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WO2000040551A1 - Procede de fabrication d'un tensioactif a base d'alkyl-benzene sulfonate lineaire et compositions de nettoyage contenant ces compositions - Google Patents

Procede de fabrication d'un tensioactif a base d'alkyl-benzene sulfonate lineaire et compositions de nettoyage contenant ces compositions Download PDF

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Publication number
WO2000040551A1
WO2000040551A1 PCT/US1999/000211 US9900211W WO0040551A1 WO 2000040551 A1 WO2000040551 A1 WO 2000040551A1 US 9900211 W US9900211 W US 9900211W WO 0040551 A1 WO0040551 A1 WO 0040551A1
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Prior art keywords
alkyl benzene
linear alkyl
added
precursor
benzene sulfonate
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English (en)
Inventor
Hsiang-Kuen Mao
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to PCT/US1999/000211 priority Critical patent/WO2000040551A1/fr
Priority to AU24518/99A priority patent/AU2451899A/en
Publication of WO2000040551A1 publication Critical patent/WO2000040551A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising

Definitions

  • the present invention relates to anionic surfactants useful in cleaning compositions. Specifically, the present invention relates to a linear alkyl benzene sulfonate surfactant, a process for making said linear alkyl benzene sulfonate surfactant, and a cleaning composition containing said linear alkyl benzene sulfonate surfactant.
  • Surfactants especially anionic surfactants, are well known to provide cleaning and detersive benefits.
  • Certain surfactants such as anionic surfactants, are especially useful in cleaning compositions, as they contain a hydrophobic portion which may attach to soils, and a hydrophilic portion which hydrogen bonds to water.
  • Typical anionic surfactants include soaps and non-soap surfactants.
  • Linear alkyl benzene sulfonate (LAS) is a common non-soap anionic surfactant in cleaning compositions, and especially laundry detergent compositions, as it provides excellent soil removal benefits, and is widely available. Recently, greater attention has been paid to the environment by society, corporations, and governments. Thus, it has become highly desirable to increase the biodegradability of cleaning products, such as detergent compositions.
  • paraffin and benzene from, for example, crude oil are typically combined in a catalytic process to produce linear alkyl benzene (LAB ⁇
  • the catalytic processes for producing LAB include catalysts containing, for example, aluminum chloride, hydrofluoric acid, and fluorine-containing mordenite.
  • the LAB is sulfonated with sulfuric acid and/or sulfur trioxide to produce a linear alkyl benzene acid active. This is subsequently neutralized with an alkaline material, to produce the corresponding alkaline salt of LAS, such as the sodium salt of LAS.
  • DBB dialkyl bi-cyclic benzene
  • the DBB content in LAB typically ranges from 2% to 8%, or more.
  • DBBS dialkyl bi-cyclic benzene sulfonate
  • DBB dialkyl bi-cyclic benzene sulfonate
  • LAS n-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoeth
  • the most hydrophobic alkyl chain is achieved when the benzene ring is attached to the alkyl chain at the 2- position, because this provides the longest hydrophobic "tail.”
  • Such an LAS is described as the "2-phenyl LAS" isomer and possesses improved surfactancy as compared to corresponding isomers where the benzene moiety is attached to the alkyl chain at, for example, the 3 or 4 positions. Such improved surfactancy may result in improved removal of hydrophobic soils from clothing.
  • the typical LAB used to form LAS contains a distribution of various LAB isomers, such as 2-phenyl LAB, 3-phenyl LAB, 4-phenyl LAB, etc.
  • the LAS crystals having such a high proportion of the 2-phenyl isomer easily form gels which result in a slower dissolution rate.
  • slow dissolution rates are unacceptable to consumers, as more rapid cleaning processes are typically preferable to slower cleaning processes.
  • LAS having such a uniform lattice structure is more difficult to process than corresponding surfactants containing a distribution of isomers
  • the need remains for a process for forming a linear alkyl benzene sulfonate surfactant having improved surfactancy, increased biodegradability, easier processing, and which also maintains an acceptable dissolution rate.
  • the need also remains for a cleaning composition comprising such a surfactant.
  • a linear alkyl benzene sulfonate surfactant may be formed which possesses improved surfactancy, increased biodegradability, and an acceptable dissolution rate. It has also been found that a cleaning composition containing such a linear alkyl benzene sulfonate surfactant may have one or more of the benefits described above.
  • the present invention relates to a process for forming a linear alkyl benzene sulfonate surfactant containing the steps of providing a linear alkyl benzene, providing an effective amount of an added hydrotrope precursor, combining the linear alkyl benzene and the hydrotrope precursor to form a precursor mixture, and sulfonating the precursor mixture to form a linear alkyl benzene acid active.
  • An alkaline material is also provided and used to neutralize the linear alkyl benzene acid active so as to form a linear alkyl benzene sulfonate surfactant.
  • the linear alkyl benzene provided herein has at least about 30 molar % 2-phenyl isomer and less than about 5 weight % dialkyl bi-cyclic benzene impurities.
  • the present invention also relates to a cleaning composition containing a linear alkyl benzene sulfonate surfactant and the balance adjunct materials.
  • the linear alkyl benzene sulfonate surfactant contains at least about 30 molar % * 2- phenyl isomer, less than about 5 weight % dialkyl bi-cyclic benzene sulfonate impurities, and an effective amount of an added hydrotrope.
  • the present invention also relates to a process for forming a linear alkyl benzene sulfonate surfactant containing the steps of providing a linear alkyl benzene, sulfonating the linear alkyl benzene to form a linear alkyl benzene acid active, providing an effective amount of an added hydrotrope precursor, and combining the linear alkyl benzene acid active with the added hydrotrope precursor to form an acid mixture.
  • An alkaline material is also provided and used to neutralize the acid mixture so as to form a linear alkyl benzene sulfonate surfactant.
  • the linear alkyl benzene provided herein has at least about 30 molar % 2-phenyl isomer and less than about 5 weight % dialkyl bi-cyclic benzene impurities.
