethylene glycol, propylene
glycol, glycerol, trimethylolpropane and mixtures thereof. The dextrose-based
materials, particularly mixtures of dextrose and an aliphatic diol or triol, are especially preferred for use in preparing halogenated polyether polyols which are
preferably employed in the composition of the invention.
Any suitable molar ratio of water and/or aliphatic polyhydric alcohol to dextrose
or sucrose may be used in preparing the dextrose- and sucrose-based materials referred
to above. It is generally preferred, however, to employ at least about 0.7, and more
preferably about 0.9 - moles each of water and/or aliphatic polyhydric alcohol per
each mole of dextrose or sucrose. A more detailed description regarding the preparation of the dextrose- and sucrose-based materials is provided in U.S. Patent No.
3,741,921, which issued to M. Lapkin on June 26, 1973.
In preparing the halogenated polyether polyol, an alkylene oxide, or mixture thereof, may be used which has one or more halogen atoms substituted on an aliphatic
carbon atom, the halogen being chlorine, bromine or a mixture thereof, and which
alkylene oxide is capable of reacting with a polyhydroxy compound to form a polyether
polyol. If desired, a mixture of a halogen-substituted and a halogen-free alkylene
oxide may be used. The halogen-substituted alkylene oxides contain an epoxide ring
and preferably have from 24 carbon atoms. Preferred among them are the vicinal
epoxides, particularly those having 3--4 carbon atoms. Representatives of these include epichlorohydrin, 3,3-dichloro-1,2-epoxypropane; 3,3-dibromo-1,2-epoxypropane; 3,3,3trichloro- 1,2-epoxypropane; 4,4,4-trichloro- 1,2-epoxybutane; 4,4,4-tribromo-1,2epoxybutane; 4,4,4,3,3 -pentachloro- 1,2-epoxybutane; 1,1,1,4,4-pentachloro-2,3-epoxy- butane; and mixtures thereof. The preferred such halogenated alkylene oxides are those having 3 halogens in the molecule, the halogen being chlorine, such as 4,4,4trichloro-2-epoxybutane.
Any suitable oxyalkylation catalyst may be employed to promote the reaction of the polyhydroxy compound with the halogenated alkylene oxide. This includes basic catalysts, such as sodium hydroxide and potassium hydroxide, and acid catalysts, such as boron trifluoride and the etherate derivatives thereof. The latter catalysts are preferably employed in preparing polyether polyols which are derived from carbohydrate-based polyhydroxy compounds.
As is well known in the art, the relative proportion of alkylene oxide, or mixture of alkylene oxides, which is used depends on the hydroxyl number which is desired in the polyether polyol product. In accordance with the preferred embodiments of the invention, a sufficient proportion of halogenated alkylene oxide or mixture thereof is employed to yield a halogenated polyether polyol having a hydroxyl number of about 100--800, more preferably about 200-700, and still more preferably about 250-650. It is also preferred to employ such a proportion of halogenated alkylene oxide as to yield a halogen content in the polvether polyol of no less than about 15%, more preferably about 2080%, and stili more preferably about 2560% by weight.
The amine catalyst which is stabilized according to the invention can be an amine that acts as a promoter for the reaction of an organic polyisocyanate with a polyol to form a polyurethane. However, the preferred amine catalysts are the conventional alkyl tertiary amines. As used in the specification and claims herein, the term "alkyl tertiary amine" is intended to include mixtures of amines and both monoand diamines; also the term "alkyl" includes cycloalkyl, alkylene, aminoalkyl and hydroxyalkyl. Illustrative are the aliphatic tertiary mono- and diamines, the cycloaliphatic tertiary amines and the tertiary aminoalkanols. All of these tertiary amines usually contain 3-10 and preferably 4-8 carbon atoms.
