US2990375A - Heavy duty liquid detergent compositions - Google Patents
Heavy duty liquid detergent compositions Download PDFInfo
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- US2990375A US2990375A US673404A US67340457A US2990375A US 2990375 A US2990375 A US 2990375A US 673404 A US673404 A US 673404A US 67340457 A US67340457 A US 67340457A US 2990375 A US2990375 A US 2990375A
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- diphenyl ether
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- 239000000203 mixture Substances 0.000 title claims description 87
- 239000007788 liquid Substances 0.000 title claims description 36
- 239000003599 detergent Substances 0.000 title claims description 28
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 122
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 description 41
- -1 alkyl diphenyl ether sulfonates Chemical class 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 27
- 238000010586 diagram Methods 0.000 description 19
- 229910052700 potassium Inorganic materials 0.000 description 17
- 239000011591 potassium Substances 0.000 description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 16
- 239000004615 ingredient Substances 0.000 description 15
- 229910052783 alkali metal Inorganic materials 0.000 description 14
- 150000003839 salts Chemical class 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 12
- 229920000388 Polyphosphate Polymers 0.000 description 12
- 150000001340 alkali metals Chemical class 0.000 description 12
- 239000001205 polyphosphate Substances 0.000 description 12
- 235000011176 polyphosphates Nutrition 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 12
- 229940048086 sodium pyrophosphate Drugs 0.000 description 12
- 235000019832 sodium triphosphate Nutrition 0.000 description 12
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 12
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 7
- 239000004305 biphenyl Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 125000006267 biphenyl group Chemical group 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000008234 soft water Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-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
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910014142 Na—O Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010412 laundry washing Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 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
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
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
- 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
- C11D1/24—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds containing ester or ether groups directly attached to the nucleus
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
Definitions
- This invention concerns certain new liquid detergent compositions. It relates more particularly to aqueous detergent compositions suitable for use in the household and in the laundry where mildror heavy-duty perfomance is required in either soft or hard Water, and comprises aqueous solutions containing alkyl diphenyl ether sulfonates and water-soluble alkali metal polyphosphate salts.
- Another object is to provide concentrated aqueous liquid detergent compositions comprising alkyl diphenyl ether sulfonates and alkali metal polyphosphate salts dissolved in water to form clear solutions, which compositions can be marketed in liquid form and are suitable for use ⁇ for cleaning or washing heavily soiled surfaces or fabrics.
- clear aqueous liquid deter- Agent compositions can readily he prepared by dissolving certain alkyl diphenyl ether sulfonates and alkali metal polyphosphate salts in water in proportions as hereinafter delined.
- compositions are transparent liquid solutions possessing excellent detergent and sudsing properties in both soft and hard water.
- the alkyl diphenyl ether sulfonates are unusual in that they have a remarkably high solubility in water, thus Ipermitting the preparation of clear heavy-duty liquid detergent compositions in highly concentrated form, thereby greatly reducing the cost of packaging and marketing the liquid compositions.
- the basic or essential ingredients of the liquid detergent compositions are (l) synthetic surface active agents which are alkyl diphenyl ether sulfonates, i.e. alkali metal salts of alkyl diphenyl ether sulfonic acids, having the general formula:
- R represents an alkyl radical containing from 9 to 15 carbon atoms
- n is an average number between 1 and 1.3
- X represents a monovalent alkali metal selected from the group consisting of sodium and potassium
- m is an average number between 1.8 and 2.4
- at least one alkali metal polyphosphate salt selected from the group consisting of sodium tripolyphosphate, potassium pyrophosphate, potassium trpolyphosphate and mixtures of potassium pyrophosphate and sodium pyrophosphate.
- alkyl diphenyl ether sulforiate and the alkali metal polyphosphate salt are dissolved in water to form transparent aqueous solutions containing said ingredients in proportions within the lines ABCDA of the trilinear diagram of the accompanying drawing, and with or without additives such as corrosion inhibitors, foam boosting and stabilizing agents or anti-redeposition agents.
- the materials are selected so that the total concentration of the metal salt of the alkyl diphenyl ether sulfonic acid and the alkali metal polyphosphate salt is not less than 10 and not more than 55 percent by weight of a 2 the solution and within the ranges defined by the trilinear diagram of the drawing.
- the proportions of the ingredients will vary depending upon the combination of sodium or potassium alkyl diphenyl ether sulfonate used and the alkali metal pyrophosphate or tripolyphosphate employed. More specifically, the ingredients can lbe employed in proportions of from 5 to 50 parts by weight of the potassium alkyl diphenyl ether sulfonate and from 5 to 45 parts of potassium pyrophosphate, per parts by weight of the aqueous liquid composition, or with from 5 to 45 parts by weight of a mixture of potassium pyrophosphate and sodium pyrophosphate containing not more than 5 parts by weight of sodium pyrophosphate, per 100 parts by weight of the composition, and within the lines ABCDA of the trilinear diagram of the drawing.
- potassium tripolyphosphate K5P3O10
- K5P3O10 potassium tripolyphosphate
- the potassium alkyl diphenyl ether sulfonate can be em-A ployed in amounts of from 5 to 20 parts by weight with ⁇ from 5 to 45 parts by weight of sodium tripolyphosphate (NasPaOw) per 100 parts by weight of the liquid composition and within the lines APQRA of the trilinear diagram of the drawing.
- the reacted mixture is -washed with water to remove the catalyst and is subjected to distillation to obtain a fraction consisting principally of monoalkylated diphenyl ether or a mixture of mono and ⁇ dialkylated diphenyl ethers, such that the distillate contains an average number of from l to 1.3 lalkyl substituents per diphenyl ether nucleus.
- the distillation can be carried out so as to separate the mono Iand dialkylated diphenyl ethers from one lanother and from lower or higher boiling ingredients, after which the monoand dialkylated diphenyl ether fractions can be combined in proportions such as to provide a mixture having an average number of nuclear alkyl substituents not exceeding 1.3 per diphenyl ether nucleus.
- the alkyl diphenyl ether or mixture of monoand dialkyl diphenyl ethers is reacted with a sulfonating agent such as chlorosulfonic acid or sulfur trioxide while having the reactants dissolved in an inert liquid polychlorinated aliphatic hydrocarbon solvent such as methylene chloride, carbon tetrachloride, perchloroethylene, symtetrachloroethane or ethylene dichloride, and at reaction temperatures between 20 and 60 C.
- a sulfonating agent such as chlorosulfonic acid or sulfur trioxide
- an inert liquid polychlorinated aliphatic hydrocarbon solvent such as methylene chloride, carbon tetrachloride, perchloroethylene, symtetrachloroethane or ethylene dichloride
- the sulfonating reaction can be carried out employing the sulfur trioxide er chlorcsulfonic acid in amounts corresponding to from 9.4 pounds of anhydrous ⁇ aluminum chloride was placed in a reaction vessel equipped with a stirrer and means for heating or cooling the contents. The mixture was stirred and heated to a temperature of 80 C. Thereafter, a charge of 119 pounds oa polypropylene fraction boiling at .temperatures between VV185" and 210 C.
