US3346629A - Process for preparing beta-ethylenically unsaturated organic sulfonates - Google Patents

Process for preparing beta-ethylenically unsaturated organic sulfonates Download PDF

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US3346629A
US3346629A US302440A US30244063A US3346629A US 3346629 A US3346629 A US 3346629A US 302440 A US302440 A US 302440A US 30244063 A US30244063 A US 30244063A US 3346629 A US3346629 A US 3346629A
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sulfonate
beta
sodium
ethylenically unsaturated
sulfonates
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George Leon Broussalian
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Monsanto Co
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Monsanto Co
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Priority to FR984682A priority patent/FR1411808A/fr
Priority to LU46754A priority patent/LU46754A1/xx
Priority to AU48110/64A priority patent/AU403871B2/en
Priority to BE651783A priority patent/BE651783A/xx
Priority to DEM62100A priority patent/DE1299791B/de
Priority to NL6409378A priority patent/NL6409378A/xx
Priority to GB33497/64A priority patent/GB1066458A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters

Definitions

  • This invention relates to new and useful detergent compositions and to processes for preparing them. More particularly, this invention relate-s to both aqueous and nonaqueous compositions which contain significant amounts of beta-ethylenically unsaturated organic sulfonate-type compounds that can be represented by Formula 1:
  • R and R are hydrophobic organic radicals containing from 1 to about 21 carbon atoms or hydrogen, the sum of the total number of carbon atoms in R plus R is from about 8 to about 21, and M is either hydrogen, an alkali metal cation, an alkaline earth metal cation, or an ammonium cation; and to processes for preparing these materials.
  • a material In order to qualify as a useful hand dishwashing surfactant, a material must have the ability to cause the formation of large quantities of foam or lather when aqueous solutions of the materials are agitated, which lather is stable when greases or greasy soils are also dissolved or dispersed therein. It has been discovered that when the above-described beta-ethylenically unsaturated sulfonate-type compounds are utilized in sufiicient amounts or proportions, either with or without other surfactants, in hand dishwas-hing compositions, for example, unexpectedly large quantities of foam or lather which is extremely stable in the presence of dissolved greases or greasy soils results therefrom.
  • compositions of this invention represent particularly useful laundry and .dishwashing detergent compositions.
  • the organic radicals (designated by R and R in Formula 1, above) that are present in the betaethylenically unsaturated organic sulfonate-type compounds of the present invention can be branched or unbranched to practically any degree without substantially eliminating all of the benefits that can result from the invention. It is generally preferred, however, that the organic radical(s) be straight-chain in nature. It is still further preferred that the sum of the total number of carbon atoms in R and R be between about 9 and about 17.
  • organic radicals R and R can contain heterocyclic, monocyclic hydrocarbyl, and polycyclic hydrocarbyl radicals (whether the rings are saturated or not), and can also contain substituents such as halides (including, for example, fluoride, chloride, bromide and iodide), ester groups, ether groups, thioe-ther groups, nitro groups, sulfone groups, sulfoxide groups, amide groups, nitroso groups, and the like, in their otherwise aliphatic or alicyclic radicals, it is preferred that R and/ or R be either hydrocarbyl in nature or that they contain only halide substituen-ts in their otherwise hydrocarbyl radicals.
  • substituents such as halides (including, for example, fluoride, chloride, bromide and iodide), ester groups, ether groups, thioe-ther groups, nitro groups, sulfone groups, sulfoxide groups, amide groups, nitroso
  • the sulfonate group in the above-described beta-ethylenically unsaturated organic sulfonate-type compounds that are contemplated for use in the practice of this invention
  • these particularly preferred compounds just described include those having a structure such as that illustrated in Formula 2:
  • HHH wherein R is a higher alkyl radical, preferably containing from about 9 to about 17 carbon atoms, and M is an alkali metal cation.
  • R is a higher alkyl radical, preferably containing from about 9 to about 17 carbon atoms, and M is an alkali metal cation.
  • R is a higher alkyl radical, preferably containing from about 9 to about 17 carbon atoms, and M is an alkali metal cation.
  • R is a higher alkyl radical, preferably containing from about 9 to about 17 carbon atoms
  • M is an alkali metal cation.