Exemplificative of the aliphatic tertiary amines are the trialkylmonoamines such as trimethylamine and triethylamine, the trialkylene diamines such as triethylene diamine, and the N,N,N',N'-tetraalkylalkylene diamines such as N,N,N',N'-tetramethylbutane diamine. The cycloaliphatic tertiary amines are exemplified by the dialkylcyclohexylamines such as dimethylcyclohexylamine and diethylcyclohexylamine; and the tertiary aminoalkanols are exemplified by the dialkyl alkanolamines, such as dimethyldiethanolamine and dimethylpropanolamine, the alkyl dialkanolamines, such as methyldiethanolamine and methyldipropanolamine, and the trialkanolamines such as trimethanolamine, triethanolamine, diethanolpropanolamine, and tripropanolamine.
The most preferred tertiary amine catalysts for use in the composition of the invention are triethylene diamine, dimethylcyclohexylamine, N,N,N',N'-tetramethylbutane diamine, triethanolamine, dimethylethanolamine, and mixtures thereof. Particularly preferred is a mixture of dimethylcyclohexylamine and dimethylethanolamine.
Any suitable proportion of the amine which is effective in catalyzing the reaction
of the halogenated polyol with organic isocyanates may be employed in the composition of the invention. Thus, catalytic proportions are usually used such as about 0.02-5, preferably about 0.05-3, and more preferably about 0.075-2 parts per every 100 parts by weight of the halogenated polyol.
Pursuant to the invention, a blocking acid is used to stabilize the amine catalyst from gradual deactivation through inter-reaction with halogenated polyols. Any suitable acid capable of forming a stable salt with the amine catalyst may be used as the blocking acid. Relatively weak carboxylic acids are preferred, including aliphatic acids such as formic, acetic, propionic, butyric, or valeric acids, or aromatic acids such as benzoic acids. Formic acid is particularly preferred.
The amine is blocked through reaction with the acid to form a salt. As shown below in Equation A, using the preferred formic acid blocking agent and a dimethylcyclohexylamine catalyst for purposes of illustration, the tertiary amine reacts with the acid to form a salt, dimethylaminohexylformate, thereby blocking the amine from reacting with or being degraded by a halogenated polyol.
C6H,1N(CH3), + HCOOH
Dimethylcyclohexylamine Formic Acid 11+ [C6H"N(CH3)2] HCOO1 Dimethylaminohexyl Formate
The blocking reaction can be accomplished by mixing the amine catalyst with the acid prior to its incorporation into a polyurethane foam premix. Preferably, though, the blocking conveniently can be performed "in-situ" by blending the acid blocking agent into the halogenated polyol premix composition prior to or concurrently with the addition of the amine catalyst, as the premix is being formulated. Advantageously, ambient temperature conditions can be used, although the blocking reaction generally can be performed at a wide range of temperatures, e.g., from about -20 to about 1000C.
In order to effectively block the amine catalyst ,at least about a stoichiometric amount or an excess of stoichiometric amount of acid is used, in relation to the amount of amine catalyst. Accordingly, about 1 mole to about 2 moles of acid per mole of amine catalyst generally is used, with a preferred ratio being about 1:1 to about 1.5:1.
The catalyzed halogenated polyol composition described herein is utilized, according to the process of the invention, in the preparation of polyurethane foam.
To this end, it is reacted with an organic polyisocyanate in the presence of a foaming agent. Conventional techniques, such as the one-shot method or the prepolymer technique, may be employed in carrying out the foam-forming reaction. Any suitable combination of polyol, organic isocyanate, foaming agent, catalyst, plasticizer, and other reactants capable of forming a polyurethane foam reaction mixture can be employed.
