US3551339A - Built detergent compositions - Google Patents
Built detergent compositions Download PDFInfo
- Publication number
- US3551339A US3551339A US602161A US3551339DA US3551339A US 3551339 A US3551339 A US 3551339A US 602161 A US602161 A US 602161A US 3551339D A US3551339D A US 3551339DA US 3551339 A US3551339 A US 3551339A
- Authority
- US
- United States
- Prior art keywords
- compounds
- triphosphonate
- sodium
- detergent
- ethane
- 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 - Lifetime
Links
- 239000000203 mixture Substances 0.000 title description 74
- 239000003599 detergent Substances 0.000 title description 61
- 150000001875 compounds Chemical class 0.000 description 61
- -1 diisopropyl bromoethanephosphonate Chemical compound 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000011734 sodium Substances 0.000 description 30
- 229910052708 sodium Inorganic materials 0.000 description 28
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 26
- 238000000034 method Methods 0.000 description 22
- 235000019832 sodium triphosphate Nutrition 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 229910052700 potassium Inorganic materials 0.000 description 16
- 239000003352 sequestering agent Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 239000011591 potassium Substances 0.000 description 15
- 239000002689 soil Substances 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000271 synthetic detergent Substances 0.000 description 12
- 235000019864 coconut oil Nutrition 0.000 description 11
- 239000003240 coconut oil Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- ODTQUKVFOLFLIQ-UHFFFAOYSA-N 2-[di(propan-2-yloxy)phosphorylmethyl-propan-2-yloxyphosphoryl]oxypropane Chemical compound CC(C)OP(=O)(OC(C)C)CP(=O)(OC(C)C)OC(C)C ODTQUKVFOLFLIQ-UHFFFAOYSA-N 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- QEIOXKCYFSJIDF-UHFFFAOYSA-N P(=O)(O)OP(=O)(O)OP(=O)O.CC Chemical class P(=O)(O)OP(=O)(O)OP(=O)O.CC QEIOXKCYFSJIDF-UHFFFAOYSA-N 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- JNONGIUWXHOEEN-UHFFFAOYSA-N 2-[bromomethyl(propan-2-yloxy)phosphoryl]oxypropane Chemical compound CC(C)OP(=O)(CBr)OC(C)C JNONGIUWXHOEEN-UHFFFAOYSA-N 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000012423 maintenance Methods 0.000 description 7
- 239000000344 soap Substances 0.000 description 7
- 239000003760 tallow Substances 0.000 description 7
- SFRLSTJPMFGBDP-UHFFFAOYSA-N 1,2-diphosphonoethylphosphonic acid Chemical compound OP(O)(=O)CC(P(O)(O)=O)P(O)(O)=O SFRLSTJPMFGBDP-UHFFFAOYSA-N 0.000 description 6
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000002168 alkylating agent Substances 0.000 description 6
- 229940100198 alkylating agent Drugs 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004900 laundering Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- KOMSQTMQKWSQDW-UHFFFAOYSA-N ethyl 5-methyl-1,2-oxazole-4-carboxylate Chemical compound CCOC(=O)C=1C=NOC=1C KOMSQTMQKWSQDW-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 5
- 159000000001 potassium salts Chemical class 0.000 description 5
- FODHIQQNHOPUKH-UHFFFAOYSA-N tetrapropylene-benzenesulfonic acid Chemical compound CC1CC11C2=C3S(=O)(=O)OC(C)CC3=C3C(C)CC3=C2C1C FODHIQQNHOPUKH-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- OYWFWDQOWQBTHK-UHFFFAOYSA-N bromomethylphosphonic acid Chemical compound OP(O)(=O)CBr OYWFWDQOWQBTHK-UHFFFAOYSA-N 0.000 description 3
- 229940096386 coconut alcohol Drugs 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000008233 hard water Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000003752 hydrotrope Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229940102859 methylene diphosphonate Drugs 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- XQRLCLUYWUNEEH-UHFFFAOYSA-L diphosphonate(2-) Chemical compound [O-]P(=O)OP([O-])=O XQRLCLUYWUNEEH-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000013213 extrapolation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical class [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- NYIQECIYDUSNRC-UHFFFAOYSA-N 1,2,3,5-tetrapropylbenzene Chemical compound CCCC1=CC(CCC)=C(CCC)C(CCC)=C1 NYIQECIYDUSNRC-UHFFFAOYSA-N 0.000 description 1
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- RNAMYOYQYRYFQY-UHFFFAOYSA-N 2-(4,4-difluoropiperidin-1-yl)-6-methoxy-n-(1-propan-2-ylpiperidin-4-yl)-7-(3-pyrrolidin-1-ylpropoxy)quinazolin-4-amine Chemical compound N1=C(N2CCC(F)(F)CC2)N=C2C=C(OCCCN3CCCC3)C(OC)=CC2=C1NC1CCN(C(C)C)CC1 RNAMYOYQYRYFQY-UHFFFAOYSA-N 0.000 description 1
- ARDLYOCKQAHHIC-UHFFFAOYSA-N 2-[2,2-bis[di(propan-2-yloxy)phosphoryl]ethyl-propan-2-yloxyphosphoryl]oxypropane Chemical compound CC(C)OP(=O)(OC(C)C)CC(P(=O)(OC(C)C)OC(C)C)P(=O)(OC(C)C)OC(C)C ARDLYOCKQAHHIC-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical class CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- YVGJZIJVVVUPLC-UHFFFAOYSA-H C(CP([O-])(=O)[O-])(P([O-])(=O)[O-])P([O-])(=O)[O-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] Chemical compound C(CP([O-])(=O)[O-])(P([O-])(=O)[O-])P([O-])(=O)[O-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] YVGJZIJVVVUPLC-UHFFFAOYSA-H 0.000 description 1
- VCCWZAQTNBYODU-UHFFFAOYSA-N CC(=C)CC(C)CCC(C)=C Chemical group CC(=C)CC(C)CCC(C)=C VCCWZAQTNBYODU-UHFFFAOYSA-N 0.000 description 1
- XPVOEBCQEBYSIM-UHFFFAOYSA-N CC(O)CS([O-])(=O)=O.CCCCCCCCCCCCCCCC[NH+](C)C Chemical compound CC(O)CS([O-])(=O)=O.CCCCCCCCCCCCCCCC[NH+](C)C XPVOEBCQEBYSIM-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ZZXDRXVIRVJQBT-UHFFFAOYSA-M Xylenesulfonate Chemical class CC1=CC=CC(S([O-])(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CXDBXTHJTZQPOJ-UHFFFAOYSA-M [Na+].CC=C.CC=C.CC=C.CC=C.[O-]S(=O)(=O)C1=CC=CC=C1 Chemical compound [Na+].CC=C.CC=C.CC=C.CC=C.[O-]S(=O)(=O)C1=CC=CC=C1 CXDBXTHJTZQPOJ-UHFFFAOYSA-M 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical class [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- RNULQUVUKWETPF-UHFFFAOYSA-N bromo(dibromophosphoryl)methane Chemical compound BrCP(Br)(Br)=O RNULQUVUKWETPF-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000005534 decanoate group Chemical class 0.000 description 1
- ZRKZFNZPJKEWPC-UHFFFAOYSA-N decylamine-N,N-dimethyl-N-oxide Chemical compound CCCCCCCCCC[N+](C)(C)[O-] ZRKZFNZPJKEWPC-UHFFFAOYSA-N 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GDNCXORZAMVMIW-UHFFFAOYSA-N dodecane Chemical compound [CH2]CCCCCCCCCCC GDNCXORZAMVMIW-UHFFFAOYSA-N 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- GGABWRGYJHJXJO-UHFFFAOYSA-N ethynylphosphonic acid Chemical compound OP(O)(=O)C#C GGABWRGYJHJXJO-UHFFFAOYSA-N 0.000 description 1
- 239000006023 eutectic alloy Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- LVJNUMIKCVDHRM-UHFFFAOYSA-N hexadecyl-dimethyl-propylsulfonyloxyazanium Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)OS(=O)(=O)CCC LVJNUMIKCVDHRM-UHFFFAOYSA-N 0.000 description 1
- 239000002035 hexane extract Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229940045996 isethionic acid Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- XDGBLAFHHLKULM-UHFFFAOYSA-N lithium;ethyne Chemical compound [Li+].[C-]#C XDGBLAFHHLKULM-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ONHFWHCMZAJCFB-UHFFFAOYSA-N myristamine oxide Chemical compound CCCCCCCCCCCCCC[N+](C)(C)[O-] ONHFWHCMZAJCFB-UHFFFAOYSA-N 0.000 description 1
- RSVIRMFSJVHWJV-UHFFFAOYSA-N n,n-dimethyloctan-1-amine oxide Chemical compound CCCCCCCC[N+](C)(C)[O-] RSVIRMFSJVHWJV-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 235000013966 potassium salts of fatty acid Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- IWMMSZLFZZPTJY-UHFFFAOYSA-M sodium;3-(dodecylamino)propane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCNCCCS([O-])(=O)=O IWMMSZLFZZPTJY-UHFFFAOYSA-M 0.000 description 1
- HWCHICTXVOMIIF-UHFFFAOYSA-M sodium;3-(dodecylamino)propanoate Chemical compound [Na+].CCCCCCCCCCCCNCCC([O-])=O HWCHICTXVOMIIF-UHFFFAOYSA-M 0.000 description 1
- MTKUWDYQPVIKLB-UHFFFAOYSA-N sodium;dipropan-2-yl phosphite Chemical compound [Na+].CC(C)OP([O-])OC(C)C MTKUWDYQPVIKLB-UHFFFAOYSA-N 0.000 description 1
- YNBRSWNUNPAQOF-UHFFFAOYSA-M sodium;phenylmethanesulfonate Chemical class [Na+].[O-]S(=O)(=O)CC1=CC=CC=C1 YNBRSWNUNPAQOF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4025—Esters of poly(thio)phosphonic acids
Definitions
- a detergent composition is provided containing an organic detergent and a triphosphonate builder, the ratio by weight of builder to detergent being from :1 to 1:3.
