WO2001089472A1 - DETERGENT CONTAINING α-SULFOFATTY ACID ESTERS AND METHODS OF MAKING AND USING THE SAME - Google Patents

DETERGENT CONTAINING α-SULFOFATTY ACID ESTERS AND METHODS OF MAKING AND USING THE SAME Download PDF

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Publication number
WO2001089472A1
WO2001089472A1 PCT/US2001/016236 US0116236W WO0189472A1 WO 2001089472 A1 WO2001089472 A1 WO 2001089472A1 US 0116236 W US0116236 W US 0116236W WO 0189472 A1 WO0189472 A1 WO 0189472A1
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WIPO (PCT)
Prior art keywords
sulfofatty acid
acid esters
enriched
mixture
oil
Prior art date
Application number
PCT/US2001/016236
Other languages
French (fr)
Inventor
Paul Danton Huish
Laurie A. Jensen
Pule B. Libe
Mark J. Fredrickson
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Huish Detergents, Inc.
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Filing date
Publication date
Application filed by Huish Detergents, Inc. filed Critical Huish Detergents, Inc.
Priority to EP01937583A priority Critical patent/EP1286656B1/en
Priority to AT01937583T priority patent/ATE490304T1/en
Priority to CA2412254A priority patent/CA2412254C/en
Priority to AU2001263301A priority patent/AU2001263301A1/en
Priority to DE60143572T priority patent/DE60143572D1/en
Publication of WO2001089472A1 publication Critical patent/WO2001089472A1/en

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    • 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
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/20—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton
    • C07C309/22—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton containing carboxyl groups bound to the carbon skeleton