- the mixture is neutralized or made slightly alkaline, e.g. is brought to a pHV value Ibetween 7 and 8, withyan alkali such as sodium hydroxide or potassium hydroxide or an Yaqueous solution of the same, to convert the alkyl diphenyl ether tothe corresponding salt,v i.e. thesodium or potassium salt of the alkyl diphenyl ether sulfonic acid.
- the aqueous and organic layers are separated.
- the salt or alkyl diphenyl ether sulfonate is recovered by heating the aqueous layer to evaporate the water.
- the neutralized or slightly alkaline mixture can be heated to vaporize and distill volatile ingredients such as water and the organic solvent employed as the reaction medium for the sulfonating reaction from the non-volatile material.
- the alkyl diphenyl ether sulfon-ate is obtained as a dry or substantially anhydrous free-dowing powder containing 75 percent by weight or more of ,the alkyl diphenyl ether sulfonate in admixture with lesser amounts of inert materials, principally alkali sulfates, e.g. sodium sulfate or potassium sulfate, ,with lesser amounts of alkali chlorides and water.
- inert materials principally alkali sulfates, e.g. sodium sulfate or potassium sulfate, ,with lesser amounts of alkali chlorides and water.
- alkali sulfates principally alkali sulfates, e.g. sodium sulfate or potassium
- liquid ,detergent compositions of the invention are prepared by dissolving an amount based on the active ingredient, of the alkyl diphenyl ether sulfonate and the inorganic polyphosphate -salt, e.g. potassium pyrophosphate or potassium tripolyphosphate, in sufficient water -to make 100 parts by weight of solution and containing said ingredients in a. total concentration between 10 and 5 5 percent b-.y weight of the solution.
- the compositions may contain additives such as corrosion inhibitors, foam boostingV and stabilizing agents or antiredeposition agents.
- the alkyl diphenyl ether sulfonate and the alkali metal polyphosphate salt are preferably employed in proportions relative to one another of from 1 to 1.5 parts by weight of the alkali metal polyphosphate salt per part of the alkyl diphenyl ether sulfonate.
- the compositions of the invention are transparent, aqueous solutions containing the alkyl diphenyl ether sulfonate andthe alkali metal polyphosphate in high concentration and are elective heavy duty liquid detergent compositions for cleansing or washing heavily soiled cotton clothes such as are encountered in home laundry washing.
- the material withdrawn from the reaction zone was mixed with an equal volume of water, then with an aqueous weight percent solution vof sodium hydroxide in amount sutlicient to bning the result-l ing mixture to a pH value of 8.
- the aqueous and organic layers were separated.
- the aqueous layer was spray dried and the solids collected as a free-owing lightV yellow powder.
- the product consisted of 90.53 percent by weight of alkyl diphenyl ether sulfonate, being diphenyl ether modified tby having an average of 1.14 tetrapropyl radicals and 2.27 sulfonate radicals of the formula SO3Na as nuclear substituents per diphenyl ethery nucleus, 3.36 percent of sodium sulfate, 2.54 percent of sodium chloride and 3.57 percent of water.
- a Terg-O-Tometer in a Terg-O-Tometer beaker and Wash the swatches at a temperature of 120 F. for l0 minutes at 100 cycles per minute. After washing, the swatches lare removed ⁇ from the wash water, wrung by hand and rinsed in water havf ing a hardness of 150 parts per million. The swatchesy are then returned tothe Terg-O-Tometer and rinsed for 5 minutes at 100 F. in water having 150 partsA per mil lion ⁇ of hardness. Thereafter, the swatches are removed from the rinse watenwrung through a hand wringer,4 placed between paper towels and pressed dry with a hand iron.
- a reflectance value for the dried swatches was" measured using a photovolt reflectometer Model y610.
- the reflect-ance value for the swatches of soiled vcloth washed withthe alkyl diphenyl ether sulfonate detergent composition was compared toV theV reliectance value for swatches of ⁇ cloth prepared asa standard gby subjecting other,V testpiecesof 'the soiled cloth to a similar Terg- O-A nooners' Tometer washing test employing a similar proportion of alkyl benzene sulfonate (Ultrawet K) and a similar amount of potassium pyrophosphate on a weight basis, 1n one liter of Water having 150 parts per million of hardness.
- Ultrawet K alkyl benzene sulfonate
- the detergency value for the aqueous cornposition - is calculated as the product of the average reectance value for the swatches washed with the alkyl diphenyl ether sulfonate wash solution divided by the average reflectance value for the swatches washed with the alkyl benzene sulfonate, standard, wash solution multiplied by 100.
- the detergency for the composition is expressed as the percent of the detergency value of the standard wash solution. A value greater than 100 percent indicates that the alkyl diphenyl ether sulfonate detergent composition has greater detergency or washing properties than has the standard wash composition.
- rIable I identities the detergent compositions and gives the proportions in percent by weight of the essential ingredients based on the weight ofthe liquid solution.V
- the table also indicates the solubility of the ingredients in the Iaqueous solution and gives a detergency. value for certain of the compositions. For purpose of comparison compositions which are not clear solutions and are outside the scope of the invention are included in the table.
- the tetrapropyl diphenyl ether sulfonate employed in the experiment was prepared by procedures similar to those described in parts A and B of Example 1 and consisted of diphenyl ether modiiied by having an average of 1.07 tetrapropyl radicals derived from tetrapropylenes and 2.23 sulfonate groups of the formula -SO3Na as nuclear substituents.
- the material was obtained as a light yellow powder having the composition 77.20 percent by weight tetrapropyl diphenyl ether sulfonate, 19.161- percent sodium sulfate and 3.64 percent water.
- a detergency value for the liquid composition was determined employing procedure similar to that employed in part C of Example 1.-- The composition had -a detergency value of 971.5 percent.
- EXAMPLE 3 Atripropyl diphenyl ether sulfonate consisting of diphenyl ether modiiied by having an average of one tripropyl radical derived ⁇ from' tripropylenes and 1.8 sulfonate groups of'the ⁇ formula -SOaNa as nuclear substituents was prepared by procedures-similar to those de-v scribed in parts A and B of Example 1. The tripropyl di ⁇ phenyl ether sulfonate was obtained ⁇ as a light yellow powder having the composition 89.97 percent by weight tripropyl diphenyl ether sulfonate, 5.76 percent sodium sulfate, 0.17 percent sodium chloride and 4.10 percent water. Y
- a charge of 20 parts by weight of the tn'propyl diphenyl ether sulfonate and 30 parts of potassium pyrophosphate were dissolved in 50 parts of water.
- a clear liquid deter'- EXAMPLE 4 A pentapropyl diphenyl ether sulfonate consisting of diphenyl ether modified by having an average of one pentapropyl radical derived from pentapropylenes and 2.17 sulfonate groups of the formula -SOaNa as nuclear substituents was prepared by procedures similar to those described in parts A and B of Example 1.