  • the added hydrotrope precursor is selected from a non-sulfonatable added hydrotrope precursor, a sulfonatable added hydrotrope precursor, and mixtures thereof, wherein the sulfonatable added hydrotrope precursor is selected from a paraffin, an alkyl benzene, an alpha olefin, a methyl or ethyl ester of a carboxylic acid, and mixtures thereof in its sulfonated acid form.
  • a linear alkyl benzene sulfonate surfactant may be formed which provides improved surfactancy as well as increased biodegradability.
  • Such a surfactant may also possess one or more other benefits, such as a more rapid dissolution rate, and easier processing. It has also surprisingly been found that when included into a cleaning composition, such a surfactant may provide one or more of the benefits described above.
  • alkyl means a hydrocarbyl moiety which is straight or branched, saturated or unsaturated. Unless otherwise specified, alkyl moieties are preferably saturated or unsaturated with double bonds, preferably with less than two double bonds. Included in the term “alkyl” is the alkyl portion of acyl groups.
  • linear as used herein, with respect to LAB and/or LAS, indicates that the alkyl portions thereof contain less than about 30%, preferably less than bout 20%, more preferably less than about 10% branched alkyl chains.
  • substantially free indicates that the amounts of such impurities are insufficient to contribute positively or negatively to the cleaning effectiveness of the composition.
  • the present invention preferably contains, by weight, less than about 5%, more preferably less than about 2%, and even more preferably less than about 0.5% of the indicated material.
  • the detergent industry has responded by, for example, reducing the DBBS levels in their formulations, developing processes to reduce the proportion of DBB produced in the LAB production process, etc.
  • the DBB themselves become excellent hydrotropes when sulfonated along with linear alkyl benzene when the surfactant is included in a solid composition.
  • an increase of 2-phenyl isomer in LAS and a reduction of the DBBS content results in an increase in gel formation.
  • the dissolution rate i.e., the rate of dissolving
  • Such gel formation and lowered dissolution rate are usually undesirable.
  • the present invention has recognized the need for an added hydrotrope precursor to be added to the LAB herein.
  • a hydrotrope is preferably added as the precursor into LAB and then sulfonated along with the LAB to form a LAS surfactant which has an acceptable dissolution rate.
  • the typical commercially-available LAB is a mixture of 2-phenyl isomers,
  • a LAB and/or LAS is provided herein which has at least about 30 molar % 2-phenyl isomer, preferably at least 40 molar % 2-phenyl isomer, more preferably at least 50 molar % 2-phenyl isomer, and even more preferably at least 60% 2-phenyl isomer.
  • the cleaning compositions herein typically comprise from about 1 % to about 99%, preferably from about 5% to about 70%, and more preferably from about 10% to about 50% LAS as described herein, by weight of the final composition.
  • Such molar percentages of 2-phenyl isomers in the LAB and/or LAS provide the improved surfactancy desired in the present invention.
  • compositional parameters of conventional LAB and LAS See, for example Surfactant Science Series, Volume 40, Chapter 7 and Surfactant Science Series, Volume 73, Chapter 7. Typically this is done by GC and/or GC-mass spectroscopy for the alkyl benzenes and HPLC for the alkyl benzene sulfonates or sulfonic acids; 13 C NMR is also commonly used. Another common practice is desulfonation. This permits GC and/or GC-mass spectroscopy to be used, since desulfonation converts the sulfonates or sulfonic acids to the alkyl benzenes which are tractable by such methods.
  • a preferred method is to prepare LAB sample solution at 100 mg/ml concentration by dissolving 0.5 g of LAB sample in 5 ml of n-hexane. 1 ⁇ L of this solution is then injected into a GC/MS equipped with an ionization detector. The resulting chromatogram is analyzed based on the MS results. The minor peaks in-between all linear alkyl benzene species are summarized and calculated as the sum of the DBB impurities, including dialkyl tetralins and dialkyl indans.
  • the GC/MS instrument suitable for such analysis can be HP 5890 II GC/HP 5971 MSD (ANI-59).
  • the GC/FID system can be HP 5890 II GC (ANI- 61).
  • the column is kept at 100 °C for 1 minute then increased to 180 °C at 2 °C/min.
  • the FIC is operated at 70 eV.
  • the mass scan was done in between 50 to 500 m/z at 3 scans/sec.
  • the sample injection was done with a splitter at a ratio of 100 to 1.
  • the system can be operated at 120 kPa helium carrier gas with all other parameters staying the same.
  • the DBB impurities are formed in the LAB production process when an alkyl chain interacts twice with a benzene moiety.
  • Typical dialkyl bi-cyclic benzene impurities have the following structures:
  • the LAB provided herein also contains, by weight of the LAB, less than about 5 weight % DBB impurities, preferably less than about 3 weight % DBB impurities, more preferably less than about 2 weight % DBB impurities, and even more preferably less than about 1 weight % DBB impurities.
  • the LAB herein contains, by weight of the LAB, less than about 2.5 weight % dialkyl tetralin impurities, preferably less than about 1.3 weight % dialkyl tetralin impurities, and more preferably less than about 0.5% dialkyl tetralin impurities.
  • the LAB herein is substantially free of DBB impurities.
  • the weight % of DBB impurities such as dialkyl tetralins and dialkyl indans may be determined by methods such as GC, or HPLC.
  • a preferred method for measuring the DBB content of a LAB sample and/or the DBBS impurities content of a LAS sample is to analyze r -Its chromatogram by gas chromatography of desulfonated LAS or its starting LAB, as described above.
  • the targeted molecules of various isomers of LAB can be easily identified by those skilled in the art.
  • the summary amount of the minor peaks in between the targeted LAB peaks measures the DBB impurities, including dialkyl tetralins and dialkyl indans.