Definitions

  • the present invention generally relates to ⁇ -sulfofatty acid ester compositions and methods for making and using such compositions. More particularly, the present invention relates to ⁇ -sulfofatty acid ester compositions that are enriched for particular ⁇ - sulfofatty acid esters, and methods for making and using such compositions.
  • Detergents have been used for many years to clean clothing and other materials.
  • Detergent compositions are generally formulated to contain components such as surfactants, builders, electrolytes and other additives dispersed or dissolved in an aqueous medium.
  • Surfactants are included in detergents to enhance their cleaning performance.
  • Typical surfactants include anionics, nonionics, zwitterionics, ampholytics, cationics and those described in Surface Active Agents, Volumes I and II by Schwartz, Perry and Berch (New York, Interscience Publishers), Nonionic Surfactants ed. by M. J. Schick (New York, M. Dekker, 1967), and in McCutcheon's Emulsifiers & Detergents (1989 Annual, M. C. Publishing Co.), the disclosures of which are inco ⁇ orated herein by reference.
  • ⁇ -sulfofatty acid esters also referred to hereinafter as "sulfofatty acids"
  • sulfofatty acids While other surfactants have similar detergency in soft water, as water hardness increases ⁇ -sulfofatty acid esters exhibit increased cleaning performance as compared with other anionic surfactants.
  • ⁇ -sulfofatty acid esters are an effective anionic surfactant that can be used in a wide variety of washing conditions.
  • ⁇ -Sulfofatty acid esters are typically manufactured as salts (i.e., a mixture of salt forms, typically mono- and di-salts).
  • Di-salts result from hydrolysis of ⁇ -sulfofatty acid ester during manufacture, storage and in detergent compositions.
  • mono-salts of ⁇ -sulfofatty acid ester hydrolyze in the presence of moisture and alkali-containing detergent components to form di-salts.
  • MES methyl ester sulfonate
  • Such high pH components can include builders, such as silicates or carbonates, and bases. This chemical instability discourages the use of such anionic surfactants in many applications.
  • ⁇ -Sulfofatty acid esters are typically made from natural fats or oils.
  • These fats and oils are usually free fatty acids or glycerol esters (i.e., mono-, di- or triglycerides). Free fatty acids are formed from glycerol esters by hydrolysis. The resulting fatty acids typically contain an even number of carbon atoms. These fatty acids are then esterif ⁇ ed to form fatty acid esters. The esters are then sulfonated to form ⁇ -sulfofatty acid esters.
  • the surface active agent properties of ⁇ -sulfofatty acid esters are related to the chain lengths of the fatty acid portion of the molecules. For example, shorter chain length molecules (e.g., C 8 -C 12 ⁇ -sulfofatty acid esters) are typically more water-soluble, but exhibit lesser surface active agent properties. Longer chain length (e.g., C 14 -C 16 ) ⁇ - sulfo fatty acid esters exhibit greater surface active agent properties, but are less water- soluble. Because ⁇ -sulfofatty acid esters are usually manufactured from natural sources, they are a mixture of different chain lengths. The properties of such mixtures are determined by the chain length distribution of the source of the fatty acids.
  • ⁇ -sulfofatty acid esters from palm kernel (stearin) oil have different surfactant properties than ⁇ -sulfofatty acid esters from tallow.
  • blends of ⁇ - sulfofatty acid esters from multiple sources are prepared. Such blends are also limited, however, by the chain length distributions of each fatty acid source. For example, combining ⁇ -sulfofatty acid esters from palm kernel (stearin) oil (C 6 -C 2 n fatty acids) with ⁇ - sulfofatty acid esters from tallow (C 14 -C 18 fatty acids) creates a mixture that has the average characteristics of the ⁇ -sulfofatty acid esters contained therein.
  • the present invention provides compositions and processes for enriching mixtures of ⁇ -sulfofatty acid esters for particular chain lengths.
  • compositions are prepared that exhibit improved cleaning performance as well as improved aqueous solubility and reduced phase separation of the ⁇ -sulfofatty acid esters from other aqueous components.
  • the present invention includes compositions that are enriched for particular chain length ⁇ -sulfofatty acid ester(s).
  • a mixture of ⁇ -sulfofatty acid esters is enriched for a particular chain length ⁇ -sulfofatty acid ester.
  • a mixture of ⁇ -sulfofatty acid esters is enriched for a range of ⁇ -sulfofatty acid ester chain lengths. Such mixtures are enriched for a narrow range of such sulfofatty acid chain lengths or for multiple discrete chain lengths. Detergent components can also be added to the enriched mixture of ⁇ -sulfofatty acid esters.
  • Suitable detergent components include builders, other anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, polymer dispersants, oxidizing agents, biocidal agents, foam regulators, binders, anticaking agents, activators, catalysts, thickeners, stabilizers, UV protectors, fragrances, soil suspending agents, fillers, brighteners, enzymes, salts, inert ingredients, and the like.
  • ⁇ -sulfofatty acid esters are also provided.
  • a mixture of ⁇ -sulfofatty acid esters is enriched for one or more ⁇ - sulfofatty acid esters of particular chain lengths.
  • ⁇ -sulfofatty acid esters prepared from cohune oil, palm kernel oil or coconut oil are enriched for C 16 ⁇ -sulfofatty acid ester.
  • a mixture of ⁇ -sulfofatty acid esters is enriched for a narrow range of ⁇ -sulfofatty acid ester chain lengths.
  • the ⁇ -sulfofatty acid ester mixture is enriched, for example, by supplementing the fatty acid feedstock with particular chain length fatty acid(s), by enriching for particular chain length fatty acid alkyl ester(s) prior to sulfonation, and/or by the addition of particular chain length ⁇ -sulfofatty acid esters to a mixture of such ⁇ -sulfofatty acids.
  • compositions comprising enriched mixtures of ⁇ -sulfofatty acid esters.
  • the mixture of ⁇ -sulfofatty acid esters include linear esters of C 6 to C 2 o ⁇ -sulfofatty acid esters.
  • the ⁇ -sulfofatty acid esters are typically of the following formula (I):
  • Ri is an unsubstituted or substituted alkyl group
  • R is an unsubstituted or substituted alkyl group
  • R 3 is hydrogen, a halogen, a metal, a monovalent or divalent cation, or an unsubstituted or substituted ammonium cation, such as monoethanolamine, diethanolamine, or triethanolamine.
  • Ri can be a C 4 to C 24 alkyl group including a C1 0 , C 12 , C 14 , and C 16 alkyl group.
  • R 2 can be a Ci to C 8 alkyl group, including a methyl group.
  • R 3 can be a metal, including a cation that forms a water soluble salt with the ⁇ -sulfofatty acid ester, such as sodium, potassium or lithium.
  • ⁇ -sulfofatty acid ester is of the following formula (II):
  • Ri is an alkyl group
  • R 2 is an alkyl group
  • M is a monovalent metal.
  • Ri is an alkyl group containing 4 to 24 carbon atoms, such as a C10, C 12 , C 14 , and C 16 alkyl group.
  • R 2 is typically a Q to C 4 alkyl group, and is more typically a methyl group.
  • M is typically an alkali metal, such as sodium.
  • the mixture of ⁇ -sulfofatty acid esters is prepared according to the desired properties of the final composition.
  • Each ⁇ -sulfofatty acid ester is typically at least 50 weight percent mono-salt, preferably at least about 70 weight percent mono-salt.
  • Methods of manufacturing ⁇ -sulfofatty acid esters are known to the skilled artisan. (See, e.g., U.S. Patent Nos.
  • ⁇ -Sulfofatty acid esters can be prepared from a variety of sources, including beef tallow, palm kernel oil, palm oil, peanut oil, coconut oil, soybean oil, canola oil, caster oil, cohune oil, coco butter, palm oil, white grease, cottonseed oil, corn oil, linseed oil, rape seed oil, yellow grease, tall oil, butter, lard, and mixtures thereof.
  • sources including beef tallow, palm kernel oil, palm oil, peanut oil, coconut oil, soybean oil, canola oil, caster oil, cohune oil, coco butter, palm oil, white grease, cottonseed oil, corn oil, linseed oil, rape seed oil, yellow grease, tall oil, butter, lard, and mixtures thereof.
  • Other sources of fatty acids to make ⁇ -sulfofatty acid esters include caprylic
  • C 8 capric (Cio) . lauric (C 12 ), myristic (C ⁇ 4 ), myristoleic (C 14 ), palmitic (C 16 ) . palmitoleic (C ⁇ 6 ), stearic (C 18 ), oleic (C 18 ), linoleic (C 18 ), linolenic (C 18 ), ricinoleic (C 18 ), arachidic (C 2 o), gadolic (C 2 o), behenic (C 22 ) and erucic (C 22 ) fatty acids.
  • ⁇ -Sulfofatty acid esters made from these sources are also within the scope of the present invention. In one embodiment, the mixture of ⁇ -sulfofatty acid esters is a "broad cut.”
  • the term "broad cut” refers to a mixture comprising at least 1% of Cio, C 12 , C 14 , C 16 and C 18 ⁇ -sulfofatty acid esters. Suitable sources of fatty acids that contain such a broad cut include palm kernel oil, coconut oil and cohune oil.
  • the mixture of ⁇ -sulfofatty acid esters is a "narrow cut," such as a mixture of C 1 and C 14 ⁇ - sulfofatty acid esters, a mixture of C 16 and C 18 ⁇ -sulfofatty acid esters, and the like.
  • different chain length ⁇ -sulfofatty acid esters are combined to form a mixture.
  • C 16 and C 18 sulfofatty acids generally provide better surface active agent properties, but can be less soluble.
  • C 8 -C 14 sulfofatty acids e.g., from palm kernel and/or coconut
  • suitable mixtures of ⁇ -sulfofatty acid esters include, for example, about 1 to about 100 weight percent of C 8 , do, C 12 , C 14 , C 16 and C 18 ⁇ - sulfofatty acid esters.
  • Other mixtures of ⁇ -sulfofatty acid esters are also within the scope of the present invention, as will be appreciated by the skilled artisan.
  • the mixture of ⁇ -sulfofatty acid esters is enriched for one or more chain length ⁇ -sulfofatty acid esters.
  • the term "enriched" means that the proportion of one or more chain length ⁇ -sulfofatty acid esters is increased relative to the proportion normally found in the ⁇ -sulfofatty acid ester mixture.
  • ⁇ -sulfofatty acid esters prepared from palm kernel oil and coconut oil typically comprise about 8.7 and 9 percent C 16 ⁇ -sulfofatty acid esters.
  • Such mixtures can be enriched by adding additional C 16 ⁇ -sulfofatty acid esters.
  • the resulting enriched mixture exhibits superior cleaning performance, good solubility and reduced phase separation.
  • the mixture of ⁇ -sulfofatty acid esters is enriched with a narrow range of ⁇ -sulfofatty acid esters.
  • ⁇ -sulfofatty acid esters prepared from palm kernel oil or cohune oil are typically a mixture of C 6 -C 18 chain lengths.
  • ⁇ -Sulfofatty acid esters derived from beef tallow are predominately C 16 -C ⁇ 8 ⁇ -sulfofatty acids.
  • a narrow range fraction of ⁇ -sulfofatty acid esters from tallow can comprise about 96 percent C 16 , about 3% C 14 and about 1% C 18 ⁇ -sulfofatty acid esters.
  • ⁇ -sulfofatty acid esters prepared from palm kernel oil or cohune oil are enriched with the narrow range (e.g., d 6 ) fraction from tallow to form an enriched mixture of ⁇ -sulfofatty acid esters.
  • the narrow range comprises less than about 10%, more typically less than about 5%, of ⁇ -sulfofatty acid esters other than the predominant (e.g., C 16 ) ⁇ -sulfofatty acid ester.
  • a mixture of shorter chain length ⁇ -sulfofatty acid esters (e.g., Cio, C 12 and C 14 ) is enriched with longer chain length ⁇ -sulfofatty acid(s) (e.g., C 16 and/or C 18 ) to form an enriched mixture.
  • the mixture of ⁇ -sulfofatty acid esters can be enriched by adding particular chain length ⁇ -sulfofatty acid ester(s) to that mixture.
  • a mixture of ⁇ -sulfofatty acid esters can also be enriched by selectively removing non-preferred chain length ⁇ -sulfofatty acid esters from that mixture.
  • the amount of enrichment can be chosen according to the desired properties of the final enriched mixture.
  • suitable proportions of enriched chain lengths to non-enriched chain lengths will include, but are not limited to, about 25 to about 50 weight percent enriched chain length to about 75 to about 50 weight percent non-enriched chain lengths.
  • the ratio of enriched to non-enriched chain lengths can range from greater than about 0.5:1, typically about 1:1 or about 2:1, and up to about 5:1 or about 6:1.
  • the enriched mixture of ⁇ -sulfofatty acid esters is part of a detergent composition.
  • Such detergent compositions preferably contain an effective amount of the ⁇ -sulfofattty acid ester mixture (i.e., an amount which exhibits the desired cleaning and surfactant properties).
  • the detergent composition contains at least about 5 weight percent of the enriched ⁇ -sulfofatty acid ester mixture. More typically, the detergent composition contains at least about 15 weight percent of the enriched ⁇ -sulfofatty acid ester mixture. In another embodiment, the detergent composition contains at least about 30 weight percent, and/or at least about 35 weight percent, of the enriched ⁇ -sulfofatty acid ester mixture.
  • Suitable detergent components that can be combined with the enriched ⁇ - sulfofatty acid ester mixture include builders, other anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, polymer dispersants, oxidizing agents, biocidal agents, foam regulators, binders, anticaking agents, activators, catalysts, thickeners, stabilizers, UN protectors, fragrances, soil suspending agents, fillers, brighteners, enzymes, salts, inert ingredients, and the like.
  • Suitable non-ionic surfactants include those containing an organic hydrophobic group and a hydrophilic group that is a reaction product of a solubilizing group (such as a carboxylate, hydroxyl, amido or amino group) with an alkylating agent, such as ethylene oxide, propylene oxide, or a polyhydration product thereof (such as polyethylene glycol).
  • a solubilizing group such as a carboxylate, hydroxyl, amido or amino group
  • an alkylating agent such as ethylene oxide, propylene oxide, or a polyhydration product thereof (such as polyethylene glycol).
  • nonionic surfactants include, for example, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyalkylene glycol fatty acid esters, alkyl polyalkylene glycol fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyalkylene castor oils, polyoxyalkylene alkylamines, glycerol fatty acid esters, alkylglucosamides, alkylglucosides, alkylamine oxides, and alkanolamides.
  • Other suitable surfactants include those disclosed in U.S.
  • composition is substantially free of nonylphenol nonionic surfactants.
  • substantially free means less than about 1 weight percent nonylphenol nonionic surfactant.
  • Suitable builders include silicated salts.
  • silicated salt means a non-phosphate salt, such as a carbonate, sulfate, alkali metal carbonate, alkali metal sulfate, ammonium carbonate, bicarbonate, sesquicarbonate, or mixtures thereof, that has been treated with a silicate salt.
  • Silicated salts and methods for preparing such salts are disclosed in U.S. Patent o. 4,973,419, the disclosure of which is incorporated herein by reference.
  • Suitable silicate builders include non-phosphate silicate salts, such as polysilicates and alkali metal silicates.
  • One preferred alkali metal silicate is a sodium silicate, such as a hydrous sodium silicate having an SiO 2 to Na 2 O ratio ranging from about 2.0 to about 2.4.
  • Suitable alkali metal silicates further include those sold by PQ Corporation under the trade names BRITESIL ® H20, BRITESIL ® H24 and BRITESIL ® C-24.
  • Other suitable silicate builders include wholly or partially crystallite layer-form silicates of the formula Na 2 Si x O 2x+1 yH 2 0, where x ranges from about 1.9 to about 4 and y ranges from 0 to about 20. Such silicates are described, for example, in U.S. Patent No. 5,900,399, the disclosure of which is incorporated herein by reference.
  • silicate builders include phyllosilicates or disilicates, such as those having the formula Na 2 O-2SiO 2 or Na Si 2 O 5 -yH 2 O, where y is an integer.
  • Preferred disilicates include ⁇ -sodium disilicates, such as those described in International Patent
  • phosphate builders means both inorganic and organic phosphate-containing builders such as alkali metal phosphates, orthophosphates, polyphosphates, tripolyphosphates, pyrophosphates, and polymeric phosphates.
  • Aluminosihcate builders include those known in the art, such as those of the formulae (III) and (IN): ⁇ a z [(AlO 2 ) z (SiO 2 ) y ] • xH 2 0 (III) where z and y are integers greater than 5, x is an integer ranging from 15 to
  • aluminosihcate builders include zeolite NaA, zeolite NaX, zeolite P, zeolite Y, hydrated zeolite 4A, zeolite MAP or mixtures thereof.
  • Suitable polymer dispersants include polymers and co-polymers of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and water-soluble salts thereof, such as alkali metal, ammonium, or substituted ammonium salts.
  • Suitable polymer dispersants further include those sold under the trade names ACUSOL ® 445 (polyacrylic acid), ACUSOL ® 445N (the sodium salt of polyacrylic acid), ACUSOL ® 460N (a maleic acid olefin copolymer sodium salt), and ACUSOL ® 820 (acrylic copolymer), all sold by
  • anionic surfactants include alkylbenzenesulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkyl or alkenyl ether carboxylates, amino acid-type surfactants, and N-acyl amino acid-type surfactants.
  • the composition is substantially free of other anionic surfactants.
  • Suitable oxidizing agents include chlorine and non-chlorine-containing oxidizing agents.