  • alkali metal sulfonate salts are preferred forms of the above-described be-ta-ethylenica'lly unsaturated sulfonate-type compounds, it is nevertheless a fact that ammonium salts, as well as alkaline earth metal salts (where, for example, M in Formulas 1 and 2, above, represents /2Ca++, /z-M-g+ /2 Ba++, /2Sr++ or /2Ra+ can be used in the practice of this invention.
  • alkali metal salts including Li, Na, K, Rb, Cs, Fr
  • the sodium and potassium salts are particularly preferred, especially from the standpoint of cost.
  • Typical, but non-limiting examples of the beta-ethylenically unsaturated organic sulfonate-type compounds that are useful in the practice of the present invention include sodium Z-n-hexadecene-l-sulfonate, sodium 12-bromo-2- n-dodecene-l-sulfonate, magnesium Z-n-tetradecene-l-sulfonate sodium 9,10-dichloro-2-n-octadecene-l-sulfonate, potassium Z-(branched) pentadecene-l-sulfonate, sodium 9 methoxy 2 n octadecene 1 sulfonate, ammonium 2-n-octadecene-l-sulfonate, sodium l-(p-n-dodecylphenyl)1-propene-3-sulfonate, sodium 2-n-pentadecene-3-sul
  • Some of the beta-ethylenically unsaturated organic sulfonate-type compounds to which the present invention relates can be manufactured starting with an appropriate carboxylic acid which is ethylenically unsaturated at a 2- position (with reference to the carboxyl group) by first reducing the carboxylic acid group to the corresponding alcohol or OH group with a reducing agent such as lithium aluminum hydride in a suitable solvent such as anhydrous ether. The resulting ethylenically unsaturated alcohol can then be converted to the corresponding bromide (where Br replaces the OH group by reacting the alcohol under anhydrous conditions with phosphorus tribromide).
  • the resulting ethylenically unsaturated bromide can then be converted to the corresponding ethylenically unsaturated sulfonic acid via sulfitation, for example by refluxing the bromide at atmospheric pressure in the presence of sodium bisulfite, methanol, and water. Subsequent neutralization of the resulting sulfonic acid then yields the more generally useful 2-ethylenically unsaturated-l-sulfonate compound.
  • Another process for manufacturing these desired betaethylenically unsaturated organic sulfonate-type compounds involves the sulfonation of an appropriate monoolefinic, hydrophobic organic compound with sulfur trioxide under circumstances in which it is believed that initially the formation of a beta-sultone such as that illustrated in Formula 3:
  • H H H RCOO-R O-SO2 wherein R and R have the same meaning as they have in Formula 1; above, is favored, followed by the controlled rearrangement of the beta-sultone to the corresponding beta-ethylenically unsaturated organic sulfonic acid;
  • This sulfonic acid is then neutralized with an appropriate base if and when desired to yield one of the abovedescribed sulfonates.
  • This monoolefin-beta sultone route for manufacturing the desired beta-ethylenically unsaturated organic sulfonate-type materials described above is a considerably less expensive method than that process described immediately above (involving the use of an un saturated carboxylic acid as a starting material). Consequently, the unsaturated-SO process constitutes a particularly preferred embodiment of the present invention.
  • the sulfonation of the monoolefinic raw material should be carried out at a temperature below about 10 C., and preferably at a temperature below about 5 C.
  • the monoolefinic material be dissolved in an inert (to S0 neutral, anhydrous solvent during the sulfonation step in order to minimize polymerization and/or degradation of the monoolefinic material in the presence of S0 Since it is believed that the fraction of the initially formed beta-sultone which remains soluble in the sulfon ation solvent thereby also remains more subject to further reaction with S0 to form the undesired carbyl sulfate, it is particularly preferred that the neutral solvent that is utilized in the sulfonation step of any of the processes of this invention be one in which the betasultone is soluble at most to the extent of about 20 weight percent.