  • the LAS herein contains, by weight of the LAS, less than about 5 weight % DBBS impurities, preferably less than about 3 weight % DBBS impurities, more preferably less than about 2 weight % DBBS impurities, and even more preferably less than about 1 weight % DBBS impurities.
  • the LAS herein contains, by weight of the LAS, less than about 2.5 weight % dialkyl tetralin sulfonate impurities, preferably less than about 1.3 weight % dialkyl tetralin sulfonate impurities, and more preferably less than about 0.5% dialkyl tetralin sulfonate impurities.
  • the LAS herein is substantially free of DBBS impurities.
  • the LAB and/or LAS useful herein has from about 8 to about 22, preferably from about 8 to about 18, and more preferably from about 10 to about 16 carbon atoms in the alkyl group, for example, the C 10 . 16 linear alkyl benzenes and C 10 . 16 linear alkyl benzene sulfonates.
  • the LAS suitable for use herein includes the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts of organic sulfuric reaction products having in their molecular structure an alkyl group containing from ab ⁇ ut 8 to about 22 carbon atoms, as described above, and a sulfonic acid group.
  • the LAS-alkali metal salts, particularly the sodium salts, the potassium salts, or mixtures thereof are preferred.
  • the DBB content also leads to problems when a highly uniform surfactant, such as the LAS of the present invention is used.
  • the DBBS e.g., dialkyl tetralin sulfonate, dialkyl indan sulfonate, etc.
  • act as excellent hydrotropes for LAS Accordingly, it has herein been recognized that reducing the DBBS content in the LAS for environmental reasons leads to an increase in gel formation and a corresponding drop in the dissolution rate of the surfactant. As discussed below, this reduction in the DBBS content also results in a significant increase in paste viscosity during processing.
  • the biodegradability of the highly soluble LAS surfactant described herein makes it highly desirable as a surfactant in any cleaning composition form, such as solids, pastes, and liquids.
  • the highly soluble LAS surfactant is especially useful in solid forms such as detergent tablets, detergent pastes, detergent bars, high and low density detergent agglomerates, high and low density detergent granules, granulated household cleaners, and general purpose cleaners.
  • High dissolution rates are especially desirable for high density laundry granules which are becoming increasingly popular both commercially and environmentally.
  • Granular household cleaners i.e., floor cleaners, can also benefit from this increased solubility.
  • an effeGte/e amount of an added hydrotrope and/or an added hydrotrope precursor should be provided to improve the dissolution rate and processing of the highly crystalline LAS described herein.
  • the effective amount of the added hydrotrope and/or the added hydrotrope precursor serves to increase the dissolution rate of the surfactant and/or the cleaning composition to a rate acceptable by consumers.
  • the effective amount of the added hydrotrope and/or the added hydrotrope precursor may also ease processing, such as by lowering the viscosity of the LAS surfactant slurry during processing.
  • the "effective amount" of added hydrotrope precursor useful herein is preferably at least about 0.1%, more preferably from about 1% to about 90%, and even more preferably from about 1% to about 30%, by weight of the LAB, or by weight of the linear alkyl benzene acid active.
  • an effective amount of an added hydrotrope may be provided and added to the LAS described herein, or a composition containing the LAS described herein.
  • the "effective amount" of added hydrotrope useful herein is preferably at least about 0.1%, more preferably from about 1 % to about 90%, and even more preferably from about 1 % to about 30%, by weight of the LAS.
  • the "added hydrotrope precursor” herein is a hydrotrope precursor which is deliberately added to the LAB and/or the linear alkyl benzene acid active described herein. This term is not intended to include those hydrotrope precursors which are present solely as by-products of the LAB production process. However, if a compound is present as a by-product, and additional amounts of this same compound are added to the LAB as a hydrotrope precursor, then these additional amounts added would be considered an "added hydrotrope precursor" herein.
  • the "added hydrotrope" herein is a hydrotrope which is deliberately added to the LAB, linear alkyl benzene acid active, LAS, and/or a composition containing the LAS, and is not intended to include those hydrotropes which are present solely as by-products of the LAB production process.
  • a compound is present as a by-product, and additional amounts of this same compound are added to the LAB, linear alkyl benzene acid active, LAS, and/or a composition containing the LAS as a hydrotrope, then these additional amounts added would be considered an
  • any added hydrotrope precursor and/or added hydrotrope be biodegradable, preferably at least as biodegradable as the LAS parent compound. — »
  • the added hydrotrope precursor useful herein may be either branched, linear, aromatic, or a mixture thereof. Linear added hydrotropes having an attached aromatic moiety are preferred herein.
  • the added hydrotrope precursor includes non-sulfonatable added hydrotrope precursors and sulfonatable added hydrotrope precursors having sulfonatable functional groups, such as an alkyl benzene, an olefin (e.g., an alpha olefin or an internal olefin) with at least one carbon-carbon double bond, a methyl or ethyl ester of a carboxylic acid, an alkyl alcohol, and mixtures thereof.
  • an alkyl benzene an olefin (e.g., an alpha olefin or an internal olefin) with at least one carbon-carbon double bond, a methyl or ethyl ester of a carboxylic acid, an alkyl alcohol, and mixtures thereof.
  • alkyls and alkyl benzenes useful herein as added hydrotrope precursors typically contain from about 1 to about 8 carbon atoms in their alkyl chains, while the olefins, methyl or ethyl esters, and alkyl alcohols typically contain less than or equal to about 10 carbon atoms therein.
  • Nonlimiting examples of a preferred added hydrotrope precursor includes toluene, xylene, cumene, naphthalene, octene, hexene, ethylhexene, octyl benzene, hexyl benzene, methyl octanoate, ethyl octanoate, methyl hexanoate, octanol hexanol, ethylhexanol, and mixtures thereof.
  • the added hydrotrope precursor as described herein also includes the sulfonated, but not yet neutralized forms of the above-described compounds.