The organic polyisocyanates used in the polyurethane foams of this invention include toluene diisocyanate, such as the 80:20 or the 65:35 isomer mixture of the 2,4- and 2,6-isomeric forms, ethylene diisocyanate, propylene diisocyanate, methylene bis ( 4-phenylisocyanate), 3,3 '-bitoluene-4,4-diisocyanate, hexamethylene diisocyanate, naphthalene 1,5-diisocyanate, the polymeric isocyanates such as polyphenylene polymethylene isocyanate, and mixtures thereof. The amount of isocyanate employed in the present process should generally be sufficient to provide at least about 0.7 NCO group per hydroxy group in the reaction system, which includes the polyols, as well as any additiona material and/or foaming agent present. In practice, the polyisocyanate is usually used in a proportion to provide no more than about 1.25 NCO groups per each hydroxy group. A 100 multiple of the ratio of NCO to OH groups in the reaction system is referred to as the "index".
Any suitable foaming agent or mixture of foaming agents may be employed.
These include inorganic foaming agents, such as water, and organic foaming agents containing up to 7 carbon atoms such as the halogenated hydrocarbons, and the low molecular weight alkanes, alkenes, and ethers. Illustrative organic agents include monofluorotrichloromethane, dichlorofluoromethane, dichlorodifluoromethane, 1, 1,2-trichloro- 1,2,2-trifluoroethane, methylene chloride, chloroform, carbon tetrachloride, methane, ethane,. ethylene, propylene, hexane, ethyl ether diisopropyl ether, and mixtures thereof.
Water and low molecular weight polyhalogenated alkanes, such as monofluorotrichloromethane and dichlorodifluoromethane, are preferred. The amount of foaming agent can be varied over a wide range. Generally, however, the halogenated hydrocarbons are employed in an amount in the range from about 1 to about 75 parts by weight per 100 parts of total polyols in the foam-forming reaction system; and generally water is employed in an amount in the range from about 0.1 to about 10 parts by weight per 100 parts of total polyols.
It is preferred in the preparation of the polyurethane foams of the invention to employ minor amounts of a conventional surfactant in order to further improve the cell structure of the polyurethane foam. Typical of such surfactants are the silicone oils and soaps, and the siloxane-oxyalkylene block copolymers. U.S. Patent No.
2,834,748 and T. H. Ferrigno, Rigid Plastic Foams (New York: Reinhold Publishing
Corp., 1963), pp. 3442, disclose various surfactants which are useful for this purpose. A preferred group of surfactants are the polysiloxanes such as may be purchased under the trademark "Niax L-5303". Generally up to 2 parts by weight of the surfactant are employed per 100 parts of total polyol.
To minimize surface friability of the resulting polyurethane foams, it is often desirable to incorporate a supplemental polyol into the foam-forming reaction mixture.
These agents are understood to accomplish this reduced friability by serving to accelerate cure and reduce viscosity of the foam reaction mass. The various polyols effective in this additive role and their methods of use are known in the art and are exemplified by the descriptions in U.S. Patents No. 3,928,257 to Fuzesi et al, and 3,928,258 to Alexander. Illustratively, the supplemental polyols include a select group of ethoxylated polyether polyols.
Any suitable proportion of the supplemental polyol may be employed which is effective in reducing the friability of the resulting foam without otherwise interfering with, or detrimentally altering, its properties. A proportion usually is used which is in the range from about 5 to about 35, preferably about 8 to about 30 parts per every 100 parts by weight of the main polyol reactant. The requisite proportion of the supplemental polyol advantageously can be blended in with the amine polyol reactant or it may be added separately to the foam-forming reaction mixture.
Various other additives may also be incorporated in the polyurethane foamforming reaction mixture, if desired, such as fillers, dyes, plasticizers, deodorants, and antioxidants.
The invention disclosed herein provides an easy and simple route for minimizing the problem of catalyst deactivation resulting from contact with a halogenated polyol.
Thus, a halogenated polyol composition is prepared, for use in the production of flame retardant polyurethane foam, which comprises an amine catalyst, the activity of which catalyst is not subject to substantial deterioration upon storage or during transport.