  • the neutral solvents referred to herein are neutral in the Lewis acid-base sense and include such a solvents as pentane, isopentane, hexane, heptane, isoheptane, octane, isooctane cyclopentane, cyclohexane, 2,2,4- trimethylpentane, 2,2-dimethylbutane, methylcyclohexane, petroleum ether petroleum benzine, naptha, ligroin, kerosene, gasoline, decalin, turpentine, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, butyl chloride, ethyl bromide, ethylene dichloride, ethylene dibromide, ethylidene chloride, ethylene chlorobromide, tetrafluoroethane, ethylene trichloride, tetra-bromoethane, propy
  • Carbyl sulfates are illustrated in Formula 4, below:
  • Typical non-limiting examples of such basic solvents include ethyl ether, isopropyl ether, dioxane, ethyl thioether, triethyl phosphate, ethyl acetate, organic nitrates such as n-hexyl-1-nitrate, isopropyl acetate, ethyl sulfate, thioxane, carbon disulfide, and the like.
  • the solvents that are used in these processes be substantially aprotic (i.e., do not contain active hydrogens) since such aprotic materials (such as amines, nitriles, acids, and the like) react with the betasultone to yield addition products which differ substantially from the beta-unsaturated sulfonates of the present invention.
  • aprotic materials such as amines, nitriles, acids, and the like
  • the molar ratio of sulfur trioxide to monoolefinic raw material that are reacted together he at most about 1.5 :1, respectively, and preferably between about 0.95 :1 and about 1.05:1, respectively, in order to minimize the formation of undesired by-products, including carbyl sulfates, which ultimately form less desirable sulfonate materials than those of the present invention; although generally the molar ratio should be at least about 0.2: 1.
  • any amounts of basic solvent above this level can be utilized, but as a practical matter, generally the use of not more than about moles of basic solvent per mole of S0 that reacted with the olefinic raw material is recommended.
  • ethyl ether and dioxane are particularly preferred for use during this stage of these preferred processes.
  • the desired rearrangement is greatly enhanced.
  • the betasultone of l-n-hexadecene is warmed from -20 C. to 15 C. over a period of 30 minutes while the sultone is in a neutral solvent such as ethylene dichloride, only about weight percent of the desired beta-ethylenically unsaturated material is formed.
  • Complexes of sulfur trioxide that tend to attenuate the reactivity of S0 can also be utilized advantageously in these preferred processes. Complexes that do not contain a nitrogen atom are generally preferred, however, because in some instances, unless great care is taken, the use of complexes of S0 with a nitrogen-containing compound such as pyridine, organic nitrile, and the like result in the reaction of the nitrogen-containing compound with the sultone with concomitant production of byproducts, rather than the desired beta-ethylenically unsaturated compound of this invention.
  • a nitrogen-containing compound such as pyridine, organic nitrile, and the like
  • the desired beta-ethylenically unsaturated organic sulfonate-type compositions of the present invention can also be manufactured by sulfonating an appropriate mono-ethylenically unsaturated compound with sulfur trioxide and without apparently manufacturing a significant or noticeable amount of the beta-sultone intermediate when the unsaturate-SO reaction is carried out at or above about 0 C. provided several precautions are observed.
  • carrying out the reaction at temperatures above about C. is generally not recommended because at these relatively high temperatures, side reactions (other than that desired) occur; generally the higher the temperature the greater the proportion of the undesired materials produced with consequently much lower yields of the desired beta-ethylenically unsaturated sulfonate.
  • One of the preferred processes of this invention involves the controlled reaction of sulfur trioxide with the raw monoolefin material in such a way as to prevent the interreaction of more than about 1.2 moles of S0 per mole of the monoolefin.
  • the proper control of this reaction can be accomplished in several ways. For example, about one molar proportion of sulfur trioxide can first be reacted with about one molar proportion of a complexing agent such as dioxane, if desired, in a non-basic solvent such as ethylene dichloride (at a very low temperature) to form a complex of S0 with dioxane. Then about one molar proportion of the monoolefin is added rapidly to the resulting mixture.
  • a complexing agent such as dioxane
  • the olefin By intermixing the olefin rapidly into the solvent-complex mixture, localized excesses of the complex (i.e., much more than about 1.221 'ratio of complex to olefin at a given small area in the resulting mixture) are minimized.
  • the resulting mixture can then be stirred for several minutes, or until the sulfonation reaction is completed to the desired extent, and the sulfonated product (largely beta-sultone) can then be warmed to room temperature.
  • at least several moles of additional dioxane (or some other basic solvent) can be added to the cold reaction product before it is warmed significantly above about 15 C.