  • Suitable non-chlorine oxidizing agents include oxygen bleaches, such as perborates, percarbonates, persulfates, dipersulfates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Other suitable non-chlorine oxidizing agents include bleach activators, such as tetraacetyl ethylene diamine (TAED), sodium benzoyl oxybenzene sulfonate, choline sulfophenyl carbonate, and those described in U.S. Patent Nos. 4,915,854 and 4,412,934, the disclosures of which are incorporated herein by reference.
  • Other suitable non-chlorine oxidizing agents include a catalyst such as manganese or other transition metals in combination with such oxygen bleaches.
  • Suitable oxidizing agents include percarboxylic acid bleaching agents and salts thereof, such as magnesium monoperoxyphthalate hexahydrate and the magnesium salts of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Other oxidizing agents include those described in U.S. Patent
  • Suitable oxidizing agents include non-oxygen-containing agents, such as photoactivated bleaching agents.
  • Suitable photoactivated bleaching agents include sulfonated zinc and metal phthalocyanines, such as aluminum and zinc phthalocyanines.
  • Chlorine-containing agents include organic and/or inorganic compounds capable of having their chlorine liberated in the form of active chlorine on dissolution in water.
  • Typical examples of such chlorine-containing agents include hypochlorites such as alkali metal (calcium and lithium) hypochlorites; chlorinated trisodium phosphate; chlorinated sulfonamides; halogenated hydantoins, such as l,3-dichloro-5,5- dimethylhydantoin; polychlorocyanurates (usually containing alkali metals such as sodium or potassium salts); chlorine-substituted isocyanuric acid; alkali-metal salts of isocyanuric acid, such as potassium or sodium dihydrate; and other anhydrous chlorine-containing agents known in the detergent industry.
  • hypochlorites such as alkali metal (calcium and lithium) hypochlorites; chlorinated trisodium phosphate; chlorinated sulfonamides; halogenated hydan
  • Suitable biocidal agents include TAED, TAED combined with a persalt, triclosan (5-chloro-2 (2,4-dichloro-phenoxy) phenol)), and quaternary ammonium compounds such as alkyl dimethyl ammonium chlorides, alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides, benzalkonium chloride, parachlorometaxylene and alkyl dimethyl benzyl ammonium chloride.
  • Other biocidal agents include those sold under the trade names BARD AC ® and BARQUAT ® by the Lonza Group and those sold under the trade name BTC by the Stepan Company.
  • Suitable optical brighteners include stilbenes such as TINOPAL ® AMS, distyrylbiphenyl derivatives such as TINOPAL ® CBS-X, stilbene/naphthotriazole blends such as TINOPAL ® RA-16, all sold by Ciba Geigy, oxazole derivatives and coumarin brighteners.
  • Suitable enzymes include any of those known in the art, such as amylolytic, proteolytic or lipolytic type, and those listed in U.S. Patent No. 5,324,649, the disclosure of which is incorporated herein by reference.
  • amylases include amylases, lipases, and cellulases, such as ALCALASE ® (bacterial protease), EVERLASE ® (protein-engineered variant of SAVINASE ® ), ESPERASE ® (bacterial protease), LIPOLASE ® (fungal lipase), LIPOLASE ULTRA (Protein-engineered variant of LIPOLASE), LTPOPRIMETM (protein-engineered variant of LIPOLASE), TERMAMYL ® (bacterial amylase), BAN (Bacterial Amylase Novo), CELLUZYME ®
  • ALCALASE ® bacterial protease
  • EVERLASE ® protein-engineered variant of SAVINASE ®
  • ESPERASE ® bacterial protease
  • LIPOLASE ® fungal lipase
  • LIPOLASE ULTRA Protein-engineered variant of LIPOLASE
  • LTPOPRIMETM protein-engineered variant of LIPOL
  • compositions according to the present invention can be prepared by any suitable process or combination of processes that yield the desired composition, according to the present invention.
  • the enriched mixture of ⁇ -sulfofatty acid esters is typically prepared by one of a variety of methods.
  • the enriched mixture of ⁇ -sulfofatty acid esters is prepared by combining particular chain length fatty acid(s) with a mixture of fatty acids of differing chain lengths.
  • the enriched fatty acid mixture is then esterified and sulfonated to form the enriched mixture of ⁇ -sulfofatty acid esters.
  • the enriched mixture is prepared by combining particular chain length fatty acid ester(s) with a mixture of fatty acid esters of differing chain lengths.
  • the enriched mixture of fatty acid esters is then sulfonated to form the enriched mixture of ⁇ -sulfofatty acid esters.
  • the enriched mixture of ⁇ -sulfofatty acid esters is prepared by combining particular chain length ⁇ -sulfofatty acid ester(s) with a mixture of ⁇ -sulfofatty acid esters of differing chain lengths.
  • the enriched mixture of ⁇ -sulfofatty acid esters are prepared by combining C 16 -enriched fatty acids, C 16 -enriched fatty acid alkyl esters, or C 16 -enriched ⁇ -sulfofatty acid esters with a mixture of fatty acids, fatty acid alkyl esters or ⁇ -sulfofatty acid esters, respectively. These mixtures are esterified and sulfonated, as necessary, to form an enriched mixture of ⁇ -sulfofatty acid esters. The proportions of carbon chain lengths in the mixture are selected according to the desired surfactant properties of the final composition.
  • One method of preparing an enriched mixture of ⁇ -sulfofatty acid esters is to provide a natural fat or oil that includes the preferred chain length fatty acids, and then fractionating the fatty acids to enrich for those preferred chain lengths.
  • a natural fat or oil has a significant concentration (at least about 25 percent and preferably about 35 percent) of the preferred chain length fatty acids.
  • a suitable fatty acid source such as palm stearine oil or tallow
  • a separation apparatus such as a fractionation tower or liquid-liquid extraction.
  • the C 16 -enriched stream exiting the separation apparatus is then combined with a mixture of fatty acids.
  • the enriched mixture of fatty acids is then esterified to make an enriched mixture of fatty acid alkyl esters, which is then sulfonated to form the enriched mixture of ⁇ -sulfofatty acid esters.
  • the other stream(s) exiting the separation apparatus can be used in any desired manner. For example, when palm stearine oil is fractionated, the stream containing mostly C 16 fatty acids is used to make the ⁇ -sulfofatty acid esters while the stream containing mostly C 18 fatty acids is used in the process of making an alkanolamide or a polyalkoxylated alkanolamide.
  • Another method is to prepare fatty acid alkyl esters comprising the preferred fatty acid alkyl esters, such as fatty acid methyl esters, and then fractionating the fatty acid alkyl esters to enrich for preferred chain length fatty acid alkyl esters.
  • fatty acid alkyl esters Preferably, such fatty acid alkyl esters have a significant concentration (at least about 25 percent and preferably about 35 percent) of the desired fatty acid alkyl esters.
  • a suitable fatty acid alkyl ester source such as esterified tallow, is provided and fed to a separation apparatus, such as a fractionation tower or liquid-liquid extraction.
  • the C 16 -enriched stream exiting the separation apparatus is then used to make d 6 -enriched ⁇ -sulfofatty acid esters.
  • the other stream(s) exiting the separation apparatus can be used in any desired manner, such as to make alkanolamides or polyalkoxylated alkanolamides.
  • the enriched ⁇ -sulfofatty acid ester mixture can also be prepared by combining a mixture of ⁇ -sulfofatty acid esters with the desired chain length ⁇ -sulfofatty acid ester(s) to enrich the mixture.
  • a broad cut mixture of ⁇ -sulfofatty acid esters from cohune oil, palm kernel oil or coconut oil can be mixed with a narrow range of C_ 6 (e.g., C 14 -Ci 6 -C 18 ) ⁇ -sulfofatty acid esters.
  • any suitable mixing apparatus can be used to combine the fatty acids, fatty acid alkyl esters or ⁇ -sulfofatty acid esters. (See, e.g., Perry 's Chemical Engineers ' Handbook (6 th Ed.), chapters 19 and 21 (1984), the disclosure of which is incorporated herein by reference.) In some embodiments, the amounts of different chain lengths can be combined in any suitable ratios.
  • a first source of fatty acids is palm kernel oil (PKO) and a second source of fatty acids is C 16 -fatty acids from palm stearine oil (PSO)
  • PKO palm kernel oil
  • PSO palm stearine oil
  • these two sources are mixed in amounts of about 40-60 weight percent PKO with about 60-40 weight percent C 16 -enriched PSO, and preferably about 50-55 weight percent PKO with about 50-45 weight percent C 16 -er_riched PSO.
  • the fatty acids are then esterified to form fatty acid alkyl esters, which are then sulfonated.
  • a first source of fatty acid alkyl esters is esterified palm kernel oil (ePKO) and a second source of fatty acid alkyl esters is esterified, C 16 - enriched palm stearine oil (ePSO)
  • these two sources are mixed in amounts of about 40-60 weight percent ePKO with about 60-40 weight percent ePSO, and preferably about 50-55 weight percent ePKO with about 50-45 weight percent C 16 -enriched ePSO.
  • the enriched mixture of fatty acid alkyl esters is then sulfonated to form the enriched mixture of ⁇ -sulfofatty acid esters.
  • the sulfonation process can be performed according to any sulfonation process as known in the art, such as the processes described in U.S. Patent Nos. 5,587,500; 5,329,030; 5,382,677; 5,384,422; 4,671,900; 4,816,188; and The Journal of American Oil Chemists Society 52:323-29 (1975), the disclosures of which are incorporated herein by reference.
  • sulfonation processes include those processes using both hydrogen peroxide and a halogen bleach in a two step bleaching operation; processes that use ultra purified fatty acid alkyl ester feedstocks along with a single step hydrogen peroxide neutral bleaching process; and re-esterification processes using only hydrogen peroxide acidic bleaching with typical quality fatty acid alkyl ester feedstocks.
  • the ⁇ -sulfofatty acid ester (e.g., a methyl ester sulfonate) is typically prepared by feeding the fatty acid alkyl ester feedstock and SO 3 gas to a suitable reactor, such as a falling film reactor.
  • a suitable reactor such as a falling film reactor.
  • Any source of SO 3 gas can be used.
  • dry air is compressed, cooled, dried and then mixed with liquid sulfur, supplied from a suitable reservoir, to make sulfur dioxide.
  • the sulfur can be uniformly combusted, for example, by using a sulfur burner to control the molar ratio of air to sulfur.
  • the sulfur dioxide is cooled, such as in a double-pipe cooler, prior to being delivered to a catalytic converter where the sulfur dioxide gas is filtered and converted to the sulfur trioxide gas.
  • the molar ratio of the methyl ester feed to the SO 3 gas is optimized for sulfonation of the fatty acid alkyl ester feedstock.
  • the step of sulfonation is typically the rapid reaction of the fatty acid alkyl ester with two molecules of SO 3 to form an adduct.
  • the second step of the sulfonation reaction which is usually slower and requires longer time and elevated temperatures, is rearrangement of the adduct to form a fatty acid alkyl ester sulfonic acid, releasing the second molecule of SO 3j which then reacts with another fatty acid alkyl ester molecule.
  • the sulfur dioxide gas that is generated in the two-step process can then be removed and can be recycled.
  • the fatty acid alkyl ester sulfonic acid can optionally be bleached. Because the elevated temperatures in the sulfonation process darken the acid, a bleaching step may be required to lighten the acid to acceptable levels.
  • An advantageous fatty acid alkyl ester sulfonic acid feedstock used in the manufacturing process is a natural oil derivative that has low acid values, a narrow molecular weight distribution, contains little or no paraffinic compounds, and has been hydro genated to reduce the iodine content, thereby reducing the presence of double bonds that cause the dark color when sulfonated.
  • the bleaching process can be carried out in two stages.
  • the fatty acid alkyl ester sulfonic acid is reacted with less than about 5 weight percent alkanol, such as methanol, to produce the desired mono-salt and to inhibit formation of the di-salt to less than about 30%.
  • hydrogen peroxide is reacted with the fatty acid alkyl ester sulfonic acid to reduce the color.
  • the order of the two bleaching steps can be changed, as desired.
  • the fatly acid alkyl ester sulfonic acid is typically degassed in an inert gas blanketed flash feed tank to remove oxygen and low molecular compounds.
  • the fatty acid alkyl ester sulfonic acid is then neutralized to form ⁇ -sulfofatty acid ester.
  • the fatty acid alkyl ester sulfonic acid is neutralized with any suitable base that will yield the desired salt.
  • sodium hydroxide (NaOH) is reacted with fatty acid alkyl ester sulfonic acid to produce sodium ⁇ -sulfofatty acid ester.
  • the ⁇ -sulfofatty acid ester is dried.
  • the product leaving the neutralizer typically contains about 65-70% solids and 10-15%o methanol.
  • the ⁇ -sulfofatty acid ester is heated to an elevated temperature and fed to a dryer, preferably a steam-heated vacuum flash dryer, to strip the methanol and water (and other volatile components).
  • the resulting product contains about 2-4% water. This product can optionally be cooled.
  • the ⁇ -sulfofatty acid ester is optionally partially or fully coated to protect the ⁇ -sulfofatty acid ester from moisture and/or minor amount of additional di-salt formation.
  • a coating can prevent the contact of bases, moisture, and other di-salt causing substances with the sulfofatty acid.
  • Such a coating can be water- resistant.
  • the coating typically has a melting point within normal washing temperatures.
  • the coating can also be water-soluble.
  • Suitable coatings include, for example, polyvinyl alcohol, partially or fully hydrolyzed polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyvinyl- methylmethacrylate copolymer, maleic acid/acrylic acid copolymer, ethylene/maleic anhydride copolymer, polyethylene glycol, acrylic acid polymer, carboxymethyl cellulose, cellulose ether, paraffin waxes, fatty acids, methyl ester sulfonate, soaps, waxes, water- soluble polymers, water-swellable polymers, or copolymers, salts or mixtures of any of these.
  • the coating can be applied to the ⁇ -sulfofatty acid ester according to techniques conventionally used in the detergent industry.
  • Other techniques for applying coatings such as those used in the pharmaceutical industry, are also within the scope of the present invention, as will be appreciated by the skilled artisan.
  • suitable techniques for applying a coating include dip coating, spin coating, spray coating, spray drying (including spray drying using counter-current or co-current techniques), agglomeration and fluid bed drying.
  • Suitable fluid bed dryers include, for example, static, vibrating, high-shear granulating, vacuum fluid bed, tablet pan coating, rotor processing and high speed fluid bed dryers.
  • the coating can be dried, as necessary, to remove excess moisture or other liquid.
  • the enriched mixture of ⁇ -sulfofatty acid esters is combined with other detergent components in any suitable mixing apparatus.
  • suitable apparatuses include dry blenders, agglomerators, spray drying equipment, fluid bed mixers, or any solid-solid, liquid-solid, or liquid-liquid mixing apparatus known in the art. (See, e.g., Perry 's Chemical Engineers ' Handbook (6 th Ed.), chapter 19 (1984).) Water and/or solvents can be added to aid in this mixing process. Further, on exiting the mixing apparatus, the composition is optionally dried and combined with other detergent components as known in the art.
  • a C 16 -enriched methyl ester sulfonate was prepared according to the following process. Palm kernel oil (“PKO”) and palm stearine oil (“PSO”) were separately esterified with an alkanol (e.g., methanol). The esterified palm stearin oil was then fractionated in a tower. The C 16 fraction of the palm stearin oil (predominately C 16 's with small amounts of C 14 and C 18 chain lengths) was then mixed with the esterified palm kernel oil in a ratio of about 1:1. The mixture was then sulfonated in a falling film reactor. The resulting fatty acid alkyl ester sulfonic acid was reacted with NaOH to obtain an enriched sodium ⁇ -sulfofatty acid ester.
  • PKO Palm kernel oil
  • PSO palm stearine oil
  • a detergent composition (i.e., one with C 16 -enriched methyl ester sulfonate) is made according to the following process.
  • palm kernel oil is esterified with an alkanol (e.g., methanol) to form a first fatty acid alkyl ester.
  • Tallow is esterified with an alkanol (e.g., methanol) to form a second fatty acid alkyl ester.
  • the second tallow fatty acid alkyl ester is then fractionated in a tower.
  • the C 16 -enriched fatty acid alkyl ester fraction is combined with the first fatty acid alkyl ester (from PKO) in a ratio of about 45-55 weight percent to 55-45 weight percent, respectively.
  • the resulting mixture is then sulfonated in a falling film reactor and the resulting fatty acid alkyl ester sulfonic acid is reacted with NaOH to obtain a sodium ⁇ -sulfofatty acid ester.
  • This sodium ⁇ -sulfofatty acid ester is then added to other detergent components to obtain a final detergent composition.
  • Ci 6 -enriched methyl ester sulfonate is prepared according to the following process. Palm kernel oil is combined with a Ci 6 -enriched fraction of fatty acids from tallow. The enriched mixture is then esterified with an alkanol and then sulfonated in a falling film reactor. The resulting fatty acid alkyl ester sulfonic acid is reacted with NaOH to obtain a sodium ⁇ -sulfofatty acid ester.

