USRE27096E - Best available copy - Google Patents
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- USRE27096E USRE27096E US27096DE USRE27096E US RE27096 E USRE27096 E US RE27096E US 27096D E US27096D E US 27096DE US RE27096 E USRE27096 E US RE27096E
- Authority
- US
- United States
- Prior art keywords
- alkyl
- detergent
- composition
- carbon atoms
- sulfonates
- 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
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- 239000000203 mixture Substances 0.000 abstract description 87
- -1 ALKYL Chemical compound 0.000 abstract description 45
- 239000003599 detergent Substances 0.000 abstract description 38
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 18
- 230000002195 synergetic effect Effects 0.000 abstract description 9
- 150000001336 alkenes Chemical class 0.000 abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 description 22
- 125000000217 alkyl group Chemical group 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 150000004996 alkyl benzenes Chemical class 0.000 description 12
- 229940077388 benzenesulfonate Drugs 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- WPUJEWVVTKLMQI-UHFFFAOYSA-N benzene;ethoxyethane Chemical compound CCOCC.C1=CC=CC=C1 WPUJEWVVTKLMQI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 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 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 125000005192 alkyl ethylene group Chemical group 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 125000001924 fatty-acyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- GDJZZWYLFXAGFH-UHFFFAOYSA-M xylenesulfonate group Chemical group C1(C(C=CC=C1)C)(C)S(=O)(=O)[O-] GDJZZWYLFXAGFH-UHFFFAOYSA-M 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- 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
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- 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
- C11D1/29—Sulfates of polyoxyalkylene ethers
Definitions
- ABSTRACT OF THE DISCLOSURE A detergent composition having outstanding sudsing and detergent properties.
- the composition is a synergistic ternary mixture of olefin sulfonates, alkyl, benzene sulfonates and alkyl ether sulfates.
- This invention relates to detergent compositions having outstanding sudsing and detergent properties, based on synergistic ternary mixtures of olefin sulfonates, alkyl benzene sulfonates and alkyl ether sulfates.
- olefins having a free hydrogen atom on a carbon in the alpha-position can be sulfonated directly using vigorous sulfonating agents.
- the sulfo radical attaches to the terminal carbon atom and the double bond remains intact, but may migrate from the alpha position.
- the sulfonates have detergent properties.
- ternary mixtures of olefin sulfonates, alkyl aryl sulfonates and alkyl ether sulfates are synergistic, and have sudsing and cleaning power bet ter than would be expected from a knowledge of their performance when used alone, and, in particular, better than would be expected from a knowledge of the performance of binary mixtures, especially mixtures of alkyl benzene sulfonates and alkyl ether sulfates. without the third component, and of the third component alone.
- a detergent composition comprising a synergistic ternary mixture of (A) an olefin sulfonate having 12 to 16 carbon atoms in the molecule, (B) an alkyl benzene sulfonate having an alkyl chain containing 10 to 18 carbon atoms and (C) an alkyl ether sulfate having the formula RO(C H,O),SO M wherein R is an alkyl chain having 10 to 18 carbon atoms, x is 1 to 5, and M is a cation.
- olefin sulfonates is used herein to mean compounds which can be produced by the sulfonation of alpha olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sultones which have been formed in the reaction are hydrolysed to give the corresponding hydroxy-alkane sulfonates.
- the sulfur trioxide may be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, fo example by liquid 80,, chlorinated hydrocarbon, etc;, when used in the liquid form, or by air, nitrogen, gaseous 50 etc., when used in the gaseous form.
- Complexes such as S0;- dioxane, are not to be used.
- the alpha olefins from which the olefin sulfonates are derived are mono-olefins having 12 to 16 carbon atoms, preferably 12 to 14 carbon atoms. Preferably, they are straight chain olefins. Olefin sulfonates having more than 16 carbon atoms do not give the desired high lathering performance in the mixtures according to the invention; those with fewer than 12 carbon atoms having reduced detergent properties.
- the olefin sulfonates may contain minor amounts of other materials, arising from impurities in the original olefin stock and from side reactions during the sulfonation process.
- a preferred embodiment of the present invention is the use herein of the olefin sulfonate compositions which are described completely in a patent application Ser. No. 516,139, filed Dec. 23, 1965, by Phillip F. Pfiaumer and Adriaan Kessler and titled, Detergent Composition.
