US2978416A - Concentrated aqueous detergent composition - Google Patents
Concentrated aqueous detergent composition Download PDFInfo
- Publication number
- US2978416A US2978416A US522165A US52216555A US2978416A US 2978416 A US2978416 A US 2978416A US 522165 A US522165 A US 522165A US 52216555 A US52216555 A US 52216555A US 2978416 A US2978416 A US 2978416A
- Authority
- US
- United States
- Prior art keywords
- sulfonate
- detergent
- benzene
- solutions
- solution
- 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
- 239000003599 detergent Substances 0.000 title claims description 55
- 239000000203 mixture Substances 0.000 title claims description 49
- -1 ALKYLBENZENE SULFONIC ACIDS Chemical class 0.000 claims description 41
- 229920001223 polyethylene glycol Polymers 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 159000000000 sodium salts Chemical class 0.000 claims description 10
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- NOJNFULGOQGBKB-UHFFFAOYSA-M sodium;3-[3-tert-butylsulfanyl-1-[[4-(6-ethoxypyridin-3-yl)phenyl]methyl]-5-[(5-methylpyridin-2-yl)methoxy]indol-2-yl]-2,2-dimethylpropanoate Chemical compound [Na+].C1=NC(OCC)=CC=C1C(C=C1)=CC=C1CN1C2=CC=C(OCC=3N=CC(C)=CC=3)C=C2C(SC(C)(C)C)=C1CC(C)(C)C([O-])=O NOJNFULGOQGBKB-UHFFFAOYSA-M 0.000 claims 1
- 239000000243 solution Substances 0.000 description 57
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 150000003839 salts Chemical class 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 150000002009 diols Chemical class 0.000 description 13
- 239000011557 critical solution Substances 0.000 description 12
- 150000004996 alkyl benzenes Chemical class 0.000 description 11
- 238000005187 foaming Methods 0.000 description 11
- 239000008233 hard water Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 9
- 238000006277 sulfonation reaction Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 8
- 229940077388 benzenesulfonate Drugs 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 7
- 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 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229920000151 polyglycol Polymers 0.000 description 7
- 239000010695 polyglycol Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 229940068917 polyethylene glycols Drugs 0.000 description 6
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229940100198 alkylating agent Drugs 0.000 description 3
- 239000002168 alkylating agent Substances 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LTEQMZWBSYACLV-UHFFFAOYSA-N Hexylbenzene Chemical compound CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- AXBNMPTWUWEFAH-UHFFFAOYSA-N (1-chloro-3-methylbutan-2-yl)benzene Chemical class CC(C)C(CCl)C1=CC=CC=C1 AXBNMPTWUWEFAH-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 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
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- XBLIFEQTVVSTIM-UHFFFAOYSA-L chembl2105392 Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=CC=C2C(O)=C1N=NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O XBLIFEQTVVSTIM-UHFFFAOYSA-L 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000727 fraction Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052920 inorganic sulfate Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920001993 poloxamer 188 Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940079842 sodium cumenesulfonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000000080 wetting agent 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
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2044—Dihydric alcohols linear
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2068—Ethers
-
- 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
- C11D3/34—Organic compounds containing sulfur
- C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
Definitions
- This invention relates to concentrated aqueous detergent compositions comprising anionic detergents of the higher alkylbenzene sulfonate type. It relates more particularly to aqueous liquid detergent compositions containing in excess of 15% by weight of water-soluble salts of a mixture of higher alkylbenzene sulfonates containing 9 to 18 non-aromatic carbon atoms together with minor amounts of certain additives which modify the solubility and other properties of the higher alkylbenzene sulfonates.
- the higher alkylbenzene sulfonates are valuable detergents, wetting agents, penetrating agents, and emulsifying agents. They owe their valuable surface-active properties in part to the fact that they are partly hydrophobic and partly hydrophilic. This molecular complexity leads to the disadvantage, however, that their solubility in water at ordinary atmospheric temperatures is limited.
- the anionic detergents of the higher alkylbenzene sulfonate type are generally produced in the form of water-soluble salts such as the alkali metal salts, and especially the sodium salt. They generally come into the market in the form of the dried solid. Since they are mostly used in aqueous solution, it is necessary for the user to dissolve them in water or other aqueous media before use.
- concentrated aqueous detergent compositions are produced containing anionic detergents of the higher alkylbenzene sulfonate type and, as modifiers of the solubility and other properties thereof, (1) a water-soluble salt of a benzene sulfonic acid containing a maximum of 6 non-aromatic carbon atoms, and (2) an open-chain diol of the type specified hereinafter.
- detergent compositions can be obtained in the form of concentrated aqueous solutions having in excess of 25% and as high as 45% by weight of a water-soluble salt of a higher alkylbenzene sulfonate (or a mixture of watersoluble salts of such sulfonates), which solutions have the ability to remain clear not only at normal atmospheric temperatures but in many cases even at lower temperatures, such as below 0 C.
- critical solution temperature-cloud point or haze point--as employed herein refers to the temperature at which the solution, upon cooling, begins to become turbid.
- benzene sulfonate having a maximum of 6 non-aromattic carbon atoms are present in the form of a mixture obtained by co-sulfonating a higher alkylbenzene hydrocarbon in admixture with a minor amount of benzene or a lower alkylbenzene, since a somewhat greater increase in solubility (lowering of the critical solution temperature) is obtained than by mixing the separately prepared sulfonates.
- anionic detergents of the higher alkylbenzene sulfonate type employed in accordance with the present invention comprise essentially water-soluble salts.
- mixtures of water-soluble salts of mononuclear aryl hydrocarbon sulfonic acids that contain a total of 9 to 18 non-aromatic carbon atoms, and preferably they have as a nuclear substituent a higher alkyl radical which contains 12 to 16 carbon atoms. 7 t
- Advantageous higher alkylbenzene sulfonate detergents for use in accordance withv the present invention are t mixturesof neutral water-soluble salts, especially sodium salts, of such higher alkylaryl sulfonic acids, particularly those in which the higher alkyl radicals contain, on the average, from about 12 to about 16 carbon atoms.