- This invention relates to and has among its objects new and useful organic compounds. More particularly, it relates to water-soluble triphosphonates which are substituted ethane compounds having the following general formula:
- the acid may be neutralized to any desired degree using a base which gives a soluble salt and is in other respects desired.
- a base which gives a soluble salt and is in other respects desired.
- the particular base material used can and will vary and, in itself, is not critical although sodium, potassium, ammonium, and low molecular weight substituted ammonium salts represent the preferred embodiments of the present invention as more fully described hereinafter.
- a principal object of the present invention is to provide a novel class of organic compounds containing three phosphonic acid groups.
- a second important object of the invention predicated on the unexpected usefulness of these compounds as excellent builders is to provide outstandingly efiicient built detergent compositions. Other objects will become apparent from the following detailed description of the present invention.
- a useful process involves the alkylation of the carbanion of the tetraisopropyl ester of methylenediphosphonate (I) with diisopropyl bromoethanephosphonate (II), with the resulting formation of sodium bromide (III), and the desired substituted ethane compound of the type indicated above (IV). This reaction proceeds according to the following general equation:
- the carbanion starting material (I) is readily obtained by an oxidation-reduction type of a reaction between a metallating agent such as sodium, sodium hydride, potassium, or potassium-sodium eutectic alloy, and a tetraalkyl ester of methylenediphosphonic acid, e.g. tetraisopropyl methylenediphosphonate.
- a metallating agent such as sodium, sodium hydride, potassium, or potassium-sodium eutectic alloy
- a tetraalkyl ester of methylenediphosphonic acid e.g. tetraisopropyl methylenediphosphonate.
- the reaction prod--. net is a carbanion derived from the active methylene grouping present in the parent methylene ester starting material.
- the equation for this step is as follows: (M rep resents one of the metallating agents such as those listed above).
- sodio or potassio carbanion derivative for example, alkylates moderately readily with a phosphonomethyl alkylating agent such as diisopropyl bromomethanephosphonate, as in Equation A above, yielding the corresponding triphosphonate ester which, if desired, can be hydrolyzed or pyrolyzed to the free acid.
- the free acid in turn, can be neutralized to any degree desired with any ordinary base material.
- the tri-, tetra-, pentaand hexa-salts are the most easily separatable forms and this degree of neutralization is usually performed.
- the alkylating agent such as the diisopropyl bromomethanephosphonate (II)
- the alkylating agent can be obtained by reaction of phosphorus tribromide, PBr with formaldehyde, CH O, by known methods to make bromomethylphosphoryldibromide, BrCH P(O)Br the desired diisopropyl bromomethanephosphonate, BrCH PO R product is obtained from this acid bromide by reaction with isopropyl alcohol.
- a suitable halogen containing alkylating agent can also be prepared by an Arbuzov rearrangement involving an excess of CH X wherein X represents chlorine, bromine or iodine, according to the following equation:
- the desired alkylating agent can be purified readily by known distillation techniques.
- Yet another method is a two step process beginning with formaldehyde and phosphorous trihalide, thus: (X can be either chlorine, bromine or iodine).
- the reaction between the carbanion and the alkylating agent is conveniently carried out in the presence of an inert diluent or solvent, for example, toluene or other aromatic hydrocarbons.
- an inert diluent or solvent for example, toluene or other aromatic hydrocarbons.
- Saturated hydrocarbons or ethers may also be used but are less desirable because they dissolve very little of the carbanion.
- the alkylating reaction requires a temperature in excess of about C. and less than about C.
- a preferred range within which to operate is from about 90 C. to about 130 C.
- the reaction requires from 30 minutes to about hours, with a preferred operable range being from about 50 minutes to about 2.5 hours.
- the following two experiments are typical examples for the preparation of the starting materials in Equation A above.
- the first relates to the formation of the ester of tetraisopropyl methylenediphosphonate from which the carbanion is prepared and the second is a preparation of the diisopropyl bromomethanephonsphonate alkylating agent.
- TETRAISOPROPYL METHYLENEDI- PHOSPHONATE 624.7 gms. of triisopropyl phosphite (3 moles, 681 ml.) and 173.9 gms. of dibromomethane (1 mole, 70 ml.) were combined in a reaction apparatus composed of a 1-liter, 3-neck flask fitted with a magnetic stirrer, a thermometer, and a fractionating column for separating the isopropyl bromide by-product from the refluxing mixture.
- the fractionating column was constructed from a 36-inch Liebig condenser that had been modified to accommodate A- inch glass helices as packing.
- a Barrett distilling receiver which had been modified by the addition of a thermometer well and thermometer was connected to the top of the fractionating column; and to the top of the Barrett receiver was fitted a Dewar condenser cooled with Dry Ice and protected from atmospheric moisture by a drying tube.
- the temperature of the reaction mixture was quickly brought to reflux at 143 C.
- the temperature of the circulating water in the packed reflux condenser was maintained at 65 C. This temperature was suflicient to return unreacted starting material and allow the by-product isopropyl bromide to be distilled.
- the heat input to the reaction was such that vigorous refluxing continued as the temperature of the mixture slowly increased. After about two hours of heating the first distillate was observed, and after five hours a total of 33 gms. of isopropyl bromide had been collected.
- the temperature of the reaction mixture was allowed to increase to 185 C. over a twelve-hour period, and by means of an electronic temperature controller it was held there for the remainder of the reaction.
- the reaction mixture was transferred to a distilling flask and the low boiling materials (excess phosphite, etc.) were removed through a short one-piece still under a vacuum of 0.1 mm. of mercury and heat temperatures up to 50 C. At this point the content of the flask weighed approximately 330 gms. and was 93% to 95% tetraisopropyl methylenediphosphonate. The purity of this material was suflicient to proceed in the synthesis of the novel compounds of this invention.
- the low boiling materials excess phosphite, etc.
- a high capacity vacuum pump can be introduced into the system and the pressure reduced to 0.005 mm. of mercury.
- the material boiling between 80 C. and 116 C. is collected and redistilled through an electrically heated 24-inch Vigreaux column.
- the diisopropyl bromomethylphosphonate and tetraisopropyl methylenediphosphonate can be distinguished by their refractive indices and proton NMR spectra, but the P NMR spectra cannot be used for identification of a mixture, as the chemical shifts (delta) for both compounds in the latter is the same, at 18 ppm, relative to 85% H PO (external standard) as zero.
- the reaction apparatus for this reaction consisted of a 1-liter, 3-neck flask, fitted with a high speed stirrer (capable of 10,000 r.p.m.), a thermometer, a 50 ml. offset additive type separatory funnel, and an Allihn condenser. A 1,2-dimethoxyethane-Dry Ice bath was used to control the reaction as was needed.
- the triphosphonate can be distinguished from the tetraisopropyl methylenediphosphonate and the diisopropyl bromomethanephosphonate by using the following data.
- P NMR spectrum gives a peak with a chemical shift of 20.5 p.p.m.
- the undistilled portion containing 83% triphosphonate, was converted to the free acid by refluxing for hours with a 100% excess of concentrated HCl.
- the acidic solution was evaporated to a constant volume and azeotroped four times with n-propanol to remove traces of HCl before dissolving the residual phosphonic acid in water and titrating to the tetrasodium salt at a pH of 8.5 with four molar equivalents of NaOH.
- the salt was purified by recrystallization from methanol-water solution to give the final product.
- novel triphosphonate compounds of the present invention also can be prepared by another route.
- This alternative method avoids the making of methanediphosphonate as an intermediate.
- acetylenemonophosphonate is prepared by a reaction between monolithium acetylide (from LiNH with chlorophosphate in a diethyl ether solvent:
- a peculiarly outstanding and surprising characteristic common to all of the new triphosphonate compounds of the present invention involves their remarkable sequestering properties. It has been discovered that these compounds possess the capacity of complexing in excess of two moles of calcium per mole of sequestrant.
- Na H [O PCH CH(PO is given below along with other compounds whose sequestering characteristics are more well known.
- This aspect of the present invention is based on the discovery of the outstanding sequestering properties of the novel triphosphonate compounds of the present invention.
- sequestering agents such as amino acid sequestrants including nitrilotriacetic acid and EDTA react with polyvalcnt ions on a mole-to-mole basis.
- the relative cfficiency of sequestrants is related to their molecular weight.
- the ethane triphosphonate compounds of the present invention are, in the order of magnitude, about three to four times as efiicient as sodium tripolyphosphate. This is evident from the information presented in Table I above.
- the ethane triphosphonate compounds of the present invention provide an efliciency improvement of considerable magnitude.
- Another distinguishing and valuable characteristic of the sequestering properties of the triphosphonate compounds is the strength of the metal ion complex which is formed.
- the calcium or other polyvalent metal is very tightly bound.
- an improved process for treating aqueous solutions containing polyvalent metal ions which comprises adding to said solution an effective amount of a triphosphonate compound.
- Specific applications of such a process include the softening of water since the ethane triphosphonate compounds form tight complexes with the metal ions which impart hardness to the aqueous solution, e.g., calcium, iron, copper, magnesium ions and the like.
- the metal ions which impart hardness to the aqueous solution, e.g., calcium, iron, copper, magnesium ions and the like.
- the ethane triphosphonates are also suitable as additivcs to dye baths for textiles, in which they form complexes with metal ions which would otherwise produce undesired shades of color.
- Yet further applications include agricultural uses such as making up concentrates of herbicides and plant treating compositions; photographic uses in which hard water elements are responsible for sludges and turbidity in developing and fixing solutions; industrial cleaning situations in which scales and sludges are formed, such as hard water scale, milk stone, beer stone, metal soaps, floor cleaning compounds, boiler and evaporator scales, and sugar evaporator scales.
- the sequestrants of the present invention can be used in conjunction with bleaching and brightening steps, and desizing and dyeing baths.