- the alkyl aryl sulfonates are preferably alkyl benzene sulfonates, and the alkyl chain preferably has 12 to 16 carbon atoms.
- the alkyl chain may be derived, for example, from branched or straight chain olefins, such as tetraor penta-propylene polymers or mixtures thereof, straight chain alpha-olefins obtained from petroleum cracking or by the polymerization of ethylene, or from halogenated paraffins.
- An alkyl chain which is a straight chain containing 12 carbon atoms is generally very suitable.
- the alkyl ether sulfates canbe made by the condensation by known methods of ethylene oxides on to monohydric alcohols having 10 to 18 carbon atoms.
- R has 12 to 14 carbon atoms.
- the alcohols may be derived from fats, e.g., coconut oil, or they may be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil are preferred. Such alcohols are reacted with 1 to 5, and especially 3, molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
- the cation in the case of all the detergent ingredients may be alkali metal, ammonium or a substituted ammonium radical, or (as further explained below) may be in part magnesium, or may be an alkaline earth metal. It may be a mixture of any two or more of these.
- preferred mixtures comprise 5 to of the olefin sulfonate, by weight of the ternary mixture and to 25% of a mixture comprising the alkyl aryl sulfonate and the alkyl ether sulfate in a ratio from 9:1 to 3:7 by weight.
- ternary mixtures containing 5 to 50% of the olefin sulfonate, and 95 to 50% of a mixture of the alkyl aryl sulfonate and the alkyl ether sulfate in a ratio of from 8.5 :1.5 to 1:1 by weight.
- the synergistic properties of the ternary mixtures of the invention are most marked when the compositions are used in hard water. Accordingly, where they may be used in soft water, it is advantageous to include some of a source of water hardness in the composition. This may be done by including a source of magnesium ion in the composition, either by adding a soluble magnesium salt, such as the sulfate or chloride or by incorporating one of the detergent ingredients at least partly in the form of its magnesium salt.
- compositions may contain any of the other ingredients usual in detergent compositions such as alkaline builder salts, bleaches, optical brighteners, sequestering agents, soil suspending agents, colors, perfumes, bacteriocides and the like.
- Other organic detergents may be present in minor proportions provided that they do not impair the performance of the ternary mixture of the invention.
- lather stabilizers while usually unnecessary, may be added; examples are fatty acyl ethanolamides, especially lauric monoanolamide.
- the ternary mixtures are useful in solid, pasty or liquid detergent compositions, and are particularly well suited to liquid ones.
- liquid compositions they are dispersed or dissolved in a liquid medium, preferably water, optionally containing solubilizing agents such as lower monohydric alcohols having 1 to 4 carbon atoms, or hydrotropic salts such as toluene or xylene sulfonates, etc.
- a frame was provided in which a number, for example six, 500 ml. cylinders could be placed and rotated about an axis perpendicular to their long axis.
- a solution of the detergent composition in water at 115 F. the concentration being selected according to the information required from the test.
- 3 ml. of a standard soil load namely, a liquid edible shortening based mainly on marine oils.
- the cylinders were then rotated in the frame for 1 minute at 20 rpm. They were then stood upright, the stoppers were removed, and the lather height above the clear liquid was measured. A further addition of 3 ml. of the soil was made and the procedure was repeated until substantially no lather remained.
- the sum of the measured lather heights is reported as the lather height.
- Example I Several different liquid detergent compositions were made, each containing a total of 40% by weight of active detergent consisting of. olefin sulfonates derived from alpha-olefin having 14 carbon atoms, tetra-propylene alkyl benzene sulfonate, and coconut alkyl triethylene glycol ether sulfate, all in the form of their sodium salts.
- active detergent consisting of. olefin sulfonates derived from alpha-olefin having 14 carbon atoms, tetra-propylene alkyl benzene sulfonate, and coconut alkyl triethylene glycol ether sulfate, all in the form of their sodium salts.
- the proportions of these components in each composition are indicated in the table below.
