US3565949A - Diaminoalkanediylidenetetraphosphonic acids useful in cleaning compositions - Google Patents
Diaminoalkanediylidenetetraphosphonic acids useful in cleaning compositions Download PDFInfo
- Publication number
- US3565949A US3565949A US660579A US3565949DA US3565949A US 3565949 A US3565949 A US 3565949A US 660579 A US660579 A US 660579A US 3565949D A US3565949D A US 3565949DA US 3565949 A US3565949 A US 3565949A
- Authority
- US
- United States
- Prior art keywords
- acid
- sodium
- builder
- acids
- detergent
- 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
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- 239000002253 acid Substances 0.000 title abstract description 28
- 239000000203 mixture Substances 0.000 title abstract description 18
- 150000007513 acids Chemical class 0.000 title description 17
- 238000004140 cleaning Methods 0.000 title 1
- 239000003599 detergent Substances 0.000 abstract description 21
- -1 alkali metal salts Chemical class 0.000 description 25
- 235000019832 sodium triphosphate Nutrition 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 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 14
- 230000014759 maintenance of location Effects 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 235000001465 calcium Nutrition 0.000 description 11
- 229960005069 calcium Drugs 0.000 description 11
- 239000013522 chelant Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- RHVWSRKGJFLDFG-UHFFFAOYSA-N [aminooxy(hydroxy)phosphoryl]methylphosphonic acid Chemical compound NOP(O)(=O)CP(O)(O)=O RHVWSRKGJFLDFG-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 6
- 229940049964 oleate Drugs 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000271 synthetic detergent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000007859 condensation product Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 159000000001 potassium salts Chemical class 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 101100476962 Drosophila melanogaster Sirup gene Proteins 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 235000020357 syrup Nutrition 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 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
- 239000011149 active material Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical class OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 2
- 235000002949 phytic acid Nutrition 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- HLHOHTNONYACFD-UHFFFAOYSA-N 1-[4-[4-morpholin-4-yl-1-[1-(pyridine-3-carbonyl)piperidin-4-yl]pyrazolo[3,4-d]pyrimidin-6-yl]phenyl]-3-pyridin-4-ylurea Chemical compound C=1C=C(C=2N=C3N(C4CCN(CC4)C(=O)C=4C=NC=CC=4)N=CC3=C(N3CCOCC3)N=2)C=CC=1NC(=O)NC1=CC=NC=C1 HLHOHTNONYACFD-UHFFFAOYSA-N 0.000 description 1
- NDVLTZFQVDXFAN-UHFFFAOYSA-N 3-(2-cyanoethylsulfanyl)propanenitrile Chemical compound N#CCCSCCC#N NDVLTZFQVDXFAN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 101100114365 Caenorhabditis elegans col-8 gene Proteins 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229960002713 calcium chloride Drugs 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000005829 chemical entities Chemical class 0.000 description 1
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical class [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- SPCNPOWOBZQWJK-UHFFFAOYSA-N dimethoxy-(2-propan-2-ylsulfanylethylsulfanyl)-sulfanylidene-$l^{5}-phosphane Chemical compound COP(=S)(OC)SCCSC(C)C SPCNPOWOBZQWJK-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LLEVMYXEJUDBTA-UHFFFAOYSA-N heptanedinitrile Chemical compound N#CCCCCCC#N LLEVMYXEJUDBTA-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000004334 oxygen containing inorganic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 108700004121 sarkosyl Proteins 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000021148 sequestering of metal ion Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 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
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical class OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- JZBRFIUYUGTUGG-UHFFFAOYSA-J tetrapotassium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JZBRFIUYUGTUGG-UHFFFAOYSA-J 0.000 description 1
- 229960001479 tosylchloramide sodium Drugs 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- JEVFKQIDHQGBFB-UHFFFAOYSA-K tripotassium;2-[bis(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O JEVFKQIDHQGBFB-UHFFFAOYSA-K 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 230000000007 visual effect Effects 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
- C11D3/364—Organic compounds containing phosphorus containing nitrogen
-
- 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)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3839—Polyphosphonic acids
- C07F9/3873—Polyphosphonic acids containing nitrogen substituent, e.g. N.....H or N-hydrocarbon group which can be substituted by halogen or nitro(so), N.....O, N.....S, N.....C(=X)- (X =O, S), N.....N, N...C(=X)...N (X =O, S)
Definitions
- This invention relates to cleansing compositions and in particular to detergent compositions having builder ingredients for augmenting the cleansing action of the detergent.
- the builder materials utilized heretofore suffer from certain limitations and disadvantages.
- the so-called condensed inorganic polyphosphates such as the alkali metal tripolyphosphates
- condensed inorganic polyphosphates such as the alkali metal tripolyphosphates
- Such compounds the most common of which is sodium tripolyphosphate, exhibit a propensity when used in detergent compositions, of hydrolyzing into less condensed derivatives having diminished builder properties.
- these less condensed products, which include orthoand pyro-phosphates may form undesirable precipitates in the aqueous washing solution.