Such a composition is of particular utility in those applications, e.g., the on-site generation of polyurethane foam, wherein the foam-forming ingredients are supplied from two containers, one container providing the organic isocyanate alone or together with a portion of the foaming agent reactant and other container providing all the
other reactants, e.g., polyol along with the amine catalyst, all or a portion of the foaming agent, surfactant and supplemental polyol. Typical foaming apparatus used in practicing on-site generation of polyurethane foam is described in detail in U.S.
Patent Nos. 3,769,232 and 3,541,021.
The following examples are provided to illustrate the invention. In these examples,
all parts and percentages are by weight unless otherwise specified.
Examples
A series of amine-catalyzed, halogenated polyol compositions was prepared by adding blocked and unblocked amine catalysts to a halogenated polyol. The various samples were analyzed for pH, ionic Cl-, and available N+, before and after aging at 60"C for 90 hours. A drop in pH with time is an indication of the dehydrohalogenation effect on the halogenated polyol by the amine catalyst. The change in ionic
Cl- present (determined by titration) in the composition after aging evidences the amount of Cl- drawn from the halogenated polyol into salt formation with an amine group of the catalyst. The available N+ consumed is a further interpretatiori of the
deactivating reaction of the amine catalyst and the halogenated polyol. The results
of these analyses, summarized in Tables I and II, clearly indicate that by acid blocking
the amine catalyst, according to the invention, the critical factor of loss in reactivity
of the amine catalyst in a foaming reaction due to deactivation through storage, pre
reaction with the halogenated polyol is effectively minimized.
In the processing runs, shown in Table III, the indicated proportions of the Side
I and II ingredients were mixed together and foamed in a square cardboard box.
Using a stop-watch, the processing times-the "cream time", the "gel time", the "tackfree time", and the "rise time" were measured; time measurements were made from the moment the mixture was placed in the cardboard box. The "cream time" is the time elapsed up to the point when foaming commences, during which time the mixture
is transformed from a liquid to a cream or emulsion. The "gel time" is the time elapsed for the resulting foam to become self-supporting as evidenced by the foam exhibiting resistance to being penetrated by a dull instrument. The "tack-free time"
is the minimum time elapsed after which the foam ceases to be tacky. The "rise
time" is the time elapsed for completion of the foaming reaction or expansion of the foam.
Amine Catalyst Stability in Halogenated Polyol Compositions
TABLE I
Ionic Cl pH Total After Available N+ Catalyst Used Before After AgingO ACI (3 Consumed in Composition Aging Aging O Triethylene diamine 8.97 5.65 0.39 0.30 71
Dimethylethanolamine 9.87 8.39 0.76 0.67 87
Tetramethylbutane- 9.97 8.07 0.80 0.71 71
diamine
Dimethylcyclohexyl- 9;84 8.14 0.53 0.44 79
amine
Triethylamine 10.51 7.98 0.83 0.74 105
Triethylenediamine 5.49 5.22 0.21 0.12 7
monoformate
Triethylenediamine 4.85 4:76 0.17 0.08 10
diformate
None 4:31 3.37 0.12 0.03
None 4:19 3.49 0.10 0.01
None 4:32 - 0.09 -
None 4:20 - 0.09 - This is a composition of a chlorinated polyether polyol having a hydroxyl number
of about 365, prepared by condensing, in the presence of boron trifluoride etherate,
4;4;4-trichloro-1,2-epoxybutane with an equimolar mixture of ethylene glycol and
a-d-glucose monohydrate, and 2.01 wt. % catalyst.
( Aged at 600C for 90 hours.
2)acr = Total Cl after aging - initial Cl- in unagdd polyol alone.