- the ethane triphosphonate compounds of the present invention are also useful as additives to synthetic rubber; in tanning processes; rate earth separations; as well as in pharmaceuticals. Still other valuable uses of sequestrants are found in the literature including a text entitled Organic sequestering Agents, Written by S. Chaberek and A. Martell, published in 1959 by John Wiley & Sons, Inc., New York, NY.
- ethane triphosphonate compounds as described herein, are useful as builder compounds and also that they are useful as sequestrants. It should be noted that the builder activity of these compounds is not directly related to the sequestering ability of these same compounds. The builder properties are clearly demonstrable, even if distilled water is used exclusively in detergency tests. Moreover, there is no predictable correlation between relative performances of sequestrants and detergent builders. Some highly efficient sequestrants are inferior as builders, While some less efiicient sequestrants are very valuable as builder compounds.
- one of the most important objects of the present invention is to combine detergent compounds with the compounds of the present invention in order to prepare highly useful built detergent compositions.
- No one prior to this invention has employed the particular combination of builder and detergent compounds in the specific and preferred proportions described herein.
- the result is a built detergent composition that offers as advantages stability against deterioration during storage and use, high detergent power at remarkably low usage level, outstanding performance in hard Water, as well as excellent whiteness and whiteness maintenance results.
- the built detergent compositions of the present invention perform equally well with either ordinary tap water which is at room temperature as well as with water which has been heated to temperatures on the order of 140-160 F., and even higher.
- detergent compositions consisting essentially of an organic detergent surfactant compound and, as a builder ingredient, an organic water soluble salt of one or a mixture of the new class of compounds identified above, the ratio by weight of the builder ingredient to the detergent surfactant compound being in the range of about :1 to about 1:3.
- the composition should provide at the usage level in solution a pH of between about 8 to about 12.
- the preferred ratio of said builder ingredient to said detergent surfactant compound is in the range of about 5:1 to about 1:2.
- the optimum pH range based on overall performance re sults in between 9 to 11. If the combination of the builder and detergent do not produce a pH in this range, alkaline compounds can be used to provide the necessary pH adjustment.
- organic detergent surfactant compounds which can be successfully built by compounds prepared according to this invention are anionic, nonionic, ampholytic and zwitterionic detergent surfactants, and mix tures thereof.
- the anionic organic detergents include both soap and non-soap detergents.
- Suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C -C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
- the non-soap anionic synthetic detergents can be broadly described as the water soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
- alkyl are higher acyl radicals.
- the synthetic detergents which form a part of the preferred compositions of the present invention are the sodium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C -C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkylbenzenesulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, especially those of the types described in US. Letters Patents Nos.
- sodium alkylglycerylethersulfonates especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid ester of the reaction product of one mole of the higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide; sodium or potassium salts of alkylphenol ethylene oxide ether sulfates with about 1 to 10 units of ethylene oxide per molecule and in which the alkyl radicals contain about 9 to about 12 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyltauride in which the fatty acids, for example, are derived from coconut oil
- Nonionic synthetic detergents This class of synthetic detergents may be broadly defined as compounds aliphatic or alkyl aromatic in nature which do not ionize in water solution.
- Pluronic a well known class of nonionic synthetic detergents is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
- the hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1200 to 2500.
- the addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.
- nonionic synthetic detergents include:
- the polyethylene oxide condensates of alkylphenols e.g., the condensation products of alkylphenols or dialkylphenols wherein the alkyl group contains from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, said ethylene oxide being present in amounts equal to 8 to 25 moles of ethylene oxide per mole of alkylphenol.
- the alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, n-octene, or n-nonene, for example.
- Those nonionic compounds derived from the con densation of ethylene Oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are satisfactory.
- compounds containing from about 40% to about polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylenediamine and excess propylene oxide, said base having a molecular weight on the order of 2,500 to 3,000 are satisfactory.
- R R R N+O Long chain tertiary amine oxides corresponding to the following general formula, R R R N+O, wherein R is an alkyl radical of from about 8 to 18 carbon atoms, and R and R are each methyl or ethyl radicals.
- the arrow in the formula is a conventional representation of a semi-polar bond.
- amine oxides suitable for use in this invention include dimethyldodecylamine oxide, dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide, dimethylhexadecylarnine oxide.
- Ampholytic synthetic detergents This class of synthetic detergents can be broadly described as derivatives of aliphatic amines which contain a long chain of about 8 to 18 carbon atoms, and an anionic water solubilizing group, eg carboxy, sulfo, or sulfato. Examples of compounds falling within this definition are sodium-3-dodecylaminopropionate and sodium 3 dodecylaminopropanesulfonate.
- Zwitterionic synthetic detergents This class of synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium compounds, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, or sulfato. Examples of compounds falling Within this definition are 3 (N,N-dimethyl-N-hexadecylammonio) propane-l-sulfonate and 3 (N,N-dimethyl-N-hexadecylammonia)-2-hydroxypropane-l-sulfonate.
- anionic, nonionic, ampholytic and zwitterionic detergent surfactants mentioned above can be used singly or in combination in the practice of the present invention, as in fact, the builder ingredients can be a single triphosphonate or a mixture of two or more of such compounds.
- the above listed examples of detergents is certainly not intended to be complete but merely illustrative of the numerous detergents which can find application within the scope of this invention.
- organic synthetic detergent compounds and the novel builder compounds of this invention can be formulated according to any of the several commercially desirable composition forms, for example, granular, flake, liquid and tablet form.
- Granular detergent compositions according to one em- 12 bodiment of this invention can contain a representative builder ingredient and a detergent active in the ratio of about 10:1 to about 1:3 by Weight.
- the preferred ratio of builder ingredient to detergent active in a granular product is about 5:1 to about 1:2.
- Another special embodiment of this invention is a liquid detergent composition also containing a builder ingredient and a detergent active in the ratio of about 10:1 to about 1:3.
- the preferred ratios and optimum detergency results with liquid compositions obtain when the builder ingredient and the detergent active are mixed in ratios by weight of about 3:1 to about 1:2, respectively.
- the potassium salt form of the builder compounds is usually preferred for use in built liquid compositions.
- a finished detergent formulation of this invention there can be added in minor amounts materials which make the product more effective or more attractive.
- materials which make the product more effective or more attractive.
- a soluble sodium carboxymethyl cellulose can be added in minor amounts to inhibit soil redeposition;
- a tarnish inhibitor such as benzotriazole or ethylenethiourea can also be added in amounts up to about 2%, fluorescers, perfume, and color while not essential in the compositions of the invention, can be added in amounts up to about 1%, an alkaline material or alkali such as sodium hydroxide or potassium hydroxide can be added in minor amounts as supplementary pH adjusters.
- suitable additives water, brightening agents, sodium sulfate, and sodium carbonate.
- Corrosion inhibitors generally are added also.
- Soluble silicates are highly efficient inhibitors and can be added to certain formulas of this invention at levels of from about 3% to about 8%.
- Alkali metal, preferably potassium or sodium, silicates having a weight ratio of SiO :M O of from 1.0:1 to 2.8:1 can be used. M in this ratio refers to sodium or potassium.
- a sodium silicate having a ratio of SiO :Na O of about 1.621 to 2.45:1 is especially preferred for economy and effectiveness.
- a hydrotropic agent may at times be found desirable.
- Suitable hydrotropes are water soluble alkali metal salts of toluenesulfonate, benzenesulfonate, and xylenesulfonate.
- Preferred hydrotropes are the potassium or sodium toluenesulfonates.
- the hydrotrope salt may be added, if desired, at levels of 0% to about 12%. While a hydrotrope will not ordinarily be found necessary it can be added, if so desired, for any reason such as to produce a product which retains its homogeneity at a low temperature.
- cleaning means the ability of a built laundering composition to remove deeply embedded soil lines or deposits such as occur at the collars and cuffs of white shirts.
- whiteness is a more general term which is a measurement of the ability of a built laundering composition to whiten areas which are only slightly or moderately soiled.
- Whiteness maintenance is a term used to describe the ability of a laundering composition to prevent the soil, which has been removed during the washing process from being redeposited upon the fabrics during the remainder of the washing cycle. Test methods are described below.
- the washed and dried fabric were then visually compared with other fabrics which had been similarly worn and soiled but which were washed with a standard detergent composition. This visual comparison was made by a group of five people who were unfamiliar with the structure and purpose of the test and who formed their judgments independently.
- the builder used for comparative purposes was sodium tripolyphosphate, STP, which is widely used and readily available commercially. Tetrasodium dihydrogen ethane- 1,1,2-triphosphonate was selected as a representative builder salt prepared according to this invention.
- the synthetic detergent compound used was dodecyl benzene sulfonate wherein the dodecyl radical was derived from tetrapropylene.
- the usage level of the surfactant in the washing solution was at a concentration of .03% by weight.
- the concentration of the substituted ethane triphosphonate builder compound was also 03%.
- Data was obtained for sodium tripolyphosphate at .03% in order to have a comparison at equal usage levels.
- the sodium tripolyphosphate was also tested at 06% in order to determine how the compounds of this invention would compare to sodium tripolyphosphate when only one-half as much ethane-1,1,2- triphosphonate was used. The results were surprising, for they showed that ethane-1,1,2-triphosphonate offered a very considerable improvement over sodium tripolyphosphate at equal usage levels of 03%.
- Whiteness measurements were made on the backs of the naturally soiled cuffs with a commercially available photoelectric trichromatic colorimeter, i.e., a Hunter Color and Color Difference Meter manufactured by Henry A. Gardner Laboratory, Inc.
- a commercially available photoelectric trichromatic colorimeter i.e., a Hunter Color and Color Difference Meter manufactured by Henry A. Gardner Laboratory, Inc.
- This instrument is designed to distinguish color differences and operates on the tristimulus colorimeter principle wherein the 45-degree diffuse reflectance of an incident light beam on a test specimen is measured through a combination of green, blue and amber filters.
- the electrical circuitry of the instrument is so designed that lightness and chromaticity values for the test specimen are read directly.