- Higher alkylaryl sulfonate detergents especially advantageous for use in accordance with the present invention are those consisting essentially of higher alkylbenzene (or higher 'alkyltoluene) 'sodium'sulfonate mixtures of which the higher alkyl groups correspond to the hydrocarbons of a petroleum fraction of a kerosene boiling range, herein referred to as keryl benzene su1-' fonates.
- keryl benzene su1-' fonates t p w
- the said anionic detergents can be obtained in various ways. Thus they can be prepared by condensing a mono.- nuclear aromatic hydrocarbon (such as, benzene, toluene,
- an alkylating agent adapted to introduce a higher alkyl radical and containing enough non-aromatic carbon atoms per molecule to make the total of nonaromatic carbon atoms in the alkylate between 9 and 18 (such as, a higher alcohol, a higher alkyl halide, an olefin or olefin polymer, or a commercial mixture of such alkylating agentsfor example, chlorinated kerosene, a mixture of olefins, or a trimer, tetramer or pentamer of propylene or mixture thereof, etc.) to form an alkylated aromatic compound or mixture of such compounds, or by condensation of ethylenewith an alkylaromatic hydro.
- an alkylating agent adapted to introduce a higher alkyl radical and containing enough non-aromatic carbon atoms per molecule to make the total of nonaromatic carbon atoms in the alkylate between 9 and 18 (such as, a higher alcohol, a higher alkyl
- alkylating agent is the mixture of chlorfhydrocarbons resulting from the chlorinationof a selected petroleum distillate, preferably of the kerosene boiling range.
- chlor-hydrocarbons can be prepared, for example, by
- the low molecular weight benzene sulfonates employed as solubilizing agents in accordance with the present invention comprise the water-soluble salts of benzene ,sulfonic acid and its homologs which contain a maximum of 6 non-aromatic carbon atoms, such as toluene, xylene, cumene, cymene, butyl benzene, amyl benzene, hexyl benzene, butyl xylene, etc. They include the alkali metal, ammonium, and organic amine salts. In view of their ready availability and low cost, the sodium salts are preferably employed.
- Benzene sulfonate of low molecular weight employed as solubilizing agent for the higher alkylbenzene sulfonate will depend upon a number of factors; such as relative cost, odor and color of the final detergent solution, etc.
- Sodium xylene sulfonate and sodium cumene sulfonate exert a greater solubilizing effect upon the higher alkylbenzene sulfonates than do benzene sulfonate and toluene sulfonatebut, when employed for the manufacture of a detergent solution by the co-sulfonation procedure, their use'leads to detergent solutions having an undesirable odor and a higher degree of color.
- sodium toluene sulfonate is preferred.
- the low molecular weight benzene sulfonates can be incorporated into the detergent solutions in any desired manner and at any stage of the preparation of the solutions. Thus, they may be preformed and added to the detergent solution, or one of the components thereof, during the preparation of the solution.
- the benzene sulfonate of low molecular weight is incorporated into the detergent solution during the course of manufacture of the higher alkylbenzene sulfonate, by co-sulfonating a 4 mixture of a hydrocarbon of the benzene series containing 9 to 18 non-aromatic carbon-atoms and a hydrocarbon of the benzene series containing not more than 6 non-aromatic carbon atoms, the latter being present in an amount from 3% to 25% of the weight of said mixture.
- the effect of the bezene sulfonate of low molecular weight as a depressor of the critical solution temperature of the detergent solution is greater when the solution is prepared by the cosulfonating procedure.
- the co-sulfonation procedure leads to a some what lowered foaming action of the resulting detergent solution in hard water.
- the specific procedure employed will depend to some extent upon the result desired to be obtained.
- the open-chain diols employed in accordance with the present invention include'the variousmembers ofthe class corresponding to the formula HO-- RO) H wherein R0 represents a radical selected from the group consisting of the CH CI-I O radical, the
- n an integer from 1 through 150, but not more than 10 R0- radicals contain 3 carbon atoms.
- they include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and higher polyethylene glycols having molecular weights from about 200 through 6000; propylene glycol, dipropylene glycol, tripropyleneglycol andhigher polypropylene glycols having molecular weights through about 600; and mixed ethylene-propylene glycol ethers having a maximum total of RO- radicals of which not more than 10 RO radicals are propoxy radicals.
- They may be employed in the form of the individual polyglycol (glycol ether), or in the form of mixtures such as are obtained commercially by the reaction of a glycol with ethylene and/or propylene oxide.
- Preferred polyglycols employed in accordance with the present invention are polyethylene glycol mixtures having an average molecular weight of about 200 to about 1250, inasmuch as said polyglycol mixtures produce a superior increase in the foaming action of the resulting detergent solution when employed in hard water.
- the open-chain diol can be incorporated into the detergent solution at any stage of the manufacture thereof subsequent to the formation of the sulfonic acid, and in any order with respect to the other components of the solution.
- An advantageous procedure for the manufacture of the solution involves carrying out the neutralization of the higher-alkylbenzene sulfonic acid in an aqueous medium containing the open-chain diol.
- the amounts of benzene sulfonate of low molecular weight and open-chain diol employed relative to the amount of higher alkylbenzene sulfonate can be varied depending upon the result desired to be obtained.
- amounts of benzene sulfonate of low molecularweight ranging from 0.5% to 15%, preferably 2% to 15%, and amounts of diol ranging from 0.5% to 10%, preferably 1% to 5% of the weight of the final solution, may be employed, a greater lowering of the critical solution temperature being generally obtained with the larger amounts.
- compositions of particular utility as stock solutions in accordance with our invention are aqueous liquid solutions containing as their essential components, by weight, about 25% to about 45%, especially about 30% of sodium kerylbenzene sulfonate, about 3% to about 12%, especially about of sodium toluene sulfonate (preferably co-sulfonated), and about 1% to about 5%, especially about 2% of a mixture of polyethylene glycols having an average molecular weight of 200 to 1250 and a major proportion of which have molecular weights within this range.