- the remainder of each composition consisted primarily of water, containing sufficient solubilizing agent (lower alcohol and, if necessary, hydrotrope) to give a homogeneous composition
- Composition Aikyl Allq'l Lather Olefin benzene ether height sulfonate sulfonate sulfate (inches) 40 0 6. 98 0 40 0 2. 74 0 0 40 2. 63 0 20 20 11. 06 O 30 10 13. 14 10 l0 13. 60 20 10 l0 12. 46
- Example II Liquid detergent compositions were made containing a total of 40% by weight of active detergent consisting of a biologically degradable alkyl benzene sulfonate having a substantially straight chain alkyl group averaging 12 carbon atoms, and the same olefin sulfonate and alkyl ether sulfate used in Example I. The remainder of each composition consisted primarily of water, containing sufficient solubilizing agent (lower alcohol and, if necessary, hydrotrope) to give a homogeneous composition. Each composition was tested as in Example I. The results are given in the following table;
- compositions e and f were according to the invention, the others being included for comparison. Both e and f had better lather power than was provided by the best binary mixture of alkyl benzene sulfonate and alkyl ether sulfate, composition d. Moreover, composition f had better lather power than would be expected of a 1:1 mixture of half the detergent ingredients of compositions a and d which would have the same formula.
- compositions according to the invention had excellent detergent properties.
- the ternary mixture may be used in any desired proportion. If the proportion isvery small, for example less than 10% by weight of the composition, then inconveniently large amounts of the composition may have to be transported and used in order to achieve a given amount of cleaning. If the proportion is very great, then there may not be suificient place for all other desired ingredients of the composition (such as builder salts in the case of solid compositions) or, it may be difficult to achieve a stable composition (in the case of liquid compositions). Suitable proportions of the ternary mixture will often be found to be within the range from 10 to 60%, by weight of the composition. Proportions within the range from 20 to' 50% are preferred for liquid compositions.
- a detergent composition consisting essentially of a synergistic ternary mixture of (A) a straight chain. monoolefin sulfonate having 12 to 16 carbon atoms in the molecule, (B) an alkyl benzene sulfonate having an alkyl chain containing 10 to 18 carbon atoms and (C) an alkyl ether sulfate having the formula RO(C H O),,SO M wherein R is an alkyl chain of 10 to 18 carbon atoms, x is a value from 1 to about 5, the cation of said sulfonate compounds and the cation M of said sulfate compound being selected from the group consisting of alkali metal, ammonium, magnesium and alkaline earth metal, the proportion of said mono-olefin sulfonate being from about 5 to 75% of the ternary mixture and to [65 25% of a mixture of said alkyl aryl sulfonate and said alkyl ether sulf
- a detergent composition according to claim 1 wherein said mono-olefin sulfonate has chain length of 12 to 14 carbon atoms.
- a detergent composition according to claim 1 wherein the alkyl benzene sulfonate has an alkyl chain of 12 to 16 carbon atoms.
- a detergent composition according to claim 1 wherein the alkyl ether sulfate has an alkyl chain of 12 to 14 carbon atoms and is derived from coconut alcohols.
- a detergent composition according to claim 6 wherein the alkyl ether sulfate has the formula nomn crr onu where R represents an alkyl group having 12 to 14 carbon atoms.
- a detergent composition according to claim 1 wherein the proportion of said mono-olefin sulfonate is from 5 to 50% of the ternary mixture and the ratio of said alkyl benzene sulfonate to said alkyl ether sulfate is from 8521.5 to 1:1.
- a detergent composition according to claim -1 which also contains a water soluble magnesium salt selected from the group consisting of magnesium sulfate and magnesium chloride.
- a liquid detergent composition consisting essentially of from 10% to 60% of the composition of claim 1 and the balance being water.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A DETERGENT COMPOSITION HAVING OUTSTANDING SUDSING AND DETERGENT PROPERTIES. THE COMPOSITIONIS A SYNERGISTIC TERNARY MIXTURE OF OLEFIN SULFONATES, ALKYL, BENZENE SULFONATES AND ALKYL ETHER SULFATES.
Description
BEST AVAlLABLE COPY Re. 27,096 Reissued Mar. 23, 1971 27,096 DETERGENT COMPOSITION Arthur Polden Walker, Whitley Bay, England, assignor to The Procter & Gamble Company, Cincinnati, Ohio No Drawing. Original No. 3,332,876, dated July 25, 1967, Ser. No. 561,374, June 29, 1966, which is a continuation of Ser. No. 423,298, Jan. 4, 1965. Application for reissue Nov. 15, 1968, Ser. No. 808.709 Claims priority, applicatior; Glrzeat Britain, Oct. 15, 1966,
5 Int. Cl. Clld 1/12, N18 US. Cl. 252-152 Claims Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
ABSTRACT OF THE DISCLOSURE A detergent composition having outstanding sudsing and detergent properties. The composition is a synergistic ternary mixture of olefin sulfonates, alkyl, benzene sulfonates and alkyl ether sulfates.