TABLE ll
Ionic Cl Total After Available N Catalyst Used Before After Aging O ACI O Consumed @in Composition Aging Aging (!) Triethylene diamine 9.10 5.84 0.32 0.13 33
Dimethylethanolamine 9.55 8.37 0.65 0.46 58
Tetramethylbutane- 9.64 7.99 0.68 0.49 50
diamine
Dimethylcyclohexyl- 9.66 7.82 0.61 0.42 75
amine
Triethylamine 10.18 8.95 0.62 0.43 61
Triethylenediamine 5.73 5.75 0.34 0.15 8
monoformate
None 6.34 5.80 0.21 0.02
None 6.33 6.30 0.19
This is a composition of a chlorinated polyether polyol, having a hydroxyl number
of about 300, prepared by condensing 4;4;4-trichloro-1,2-epoxybutane with an
equimolar mixture of hexanediol-caprolactone, and dextrose, and 2.0 wt. % catalyst.
Aged at 600C for 90 hours.
A Cl- = Total C after aging - initial Cl- in unaged polyol alone.
Processing Characteristics of Stabilized Amine
Catalyzed Halogenated Polyol Foam Reaction Formulations
TABLE Ill
Composition Parts by Weight
Side I
Halogenated Polyol 100 100 100 100 100 100 100
Supplemental Polyol 20 20 20 20 20 20 20
Surfactant 2 2 2 2 2 2 22
Blocked Amine Catalysts Dimethylethanolamine 3 6 - - - - - formate
Tetramethylbutane - - 3 5 - -
diamine monoformate
Dimethylcyclohexylamine - - - - 5 - format Tetramethylbutane - - - - - 5 8
diamine diformate
Blowing Agent 5 36 36 36 36 36 36 36
Side II
Polymethylene poly
phenylisocyanate 06 117.5 117.5 117.5 117.5 117.5 117.5 117.5
(115 Index)
Processing Times Seconds
Cream Time 40 18 25 14 30 22 12
Gel time - 180 132 72 180 200
Tack-free time - - 220 105 240 240
Rise time - - - 130 300 - This is a composition of a chlorinated polyether polyol having a hydroxyl number of
about 365, prepared by condensing, in the presence of boron trifluoride etherate,
4;4;4-trichloro-1,2-epoxybutane with an equimolar mixture of ethylene glycol and
a-d-glucose monohydrate.
Copolymer of glycerol and caprolactone available commercially from Union Carbide
under the trademark PCP-0300.
This is a silicone-glycol copolymer described as Dow Corning (Trade Mark) 193
Surfactant in an August, 1968 Dow Corning Bulletin No. 05-146.
4 All catalysts were diluted 50/50 with tripropylene glycol; formates were prepared
by reacting the amine catalyst with about a stoichiometric amount of formic acid
in a propylene glycol solvent medium.
Footnotes for Table ill (continued).
O This is a trichlorofluoromethane blowing agent available from DuPont under the
trademark "Freon 11B".
) This is a polymethylene polyphenylisocyanate having a functionality of 2.6,
available commercially from Upjohn Company under the trademark "PAPI".
WHAT WE CLAIM IS:
1. A catalytically stable polyol composition for use in the preparation of poly
urethane foam, comprising a halogenated polyol (as herein defined) and an acid
blocked amine catalyst.
2. The composition of Claim 1 wherein said polyol is a polyether polyol which
is the product of condensing a polyhydroxy compound having from 2-8 hydroxy
groups with a halogenated alkylene oxide.
3. The composition of Claim 2 wherein said polyhydroxy compound is a dextrose
based material (as herein defined) or a sucrose-based material (as herein defined)
and said polyol has a hydroxyl number of about 250650.
4. The composition of Claim 3 wherein said halogenated alkylene oxide contains
3-4 carbon atoms and at least 2 halogens in the molecule.
5. The composition of Claim 4 wherein said halogenated alkylene oxide is 4,4,4
trichloro- 1,2-epoxybutane.
6. The composition of Claim 5 wherein said amine catalyst is an alkyl tertiary
amine (as herein defined).
7. The composition of Claim 6 wherein said acid-blocked alkyl tertiary amine
catalyst is the product of reacting an amine catalyst with a carboxylic acid.