- the temperatures are in degrees centigrade and the parts and percentages are by weight, unless designated as parts by volume. Where parts are by volume, the amount signifies the volume occupied by the same number of parts by weight of water at 4 C.
- Example 1 Part 1.-A refined higher alkylbenzene was prepared in a manner similar to that described in U.S.P. 2,364,782 by chlorinating a kerosene fraction of petroleum distillate; condensing the resulting chlorination product with benzene in the presence of anhydrous aluminum chloride; separating the alkylbenzene-containing oil from the condensation reaction mixture by decantation; recovering an alkylbenzene mixture by fractional distillation of the oil; and subjecting the alkylbenzene mixture to a refining extraction treatment with sulfuric acid.
- the kerosene fraction had a boiling point ranging from about 198 to 251 and consisted predominantly of C -C parafiin and naphthene hydrocarbons.
- the keryl benzene had an average molecular weight of 260 to 265.
- CST critical solution temperature
- Percent the solution to be tested is immersed in a cooling bath containing ice and salt, to a depth such that the liquid level of the sample remains just above the liquid level of the cooling bath. The'sample is allowed to cool slowly while being stirred with a thermometer. The temperature at which turbidity first becomes evident is taken as the. critical solution temperature.
- the detergent solutions were tested for hard water foaming by the Ross-Miles procedure described in Oil and Soap, volume 18, pages 99-102 (May 1941).
- the detergent solutions were diluted with water having a hardness of 15 to give a test solution having a concentration of solutes (originating from the detergent solution) as given in the table.
- the last column of the table gives the heights of the foam columns obtained from the different solutions by the test procedure.
- ExampleZ Detergent solutions were prepared in the manner described in Example 1, Part 2, from a kerylbenzene obtained as described in Example 1, Part 1.
- the proportions of components were as set out below in Table 2.
- the polyethylene glycols were commercial products having the 1 average molecular weights set out in the table. The results obtained are set out in Table 2.
- Example 3 Detergent solutions were prepared in the manner described in Example 1, Part 2, from a commercial higher alkylbenzene mixture resulting from the alkylation of benzene with a propylene polymer, predominantly the tetramer (Detergent Alkylate No. 2 of Atlantic Refining Co.) The proportions of components were as set out below in Table 3.
- Example 1 Detergent solutions were prepared in the manner described in Example 1, Part 2, from a kerylbenzene obtained as described in Example 1, Part 1. The proportions of components were as set out below in Table 4.
- the polyethylene glycol was a commercial product having an average molecular weight of about 400.
- Example 5 Detergent solutions were prepared in the manner de scribed in Example 1, Part 2, from kerylbenzenes obtained as described in Example 1, Part 1, with and without the addition of toluene in the sulfonation. The results obtained with parts by weight of various diols are set out in Table 5.
- the products identified as Carbowax were commercial polyethylene glycols having the average molecular weight represented by the number following the name.
- the products identified as Pluronic L-44 and F-68 were ethylene oxide derivatives of polypropylene glycols corresponding to the formula in which a, b and c are integers.
- the central core of propoxy groups has an average molecular weight of 1000-1200, the terminal chains of ethoxy groups have a total molecular weight of approximately 800-1000, the total molecular weight being 2000.
- the central core of propoxy groups has a molecular weight of 18002100 and the 6 terminal chains of ethoxy groups have a molecular weight of 5900 to 6200, the total molecular weight being 8000.
- the critical solution temperatures were determined on the solutions as obtained, without as in the preceding examples first diluting them to a total solutes concentration of 41%.
- the composition Tof the total solutes fraction of the detergent solutions averaged about as follows: Sodium kerylbenzene sulfonate 75.4%, sodium toluene sulfonate 12.8%, sodium tripolyphosphate 1.3%, other alcohol insolubles (principally sodium sulfate) 10%, and sodium chloride 0.5%, all by weight.
- the conditions of sulfonation also may be varied in the manner known in the art, as illustrated by the patents referred to above.
- others of the usual sulfonating agents may be employed; as, for example, sulfuric acid, chlorosulfonic acid, oleum of 5 various strengths, sulfur trioxide, stabilized sulfur trioxide, etc.
- the expression detergent solution means that the product is a clear, stable liquid having the visible appearance and characteristics of a solution; it does not necessarily mean that all components are in a state of molecular dispersion, rather than in the form of micelles or fine colloid particles.
- a concentrated aqueous detergent composition having the appearance and characteristics of a solution and consisting essentially of water and solutes, said solutes consisting essentially, by weight of the aqueous detergent composition, of about 30% of a mixture of the sodium salts of higher alkylbenzene sulfonic acids having an average of 12 to 16 non-aromatic carbon atoms, about 5% of the sodium salt of toluene sulfonic acid, and 1% to 2% of a polyethylene glycol selected from the group consisting of diethylene glycol, triethylene glycol and mixtures of polyethylene glycols which have an average molecular weight of 200 to 1250 and a major proportion of which have molecular weights within said range.
- the polyethylene glycol is a mixture of polyethylene A glycols having an average molecular weight of about 400.
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Description
United States Patent CONCENTRATED AQUEOUS DETERGENT COMPOSITION Marvin M. Fein, Westfield, N.J., and Cecil A. Friedman,
Buffalo, N.Y., assignors to Allied Chemical Corporation, a corporation of New York No Drawing. Filed July 14, 1955, Ser. No. 522,165
3 Claims. (Cl. 252-161) This invention relates to concentrated aqueous detergent compositions comprising anionic detergents of the higher alkylbenzene sulfonate type. It relates more particularly to aqueous liquid detergent compositions containing in excess of 15% by weight of water-soluble salts of a mixture of higher alkylbenzene sulfonates containing 9 to 18 non-aromatic carbon atoms together with minor amounts of certain additives which modify the solubility and other properties of the higher alkylbenzene sulfonates.