- the departure from white (MgO being taken as a standard white) of the test specimen is calculated by a calibrated weighting (i.e., calibrated previously against visual impressions of whiteness differences) of the lightness and chromaticity value so obtained.
- An evaluation of relative whiteness performance compared to a standard detergent composition is thus obtained for the test formulations. These are later compared with other values obtained from other test samples.
- the whiteness maintenance evaluation was performed by the following method. Unsoiled swatches of cotton terrycloth were added to the collar and cuff samples which were washed according to the above cleaning and whiteness examples. The cotton swatches were thereafter independently evaluated to determine the whiteness maintenance property of the particular built laundering compositions. As mentioned above, soil carried by the cotton terrycloth swatches after the washing cycle represents soil polyphosphate built composition tested at pH 10 and 140 F., or Composition in the table below.
- composition Composition:
- composition B 03% tetrapropylene benzene sulfonate B 03% tetrasodium dihydrogen ethane l,l,2- 04 triphosphonatc. ⁇ 03% tetrapropylene benzene sulfonate .1 00 C 00% sodium tripolyphosphate Hf
- the superior whiteness maintenance results obtained Composition B were again at the expense of Composition C notwithstanding that the usage level or concentration of the builder in Composition C was twice that of Composition B again evidencing the remarkable efiiciency of detergent composition built with builder compounds of the present invention.
- the values of .00 for the sodium tripolyphosphate built Composition C represents an extrapolation from actual measurements by the Hunter Color and Color Difference Meter.
- the detergent compounds used were tetrapropylene benzene sulfonate and 3-(N,N-dimethyl, N-hexadecylammonio)propane-l-sulfonate.
- the concentration in solution was .03 by weight of the detergent and either 03% or .06% of the builder as seen from Table V below.
- composition 2 tetrasodium dihydrogen ethane-1,1,2-triphosphonate at 03% (Column 1) performs equally as well as sodium tripolyphosphate does at double the concentration or at 06%, pH 10 and 140 F. (Composition 5 and Column 3). At equal concentrations of .06% tetrasodium dihydrogen ethane-1,1,2-triphosphonate (Column 2) and .06% sodium tripolyphosphate (Column 3) perform equally well with the same detergent active. The percentages for Compositions 1 and 2 average 55.4% which is not significantly different from 55.8% for the sodium tripolyphosphate built-composition 5.
- compositions in which the percentages are by weight will serve to illustrate but not limit this invention.
- the compositions in the examples should be used for best results in a solution having a pH within the desired range of from about 8 to about 12. This may in some instances require supplementary amounts of the alkaline materials mentioned above as pH adjusters.
- a built detergent composition consisting essentially of (a) an organic detergent selected from the group consisting of anionic, nonionic, ampholytic, and zwitterionic detergents, and mixtures thereof, and (b) as a builder, a compound having the following general formula:
- Y substituent is selected from the group consisting of hydrogen, sodium, potassium, ammonium, ammonium substituted with lower alkyl radicals containing less than seven carbon atoms and lower hydroxyalkyl radicals containing less than seven carbon atoms,
- ratio by weight of said builder to said detergent is in the range of from about 10:1 to about 1:3.
- a built detergent composition according to claim 1 wherein the ratio by weight of said builder to said detergent is from about 5:1 to about 1:2.
- JIIGIIC (190 Along; pun qmooog 30 em;
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Description
United States Patent 3,551,339 BUILT DETERGENT COMPOSITIONS Oscar T. Quimby, Colerain Township, Hamilton County, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Dec. 16, 1966, Ser. No. 602,161
Int. Cl. C11d 3/26, 3/36 US. Cl. 252-152 5 Claims ABSTRACT OF THE DISCLOSURE A detergent composition is provided containing an organic detergent and a triphosphonate builder, the ratio by weight of builder to detergent being from :1 to 1:3.
This invention relates to and has among its objects new and useful organic compounds. More particularly, it relates to water-soluble triphosphonates which are substituted ethane compounds having the following general formula:
l P OaYz The acid may be neutralized to any desired degree using a base which gives a soluble salt and is in other respects desired. The particular base material used can and will vary and, in itself, is not critical although sodium, potassium, ammonium, and low molecular weight substituted ammonium salts represent the preferred embodiments of the present invention as more fully described hereinafter.
A principal object of the present invention is to provide a novel class of organic compounds containing three phosphonic acid groups. A second important object of the invention predicated on the unexpected usefulness of these compounds as excellent builders is to provide outstandingly efiicient built detergent compositions. Other objects will become apparent from the following detailed description of the present invention.
According to the present invention, the synthesis of these compounds can be accomplished in various ways. A useful process involves the alkylation of the carbanion of the tetraisopropyl ester of methylenediphosphonate (I) with diisopropyl bromoethanephosphonate (II), with the resulting formation of sodium bromide (III), and the desired substituted ethane compound of the type indicated above (IV). This reaction proceeds according to the following general equation:
(Equation A) The carbanion starting material (I) is readily obtained by an oxidation-reduction type of a reaction between a metallating agent such as sodium, sodium hydride, potassium, or potassium-sodium eutectic alloy, and a tetraalkyl ester of methylenediphosphonic acid, e.g. tetraisopropyl methylenediphosphonate. This reaction is highly exothermic and it is essential that it be conducted at low temperatures on the order of 0 C. to about 35 C., and preferably between 15 C. and 30 C. The reaction prod--. net is a carbanion derived from the active methylene grouping present in the parent methylene ester starting material. The equation for this step is as follows: (M rep resents one of the metallating agents such as those listed above).
The resulting sodio or potassio carbanion derivative, for example, alkylates moderately readily with a phosphonomethyl alkylating agent such as diisopropyl bromomethanephosphonate, as in Equation A above, yielding the corresponding triphosphonate ester which, if desired, can be hydrolyzed or pyrolyzed to the free acid. The free acid, in turn, can be neutralized to any degree desired with any ordinary base material. As it turns out, however, the tri-, tetra-, pentaand hexa-salts are the most easily separatable forms and this degree of neutralization is usually performed.
The alkylating agent, such as the diisopropyl bromomethanephosphonate (II), can be obtained by reaction of phosphorus tribromide, PBr with formaldehyde, CH O, by known methods to make bromomethylphosphoryldibromide, BrCH P(O)Br the desired diisopropyl bromomethanephosphonate, BrCH PO R product is obtained from this acid bromide by reaction with isopropyl alcohol.
A suitable halogen containing alkylating agent can also be prepared by an Arbuzov rearrangement involving an excess of CH X wherein X represents chlorine, bromine or iodine, according to the following equation:
In either case, the desired alkylating agent can be purified readily by known distillation techniques. Yet another method is a two step process beginning with formaldehyde and phosphorous trihalide, thus: (X can be either chlorine, bromine or iodine).
The reaction between the carbanion and the alkylating agent is conveniently carried out in the presence of an inert diluent or solvent, for example, toluene or other aromatic hydrocarbons. Saturated hydrocarbons or ethers may also be used but are less desirable because they dissolve very little of the carbanion.
The alkylating reaction requires a temperature in excess of about C. and less than about C. A preferred range within which to operate is from about 90 C. to about 130 C. The reaction requires from 30 minutes to about hours, with a preferred operable range being from about 50 minutes to about 2.5 hours.
The following two experiments are typical examples for the preparation of the starting materials in Equation A above. The first relates to the formation of the ester of tetraisopropyl methylenediphosphonate from which the carbanion is prepared and the second is a preparation of the diisopropyl bromomethanephonsphonate alkylating agent.
TETRAISOPROPYL METHYLENEDI- PHOSPHONATE 624.7 gms. of triisopropyl phosphite (3 moles, 681 ml.) and 173.9 gms. of dibromomethane (1 mole, 70 ml.) were combined in a reaction apparatus composed of a 1-liter, 3-neck flask fitted with a magnetic stirrer, a thermometer, and a fractionating column for separating the isopropyl bromide by-product from the refluxing mixture. The fractionating column was constructed from a 36-inch Liebig condenser that had been modified to accommodate A- inch glass helices as packing. A Barrett distilling receiver, which had been modified by the addition of a thermometer well and thermometer was connected to the top of the fractionating column; and to the top of the Barrett receiver was fitted a Dewar condenser cooled with Dry Ice and protected from atmospheric moisture by a drying tube. The temperature of the reaction mixture was quickly brought to reflux at 143 C. The temperature of the circulating water in the packed reflux condenser was maintained at 65 C. This temperature was suflicient to return unreacted starting material and allow the by-product isopropyl bromide to be distilled. The heat input to the reaction was such that vigorous refluxing continued as the temperature of the mixture slowly increased. After about two hours of heating the first distillate was observed, and after five hours a total of 33 gms. of isopropyl bromide had been collected. The temperature of the reaction mixture was allowed to increase to 185 C. over a twelve-hour period, and by means of an electronic temperature controller it was held there for the remainder of the reaction.
After approximately 16 hours, the reaction was essentially complete as judged by the yield of isopropyl bromide, 231 gms. which represented a yield of about 92%. Further heating served no useful purpose and may cause partial pyrolysis to the free acid; however, longer reaction times can be used, if desired, when for any reason the acidification is a desired result.
When the reaction was complete, the reaction mixture was transferred to a distilling flask and the low boiling materials (excess phosphite, etc.) were removed through a short one-piece still under a vacuum of 0.1 mm. of mercury and heat temperatures up to 50 C. At this point the content of the flask weighed approximately 330 gms. and was 93% to 95% tetraisopropyl methylenediphosphonate. The purity of this material was suflicient to proceed in the synthesis of the novel compounds of this invention.
If a purer product is desired, a high capacity vacuum pump can be introduced into the system and the pressure reduced to 0.005 mm. of mercury. The material boiling between 80 C. and 116 C. is collected and redistilled through an electrically heated 24-inch Vigreaux column. A complete example of this type of process is presented in a copending patent application, Ser. No. 218,862, filed Aug. 23, 1962, by Clarence H. Roy, now issued as U.S. Pat. 3,251,907, dated May 17, 1966.