  • Another procedure for controlling the amount of S0 that reacts with the above-described monoolefinic raw materials involves initially the dissolution of the olefin in a non-basic, inert (to S0 solvent such as n-hexane and then adding sulfur trioxide slowly to the cooled solution or partial dispersion of the olefin in the solvent (which solvent can also contain a small amount of one of the above-described desirable complexing agents). After about one mole of S0 per mole of olefin has been introduced into the cold reaction medium, the resulting reaction product can be allowed to warm to room temperature.
  • S0 solvent such as n-hexane
  • beta-ethylenically unsaturated sulfonate-type compounds that are useful in the practice of the present invention can be utilized advantageously as general purpose detergent active ingredients either alone or in combination with practically any material than can be employed in combination with known organic detergent anionic and nonionic surface active agents, such as soap, the alkali metal fatty alcohol sulfates, the alkali metal, ammonium, and alkaline earth metal alkylaryl sulfonates; higher alcohol-ethylene oxide condensates, alkylphenolethylene oxide condensation products, fatty acid-ethylene oxide condensation products, for example, sodium dodecylbenzene sulfonate; and other similar surfactants.
  • organic detergent anionic and nonionic surface active agents such as soap, the alkali metal fatty alcohol sulfates, the alkali metal, ammonium, and alkaline earth metal alkylaryl sulfonates; higher alcohol-ethylene oxide condensates, alkylphenolethylene oxide condensation products, fatty acid-ethylene oxide condensation products
  • the types of materials that than can be employed in the formulation of socalled polyphosphate built detergents, liquid heavyduty detergents, light-duty detergents, flake and powdered compositions include such materials as other organic anionic and/ or nonionic and/ or ampholytic surface active agents or materials, polyphosphate complexing agents and other inorganic and organic builders, antiredeposition agents, optical brightener, bleaching agents, and the like; all of which are well-known in the detergent art and need not be detailed here.
  • the beta-ethylenically unsaturated sulfonate-type materials of this invention can be utilized advantageously in practically any of the compositions in which the alkylaryl sulfonates, for example, can be utilized. It should be noted, however, that whenever these beta-ethylenically unsaturated sulfonates are utilized in combination with other organic surface-active agents such as the higher alkyl benzene sulfonates, for example; generally in order for the unexpectedly desirable properties of the beta-ethylenically unsaturated sulfonate to become readily apparent when the mixture or combination of organic surfactants is ultimately dissolved in water, the amount of the beta-ethylenically unsaturated sulfonatein the organic surfactant combination should be at least about 10 weight percent, based on the total combined weight of the organic surfactants in the combination. Preferably, this proportion of the beta-ethylenically unsaturated sulfonate should be at least about
  • the beta-ethylenically unsaturated sulfonates described above are particularly useful when they are formulated into so-c-alled built detergent compositions and used as such, for example, as light duty or heavy duty laundering detergents.
  • Built detergents are those that contain, in addition to the detergent active material, at least one water-soluble inorganic builder salt such as an alkali metal pyrophosphate, tripolyphosphate, carbonate, sulfate, or the like.
  • the outvention can readily be appreciated when the composition contains at least about weight percent, and up to about 50 weight percent or more; preferably from about to about 35 weight percent; of these beta-ethylenically unsaturated sulfonate (s).
  • beta-ethylenically unsaturated sulfonates described above can advantageously be utilized along with any other anionic, nonionic, or ampholytic detergent active materials (surfactants) or mixtures thereof in the proportions specified above.