The higher alkylbenzene sulfonates are valuable detergents, wetting agents, penetrating agents, and emulsifying agents. They owe their valuable surface-active properties in part to the fact that they are partly hydrophobic and partly hydrophilic. This molecular complexity leads to the disadvantage, however, that their solubility in water at ordinary atmospheric temperatures is limited.
The anionic detergents of the higher alkylbenzene sulfonate type are generally produced in the form of water-soluble salts such as the alkali metal salts, and especially the sodium salt. They generally come into the market in the form of the dried solid. Since they are mostly used in aqueous solution, it is necessary for the user to dissolve them in water or other aqueous media before use.
To avoid the necessity of dissolving the higher alkylbenzene sulfonates at the point of use, it has been proposed to prepare stock solutions of the sulfonates in water and dilute them to the required degree at the point of use. One disadvantage of the solutions heretofore employed is the relatively low maximum concentration of sulfonate obtainable at ordinary atmospheric temperatures. A further disadvantage is the precipitation of the sulfonate and inorganic sulfate. from saturated solutions which occurs upon a decrease in the surrounding temperature; it is costly and troublesome to redissolve the precipitated matter. These disadvantages represent a handicap to the shipment of detergent solutions in tank cars and the storage of the solutions in storage tanks exposed to the atmosphere, especially in cold weather.
According to the present invention, concentrated aqueous detergent compositions are produced containing anionic detergents of the higher alkylbenzene sulfonate type and, as modifiers of the solubility and other properties thereof, (1) a water-soluble salt of a benzene sulfonic acid containing a maximum of 6 non-aromatic carbon atoms, and (2) an open-chain diol of the type specified hereinafter.
We have discovered that, by incorporating into aqueous solutions of such anionic detergents a minor amount of a water-soluble salt of benzene .sulfonic acid or a lower alkyl derivative thereof (containing 1 to 6 non aromatic carbon atoms) and a small amount of an open chain diol of the type hereinafter set forth, detergent compositions can be obtained in the form of concentrated aqueous solutions having in excess of 25% and as high as 45% by weight of a water-soluble salt of a higher alkylbenzene sulfonate (or a mixture of watersoluble salts of such sulfonates), which solutions have the ability to remain clear not only at normal atmospheric temperatures but in many cases even at lower temperatures, such as below 0 C.
We have discovered that the critical solution temperatures of concentrated aqueous solutions of watersoluble salts of said higher alkylbenzene sulfonic acids can be lowered substantially by including in said solutions both of said modifiers in a minor total amount, without reducing the detergent properties of the solutions to a substantial degree. This result is surprising because the addition of water-soluble salts of toluene sulfonic acid to such concentrated aqueous solutions reduces substantially the foaming power in hard water of said detergents.
(The term critical solution temperature-cloud point or haze point--as employed herein refers to the temperature at which the solution, upon cooling, begins to become turbid.)
Preferably, in accordance with the present invention,
the higher alkylbenzene'sulfonate and the. benzene sulfonate having a maximum of 6 non-aromattic carbon atoms are present in the form of a mixture obtained by co-sulfonating a higher alkylbenzene hydrocarbon in admixture with a minor amount of benzene or a lower alkylbenzene, since a somewhat greater increase in solubility (lowering of the critical solution temperature) is obtained than by mixing the separately prepared sulfonates.
The anionic detergents of the higher alkylbenzene sulfonate type employed in accordance with the present invention comprise essentially water-soluble salts. or
mixtures of water-soluble salts of mononuclear aryl hydrocarbon sulfonic acids that contain a total of 9 to 18 non-aromatic carbon atoms, and preferably they have as a nuclear substituent a higher alkyl radical which contains 12 to 16 carbon atoms. 7 t
Advantageous higher alkylbenzene sulfonate detergents for use in accordance withv the present invention are t mixturesof neutral water-soluble salts, especially sodium salts, of such higher alkylaryl sulfonic acids, particularly those in which the higher alkyl radicals contain, on the average, from about 12 to about 16 carbon atoms. Higher alkylaryl sulfonate detergents especially advantageous for use in accordance with the present invention are those consisting essentially of higher alkylbenzene (or higher 'alkyltoluene) 'sodium'sulfonate mixtures of which the higher alkyl groups correspond to the hydrocarbons of a petroleum fraction of a kerosene boiling range, herein referred to as keryl benzene su1-' fonates. t p w The said anionic detergents can be obtained in various ways. Thus they can be prepared by condensing a mono.- nuclear aromatic hydrocarbon (such as, benzene, toluene,
Patented Apr. 4, 1961 xylene, etc.) with an alkylating agent adapted to introduce a higher alkyl radical and containing enough non-aromatic carbon atoms per molecule to make the total of nonaromatic carbon atoms in the alkylate between 9 and 18 (such as, a higher alcohol, a higher alkyl halide, an olefin or olefin polymer, or a commercial mixture of such alkylating agentsfor example, chlorinated kerosene, a mixture of olefins, or a trimer, tetramer or pentamer of propylene or mixture thereof, etc.) to form an alkylated aromatic compound or mixture of such compounds, or by condensation of ethylenewith an alkylaromatic hydro. carbon (suchas, toluene or cumene); sulfonating the re sulting alkylated benzene compound or mixture, with or without intermediate purification operations (or, in some cases, sulfonating in the course of the condensation); and neutralizing the resulting sulfonic acid product to form the higher alkylbenzene-sulfonate, usually in the form of the alkali metaL especialIy sodium, salt.
It is advantageous to use, as the source of the alkyl radical introduced into the aromatic nucleus, naturallyoccurring or synthetically-prepared non-aromatic hydrocarbon rnixtures. For example, the various fractions of petroleum ditillates, hydrogenated coal distillates, polymerized gaseous olefins, etc., represent available and inexpensive sources of alkylating agents for thepreparation of the higher alkylarylsulfonates. A preferred alkylating agent is the mixture of chlorfhydrocarbons resulting from the chlorinationof a selected petroleum distillate, preferably of the kerosene boiling range. Such a mixture of chlor-hydrocarbons can be prepared, for example, by
chlorinating with gaseous chlorine a kerosent fraction of i the petroleum distillate.