- the pentapropyl diphenyl ether sulfonate was obtained as a light yellow powder having the composition 87.16 percent by weight pentapropyl diphenyl ether sulfonate, 7.90 percent sodium sulfate, 0.09 percent sodium chloride and 4.75 percent Water. Twenty parts by weight of the pentapropyl diphenyl ether sulfonate and 30 parts of potassium pyrophosphate were .dissolved in 50 parts of water. A clear aqueous liquid detergent solution was obtained. The solution had a detergency value of 103 percent.
- EXAMPLE 5 A tetrapropyl diphenyl ether sulfonate consisting of diphenyl ether modified by having an average of 1.14 tetra propyl radicals derived from tetrapropylenes and 1.95 sulfonate groups of the formula 5803K as nuclear substituents. was prepared by procedures similar to those described in parts A and B of Example l, except that the tetrapropyl diphenyl .ether sulfonic -acid was neutralized vwith potassium hydroxide to lobtain the corresponding salt. The tetrapropyl diphenyl ether sulfonic acid, potassium salt, was obtained as a free-ilowng powder.
- EXAMPLE 6 A charge of 20 parts by weight of tetrapropyl diphenyl ether sulfonate similar to Ithat described in part B of Example 1 was dissolved in 70 parts of water containing l0 parts ofpotassium tripolyphosphate. A clear aqueous ⁇ solution was obtained. The liquid composition had good detergency properties.
- EXAMPLE 7 solving 5 parts by weight of tetrapropyl diphenyl ether sulfonate similar to that described in part B of Example 1, 15 parts of potassium pyrophosphate, 5 parts of sodium silicate having an Na-O/SiOz ratio of 1:1.8 and 0.2 part of sodium carboxymethyl cellulose (detergent grade) in 75.parts of water. A clear aqueous solution was obtained. The liquid composition had good detergency properties and was suitable for washing heavily soiled fabrics.
- sulfonate groups of the formula ⁇ 403K as nuclear substituents per diphenyl ether nucleus was mixed with water and potassium pyrophosphate in proportions as stated in the following table.
- the mixture V was stirred and heated to a temperature of 90 C. then allowed to cool to room temperature. After standing for three days the mixtures were examined.
- Table II identifies the mixtures and heated to a temperature off 90 C., then allowed to cool to room temperature. Afterstanding for three days the mixture was examined.
- Table IV ideuties thev mixtures and indicates the solubility ofthe-product.
- compositions which form clear solutions in Table III' are within the lines APQRA of the trilinear diagram of the drawing.
- a clear transparent aqueous liquid detergent composition consisting of a transparent aqueous solution con. taining (l) an alkyl diphenyl ether sulfonate having the general formula:
- R represents an alkyl radical containing from 9 to 15 carbon atoms and n is an average number from 1 to 1.3, X represents a member ofthe group consisting of sodium and potassium and m is an average number from 1.8 to 2.4, and (2) an inorganic phosphate selected from the Igroup consisting of sodium tripolyphosphate, potassium tripolyphosphate, potassium pyrophosphate and mixtures of potassium pyrophosphate and sodium pyrophosphate, said solution containing a combination of ingredients in proportions by weight, based on 100 parts by weight of the solution, which combination is selected from the group consisting of: (a) from 5 to 50 parts by weight of the potassium alkyl diphenyl ether sulfonate (l) and from 5 to 45 parts of inorganic phosphate (2) selected from the group consisting of potassium pyrophosphate and mixtures of potassium pyrophosphate and sodium pyrophosphate, which mixtures contain not more than 5 parts by weight of sodium pyrophosphate, and in a total concentration between
- a liquid detergent composition as claimed in claim l wherein the aqueous solution contains from 5 to 50 parts by weight of the potassium alkyl diphenyl ether sulfonate (1) ⁇ and from 5 to 45 parts of potassium pyrophosphate per parts by weight of the solution, and in a total concentration between l0 and 55 percent by weight of the solution and within the lines ABCDA of the trilinear diagram of the drawing.
- a liquid detergent composition as claimed in claim l wherein the aqueous solution contains from 5 to 40 parts by weight of the sodium alkyl diphenyl ether sulfonate (l) and from 5 to 40 parts of potassium tripolyphosphate per 100 parts by weight of the solution and in a total concentration between 10 and 55 percent by weight of the solution and within the lines A-JKLMNOA of the trilinear diagram of the drawing.
- a liquid detergent composition as claimed in claim l wherein the aqueous solution contains from 5 to 25 parts bym/eight of the sodium alkyl diphenyl ether snlfonate (l) and from 5 to 35 parts of potassium pyrophosphate per 100 parts by weight of the solution and in a total concentration between l0 and 50 percent by weight of the solution and within the lines AEFGHIA of the trilinear diagram of the drawing.
- a liquid detergent composition as claimed in claim l wherein the aqueous solution contains from 5 to 25 parts by weight of the sodium alkyl diphenyl ether sulfonate (1) and from 5 to 35 parts of a mixture of potassium pyrophosphate and sodium pyrophosphate, which mixture contains not more than 5 parts by Weight of sodium pyrophosphate, per 100 parts by Weight of the solution and in a total concentration between 10 and 50 percent by weight of the solution and within the lines AEFGHIA of the trilinear diagram of the drawing.
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Description
`Tune 27, 1961 A. F. sTx-:lNHAUER ET Ar. 2,990,375
HEAVY DUTY LIQUID DETERGENT COMPOSITIONS Filed July 22, 1957 United States Patent' ce 2,lltl,375A Patented .lune 27, 19631V Filed July 22, 1957, Ser. No. 673,404 6 Claims. (Cl. 252-138) This invention concerns certain new liquid detergent compositions. It relates more particularly to aqueous detergent compositions suitable for use in the household and in the laundry where mildror heavy-duty perfomance is required in either soft or hard Water, and comprises aqueous solutions containing alkyl diphenyl ether sulfonates and water-soluble alkali metal polyphosphate salts.
It is an object of the invention to prepare clear aqueous liquid detergent compositions containing alkyl diphenyl ether sulfonates `and alkali metal polyphosphate salts, which compositions are suitable for cleansing and washing purposes in both soft and hard wate Another object is to provide concentrated aqueous liquid detergent compositions comprising alkyl diphenyl ether sulfonates and alkali metal polyphosphate salts dissolved in water to form clear solutions, which compositions can be marketed in liquid form and are suitable for use `for cleaning or washing heavily soiled surfaces or fabrics. Other and related objects may appear from the following description of the invention.
According to the invention clear aqueous liquid deter- Agent compositions can readily he prepared by dissolving certain alkyl diphenyl ether sulfonates and alkali metal polyphosphate salts in water in proportions as hereinafter delined.
'I'he new compositions are transparent liquid solutions possessing excellent detergent and sudsing properties in both soft and hard water. The alkyl diphenyl ether sulfonates are unusual in that they have a remarkably high solubility in water, thus Ipermitting the preparation of clear heavy-duty liquid detergent compositions in highly concentrated form, thereby greatly reducing the cost of packaging and marketing the liquid compositions.