- diaminoalkanediylidenetetraphosphonic acid builder materials herein can be depicted by the following general formula wherein A is a 2-6 carbon alkylene bridge which may be centrally interrupted by oxygen or sulfur and R is a hydrogen or lower hydroxyalkyl such as HOCH HOCH CH HO(
- a lower hydroxyalkyl means that the hydrocarbon moiety may contain from l-S carbon atoms.
- the builder materials of the present invention have a molecular structure in which two phosphono groups and one amino group are attached to the terminal carbon atoms of a saturated hydrocarbon bridge optionally interrupted by sulfur or oxygen.
- a saturated hydrocarbon bridge having two unsatisfied valences on each of its terminal carbon atoms is referred to as an alkanediylidene radical and can be illustrated by the formula Where the connecting alkanediylidene bridge contains no interrupting oxygen or sulfur atoms, the resulting compounds are known chemical entities and are described in the technical literature. They are obtained by reacting phosphorus trihalides with organic nitriles. The reaction is carried out at temperatures between about C. and 100 C.
- the builder materials herein are all hexabasic acids having a total of 8 protons, two of which are held by the amino groups, thereby forming inner salts.
- the pK values of the fifth and sixth protons ranged from 5.7, for the six carbon chain, and 5.9 for the seven carbon chain.
- the pK values are 9.1 and 9.4 respectively.
- the tetraphosphonic acids containing an interrupting hetero atom in the alkylene bridge provide buffering in a region which is particularly desirable for detergent builder applications.
- our new diaminoalkanediylidenetetraphosphonic acids, containing an inter.- rupting hetero atom constitute a sub-class which are more effective detergent builders than the general category of this type of organophosphorus acids.
- Anionic Synthetic Detergents These may be designated as Water-soluble salts of organic sulfuric reaction products having in their molecular structure an alkyl or acyl radical of carbon atom content within the range of about 8 to about 18 in a sulfonic acid or sulfuric acid ester radical.
- sodium or potassium alkyl benzene sulfonate in which the alkyl group contains about 9 to about carbon atoms in either a straight chain or a branched chain; sodium and potassium alkyl glyceryl ether sulfonates, especially those ethers of higher fatty alcohols derived from the reduction of coconut oil; the reaction product of higher fatty acids with sodium or potassium isothionate, where, for example, the fatty acids are derived from coconut oil; sodium or potassium alkyl sulfonates and sulfates especially those alkyl sulfates derived by the sulfation of coconut or tallow fatty alcohols and mixtures of such alkyl sulfates, dialkyl esters of sodium or potassium salts of sulfosuccinic acid, for example, the dihexyl ester; sodium and potassium salts of sulfated or sulfonated monoglycerides derived, for example, from coconut oil, sodium or potassium
- acyl sarcosinates e.g., sodium N-lauroyl sarcosinate.
- Nonionic Non-Soap Synthetic Dete-rgents These may be broadly classed as being constituted of a watersolubilizing polyoxyethylene group in chemical combination with an organic hydrophobic compound such as polyoxypropylene, alkyl phenol, the reaction product of an excess of propylene oxide and ethylenediamine, and aliphatic alcohols.
- the nonionic synthetic detergents have a molecular weight in the range of from about 800 to about 11,000.
- Pluronic One well-known class of nonionic 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 molecular weight of the hydrophobic base is of the order of 1,500 to 1,800. The addition of polyoxyethylene radicals to this hydrophobic base increases the water solubility of the entire molecule. Liquid products are obtained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product; higher proportions of polyoxyethylene renders the products solid in consistency.
- the molecular weights of Pluronic L61, L64 and L68, for example, are approximately 2,000, 3,000 and 8,000 respectively.
- nonionic synthetic detergents useful in the present invention are: condensation products of 6 to 30 moles of ethylene oxide with one mole of an alkyl phenol containing 6 to 12 carbon atoms, either in a straight or branched chain, in the alkyl group (e.g., nonyl or octylphenol); condensation products of 6 to 30 moles of ethyl- .ene oxide with one mole of an aliphatic straight chain or branched chain alcohol containing 8 to 18 carbon atoms (e.g., lauryl alcohol or tallow fatty alcohol); condensation products of ethylene oxide and the reaction product of propylene oxide and ethylene diamine wherein the reaction product has a molecular weight of 2,5003,000, for example, and the condensation product has a polyoxyethylene content of 40% to
- the builder materials of the invention are compatible with the usual cleansing composition additives and in this connection mention is made of such common adjuncts as bactericidal additives, fillers such as sodium carbonate and sodium sulfate,
- the ratio of detergent surfactant to the builders of the invention can vary over wide limits although the usual ratio ranges from about 20:1 to about 1:20 where no other builders are present.
- the ratio of detergent surfactant to the builders of the invention can vary from about 1:100 to about :1.
- the diaminoalkanediylidenetetraphosphonic acids herein possess a number of characteristics which render them excellent materials for use as detergent builders.
- One such property is their excellent metal sequestering and chelating ability, the compounds being superior in this respect to the builder most commonly used at present, namely, sodium tripolyphosphate.
- the metal sequestering abilities of the builder materials herein are summarized in Table 1; the chelate stability ratings in Table 2. Comparison data also are given for sodium tripolyphosphate and some typical organic builders.