Higher alkylbenzene sulfonate detergent compositions of this type and methods for their preparation are disclosed, for example, in US. Patents 2,233,408; 2,247,365; 2,267,725; 2,283,199; 2,298,650; 2,298,651; 2,298,696; 2,333,830; 2,340,654; 2,364,782; 2,387,572; 2,393,526; and 2,477,383; and British Patent 416,379.
The low molecular weight benzene sulfonates employed as solubilizing agents in accordance with the present invention comprise the water-soluble salts of benzene ,sulfonic acid and its homologs which contain a maximum of 6 non-aromatic carbon atoms, such as toluene, xylene, cumene, cymene, butyl benzene, amyl benzene, hexyl benzene, butyl xylene, etc. They include the alkali metal, ammonium, and organic amine salts. In view of their ready availability and low cost, the sodium salts are preferably employed.
The choice of the particular benzene sulfonate of low molecular weight employed as solubilizing agent for the higher alkylbenzene sulfonate will depend upon a number of factors; such as relative cost, odor and color of the final detergent solution, etc. Sodium xylene sulfonate and sodium cumene sulfonate exert a greater solubilizing effect upon the higher alkylbenzene sulfonates than do benzene sulfonate and toluene sulfonatebut, when employed for the manufacture of a detergent solution by the co-sulfonation procedure, their use'leads to detergent solutions having an undesirable odor and a higher degree of color. Accordingly, for the preferred manufacture of detergent solutions having general .utility and acceptability, as well as a desirably low critical solution temperature at high concentrations of higher alkylbenzene sulfonate, sodium toluene sulfonate is preferred.
The low molecular weight benzene sulfonates can be incorporated into the detergent solutions in any desired manner and at any stage of the preparation of the solutions. Thus, they may be preformed and added to the detergent solution, or one of the components thereof, during the preparation of the solution.
In the preferred practice'of our invention, the benzene sulfonate of low molecular weight is incorporated into the detergent solution during the course of manufacture of the higher alkylbenzene sulfonate, by co-sulfonating a 4 mixture of a hydrocarbon of the benzene series containing 9 to 18 non-aromatic carbon-atoms and a hydrocarbon of the benzene series containing not more than 6 non-aromatic carbon atoms, the latter being present in an amount from 3% to 25% of the weight of said mixture. The effect of the bezene sulfonate of low molecular weight as a depressor of the critical solution temperature of the detergent solution is greater when the solution is prepared by the cosulfonating procedure. On the other hand, in some cases the co-sulfonation procedure leads to a some what lowered foaming action of the resulting detergent solution in hard water. Thus, the specific procedure employed will depend to some extent upon the result desired to be obtained.
The open-chain diols employed in accordance with the present invention include'the variousmembers ofthe class corresponding to the formula HO-- RO) H wherein R0 represents a radical selected from the group consisting of the CH CI-I O radical, the
radical and the --CHCH:O-
radical, and
n represents an integer from 1 through 150, but not more than 10 R0- radicals contain 3 carbon atoms.
Thus, they include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and higher polyethylene glycols having molecular weights from about 200 through 6000; propylene glycol, dipropylene glycol, tripropyleneglycol andhigher polypropylene glycols having molecular weights through about 600; and mixed ethylene-propylene glycol ethers having a maximum total of RO- radicals of which not more than 10 RO radicals are propoxy radicals. They may be employed in the form of the individual polyglycol (glycol ether), or in the form of mixtures such as are obtained commercially by the reaction of a glycol with ethylene and/or propylene oxide. Preferred polyglycols employed in accordance with the present invention are polyethylene glycol mixtures having an average molecular weight of about 200 to about 1250, inasmuch as said polyglycol mixtures produce a superior increase in the foaming action of the resulting detergent solution when employed in hard water.
The open-chain diol can be incorporated into the detergent solution at any stage of the manufacture thereof subsequent to the formation of the sulfonic acid, and in any order with respect to the other components of the solution. An advantageous procedure for the manufacture of the solution involves carrying out the neutralization of the higher-alkylbenzene sulfonic acid in an aqueous medium containing the open-chain diol.
The amounts of benzene sulfonate of low molecular weight and open-chain diol employed relative to the amount of higher alkylbenzene sulfonate can be varied depending upon the result desired to be obtained. Thus, for the preparation of aqueous liquid detergent solutions containing, by weight, 15% to 45% of higher alkylbenzene sulfonate, amounts of benzene sulfonate of low molecularweight ranging from 0.5% to 15%, preferably 2% to 15%, and amounts of diol ranging from 0.5% to 10%, preferably 1% to 5% of the weight of the final solution, may be employed, a greater lowering of the critical solution temperature being generally obtained with the larger amounts. of solubilizing sulfonate and open-chain diol. In general the solutions contain 40% to 75% of water. Compositions of particular utility as stock solutions in accordance with our invention are aqueous liquid solutions containing as their essential components, by weight, about 25% to about 45%, especially about 30% of sodium kerylbenzene sulfonate, about 3% to about 12%, especially about of sodium toluene sulfonate (preferably co-sulfonated), and about 1% to about 5%, especially about 2% of a mixture of polyethylene glycols having an average molecular weight of 200 to 1250 and a major proportion of which have molecular weights within this range.
The invention will be illustrated by the following specific examples, but it is to be understood that it is not limited to the details thereof and that changes may be made without departing from the scope of the invention.
The temperatures are in degrees centigrade and the parts and percentages are by weight, unless designated as parts by volume. Where parts are by volume, the amount signifies the volume occupied by the same number of parts by weight of water at 4 C.