Abstract

The present invention includes a composition comprising an enriched mixture of α-sulfofatty acid esters. Increasing the concentration of specific chain length α-sulfofatty acid esters, relative to the proportions of the other chain lengths, allows the detergent compositions to exhibit an improved cleaning performance while simultaneously cleaning a wide variety of materials.

Description

DETERGENT CONTAINING α-SULFOFATTY ACID ESTERS AND METHODS
OF MAKING AND USING THE SAME
BACKGROUND OF THE INVENTION
The present invention generally relates to α-sulfofatty acid ester compositions and methods for making and using such compositions. More particularly, the present invention relates to α-sulfofatty acid ester compositions that are enriched for particular α- sulfofatty acid esters, and methods for making and using such compositions.
Detergents have been used for many years to clean clothing and other materials. Detergent compositions are generally formulated to contain components such as surfactants, builders, electrolytes and other additives dispersed or dissolved in an aqueous medium. Surfactants are included in detergents to enhance their cleaning performance. Typical surfactants include anionics, nonionics, zwitterionics, ampholytics, cationics and those described in Surface Active Agents, Volumes I and II by Schwartz, Perry and Berch (New York, Interscience Publishers), Nonionic Surfactants ed. by M. J. Schick (New York, M. Dekker, 1967), and in McCutcheon's Emulsifiers & Detergents (1989 Annual, M. C. Publishing Co.), the disclosures of which are incoη orated herein by reference.
Recently, interest in α-sulfofatty acid esters (also referred to hereinafter as "sulfofatty acids") has increased due to the superior cleaning properties of these surfactants in hard water. While other surfactants have similar detergency in soft water, as water hardness increases α-sulfofatty acid esters exhibit increased cleaning performance as compared with other anionic surfactants. Thus, α-sulfofatty acid esters are an effective anionic surfactant that can be used in a wide variety of washing conditions. α-Sulfofatty acid esters are typically manufactured as salts (i.e., a mixture of salt forms, typically mono- and di-salts). Di-salts result from hydrolysis of α-sulfofatty acid ester during manufacture, storage and in detergent compositions. In particular, mono-salts of α-sulfofatty acid ester hydrolyze in the presence of moisture and alkali-containing detergent components to form di-salts. For example, in formulations containing methyl ester sulfonate ("MES") that is well mixed with high pH components under aqueous conditions, the MES will hydrolyze nearly completely to the di-salt form. Such high pH components can include builders, such as silicates or carbonates, and bases. This chemical instability discourages the use of such anionic surfactants in many applications. α-Sulfofatty acid esters are typically made from natural fats or oils. These fats and oils are usually free fatty acids or glycerol esters (i.e., mono-, di- or triglycerides). Free fatty acids are formed from glycerol esters by hydrolysis. The resulting fatty acids typically contain an even number of carbon atoms. These fatty acids are then esterifϊed to form fatty acid esters. The esters are then sulfonated to form α-sulfofatty acid esters.
The surface active agent properties of α-sulfofatty acid esters are related to the chain lengths of the fatty acid portion of the molecules. For example, shorter chain length molecules (e.g., C8-C12 α-sulfofatty acid esters) are typically more water-soluble, but exhibit lesser surface active agent properties. Longer chain length (e.g., C14-C16) α- sulfo fatty acid esters exhibit greater surface active agent properties, but are less water- soluble. Because α-sulfofatty acid esters are usually manufactured from natural sources, they are a mixture of different chain lengths. The properties of such mixtures are determined by the chain length distribution of the source of the fatty acids. Thus, α-sulfofatty acid esters from palm kernel (stearin) oil have different surfactant properties than α-sulfofatty acid esters from tallow. To overcome the limitations of single sources, blends of α- sulfofatty acid esters from multiple sources are prepared. Such blends are also limited, however, by the chain length distributions of each fatty acid source. For example, combining α-sulfofatty acid esters from palm kernel (stearin) oil (C6-C2n fatty acids) with α- sulfofatty acid esters from tallow (C14-C18 fatty acids) creates a mixture that has the average characteristics of the α-sulfofatty acid esters contained therein.
It has not been previously appreciated that the properties of α-sulfofatty acid ester mixtures can be improved by enriching such mixtures with particular chain length α- sulfofatty acid esters. Such enrichment allows certain beneficial properties (associated with particular chain length α-sulfofatty acid ester) to be enhanced without diluting such mixtures with other α-sulfofatty acid ester chain lengths.
SUMMARY OF THE INVENTION The present invention provides compositions and processes for enriching mixtures of α-sulfofatty acid esters for particular chain lengths. By increasing the proportion of particular chain length α-sulfofatty acid esters, compositions are prepared that exhibit improved cleaning performance as well as improved aqueous solubility and reduced phase separation of the α-sulfofatty acid esters from other aqueous components. The present invention includes compositions that are enriched for particular chain length α-sulfofatty acid ester(s). In one embodiment, a mixture of α-sulfofatty acid esters is enriched for a particular chain length α-sulfofatty acid ester. In another embodiment, a mixture of α-sulfofatty acid esters is enriched for a range of α-sulfofatty acid ester chain lengths. Such mixtures are enriched for a narrow range of such sulfofatty acid chain lengths or for multiple discrete chain lengths. Detergent components can also be added to the enriched mixture of α-sulfofatty acid esters. Suitable detergent components include builders, other anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, polymer dispersants, oxidizing agents, biocidal agents, foam regulators, binders, anticaking agents, activators, catalysts, thickeners, stabilizers, UV protectors, fragrances, soil suspending agents, fillers, brighteners, enzymes, salts, inert ingredients, and the like.
Processes for enriching mixtures of α-sulfofatty acid esters are also provided. In one embodiment, a mixture of α-sulfofatty acid esters is enriched for one or more α- sulfofatty acid esters of particular chain lengths. For example, α-sulfofatty acid esters prepared from cohune oil, palm kernel oil or coconut oil are enriched for C16 α-sulfofatty acid ester. In another embodiment, a mixture of α-sulfofatty acid esters is enriched for a narrow range of α-sulfofatty acid ester chain lengths. The α-sulfofatty acid ester mixture is enriched, for example, by supplementing the fatty acid feedstock with particular chain length fatty acid(s), by enriching for particular chain length fatty acid alkyl ester(s) prior to sulfonation, and/or by the addition of particular chain length α-sulfofatty acid esters to a mixture of such α-sulfofatty acids.
DETAILED DESCRIPTION OF THE INVENTION The following description provides specific details, such as materials and dimensions, to provide a thorough understanding of the present invention. The skilled artisan, however, will appreciate that the present invention may be practiced without employing these specific details. Indeed, the present invention can be practiced in conjunction with processing, manufacturing or fabricating techniques conventionally used in the detergent industry. Moreover, the processes below describe only steps, rather than a complete process flow, for manufacturing the inventive compositions, and detergents containing the invented compositions. A preferred embodiment is directed to compositions comprising enriched mixtures of α-sulfofatty acid esters. The mixture of α-sulfofatty acid esters include linear esters of C6 to C2o α-sulfofatty acid esters. The α-sulfofatty acid esters are typically of the following formula (I):
RιCHCOOR2
I (i)
SO3R3
where Ri is an unsubstituted or substituted alkyl group, R is an unsubstituted or substituted alkyl group, and R3 is hydrogen, a halogen, a metal, a monovalent or divalent cation, or an unsubstituted or substituted ammonium cation, such as monoethanolamine, diethanolamine, or triethanolamine. Ri can be a C4 to C24 alkyl group including a C10, C12, C14, and C16 alkyl group. R2 can be a Ci to C8 alkyl group, including a methyl group. R3 can be a metal, including a cation that forms a water soluble salt with the α-sulfofatty acid ester, such as sodium, potassium or lithium.
More typically, the α-sulfofatty acid ester is of the following formula (II):
R,CHCOOR2
I (ii)
SO3M
wherein Ri is an alkyl group, R2 is an alkyl group, and M is a monovalent metal. Typically, Ri is an alkyl group containing 4 to 24 carbon atoms, such as a C10, C12, C14, and C16 alkyl group. R2 is typically a Q to C4 alkyl group, and is more typically a methyl group. M is typically an alkali metal, such as sodium.
The mixture of α-sulfofatty acid esters is prepared according to the desired properties of the final composition. Each α-sulfofatty acid ester is typically at least 50 weight percent mono-salt, preferably at least about 70 weight percent mono-salt. Methods of manufacturing α-sulfofatty acid esters are known to the skilled artisan. (See, e.g., U.S. Patent Nos. 5,587,500; 5,329,030; 5,382,677; 5,384,422; 4,671,900; 4,816,188; and The Journal of American Oil Chemists Society 52:323-29 (1975); the disclosures of which are incorporated herein by reference.) The mixture of α-sulfofatty acid esters can be manufactured according to any of these methods. α-Sulfofatty acid esters can be prepared from a variety of sources, including beef tallow, palm kernel oil, palm oil, peanut oil, coconut oil, soybean oil, canola oil, caster oil, cohune oil, coco butter, palm oil, white grease, cottonseed oil, corn oil, linseed oil, rape seed oil, yellow grease, tall oil, butter, lard, and mixtures thereof. Other sources of fatty acids to make α-sulfofatty acid esters include caprylic
(C8), capric (Cio). lauric (C12), myristic (Cι4), myristoleic (C14), palmitic (C16). palmitoleic (Cι6), stearic (C18), oleic (C18), linoleic (C18), linolenic (C18), ricinoleic (C18), arachidic (C2o), gadolic (C2o), behenic (C22) and erucic (C22) fatty acids. α-Sulfofatty acid esters made from these sources are also within the scope of the present invention. In one embodiment, the mixture of α-sulfofatty acid esters is a "broad cut."
As used herein, the term "broad cut" refers to a mixture comprising at least 1% of Cio, C12, C14, C16 and C18 α-sulfofatty acid esters. Suitable sources of fatty acids that contain such a broad cut include palm kernel oil, coconut oil and cohune oil. In another embodiment, the mixture of α-sulfofatty acid esters is a "narrow cut," such as a mixture of C1 and C14α- sulfofatty acid esters, a mixture of C16 and C18 α-sulfofatty acid esters, and the like. In another embodiment, different chain length α-sulfofatty acid esters are combined to form a mixture. For example, C16 and C18 sulfofatty acids (e.g., from tallow and/or palm stearin) generally provide better surface active agent properties, but can be less soluble. C8-C14 sulfofatty acids (e.g., from palm kernel and/or coconut) are more soluble in water, but have lesser surface active agent properties. Thus, suitable mixtures of α-sulfofatty acid esters include, for example, about 1 to about 100 weight percent of C8, do, C12, C14, C16 and C18 α- sulfofatty acid esters. Other mixtures of α-sulfofatty acid esters are also within the scope of the present invention, as will be appreciated by the skilled artisan.
The mixture of α-sulfofatty acid esters is enriched for one or more chain length α-sulfofatty acid esters. As used herein, the term "enriched" means that the proportion of one or more chain length α-sulfofatty acid esters is increased relative to the proportion normally found in the α-sulfofatty acid ester mixture. For example, α-sulfofatty acid esters prepared from palm kernel oil and coconut oil typically comprise about 8.7 and 9 percent C16 α-sulfofatty acid esters. Such mixtures can be enriched by adding additional C16 α-sulfofatty acid esters. The resulting enriched mixture exhibits superior cleaning performance, good solubility and reduced phase separation. In another embodiment, the mixture of α-sulfofatty acid esters is enriched with a narrow range of α-sulfofatty acid esters. For example, α-sulfofatty acid esters prepared from palm kernel oil or cohune oil are typically a mixture of C6-C18 chain lengths. α-Sulfofatty acid esters derived from beef tallow are predominately C16-Cι8 α-sulfofatty acids. A narrow range fraction of α-sulfofatty acid esters from tallow can comprise about 96 percent C16, about 3% C14 and about 1% C18 α -sulfofatty acid esters. Thus, α-sulfofatty acid esters prepared from palm kernel oil or cohune oil are enriched with the narrow range (e.g., d6) fraction from tallow to form an enriched mixture of α-sulfofatty acid esters. In another embodiment, the narrow range comprises less than about 10%, more typically less than about 5%, of α-sulfofatty acid esters other than the predominant (e.g., C16) α-sulfofatty acid ester. In still another embodiment, a mixture of shorter chain length α-sulfofatty acid esters (e.g., Cio, C12 and C14) is enriched with longer chain length α-sulfofatty acid(s) (e.g., C16 and/or C18) to form an enriched mixture.