  • Other non-sulfonatable added hydrotrope precursors include octanol ethoxylates, hexanol ethoxylates, ethylhexanol ethoxylates, secondary alcohol ethoxylates, octanol monoglyceride, hexanol monoglycehde, ethylhexanol glyceride, octyl glycoside or di-glycosides, octanoic mono-amine glucose amide, hexanoic mono-amine glucose amide, paraffin sulfonates and paraffin sulfonic acids, amine oxides and mixtures thereof.
  • added hydrotrope precursors are widely available from most detergent raw material suppliers, such as Basis Petroleum; Exxon; Texaco of Houston, Texas, U. S. A.; Petroquimica Uniao Sa of San Paulo, Brazil; Fina Oil of Dallas, Texas, U. S. A.; etc.
  • the added hydrotrope precursor useful herein is preferably sulfonated to form an added hydrotrope for the LAS described herein.
  • the added hydrotrope may not require sulfonation because it is either already sulfonated, or simply does not require sulfonation to act as a hydrotrope.
  • the preferred added hydrotrope useful herein includes the sulfonated alkali metal and ammonium salts of the above-mentioned added hydrotrope precursors.
  • the added hydrotrope useful herein includes a paraffin sulfonate, an alkyl benzene sulfonate, an olefin sulfonate, a methyl or ethyl ester sulfonate, an alkyl sulphate, non-sulfonated added hydrotropes,-afid mixtures thereof.
  • the added hydrotropes may be added to the cleaning composition at any step in the cleaning composition production process, provided that the added hydrotropes are allowed to mix with the LAS raw material (e.g., the LAB, and/or the linear alkyl benzene acid active) thoroughly.
  • the LAS raw material e.g., the LAB, and/or the linear alkyl benzene acid active
  • Nonlimiting examples of preferred added hydrotropes include the alkali metal, alkali earth metal, and ammonium salts, preferably the sodium, potassium, ammonium, and magnesium salts of toluene sulfonate, xylene sulfonate, cumene sulfonate, naphthalene sulfonate, octanol sulfate, hexanol sulfate, ethylhexanol sulfate, and mixtures thereof.
  • the added hydrotrope may be formed along with the LAS or may be provided and added thereto. Such added hydrotropes are commonly available from, for example, Rutgers Organics Corp. in U.S.A.; Albright & Wilson Corporation, of U.K.; and Marchon Corporation, of France or Italy.
  • LAS as described herein may be formed, an added hydrotrope then added thereto, and then the entire mix may be combined with adjunct materials to form a cleaning composition.
  • an added hydrotrope precursor is provided and combined with the LAB described herein to form a precursor mixture.
  • the LAB and the hydrotrope precursor may be combined via mixing, blending, or homogenizing; preferably the hydrotrope and the LAB are evenly dispersed or dissolved in each other to form a homogenized precursor mixture.
  • Such combining of the added hydrotrope precursor with the LAS may take place in a mixer, blender, storage tank, or combination thereof.
  • the desired hydrotrope precursor may be added by, for example, the LAB manufacturers before shipping the LAB to the LAS sulfonators or detergent manufacturers. Since the preferred hydrotrope precursors are soluble in LAB, any common liquid blending process would be applicable to this operation.
  • the LAB or in the preferred process, the precursor mixture, is then sulfonated to form a linear alkyl benzene acid active containing the sulfonate or sulfated hydrotropes.
  • a linear alkyl benzene acid active containing the sulfonate or sulfated hydrotropes.
  • Such a process which sulfonates both the added hydrotrope precursors and the LAB described herein at the same time is especially advantageous in that it avoids potential difficulties in mixing the added hydrotrope with an already-formed LAS as described above, and provides a molecular level of mixing between the hydrotropes and the LAS to maximize the effect of the hydrotropes.
  • this sulfonation step may be accomplished using any of the well-known sulfonation systems and equipment, including those described in "Detergent Manufacture Including Zeolite Builders and other New Materials", Ed. Sittig., Noyes Data Corp. (1979), as well as in Vol.
  • the resulting linear alkyl benzene acid active may be stored and/or used directly in a detergent manufacturing process, provided that the selected hydrotropes do not include the sulfate types.
  • these sulfated hydrotropes i.e., alcohol sulfuric acids, are not long- term storage stable.
  • Such sulfated hydrotropes should be neutralized and used as a high-pH paste for storage and follow-up processing.
  • the starting material of the present invention will be the linear alkyl benzene acid active, rather than the LAB itself.
  • an already sulfonated added hydrotrope precursor is added to the linear alkyl benzene acid active, to form an acid mixture.
  • any of the above added hydrotrope precursors are useful herein, except for the alkyl alcohol.
  • the added hydrotrope precursor is selected from a non-sulfonatable added hydrotrope precursors, a sulfonatable added hydrotrope precursor, and mixtures thereof in its sulfonated acid form, wherein the sulfonatable added hydrotrope precursor is selected from an alkyl benzene, an olefin, a methyl or ethyl ester of a carboxylic acid, and mixtures thereof.
  • alcohol sulfuric acids are not preferred, as they are not long-term storage stable, and must be used and neutralized virtually immediately after the formation thereof. This precursor mixture is then neutralized by an alkaline material to form the LAS of the present invention.
  • any convenient workup steps may be used in the present process.
  • the common practice after sulfonation is to neutralize the linear alkyl benzene acid active with any suitable alkaline material, as described below.
  • the invention encompasses any of these derivative forms of the LAS as produced by the present process and their use in a cleaning composition.
  • the linear alkyl benzene acid active may be added directly to acidic cleaning products, or may be mixed with cleaning ingredients and then neutralized with an alkaline material contained therein.
  • an alkaline material is also provided.
  • the linear alkyl benzene acid active is subsequently neutralized with the alkaline material to form a linear alkyl benzene sulfonate surfactant which already contains the added hydrotrope therein.
  • the alkaline material provided herein may neutralize the linear alkyl benzene acid active in a separate neutralization step, or may comprise an adjunct material contained in the cleaning composition, to which the linear alkyl benzene acid active is added.