Example 1 Part 1.-A refined higher alkylbenzene was prepared in a manner similar to that described in U.S.P. 2,364,782 by chlorinating a kerosene fraction of petroleum distillate; condensing the resulting chlorination product with benzene in the presence of anhydrous aluminum chloride; separating the alkylbenzene-containing oil from the condensation reaction mixture by decantation; recovering an alkylbenzene mixture by fractional distillation of the oil; and subjecting the alkylbenzene mixture to a refining extraction treatment with sulfuric acid. The kerosene fraction had a boiling point ranging from about 198 to 251 and consisted predominantly of C -C parafiin and naphthene hydrocarbons. The keryl benzene had an average molecular weight of 260 to 265.
Part 2.Detergent solutions were prepared from the resulting keryl benzene in the following manner:
150 parts of the keryl benzene, or 150 parts of a mixture of the keryl benzene and toluene in the proportions set out below in Table 1, were reacted with 210 parts of 100% sulfuric acid at 55-60 for one hour. The sulfonation mass was agitated with 50 parts of water, whereafter it was allowed to settle out and stratify. The lower layer of spent sulfonating acid was withdrawn. The upper layer of sulfonation product, weighing 220 parts,
consisted of aromatic sulfonic acid(s) and some free sulfuric acid. Separate streams of the sulfonation product and of 30% NaOH solution (about 90-100 parts by volume) were charged simultaneously to 150 parts of an aqueous medium consisting of water or water containing a commercial polyethylene glycol having an average molecular weight of about 400 in the amounts set out in Table 1. Near the end of the neutralization procedure, the batch was treated successively with (1) a solution of 3 parts of sodium tripolyphosphate in 10 parts by volume of waterwhich serves as a sequestering agent for iron and other undesirable metallic compounds in the subsequent use of the detergent solutions, (2) 1 part by volume of 10% sodium hypochlorite solution-which functions as a purifying agent in accordance with U.S.P. 2,333,830, and (3) a solution of 0.7 part of sodium bi sulfite in 2 parts by volume of waterwhich serves to decompose the residual sodium hypochlorite in the treated solution. The acidity of the solution was finally adjusted to a grass-green color test on Nitrazine Yellow test paper (a pH 6.3 to 6.7).
The resulting solutions were tested for critical solution temperature (CST) after being diluted to a total solutes concentration of 41%. (The total solutes frac tion is the residue after evaporation of the water; it includes all other components of the solution except the water.)
The results obtained are set out in Table 1.
TABLE 1 Polyethylene Ross-Miles Test Glycol for Hard Water CST in Foaming Weight Weight C. at M of Keryl oi Benzene Toluene Average Salutes Solutes Foam Molecular Weight Cone. Concen- Height, Weight tratlon, mm.
Percent the solution to be tested is immersed in a cooling bath containing ice and salt, to a depth such that the liquid level of the sample remains just above the liquid level of the cooling bath. The'sample is allowed to cool slowly while being stirred with a thermometer. The temperature at which turbidity first becomes evident is taken as the. critical solution temperature.
The detergent solutions were tested for hard water foaming by the Ross-Miles procedure described in Oil and Soap, volume 18, pages 99-102 (May 1941). The detergent solutions were diluted with water having a hardness of 15 to give a test solution having a concentration of solutes (originating from the detergent solution) as given in the table. The last column of the table gives the heights of the foam columns obtained from the different solutions by the test procedure.
ExampleZ Detergent solutions were prepared in the manner described in Example 1, Part 2, from a kerylbenzene obtained as described in Example 1, Part 1. The proportions of components were as set out below in Table 2. The polyethylene glycols were commercial products having the 1 average molecular weights set out in the table. The results obtained are set out in Table 2.
The data set forth in Tables 1 and 2 show that polyethyl ene glycols having average molecular weights of 200, 400 and 600 have a synergistic effect, in that they boost the foaming capacity of the detergent in hard water and thereby overcome or reduce the loss in hard water foaming capacity resulting from the use of toluene sulfonate as a solubilizer. Thus, the data show that, while toluene sulfonate lowers the critical solution temperature of kerylbenzene sodium sulfonate detergent solutions, it also lowers the hard water foaming capacity of these solutions. Addition of the polyglycols, while further lowering the critical solution temperatures of the solutions, increases their hard water foaming capacity, the increase in hard water foaming capacity resulting from the use of the polyglycols being greater than the decrease in hard water foaming capacity resulting from the inclusion of the toluene sulfonate. Toluene sulfonate and the polyglycols'thus 7 Example 3 Detergent solutions were prepared in the manner described in Example 1, Part 2, from a commercial higher alkylbenzene mixture resulting from the alkylation of benzene with a propylene polymer, predominantly the tetramer (Detergent Alkylate No. 2 of Atlantic Refining Co.) The proportions of components were as set out below in Table 3.
Detergent solutions were prepared in the manner described in Example 1, Part 2, from a kerylbenzene obtained as described in Example 1, Part 1. The proportions of components were as set out below in Table 4. The polyethylene glycol was a commercial product having an average molecular weight of about 400.
The results obtained are set out in Table 4.
TABLE 4 Lower Allrylbenzene Weight of Weight of Kcryl Polyethyl- CST at 41% Benzene, Parts ene Glycol Solu tes Kind Weight, (M.W. 400), Gone, C.
Parts Parts 135 Toluene... 15 11 135... ...do 15 10 0 145... 5 0 48 145 5 20 0 145.-. 5 0 38 145 5 20 1 150 0 78 150- 20 13 Example 5 Detergent solutions were prepared in the manner de scribed in Example 1, Part 2, from kerylbenzenes obtained as described in Example 1, Part 1, with and without the addition of toluene in the sulfonation. The results obtained with parts by weight of various diols are set out in Table 5. The products identified as Carbowax were commercial polyethylene glycols having the average molecular weight represented by the number following the name. The products identified as Pluronic L-44 and F-68 were ethylene oxide derivatives of polypropylene glycols corresponding to the formula in which a, b and c are integers.