This application is a continuation of Ser. No. 423,298, filed Jan. 4, 1965, by Arthur Polden Walker, entitled, Detergent Composition.
This invention relates to detergent compositions having outstanding sudsing and detergent properties, based on synergistic ternary mixtures of olefin sulfonates, alkyl benzene sulfonates and alkyl ether sulfates.
Mixtures of alkyl benzene sulfonates and alkyl ethylene glycol or polyethylene glycol ether sulfates have previously been used in combination detergent compositions and have synergistic properties. Thus the detergent power and sudsing power of mixtures of these detergents are greater than would be expected from consideration of their performance when used alone.
It is also known that olefins having a free hydrogen atom on a carbon in the alpha-position can be sulfonated directly using vigorous sulfonating agents. The sulfo radical attaches to the terminal carbon atom and the double bond remains intact, but may migrate from the alpha position. When the olefins have suitable molecular weight, the sulfonates have detergent properties.
It has now been found that ternary mixtures of olefin sulfonates, alkyl aryl sulfonates and alkyl ether sulfates are synergistic, and have sudsing and cleaning power bet ter than would be expected from a knowledge of their performance when used alone, and, in particular, better than would be expected from a knowledge of the performance of binary mixtures, especially mixtures of alkyl benzene sulfonates and alkyl ether sulfates. without the third component, and of the third component alone.
According to the invention therefore there is provided a detergent composition comprising a synergistic ternary mixture of (A) an olefin sulfonate having 12 to 16 carbon atoms in the molecule, (B) an alkyl benzene sulfonate having an alkyl chain containing 10 to 18 carbon atoms and (C) an alkyl ether sulfate having the formula RO(C H,O),SO M wherein R is an alkyl chain having 10 to 18 carbon atoms, x is 1 to 5, and M is a cation.
The term olefin sulfonates" is used herein to mean compounds which can be produced by the sulfonation of alpha olefins by means of uncomplexed sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sultones which have been formed in the reaction are hydrolysed to give the corresponding hydroxy-alkane sulfonates. The sulfur trioxide may be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, fo example by liquid 80,, chlorinated hydrocarbon, etc;, when used in the liquid form, or by air, nitrogen, gaseous 50 etc., when used in the gaseous form. Complexes such as S0;- dioxane, are not to be used.
The alpha olefins from which the olefin sulfonates are derived are mono-olefins having 12 to 16 carbon atoms, preferably 12 to 14 carbon atoms. Preferably, they are straight chain olefins. Olefin sulfonates having more than 16 carbon atoms do not give the desired high lathering performance in the mixtures according to the invention; those with fewer than 12 carbon atoms having reduced detergent properties.
In addition to the true alkene sulfonates and a proportion of hydroxy-alkane sulfonates, the olefin sulfonates may contain minor amounts of other materials, arising from impurities in the original olefin stock and from side reactions during the sulfonation process.
A preferred embodiment of the present invention is the use herein of the olefin sulfonate compositions which are described completely in a patent application Ser. No. 516,139, filed Dec. 23, 1965, by Phillip F. Pfiaumer and Adriaan Kessler and titled, Detergent Composition.
The alkyl aryl sulfonates are preferably alkyl benzene sulfonates, and the alkyl chain preferably has 12 to 16 carbon atoms. The alkyl chain may be derived, for example, from branched or straight chain olefins, such as tetraor penta-propylene polymers or mixtures thereof, straight chain alpha-olefins obtained from petroleum cracking or by the polymerization of ethylene, or from halogenated paraffins. An alkyl chain which is a straight chain containing 12 carbon atoms is generally very suitable.