  • the alkaline material useful herein is typically provided in at least a stoichiometric molar ratio sufficient to completely neutralize the linear alkyl benzene acid active, more preferably, the alkaline material is in stoichiometric excess.
  • the preferred stoichiometric molar ratio of alkaline material to linear alkyl benzene acid active is at least 1 :1 , more preferably at least 1.2:1. In certain processes, such as an agglomeration process, this stoichiometric molar ratio of alkaline material to linear alkyl benzene acid active may reach 8:1 , or more.
  • the alkaline material useful herein is typically selected from the alkali metal and alkali earth metal salts of, for example, carbonate, phosphate, silicate, layered silicate, hydroxide, and mixtures thereof.
  • the carbonate useful herein include the bicarbonates and sesquicarbonates, more preferably, sodium carbonate (L ⁇ -, soda ash), potassium carbonate, and mixtures thereof.
  • alkali and alkali earth metal phosphates are especially useful herein as they may serve the dual purpose of acting as an alkaline material, as well as a builder. If present, the builder may assist in controlling mineral hardness and in the removal of particulate soils.
  • Preferred phosphates useful herein include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, and mixtures thereof.
  • the cleaning composition is substantially free of phosphate, such that the cleaning composition contains less than 10% preferably less than 1% phosphate.
  • alkali metal and alkali earth metal silicate and layered silicate are also useful herein.
  • silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst-Clariant (commonly abbreviated herein as "SKS-6").
  • SKS-6 has the delta-Na2Si ⁇ 5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ + ⁇ -y ⁇ O wherein M is sodium or hydrogen, x is a number from 1.9 to
  • layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
  • NaSKS-11 as the alpha, beta and gamma forms.
  • delta- Na2Si ⁇ 5 (SKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • the hydroxide useful herein is preferably sodium hydroxide or potassium hydroxide, such as is used in a caustic neutralization process.
  • an aqueous solution of caustic sodium hydroxide is added to the mixer, in a neutralization step.
  • the neutralization step may take place in any appropriate container, but is preferably conducted in a mixer, a crutcher, a mill, or a combination thereof, flqe neutralization step preferably homogenizes the linear alkyl benzene acid active with the alkaline material to form the linear alkyl benzene sulfonate surfactant of the present invention.
  • flqe neutralization step preferably homogenizes the linear alkyl benzene acid active with the alkaline material to form the linear alkyl benzene sulfonate surfactant of the present invention.
  • One or more adjunct materials discussed below may also be present during the neutralization step, and homogenized therein.
  • the neutralization of the linear alkyl benzene acid active is substantially completed in the neutralization step to form a water-soluble salt of the linear alkyl benzene sulfonate surfactant described herein.
  • An alternate neutralization process is to spray the linear alkyl benzene acid active directly onto a bed of caustic alkaline materials containing, but not limited to, soda ash, sodium hydroxide, potassium hydroxide, magnesium hydroxide, silicates, layered silicates, chained silicates, phosphates, pyrophosphates, thpolyphosphates, organic amines, and mixtures thereof, followed by physical mixing, to assist in neutralization.
  • the resulting neutralized surfactant paste containing the LAS of the present invention may then be further stored and/or processed according to methods known in the art. Adjunct materials may be added to the LAB and/or the LAS of the present invention, to provide other cleaning and/or aesthetic benefits.
  • the LAS described herein may be further processed to form a solid, paste, and/or liquid cleaning compositions, with one or more pieces of equipment known in the art, such as: a blender, a mill, a crutcher, a batch mixer, an agglomerator, a mixer/densifier, a spray drying tower, a refining plodder, a vacuum tunnel, etc.
  • a blender a mill
  • a crutcher a batch mixer
  • an agglomerator a mixer/densifier
  • spray drying tower a refining plodder
  • refining plodder a vacuum tunnel, etc.
  • specific production processes and equipment useful in making such cleaning compositions are also well known.
  • the linear alkyl benzene acid active is added to an alkaline material to form a slurry. This typically takes place within a mixer or apparatus which homogenizes the slurry.
  • the slurry is then formed into a cleaning composition by, for example, spray drying, or agglomeration processes known in the art.
  • the slurry is formed into spray-dried granules in a conventional spray drying tower operated at an inlet temperature range of from about 180°C to about 450°C.
  • a known apparatus operates by spraying the slurry via nozzles into a counter-current (or co-current) stream of hot air which dries the slurry and ultimately forms porous spray-dried granules.
  • the cleaning composition of the present invention contains a linear alkyl benzene sulfonate surfactant as described herein, and the balance adjunct materials.
  • the cleaning composition is preferably in the form of a solid composition.
  • Typical preferred adjunct materials useful herein include a bleach, a builder, a chelating agent, an enzyme, other surfactants, and mixtures thereof.
  • the bleach useful herein is typically a bleach precursor product, but may include an actual bleach, such as, for example, a hypochlorite bleach or a preformed peroxygen acid.
  • a bleach precursor product containing an active oxygen source is provided herein.
  • the active oxygen source useful herein includes compounds which form available peroxyacid oxygen when exposed to a bleach activator, an alkalinity source, and moisture.
  • An active oxygen source can be hydrophilic, hydrophobic, or both.
  • the active oxygen source useful in the present invention can be any of the oxidizing agents known for laundry, hard surface cleaning, automatic dishwashing, or denture cleaning purposes, including oxygen.
  • a preferred active oxygen source of the peroxygen type includes hydrogen peroxide, inorganic per-compounds, inorganic peroxohydrates, organic peroxohydrates, and mixtures thereof; a more preferred active oxygen source includes hydrogen peroxide, perborate, percarbonate, and mixtures thereof. If present, an active oxygen source will typically be at a level of from about 1% to about 90%, more typically from about 3% to about 50%, of the cleaning product, especially for fabric laundering.
  • a bleach activator may comprise an alkalinity source, either alone, or in conjunction with amides, imides, esters, anhydrides, and mixtures thereof.