. The basic or essential ingredients of the liquid detergent compositions are (l) synthetic surface active agents which are alkyl diphenyl ether sulfonates, i.e. alkali metal salts of alkyl diphenyl ether sulfonic acids, having the general formula:
wherein R represents an alkyl radical containing from 9 to 15 carbon atoms, n is an average number between 1 and 1.3, X represents a monovalent alkali metal selected from the group consisting of sodium and potassium, and m is an average number between 1.8 and 2.4, and (2) at least one alkali metal polyphosphate salt selected from the group consisting of sodium tripolyphosphate, potassium pyrophosphate, potassium trpolyphosphate and mixtures of potassium pyrophosphate and sodium pyrophosphate.
- The alkyl diphenyl ether sulforiate and the alkali metal polyphosphate salt are dissolved in water to form transparent aqueous solutions containing said ingredients in proportions within the lines ABCDA of the trilinear diagram of the accompanying drawing, and with or without additives such as corrosion inhibitors, foam boosting and stabilizing agents or anti-redeposition agents.
. The materials are selected so that the total concentration of the metal salt of the alkyl diphenyl ether sulfonic acid and the alkali metal polyphosphate salt is not less than 10 and not more than 55 percent by weight of a 2 the solution and within the ranges defined by the trilinear diagram of the drawing.
The proportions of the ingredients will vary depending upon the combination of sodium or potassium alkyl diphenyl ether sulfonate used and the alkali metal pyrophosphate or tripolyphosphate employed. More specifically, the ingredients can lbe employed in proportions of from 5 to 50 parts by weight of the potassium alkyl diphenyl ether sulfonate and from 5 to 45 parts of potassium pyrophosphate, per parts by weight of the aqueous liquid composition, or with from 5 to 45 parts by weight of a mixture of potassium pyrophosphate and sodium pyrophosphate containing not more than 5 parts by weight of sodium pyrophosphate, per 100 parts by weight of the composition, and within the lines ABCDA of the trilinear diagram of the drawing. The ingredient sodium alkyl diphenyl ether sulfonate can be employed in amount corresponding to from 5 to 25 parts by weight with from 5 to 35 parts lby weight of potassium pyrophosphate or with from 5 to 35 parts by weight of -a mixture of potassium pyrophosphate and sodium pyrophosphate containing not more than 5 parts by weight of sodium pyrophosphate, per 100 parts by weight of the aqueous -liquid composition and within the lines AEFGHIA of the trilinear diagram of the drawing. The sodium or potassium alkyl diphenyl ether` sulfonate can be used in amounts of from 5 to 40 parts. by weight with from 5 to 40 parts by weight of potassium tripolyphosphate (K5P3O10) per '100 parts by weight of` the aqueous liquid composition 'and Within the lines. AJKLMNOA of the trilinear diagram of the drawing.. The potassium alkyl diphenyl ether sulfonate can be em-A ployed in amounts of from 5 to 20 parts by weight with` from 5 to 45 parts by weight of sodium tripolyphosphate (NasPaOw) per 100 parts by weight of the liquid composition and within the lines APQRA of the trilinear diagram of the drawing.
The alkyl diphenyl ether sulfonates to be employed in preparing the liquid detergent compositions consist essentially of diphenyl ether modified by having an average of from l to 1.3 alkyl radicals and from 1.8 to 2.4 sulfonate: radicals as nuclear substituents, each alkyl radical containing from 9 to 15 carbon atoms.
The alkyl diphenyl ether sulfonate starting material can be prepared -by a series of steps. In brief, an alkyl di phenyl ether is prepared by reacting Ian olefin or an olefin halide such as tripropylenes, tetrapropylenes, pentapropylenes, or dodecyl bromide, with diphenyl ether at reaction temperatures between 50 and 100 C. in the presence of a Friedel-Crafts type catalyst, e.g. aluminum chloride. The reacted mixture is -washed with water to remove the catalyst and is subjected to distillation to obtain a fraction consisting principally of monoalkylated diphenyl ether or a mixture of mono and `dialkylated diphenyl ethers, such that the distillate contains an average number of from l to 1.3 lalkyl substituents per diphenyl ether nucleus. In an alternate procedure, the distillation can be carried out so as to separate the mono Iand dialkylated diphenyl ethers from one lanother and from lower or higher boiling ingredients, after which the monoand dialkylated diphenyl ether fractions can be combined in proportions such as to provide a mixture having an average number of nuclear alkyl substituents not exceeding 1.3 per diphenyl ether nucleus.
The alkyl diphenyl ether or mixture of monoand dialkyl diphenyl ethers is reacted with a sulfonating agent such as chlorosulfonic acid or sulfur trioxide while having the reactants dissolved in an inert liquid polychlorinated aliphatic hydrocarbon solvent such as methylene chloride, carbon tetrachloride, perchloroethylene, symtetrachloroethane or ethylene dichloride, and at reaction temperatures between 20 and 60 C. The sulfonating reaction can be carried out employing the sulfur trioxide er chlorcsulfonic acid in amounts corresponding to from 9.4 pounds of anhydrous `aluminum chloride was placed in a reaction vessel equipped with a stirrer and means for heating or cooling the contents. The mixture was stirred and heated to a temperature of 80 C. Thereafter, a charge of 119 pounds oa polypropylene fraction boiling at .temperatures between VV185" and 210 C. at 760 millimeters absolute pressuu'e and consisting of tetrapropylenes as the principal components, was added over a period of 4 hours, together with a4 total of 0.5 pound from 2 4to 2.5 moles per diphenyl ether nucleus in the Y starting material to be sulfonated.
' Upon completing the sulfonating reaction, the mixture is neutralized or made slightly alkaline, e.g. is brought to a pHV value Ibetween 7 and 8, withyan alkali such as sodium hydroxide or potassium hydroxide or an Yaqueous solution of the same, to convert the alkyl diphenyl ether tothe corresponding salt,v i.e. thesodium or potassium salt of the alkyl diphenyl ether sulfonic acid. The aqueous and organic layers are separated. The salt or alkyl diphenyl ether sulfonate is recovered by heating the aqueous layer to evaporate the water. In an alternate procedure the neutralized or slightly alkaline mixture can be heated to vaporize and distill volatile ingredients such as water and the organic solvent employed as the reaction medium for the sulfonating reaction from the non-volatile material. The alkyl diphenyl ether sulfon-ate is obtained as a dry or substantially anhydrous free-dowing powder containing 75 percent by weight or more of ,the alkyl diphenyl ether sulfonate in admixture with lesser amounts of inert materials, principally alkali sulfates, e.g. sodium sulfate or potassium sulfate, ,with lesser amounts of alkali chlorides and water. The presence of such inert materials in small quantities is not disadvantageous in the invention. f A
In practice, the liquid ,detergent compositions of the invention are prepared by dissolving an amount based on the active ingredient, of the alkyl diphenyl ether sulfonate and the inorganic polyphosphate -salt, e.g. potassium pyrophosphate or potassium tripolyphosphate, in sufficient water -to make 100 parts by weight of solution and containing said ingredients in a. total concentration between 10 and 5 5 percent b-.y weight of the solution. The compositions may contain additives such as corrosion inhibitors, foam boostingV and stabilizing agents or antiredeposition agents. ln preparing the compositions or liquid detergent compositions, obviously care should be taken to avoid the addition of materials that will promote the formation of highly insoluble compounds or precipitation by common-ion effects, etc. The materials are selected so that the total concentration of the alkyl diphenyl other sulfonate and the alkali metal polyphosphate salt is not less than 10 and not more than 55 percent by weight of the solution and within the ranges defined by the trilinear diagram of the drawing. At higher concentrations the solutions tend to become opaque or cloudy or are viscous liquids which are difficult to pour. The alkyl diphenyl ether sulfonate and the alkali metal polyphosphate salt are preferably employed in proportions relative to one another of from 1 to 1.5 parts by weight of the alkali metal polyphosphate salt per part of the alkyl diphenyl ether sulfonate. The compositions of the invention are transparent, aqueous solutions containing the alkyl diphenyl ether sulfonate andthe alkali metal polyphosphate in high concentration and are elective heavy duty liquid detergent compositions for cleansing or washing heavily soiled cotton clothes such as are encountered in home laundry washing.