- STPP Sodium tripolyphosphate
- NTA Nitrilotn'acetic acid
- AMDP Aminomethylenediphosphonic acid
- Dequest Nitrilotrimethylenephosphonic acid
- Raising the temperature from C. to 50 C. has little effect on the magnesium sequestering capacity of STPP and AMDP although it increases the magnesium sequestering capacity of compound 3 by 14% and the capacity of compound 1 by 22%.
- Calcium and magnesium chelate stabilities of the tetraphosphonic acids calculated from metal sequestering capacities determined by divalent ion electrode/oleate indicator methods described elsewhere herein were found, where measurable, to be sufficiently high to maintain calcium and magnesium ion concentrations low enough for good detergent building.
- Cupric copper and manganous manganese sequestering capacities were determined by titration with 0.1 M. cupric sulfate or manganous acetate solution to a visual endpoint. Hydroxyl ion was the precipitant in both instances.
- the effectiveness of the compounds herein in reducing calcium and magnesium ion concentrations is determined by the chelate stability constants of the respective metal ions.
- the calcium and magnesium chelate stability constants given in Table 2 were ascertained from the metal ion sequestering capacities using the electrode and oleate methods and the solubility product of the metal oleate.
- the aminoalkanetetraphosphonic acids are hexabasic, two of the total of 8 protons being held by the amino groups forming inner salts.
- the pK values of the fifth electrode chelate capacity-oleate chelate capacity oleate chelate capacity show that the alkanediylidenetetraphosphonic acids are capable of maintaining calcium and magnesium ion concentrations lower than is possible with sodium tripolyphosphate.
- Example 1 Adiponitrile (10.8 g., 0.10 mole) and 52.2 g. (0.6 mole) of orthophosphorous acid were charged into a 250 ml., 3-necked, round-bottomed flask fitted with a mechanical stirrer, thermometer, additional funnel and cal cium chloride drying tube. To the mixture was added with stirring 111.0 g. (0.41 mole) of phosphorus tribromide over a seven-minute period. An exotherm occurred causing the temperature to rise to 44 C. over the next twenty minutes. The reaction temperature was maintained at 4550 C. for a total of 4.5 hours by means of a heating bath. The reaction mixture, which was now a talfy-like mass, was slowly quenched with 120 ml.
- Neutralization Equivalent 478.Theory is 472. Equivalence points were obtained at pH 4.1 and 7.9 corresponding to pK values of 2.9, 5.7 and 5.7.
- Neutralization Equivalent 461. Theory is 450. Equivalence points were obtained at pH 4.2 and 8.1 corresponding to pK values of 2.9, 5.9 and 5.9.
- Neutralization Equivalent 476.Theory 486. Equivalence points were obtained at pH 3.8, 7.6 and 10.5 corresponding to pK values of 2.4, 5.6 and 9.4.
- Example 5 Detergency tests. The subject materials were tested for building properties and compared with STPP, NTA and AMDP using a detergency test developed by Spangler, Cross and Schaafsma, I. Am. Oil Chem. Soc., 42, 723 (1955). Test conditions were: Hardness and 300 p.p.m.; total detergent concentration 0.15%; temperature 120 F.; pH 9.5. The active material was sodium linear alkylarylsulfonate (Sulframin 85, Ultra Div. Witco Chem. Co.). Detergent formulation compositions were:
- STPP sodium tripolyphosphate
- alkanediylidenetetraphosphonic acids of the invention have several advantages over sodium tripolyphosphate which is the detergent builder now commonly used. It is particularly significant to note that the compounds herein are orders of magnitude more hydrolytically stable and thus do not lose their metal sequestering ability over extended periods of time and at elevated temperatures; they have a capacity for sequestering calcium which exceeds that of sodium tripolyphosphate by a factor of 3 on a weight basis (some members are capable of maintaining the calcium and magnesium ion concentration lower than is possible with sodium tripolyphosphate). It is generally believed by those in the art that this is an important factor in detergency;
- alkanediylidenetetraphosphonic acid builders of the invention include and encompass the free acids per se as well as the ammonium and alkali metal salts as exemplified by their ammonium, trimethylammonium, triethylammonium, dimethylamrnonium, lithium and potassium salts.
- ammonium and alkali metal salts as exemplified by their ammonium, trimethylammonium, triethylammonium, dimethylamrnonium, lithium and potassium salts.
- X is oxygen or sulfur and n is 1 to 3.
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Abstract
CLEANSING COMPOSITIONS ARE DESCRIBED CONTAINING A SYNTHETIC ORGANIC DETERGENT AND AS A BUILDER THEREFOR A DIAMINOALKANEDIYLIDENETETRAPHOSPHONIC ACID.
Description
United States Patent O US. Cl. 260502.5 3 Claims ABSTRACT OF THE DISCLOSURE Cleansing compositions are described containing a synthetic organic detergent and as a builder therefor a diaminoalkanediylidenetetraphosphonic acid.
BACKGROUND OF THE INVENTION (A) Field of the invention This invention relates to cleansing compositions and in particular to detergent compositions having builder ingredients for augmenting the cleansing action of the detergent.