  • at least one substituted or unsubstituted acyl moiety is present, covalently connected to a leaving group as in the structure R-C(O)-L.
  • the atom in the leaving group connecting to the peracid-forming acyl moiety R(C)0- is most typically O or N.
  • a bleach activator can have non-charged, positively or negatively charged peracid- forming moieties and/or noncharged, positively or negatively charged leaving groups.
  • One or more peracid-forming moieties or leaving-groups can be present.
  • a preferred class of bleach activator includes the esters, including acyl phenol sulfonates, acyl alkyl phenol sulfonates or acyl oxybenzenesulfonates
  • a preferred hydrophobic bleach activator includes sodium nonanoyloxybenzene sulfonate (NOBS or SNOBS), sodium decanoyloxybenzene sulfonate (DOBS), sodium dodecanoiyloxybenzene sulfonate (LOBS), sodium nonanoyloxybenzene carboxylate (NOBA), sodium nonanoyloxybenzene carboxylate (DOBA), sodium dodecanoyloxybenzene carboxylate (LOBA), substituted amide types described in detail hereinafter, and the bleach activators related to certain imidoperacid bleaches.
  • NOBS or SNOBS sodium decanoyloxybenzene sulfonate
  • DOBS sodium dodecanoiyloxybenzene sulfonate
  • NOBA sodium nonanoyloxybenzene carboxylate
  • DOBA sodium nonanoyloxybenzene carboxylate
  • LOBA sodium dodecanoyloxybenzene carboxylate
  • Another suitable bleach activator includes sodium-4-benzoyloxy benzene sulfonate (SBOBS); sodium-1-methyl-2-benzoyloxy benzene-4- sulphonate; sodium-4-methyl-3-benzoyloxy benzoate; trimethyl ammonium toluyloxy-benzene sulfonate; sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate (STHOBS), and mixtures thereof.
  • a preferred bleach activator includes N,N,N'N'-tetraacetyl ethylene diamine (TAED) or any of its close relatives including the triacetyl or other unsymmetrical derivatives, and mixtures thereof.
  • TAED and the acetylated carbohydrates such as glucose pentaacetate and tetraacetyl xylose are preferred.
  • Builders can optionally be included in the cleaning compositions herein to assist in controlling mineral hardness. Certain alkaline materials described above may also be present in the compositions described herein, as builders. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils. The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Useful inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates such as zeolites.
  • polyphosphates exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates
  • phosphonates phosphonates
  • phytic acid e.g., silicates
  • carbonates including bicarbonates and sesquicarbonates
  • sulphates sulphates
  • aluminosilicates such as zeolites.
  • non-phosphate builders -we required in some locales.
  • compositions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • the optional chelating agent may be one or more iron and/or manganese chelating agents.
  • Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally- substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetrace- tates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylene- triaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents when at least low levels of total phosphorus are permitted in the cleaning product, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST.
  • these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21 , 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy-3,5-disulfobenzene.
  • a preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • these chelating agents will generally comprise from about 0.1% to about 15% by weight of the cleaning product. More preferably, if utilized, the chelating agents will comprise from about 0.1 % to about 3.0% by weight of such cleaning products.
  • An enzyme may also be useful herein for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration.
  • a suitable enzyme herein includes an amylase, a cutinase, a lipase, a peroxidase, a protease, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like.
  • bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • An amylase useful herein includes, for example, -amylases described in
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5.
  • U.S. 4,435,307 to Barbesgoard, et al., March 6, 1984 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
  • Suitable cellulases are also disclosed in GB-B-2,075,028 to Barbesgaar, et al., issued March 28, 1984; GB-B-2,095,275 to Murata, et al., issued August 7, 1985 and DE-OS-2,247,832 to Hohkoshi and Ikeda, issued June 27 1974.
  • CAREZYME® and CELLUZYME® are especially useful. See also WO 91/17243 to Hagen, et al., published November 14, 1991. Cutinase enzymes suitable for use herein are described in WO 88/09367A to Kolattukudy, et al., published December 1 , 1988.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1 ,372,034 to Dijk and Berg, published October 30, 1974. See also lipases in Japanese Patent Application 53-20487 to Inugai, published February 24, 1978. This lipase is available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” or "Amano-P.”
  • Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • LIPOLASE® from Novo, is a preferred lipase for use herein.
  • LIPOLASE® is derived from Humicola lanuginosa, ⁇ see also EP 341 ,947 to Cornelissen, et al., issued August 31 , 1994.
  • Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 94/14951 to Halkier, et al., published July 7, 1994 A to Novo. See also WO 92/05249 to Clausen, et al., published April 2, 1992.
  • Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution.
  • oxygen sources e.g., percarbonate, perborate, hydrogen peroxide, etc.
  • Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed in WO 89/09813 A to Damhus, et al., published October 19, 1989.
  • a suitable example of a protease is a subtilisin, which is obtained from particular strains of B. subtilis and B.
  • protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo.
  • ESPERASE® is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo.
  • Other examples of a suitable protease includes ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., the Netherlands; as well as Protease A and Protease B as disclosed in EP 130,756 A to Bott, published January 9, 1985.
  • An especially preferred protease referred to as "Protease D," as described in U.S. Patent 5,679,630 to A.
  • enzymes are typically available as an enzyme prill, an enzyme marume, a high-shear granule, or even an already-coated granule. Any of these enzyme forms may be coated by the improved encapsulation coating described herein.
  • a preferred embodiment comprises an enzyme prill which contains an enzyme.
  • Preferred examples of commercially- available enzymes useful herein include SAVINASE®, sold by Novo Corporation, Maxacal sold by Gist-brocades, Opticlean sold by Solvay-lnterox, Co, and Enzoguard sold by Genencor.
  • Other surfactants may also be included herein in addition to the linear alkyl benzene sulfonate described herein.