The following examplesv illustrate ways in which the principle of theinvention has been applied, but are notv to be construed as limiting its scope.
EXAMPLE 1 (A) A Charge ef 18o permis ofgdiphenyi allerhand;
of gaseous hydrogen chloride, While maintaining the reacting mixture at Vteniperatures between 78 and 85 C. Stirring kand heating of the mixture was continued for a period of 0.5 hour after -addition of the tetrapropylenes. The reacted mixture 4was washed with water to remove the catalyst, then was distilled; A fraction of the alkylated diphenyl ether product boiling at 185-245 C. at 8 millimeters was separated. The product was a mixture ofy monoand dialkylated diphenyl ether and contained an average of 1.14 tetrapropyl radicals per diphenyl'ether nucleus.
(B) A charge of the -alkyly diphenyl ether product boiling at 185'245 C. at 8 millimeters prepared in part A above was dissolved methylene chloride to form a solution containing 6.6 percent by weight of the alkyl diphenyl ether. The solution was fed to a reaction zone underV pressure and into adm-ixture with sulfur trioxide in amount corresponding to 2.3 moles of the sulfur trioxide per diphenyl ether nucleus in the alkyl diphenyl etherstarting material. The resulting mixture was mainv tained Vin the reaction zone under a pressure of 30 pounds per square inch, gauge pressure, at react-ion temperatures between 40- and 60 C. for a period of l0 seconds, then was withdrawn. The material withdrawn from the reaction zone was mixed with an equal volume of water, then with an aqueous weight percent solution vof sodium hydroxide in amount sutlicient to bning the result-l ing mixture to a pH value of 8. The aqueous and organic layers were separated. The aqueous layer was spray dried and the solids collected as a free-owing lightV yellow powder. The product consisted of 90.53 percent by weight of alkyl diphenyl ether sulfonate, being diphenyl ether modified tby having an average of 1.14 tetrapropyl radicals and 2.27 sulfonate radicals of the formula SO3Na as nuclear substituents per diphenyl ethery nucleus, 3.36 percent of sodium sulfate, 2.54 percent of sodium chloride and 3.57 percent of water.
(C) In each of a series of lexperiments a charge of the `alkyl diphenyl ether4 sulfonate powder obtained in part B above was dissolved in water having 150 partsv per million of hardness, together with potassium pyrophosphate in amounts -as stated in the following table to form liquid detergent compositions. A number of the compositions were tested for detergency. The1 procedure for determining Ya detergency value for the composition w-as to add 4 grams of the liquid detergent composition to one liter of water having 150 parts per million of hard-lV ness, Vplace the solution, together with three swatches of soiled cloth, American Conditioning House No. 115, in a Terg-O-Tometer beaker and Wash the swatches at a temperature of 120 F. for l0 minutes at 100 cycles per minute. After washing, the swatches lare removed `from the wash water, wrung by hand and rinsed in water havf ing a hardness of 150 parts per million. The swatchesy are then returned tothe Terg-O-Tometer and rinsed for 5 minutes at 100 F. in water having 150 partsA per mil lion` of hardness. Thereafter, the swatches are removed from the rinse watenwrung through a hand wringer,4 placed between paper towels and pressed dry with a hand iron. A reflectance value for the dried swatches was" measured using a photovolt reflectometer Model y610. The reflect-ance value for the swatches of soiled vcloth washed withthe alkyl diphenyl ether sulfonate detergent composition was compared toV theV reliectance value for swatches of` cloth prepared asa standard gby subiecting other,V testpiecesof 'the soiled cloth to a similar Terg- O-A nooners' Tometer washing test employing a similar proportion of alkyl benzene sulfonate (Ultrawet K) and a similar amount of potassium pyrophosphate on a weight basis, 1n one liter of Water having 150 parts per million of hardness. The detergency value for the aqueous cornposition -is calculated as the product of the average reectance value for the swatches washed with the alkyl diphenyl ether sulfonate wash solution divided by the average reflectance value for the swatches washed with the alkyl benzene sulfonate, standard, wash solution multiplied by 100. Thus, the detergency for the composition is expressed as the percent of the detergency value of the standard wash solution. A value greater than 100 percent indicates that the alkyl diphenyl ether sulfonate detergent composition has greater detergency or washing properties than has the standard wash composition. rIable I identities the detergent compositions and gives the proportions in percent by weight of the essential ingredients based on the weight ofthe liquid solution.V The table also indicates the solubility of the ingredients in the Iaqueous solution and gives a detergency. value for certain of the compositions. For purpose of comparison compositions which are not clear solutions and are outside the scope of the invention are included in the table.
Table I Starting Materials Product Run Alkyl N o. Di henyl K4PO7, Water, Detergency ther Wt. Wt. Solution, compared Sulionate, Percent Percent Kind to Standard, Wt. Percent Percent 5 45 50 lnsoluble. 5 35 60 clear 101 35 55 -do 35 50 do 30 50 d0- 103 25 50 d0 25 15 60 do 101.5 l0 60 inso1ub1e EXAMPLE 2 A charge of 20 parts by weight of tetrapropyl diphenyl ether sulfonate and 30 parts of potassium pyrophosphate was dissolved in 50 parts of water. A clear detergent solution was obtained. The tetrapropyl diphenyl ether sulfonate employed in the experiment was prepared by procedures similar to those described in parts A and B of Example 1 and consisted of diphenyl ether modiiied by having an average of 1.07 tetrapropyl radicals derived from tetrapropylenes and 2.23 sulfonate groups of the formula -SO3Na as nuclear substituents. The material was obtained as a light yellow powder having the composition 77.20 percent by weight tetrapropyl diphenyl ether sulfonate, 19.161- percent sodium sulfate and 3.64 percent water. A detergency value for the liquid composition was determined employing procedure similar to that employed in part C of Example 1.-- The composition had -a detergency value of 971.5 percent.