4 DIISOPROPYL BROMOMETHANEPHOSPHONATE BI'CHQPO OC3H7) 2 1738.35 gms. of methylene bromide (10 moles) were combined with 1040.2 gms. of triisopropyl phosphite (5 moles) and brought to reflux at C. under a 24-inch Liebig column packed with glass helices. After the liquid had refluxed for 16 hours, the jacket temperature in the reflux condenser was raised from 18 C. to 63 C. so that the low boiling isopropyl bormide would be fractionated otf as it was formed. A Barrett collector modifled by the addition of a thermometer well (fitted with a themometer) and another reflux condenser, this one with a jacket temperature of 18 C., was used to collect the isopropyl bromide. The reaction was continued until a total of 41 hours of heating time was reached, during which 62.5%, 384 gms., of the theoretical amount of isopropyl bromide was collected.
The reaction was deliberately stopped at this point to prevent excessive reaction of the diisopropyl bromomethylphosphonate with the remaining triisopropyl phosphite to make tetraisopropyl methylenediphosphonate.
The reflux temperature rose slowly during the heating period from the starting temperature of 105 to after the given time as the lower boiling methylene bromide was consumed to give a much higher boiling diisopropyl bromomethylphosphonate.
The excess and unreacted reagents were then removed by distillation at less than 60 C. with a vacuum of 5 mm. Hg. After a gross distillation of the remaining material, a refractionation through a 6-inch vacuum jacketed silvered column, packed with glass helices, gave 479.2 gms. (yield37%) of diisopropyl bromomethylphosphonate, B.P. 48 at 10 microns vacuum. This column was ideal for the refractionation, as the diisopropyl bromomethylphosphonate easily distills, while the higher boiling impurity of tetraisopropyl methylenediphosphonate can be distilled only with much more difliculty and at a much higher temperature. This being the case the 143 gms. (0.415 mole) of diphosphonate were left undistilled.
The diisopropyl bromomethylphosphonate and tetraisopropyl methylenediphosphonate can be distinguished by their refractive indices and proton NMR spectra, but the P NMR spectra cannot be used for identification of a mixture, as the chemical shifts (delta) for both compounds in the latter is the same, at 18 ppm, relative to 85% H PO (external standard) as zero. The refractive index (at 25 C.) for methylenediphosphonate is 1.4318 compared to 1.4500 for bromomethylphosphonate, and the proton NMR spectrum of the diphosphonate gives a triplet at tau=7.8 p.p.m. (protons in tetramethylsilane set equal to 10.0 p.p.m.), J=20.1 cps., compared to a doublet at tau=6.9 p.p.m., 1:10 cps., for bromomethylphosphonate.
Having described above typical methods for preparing the individual reactants, there is now presented a complete example covering the preparation of tetrasodium dihydrogen ethane-1,1,2-triphosphonate.
TETRASODIUM DIHYDROGEN ETHANE-l,1,2- TRIPHOSPHONATE The reaction apparatus for this reaction consisted of a 1-liter, 3-neck flask, fitted with a high speed stirrer (capable of 10,000 r.p.m.), a thermometer, a 50 ml. offset additive type separatory funnel, and an Allihn condenser. A 1,2-dimethoxyethane-Dry Ice bath was used to control the reaction as was needed.
19.55 gms. of potassium (0.5 mole) and ml. of toluene were placed in the reaction vessel, which had been dried by baking in an oven at 110 C. The mixture was heated to 70 C., and a potassium dispersion was made by stirring at 9,000 r.p.m. for 5 minutes, removing the heat and maintaining that speed until the temperature dropped below 50 C. The stirrer was slowed to give steady agitation while the temperature of the dispersion was dropped at 25 C. 172.17 gms. of tetraisopropyl methylenediphosphonate (0.5 mole) were then added dropwise over a 40 minute period, while the reaction temperature was maintained at about 20-25 C. by cooling with the Dry Ice bath. All of the potassium was thus consumed in the reaction. The reaction mixture was left stirring for one hour. 129.54 gms. (0.5 mole) of diisopropyl bromomethanephosphonate was added dropwise to the reaction mixture. An immediate red-organe color developed, but no heat evolution or KBr precipitation was observed. The reaction mixture was cautiously heated, and as the temperature reached 110 C., exothermic reaction began to occur which was enough to raise the reaction temperature to 130 only momentarily. After the temperature began to drop, suificient heat was applied to keep the reaction temperature at 110 for 2 hours. The solvent was then evaporated off and the residue dissolved in 200 ml. of water. This solution was placed in a liquidliquid extractor and extracted for 20 hours with hexane. Evaporation of the water solution gave a white precipitate, filtered to give 78% of the theoretical amount of potassium bromide (analysis showed 32.7% K, 65.7% Br, 0.9% H A small amount of gummy material remained in the concentrated filtrate. The hexane extract was dried with MgSO concentrated and partially distilled through a short path column. The distillate was composed of a mixture of tetraisopropyl methylenediphosphonate and diisopropyl bromomethanephosphonate while the undistilled portion, 38.3% of the total reaction product contained 83% of hexaisopropyl ethane-1,1,2- triphosphonate (261.252 grns.) making a 33.7% overall yield of the desired triphosphonate. The triphosphonate can be distinguished from the tetraisopropyl methylenediphosphonate and the diisopropyl bromomethanephosphonate by using the following data. Triphosphonate: 11 1.4430, P NMR spectrum gives a peak with a chemical shift of 20.5 p.p.m. Methylenediphosphonate: n 1.4318, P NMR spectrum gives a triplet at tau=--18 p.p.m., proton NMR gives a triplet at tau=7.8 p.p.m., 1:20 cps. Bromomethanephosphonate: 11 1.4500, P NMR spectrum gives a peak at delta=18 p.p.m., proton NMR gives a doublet at tau =6.9 p.p-.-m., I =10 cps.
The undistilled portion, containing 83% triphosphonate, was converted to the free acid by refluxing for hours with a 100% excess of concentrated HCl. The acidic solution was evaporated to a constant volume and azeotroped four times with n-propanol to remove traces of HCl before dissolving the residual phosphonic acid in water and titrating to the tetrasodium salt at a pH of 8.5 with four molar equivalents of NaOH. The salt was purified by recrystallization from methanol-water solution to give the final product.
Analysis.Calculated for C H O P Na (percent): C, 6.71; H, 1.41; P, 25.96; Na, 25.69. Found (percent): C, 6.71; H, 1.35; P, 24.8; Na, 25.9.
Neutron Magnetic Resonance Spectra-P A single broad peak at delta=21.0 p.p.m.; H Complex and unanalyzed set of peaks for CH CH in the range of tau=7.1 to 8.2 ppm. plus a sharp singlet at tau:4.96 p.p.m. for POH.
The novel triphosphonate compounds of the present invention also can be prepared by another route. This alternative method avoids the making of methanediphosphonate as an intermediate. Instead, acetylenemonophosphonate is prepared by a reaction between monolithium acetylide (from LiNH with chlorophosphate in a diethyl ether solvent:
in E1120 HCCLi OlP 03132 LiCl HCCPOsRz This product is then converted to tetraisopropyl ethane-1,1,2-triphosphonate by reaction with diisopropyl hydrogen phosphite in the presence of catalytic amounts of an alkali metal derivative of the latter, e.g. sodium diisopropyl phosphite. This conversion proceeds according to the following equation:
trisodium trihydrogen ethane-1,1,2-triphosphonate Na H 2] tetrasodium dihydrogen ethane-1,1,2-triphosphonate pentasodium hydrogen ethane-1,1 ,2-triphosphonate Na H 2] hexasodium ethane-1,1,2-triphosphonate The corresponding potassium, ammonium and low molecular weight and substituted ammonium salts are equally valuable. With respect to the ammonium derivatives, the triand tetra-salts are the most readily prepared and are the preferred compounds of that particular group. Specific examples of useful substituted ammonium compounds in terms of the present invention are the following:
tris (tetramethylammonium) trihydrogen ethane-1, 1,2-
triphosphonate tetrakis (tetraethylammonium dihydrogen ethane-1,1,2-
triphosphonate Other lower alkyl radicals up to and including hexyl can be used to replace the methyl and ethyl radicals in the preceding formulas.
Specific examples of useful forms of ammonium derivatives substituted with lower hydroxyalkyl radicals containing less than seven carbon atoms are the following:
tris (triethanolammonium) trihydrogen ethane-1,1,2-
triphosphonate z z 3] 3 3 a 2 3 2] tetrakis (monoethanolammonium dihydrogen ethane- 1,1,2-triphosphonate l s (CH2CHZOH) ]4 2 s z 3) 2] A peculiarly outstanding and surprising characteristic common to all of the new triphosphonate compounds of the present invention involves their remarkable sequestering properties. It has been discovered that these compounds possess the capacity of complexing in excess of two moles of calcium per mole of sequestrant. As a typical illustration, for example, data for the tetrasodium salt, Na H [O PCH CH(PO is given below along with other compounds whose sequestering characteristics are more well known.