  • the cleaning product comprises at least about 0.01% of an other surfactant; more preferably at least about 0.1%; more preferably at least about 1%; more preferably still, from about 1% to about 55%.
  • Preferred other surfactants are cationic surfactants, nonionic surfactants, ampholytic surfactants, zwitterionic surfactants, other anionic surfactants, and mixtures thereof, further described herein below.
  • Nonlimiting examples of other surfactants useful in the cleaning product include, the primary, branched-chain and random C-10-C20 a ' sulfates, the C-
  • the conventional nonionic and amphoteric surfactants such as the C-12-C 8 alkyl ethoxylates including the so- called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C-I8 betaines and sulfobetaines, C-10-C18 amine oxides, and the like, can also be included in the overall compositions.
  • the C-)o-Ci8 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C-
  • the N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts, and are useful herein as well.
  • adjunct materials useful in cleaning compositions and detergent compositions may also be useful herein, including other active ingredients such as carriers, processing aids, suds supressors, suds boosters, dyes, pigments, perfumes, dye transfer inhibitors, optical brighteners, soil suspension agents, dispersants, processing aids, clay soil removal agents, anti-redeposition agents, soil release agents, etc. ⁇ " *
  • a linear alkyl benzene sulfonate surfactant is made by the process of the present invention.
  • 100 kg of a C 10 to C 16 linear alkyl benzene having about 30 molar % 2-phenyl isomer and about 1 weight % dialkyl bi-cyclic benzene impurities (DETAL® LAB, available from Petresa, Canada) is combined in a liquid mixer with 10 kg of toluene, a hydrotrope precursor.
  • the linear alkyl benzene and the toluene are combined and blended for 20 minutes in the mixer to form a homogenized precursor mixture.
  • the resulting mixture is then fed through a standard falling film sulfonator, such as marketed by Chemithon, to form a linear alkyl benzene acid active.
  • This linear alkyl benzene acid active may be stored and applied directly in most detergent manufacturing processes, i.e., adding it into the crutcher with neutralization for the spray drying granular detergent manufacturing process, spaying it onto a bed of sodium tripolyphosphate and soda ash with mixing to form high density phosophated granular detergents, or neutralized with about 15 kg active of 50% NaOH concentrates to form a high active NaLAS paste.
  • the detergent products manufactured from this linear alkyl benzene sulfonate surfactant formed has excellent surfactancy, a more rapid dissolution rate. A faster production rate is also realized when spray drying is employed in the detergent manufacturing process.
  • a linear alkyl benzene sulfonate surfactant is produced as in Example 1 , except that the initial linear alkyl benzene has about 70 molar % 2-phenyl isomer and about 2 weight % dialkyl bi-cyclic benzene impurities. Also, cumene is provided as the added hydrotrope precursor.
  • This linear alkyl benzene sulfonate surfactant is combined with adjunct materials (see Table I) in a mixer to form a surfactant slurry. This surfactant slurry is then pumped to a spray-drying tower and spray dried to produce granules suitable for use as a laundry detergent.
  • the granular deter ent com osition formulations are described below:
  • the granules formed have excellent surfactancy, a more rapid dissolution rate, and a high level of biodegradability.
  • composition E-G are agglomerated particles, while Composition H is a spray dried particle and Composition I is a tablet.
  • All percentages are by weight of the final composition.
  • linear alkyl benzene sulfonate surfactant having about 50 molar % 2-phenyl LAS and about 2 weight % dialkyl bi-cyclic benzene sulfonate impurities.
  • linear alkyl benzene sulfonate surfactant having about 70 molar % 2-phenyl LAS and about 1 weight % dialkyl bi-cyclic benzene sulfonate impurities.
  • compositions possess excellent surfactancy, low gel formation, and a high level of biodegradability.
  • EXAMPLE 5 Another granular detergent of the present invention is prepared as follows: 7.8 kg of linear alkyl benzene acid active containing 30+% of 2-phenyl isomer and less than 1% alkyl tetralin sulfonate is mixed with 0.5 kg of 1:1 acid- form mixture of xylene sulfonic acid and cumene sulfonic acid, is sprayed onto 18 kg of SKS-6 granulate, and is followed by mixing. The resulting granule is controlled to contain less than 1% moisture, and the particle size is sized to be below 1000 microns. The granule may be blended with a second detergent particle to give a final product with an acceptable dissolution rate and improved surfactancy.
  • the second detergent particle may contain: 14 parts additional LAS of the present invention, 1% of cationic surfactant of the type dihydroxyethyl monododecyl ammonium methyl sulfate or chloride, a chelating agent, i.e., diethylene triamine penta acetate sodium salt, 12 parts of 1 :1 polyacrylic/polymaleic copolymer of MW around 10,000, 20 parts of soda ash, and 0.20 parts of optical brighteners.
  • additional LAS of the present invention 1% of cationic surfactant of the type dihydroxyethyl monododecyl ammonium methyl sulfate or chloride, a chelating agent, i.e., diethylene triamine penta acetate sodium salt, 12 parts of 1 :1 polyacrylic/polymaleic copolymer of MW around 10,000, 20 parts of soda ash, and 0.20 parts of optical brighteners.
  • a chelating agent i.e.,
  • the above detergent granules may be manufactured with standard spray- drying processes, followed by compaction, grinding and sizing, if high density is desired.
  • Other adjuncts i.e., zeolites, sodium percarbonate, sodium perborate, bleach activators, suds suppressors, soil release agents, enzymes, perfume, may be dry blended, or sprayed on at the finishing step.