The mixture of α-sulfofatty acid esters can be enriched by adding particular chain length α-sulfofatty acid ester(s) to that mixture. A mixture of α-sulfofatty acid esters can also be enriched by selectively removing non-preferred chain length α-sulfofatty acid esters from that mixture. The amount of enrichment can be chosen according to the desired properties of the final enriched mixture. For example, suitable proportions of enriched chain lengths to non-enriched chain lengths will include, but are not limited to, about 25 to about 50 weight percent enriched chain length to about 75 to about 50 weight percent non-enriched chain lengths. In another embodiment, the ratio of enriched to non-enriched chain lengths can range from greater than about 0.5:1, typically about 1:1 or about 2:1, and up to about 5:1 or about 6:1.
In some embodiments, the enriched mixture of α-sulfofatty acid esters is part of a detergent composition. Such detergent compositions preferably contain an effective amount of the α-sulfofattty acid ester mixture (i.e., an amount which exhibits the desired cleaning and surfactant properties). Typically, the detergent composition contains at least about 5 weight percent of the enriched α-sulfofatty acid ester mixture. More typically, the detergent composition contains at least about 15 weight percent of the enriched α-sulfofatty acid ester mixture. In another embodiment, the detergent composition contains at least about 30 weight percent, and/or at least about 35 weight percent, of the enriched α-sulfofatty acid ester mixture. Suitable detergent components that can be combined with the enriched α- sulfofatty acid ester mixture include builders, other anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, polymer dispersants, oxidizing agents, biocidal agents, foam regulators, binders, anticaking agents, activators, catalysts, thickeners, stabilizers, UN protectors, fragrances, soil suspending agents, fillers, brighteners, enzymes, salts, inert ingredients, and the like.
Suitable non-ionic surfactants include those containing an organic hydrophobic group and a hydrophilic group that is a reaction product of a solubilizing group (such as a carboxylate, hydroxyl, amido or amino group) with an alkylating agent, such as ethylene oxide, propylene oxide, or a polyhydration product thereof (such as polyethylene glycol). Such nonionic surfactants include, for example, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyalkylene glycol fatty acid esters, alkyl polyalkylene glycol fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyalkylene castor oils, polyoxyalkylene alkylamines, glycerol fatty acid esters, alkylglucosamides, alkylglucosides, alkylamine oxides, and alkanolamides. Other suitable surfactants include those disclosed in U.S. Patent Νos. 5,133,892 and 6,034,045, the disclosures of which are incorporated herein by reference. In one embodiment, the composition is substantially free of nonylphenol nonionic surfactants. In this context, the term "substantially free" means less than about 1 weight percent nonylphenol nonionic surfactant.
Suitable builders include silicated salts. The term "silicated salt" means a non-phosphate salt, such as a carbonate, sulfate, alkali metal carbonate, alkali metal sulfate, ammonium carbonate, bicarbonate, sesquicarbonate, or mixtures thereof, that has been treated with a silicate salt. Silicated salts and methods for preparing such salts are disclosed in U.S. Patent o. 4,973,419, the disclosure of which is incorporated herein by reference.
Suitable silicate builders include non-phosphate silicate salts, such as polysilicates and alkali metal silicates. One preferred alkali metal silicate is a sodium silicate, such as a hydrous sodium silicate having an SiO2 to Na2O ratio ranging from about 2.0 to about 2.4. Suitable alkali metal silicates further include those sold by PQ Corporation under the trade names BRITESIL® H20, BRITESIL® H24 and BRITESIL® C-24. Other suitable silicate builders include wholly or partially crystallite layer-form silicates of the formula Na2SixO2x+1 yH20, where x ranges from about 1.9 to about 4 and y ranges from 0 to about 20. Such silicates are described, for example, in U.S. Patent No. 5,900,399, the disclosure of which is incorporated herein by reference.
Other suitable silicate builders include phyllosilicates or disilicates, such as those having the formula Na2O-2SiO2 or Na Si2O5-yH2O, where y is an integer. Preferred disilicates include β-sodium disilicates, such as those described in International Patent
Application WO-A-91-08171, the disclosure of which is incorporated herein by reference.
Disilicates sold under the trade names SKS® 6 and SKS® 7 by Hoescht AG and Clariant
Corporation can also be used. Other suitable builders include phosphate and aluminosihcate builders. The term "phosphate builders" means both inorganic and organic phosphate-containing builders such as alkali metal phosphates, orthophosphates, polyphosphates, tripolyphosphates, pyrophosphates, and polymeric phosphates. Aluminosihcate builders include those known in the art, such as those of the formulae (III) and (IN): Νaz[(AlO2)z(SiO2)y] • xH20 (III) where z and y are integers greater than 5, x is an integer ranging from 15 to
264, and the molar ratio of z to y ranges from about 1.0 to about 0.5; and
Mz(zAlO2- ySiO2) (TV) where M is sodium, potassium, ammonium, or substituted ammonium, z ranges from about 0.5 to about 2, and y is 1. Examples of such aluminosihcate builders include zeolite NaA, zeolite NaX, zeolite P, zeolite Y, hydrated zeolite 4A, zeolite MAP or mixtures thereof.
Suitable polymer dispersants include polymers and co-polymers of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and water-soluble salts thereof, such as alkali metal, ammonium, or substituted ammonium salts. Suitable polymer dispersants further include those sold under the trade names ACUSOL® 445 (polyacrylic acid), ACUSOL® 445N (the sodium salt of polyacrylic acid), ACUSOL® 460N (a maleic acid olefin copolymer sodium salt), and ACUSOL® 820 (acrylic copolymer), all sold by
Rohm and Haas. Other anionic surfactants include alkylbenzenesulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkyl or alkenyl ether carboxylates, amino acid-type surfactants, and N-acyl amino acid-type surfactants. In another embodiment, the composition is substantially free of other anionic surfactants.
Suitable oxidizing agents include chlorine and non-chlorine-containing oxidizing agents. Suitable non-chlorine oxidizing agents include oxygen bleaches, such as perborates, percarbonates, persulfates, dipersulfates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Other suitable non-chlorine oxidizing agents include bleach activators, such as tetraacetyl ethylene diamine (TAED), sodium benzoyl oxybenzene sulfonate, choline sulfophenyl carbonate, and those described in U.S. Patent Nos. 4,915,854 and 4,412,934, the disclosures of which are incorporated herein by reference. Other suitable non-chlorine oxidizing agents include a catalyst such as manganese or other transition metals in combination with such oxygen bleaches.
Other suitable oxidizing agents include percarboxylic acid bleaching agents and salts thereof, such as magnesium monoperoxyphthalate hexahydrate and the magnesium salts of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Other oxidizing agents include those described in U.S. Patent
Nos. 4,483,781, 4,634,551, and 4,412,934, as well as European Patent Application No.
0,133,354, the disclosures of which are incorporated herein by reference.
Suitable oxidizing agents include non-oxygen-containing agents, such as photoactivated bleaching agents. Suitable photoactivated bleaching agents include sulfonated zinc and metal phthalocyanines, such as aluminum and zinc phthalocyanines.
Other suitable photoactivated bleaching agents are described in U.S. Patent No. 4,033,718, the disclosure of which is incorporated herein by reference.
Chlorine-containing agents include organic and/or inorganic compounds capable of having their chlorine liberated in the form of active chlorine on dissolution in water. Typical examples of such chlorine-containing agents include hypochlorites such as alkali metal (calcium and lithium) hypochlorites; chlorinated trisodium phosphate; chlorinated sulfonamides; halogenated hydantoins, such as l,3-dichloro-5,5- dimethylhydantoin; polychlorocyanurates (usually containing alkali metals such as sodium or potassium salts); chlorine-substituted isocyanuric acid; alkali-metal salts of isocyanuric acid, such as potassium or sodium dihydrate; and other anhydrous chlorine-containing agents known in the detergent industry. Suitable biocidal agents include TAED, TAED combined with a persalt, triclosan (5-chloro-2 (2,4-dichloro-phenoxy) phenol)), and quaternary ammonium compounds such as alkyl dimethyl ammonium chlorides, alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides, benzalkonium chloride, parachlorometaxylene and alkyl dimethyl benzyl ammonium chloride. Other biocidal agents include those sold under the trade names BARD AC® and BARQUAT® by the Lonza Group and those sold under the trade name BTC by the Stepan Company.
Suitable optical brighteners include stilbenes such as TINOPAL® AMS, distyrylbiphenyl derivatives such as TINOPAL® CBS-X, stilbene/naphthotriazole blends such as TINOPAL® RA-16, all sold by Ciba Geigy, oxazole derivatives and coumarin brighteners.
Suitable enzymes include any of those known in the art, such as amylolytic, proteolytic or lipolytic type, and those listed in U.S. Patent No. 5,324,649, the disclosure of which is incorporated herein by reference. One preferred protease, sold under the trademark SAVTNASE® by NOVO Industries A/S, is a subtillase from Bacillus lentus. Other suitable enzymes include amylases, lipases, and cellulases, such as ALCALASE® (bacterial protease), EVERLASE® (protein-engineered variant of SAVINASE®), ESPERASE® (bacterial protease), LIPOLASE® (fungal lipase), LIPOLASE ULTRA (Protein-engineered variant of LIPOLASE), LTPOPRIME™ (protein-engineered variant of LIPOLASE), TERMAMYL® (bacterial amylase), BAN (Bacterial Amylase Novo), CELLUZYME®
(fungal enzyme), and CAREZYME® (monocomponent cellulase), sold by Novo Industries A/S.
Compositions according to the present invention can be prepared by any suitable process or combination of processes that yield the desired composition, according to the present invention. The enriched mixture of α-sulfofatty acid esters is typically prepared by one of a variety of methods. In one embodiment, the enriched mixture of α-sulfofatty acid esters is prepared by combining particular chain length fatty acid(s) with a mixture of fatty acids of differing chain lengths. The enriched fatty acid mixture is then esterified and sulfonated to form the enriched mixture of α-sulfofatty acid esters. In another embodiment, the enriched mixture is prepared by combining particular chain length fatty acid ester(s) with a mixture of fatty acid esters of differing chain lengths. The enriched mixture of fatty acid esters is then sulfonated to form the enriched mixture of α-sulfofatty acid esters. In yet another embodiment, the enriched mixture of α-sulfofatty acid esters is prepared by combining particular chain length α-sulfofatty acid ester(s) with a mixture of α-sulfofatty acid esters of differing chain lengths.
In a preferred embodiment, the enriched mixture of α-sulfofatty acid esters are prepared by combining C16-enriched fatty acids, C16-enriched fatty acid alkyl esters, or C16-enriched α-sulfofatty acid esters with a mixture of fatty acids, fatty acid alkyl esters or α -sulfofatty acid esters, respectively. These mixtures are esterified and sulfonated, as necessary, to form an enriched mixture of α-sulfofatty acid esters. The proportions of carbon chain lengths in the mixture are selected according to the desired surfactant properties of the final composition.