In Pluronic L-44, the central core of propoxy groups has an average molecular weight of 1000-1200, the terminal chains of ethoxy groups have a total molecular weight of approximately 800-1000, the total molecular weight being 2000. In Pluronic" F-68, the central core of propoxy groups has a molecular weight of 18002100 and the 6 terminal chains of ethoxy groups have a molecular weight of 5900 to 6200, the total molecular weight being 8000.
The critical solution temperatures were determined on the solutions as obtained, without as in the preceding examples first diluting them to a total solutes concentration of 41%. Exclusive of the diol additive, the composition Tof the total solutes fraction of the detergent solutions averaged about as follows: Sodium kerylbenzene sulfonate 75.4%, sodium toluene sulfonate 12.8%, sodium tripolyphosphate 1.3%, other alcohol insolubles (principally sodium sulfate) 10%, and sodium chloride 0.5%, all by weight.
TABLE 5 Detergent Solution From Co-Sulionated Detergent Solution Mixture of 90% From Sullonated Keryl Benzene Keryl Benzene Diol Additive and 10% Toluene CST, solutes CST, Solutes 0. Cone.. 0. Cone Percent Percent None +12. 5 45. 5 90 47. 5 Ethylene GlycoL. +5.0 47.9 75 46.8 Dicthylene Glycol. -2. 5 46.8 77 47.6 Triethylene Glycol. 3. 0 48. 3 78 47. 5 Polyethylene Glycol MW 200 -6. 5 46. 4 77 48. 6 Polyethylene Glycol M.W.
300 6. 0 47. 9 74 47. 0 Polyethylene Glycol M.W.
400 5. 5 48. 7 73 4B. 8 Polyethylene Glycol M W.
-4. 5 48. 0 80 48. 8 "Carbon/ax 1000. 2.0 48 0 59 48.0 Carbowax" 1500. 4. 0 46. 8 78 48. 4 Carbowax" 4000..-- +4.0 40. G 74 48. 6 Carbowax" 6000.... +3. 5 47. 5 80 49. 8 Propylene Glycol +3. 5 46. 7 03 46. 9 Polypropylene Glycol M.W. 400 +3.0 48.8 81 48.3 Polypropylene Glycol M.W.
750 +20. 0 46. 0 87 47. 0 Pluronic L44----- +11. 0 47. 6 76 40. 0 Pluronic" F-68 +15. 0 47. 8 65 40. 2
The data of Table 5 show inter alia that not all polyglycols are effective in reducing the critical solution temperature of detergent solutions made from sodium keryl benzene sulfonate in admixture with a minor amount of sodium toluene sulfonate. Thus, Pluronic L-44 has a negligible effect in further increasing the solubility (lowering the criticial solution temperature) of such solutions, while Pluronic F-68 and polypropylene glycol having a molecular weight of about 750 actually decrease the solubility of the detergent.
It will be realized by those skilled in the art that changes may be made in the compositions and methods of preparing them hereinbefore described without departing from the scope of the invention. Thus, in place of the higher alkylbenzene sulfonic acid salts employed in the above specific examples, one or more other watersoluble salts of higher alkylbenzene sulfonic acids of the class hereinbefore disclosed may be employed: and, in place of the salts of benzene sulfonic acids of low molecular weight and diols employed in the specific examples, one or a mixture of other water-soluble salts of alkylbenzene sulfonic acids of low molecular weight and diols of the classes hereinbefore disclosed may be employed. Similarly, the proportions of the higher alkylbenzene sulfonate and benzene sulfonate of low molecular weight and diol may be varied, as hereinbefore disclosed.
The conditions of sulfonation also may be varied in the manner known in the art, as illustrated by the patents referred to above. Thus, in carrying out the sulfonation of the higher alkylbenzene, or mixture of higher alkylbenzene and benzene or lower alkylbenzene, others of the usual sulfonating agents may be employed; as, for example, sulfuric acid, chlorosulfonic acid, oleum of 5 various strengths, sulfur trioxide, stabilized sulfur trioxide, etc.
The neutralization of the sulfonic acids and/or conversion to water-soluble salts need not be carried out in the manner disclosed in the specific examples, but can be elfected in any other of the usual ways illustrated in the patents referred to above, and USP 2,652,427.
As employed herein, the expression detergent solution means that the product is a clear, stable liquid having the visible appearance and characteristics of a solution; it does not necessarily mean that all components are in a state of molecular dispersion, rather than in the form of micelles or fine colloid particles.
We claim:
1. A concentrated aqueous detergent composition having the appearance and characteristics of a solution and consisting essentially of water and solutes, said solutes consisting essentially, by weight of the aqueous detergent composition, of about 30% of a mixture of the sodium salts of higher alkylbenzene sulfonic acids having an average of 12 to 16 non-aromatic carbon atoms, about 5% of the sodium salt of toluene sulfonic acid, and 1% to 2% of a polyethylene glycol selected from the group consisting of diethylene glycol, triethylene glycol and mixtures of polyethylene glycols which have an average molecular weight of 200 to 1250 and a major proportion of which have molecular weights within said range.
2. A concentrated liquid aqueous detergent composition as defined in claim 1, wherein the mixture of sodium salts of higher alkylbenzene sulfonic acids is the sodium salt of a kerylbenzene sulfonic acid.
3. A concentrated liquid aqueous detergent composition as defined in claim 1, wherein the mixture of the sodium salts of higher alkylbenzene sulfonic acids and the sodium salt of toluene sulfonic acid have been obtained from a mixture of sulfonic acids resulting from I:
the co-sulfonation of a kerylbenzene and toluene, and
the polyethylene glycol is a mixture of polyethylene A glycols having an average molecular weight of about 400.
References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Oarbowax, Carbide &- Carbon Corp, 16 page boo let, 1946.
Harris: American Perfumer and Essential Oil Review, vol. 48, No. 11, November 1946, pages 54-56.