  • anionic surfactants encompasses such materials as the alkali metal salts of fatty acids and fatty acid derivatives, commonly known as soaps (such as sodium laurate, sodium palmitate, and the potassium salts of coconut fatty acids); the alkali metal salts of sulfuric esters [such as sodium lauryl alcohol sulfate, potassium hexadecanol sulfate, lithium petroleum alcohol (average C chain length) sulfate as well as the alkali metal sulfates of condensation products of alcohols containing from about 10 to about 30 carbon atoms with from about 2 to about 40 moles of a lower alkylene oxide such as ethylene oxide, propylene oxide, or mixtures thereof]; the alkali metal salts of alkanesulfonates, preferably straightchain alkanesulfonates (such as those prepared by sulfonating certain petroleum fractions with S0 the alkali metal and alkaline earth metal salts of esterand etherlinked sulfonates [
  • nonionic surfactants encompasses such materials as the condensation products of several moles of a lower alkylene oxide such as ethylene-, propylene-, or butylene-oxide with a mole of a higher alkyl alcohol, alkylphenol, fatty acid, and the like (wherein the alkyl group contains from about 10 to about 20 or more carbon atoms); the fatty alkanolarnides (such as the diethanolamide of tall oil fatty acids and the diethanolamide of lauric acid); and the polyhydroxy nonionic surfactants (such as sorbitol monolaurate, and the reaction products of fatty primary amines with delta-gluconolactone).
  • a lower alkylene oxide such as ethylene-, propylene-, or butylene-oxide
  • alkyl group contains from about 10 to about 20 or more carbon atoms
  • the fatty alkanolarnides such as the diethanolamide of tall oil fatty acids and the diethanolamide of lauric acid
  • ampholytic surfactants contain both acidic and basic functional groups in their individual molecules, and include such materials as dodecyl-beta-alanine, sodium Ndodecyl taurate, and the products from reacting benzene amino sulfonic acid, for example, with n-hexadecylchloride.
  • organic anionic, nonionic and ampholytic surfactants that can also be present in compositions containing the betaethylenically unsaturated sulfonate materials described above can be found in Surface Active Agents and Detergents, by Schwartz et al., Interscience Publishers, Inc., New York (1958), volume II.
  • the pure beta-ethylenically unsaturated sulfonate compounds of this invention as well as compositions containing them such as those described above, have physical and chemical properties that make them particularly outstanding detergents for use in the form of aqueous solutions (containing them) to clean various solid substrates in the presence of dissolved and dispersed greases, for example, as a hand dishwashing detergent composition.
  • beta-ethylenically unsaturated sulfonates of this invention can be readily appreciated when these materials are present (dissolved) in water at a level of at least about 0.005 weight percent (so that they represent at least about 10 weight percent of the total surfactant therein). For optimum results, this level should be generally between about 0.010 and about 20 weight percent, and preferably between about 0.015 and about 10 weight percent of the total aqueous solution weight.
  • EXAMPLE I Process Into a conventional glass-lined reaction vessel fitted with a fairly efficient stirrer are poured 1000 parts of ethylene dichloride, 88 parts of dioxane, and 224 parts of n-hexadecene-l. The resulting solution is then cooled to a temperature of about 20 C. Then, with constant agitation, a total of 88 parts of sulfur trioxide in the gaseous form (preblended with an equal volume of dry nitrogen) are introduced into the bottom of the reaction vessel gradually over a period of about 120 minutes. As the reaction progresses, the desired beta-sultone is observed crystallizing out of solution.
  • the resulting reaction product (almost entirely the beta-sultone dispersed in a mixture of ethylene dichloride and dioxane) is further diluted with 200 parts of dioxane, and then warmed slowly (over a period of about 60 minutes) to room temperature. During this warming, the insoluble beta-sultone gradually disappears.
  • the resulting solution of Z-n-hexadecene-l-sulfonic acid is then neutralized with about parts of a 50 weight percent aqueous solution of sodium hydroxide.
  • Subsequent distillation of the solvent mixture at about 15 C. at a pressure of about 20 mm.-Hg yields a residue containing about 80 weight percent of the desired sodium 2-n-hexadecene-1-sulfonate.
  • the remainder is a mixture of unreacted n-hexadecene-l, and by-products sodium hydroxy-n-hexadecane-l-sulfonate, l-n-hexadecene-l-sulfonate, and a very small amount of other unidentified material.
  • Relatively pure sodium 2-n-hexadecene-l-sulfonate can be isolated from this mixture by simply extracting the mixture with methanol and filtering to remove the hydroxy sulfonates. Then the methanol solution can be concentrated to a small volume by distilling off the methanol. After most of the methanol is removed and the concentrated product cooled to about room temperature a precipitate of the product, sodium 2-n-hexadecene-l-sulfonate, is formed.