One method of preparing an enriched mixture of α-sulfofatty acid esters is to provide a natural fat or oil that includes the preferred chain length fatty acids, and then fractionating the fatty acids to enrich for those preferred chain lengths. Typically, such a natural fat or oil has a significant concentration (at least about 25 percent and preferably about 35 percent) of the preferred chain length fatty acids. For example, a suitable fatty acid source, such as palm stearine oil or tallow, is provided and fed to a separation apparatus, such as a fractionation tower or liquid-liquid extraction. (See, e.g., Perry 's Chemical Engineers ' Handbook (6th Ed.), chapter 15 (1984), the disclosure of which is incorporated herein by reference). The C16-enriched stream exiting the separation apparatus is then combined with a mixture of fatty acids. The enriched mixture of fatty acids is then esterified to make an enriched mixture of fatty acid alkyl esters, which is then sulfonated to form the enriched mixture of α-sulfofatty acid esters. The other stream(s) exiting the separation apparatus can be used in any desired manner. For example, when palm stearine oil is fractionated, the stream containing mostly C16 fatty acids is used to make the α-sulfofatty acid esters while the stream containing mostly C18 fatty acids is used in the process of making an alkanolamide or a polyalkoxylated alkanolamide.
Another method is to prepare fatty acid alkyl esters comprising the preferred fatty acid alkyl esters, such as fatty acid methyl esters, and then fractionating the fatty acid alkyl esters to enrich for preferred chain length fatty acid alkyl esters. Preferably, such fatty acid alkyl esters have a significant concentration (at least about 25 percent and preferably about 35 percent) of the desired fatty acid alkyl esters. For example, a suitable fatty acid alkyl ester source, such as esterified tallow, is provided and fed to a separation apparatus, such as a fractionation tower or liquid-liquid extraction. (See, e.g., Perry's Chemical Engineer ' Handbook (6th Ed.), chapter 15 (1984), the disclosure of which is incorporated herein by reference.) The C16-enriched stream exiting the separation apparatus is then used to make d6-enriched α-sulfofatty acid esters. The other stream(s) exiting the separation apparatus can be used in any desired manner, such as to make alkanolamides or polyalkoxylated alkanolamides.
The enriched α-sulfofatty acid ester mixture can also be prepared by combining a mixture of α-sulfofatty acid esters with the desired chain length α-sulfofatty acid ester(s) to enrich the mixture. For example, a broad cut mixture of α-sulfofatty acid esters from cohune oil, palm kernel oil or coconut oil can be mixed with a narrow range of C_6 (e.g., C14-Ci6-C18) α-sulfofatty acid esters.
Any suitable mixing apparatus can be used to combine the fatty acids, fatty acid alkyl esters or α-sulfofatty acid esters. (See, e.g., Perry 's Chemical Engineers ' Handbook (6th Ed.), chapters 19 and 21 (1984), the disclosure of which is incorporated herein by reference.) In some embodiments, the amounts of different chain lengths can be combined in any suitable ratios. For example, when a first source of fatty acids is palm kernel oil (PKO) and a second source of fatty acids is C16-fatty acids from palm stearine oil (PSO), these two sources are mixed in amounts of about 40-60 weight percent PKO with about 60-40 weight percent C16-enriched PSO, and preferably about 50-55 weight percent PKO with about 50-45 weight percent C16-er_riched PSO. The fatty acids are then esterified to form fatty acid alkyl esters, which are then sulfonated.
In another example, when a first source of fatty acid alkyl esters is esterified palm kernel oil (ePKO) and a second source of fatty acid alkyl esters is esterified, C16- enriched palm stearine oil (ePSO), these two sources are mixed in amounts of about 40-60 weight percent ePKO with about 60-40 weight percent
Figure imgf000013_0001
ePSO, and preferably about 50-55 weight percent ePKO with about 50-45 weight percent C16-enriched ePSO. The enriched mixture of fatty acid alkyl esters is then sulfonated to form the enriched mixture of α-sulfofatty acid esters.
The sulfonation process can be performed according to any sulfonation process as known in the art, such as the processes described in U.S. Patent Nos. 5,587,500; 5,329,030; 5,382,677; 5,384,422; 4,671,900; 4,816,188; and The Journal of American Oil Chemists Society 52:323-29 (1975), the disclosures of which are incorporated herein by reference. Other sulfonation processes known in the art include those processes using both hydrogen peroxide and a halogen bleach in a two step bleaching operation; processes that use ultra purified fatty acid alkyl ester feedstocks along with a single step hydrogen peroxide neutral bleaching process; and re-esterification processes using only hydrogen peroxide acidic bleaching with typical quality fatty acid alkyl ester feedstocks.
The α-sulfofatty acid ester (e.g., a methyl ester sulfonate) is typically prepared by feeding the fatty acid alkyl ester feedstock and SO3 gas to a suitable reactor, such as a falling film reactor. Any source of SO3 gas can be used. For example, to generate SO3 gas, dry air is compressed, cooled, dried and then mixed with liquid sulfur, supplied from a suitable reservoir, to make sulfur dioxide. The sulfur can be uniformly combusted, for example, by using a sulfur burner to control the molar ratio of air to sulfur. The sulfur dioxide is cooled, such as in a double-pipe cooler, prior to being delivered to a catalytic converter where the sulfur dioxide gas is filtered and converted to the sulfur trioxide gas. In the sulfonation reaction, or sulfonator, the molar ratio of the methyl ester feed to the SO3 gas is optimized for sulfonation of the fatty acid alkyl ester feedstock. The step of sulfonation is typically the rapid reaction of the fatty acid alkyl ester with two molecules of SO3 to form an adduct. The second step of the sulfonation reaction, which is usually slower and requires longer time and elevated temperatures, is rearrangement of the adduct to form a fatty acid alkyl ester sulfonic acid, releasing the second molecule of SO3j which then reacts with another fatty acid alkyl ester molecule. The sulfur dioxide gas that is generated in the two-step process can then be removed and can be recycled.
The fatty acid alkyl ester sulfonic acid can optionally be bleached. Because the elevated temperatures in the sulfonation process darken the acid, a bleaching step may be required to lighten the acid to acceptable levels. An advantageous fatty acid alkyl ester sulfonic acid feedstock used in the manufacturing process is a natural oil derivative that has low acid values, a narrow molecular weight distribution, contains little or no paraffinic compounds, and has been hydro genated to reduce the iodine content, thereby reducing the presence of double bonds that cause the dark color when sulfonated. The bleaching process can be carried out in two stages. First, the fatty acid alkyl ester sulfonic acid is reacted with less than about 5 weight percent alkanol, such as methanol, to produce the desired mono-salt and to inhibit formation of the di-salt to less than about 30%. Second, hydrogen peroxide is reacted with the fatty acid alkyl ester sulfonic acid to reduce the color. The order of the two bleaching steps can be changed, as desired. The fatly acid alkyl ester sulfonic acid is typically degassed in an inert gas blanketed flash feed tank to remove oxygen and low molecular compounds.
The fatty acid alkyl ester sulfonic acid is then neutralized to form α-sulfofatty acid ester. The fatty acid alkyl ester sulfonic acid is neutralized with any suitable base that will yield the desired salt. Typically, sodium hydroxide (NaOH) is reacted with fatty acid alkyl ester sulfonic acid to produce sodium α-sulfofatty acid ester.
Finally, the α-sulfofatty acid ester is dried. The product leaving the neutralizer typically contains about 65-70% solids and 10-15%o methanol. The α-sulfofatty acid ester is heated to an elevated temperature and fed to a dryer, preferably a steam-heated vacuum flash dryer, to strip the methanol and water (and other volatile components). The resulting product contains about 2-4% water. This product can optionally be cooled.
In another embodiment, the α-sulfofatty acid ester is optionally partially or fully coated to protect the α-sulfofatty acid ester from moisture and/or minor amount of additional di-salt formation. Such a coating can prevent the contact of bases, moisture, and other di-salt causing substances with the sulfofatty acid. Such a coating can be water- resistant. In such an embodiment, the coating typically has a melting point within normal washing temperatures. The coating can also be water-soluble.
Suitable coatings include, for example, polyvinyl alcohol, partially or fully hydrolyzed polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyvinyl- methylmethacrylate copolymer, maleic acid/acrylic acid copolymer, ethylene/maleic anhydride copolymer, polyethylene glycol, acrylic acid polymer, carboxymethyl cellulose, cellulose ether, paraffin waxes, fatty acids, methyl ester sulfonate, soaps, waxes, water- soluble polymers, water-swellable polymers, or copolymers, salts or mixtures of any of these.
The coating can be applied to the α-sulfofatty acid ester according to techniques conventionally used in the detergent industry. Other techniques for applying coatings, such as those used in the pharmaceutical industry, are also within the scope of the present invention, as will be appreciated by the skilled artisan. Examples of suitable techniques for applying a coating include dip coating, spin coating, spray coating, spray drying (including spray drying using counter-current or co-current techniques), agglomeration and fluid bed drying. Suitable fluid bed dryers include, for example, static, vibrating, high-shear granulating, vacuum fluid bed, tablet pan coating, rotor processing and high speed fluid bed dryers. Following coating at least a portion of the α-sulfofatty acid ester, the coating can be dried, as necessary, to remove excess moisture or other liquid. In another embodiment, the enriched mixture of α-sulfofatty acid esters is combined with other detergent components in any suitable mixing apparatus. Suitable apparatuses include dry blenders, agglomerators, spray drying equipment, fluid bed mixers, or any solid-solid, liquid-solid, or liquid-liquid mixing apparatus known in the art. (See, e.g., Perry 's Chemical Engineers ' Handbook (6th Ed.), chapter 19 (1984).) Water and/or solvents can be added to aid in this mixing process. Further, on exiting the mixing apparatus, the composition is optionally dried and combined with other detergent components as known in the art.
Other embodiments of the present invention are exemplified in the following examples, which illustrate embodiments of the present invention, although the invention is not intended to be limited by or to these examples.
Example 1:
A C16-enriched methyl ester sulfonate was prepared according to the following process. Palm kernel oil ("PKO") and palm stearine oil ("PSO") were separately esterified with an alkanol (e.g., methanol). The esterified palm stearin oil was then fractionated in a tower. The C16 fraction of the palm stearin oil (predominately C16's with small amounts of C14 and C18 chain lengths) was then mixed with the esterified palm kernel oil in a ratio of about 1:1. The mixture was then sulfonated in a falling film reactor. The resulting fatty acid alkyl ester sulfonic acid was reacted with NaOH to obtain an enriched sodium α-sulfofatty acid ester.
Example 2:
A detergent composition (i.e., one with C16-enriched methyl ester sulfonate) is made according to the following process. First, palm kernel oil is esterified with an alkanol (e.g., methanol) to form a first fatty acid alkyl ester. Tallow is esterified with an alkanol (e.g., methanol) to form a second fatty acid alkyl ester. The second tallow fatty acid alkyl ester is then fractionated in a tower. The C16-enriched fatty acid alkyl ester fraction is combined with the first fatty acid alkyl ester (from PKO) in a ratio of about 45-55 weight percent to 55-45 weight percent, respectively. The resulting mixture is then sulfonated in a falling film reactor and the resulting fatty acid alkyl ester sulfonic acid is reacted with NaOH to obtain a sodium α-sulfofatty acid ester. This sodium α-sulfofatty acid ester is then added to other detergent components to obtain a final detergent composition.
Example 3:
A Ci6-enriched methyl ester sulfonate is prepared according to the following process. Palm kernel oil is combined with a Ci6-enriched fraction of fatty acids from tallow. The enriched mixture is then esterified with an alkanol and then sulfonated in a falling film reactor. The resulting fatty acid alkyl ester sulfonic acid is reacted with NaOH to obtain a sodium α-sulfofatty acid ester.
The previous examples are provided to illustrate but not to limit the scope of the claimed inventions. Other variants of the inventions will be readily apparent to those of ordinary skill in the art and encompassed by the appended claims. All publications, patents, patent applications and other references cited herein are hereby incorporated by reference.