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Abstract

L'invention concerne un procédé de fabrication d'un tensioactif à base d'alkyl-benzène sulfonate linéaire. Ce procédé consiste à combiner un alkyl-benzène sulfonate linéaire et une quantité efficace d'un précurseur d'hydrotrope ajouté afin d'obtenir un mélange précurseur, puis à faire subir une sulfonation à ce mélange précurseur afin d'obtenir un agent actif acide à base d'alkyl-benzène sulfonate linéaire. Une matière alcaline est également utilisée afin de neutraliser cet agent actif acide à base d'alkyl-benzène sulfonate linéaire et d'obtenir ainsi un tensioactif à base d'alkyl-benzène sulfonate linéaire. L'alkyl-benzène sulfonate linéaire selon l'invention comprend environ 30 % en mole de 2-phényl isomère et moins d'environ 5 % en poids d'impuretés de dialkyle bicyclique benzène. L'invention concerne également une composition de nettoyage contenant un tensioactif à base d'alkyl-benzène sulfonate linéaire et les matières d'équilibrage ajoutées. Ce tensioactif à base d'alkyl-benzène sulfonate linéaire contient au moins environ 30 % en mole de 2-phényl isomère, moins d'environ 5 % en poids d'impuretés de dialkyle bicyclique benzène sulfonate et une quantité efficace d'un hydrotrope ajouté.
PCT/US1999/000211 1999-01-06 1999-01-06 Procede de fabrication d'un tensioactif a base d'alkyl-benzene sulfonate lineaire et compositions de nettoyage contenant ces compositions Ceased WO2000040551A1 (fr)

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AU24518/99A AU2451899A (en) 1999-01-06 1999-01-06 Process for forming highly soluble linear alkyl benzene sulfonate surfactant andcleaning compositions containing same

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Cited By (10)

* Cited by examiner, † Cited by third party
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WO2001055287A1 (fr) * 2000-01-28 2001-08-02 Huntsman Petrochemical Corporation Alkylbenzenesulfonates solides et compositions de nettoyage possedant une tolerance superieure a la durete de l'eau
WO2002024845A3 (fr) * 2000-09-19 2002-07-11 Huntsman Spec Chem Corp Detergents de sulfonate d'alkyltoluene
WO2006108883A1 (fr) * 2005-04-12 2006-10-19 Petroquímica Española S.A. Petresa Procede destine a obtenir un alkylbenzene lineaire hautement soluble
WO2007104805A1 (fr) * 2006-03-16 2007-09-20 Petroquímica Española, S.A. (Petresa) Procédé d'obtention de sulfonates d'alkylbenzène linéaire fortement solubles
RU2396254C2 (ru) * 2006-03-16 2010-08-10 Сепса Кимика, С.А. Способ получения высокорастворимых линейных алкилбензолсульфонатов
EP1954672A4 (fr) * 2005-12-21 2010-11-17 Chevron Oronite Co Procede de fabrication d un sulfonate de petrole synthetique
US10626350B2 (en) 2015-12-08 2020-04-21 Ecolab Usa Inc. Pressed manual dish detergent
US10626318B2 (en) 2016-09-29 2020-04-21 Ecolab Usa Inc. Paraffin suppressant compositions and methods
US10738138B2 (en) 2016-09-29 2020-08-11 Ecolab Usa Inc. Paraffin inhibitors, and paraffin suppressant compositions and methods
CN116354856A (zh) * 2023-04-04 2023-06-30 太原理工大学 烷基四氢萘磺酸盐及其制备工艺与应用

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GB2205580A (en) * 1987-06-04 1988-12-14 Procter & Gamble Detergent bars
WO1997014676A1 (fr) * 1995-10-20 1997-04-24 Stepan Company Procede ameliore de preparation de sulfonates d'alkylbenzene lineaires

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GB2205580A (en) * 1987-06-04 1988-12-14 Procter & Gamble Detergent bars
WO1997014676A1 (fr) * 1995-10-20 1997-04-24 Stepan Company Procede ameliore de preparation de sulfonates d'alkylbenzene lineaires

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001055287A1 (fr) * 2000-01-28 2001-08-02 Huntsman Petrochemical Corporation Alkylbenzenesulfonates solides et compositions de nettoyage possedant une tolerance superieure a la durete de l'eau
WO2002024845A3 (fr) * 2000-09-19 2002-07-11 Huntsman Spec Chem Corp Detergents de sulfonate d'alkyltoluene
WO2006108883A1 (fr) * 2005-04-12 2006-10-19 Petroquímica Española S.A. Petresa Procede destine a obtenir un alkylbenzene lineaire hautement soluble
US8158819B2 (en) 2005-04-12 2012-04-17 Cepsa Quimica S.A. Process to obtain a highly soluble linear alkylbenzene sulfonate
EP1954672A4 (fr) * 2005-12-21 2010-11-17 Chevron Oronite Co Procede de fabrication d un sulfonate de petrole synthetique
US8034973B2 (en) 2006-03-16 2011-10-11 Cepsa Quimica, S.A. Process for obtaining highly soluble linear alkylbenzene sulfonates
RU2396254C2 (ru) * 2006-03-16 2010-08-10 Сепса Кимика, С.А. Способ получения высокорастворимых линейных алкилбензолсульфонатов
WO2007104805A1 (fr) * 2006-03-16 2007-09-20 Petroquímica Española, S.A. (Petresa) Procédé d'obtention de sulfonates d'alkylbenzène linéaire fortement solubles
US10626350B2 (en) 2015-12-08 2020-04-21 Ecolab Usa Inc. Pressed manual dish detergent
US11268045B2 (en) 2015-12-08 2022-03-08 Ecolab Usa Inc. Pressed manual dish detergent
US11746304B2 (en) 2015-12-08 2023-09-05 Ecolab Usa Inc. Pressed manual dish detergent
US12227717B2 (en) 2015-12-08 2025-02-18 Ecolab Usa Inc. Pressed manual dish detergent
US10626318B2 (en) 2016-09-29 2020-04-21 Ecolab Usa Inc. Paraffin suppressant compositions and methods
US10738138B2 (en) 2016-09-29 2020-08-11 Ecolab Usa Inc. Paraffin inhibitors, and paraffin suppressant compositions and methods
CN116354856A (zh) * 2023-04-04 2023-06-30 太原理工大学 烷基四氢萘磺酸盐及其制备工艺与应用

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