  • the residue (after removal of the solvent mixture) from Example I is itself an excellent very high foaming surfactant; yielding an extremely high volume of foam when it is dissolved in water at a level of about 0.1 weight percent and the water is subsequently agitated, which foam is unexpectedly stable in the presence of dissolved greases, as for example, after many greasy dishes are washed in the aqueous solution.
  • the form in which the beta-ethylenically unsaturated sulfonic acids and sulfonates of the pres ent invention will most likely be sold and utilized for and in the practice of the present invention is in admixture with such other aliphatic sulfonates.
  • the particular sulfonates which are in admixture with a particular betaethylenically unsaturated sulfonate will depend upon the particular raw monoolefinic material from which they were manufactured, as well as the particular conditions observed and practiced during the sulfonation and reorganization steps of the processes of this invention.
  • beta-ethylenically unsaturated sulfonates While beneficial mixtures of aliphatic sulfonates (which for the foregoing reasons constitute preferred embodiments of the present invention) as little as about 15 weight percent of the beta-ethylenically unsaturated sulfonates, generally the beta-ethylenically unsaturated sulfonates should be present in the mixtures in an amount larger than that in which any of the other (alpha-unsaturated, or Z-hydroxy) sulfonates are present therein.
  • a procedure such as that described in Example I, above, can be utilized to manufacture any of the betaethylenically unsaturated sulfonates useful in the practice of the present invention. This can be accomplished simply by substituting appropriate mono-ethylenically unsaturated starting materials for reaction with sulfur trioxide, and subsequently neutralizing the resulting sulfonic acid with an appropriate base.
  • the beta-ethylenically unsaturated organic sulfonate-type compounds of this invention have generally been referred to as though they were pure components, containing for example hydrophobic radicals, alkyl groups, and the like (as R and R is Formulae 1 and 2) which are all identical. It is well known by those skilled in the art, however, that a high degree of purity in such compounds is very rarely if ever attainable in practical commercial operations for manufacturing detergents.
  • such mixtures of materials contain at most about 10 weight percent of materials varying more than about 3 carbon atoms on either side of the named average.
  • sodium 2-n-hexadecene-l-sulfonate includes not only the pure hexadecene material but also mixtures containing from about tridecene to about nonadecene wherein the average chain length of the mixture is C and less than a total of 10 Weight percent of the materials in the mixtures have chain lengths less than C or more than C
  • material containing the named average number of carbon atoms will be the largest single component in the mixtures.
  • Table 1 illustrates the valuable benefits which can be obtained when the preferred beta-ethylenically unsaturated sulfonates of this invention are utilized as laundering detergents.
  • Table 2 below, illustrates the very valuable benefits that can be obtained by utilizing these materials as hand dishwashing detergents both alone and in combination with other surface active agents. Details on the test procedure for evaluating hand dishwashing detergents are described after Table 2.
  • This hand dishwashing test involves the washing by hand of nine-inch dinner plates which are pre-soiled with one teaspoonful each of a synthetic soil mixture consisting of 75 Weight percent of shortening and 25 weight percent of flour. Washing of the plates is performed (using a dishcloth to remove the synthetic soil) in 4 liters of Water having an initial temperature of about 50 C. and containing 0.075 weight percent of the surfactant or surfactant mixture being tested. The number of plates washed is determined by the number of plates which can be cleaned in the normal fashion by the time the lather on the surface of the dishpan has broken to the extent that less than half of the surface remains covered with lather. The manipulative procedures of this test are described in greater detail in the Proceedings of the 43rd Annual Meeting of the Chemical Specialties Manufacturers Association, December 1956; Procedure No. 3, page 191.
  • Table 3 are tabulated data showing some typical surfactant properties of one of the outstanding preferred -betaethylenically unsaturated sulfonates of the present invention (practically pure sodium-Z-hexadecene-l-sulfonate) TABLE 3.-SURFACTANT EVALUATION DATA 1 In 300 p.p.m. hard water. Test described by Jay C. Harris in Evaluation of Surface Active Agents, ASTM Bulletin, May, 1946.