TABLE I sequestering efiiciency, g. Ctr/100 g. sequcstrant Formula of Salt in 4 Compound free acid tested pH 9 pH 10 pH 11 p11 Sodium ethane-1,1,2-triphosphonatc (I'IQOGP)QOI{CIIZPOEIIQ Nm 1. 9 .17) 21. 2.15) 25. 2 2. 2s) 25. 0 2. 21) Sodium tripolyphosphatc IIsIaOio N85 7. (0. 69) 8. 1 (0. 75) 7. 0 (0. 73) 0. 0 (0.01) Sodium pyrophosphate IIiPiOv N114 2, 7 (0.18) 4. 6 (0.31) 5. O (0. 33) 4. 0 (0. 27) Sodium nitrilotriacctate N(CH2COO )a Naa 11. 4 (0. 73) 13. 4 (0. 86) 13. 6 (0. 87) 13. 2 (O. 85) Sodium ethylene diamine tctrancctateunnh. [CIIzN(CII;C00I'I)2]q Nut 10. 2 (0. 07) 10. 2 (0. 97) 10. 1 (CIv 96) 10. 1 (0. U6)
1 As determined by a slightly modified version of a standardized testing method as published in the Journal of Physical Chemistry 64, 1398 (1960): Metal Complexing by Phosphorous Compounds. I. The Thermodynamics of Association of Linear Polyphosphatos with Calcium" by R. R. Irani and C. F. Callis. It especially will be noted that at pH of 10, 11 and 12 the sodium ethane-1,l,2 triphosphonate compound has sequestered more than two moles of calcium per mole of the triphosphonate used in the test. The only change in the published procedure is in the substitution of caprate C0111- pounds for oxalate compounds. This amount is far in excess of the moles of calcium sequestered by the other compounds tested. This is all the more surprising in view of the fact that the four compounds selected for comparison are all reputedly known scqnestrants which are commonly recommended for sequestering applications. The compounds of this invention can be usefully substituted in place of these other materials in all analytical, biological, physiological and industrial applications which are well documented, as for instance, in the text entitled Organic sequestering Agents written by Chabcrek and Martcll, copyright 1959.
1 Moles Ca/Molc Scqucstrant.
This discovery of the remarkable sequestering properties of the triphosphonate compounds described herein now makes possible an efiicient process for treating aqueous solutions containing metal ions, particularly polyvalent metal ions such as calcium, iron, magnesium, zinc and copper, and the like. In many industrial, institutional and household processes and products, metal ion contaminates present in water may adversely affect color, stability, appearance, quality and saleability of a product or the efficiency of a process. The role of a scquestrant or complexing agent in helping to overcome such adverse affects of metal ions is fairly well recognized and appree ciated. There is a continuing need, however, for new compounds which offer superior results.
Therefore, it is another embodiment of the present invention to provide a highly-improved process for treating aqueous solutions containing polyvalent metal ions which comprises adding to the solution an effective amount of an ethane-l,l,2-triphosphonate compound of the type dcscribcd herein. Ordinarily, this amount should range from about .25 p.p.m. to 10,000 ppm. of the aqueous solution. This aspect of the present invention is based on the discovery of the outstanding sequestering properties of the novel triphosphonate compounds of the present invention.
It has been generally recognized that sequestering agents such as amino acid sequestrants including nitrilotriacetic acid and EDTA react with polyvalcnt ions on a mole-to-mole basis. The relative cfficiency of sequestrants is related to their molecular weight. By this criteria, the ethane triphosphonate compounds of the present invention are, in the order of magnitude, about three to four times as efiicient as sodium tripolyphosphate. This is evident from the information presented in Table I above.
As a result of this discovery, it is possible to employ only a fraction of a mole of an ethane triphosphonate compound to sequester or complex as much of a metal ion in aqueous solution as it takes a whole mole of sodium tripolyphosphate to do. In other words, the ethane triphosphonate compounds of the present invention provide an efliciency improvement of considerable magnitude.
In addition to the marked efficiency of the ethane triphosphonate compounds as evidenced, for example, in Table I, there is another noteworthy feature that distinguishes the present invention from previously-known scquestrant compounds. It has been discovered that a complex formed between a polyvalent ion such as calcium and a triphosphonate sequestrant as described herein occurs in a molar ratio of calcium to triphosphonate on the order of about 2:1. Thus, each mole of sodium ethanel,l,2-triphosphonate complexes about two moles of calcium per mole of triphosphonate. More conventional sequestrants such as sodium tripolyphosphate (STP) and EDTA tend to form complexes in a 1:1 molar ratio.
Another distinguishing and valuable characteristic of the sequestering properties of the triphosphonate compounds is the strength of the metal ion complex which is formed. The calcium or other polyvalent metal is very tightly bound.
Based on the outstanding sequestering properties of the ethane triphosphonate of the present invention, there is provided an improved process for treating aqueous solutions containing polyvalent metal ions which comprises adding to said solution an effective amount of a triphosphonate compound. Specific applications of such a process include the softening of water since the ethane triphosphonate compounds form tight complexes with the metal ions which impart hardness to the aqueous solution, e.g., calcium, iron, copper, magnesium ions and the like. In such a process, as has been pointed out above, it is not necessary to add stoichiomctric quantities of the sequestrant, since the use of less than stoichiometric amounts effectively retards or inhibits calcite formation.
Further applications are also apparent from the foregoing description of the invention. Among these are descaling of textiles in which alkaline earth metal salts have been deposited; the lessening of the ash content in fabrics which have been treated with soap or pyrophosphate containing washing agents; in cleaning processes such as in the washing of bottles in which precipitation of calcite is avoided by adding to the washing solution effective amounts of a triphosphonate sequestrant.
The ethane triphosphonates are also suitable as additivcs to dye baths for textiles, in which they form complexes with metal ions which would otherwise produce undesired shades of color. Yet further applications include agricultural uses such as making up concentrates of herbicides and plant treating compositions; photographic uses in which hard water elements are responsible for sludges and turbidity in developing and fixing solutions; industrial cleaning situations in which scales and sludges are formed, such as hard water scale, milk stone, beer stone, metal soaps, floor cleaning compounds, boiler and evaporator scales, and sugar evaporator scales. In textile finishing and dyeing, the sequestrants of the present invention can be used in conjunction with bleaching and brightening steps, and desizing and dyeing baths.
The ethane triphosphonate compounds of the present invention are also useful as additives to synthetic rubber; in tanning processes; rate earth separations; as well as in pharmaceuticals. Still other valuable uses of sequestrants are found in the literature including a text entitled Organic sequestering Agents, Written by S. Chaberek and A. Martell, published in 1959 by John Wiley & Sons, Inc., New York, NY.
The foregoing discussion has indicated that ethane triphosphonate compounds, as described herein, are useful as builder compounds and also that they are useful as sequestrants. It should be noted that the builder activity of these compounds is not directly related to the sequestering ability of these same compounds. The builder properties are clearly demonstrable, even if distilled water is used exclusively in detergency tests. Moreover, there is no predictable correlation between relative performances of sequestrants and detergent builders. Some highly efficient sequestrants are inferior as builders, While some less efiicient sequestrants are very valuable as builder compounds.
As mentioned previously, one of the most important objects of the present invention is to combine detergent compounds with the compounds of the present invention in order to prepare highly useful built detergent compositions. No one prior to this invention has employed the particular combination of builder and detergent compounds in the specific and preferred proportions described herein. The result is a built detergent composition that offers as advantages stability against deterioration during storage and use, high detergent power at remarkably low usage level, outstanding performance in hard Water, as well as excellent whiteness and whiteness maintenance results. In addition, the built detergent compositions of the present invention perform equally well with either ordinary tap water which is at room temperature as well as with water which has been heated to temperatures on the order of 140-160 F., and even higher.
These and other advantages are obtained according to this invention by providing detergent compositions consisting essentially of an organic detergent surfactant compound and, as a builder ingredient, an organic water soluble salt of one or a mixture of the new class of compounds identified above, the ratio by weight of the builder ingredient to the detergent surfactant compound being in the range of about :1 to about 1:3. The composition should provide at the usage level in solution a pH of between about 8 to about 12. The preferred ratio of said builder ingredient to said detergent surfactant compound is in the range of about 5:1 to about 1:2. The optimum pH range based on overall performance re sults in between 9 to 11. If the combination of the builder and detergent do not produce a pH in this range, alkaline compounds can be used to provide the necessary pH adjustment.
The concept underlying the use of certain compounds to aid in the detergency process and to boost, improve or build, as it has become to be known, the cleaning effectiveness of detergent compounds is well known. As detergency and cleaning in general is a tremendously complex and little understood phenomenon similarly the behavior of so-called builder compounds is also as yet unexplained. For this reason, no explanation is given herein for the unusually effective performances obtained with the compounds of this invention when employed as detergency builders. It is quite likely that one factor in the improved efiiciency of the builder compounds presented by this invention is their excellent sequestering propetries described above. It is Well known however, that numerous other factors involving both the chemical and physical characteristics go into the preparation of a superior performing built composition.
Among the many facets of built detergency systems in which builder materials are thought to have some effect are such factors as stabilization of solid soil suspensions, emulsification of soil particles, the surface activity of the aqueous detergent solution, solubilization of water-insoluble materials, foaming or suds producing characteristics of the washing solutions, peptization of soil agglomerates, neutralization of acid soil and sequestration of mineral constituents present in the washing solution tending to harden it.
Among the organic detergent surfactant compounds which can be successfully built by compounds prepared according to this invention are anionic, nonionic, ampholytic and zwitterionic detergent surfactants, and mix tures thereof.
(a) The anionic organic detergents include both soap and non-soap detergents.
Examples of suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C -C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
The non-soap anionic synthetic detergents can be broadly described as the water soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl are higher acyl radicals.) Important examples of the synthetic detergents which form a part of the preferred compositions of the present invention are the sodium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C -C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkylbenzenesulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, especially those of the types described in US. Letters Patents Nos. 2,220,099 and 2,477,383; sodium alkylglycerylethersulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid ester of the reaction product of one mole of the higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide; sodium or potassium salts of alkylphenol ethylene oxide ether sulfates with about 1 to 10 units of ethylene oxide per molecule and in which the alkyl radicals contain about 9 to about 12 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyltauride in which the fatty acids, for example, are derived from coconut oil, and others known in the prior art, a number being specifically set forth in US. Pats. Nos. 2,486,921, 2,486,- 922, and 2,386,278.
(b) Nonionic synthetic detergents: This class of synthetic detergents may be broadly defined as compounds aliphatic or alkyl aromatic in nature which do not ionize in water solution.
For example, a well known class of nonionic synthetic detergents is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1200 to 2500. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.