EXAMPLE 3 Atripropyl diphenyl ether sulfonate consisting of diphenyl ether modiiied by having an average of one tripropyl radical derived `from' tripropylenes and 1.8 sulfonate groups of'the `formula -SOaNa as nuclear substituents was prepared by procedures-similar to those de-v scribed in parts A and B of Example 1. The tripropyl di` phenyl ether sulfonate was obtained `as a light yellow powder having the composition 89.97 percent by weight tripropyl diphenyl ether sulfonate, 5.76 percent sodium sulfate, 0.17 percent sodium chloride and 4.10 percent water. Y
A charge of 20 parts by weight of the tn'propyl diphenyl ether sulfonate and 30 parts of potassium pyrophosphate were dissolved in 50 parts of water. A clear liquid deter'- EXAMPLE 4 A pentapropyl diphenyl ether sulfonate consisting of diphenyl ether modified by having an average of one pentapropyl radical derived from pentapropylenes and 2.17 sulfonate groups of the formula -SOaNa as nuclear substituents was prepared by procedures similar to those described in parts A and B of Example 1. The pentapropyl diphenyl ether sulfonate was obtained as a light yellow powder having the composition 87.16 percent by weight pentapropyl diphenyl ether sulfonate, 7.90 percent sodium sulfate, 0.09 percent sodium chloride and 4.75 percent Water. Twenty parts by weight of the pentapropyl diphenyl ether sulfonate and 30 parts of potassium pyrophosphate were .dissolved in 50 parts of water. A clear aqueous liquid detergent solution was obtained. The solution had a detergency value of 103 percent.
EXAMPLE 5 A tetrapropyl diphenyl ether sulfonate consisting of diphenyl ether modified by having an average of 1.14 tetra propyl radicals derived from tetrapropylenes and 1.95 sulfonate groups of the formula 5803K as nuclear substituents. was prepared by procedures similar to those described in parts A and B of Example l, except that the tetrapropyl diphenyl .ether sulfonic -acid was neutralized vwith potassium hydroxide to lobtain the corresponding salt. The tetrapropyl diphenyl ether sulfonic acid, potassium salt, was obtained as a free-ilowng powder. Twenty parts by weight of the tetrapropyl diphenyl ether sulfonate and 30 parts of potassium pyrophosphate were dissolved in 50 parts of Water. A clear aqueous solution was obtained. The solution had good detergency properties.
EXAMPLE 6 A charge of 20 parts by weight of tetrapropyl diphenyl ether sulfonate similar to Ithat described in part B of Example 1 was dissolved in 70 parts of water containing l0 parts ofpotassium tripolyphosphate. A clear aqueous `solution was obtained. The liquid composition had good detergency properties.
EXAMPLE 7 solving 5 parts by weight of tetrapropyl diphenyl ether sulfonate similar to that described in part B of Example 1, 15 parts of potassium pyrophosphate, 5 parts of sodium silicate having an Na-O/SiOz ratio of 1:1.8 and 0.2 part of sodium carboxymethyl cellulose (detergent grade) in 75.parts of water. A clear aqueous solution was obtained. The liquid composition had good detergency properties and was suitable for washing heavily soiled fabrics.
' EXAMPLE 9 In each of a series of experiments, a potassium tetrapropyl diphenyl ether sulfonate having an average of 1.14
tetrapropyl radicals derived from tetrapropylenes and 1.95
sulfonate groups of the formula `403K as nuclear substituents per diphenyl ether nucleus, and similar to that employed in Example 5, was mixed with water and potassium pyrophosphate in proportions as stated in the following table. The mixture Vwas stirred and heated to a temperature of 90 C. then allowed to cool to room temperature. After standing for three days the mixtures were examined. Table II identifies the mixtures and heated to a temperature off 90 C., then allowed to cool to room temperature. Afterstanding for three days the mixture was examined. Table IV ideuties thev mixtures and indicates the solubility ofthe-product.
gives the proportions ofthe ingredients based on the 5 Table IV weight of the mixture. The table also indicates the solu- Y bility of the ingredients 1n the aqueouszllqmd. Starting Matms'ls Broduct Table Il Y 1o n N Nametia' Y un o. Drop? Starting Materials Product Diphenyl KiPsOiu, Water, Solution.
Ether Wt. Wt. Kind K Tetra Sulfvorrate, Percent Percent Run No. propyl Percent Diuhenyl KtPlOv, Water, Solution.
Ether Wt. Wt. Kind Suifonate, Percent Percent 5 5 90 clear.
Wt. s 40 55 Do. Percent 5 50 45 insoluble.
la r. t ce b i .2 e das" a i5 nii 6 50 45 insoluble 25 30 4g along. l 45 45 clear. a() 25 45 D0` 8 gg t; hllesguble -30 ao 4o insoluble. ig illisoliible g 5g elegir? 0 0631. so 25 45 no.V 40 5 55 D9' 35 2o 45 Do. 25 Y g3 1g i? ggf The compositions in Table IV which form clear solu- 55 5 4o opaque Y tions are within the lines AIKLMNOA ofY the trilineai gg g Clegg diagram of the drawing. Y 25 5 ,7 m' EXAMPLE V12 The compositions in Table Il whichV form clear solutions are within the lines ABCDA of the tri-linear diagram of the drawing. l
' EXAMPLE l0 In each of a series of experiments, a potassium'tetra'- propyl diphenyl ether sulfonate similar to that employed in Example 9, was mixed with Water and sodium tripolyphosphate in proportions as stated in the following table. The mixture was stirred and heated` to a temperature of 90 C. then allowed to cool vto room temperature and stand Vfor three days. Table III identiiies the mixtures and indicates the solubility of the ingredients in the aqueous liquid.
In each of a series of experiments, a sodium tetrapropyl diphenyl ether sulfonate similar to that employed in Example 11 was mixed with water and potassium pyrophosphate in proportions as stated in the following table. The mixture was stirred and heated to a temperature of 90 C. then allowed to cool and stand at room temperature for a period of three days. Table V identies the mixtures and indicates the solubility of the ingredients in the aqueous liquid.
Table V Starting Materials Product Na-Tetra- Run No. propyl Dipbenyl KPiOy, Water, Solution, Ether Wt. Wt. Kind Sulfgxate, Percent Percent Percent 5 5 90 clear. 5 35 60 Do. 5 40 55 insoluble. 35 55 clear. 10 40 5() insoluble. 35 50 clear. 15 40 45 insoluble. 30 50 clear. 20 35 45 insoluble. 25 50 clear. 25 30 45 insoluble. 28.5 2l..5 50 Do.
25 20 55 clear. 25 15 60 Do. 10 60 insoluble'. 25 10 65 Do. 23. 5 11. 5 65 clear.
25 5 70 insoluble. 21. 5 8. 5 70 clear.
The compositions which form clear solutions in Table III' are within the lines APQRA of the trilinear diagram of the drawing.
EXAMPLE 1l The compositions in Table V which form clear solu tions are within the lines AEFGHIA of the trilinear diagram of the drawing.