(B) Description of the prior art In the cleansing art it is well-known that the efficacy of soap or detergent is considerably improved by the presence of certain supplementary substances commonly referred to as builders. While the benefits derived from such entities are widely appreciated, the mechanism by which they increase detergency has never been fully elucidated. Very likely several phenomena come into play thereby greatly complicating the formulation of any single theory to account for the behavior of builders. This is lent credence when it is realized that detergency itself is highly complex in nature involving many factors. Among those believed to have some effect on built detergency systems are stabilization of solid soil, emulsification of soil particles, the surface activity of the aqueous detergent solution, solubilization of water insoluble materials, foaming or suds forming characteristics of the washing solution, peptization of soil agglomerates, neutralization of acid soil and sequestration of mineral hardening constituents present in the washing solution. Other less well defined and understood factors also may exert some influence. Since no general rule is known which enables one to predict Whether a particular substance is capable of performing as an overall detergency builder, resort must be had to a great deal of empirical testing and investigation of candidate materials.
Among the known builders, representatives may be found which are of the organic and inorganic types. Examples of the latter are the water-soluble inorganic alkaline salts as typified by alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, silicates and the like. Examples of the former are alkali metal, ammonium and substituted ammonium aminopolycarboxylates as represented by sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethy1)- ethylenediaminetriacetate, sodium and potassium nitrilotriacetate, sodium, potassium and triethanolammonium-N- Patented Feb. 23, 1971 ice (Z-hydroxyethyl)nitrilodiacetate as well as the alkali metal salts of phytic acid, e.gt, sodium or potassium phytate, etc.
Although generally satisfactory, the builder materials utilized heretofore suffer from certain limitations and disadvantages. Even the most widely accepted group of builder materials, the so-called condensed inorganic polyphosphates such as the alkali metal tripolyphosphates, are not without their shortcomings. Such compounds, the most common of which is sodium tripolyphosphate, exhibit a propensity when used in detergent compositions, of hydrolyzing into less condensed derivatives having diminished builder properties. In fact these less condensed products, which include orthoand pyro-phosphates, may form undesirable precipitates in the aqueous washing solution.
As the need for detergent builders has grown and expanded, more attention is being given to the development of new and improved members of this class of cleanser adjuncts.
SUMMARY OF THE INVENTION It has now been discovered that excellent builder characteristics can be realized by the use of certain organo-phosphorus acids collectively referred to as diaminoalkanediylidene-tetraphosphonic acids wherein two phosphono groups and one amino group are attached to each terminal carbon atom of the alkanediylidene, and the provision of cleansing compositions containing them in combination with a water-soluble non-soap synthetic detergent surfactant as well as the preparation and use of such compositions constitutes the principal object and purpose of the invention. Other objects and purposes will become apparent in the ensuing description.
DESCRIPTION OF THE INVENTION AND THE PREFERRED EMBODIMENTS The diaminoalkanediylidenetetraphosphonic acid builder materials herein can be depicted by the following general formula wherein A is a 2-6 carbon alkylene bridge which may be centrally interrupted by oxygen or sulfur and R is a hydrogen or lower hydroxyalkyl such as HOCH HOCH CH HO(|JHCH2-, HOCH-CH, etc.
CH3 CH3 CH3 As understood herein a lower hydroxyalkyl means that the hydrocarbon moiety may contain from l-S carbon atoms.
As can be seen from an inspection of the formula, the builder materials of the present invention have a molecular structure in which two phosphono groups and one amino group are attached to the terminal carbon atoms of a saturated hydrocarbon bridge optionally interrupted by sulfur or oxygen. According to Chemical Abstracts, a saturated hydrocarbon bridge having two unsatisfied valences on each of its terminal carbon atoms is referred to as an alkanediylidene radical and can be illustrated by the formula Where the connecting alkanediylidene bridge contains no interrupting oxygen or sulfur atoms, the resulting compounds are known chemical entities and are described in the technical literature. They are obtained by reacting phosphorus trihalides with organic nitriles. The reaction is carried out at temperatures between about C. and 100 C. using about two moles of phosphorus trihalide per mole of the nitrile. Either during or after the reaction, an organic acid, such as glacial acetic acid or oxygen-containing inorganic acid such as phosphorus acid, are added. After this treatment, the product is hydrolyzed with water to generate the free acids; or the monoor di-esters are produced by reaction with suitable alcohols or phenols, preferably in the presence of acid-binding agents. A detailed description of these organophosphorus compounds, including their preparation, is given in British Pat. No. 995,462.
Certain of the compounds falling within the ambit of Formula I have not been previously described and these can be represented by the following configuration:
RNR RNR wherein R has the significance as above set forth, and n is an integer of 1-3. These patentably new entities can be realized by condensing a phosphorus trihalide, orthophosphorous acid and a bis( terminally substituted cyano-alkyl) sulfide or ether. After the initial exothermic reaction had subsided, a slightly elevated temperature was maintained for a time interval sufficient to complete the reaction. After hydrolyzing, the products were isolated in the form of white solids. They may be purified by dissolving in a base and reprecipitated by acidification.