Other suitable nonionic synthetic detergents include:
1) The polyethylene oxide condensates of alkylphenols, e.g., the condensation products of alkylphenols or dialkylphenols wherein the alkyl group contains from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, said ethylene oxide being present in amounts equal to 8 to 25 moles of ethylene oxide per mole of alkylphenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, n-octene, or n-nonene, for example.
(2) Those nonionic compounds derived from the con densation of ethylene Oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. For example, compounds containing from about 40% to about polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylenediamine and excess propylene oxide, said base having a molecular weight on the order of 2,500 to 3,000, are satisfactory.
(3) The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensation having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.
(4) Long chain tertiary amine oxides corresponding to the following general formula, R R R N+O, wherein R is an alkyl radical of from about 8 to 18 carbon atoms, and R and R are each methyl or ethyl radicals. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of amine oxides suitable for use in this invention include dimethyldodecylamine oxide, dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide, dimethylhexadecylarnine oxide.
() Long chain tertiary phosphine oxides corresponding to the following general formula RRRP O wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chain length and R and R are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are:
(c) Ampholytic synthetic detergents: This class of synthetic detergents can be broadly described as derivatives of aliphatic amines which contain a long chain of about 8 to 18 carbon atoms, and an anionic water solubilizing group, eg carboxy, sulfo, or sulfato. Examples of compounds falling within this definition are sodium-3-dodecylaminopropionate and sodium 3 dodecylaminopropanesulfonate.
(d) Zwitterionic synthetic detergents: This class of synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium compounds, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, or sulfato. Examples of compounds falling Within this definition are 3 (N,N-dimethyl-N-hexadecylammonio) propane-l-sulfonate and 3 (N,N-dimethyl-N-hexadecylammonia)-2-hydroxypropane-l-sulfonate.
The anionic, nonionic, ampholytic and zwitterionic detergent surfactants mentioned above can be used singly or in combination in the practice of the present invention, as in fact, the builder ingredients can be a single triphosphonate or a mixture of two or more of such compounds. The above listed examples of detergents is certainly not intended to be complete but merely illustrative of the numerous detergents which can find application within the scope of this invention.
The foregoing organic synthetic detergent compounds and the novel builder compounds of this invention can be formulated according to any of the several commercially desirable composition forms, for example, granular, flake, liquid and tablet form.
Granular detergent compositions according to one em- 12 bodiment of this invention can contain a representative builder ingredient and a detergent active in the ratio of about 10:1 to about 1:3 by Weight. The preferred ratio of builder ingredient to detergent active in a granular product is about 5:1 to about 1:2.
Another special embodiment of this invention is a liquid detergent composition also containing a builder ingredient and a detergent active in the ratio of about 10:1 to about 1:3. On the other hand, the preferred ratios and optimum detergency results with liquid compositions obtain when the builder ingredient and the detergent active are mixed in ratios by weight of about 3:1 to about 1:2, respectively. The potassium salt form of the builder compounds is usually preferred for use in built liquid compositions.
In a finished detergent formulation of this invention there can be added in minor amounts materials which make the product more effective or more attractive. The following are mentioned only by way of example: A soluble sodium carboxymethyl cellulose can be added in minor amounts to inhibit soil redeposition; a tarnish inhibitor such as benzotriazole or ethylenethiourea can also be added in amounts up to about 2%, fluorescers, perfume, and color while not essential in the compositions of the invention, can be added in amounts up to about 1%, an alkaline material or alkali such as sodium hydroxide or potassium hydroxide can be added in minor amounts as supplementary pH adjusters. There might also be mentioned as suitable additives water, brightening agents, sodium sulfate, and sodium carbonate.
Corrosion inhibitors generally are added also. Soluble silicates are highly efficient inhibitors and can be added to certain formulas of this invention at levels of from about 3% to about 8%. Alkali metal, preferably potassium or sodium, silicates having a weight ratio of SiO :M O of from 1.0:1 to 2.8:1 can be used. M in this ratio refers to sodium or potassium. A sodium silicate having a ratio of SiO :Na O of about 1.621 to 2.45:1 is especially preferred for economy and effectiveness.
In the embodiment of this invention which provides or a built liquid detergent, a hydrotropic agent may at times be found desirable. Suitable hydrotropes are water soluble alkali metal salts of toluenesulfonate, benzenesulfonate, and xylenesulfonate. Preferred hydrotropes are the potassium or sodium toluenesulfonates. The hydrotrope salt may be added, if desired, at levels of 0% to about 12%. While a hydrotrope will not ordinarily be found necessary it can be added, if so desired, for any reason such as to produce a product which retains its homogeneity at a low temperature.
Three different performance characteristics of the new builder compounds were evaluated: cleaning, whiteness and whiteness maintenance. For the purposes of this invention, these terms have the following meanings. The term cleaning means the ability of a built laundering composition to remove deeply embedded soil lines or deposits such as occur at the collars and cuffs of white shirts. whiteness is a more general term which is a measurement of the ability of a built laundering composition to whiten areas which are only slightly or moderately soiled. Whiteness maintenance is a term used to describe the ability of a laundering composition to prevent the soil, which has been removed during the washing process from being redeposited upon the fabrics during the remainder of the washing cycle. Test methods are described below.
One series of experiments which revealed the surprising efficiency of substituted ethane compounds of the present invention in cleaning characteristics as the term is defined in the preceding paragraph, involved the laundering of naturally soiled white dress shirts with detergent compositions built with different builder materials. Shirts with detachable collars were worn by male subjects under ordinary conditions. The collars and cuffs were then detached and laundered in a small agitator type washing machine using solutions of the detergents com- 13 positions to be evaluated for comparison purposes. The specific washing conditions are described below.
The washed and dried fabric were then visually compared with other fabrics which had been similarly worn and soiled but which were washed with a standard detergent composition. This visual comparison was made by a group of five people who were unfamiliar with the structure and purpose of the test and who formed their judgments independently.
Their visual judgments were expressed on a scale ranging from zero to ten where zero represents the cleaning level obtained by washing with water alone and a value of ten represents the'cleaning level of an excellent standardized detergent composition under optimum conditions. Scores intermediate zero and ten allow for relative comparisons to be made between the different compositions being evaluated.
The preceding procedure was followed using detergent compositions consisting solely of a detergent surfactant, and a builder compound. No fluorescers, bleaches, or anti-redeposition agents were used to preclude any possible interference or masking over of the effectiveness of the respective builders used. The washing solutions containing seven grains (equivalent CaOO per gallon hardness were adjusted with NaOH to a pH of at a temperature of 140 F.
The builder used for comparative purposes was sodium tripolyphosphate, STP, which is widely used and readily available commercially. Tetrasodium dihydrogen ethane- 1,1,2-triphosphonate was selected as a representative builder salt prepared according to this invention. The synthetic detergent compound used was dodecyl benzene sulfonate wherein the dodecyl radical was derived from tetrapropylene.
The usage level of the surfactant in the washing solution was at a concentration of .03% by weight. The concentration of the substituted ethane triphosphonate builder compound was also 03%. Data was obtained for sodium tripolyphosphate at .03% in order to have a comparison at equal usage levels. The sodium tripolyphosphate was also tested at 06% in order to determine how the compounds of this invention would compare to sodium tripolyphosphate when only one-half as much ethane-1,1,2- triphosphonate was used. The results were surprising, for they showed that ethane-1,1,2-triphosphonate offered a very considerable improvement over sodium tripolyphosphate at equal usage levels of 03%. The results also showed that ethane-1,1,2-triphosphonate at .O 3% substantially equaled the cleaning performance of sodium tripolyphosphate at .06% concentration. These results were not expected. Such favorable results are all the more surprising when one considers that both sodium tripolyphosphate and ethane-l,1,2-triphosphonate each have three TABLE II Cleaning Detergent composition grade Composition:
{03% tetrapropylene benzene sulfonate A .03% sodium tripolyphosphate {03% tetrapropylene benzene sulionate B .03% tetrasodium hydrogen ethane-1,1,2-
triphosphonate. .03% tetrapropylene benzene sullonate C .06% sodium tripolyphosphate Each of the other substituted ethane compounds identified above which can be prepared according to the present invention perform in substantially the same relative manner, that is superiority over sodium tripolyphosphate at equal concentration of .03% and parity in performance between compositions wherein twice the concentration level of sodium tripolyphosphate, e.g., .06%, as compared to .03% concentration of ethane-1,1,2-triphosphate.
The significance of these experimental results is that, as a result of this invention, it is now possible to use only one-half of the ordinary concentration of builder generally recommended for good laundering results without noticeably sacrificing cleaning performance.
Two of the groups of fabric cuff samples washed with the detergent compositions described in Table II were also examined for whiteness results and the comparative values are presented in Table III below.
Whiteness measurements were made on the backs of the naturally soiled cuffs with a commercially available photoelectric trichromatic colorimeter, i.e., a Hunter Color and Color Difference Meter manufactured by Henry A. Gardner Laboratory, Inc. This instrument is designed to distinguish color differences and operates on the tristimulus colorimeter principle wherein the 45-degree diffuse reflectance of an incident light beam on a test specimen is measured through a combination of green, blue and amber filters. The electrical circuitry of the instrument is so designed that lightness and chromaticity values for the test specimen are read directly. The departure from white (MgO being taken as a standard white) of the test specimen is calculated by a calibrated weighting (i.e., calibrated previously against visual impressions of whiteness differences) of the lightness and chromaticity value so obtained. An evaluation of relative whiteness performance compared to a standard detergent composition is thus obtained for the test formulations. These are later compared with other values obtained from other test samples.
A more comprehensive description of this instrument and its mode of operation appears in Color in Business, Science and Industry, by Deane B. Judd, pp. 260 262; published by John Wiley & Sons, New York (1952).