8. The composition of Claim 7 wherein said carboxylic acid is formic acid.
9. The composition of Claim 8 wherein said polyhydroxy compound is a dextrose
based material (as herein defined).
10. The composition of Claim 9 wherein said dextrose-based material is a
mixture of dextrose and an aliphatic diol or an aliphatic triol.
11. The composition of Claim 10 wherein said dextrose-based material is a
mixture of dextrose with ethylene glycol, propylene glycol, glycerol, tnmetnytoipropane, or a mixture thereof.
12. The composition of Claim 11 wherein said halogenated polyol is prepared
by condensing, in the presence of boron trifluoride or an etherate d
Claims (20)
1. A catalytically stable polyol composition for use in the preparation of poly
urethane foam, comprising a halogenated polyol (as herein defined) and an acid
blocked amine catalyst.
2. The composition of Claim 1 wherein said polyol is a polyether polyol which
is the product of condensing a polyhydroxy compound having from 2-8 hydroxy
groups with a halogenated alkylene oxide.
3. The composition of Claim 2 wherein said polyhydroxy compound is a dextrose
based material (as herein defined) or a sucrose-based material (as herein defined)
and said polyol has a hydroxyl number of about 250650.
4. The composition of Claim 3 wherein said halogenated alkylene oxide contains
3-4 carbon atoms and at least 2 halogens in the molecule.
5. The composition of Claim 4 wherein said halogenated alkylene oxide is 4,4,4
trichloro- 1,2-epoxybutane.
6. The composition of Claim 5 wherein said amine catalyst is an alkyl tertiary
amine (as herein defined).
7. The composition of Claim 6 wherein said acid-blocked alkyl tertiary amine
catalyst is the product of reacting an amine catalyst with a carboxylic acid.
8. The composition of Claim 7 wherein said carboxylic acid is formic acid.
9. The composition of Claim 8 wherein said polyhydroxy compound is a dextrose
based material (as herein defined).
10. The composition of Claim 9 wherein said dextrose-based material is a
mixture of dextrose and an aliphatic diol or an aliphatic triol.
11. The composition of Claim 10 wherein said dextrose-based material is a
mixture of dextrose with ethylene glycol, propylene glycol, glycerol, tnmetnytoipropane, or a mixture thereof.
12. The composition of Claim 11 wherein said halogenated polyol is prepared
by condensing, in the presence of boron trifluoride or an etherate derivative thereof,
said 4,4,4-trichloro-1,2-epoxybutane with a mixture of about 1 mole of d-glucose
monohydrate per mole of said ethylene glycol.
13. The composition of Claim 12 wherein said alkyl tertiary amine contains 3-10 carbon atoms and is selected from a trialkylmonoamine, trialkylene diamine,
a N,N,N',N'-tetraalkyl alkylene diamine, a dialkylcyclohexylamine, a dialkyl alkanol
amine, an alkyl dialkanolamine, and a trialkanolamine.
14. The composition of Claim 13 wherein said trialkylmonoamine is trimethyl
amine or triethylamine, said trialkylene diamine is triethylene diamine, said N,N,N',N'
tetraalkyl alkylene diamine is N,N,N',N'-tetramethylbutylene diamine, said dialkyl
cyclohexylamine is dimethylcyclohexylamine or diethylcyclohexylamine, said dialkyl
alkanolamine is dimethylethanolamine or dimethylpropanolamine, said alkyl dialkanol
amine is methyl diethanolamine or methyl dipropanolamine, and said trialkanolamine
is trimethanolamine, triethanolamine, diethanolpropanolamine, and tripropanolamine.
15. The composition of Claim 14 wherein said alkyl tertiary amine is selected
from triethylene diamine, dimethylcyclohexylamine, N,N,N',N'-tetramethylbutylene
diamine, triethanolamine, dimethylethanolamine, and mixtures thereof.
16. The composition of Claim 15 wherein the mole ratio of acid to amine catalyst
is 1:1 to 1.5:1.