The alkyl ether sulfates canbe made by the condensation by known methods of ethylene oxides on to monohydric alcohols having 10 to 18 carbon atoms. Preferably, R has 12 to 14 carbon atoms. The alcohols may be derived from fats, e.g., coconut oil, or they may be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil are preferred. Such alcohols are reacted with 1 to 5, and especially 3, molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
The cation in the case of all the detergent ingredients may be alkali metal, ammonium or a substituted ammonium radical, or (as further explained below) may be in part magnesium, or may be an alkaline earth metal. It may be a mixture of any two or more of these.
While the addition of even small amounts of the olefin sulfonates to any mixtures of the alkyl aryl sulfonates and the alkyl ether sulfates provides synergistic mixtures, preferred mixtures comprise 5 to of the olefin sulfonate, by weight of the ternary mixture and to 25% of a mixture comprising the alkyl aryl sulfonate and the alkyl ether sulfate in a ratio from 9:1 to 3:7 by weight. Especially good performance is given by ternary mixtures containing 5 to 50% of the olefin sulfonate, and 95 to 50% of a mixture of the alkyl aryl sulfonate and the alkyl ether sulfate in a ratio of from 8.5 :1.5 to 1:1 by weight.
It is found that the synergistic properties of the ternary mixtures of the invention are most marked when the compositions are used in hard water. Accordingly, where they may be used in soft water, it is advantageous to include some of a source of water hardness in the composition. This may be done by including a source of magnesium ion in the composition, either by adding a soluble magnesium salt, such as the sulfate or chloride or by incorporating one of the detergent ingredients at least partly in the form of its magnesium salt.
The compositions may contain any of the other ingredients usual in detergent compositions such as alkaline builder salts, bleaches, optical brighteners, sequestering agents, soil suspending agents, colors, perfumes, bacteriocides and the like. Other organic detergents may be present in minor proportions provided that they do not impair the performance of the ternary mixture of the invention. In particular, lather stabilizers, while usually unnecessary, may be added; examples are fatty acyl ethanolamides, especially lauric monoanolamide.
The ternary mixtures are useful in solid, pasty or liquid detergent compositions, and are particularly well suited to liquid ones. In such liquid compositions they are dispersed or dissolved in a liquid medium, preferably water, optionally containing solubilizing agents such as lower monohydric alcohols having 1 to 4 carbon atoms, or hydrotropic salts such as toluene or xylene sulfonates, etc.
The following examples serve to illustrate the invention. In these examples, the lathering power of the detergent compositions was measured by the following test.
A frame was provided in which a number, for example six, 500 ml. cylinders could be placed and rotated about an axis perpendicular to their long axis. Into each cylinder was placed 100 ml. of a solution of the detergent composition in water at 115 F., the concentration being selected according to the information required from the test. To each solution was added 3 ml. of a standard soil load, namely, a liquid edible shortening based mainly on marine oils. The cylinders were then rotated in the frame for 1 minute at 20 rpm. They were then stood upright, the stoppers were removed, and the lather height above the clear liquid was measured. A further addition of 3 ml. of the soil was made and the procedure was repeated until substantially no lather remained.
The sum of the measured lather heights is reported as the lather height.
Example I Several different liquid detergent compositions were made, each containing a total of 40% by weight of active detergent consisting of. olefin sulfonates derived from alpha-olefin having 14 carbon atoms, tetra-propylene alkyl benzene sulfonate, and coconut alkyl triethylene glycol ether sulfate, all in the form of their sodium salts. The proportions of these components in each composition are indicated in the table below. The remainder of each composition consisted primarily of water, containing sufficient solubilizing agent (lower alcohol and, if necessary, hydrotrope) to give a homogeneous composition. Each composition was dissolved in hard water (18) to give a solution containing 0.26% of the composition, and tested for lather power by the method described above. The results are given in the following table:
Composition Aikyl Allq'l Lather Olefin benzene ether height sulfonate sulfonate sulfate (inches) 40 0 6. 98 0 40 0 2. 74 0 0 40 2. 63 0 20 20 11. 06 O 30 10 13. 14 10 l0 13. 60 20 10 l0 12. 46
4 Example II Liquid detergent compositions were made containing a total of 40% by weight of active detergent consisting of a biologically degradable alkyl benzene sulfonate having a substantially straight chain alkyl group averaging 12 carbon atoms, and the same olefin sulfonate and alkyl ether sulfate used in Example I. The remainder of each composition consisted primarily of water, containing sufficient solubilizing agent (lower alcohol and, if necessary, hydrotrope) to give a homogeneous composition. Each composition was tested as in Example I. The results are given in the following table;
Composition Alkyl Alkyl Luther Olefin benzene ether height sulfonate sulfonate sulfate (inches) 40 0 0 7. 55 0 40 0 2. 00 0 0 40 2. 33 0 20 20 9. 56 10 20 l0 1O. 81 20 10 1O 10. 87
Compositions e and f were according to the invention, the others being included for comparison. Both e and f had better lather power than was provided by the best binary mixture of alkyl benzene sulfonate and alkyl ether sulfate, composition d. Moreover, composition f had better lather power than would be expected of a 1:1 mixture of half the detergent ingredients of compositions a and d which would have the same formula.