TABLE IIL-WHITENESS EVALUATION The whiteness figures presented above in Table III illustrate the superior whiteness results obtained with the tetrasodium dihydrogen ethane-1,1,2-triphosphonate built composition. The higher figure of +37 indicates better whiteness levels, i.e., less departure from a standard white. It should be noted that the superior whiteness results which the above figures demonstrate on behalf of Composition B were obtained with only one-half the builder concentration of ethane-l,l,2-triphosphonate, that is, a concentration of .03% ethane 1,1,2 triphosphonate as compared to O6% sodium tripolyphosphate in Composition C. The value of .00 assigned to Composition C is an extrapolation from the actual measurements, and while the figures are not significant in themselves, and while the the two different compositions is highly pertinent.
The whiteness maintenance evaluation was performed by the following method. Unsoiled swatches of cotton terrycloth were added to the collar and cuff samples which were washed according to the above cleaning and whiteness examples. The cotton swatches were thereafter independently evaluated to determine the whiteness maintenance property of the particular built laundering compositions. As mentioned above, soil carried by the cotton terrycloth swatches after the washing cycle represents soil polyphosphate built composition tested at pH 10 and 140 F., or Composition in the table below.
TABLE V. SOIL REMOVAL OF ORIGINAL SOIL ON SWA'ICIIES Col. 1 Col. 2 Col. 3
03% tetra- 06% tetrasodium dihysodium dihydrogen drogen ethaneethane- 06% sodium 1,1,2-triphos- 1,l,2triphostripolyphonate, phonate, phosphate, percent percent percent Composition:
(1) 03% tetrapropylene benzene sulfonate (pH 9.5; 140 F.) 48. 6 51. 5 (2) 03% tetrapropylene benzene sulfonate (pH 10.5; 140 F.) 58. 6 I 59. 3 .O37Z13-(N,N-dimetliyl,N-liexadecylammonio)propane-l-suitonate.. 59.2 (4 o 65.8 (5) 03% tetrapropylene benzene sulfonate (pH 10; 110 F.) 55. 8
TABLE IV.WIIITENESS MAINTENANCE EVALUATION Measured Detergent composition values Composition:
03% tetrapropylene benzene sulfonate B 03% tetrasodium dihydrogen ethane l,l,2- 04 triphosphonatc. {03% tetrapropylene benzene sulfonate .1 00 C 00% sodium tripolyphosphate Hf The superior whiteness maintenance results obtained Composition B were again at the expense of Composition C notwithstanding that the usage level or concentration of the builder in Composition C was twice that of Composition B again evidencing the remarkable efiiciency of detergent composition built with builder compounds of the present invention. As pointed out above, the values of .00 for the sodium tripolyphosphate built Composition C represents an extrapolation from actual measurements by the Hunter Color and Color Difference Meter.
In a third detergency evaluation naturally soiled fabric swatches (desized cotton print cloth) were washed for ten minutes in an aqueous solution having a temperature of 80 F. or 140 F. as specified in Table V below. The washing solution had a pH ranging in different runs from 9.5, 10, 10.5, to 11.5, as spelled out in Table V below. Seven grains equivalent CaCO per gallon hardness were present in the washing solution. Again test compositions were prepared containing only the basic essentials according to the present invention, i.e., a detergent compound and a builder compound. The detergent compounds used were tetrapropylene benzene sulfonate and 3-(N,N-dimethyl, N-hexadecylammonio)propane-l-sulfonate. The concentration in solution was .03 by weight of the detergent and either 03% or .06% of the builder as seen from Table V below.
In Table V the several built detergent compositions tested are ranked according to their relative soil removing properties. Soil removal is expressed as a percentage of the soil originally present on the soiled swatches. A solvent extraction technique was used to determine the amount of soil present on the cloth swatches after washing and drying as well as on similarly soiled but unwashed swatches. Calculations with the data so obtained yielded the figures in Table V.
It is pointed out that the benchmark figure for this set of runs is a tetrapropylene benzene sulfonate-sodium tri- It will be noted that the test results presented in the table above, confirm the previously described performance results which show the marked efiiciency of tetrasodium dihydrogen ethane-1,1,2-triphosphonate as a builder at the lower concentration of .03%. In combination with tetrapropylene benzene sulfonate at 0.3%, pH 9.5 and F. (Composition 1), and also with tetrapropylene benzene sulfonate at 03%, pH 10.5 and 140 F. (Composition 2), tetrasodium dihydrogen ethane-1,1,2-triphosphonate at 03% (Column 1) performs equally as well as sodium tripolyphosphate does at double the concentration or at 06%, pH 10 and 140 F. (Composition 5 and Column 3). At equal concentrations of .06% tetrasodium dihydrogen ethane-1,1,2-triphosphonate (Column 2) and .06% sodium tripolyphosphate (Column 3) perform equally well with the same detergent active. The percentages for Compositions 1 and 2 average 55.4% which is not significantly different from 55.8% for the sodium tripolyphosphate built-composition 5.
The following compositions, in which the percentages are by weight, will serve to illustrate but not limit this invention. The compositions in the examples should be used for best results in a solution having a pH within the desired range of from about 8 to about 12. This may in some instances require supplementary amounts of the alkaline materials mentioned above as pH adjusters.
The foregoing description of the invention has been presented describing certain operable and preferred embodiments. It is not intended that the invention should be so limited since variations and modifications thereof will be obvious to those skilled in the art, all of which are within the spirit and scope of this invention.
What is claimed is:
1. A built detergent composition consisting essentially of (a) an organic detergent selected from the group consisting of anionic, nonionic, ampholytic, and zwitterionic detergents, and mixtures thereof, and (b) as a builder, a compound having the following general formula:
PO3Y2 POaYz iOsY: 1 1
in which the Y substituent is selected from the group consisting of hydrogen, sodium, potassium, ammonium, ammonium substituted with lower alkyl radicals containing less than seven carbon atoms and lower hydroxyalkyl radicals containing less than seven carbon atoms,
wherein the ratio by weight of said builder to said detergent is in the range of from about 10:1 to about 1:3.
2. A built detergent composition according to claim 1 wherein the ratio by weight of said builder to said detergent is from about 5:1 to about 1:2.
3. A built detergent composition according to claim 1 in which the builder is a sodium salt of ethane-1,1,2- triphosphonic acid.
4. A built detergent composition according to claim ACTIVE nmzmmr RATIO OF mm mm IONIC nmnm mm:
mm w m DEBO- mm. mm:
JIIGIIC (190 Along; pun qmooog 30 em;
m UT 1 5 IPS WINS t lw "IN mm "Percentage: and Ration are 8 1 Right 1 in which the builder is a potassium salt of ethane-1,1,2- triphosphonic acid.
5. A detergent composition according to claim 1 in which the anionic detergent is selected from a sodium or potassium alkyl sulfate having 8 to 18 carbon atoms, sodium or potassium alkyl benzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms sodium alkyl glyceryl ether sulfonates derived from talloW and coconut oil, sodium coconut oil fatty acid monoglyceride sulfonates, sodium coconut oil fatty acid monoglyceride sulfates, sodium or potassium salts of sulfuric acid esters of the reaction product of 1 mole of a tallow or coconut oil alcohol and about 1 to 6 moles of ethylene oxide, and sodium or potassium salts References Cited UNITED STATES PATENTS 11/1967 Zimmerer 252138X LEON D. ROSDOL, Primary Examiner M. HALPERN, Assistant Examiner US. Cl. X.R.
Applications Claiming Priority (2)
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US60216166A | 1966-12-16 | 1966-12-16 | |
US1322470A | 1970-02-05 | 1970-02-05 |
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US3551339A true US3551339A (en) | 1970-12-29 |
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US602161A Expired - Lifetime US3551339A (en) | 1966-12-16 | 1966-12-16 | Built detergent compositions |
US13224A Expired - Lifetime US3617575A (en) | 1966-12-16 | 1970-02-05 | Process of treating aqueous solutions with an ethane triphosphonic acid compound |
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US13224A Expired - Lifetime US3617575A (en) | 1966-12-16 | 1970-02-05 | Process of treating aqueous solutions with an ethane triphosphonic acid compound |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3683080A (en) * | 1970-08-28 | 1972-08-08 | Procter & Gamble | Compositions for inhibiting anomalous deposition and mobilization of calcium phosphate in animal tissue |
US3975281A (en) * | 1973-12-26 | 1976-08-17 | Texaco Inc. | Method for treating scale |
EP0353973A2 (en) * | 1988-07-30 | 1990-02-07 | Icn Biomedicals Limited | Phosphate-free detergents |
US11225632B1 (en) | 2020-08-13 | 2022-01-18 | Donald Richard Wilshe | Cleaning composition for facilitating cleaning surfaces of an object using femtotechnology |
WO2023227357A1 (en) | 2022-05-27 | 2023-11-30 | Unilever Ip Holdings B.V. | Composition |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2621606C2 (en) * | 1976-05-14 | 1987-04-16 | Bayer Ag, 5090 Leverkusen | Use of propane-1,3-diphosphonic acids for water conditioning |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA813301A (en) * | 1966-09-06 | 1969-05-20 | E. Zimmerer Roger | Detergent composition |
-
1966
- 1966-12-16 US US602161A patent/US3551339A/en not_active Expired - Lifetime
-
1970
- 1970-02-05 US US13224A patent/US3617575A/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3683080A (en) * | 1970-08-28 | 1972-08-08 | Procter & Gamble | Compositions for inhibiting anomalous deposition and mobilization of calcium phosphate in animal tissue |
US3975281A (en) * | 1973-12-26 | 1976-08-17 | Texaco Inc. | Method for treating scale |
EP0353973A2 (en) * | 1988-07-30 | 1990-02-07 | Icn Biomedicals Limited | Phosphate-free detergents |
EP0353973A3 (en) * | 1988-07-30 | 1990-10-17 | Icn Biomedicals Limited | Phosphate-free detergents |
US11225632B1 (en) | 2020-08-13 | 2022-01-18 | Donald Richard Wilshe | Cleaning composition for facilitating cleaning surfaces of an object using femtotechnology |
WO2023227357A1 (en) | 2022-05-27 | 2023-11-30 | Unilever Ip Holdings B.V. | Composition |
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