17. A process for preparing a polyurethane foam which comprises reacting the
catalytically stable polyol composition of any preceding claim with an organic poly
isocyanate in the presence of a foaming agent.
18. The composition of Claim 1 substantially as hereinbefore described in any
of the Examples.
19. A polyurethane foam when prepared by the process of Claim 17.
20. A polyurethane foam according to Claim 19, substantially as hereinbefore
described in any of the Examples.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US80167677A | 1977-05-31 | 1977-05-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1586019A true GB1586019A (en) | 1981-03-11 |
Family
ID=25181774
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB16548/78A Expired GB1586019A (en) | 1977-05-31 | 1978-04-26 | Polyol composition |
Country Status (7)
Country | Link |
---|---|
JP (1) | JPS53149299A (en) |
BR (1) | BR7803348A (en) |
DE (1) | DE2822819A1 (en) |
ES (1) | ES470307A1 (en) |
FR (1) | FR2393024A1 (en) |
GB (1) | GB1586019A (en) |
IT (1) | IT1104720B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT383133B (en) * | 1981-07-09 | 1987-05-25 | Kabel & Gummiwerke Ag | METHOD FOR PRODUCING A FOAM |
CN112225859A (en) * | 2020-09-29 | 2021-01-15 | 苏州思德新材料科技有限公司 | Catalyst for polyurethane foam production and preparation method thereof |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4239642A (en) * | 1979-06-29 | 1980-12-16 | Air Products And Chemicals, Inc. | Stabilization of halogenated polyols for polyurethane production |
JP2002069417A (en) * | 2000-08-24 | 2002-03-08 | Nippon Polyurethane Ind Co Ltd | Adhesive composition for hot press molded article of lignocellulosic material, and hot press molded article using the same and its manufacturing method |
SI1773902T1 (en) | 2004-08-04 | 2018-04-30 | Foam Supplies, Inc. | Reactivity drift and catalyst degradation in polyurethane foam |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3372130A (en) * | 1964-09-16 | 1968-03-05 | Upjohn Co | Control of rate of rise of polyurethane foams with phosphoric acid and a tertiary amine |
JPS5756491B2 (en) * | 1973-11-30 | 1982-11-30 | ||
US4040992A (en) * | 1975-07-29 | 1977-08-09 | Air Products And Chemicals, Inc. | Catalysis of organic isocyanate reactions |
-
1978
- 1978-04-26 GB GB16548/78A patent/GB1586019A/en not_active Expired
- 1978-05-24 DE DE19782822819 patent/DE2822819A1/en not_active Withdrawn
- 1978-05-26 BR BR787803348A patent/BR7803348A/en unknown
- 1978-05-30 IT IT49608/78A patent/IT1104720B/en active
- 1978-05-30 FR FR7816143A patent/FR2393024A1/en active Granted
- 1978-05-30 ES ES470307A patent/ES470307A1/en not_active Expired
- 1978-05-30 JP JP6485478A patent/JPS53149299A/en active Granted
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT383133B (en) * | 1981-07-09 | 1987-05-25 | Kabel & Gummiwerke Ag | METHOD FOR PRODUCING A FOAM |
CN112225859A (en) * | 2020-09-29 | 2021-01-15 | 苏州思德新材料科技有限公司 | Catalyst for polyurethane foam production and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
DE2822819A1 (en) | 1978-12-07 |
JPS53149299A (en) | 1978-12-26 |
IT1104720B (en) | 1985-10-28 |
BR7803348A (en) | 1979-01-16 |
FR2393024B1 (en) | 1982-06-25 |
JPS6141928B2 (en) | 1986-09-18 |
FR2393024A1 (en) | 1978-12-29 |
ES470307A1 (en) | 1979-10-01 |
IT7849608A0 (en) | 1978-05-30 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PS | Patent sealed [section 19, patents act 1949] | ||
PCNP | Patent ceased through non-payment of renewal fee |