  • R and R in each instance are selected from the group consisting of hydrogen, alkyl radicals and halogen, lower alkoxy, phenyl, hydroxy, methyl mercapto, naphthyl, epoxy acetoxy, carboethoxy, carbamido, nitroso, and cyclohexyl substituted al'kyl radicals, the total number of carbon atoms in R plus R being from about 8 to about 21, and wherein M is selected from the group consisting of hydrogen, alkali metal cations, alkaline earth metal cations, and ammonium cations, which comprises reacting together in a neutral, in the Lewis acid-base sense, solvent and at a temperature below about C.
  • said monoolefinically unsaturated organic compound is a mixture of olefins having an average chain length of from about 12 to about 20 carbon atoms; said olefins being reacted with said sulfur trioxide at a temperature below about 5 C.
  • alpha-olefins are nalpha-olefins.
  • a process for preparing a compound of the formula wherein R is an alkyl radical containing from about 9 to about 17 carbon atoms and M represents an alkali metal cation which comprises forming a beta-sultone by reacting together in an anhydrous, neutral, in the Lewis acidbase sense, inert solvent system at a temperature below about 5 C.
  • alpha-olefin is a mixture of alpha-olefins having an average of from about 12 to about 20 carbon atoms.
  • alpha-olefins are n-alpha-olefins and have an average chain length of about 16 carbon atoms.
  • said anhydrous solvent system comprises ethylene dichloride as the principal solvent.

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US302440A US3346629A (en) 1963-08-15 1963-08-15 Process for preparing beta-ethylenically unsaturated organic sulfonates
FR984682A FR1411808A (fr) 1963-08-15 1964-08-10 Nouvelles compositions détergentes
LU46754A LU46754A1 (enrdf_load_stackoverflow) 1963-08-15 1964-08-12
BE651783A BE651783A (enrdf_load_stackoverflow) 1963-08-15 1964-08-13
AU48110/64A AU403871B2 (en) 1963-08-15 1964-08-13 Detergent compositions and processes
DEM62100A DE1299791B (de) 1963-08-15 1964-08-14 Stark schaeumendes Reinigungsmittel
NL6409378A NL6409378A (enrdf_load_stackoverflow) 1963-08-15 1964-08-14
GB33497/64A GB1066458A (en) 1963-08-15 1964-08-17 Unsaturated sulphonic acids and salts thereof

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3462525A (en) * 1966-09-15 1969-08-19 Colgate Palmolive Co Dental compositions comprising long-chain olefin sulfonates
US3487104A (en) * 1966-04-28 1969-12-30 Gulf Research Development Co Process for preparing alkene sulfonates
US3523089A (en) * 1966-03-18 1970-08-04 Lever Brothers Ltd Toilet bar
US3637512A (en) * 1968-07-22 1972-01-25 Continental Oil Co Hydrocarbon solvent composition
US3673122A (en) * 1969-03-27 1972-06-27 Chevron Res Hydrogenated olefin sulfonate detergent bars
US3676372A (en) * 1968-10-24 1972-07-11 Chevron Res Hydrogenated olefin sulfonate-fatty acid amide detergent compositions
US3720629A (en) * 1967-11-27 1973-03-13 Chevron Res Detergent composition containing hydrogenated alpha olefin sulfonates
US3819519A (en) * 1968-11-27 1974-06-25 Chevron Res Foam circulation fluids
US5078916A (en) * 1989-01-03 1992-01-07 Shell Oil Company Detergent composition containing an internal olefin sulfonate component having an enhanced content of beta-hydroxy alkane sulfonate compounds
US9877907B2 (en) 2013-02-13 2018-01-30 Kao Corporation Internal olefin sulfonate composition
US10201488B2 (en) 2012-09-20 2019-02-12 Kao Corporation Internal olefin sulfonate composition and cleansing composition containing same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA787878A (en) * 1965-01-04 1968-06-18 F. Pflaumer Phillip Detergent composition
US3332880A (en) * 1965-01-04 1967-07-25 Procter & Gamble Detergent composition
US3332877A (en) * 1965-01-04 1967-07-25 Procter & Gamble Detergent composition