The builder materials herein are all hexabasic acids having a total of 8 protons, two of which are held by the amino groups, thereby forming inner salts. The pK values of the fifth and sixth protons ranged from 5.7, for the six carbon chain, and 5.9 for the seven carbon chain. However when an oxygen or sulfur atom is interposed in the alkylene chain, the pK values are 9.1 and 9.4 respectively. Thus, the tetraphosphonic acids containing an interrupting hetero atom in the alkylene bridge, provide buffering in a region which is particularly desirable for detergent builder applications. Thus our new diaminoalkanediylidenetetraphosphonic acids, containing an inter.- rupting hetero atom, constitute a sub-class which are more effective detergent builders than the general category of this type of organophosphorus acids.
Among the detergent surfactant compounds, whose cleansing power is enhanced by the diaminoalkanediylidenetetraphosphonic acids of the invention are the following categories and examples:
(1) Anionic Synthetic Detergents.These may be designated as Water-soluble salts of organic sulfuric reaction products having in their molecular structure an alkyl or acyl radical of carbon atom content within the range of about 8 to about 18 in a sulfonic acid or sulfuric acid ester radical. Included are sodium or potassium alkyl benzene sulfonate in which the alkyl group contains about 9 to about carbon atoms in either a straight chain or a branched chain; sodium and potassium alkyl glyceryl ether sulfonates, especially those ethers of higher fatty alcohols derived from the reduction of coconut oil; the reaction product of higher fatty acids with sodium or potassium isothionate, where, for example, the fatty acids are derived from coconut oil; sodium or potassium alkyl sulfonates and sulfates especially those alkyl sulfates derived by the sulfation of coconut or tallow fatty alcohols and mixtures of such alkyl sulfates, dialkyl esters of sodium or potassium salts of sulfosuccinic acid, for example, the dihexyl ester; sodium and potassium salts of sulfated or sulfonated monoglycerides derived, for example, from coconut oil, sodium or potassium salts of the higher fatty alcohol esters of sulfo-carboxylic acids, for example, the sodium salt of the lauryl alcohol ester of sulfo-acetie acid; sodium or potassium salts of a higher fatty acid amide of methyl taurine in which the higher acyl radicals, for example, are derived from coconut oil; and others known in the art, a number being specifically set forth in U.S. Pat. 2,486,921, issued to Byerly on Nov. 1, 1949. Examples of other useful anionic non-soap synthetic detergents are acyl sarcosinates, e.g., sodium N-lauroyl sarcosinate.
(2) Nonionic Non-Soap Synthetic Dete-rgents. These may be broadly classed as being constituted of a watersolubilizing polyoxyethylene group in chemical combination with an organic hydrophobic compound such as polyoxypropylene, alkyl phenol, the reaction product of an excess of propylene oxide and ethylenediamine, and aliphatic alcohols. The nonionic synthetic detergents have a molecular weight in the range of from about 800 to about 11,000.
One well-known class of nonionic 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 molecular weight of the hydrophobic base is of the order of 1,500 to 1,800. The addition of polyoxyethylene radicals to this hydrophobic base increases the water solubility of the entire molecule. Liquid products are obtained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product; higher proportions of polyoxyethylene renders the products solid in consistency. The molecular weights of Pluronic L61, L64 and L68, for example, are approximately 2,000, 3,000 and 8,000 respectively.
Examples of other nonionic synthetic detergents useful in the present invention are: condensation products of 6 to 30 moles of ethylene oxide with one mole of an alkyl phenol containing 6 to 12 carbon atoms, either in a straight or branched chain, in the alkyl group (e.g., nonyl or octylphenol); condensation products of 6 to 30 moles of ethyl- .ene oxide with one mole of an aliphatic straight chain or branched chain alcohol containing 8 to 18 carbon atoms (e.g., lauryl alcohol or tallow fatty alcohol); condensation products of ethylene oxide and the reaction product of propylene oxide and ethylene diamine wherein the reaction product has a molecular weight of 2,5003,000, for example, and the condensation product has a polyoxyethylene content of 40% to The builder materials of the invention are compatible with the usual cleansing composition additives and in this connection mention is made of such common adjuncts as bactericidal additives, fillers such as sodium carbonate and sodium sulfate, excipients such as sodium stearate and vegetable fats, optical brighteners, anti-redeposition agents such as carboxymethylcellulose, dyes, pigments, dedusters such as mineral oil, foam stabilizers, tarnish inhibitors, ammonium chloride as 'well as the other known builder materials such as the condensed phosphate, e.g., tripolyphosphate, pyrophosphates and the like. The builder material herein also admits the inclusion of bleach agents in the detergent or cleanser compositions such as the chlorinated cyanuric acids, chloramine-T and similar bleaching agents.
Generally speaking, the ratio of detergent surfactant to the builders of the invention can vary over wide limits although the usual ratio ranges from about 20:1 to about 1:20 where no other builders are present. When used in combination with other builder materials such as sodium tripolyphosphate or in special cleansing formulations, the ratio of detergent surfactant to the builders of the invention can vary from about 1:100 to about :1.