Great Britain May 4, 1955'
Claims (1)
1. A CONCENTRATED AQUEOUS DETERGENT COMPOSITION HAVING THE APPEARANCE AND CHARACTERISTICS OF A SOLUTION AND CONSISTING ESSENTIALLY OF WATER AND SOLUTES, SAID SOLUTES CONSISTING ESSENTIALLY, BY WEIGHT OF THE AQUEOUS DETERGENT COMPOSITION, OF ABOUT 30% OF A MIXTURE OF THE SODIUM SALTS OF HIGHER ALKYLBENZENE SULFONIC ACIDS HAVING AN AVERAGE OF 12 TO 16 NON-AROMATIC CARBON ATOMS, ABOUT 5% OF THE SODIUM SALT OF TOLUENE SULFONIC ACID, AND 1% TO 2% OF A POLYETHYLENE GLYCOL SELECTED FROM THE GROUP CONSISTING OF DIETHYLENE GYLCOL, TRIETHYLENE GLYCOL AND MIXTURES OF POLYETHYLENE GLYCOLS WHICH HAVE AN AVERAGE MOLECULAR WEIGHT OF 200 TO 1250 AND A MAJOR PROPORTION OF WHICH HAVE MOLECULAR WEIGHTS WITHIN SAID RANGE.
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US522165A US2978416A (en) | 1955-07-14 | 1955-07-14 | Concentrated aqueous detergent composition |
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US522165A US2978416A (en) | 1955-07-14 | 1955-07-14 | Concentrated aqueous detergent composition |
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US2978416A true US2978416A (en) | 1961-04-04 |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3140261A (en) * | 1960-11-15 | 1964-07-07 | Shell Oil Co | Detergent composition |
US3331878A (en) * | 1960-08-11 | 1967-07-18 | Lever Brothers Ltd | Tertiary phosphine oxides |
US3350319A (en) * | 1966-01-18 | 1967-10-31 | Mo Och Domsjoe Ab | Aqueous detergent-inorganic builder concentrates |
US3393154A (en) * | 1965-10-23 | 1968-07-16 | Colgate Palmolive Co | Pearlescent liquid detergent compositions |
US3457175A (en) * | 1965-01-04 | 1969-07-22 | Lever Brothers Ltd | Shampoos |
US3819528A (en) * | 1968-12-23 | 1974-06-25 | Procter & Gamble | Stabilized aqueous enzyme compositions |
US3928249A (en) * | 1972-02-07 | 1975-12-23 | Procter & Gamble | Liquid detergent composition |
US3997453A (en) * | 1974-02-11 | 1976-12-14 | Colgate-Palmolive Company | Softener dispersion |
EP0153857A2 (en) * | 1984-02-29 | 1985-09-04 | Unilever N.V. | Detergent compositions |
US4690779A (en) * | 1983-06-16 | 1987-09-01 | The Clorox Company | Hard surface cleaning composition |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2088085A (en) * | 1933-10-06 | 1937-07-27 | Ig Farbenindustrie Ag | Production of stable and efficient foam |
US2607740A (en) * | 1950-05-03 | 1952-08-19 | Colgate Palmolive Peet Co | Liquid anionic-dialkylolamide detergent composition |
US2615847A (en) * | 1950-01-27 | 1952-10-28 | Atlantic Refining Co | Alkaryl sulfonate detergents |
GB729531A (en) * | 1952-06-02 | 1955-05-04 | Unilever Ltd | Liquid detergent compositions |
-
1955
- 1955-07-14 US US522165A patent/US2978416A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2088085A (en) * | 1933-10-06 | 1937-07-27 | Ig Farbenindustrie Ag | Production of stable and efficient foam |
US2615847A (en) * | 1950-01-27 | 1952-10-28 | Atlantic Refining Co | Alkaryl sulfonate detergents |
US2607740A (en) * | 1950-05-03 | 1952-08-19 | Colgate Palmolive Peet Co | Liquid anionic-dialkylolamide detergent composition |
GB729531A (en) * | 1952-06-02 | 1955-05-04 | Unilever Ltd | Liquid detergent compositions |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3331878A (en) * | 1960-08-11 | 1967-07-18 | Lever Brothers Ltd | Tertiary phosphine oxides |
US3140261A (en) * | 1960-11-15 | 1964-07-07 | Shell Oil Co | Detergent composition |
US3457175A (en) * | 1965-01-04 | 1969-07-22 | Lever Brothers Ltd | Shampoos |
US3393154A (en) * | 1965-10-23 | 1968-07-16 | Colgate Palmolive Co | Pearlescent liquid detergent compositions |
US3350319A (en) * | 1966-01-18 | 1967-10-31 | Mo Och Domsjoe Ab | Aqueous detergent-inorganic builder concentrates |
US3819528A (en) * | 1968-12-23 | 1974-06-25 | Procter & Gamble | Stabilized aqueous enzyme compositions |
US3928249A (en) * | 1972-02-07 | 1975-12-23 | Procter & Gamble | Liquid detergent composition |
US3997453A (en) * | 1974-02-11 | 1976-12-14 | Colgate-Palmolive Company | Softener dispersion |
US4690779A (en) * | 1983-06-16 | 1987-09-01 | The Clorox Company | Hard surface cleaning composition |
US4615819A (en) * | 1984-02-26 | 1986-10-07 | Lever Brothers Company | Detergent gel compositions in hexagonal liquid crystal form |
EP0153857A2 (en) * | 1984-02-29 | 1985-09-04 | Unilever N.V. | Detergent compositions |
EP0153857A3 (en) * | 1984-02-29 | 1986-05-14 | Unilever Nv | Detergent compositions |
TR22431A (en) * | 1984-02-29 | 1987-06-02 | Unilever Nv | DETERGENT COMPOUNDS IN A STABLE, TRANSPARENT TRANSPARENT OR SEMI-TRANSPARENT, WATER-COEZUELABLE GEL SHAPE. |
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