US3332879A (en) * 1966-12-05 1967-07-25 Procter & Gamble Ternary synergistic sudsing detergent compositions
US3332878A (en) * 1966-12-05 1967-07-25 Procter & Gamble Detergent composition having synergistic sudsing properties containing amides and sulfonate-containing detergents

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US2240920A (en) * 1941-05-06 Sulphonation of organic compounds
US2243331A (en) * 1939-08-29 1941-05-27 Shell Dev Sulphonate
US2303212A (en) * 1939-05-26 1942-11-24 Solvay Process Co Soap composition
US2337552A (en) * 1940-08-15 1943-12-28 Du Pont Purification of saturated hydrocarbon sulphonic acids
DE899939C (de) * 1943-03-04 1953-12-17 Boehme Fettchemie G M B H Verfahren zur Herstellung chlorierter oder bromierter Sultone
US2789133A (en) * 1954-07-13 1957-04-16 Rohm & Haas Alkoxypentenyl sulfonates
US2807642A (en) * 1954-12-31 1957-09-24 Universal Oil Prod Co Method of sulfonation to produce inorganic salt-free product
US2894912A (en) * 1954-09-21 1959-07-14 Lever Brothers Ltd Isethionate detergent bar
FR1307710A (fr) * 1960-12-09 1962-10-26 Hoechst Ag Procédé de préparation d'anhydrides d'acides beta-hydroxy-alpha-sulfoniques et de leurs dérivés

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Publication number Priority date Publication date Assignee Title
US2240920A (en) * 1941-05-06 Sulphonation of organic compounds
US2303212A (en) * 1939-05-26 1942-11-24 Solvay Process Co Soap composition
US2243331A (en) * 1939-08-29 1941-05-27 Shell Dev Sulphonate
US2337552A (en) * 1940-08-15 1943-12-28 Du Pont Purification of saturated hydrocarbon sulphonic acids
DE899939C (de) * 1943-03-04 1953-12-17 Boehme Fettchemie G M B H Verfahren zur Herstellung chlorierter oder bromierter Sultone
US2789133A (en) * 1954-07-13 1957-04-16 Rohm & Haas Alkoxypentenyl sulfonates
US2894912A (en) * 1954-09-21 1959-07-14 Lever Brothers Ltd Isethionate detergent bar
US2807642A (en) * 1954-12-31 1957-09-24 Universal Oil Prod Co Method of sulfonation to produce inorganic salt-free product
FR1307710A (fr) * 1960-12-09 1962-10-26 Hoechst Ag Procédé de préparation d'anhydrides d'acides beta-hydroxy-alpha-sulfoniques et de leurs dérivés

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3523089A (en) * 1966-03-18 1970-08-04 Lever Brothers Ltd Toilet bar
US3487104A (en) * 1966-04-28 1969-12-30 Gulf Research Development Co Process for preparing alkene sulfonates
US3462525A (en) * 1966-09-15 1969-08-19 Colgate Palmolive Co Dental compositions comprising long-chain olefin sulfonates
US3720629A (en) * 1967-11-27 1973-03-13 Chevron Res Detergent composition containing hydrogenated alpha olefin sulfonates
US3637512A (en) * 1968-07-22 1972-01-25 Continental Oil Co Hydrocarbon solvent composition
US3676372A (en) * 1968-10-24 1972-07-11 Chevron Res Hydrogenated olefin sulfonate-fatty acid amide detergent compositions
US3819519A (en) * 1968-11-27 1974-06-25 Chevron Res Foam circulation fluids
US3673122A (en) * 1969-03-27 1972-06-27 Chevron Res Hydrogenated olefin sulfonate detergent bars
US5078916A (en) * 1989-01-03 1992-01-07 Shell Oil Company Detergent composition containing an internal olefin sulfonate component having an enhanced content of beta-hydroxy alkane sulfonate compounds
US10201488B2 (en) 2012-09-20 2019-02-12 Kao Corporation Internal olefin sulfonate composition and cleansing composition containing same
US9877907B2 (en) 2013-02-13 2018-01-30 Kao Corporation Internal olefin sulfonate composition

Also Published As

Publication number Publication date
FR1411808A (fr) 1965-09-24
DE1299791B (de) 1969-07-24
BE651783A (enrdf_load_stackoverflow) 1965-02-15
AU4811064A (en) 1966-02-17
NL6409378A (enrdf_load_stackoverflow) 1965-02-16
GB1066458A (en) 1967-04-26
LU46754A1 (enrdf_load_stackoverflow) 1965-02-12
AU403871B2 (en) 1970-06-25

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