We claim:
1. A clear transparent aqueous liquid detergent composition consisting of a transparent aqueous solution con. taining (l) an alkyl diphenyl ether sulfonate having the general formula:
wherein R represents an alkyl radical containing from 9 to 15 carbon atoms and n is an average number from 1 to 1.3, X represents a member ofthe group consisting of sodium and potassium and m is an average number from 1.8 to 2.4, and (2) an inorganic phosphate selected from the Igroup consisting of sodium tripolyphosphate, potassium tripolyphosphate, potassium pyrophosphate and mixtures of potassium pyrophosphate and sodium pyrophosphate, said solution containing a combination of ingredients in proportions by weight, based on 100 parts by weight of the solution, which combination is selected from the group consisting of: (a) from 5 to 50 parts by weight of the potassium alkyl diphenyl ether sulfonate (l) and from 5 to 45 parts of inorganic phosphate (2) selected from the group consisting of potassium pyrophosphate and mixtures of potassium pyrophosphate and sodium pyrophosphate, which mixtures contain not more than 5 parts by weight of sodium pyrophosphate, and in a total concentration between l and 55 percent by weight of the solution and within the lines ABCDA of the trilinear diagram of the drawing; (b) from to 25 parts by weight of the sodium alkyl diphenyl ether sulfonate (l) and from 5 to 35 parts by weight of the inorganic phosphate (2) selected from the group consisting of potassium pyrophosphate and mixtures of potassium pyrophosphate and sodium pyrophosphate, which mixtures contain not more than 5 parts by weight of sodium pyrophosphate, and in a total concentration between and 50 percent by weight of the solution and within the lines AEFGHIA of the trilinear diagram of the drawing; (c) from 5 to 40 parts by weight of the alkyl diphenyl ether snlfonate (1) and from 5 to 40 parts of the inorganic phosphate (2) consisting of potassium tripolyphosphate, and in a total concentration between 10 and 55 percent by weight of the solution and within the lines AJKLMNOA of the trilinear diagram of the drawing; and (d) from 5 to 45 parts by weight of the potassium alkyl diphenyl ether sulfonate (l) and from 5 to 20 parts by weight of the inorganic phosphate (2) consisting of sodium tripolyphosphate, and in a total concentration between 10 and 50 percent by weight of the solution and within the lines APQRA of the trilinear diagram of the drawing, said inorganic phosphate (2) being in proportions of from l to 1.5 parts by weight per part by weight of the alkyl diphenyl ether sulfonate (l).
2. A liquid detergent composition as claimed in claim l, wherein the aqueous solution contains from 5 to 50 parts by weight of the potassium alkyl diphenyl ether sulfonate (1) `and from 5 to 45 parts of potassium pyrophosphate per parts by weight of the solution, and in a total concentration between l0 and 55 percent by weight of the solution and within the lines ABCDA of the trilinear diagram of the drawing.
3. A liquid detergent composition as claimed in claim l, wherein the aqueous solution contains from 5 to 40 parts by weight of the sodium alkyl diphenyl ether sulfonate (l) and from 5 to 40 parts of potassium tripolyphosphate per 100 parts by weight of the solution and in a total concentration between 10 and 55 percent by weight of the solution and within the lines A-JKLMNOA of the trilinear diagram of the drawing.
4. A liquid detergent composition as claimed in claim l, wherein the aqueous solution contains from 5 to 25 parts bym/eight of the sodium alkyl diphenyl ether snlfonate (l) and from 5 to 35 parts of potassium pyrophosphate per 100 parts by weight of the solution and in a total concentration between l0 and 50 percent by weight of the solution and within the lines AEFGHIA of the trilinear diagram of the drawing.
5. A liquid detergent composition as claimed in claim 4, wherein the potassium pyrophosphate and the sodium alkyl diphenyl ether sulfonate are employed in proportions corresponding to from l to 1.5 parts by weight of the potassium pyrophosphate per part of sodium alkyl diphenyl ether sulfonate.
6. A liquid detergent composition as claimed in claim l, wherein the aqueous solution contains from 5 to 25 parts by weight of the sodium alkyl diphenyl ether sulfonate (1) and from 5 to 35 parts of a mixture of potassium pyrophosphate and sodium pyrophosphate, which mixture contains not more than 5 parts by Weight of sodium pyrophosphate, per 100 parts by Weight of the solution and in a total concentration between 10 and 50 percent by weight of the solution and within the lines AEFGHIA of the trilinear diagram of the drawing.
References Cited in the le of this patent UNITED STATES PATENTS 2,081,876 Prahl May 25, 1937 2,204,339 Bowles June l1, 1940 2,383,502 Quimby Aug. 28, 1945 2,486,921 Byerly Nov. l, 1949 2,854,477 Steinhauer Sept. 30, 1958 FOREIGN PATENTS 475,955 Great Britain Feb. 24, 1936
Claims (1)
1. A CLEAR TRANSPARENT AQUEOUS LIQUID DETERGENT COMPOSITION CONSISTING OF A TRANSPARENT AQUEOUS SOLUTION CONTAINING (1) AN ALKYL DIPHENYL ETHER SULFONATE HAVING THE GENERAL FORMULA:
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|---|---|---|---|
| US673404A US2990375A (en) | 1957-07-22 | 1957-07-22 | Heavy duty liquid detergent compositions |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US673404A US2990375A (en) | 1957-07-22 | 1957-07-22 | Heavy duty liquid detergent compositions |
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| Publication Number | Publication Date |
|---|---|
| US2990375A true US2990375A (en) | 1961-06-27 |
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| US673404A Expired - Lifetime US2990375A (en) | 1957-07-22 | 1957-07-22 | Heavy duty liquid detergent compositions |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3216932A (en) * | 1962-11-08 | 1965-11-09 | Diamond Crystal Salt Co | Salt product and method of making and using same |
| US3219584A (en) * | 1961-06-09 | 1965-11-23 | Alexander J Stirton | Wetting agents and surface active compositions therefrom |
| US3245914A (en) * | 1959-09-28 | 1966-04-12 | Dow Chemical Co | Germicidal alkylhalodiphenyl oxide sulfonate compositions |
| US3247258A (en) * | 1961-10-25 | 1966-04-19 | Chevron Res | Methyl-beta-hydroxyalkyl sulfoxides |
| US3248335A (en) * | 1965-04-01 | 1966-04-26 | Dow Chemical Co | Detergent composition for hard surfaces |