Claims

CLAIMS: We claim:
1. A composition, comprising a mixture of α-sulfofatty acid esters and having an enriched α-sulfofatty acid ester concentration.
2. The composition of claim 1 , wherein the mixture is enriched for C16 oc -sulfofatty acid esters.
3. The composition of claim 2, wherein the C16-enriched α-sulfofatty acid ester concentration is at least about 25 weight percent C16-enriched α-sulfofatty acid ester of the total α-sulfofatty acid esters.
4. The composition of claim 2, wherein the C16-enriched α-sulfofatty acid ester concentration is at least about 35 weight percent de-enriched α-sulfofatty acid ester of the total α-sulfofatty acid esters.
5. The composition of claim 2, wherein the Ci 6-enriched α-sulfofatty acid ester concentration is at least about 50 weight percent C16-er_riched α-sulfofatty acid ester of the total α-sulfofatty acid esters.
6. The composition of claim 1, wherein the α-sulfofatty acid esters are derived from natural fats or oils.
7. The composition of claim 1, wherein the α-sulfofatty acid esters are methyl ester sulfonates.
8. The composition of claim 1, wherein the α-sulfofatty acid esters comprise a first and a second α-sulfofatty acid ester.
9. The composition of claim 8, wherein the first α-sulfofatty acid ester is prepared from palm kernel oil, cohune oil or coconut oil, and the second α-sulfofatty acid ester is prepared from palm stearine oil or tallow.
10. The composition of claim 8, wherein the second α-sulfofatty acid ester comprises predominately C16 chain lengths.
11. The composition of claim 8, wherein the first α-sulfofatty acid ester comprises C8, do, C12, C14, C16, and C18 chain lengths and the second α-sulfofatty acid esters comprises predominately C16 chain lengths.
12. A detergent composition, comprising at least about 15 weight percent of a mixture of α-sulfofatty acid esters and having a C16-enriched α-sulfofatty acid ester concentration.
13. The detergent composition of claim 12, wherein the mixture comprises a first α-sulfofatty acid ester comprising C8, do, C12, C14, C16, and C18 chain lengths and a second α-sulfofatty acid ester comprising predominately C16 chain lengths.
14. The detergent composition of claim 13, wherein the second α- sulfofatty acid ester comprises at least about 35 weight percent C16 chain lengths.
15. The detergent composition of claim 13 , wherein the second α- sulfofatty acid ester consists of C16 chain lengths.
16. The detergent composition of claim 12, wherein the mixture of sulfofatty acid esters comprises methyl ester sulfonates.
17. A detergent composition, comprising at least about 35 weight percent of α-sulfofatty acid esters, comprising: a first α-sulfofatty acid ester comprising a mixture of different chain lengths; and a second α-sulfofatty acid ester comprising at least about 35 weight C16 chain lengths.
18. A composition, comprising: about 60 to about 40 weight percent methyl ester sulfonate comprising a mixture of chain lengths; and about 40 to about 60 weight percent methyl ester sulfonate consisting essentially of C16 chain lengths.
19. A method for making a detergent composition, comprising: providing a mixture of α-sulfofatty acid esters with a C16 enriched concentration; and combining the mixture of α-sulfofatty acid esters with at least one other detergent component.
20. The method of claim 19, wherein the α-sulfofatty acid esters comprise methyl ester sulfonates.
21. The method of claim 20, including providing the mixture of α- sulfofatty acid esters by providing a methyl ester feedstock and then sulfonating the methyl ester feed to make the methyl ester sulfonates.
22. The method of claim 21, including sulfonating the methyl ester feedstock by reacting the methyl ester feedstock with gaseous SO3.
23. The method of claim 21 , wherein the methyl ester is prepared from a natural fat or oil.
24. The method of claim 21, further comprising enriching the C16 content of the methyl ester feedstock.
25. The method of claim 21 , further comprising combining a natural fat or oil and a enriched natural fat or oil to form the methyl ester feedstock.
26. The method of claim 25, including combining about 60 to about 40 weight percent of the natural fat or oil with 40 to about 60 weight percent of the enriched natural fat or oil.
27. A method for making a detergent composition, comprising: providing a methyl ester feedstock containing methyl esters having a C16 enriched concentration; sulfonating the methyl ester feedstock to obtain methyl ester sulfonate; and combining the methyl ester sulfonates with at least one other detergent component.
28. The method of claim 27, the methyl ester comprising a first natural fat or oil comprising a mixture of chain lengths and a second natural fat or oil comprising predominately C16 chain lengths.
29. The method of claim 27, further comprising enriching the C16 content of the second natural fat or oil by removing at least some of the non-C16 chain lengths.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007148276A2 (en) * 2006-06-19 2007-12-27 The Procter & Gamble Company Process for manufacturing liquid detergent containing methyl ester sulfonate
WO2007148275A2 (en) * 2006-06-19 2007-12-27 The Procter & Gamble Company Laundry detergent containing methyl ester sulfonate
EP2349989B1 (en) * 2008-10-24 2014-06-18 Cognis IP Management GmbH Mixtures of alkylsulfosuccinates and their use

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6780830B1 (en) * 2000-05-19 2004-08-24 Huish Detergents, Incorporated Post-added α-sulfofatty acid ester compositions and methods of making and using the same
US6683039B1 (en) 2000-05-19 2004-01-27 Huish Detergents, Inc. Detergent compositions containing alpha-sulfofatty acid esters and methods of making and using the same
US6468956B1 (en) * 2000-05-24 2002-10-22 Huish Detergents, Inc. Composition containing α-sulfofatty acid ester and hydrotrope and methods of making and using the same
US20080009430A1 (en) * 2006-06-19 2008-01-10 Hecht Stacie E Surfactants systems for cold water cleaning
CN102939367A (en) 2010-05-14 2013-02-20 太阳产品公司 Polymer-containing cleaning compositions and methods of production and use thereof
KR101891839B1 (en) 2010-08-23 2018-08-24 헨켈 아이피 앤드 홀딩 게엠베하 Unit dose detergent compositions and methods of production and use thereof
EP2751240B1 (en) 2011-09-20 2019-07-24 Henkel IP & Holding GmbH Cleaning formulations with improved surfactant solubility and use thereof
WO2015064746A1 (en) * 2013-10-31 2015-05-07 ライオン株式会社 Surfactant-containing solution
EP3408180A4 (en) 2016-01-29 2019-10-09 Henkel IP & Holding GmbH Multi-compartment detergent compositions and methods of production and use thereof
US10619124B2 (en) 2017-01-06 2020-04-14 Henkel IP & Holding GmbH Color care additive compositions
EP4234663A1 (en) * 2022-02-25 2023-08-30 Basf Se Macaúba oil for the production of oleochemicals
EP4234665A1 (en) * 2022-02-25 2023-08-30 Basf Se Macaúba oil for the production of oleochemicals
WO2023161334A1 (en) * 2022-02-25 2023-08-31 Basf Se Macaúba oil for the production of oleochemicals
EP4234535A1 (en) * 2022-02-25 2023-08-30 Basf Se Macaúba oil for the production of oleochemicals
EP4234534A1 (en) * 2022-02-25 2023-08-30 Basf Se Macaúba oil for the production of oleochemicals

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4671900A (en) 1980-12-19 1987-06-09 Henkel Kommanditgesellschaft Auf Aktien Preparation of light-colored, wash active α-sulfofatty acid
US4816188A (en) 1984-10-20 1989-03-28 Lion Corporation Process for the preparation of saturated/unsaturated mixed fatty acid ester sulfonates
EP0336740A2 (en) * 1988-04-06 1989-10-11 Unilever Plc Detergent composition
US5329030A (en) 1990-11-12 1994-07-12 Henkel Kommanditgesellschaft Auf Aktien Process for the production of concentrated aqueous dispersions of α-sulfofatty acide mono- and/or disalt
US5382677A (en) 1990-05-30 1995-01-17 Henkel Kommanditgesellschaft Auf Aktien Process for the production of highly concentrated pastes of α-sulfofatty acid alkyl ester alkali metal salts
US5384422A (en) 1990-05-30 1995-01-24 Henkel Kommanditgesellschaft Auf Aktien Process for the production of light-colored α-sulfofatty acid alkyl ester alkali metal salt pastes
US5475134A (en) * 1993-12-16 1995-12-12 The Procter & Gamble Co. Process for making sulfonated fatty acid alkyl ester surfactant
US5587500A (en) 1993-09-17 1996-12-24 The Chemithon Corporation Sulfonation of fatty acid esters
US6057280A (en) * 1998-11-19 2000-05-02 Huish Detergents, Inc. Compositions containing α-sulfofatty acid esters and methods of making and using the same