The diaminoalkanediylidenetetraphosphonic acids herein possess a number of characteristics which render them excellent materials for use as detergent builders. One such property is their excellent metal sequestering and chelating ability, the compounds being superior in this respect to the builder most commonly used at present, namely, sodium tripolyphosphate. The metal sequestering abilities of the builder materials herein are summarized in Table 1; the chelate stability ratings in Table 2. Comparison data also are given for sodium tripolyphosphate and some typical organic builders.
6 bridge, Massachusetts. Magnesium sequestering capacities were determined by titration with 0.1 M. magnesium acetate solution to a potentiometric endpoint using a divalent TABLE 1 (RHO P-gCAC(P03HR) sequestering capacity (25 0.,
pH 10) (gram ions metal/mole) RNR RNR A R Ca++ Mg+ Cu Mn++ (A) Compounds of the invention:
(1) CH2CH2SCH2CH2 H 3. 5 3. 2 2. 1 3. 7 (2) -CH2CH2OCI'I2CH2 H- 3. 2. 1 (3) -(OH2)5 H 3. 4 3. 4 2.0 3. 6 (4) -(CH2) H- 2. 9 (CH2)4 HOOH2CH2 1. 7
(B) Compounds of the prior art:
Sodium tripolyphosphate (STPP) 1. 0 1. 2 1. 2 1. 2 Nitrilotn'acetic acid (NTA) 1.0 0. 9 1. 3 2. 7 Aminomethylenediphosphonic acid (AMDP) 1. 5 1. 6 1. 2 1. 8 Nitrilotrimethylenephosphonic acid (Dequest) 0.7 0. 9 1. 2 1. 5
As Tables 1 and 2 show, the presence of sulfur or oxygen in the alkanediylidene bridge increases the watersolubility of the alkaline earth metal chelates of the tetraphosphonic acids.
Calcium sequestering capacities of the tetraphosphonic acids vary with pH in the range from 9 to 11. Thus, Compound 1 exhibits increased sequestering capacity as the pH changes from pH 9 to pH 11 while compound 3 shows a 3% decrease over the same range. In contrast, the calcium sequestering capacity of a typical organic builder, aminomethylenediphosphonic acidAMDP-increases by 50% over the pH range 9 to 11.
Raising the temperature from C. to 50 C. has little effect on the magnesium sequestering capacity of STPP and AMDP although it increases the magnesium sequestering capacity of compound 3 by 14% and the capacity of compound 1 by 22%.
Calcium and magnesium chelate stabilities of the tetraphosphonic acids calculated from metal sequestering capacities determined by divalent ion electrode/oleate indicator methods described elsewhere herein were found, where measurable, to be sufficiently high to maintain calcium and magnesium ion concentrations low enough for good detergent building.
ion electrode made by Orion Research, Inc. Cupric copper and manganous manganese sequestering capacities were determined by titration with 0.1 M. cupric sulfate or manganous acetate solution to a visual endpoint. Hydroxyl ion was the precipitant in both instances.
The effectiveness of the compounds herein in reducing calcium and magnesium ion concentrations is determined by the chelate stability constants of the respective metal ions. The calcium and magnesium chelate stability constants given in Table 2 were ascertained from the metal ion sequestering capacities using the electrode and oleate methods and the solubility product of the metal oleate.
(metal chelateY +A l ll l K mstabrhtypK instability=log K instability Solubility product of metal oleate 1'7 33 From which [M++] can be calculated given TABLE 2 (RHO P -C-AC(PO3HR) Calcium Magnesium chelate chelate RNR RNR stability stability (pK in- (pK in- A R stability) stability) (A) Compounds of the invention:
(1) CH2CH2SCH2CH2 H (i. 8 6. 3 (2) CHgCH OCH CH2 II- 6.0 6.1 2)s (i) 6.4 (4) (CH2)4- H- (1) (5) (CH2)4- HOCHQCH 5.0
(B) Compounds of the prior art:
Sodium tripolyphosphate (SIPP) 5. 4 5. 8 Nitrilotriacetic acid (NTA) 6. 2 G. O Aminomethylenediphosphouic acid (AMDP) 5. 9 5. O Nitrilotrimethylenephosphonic acid (Dequest) (z) 5. 4
1 Chelate too insoluble to allow measurement. 2 Stability too low to measure.
The aminoalkanetetraphosphonic acids are hexabasic, two of the total of 8 protons being held by the amino groups forming inner salts. The pK values of the fifth electrode chelate capacity-oleate chelate capacity oleate chelate capacity The data of Table 2 show that the alkanediylidenetetraphosphonic acids are capable of maintaining calcium and magnesium ion concentrations lower than is possible with sodium tripolyphosphate.
Reference is now made to the following non-limiting examples.
Example 1 Adiponitrile (10.8 g., 0.10 mole) and 52.2 g. (0.6 mole) of orthophosphorous acid were charged into a 250 ml., 3-necked, round-bottomed flask fitted with a mechanical stirrer, thermometer, additional funnel and cal cium chloride drying tube. To the mixture was added with stirring 111.0 g. (0.41 mole) of phosphorus tribromide over a seven-minute period. An exotherm occurred causing the temperature to rise to 44 C. over the next twenty minutes. The reaction temperature was maintained at 4550 C. for a total of 4.5 hours by means of a heating bath. The reaction mixture, which was now a talfy-like mass, was slowly quenched with 120 ml. of water with stirring resulting in a temperature rise to 90 C. A white precipitate which formed during the hydrolysis was separated by filtration at C., washed with several portions at acetone and vacuum dried at 100 C. to give 7.0 g. of white solid, M.P. 234262 C. The solid gave a negative test for orthophosphate.