| US3249640A (en) * | 1962-05-07 | 1966-05-03 | Procter & Gamble | Alkylsulfonyl phenols |
| US3251777A (en) * | 1964-03-02 | 1966-05-17 | Dow Chemical Co | Powderless etching bath |
| US3264242A (en) * | 1961-10-03 | 1966-08-02 | Dow Chemical Co | Aqueous dispersions containing alkylated diphenyloxidedisulfonic acid and a non-ionic surface active agent |
| US3264243A (en) * | 1961-04-20 | 1966-08-02 | Dow Chemical Co | Vinyl base adhesive compositions with improved water resistance |
| US3288859A (en) * | 1965-03-30 | 1966-11-29 | Procter & Gamble | Reactions of alkali metal salts of sulfinyl carbanions and alkanesulfenates with epoxy compounds and novel compounds derived therefrom |
| US3409637A (en) * | 1963-07-22 | 1968-11-05 | Continental Oil Co | Sulfonating olefins with gaseous sulfur trioxide and compositions obtained thereby |
| US3717590A (en) * | 1970-12-17 | 1973-02-20 | R Fetty | Liquid water-soluble detergent compositions |
| US3720621A (en) * | 1969-06-17 | 1973-03-13 | Citrex Sa | Aquenous detergent compositions |
| US3793212A (en) * | 1971-07-23 | 1974-02-19 | Colgate Palmolive Co | Detergent composition and method of preparing same |
| US4627936A (en) * | 1984-10-05 | 1986-12-09 | Gould Paper Corp. | Towel premoistened with antistatic solution for cleaning cathode-ray tubes and the like |
| US4645623A (en) * | 1984-12-17 | 1987-02-24 | Monsanto Company | Alkylaryl sulfonate compositions |
| US4687593A (en) * | 1984-12-17 | 1987-08-18 | Monsanto Company | Alkylaryl sulfonate compositions |
| US20030215754A1 (en) * | 2002-05-07 | 2003-11-20 | Shipley Company, L.L.C. | Residue reducing stable concentrate |
| US6743764B1 (en) | 1999-07-30 | 2004-06-01 | Dow Global Technologies Inc. | Low viscosity alkyl diphenyl oxide sulfonic acid blends |
| US10767104B2 (en) | 2015-02-27 | 2020-09-08 | Ecolab Usa Inc. | Compositions for enhanced oil recovery |
| US10808165B2 (en) | 2016-05-13 | 2020-10-20 | Championx Usa Inc. | Corrosion inhibitor compositions and methods of using same |
| US11203709B2 (en) | 2016-06-28 | 2021-12-21 | Championx Usa Inc. | Compositions for enhanced oil recovery |
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| US2081876A (en) * | 1935-02-25 | 1937-05-25 | Du Pont | Diaryl oxide sulphonic acids and processes for preparing the same |
| GB475955A (en) * | 1935-02-25 | 1937-11-29 | Du Pont | Surface-active compounds and their manufacture |
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| US2486921A (en) * | 1944-10-16 | 1949-11-01 | Procter & Gamble | Detergent composition |
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| US2081876A (en) * | 1935-02-25 | 1937-05-25 | Du Pont | Diaryl oxide sulphonic acids and processes for preparing the same |
| GB475955A (en) * | 1935-02-25 | 1937-11-29 | Du Pont | Surface-active compounds and their manufacture |
| US2204339A (en) * | 1938-09-19 | 1940-06-11 | Reilly Whiteman Walton Company | Alkylated phenols and a process of producing them |
| US2383502A (en) * | 1941-02-06 | 1945-08-28 | Procter & Gamble | Acid triphosphates as builders for alkyl sulphates and other soapless detergents |
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| US2854477A (en) * | 1956-11-20 | 1958-09-30 | Dow Chemical Co | Method of making alkyl diphenyl ether sulfonates |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3245914A (en) * | 1959-09-28 | 1966-04-12 | Dow Chemical Co | Germicidal alkylhalodiphenyl oxide sulfonate compositions |
| US3264243A (en) * | 1961-04-20 | 1966-08-02 | Dow Chemical Co | Vinyl base adhesive compositions with improved water resistance |
| US3219584A (en) * | 1961-06-09 | 1965-11-23 | Alexander J Stirton | Wetting agents and surface active compositions therefrom |
| US3264242A (en) * | 1961-10-03 | 1966-08-02 | Dow Chemical Co | Aqueous dispersions containing alkylated diphenyloxidedisulfonic acid and a non-ionic surface active agent |
| US3247258A (en) * | 1961-10-25 | 1966-04-19 | Chevron Res | Methyl-beta-hydroxyalkyl sulfoxides |
| US3249640A (en) * | 1962-05-07 | 1966-05-03 | Procter & Gamble | Alkylsulfonyl phenols |
| US3249549A (en) * | 1962-05-07 | 1966-05-03 | Procter & Gamble | Detergent compositions containing sulfonylphenol compounds |
| US3216932A (en) * | 1962-11-08 | 1965-11-09 | Diamond Crystal Salt Co | Salt product and method of making and using same |
| US3409637A (en) * | 1963-07-22 | 1968-11-05 | Continental Oil Co | Sulfonating olefins with gaseous sulfur trioxide and compositions obtained thereby |
| US3251777A (en) * | 1964-03-02 | 1966-05-17 | Dow Chemical Co | Powderless etching bath |
| US3288859A (en) * | 1965-03-30 | 1966-11-29 | Procter & Gamble | Reactions of alkali metal salts of sulfinyl carbanions and alkanesulfenates with epoxy compounds and novel compounds derived therefrom |
| US3336233A (en) * | 1965-03-30 | 1967-08-15 | Procter & Gamble | Built detergent compositions containing 3-hydroxyalkyl alkyl sulfoxides |
| US3248335A (en) * | 1965-04-01 | 1966-04-26 | Dow Chemical Co | Detergent composition for hard surfaces |
| US3720621A (en) * | 1969-06-17 | 1973-03-13 | Citrex Sa | Aquenous detergent compositions |
| US3717590A (en) * | 1970-12-17 | 1973-02-20 | R Fetty | Liquid water-soluble detergent compositions |
| US3793212A (en) * | 1971-07-23 | 1974-02-19 | Colgate Palmolive Co | Detergent composition and method of preparing same |
| US4627936A (en) * | 1984-10-05 | 1986-12-09 | Gould Paper Corp. | Towel premoistened with antistatic solution for cleaning cathode-ray tubes and the like |
| US4645623A (en) * | 1984-12-17 | 1987-02-24 | Monsanto Company | Alkylaryl sulfonate compositions |
| US4687593A (en) * | 1984-12-17 | 1987-08-18 | Monsanto Company | Alkylaryl sulfonate compositions |
| US6743764B1 (en) | 1999-07-30 | 2004-06-01 | Dow Global Technologies Inc. | Low viscosity alkyl diphenyl oxide sulfonic acid blends |
| US20030215754A1 (en) * | 2002-05-07 | 2003-11-20 | Shipley Company, L.L.C. | Residue reducing stable concentrate |
| US10767104B2 (en) | 2015-02-27 | 2020-09-08 | Ecolab Usa Inc. | Compositions for enhanced oil recovery |
| US10808165B2 (en) | 2016-05-13 | 2020-10-20 | Championx Usa Inc. | Corrosion inhibitor compositions and methods of using same |
| US11203709B2 (en) | 2016-06-28 | 2021-12-21 | Championx Usa Inc. | Compositions for enhanced oil recovery |
| US11912925B2 (en) | 2016-06-28 | 2024-02-27 | Championx Usa Inc. | Compositions for enhanced oil recovery |
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