The compositions according to the invention had excellent detergent properties.
In the compositions of the present invention, the ternary mixture may be used in any desired proportion. If the proportion isvery small, for example less than 10% by weight of the composition, then inconveniently large amounts of the composition may have to be transported and used in order to achieve a given amount of cleaning. If the proportion is very great, then there may not be suificient place for all other desired ingredients of the composition (such as builder salts in the case of solid compositions) or, it may be difficult to achieve a stable composition (in the case of liquid compositions). Suitable proportions of the ternary mixture will often be found to be within the range from 10 to 60%, by weight of the composition. Proportions within the range from 20 to' 50% are preferred for liquid compositions.
What is claimed is:
1. A detergent composition consisting essentially of a synergistic ternary mixture of (A) a straight chain. monoolefin sulfonate having 12 to 16 carbon atoms in the molecule, (B) an alkyl benzene sulfonate having an alkyl chain containing 10 to 18 carbon atoms and (C) an alkyl ether sulfate having the formula RO(C H O),,SO M wherein R is an alkyl chain of 10 to 18 carbon atoms, x is a value from 1 to about 5, the cation of said sulfonate compounds and the cation M of said sulfate compound being selected from the group consisting of alkali metal, ammonium, magnesium and alkaline earth metal, the proportion of said mono-olefin sulfonate being from about 5 to 75% of the ternary mixture and to [65 25% of a mixture of said alkyl aryl sulfonate and said alkyl ether sulfate in a ratio of from 9:1 to 3:7 by weight.
2. A detergent composition according to claim 1 wherein said mono-olefin sulfonate has chain length of 12 to 14 carbon atoms.
3. A detergent composition according to claim 1 wherein the alkyl benzene sulfonate has an alkyl chain of 12 to 16 carbon atoms.
4. A detergent composition according to claim 3 wherein the alkyl group of the alkyl benzene sulfonate is derived from the group consisting of tetrapropylene, pentapropylene. and mixtures thereof.
5. A detergent composition according to claim 3 wherein the alkyl group of the alkyl benzene sulfonate is a straight chain having 12 carbon atoms.
6. A detergent composition according to claim 1 wherein the alkyl ether sulfate has an alkyl chain of 12 to 14 carbon atoms and is derived from coconut alcohols.
7. A detergent composition according to claim 6 wherein the alkyl ether sulfate has the formula nomn crr onu where R represents an alkyl group having 12 to 14 carbon atoms.
8. A detergent composition according to claim 1 Wherein the proportion of said mono-olefin sulfonate is from 5 to 50% of the ternary mixture and the ratio of said alkyl benzene sulfonate to said alkyl ether sulfate is from 8521.5 to 1:1.
9. A detergent composition according to claim -1 which also contains a water soluble magnesium salt selected from the group consisting of magnesium sulfate and magnesium chloride.
10. A liquid detergent composition consisting essentially of from 10% to 60% of the composition of claim 1 and the balance being water.
References Cited The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent.
OTHER REFERENCES Chem. Ber., 97, #10, 2903-13 (October 1964); Higher Molecular Aliphatic Sulfonic Acids. I. 2-hydroxy-1-n- Alkanesulfonic Acids, F. Puschel and Claus Kaiser.
Chem. Ber. 97, #10, 2917-25 (October 1964); Higher 15 Molecular Aliphatic Sulfonic Acids. II. 3-hydroxy-l-n- Alkanesulfonic Acids and Their Inner Esters (1,3-sultones). F. Puschel and Claus Kaiser.