Neutralization Equivalent: 478.Theory is 472. Equivalence points were obtained at pH 4.1 and 7.9 corresponding to pK values of 2.9, 5.7 and 5.7.
Pimelonitrile (36.6 g., 0.30 mole) and 156.6 g. (1.90 moles) orthophosphorous acid were charged into a 500 ml. reactor fitted as described in Example 1. To the mixture was added with stirring 333.0 g. (1.23 moles) of phosphorus tribromide over a seven-minute period. The reaction mixture was held at 40-50 C. for 7 hours and at 25 C. for 64 hours. The reaction mixture was diluted with 165 ml. of Water resulting in a clear solution. Dilution of the solution with 2,000 m1. of acetone caused the product to precipitate. It was recovered by filtration, 'washed with acetone and vacuum dried to give 71.3 g. of crude product. Purification of the crude by dissolution in 10% sodium hydroxide and reprecipitation by acidification with 10% hydrochloric acid gave 29.2 g. of white solid, M.P. 245-257 C.
Neutralization Equivalent: 461.Theory is 450. Equivalence points were obtained at pH 4.2 and 8.1 corresponding to pK values of 2.9, 5.9 and 5.9.
Bis(2-cyanoethyl) sulfide (200 g., 1.43 moles) and 748 g. (9.13 moles) orthophosphorous acid were charged into a 3,000 ml. reactor fitted as described in Example 1. To the mixture was added with stirring 1,580 g. (5.93 moles) of phosphorus tribromide. The reaction mixture was held at 50-60 C. for 6 hours and diluted with 600 m1. of water. The resulting clear, yellow solution was vacuum stripped on a rotating evaporator to give a sirup. Dilution of the sirup with 1,000 ml. of denatured ethyl alcohol caused a solid to precipitate which was collected on a filter, washed with acetone and vacuum dried to give 384 g. of crude product. The crude product was purified by dissolution in 10% sodium hydroxide and precipitation by acidification with 10% hydrochloric acid. The solid after separation, washing with acetone and drying weighed 71.3 g., M.P. 220239 C.
Neutralization Equivalent: 476.Theory 486. Equivalence points were obtained at pH 3.8, 7.6 and 10.5 corresponding to pK values of 2.4, 5.6 and 9.4.
Bis(Z-cyanoethyl) ether (25 g., 0.20 mole) and g. (1.28 moles) orthophosphorous acid were charged into a 250 ml. reactor fitted as described in Example 1. To the mixture was added with stirring 224 g. (0.82 mole) phosphorous tribromide. The reaction mixture Was held at 40-50 C. for 30 hours and at 25 C. for hours. Dilution with 120 ml. of water gave a clear yellow solution which was vacuum stripped yielding a sirup. The sirup was diluted with 5,000 ml. of acetone to precipitate product which was recovered by filtration, Washing with acetone and drying to give 23.9 g. of white solid, M.P. 127- Neutralization Equivalent: 450.-Theory 452. Equivalence points were obtained at pH 4.0, 7.4 and 10.5, corresponding to pK value of 2.3, 5.8 and 9.1.
Example 5 Detergency tests.The subject materials were tested for building properties and compared with STPP, NTA and AMDP using a detergency test developed by Spangler, Cross and Schaafsma, I. Am. Oil Chem. Soc., 42, 723 (1955). Test conditions were: Hardness and 300 p.p.m.; total detergent concentration 0.15%; temperature 120 F.; pH 9.5. The active material was sodium linear alkylarylsulfonate (Sulframin 85, Ultra Div. Witco Chem. Co.). Detergent formulation compositions were:
Percent by weight Active material 20.0 Sodium metasilicate S-hydrate 12.0 Carboxymethyl cellulose (CMC) 0.5 Builder 50.0 Sodium sulfate Balance The tests were run in a Tergotometer on fabric specimens soiled with a synthetic natural-type soil. The results, given in Table 3 below, are average final percent reflectance readings of fabric specimens after 3 soilings and 3 washes. Water of 150 p.p.m. hardness was used for rinsing. Active material to builder ratio was 20/50. The results show that the tetraphosphonic acids are close to the best of the known builders as represented by STPP, NTA and AMDP in builder eifectiveness under the conditions used.
l Expressed as percent of sodium tripolyphosphate (STPP) standard. Anionic surfactant; Surfactant/Builder: 20/50 and 20/25; concentration: 0.15%; 120 F.; pH 9.5; Hardness, 150 p.p.m. and 300 p.p.m.