Family Cites Families (74)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2043476A (en) * 1936-06-09 Cabboxylates of aliphatic alcohols
US4033718A (en) 1973-11-27 1977-07-05 The Procter & Gamble Company Photoactivated bleaching process
JPS5331133B2 (en) 1974-04-22 1978-08-31
US3962107A (en) 1974-06-24 1976-06-08 Johnson & Johnson Enzyme-containing denture cleanser tablet
US4064062A (en) 1975-12-15 1977-12-20 Colgate-Palmolive Stabilized activated percompound bleaching compositions and methods for manufacture thereof
GB2041966A (en) * 1977-11-29 1980-09-17 Procter & Gamble Detergent tablet having a hydrated salt coating and process for preparing the tablet
JPS5920718B2 (en) 1980-11-27 1984-05-15 花王株式会社 hypoallergenic cleaning agent
JPS57180699A (en) * 1981-04-30 1982-11-06 Lion Corp Granular detergent composition
JPS58117292A (en) 1981-12-30 1983-07-12 ライオン株式会社 Detergent composition
US4487710A (en) * 1982-03-01 1984-12-11 The Procter & Gamble Company Granular detergents containing anionic surfactant and ethoxylated surfactant solubility aid
US4476043A (en) * 1982-05-13 1984-10-09 Henkel Corporation Surfactant product
US4412934A (en) 1982-06-30 1983-11-01 The Procter & Gamble Company Bleaching compositions
US4483781A (en) 1983-09-02 1984-11-20 The Procter & Gamble Company Magnesium salts of peroxycarboxylic acids
DE3237001A1 (en) 1982-10-06 1984-04-12 Lion Corp., Tokyo Process for the production of a detergent or cleaner with a salt of an alpha -sulpho fatty acid ester
US4597898A (en) * 1982-12-23 1986-07-01 The Proctor & Gamble Company Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
GB8321404D0 (en) 1983-08-09 1983-09-07 Interox Chemicals Ltd Tablets
US4488989A (en) * 1983-11-14 1984-12-18 Lever Brothers Company Aqueous compositions containing urea as a hydrotrope
US4552681A (en) * 1983-12-10 1985-11-12 Henkel Kommanditgesellschaft Auf Aktien Granular, free-flowing detergent component and method for its production
JPS60133095A (en) 1983-12-20 1985-07-16 ライオン株式会社 Granular detergent composition
US4634551A (en) 1985-06-03 1987-01-06 Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain
US5213705A (en) * 1985-04-30 1993-05-25 Ecolab Inc. Encapsulated halogen bleaches and methods of preparation and use
GB8525269D0 (en) * 1985-10-14 1985-11-20 Unilever Plc Detergent composition
DE3545947A1 (en) * 1985-12-23 1987-07-02 Henkel Kgaa PHOSPHATE-FREE, GRANULAR DETERGENT
US4705644A (en) * 1986-03-06 1987-11-10 Colgate Palmolive Company Alpha-sulfo-higher fatty acid-lower alcohol ester- and amide-based detergent laundry bars and process for manufacture thereof
US4915854A (en) 1986-11-14 1990-04-10 The Procter & Gamble Company Ion-pair complex conditioning agent and compositions containing same
US5026400A (en) 1987-08-10 1991-06-25 Colgate-Palmolive Company Built particulate detergent containing a narrow range alcohol ethoxylate and a pet-poet copolymer soil release agent
US4931202A (en) * 1988-07-07 1990-06-05 Diversey Corporation Detergent pellet composition and process therefor
US5380453A (en) * 1988-09-26 1995-01-10 Unichema Chemie B.V. Composition comprising alkyl esters of aliphatic (C8 -C22) monocarboxylic acids and oil in water emulsifier
DK533188D0 (en) * 1988-09-26 1988-09-26 Aarhus Oliefabrik As APPLICATION OF (C1-C5) ALKYL ESTERS OF ALIFATIC (C8-C22) MONOCARBOXYLIC ACIDS FOR THE PURIFICATION OF Grease, PAINT, PRINT COLORS O.L. AND CLEANER CONTAINING SUCH ESTERS
US4973419A (en) 1988-12-30 1990-11-27 Lever Brothers Company, Division Of Conopco, Inc. Hydrated alkali metal phosphate and silicated salt compositions
YU221490A (en) 1989-12-02 1993-10-20 Henkel Kg. PROCEDURE FOR HYDROTHERMAL PRODUCTION OF CRYSTAL SODIUM DISILICATE
US5104567A (en) * 1990-03-27 1992-04-14 A/S Alaska Gruppen Liquid for cleaning off ink from printing machines
DE4017466A1 (en) 1990-05-30 1991-12-05 Henkel Kgaa METHOD FOR PRODUCING LIGHT-COLORED PASTES OF ALPHA SULFAT FATTY ACID ALKYLESTER ALKALIMETAL SALTS
GB9015504D0 (en) * 1990-07-13 1990-08-29 Unilever Plc Detergents composition
US5133892A (en) 1990-10-17 1992-07-28 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing detergent tablets
US5397494A (en) 1990-10-30 1995-03-14 The Procter & Gamble Company Improving the color of surfactant agglomerates by admixing a solid bleaching agent
US5324649A (en) 1991-10-07 1994-06-28 Genencor International, Inc. Enzyme-containing granules coated with hydrolyzed polyvinyl alcohol or copolymer thereof
DE4141584A1 (en) 1991-12-17 1993-06-24 Henkel Kgaa Granulate contg. no alkali and with low residual moisture content
GB9201519D0 (en) * 1992-01-24 1992-03-11 Unilever Plc Detergent compositions
US5637560A (en) 1992-02-12 1997-06-10 Henkel Kommanditgesellschaft Auf Aktien Process for the production of surface-active anionic surfactant salts using superheated steam
US5411596A (en) * 1993-04-01 1995-05-02 Deluxe Corporation Oil based composition clean up method and composition for use therein
US5429773A (en) 1993-02-05 1995-07-04 The Procter & Gamble Company Process to improve alkyl ester sulfonate surfactant compositions
US5968891A (en) * 1993-07-13 1999-10-19 Colgate-Palmolive Co. Process for preparing detergent composition having high bulk density
US5691296A (en) * 1993-07-14 1997-11-25 The Procter & Gamble Company Percarbonate bleach particles coated with a partially hydrated crystalline aluminosilicate flow aid
US5688982A (en) 1993-08-20 1997-11-18 The Procter & Gamble Company No-bleach process for making sulfonated fatty acid alkyl ester surfactant
DE69423225T2 (en) 1993-10-12 2000-06-21 Stepan Co ALPHA SULFONATED METHYL OR ETHYL FATTY ACID ESTER SALTS AND ANIONIC SURFACE ACTIVE AGENTS LIQUID DETERGENT COMPOSITIONS
DE4404279A1 (en) 1994-02-10 1995-08-17 Henkel Kgaa Tablet with builder substances
JP2958506B2 (en) * 1994-06-15 1999-10-06 花王株式会社 Method for producing fine solid builder
WO1996008552A1 (en) * 1994-09-13 1996-03-21 Kao Corporation Washing method and clothes detergent composition
US5624906A (en) * 1994-12-08 1997-04-29 Lever Brothers Company, Division Of Conopco, Inc. Oral hygiene compositions comprising heteroatom containing alkyl aldonamide compounds
US5874393A (en) 1994-12-15 1999-02-23 Colgate-Palmolive Co. Microemulsion light duty liquid cleansing composition
US5482644A (en) * 1995-02-27 1996-01-09 Nguyen; Sach D. Nonirritating liquid detergent compositions
US5980580A (en) * 1995-09-04 1999-11-09 Kao Corporation Washing method and detergent compositions
PL185641B1 (en) * 1995-09-04 2003-06-30 Unilever Nv Detergent compositions and method of obtaining them
DE19533790A1 (en) 1995-09-13 1997-03-20 Henkel Kgaa Process for the preparation of an amorphous alkali silicate with impregnation
US5945394A (en) 1995-09-18 1999-08-31 Stepan Company Heavy duty liquid detergent compositions comprising salts of α-sulfonated fatty acid methyl esters and use of α-sulphonated fatty acid salts to inhibit redeposition of soil on fabric
JPH09175010A (en) * 1995-12-27 1997-07-08 Tomoegawa Paper Co Ltd Ink jet recording sheet
CA2248160C (en) * 1996-03-08 2002-08-06 The Procter & Gamble Company Preparation of secondary alkyl sulfate particles with improved solubility
US6013611A (en) * 1996-08-26 2000-01-11 Colgate Palmolive Company Light duty liquid cleaning compositions
US5783540A (en) * 1996-12-23 1998-07-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets delivering a rinse aid benefit
US6034045A (en) 1997-02-25 2000-03-07 Church & Dwight Co., Inc. Liquid laundry detergent composition containing a completely or partially neutralized carboxylic acid-containing polymer
US5972861A (en) 1997-03-27 1999-10-26 Corporacion Cressida Laundry detergent bar containing soap, and methylester sulfonate surfactants
GB9711356D0 (en) 1997-05-30 1997-07-30 Unilever Plc Particulate detergent composition
US5965500A (en) * 1997-07-24 1999-10-12 Levers Brothers Company, Division Of Conopco, Inc. Stable liquid composition comprising high levels of emollients
US5965508A (en) * 1997-10-21 1999-10-12 Stepan Company Soap bar compositions comprising alpha sulfonated fatty acid alkyl esters and long chain fatty acids
US5851976A (en) * 1997-12-08 1998-12-22 Colgate Palmolive Company Microemulsion all purpose liquid cleaning compositions
US6060440A (en) 1999-10-12 2000-05-09 Colgate-Palmolive Co. Homogenous solution of an alpha olefin sulfonate surfactant
US6407050B1 (en) 2000-01-11 2002-06-18 Huish Detergents, Inc. α-sulfofatty acid methyl ester laundry detergent composition with reduced builder deposits
US6683039B1 (en) 2000-05-19 2004-01-27 Huish Detergents, Inc. Detergent compositions containing alpha-sulfofatty acid esters and methods of making and using the same
US6534464B1 (en) 2000-05-19 2003-03-18 Huish Detergents, Inc. Compositions containing α-sulfofatty acid ester and polyalkoxylated alkanolamide and methods of making and using the same
US6780830B1 (en) 2000-05-19 2004-08-24 Huish Detergents, Incorporated Post-added α-sulfofatty acid ester compositions and methods of making and using the same
US6468956B1 (en) 2000-05-24 2002-10-22 Huish Detergents, Inc. Composition containing α-sulfofatty acid ester and hydrotrope and methods of making and using the same
US6509310B1 (en) 2000-06-01 2003-01-21 Huish Detergents, Inc. Compositions containing α-sulfofatty acid esters and method of making the same
US6764989B1 (en) 2000-10-02 2004-07-20 Huish Detergents, Inc. Liquid cleaning composition containing α-sulfofatty acid ester

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4671900A (en) 1980-12-19 1987-06-09 Henkel Kommanditgesellschaft Auf Aktien Preparation of light-colored, wash active α-sulfofatty acid
US4816188A (en) 1984-10-20 1989-03-28 Lion Corporation Process for the preparation of saturated/unsaturated mixed fatty acid ester sulfonates
EP0336740A2 (en) * 1988-04-06 1989-10-11 Unilever Plc Detergent composition
US5382677A (en) 1990-05-30 1995-01-17 Henkel Kommanditgesellschaft Auf Aktien Process for the production of highly concentrated pastes of α-sulfofatty acid alkyl ester alkali metal salts
US5384422A (en) 1990-05-30 1995-01-24 Henkel Kommanditgesellschaft Auf Aktien Process for the production of light-colored α-sulfofatty acid alkyl ester alkali metal salt pastes
US5329030A (en) 1990-11-12 1994-07-12 Henkel Kommanditgesellschaft Auf Aktien Process for the production of concentrated aqueous dispersions of α-sulfofatty acide mono- and/or disalt
US5587500A (en) 1993-09-17 1996-12-24 The Chemithon Corporation Sulfonation of fatty acid esters
US5475134A (en) * 1993-12-16 1995-12-12 The Procter & Gamble Co. Process for making sulfonated fatty acid alkyl ester surfactant
US6057280A (en) * 1998-11-19 2000-05-02 Huish Detergents, Inc. Compositions containing α-sulfofatty acid esters and methods of making and using the same

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"Nonionic Surfactants", 1967, M. DEKKER
"PERRY'S CHEMICAL ENGINEERS' HANDBOOK", 1984
"Perry's Chemical Engineers", 1984
MCCUTCHEON'S: "Emulsifiers & Detergents", 1989, M. C. PUBLISHING CO.
SCHWARTZ; PERRY; BERCH: "Surface Active Agents", INTERSCIENCE PUBLISHERS
THE JOURNAL OF AMERICAN OIL CHEMISTS SOCIETY, vol. 52, 1975, pages 323 - 29

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007148276A2 (en) * 2006-06-19 2007-12-27 The Procter & Gamble Company Process for manufacturing liquid detergent containing methyl ester sulfonate
WO2007148275A2 (en) * 2006-06-19 2007-12-27 The Procter & Gamble Company Laundry detergent containing methyl ester sulfonate
WO2007148276A3 (en) * 2006-06-19 2008-02-21 Procter & Gamble Process for manufacturing liquid detergent containing methyl ester sulfonate
WO2007148275A3 (en) * 2006-06-19 2008-03-06 Procter & Gamble Laundry detergent containing methyl ester sulfonate
EP2349989B1 (en) * 2008-10-24 2014-06-18 Cognis IP Management GmbH Mixtures of alkylsulfosuccinates and their use

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