Chem. Ber. 97, #10, 2926-33 (October 1964); Higher Molecular Unsaturated Sulfonic Acids and the Hydrolysis 2d of 1,3-alkanesultones. F. Puschel and Claus Kaiser.
Chem. Ber. 98, 735-742 (1965); Higher Molecular Aliphatic Sulfonic Acids. IV. Sulfonation of Unbranched Alpha-Olefins With S0 F. Pusched and Claus Kaiser.
Stupel: Manufacturing Chemist, Combination of Raw 25 Materials Improves Synthetic Detergents, March 1952,
MAYER WEINBLATT, Primary Examiner US. Cl. X.R.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB4211264 | 1964-10-15 | ||
| US561374A US3332876A (en) | 1964-10-15 | 1966-06-29 | Detergent composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE27096E true USRE27096E (en) | 1971-03-23 |
Family
ID=26264823
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US561374A Expired - Lifetime US3332876A (en) | 1964-10-15 | 1966-06-29 | Detergent composition |
| US27096D Expired USRE27096E (en) | 1964-10-15 | 1968-11-15 | Best available copy |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US561374A Expired - Lifetime US3332876A (en) | 1964-10-15 | 1966-06-29 | Detergent composition |
Country Status (11)
| Country | Link |
|---|---|
| US (2) | US3332876A (en) |
| AT (1) | AT257784B (en) |
| BE (1) | BE670913A (en) |
| CA (1) | CA776614A (en) |
| CH (1) | CH485842A (en) |
| DE (1) | DE1467663A1 (en) |
| DK (1) | DK127071B (en) |
| FI (1) | FI44927B (en) |
| FR (1) | FR1457000A (en) |
| GB (1) | GB1050848A (en) |
| NL (1) | NL6513298A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239662A (en) | 1978-02-17 | 1980-12-16 | The Lion Fat And Oil Co., Ltd. | Liquid detergent compositions |
| US4537709A (en) | 1982-11-16 | 1985-08-27 | Lever Brothers Company | Liquid detergent composition comprising selected alkylbenzene sulphonates and alkyl ether sulphates |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3513099A (en) * | 1966-12-06 | 1970-05-19 | Purex Corp Ltd | Las detergents containing primary and secondary alkoxy alkanol ammonium sulfates |
| JPS5033488B1 (en) * | 1969-07-10 | 1975-10-31 | ||
| BE759360A (en) * | 1969-11-25 | 1971-05-24 | Procter & Gamble Europ | |
| US3780860A (en) * | 1971-05-17 | 1973-12-25 | Stephan Chem Co | Flotation of copper sulfide ores |
| US3827557A (en) * | 1971-05-17 | 1974-08-06 | Stepan Chemical Co | Method of copper sulfide ore flotation |
| AU464487B2 (en) * | 1971-06-16 | 1975-08-11 | Colgate-Palmolive Pty. Ltd. | Light duty detergent formulations |
| US3852221A (en) * | 1971-08-19 | 1974-12-03 | Jefferson Chem Co Inc | Liquid olefin sulfonate detergent |
| US4013577A (en) * | 1972-04-14 | 1977-03-22 | Colgate-Palmolive Company | Heavy duty dry biodegradable detergent composition |
| DE2355983A1 (en) * | 1972-11-13 | 1974-05-22 | Procter & Gamble | GRANULATED SPRAY-DRIED DETERGENTS AND DETERGENTS |
| PH10778A (en) * | 1972-11-13 | 1977-09-05 | Procter & Gamble | Detergent compositions |
| US4064076A (en) * | 1973-04-09 | 1977-12-20 | Colgate-Palmolive | Olefin sulfonate detergent compositions |
| US4024078A (en) * | 1975-03-31 | 1977-05-17 | The Procter & Gamble Company | Liquid detergent composition |
| US4018720A (en) * | 1975-07-14 | 1977-04-19 | The Procter & Gamble Company | Laundry detergent compositions in emulsion/suspension |
| JPS5236106A (en) * | 1975-09-16 | 1977-03-19 | Kao Corp | Liquid detergent composition |
| US4166048A (en) * | 1975-09-22 | 1979-08-28 | Kao Soap Co., Ltd. | High foaming detergent composition having low skin irritation properties |