From an inspection of the data reported in the tables, it is at once evident that the alkanediylidenetetraphosphonic acids of the invention have several advantages over sodium tripolyphosphate which is the detergent builder now commonly used. It is particularly significant to note that the compounds herein are orders of magnitude more hydrolytically stable and thus do not lose their metal sequestering ability over extended periods of time and at elevated temperatures; they have a capacity for sequestering calcium which exceeds that of sodium tripolyphosphate by a factor of 3 on a weight basis (some members are capable of maintaining the calcium and magnesium ion concentration lower than is possible with sodium tripolyphosphate). It is generally believed by those in the art that this is an important factor in detergency;
they exhibit appreciably better sequestering capacity for calcium, magnesium, copper and manganese ions than sodium tripolyphosphate or nitrilotriacetic acid and their calcium and magnesum chelate stability constants generally exceed those of sodium tripolyphosphate or nitrilotriacetic acid.
It is to be understood that the alkanediylidenetetraphosphonic acid builders of the invention include and encompass the free acids per se as well as the ammonium and alkali metal salts as exemplified by their ammonium, trimethylammonium, triethylammonium, dimethylamrnonium, lithium and potassium salts. Those skilled in the art will select that form of the builder herein which best suits their particular detergent formulation and needs.
Pursuant to the requirements of the patent statutes, the principle of this invention has been explained and exemplified in a manner so that it can be readily practiced by those skilled in the art, such exemplification including what is considered to represent the best embodiment of the invention. However, it should be clearly understood, that, within the scope of the appended claims, the invention may be practiced by those skilled artisans having the benefit of this disclosure otherwise than as specifically described and exemplified herein.
What is claimed is:
1. A compound of the formula NHz NH;
wherein X is oxygen or sulfur and n is 1 to 3.
2. The compound of claim 1 wherein the formula is 3. The compound of claim 1 wherein the formula is FOREIGN PATENTS 1,171,401 6/1964 Germany 260-5025 LEON ZITVER, Primary Examiner I. E. EVANS, Assistant Examiner US. Cl. X.R.
UMTED STATES PATENT OFFICE CERTEFICATE OF CORRECTION Patent No. 3 5 5 9"9 Dated February 3, 1971 Inventor(s) Richard Williamson Cummins It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Col. 3, Formula II, that portion of the formula reading (PO3HR)n should read (PO HR) Col. 7, Example 3, that portion of the formula reading (PO H should read (PO H Col. 7, Example '4, that portion of the formula reading (POZHZ )2 should read (PO HZ 2 G01 8, line 21 "(1955)" should read --(l965)-- Col 8, line 57 "acid" should be omitted Col 9, Claim 1 that portion of the formula reading {0H) should read (CH Col. 10, Claim 3, that portion of the formula reading Should read Signed and sealed this 18th day of April 1972.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US66057967A | 1967-08-15 | 1967-08-15 |
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US3565949A true US3565949A (en) | 1971-02-23 |
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Application Number | Title | Priority Date | Filing Date |
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US660579A Expired - Lifetime US3565949A (en) | 1967-08-15 | 1967-08-15 | Diaminoalkanediylidenetetraphosphonic acids useful in cleaning compositions |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3870750A (en) * | 1969-11-19 | 1975-03-11 | Henkel & Cie Gmbh | Process for the production of aminomethane-diphosphonic acid and its salts |
US3903142A (en) * | 1972-01-25 | 1975-09-02 | Benckiser Knapsack Gmbh | Process of producing amino methane diphosphonic acid and its salts |
US3919296A (en) * | 1970-10-06 | 1975-11-11 | Henkel & Cie Gmbh | Production of 1-aminoalkane-1,1-diphosphonic acids using nitriles, phosphorous acid and hydrogen halide |
US3925456A (en) * | 1973-08-27 | 1975-12-09 | Henkel & Cie Gmbh | Cyclic aminophosphonic acids |
US4006182A (en) * | 1971-03-31 | 1977-02-01 | Henkel & Cie G.M.B.H. | Process for the preparation of 1-aminoalkane-1,1-diphosphonic acids |
US4239695A (en) * | 1977-03-24 | 1980-12-16 | Magna Corporation | Method of preparing phosphonates from nitriles |
-
1967
- 1967-08-15 US US660579A patent/US3565949A/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3870750A (en) * | 1969-11-19 | 1975-03-11 | Henkel & Cie Gmbh | Process for the production of aminomethane-diphosphonic acid and its salts |
US3919296A (en) * | 1970-10-06 | 1975-11-11 | Henkel & Cie Gmbh | Production of 1-aminoalkane-1,1-diphosphonic acids using nitriles, phosphorous acid and hydrogen halide |
US4006182A (en) * | 1971-03-31 | 1977-02-01 | Henkel & Cie G.M.B.H. | Process for the preparation of 1-aminoalkane-1,1-diphosphonic acids |
US3903142A (en) * | 1972-01-25 | 1975-09-02 | Benckiser Knapsack Gmbh | Process of producing amino methane diphosphonic acid and its salts |
US3925456A (en) * | 1973-08-27 | 1975-12-09 | Henkel & Cie Gmbh | Cyclic aminophosphonic acids |
US4239695A (en) * | 1977-03-24 | 1980-12-16 | Magna Corporation | Method of preparing phosphonates from nitriles |
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