| US4129515A (en) * | 1976-09-13 | 1978-12-12 | The Procter & Gamble Company | Heavy-duty liquid detergent and process |
| US4614612A (en) * | 1977-12-22 | 1986-09-30 | Lever Brothers Company | Liquid detergent composition |
| NO148037C (en) * | 1977-12-22 | 1983-08-24 | Unilever Nv | LIQUID DETERGENT MIXTURE. |
| DE3168008D1 (en) | 1980-04-24 | 1985-02-14 | Procter & Gamble | Liquid detergent compositions |
| US4536317A (en) * | 1982-04-26 | 1985-08-20 | The Procter & Gamble Company | Foaming surfactant compositions |
| GB8310529D0 (en) * | 1983-04-19 | 1983-05-25 | Unilever Plc | General-purpose cleaning composition |
| US4601844A (en) * | 1984-08-31 | 1986-07-22 | The Procter & Gamble Company | Granular automatic dishwasher detergent with alkyl phosphate and calcium ion source |
| US4842767A (en) * | 1986-09-10 | 1989-06-27 | Colgate-Palmolive Company | Heavy duty built aqueous liquid detergent composition containing stabilized enzymes |
| US5912222A (en) * | 1994-08-26 | 1999-06-15 | Colgate Palmolive Company | Microemulsion light duty liquid cleaning compositions |
| EP2380956A1 (en) * | 2010-04-19 | 2011-10-26 | The Procter & Gamble Company | Process for making a detergent |
| ES2682051T3 (en) | 2010-04-23 | 2018-09-18 | The Procter & Gamble Company | Detergent composition |
| PL2380962T3 (en) | 2010-04-23 | 2017-01-31 | The Procter And Gamble Company | Particle |
| EP2383329A1 (en) | 2010-04-23 | 2011-11-02 | The Procter & Gamble Company | Particle |
| CN108368453B (en) * | 2015-12-10 | 2021-03-26 | 花王株式会社 | Surfactant composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2846402A (en) * | 1958-08-05 | Alkyl sulfate detergent compositions | ||
| US2061617A (en) * | 1936-11-24 | Stllphonic acid derivatives of aii | ||
| US2086215A (en) * | 1936-12-24 | 1937-07-06 | Tret O Lite Company | Processes for breaking petroleum emulsions |
| BE507612A (en) * | 1950-12-08 | |||
| US2972583A (en) * | 1956-05-17 | 1961-02-21 | Colgate Palmolive Co | Detergent cake and method of making same |
-
0
- CA CA776614A patent/CA776614A/en not_active Expired
- GB GB1050848D patent/GB1050848A/en active Active
-
1965
- 1965-09-24 FI FI2285/65A patent/FI44927B/fi active
- 1965-10-13 FR FR34851A patent/FR1457000A/en not_active Expired
- 1965-10-13 CH CH1413365A patent/CH485842A/en not_active IP Right Cessation
- 1965-10-14 AT AT931665A patent/AT257784B/en active
- 1965-10-14 NL NL6513298A patent/NL6513298A/xx unknown
- 1965-10-14 DE DE19651467663 patent/DE1467663A1/en active Pending
- 1965-10-14 BE BE670913D patent/BE670913A/xx unknown
- 1965-10-14 DK DK526865AA patent/DK127071B/en unknown
-
1966
- 1966-06-29 US US561374A patent/US3332876A/en not_active Expired - Lifetime
-
1968
- 1968-11-15 US US27096D patent/USRE27096E/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239662A (en) | 1978-02-17 | 1980-12-16 | The Lion Fat And Oil Co., Ltd. | Liquid detergent compositions |
| US4537709A (en) | 1982-11-16 | 1985-08-27 | Lever Brothers Company | Liquid detergent composition comprising selected alkylbenzene sulphonates and alkyl ether sulphates |
Also Published As
| Publication number | Publication date |
|---|---|
| US3332876A (en) | 1967-07-25 |
| DE1467663A1 (en) | 1969-05-22 |
| BE670913A (en) | 1966-04-14 |
| DK127071B (en) | 1973-09-17 |
| NL6513298A (en) | 1966-04-18 |
| CA776614A (en) | 1968-01-23 |
| AT257784B (en) | 1967-10-25 |
| FI44927B (en) | 1971-11-01 |
| GB1050848A (en) | |
| CH485842A (en) | 1970-02-15 |
| FR1457000A (en) | 1966-07-08 |
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