Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/001—Softening compositions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
  • B01J8/003—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor in a downward flow
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
  • C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
  • C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
  • C07C323/66—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfo, esterified sulfo or halosulfonyl groups, bound to the carbon skeleton
• • 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
  • C11D1/002—Surface-active compounds containing sulfur
• • 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

Definitions

• R is a straight or branched higher alkyl group of C to Q and preferably C to C NOVEL COMPOUNDS WITH DETERGENCY AND FABRIC-SOFTENING ABILITY AND METHOD OF MAKING THE SAME
• R is a straight or branched higher alkyl group of C to Q and preferably C to C NOVEL COMPOUNDS WITH DETERGENCY AND FABRIC-SOFTENING ABILITY AND METHOD OF MAKING THE SAME
• the present invention relates to novel compounds uniquely containing foaming and detergency properties in addition to fabric-softening ability, methods of preparing the same, and novel intermediate compounds useful in their preparation. More particularly, the present invention relates to such novel compounds of the hydroxy ether (including thioether) sulfonate type.
• a yet further object of the present invention is to provide certain novel hydroxy ether sulfonates which possess detergent and foaming characteristics substantially equivalent to or superior to conventional anionic detergents and fabric-softening ability substantially equivalent to conventional cationic quaternary ammonium softeners.
• Still a further object of the present invention is to provide novel methods of producing certain hydroxy ether sulfonates possessing both detergency and fabric-softening ability, such processes including the reaction of an unsaturated alcohol with a long-chain epoxide with subsequent sulfonation of the reaction product.
• Yet a further object of the present invention is to provide novel unsaturated hydroxy ethers useful as intermediates in the production of the hydroxy ether sulfonates of the present invention.
• Still another further object of the present invention is the provision of novel hydroxy ether sulfonates which are compatible with builder salts and particularly tetrapotassium pyrophosphate in aqueous systems obviating the need for hydrotropic agents.
• R is a straight or branched higher alkyl group of C to C and preferably C to C 2.
• R is a straight or branched alkylene of C to C and preferably C to C 3
• R to R are, independently, hydrogen or straight or branched alkyl of C to C and preferably hydrogen or lower alkyl of C to C 4.
• Z is oxygen (-0-) or sulfur (S);
• M is a cation such as hydrogen, alkali metal, ammonium, substituted ammonium or amine and preferably a water-solubilizing, salt-forming group.
• sodium salts of the hydroxy ether sulfonates of the present invention are preferred, it is of course possible to advantageously employ other alkali metals such as potassium or lithium. Additionally, ammonium and amine salts, e.g., trialkanolamine salts such as triethanolamine can be advantageously employed with exceptional results.
• the novel hydroxy ether sulfonates of the present invention may be prepared by reacting an epoxy alkane with an unsaturated aliphatic alcohol with subsequent sulfonation of the reaction product.
• the epoxy alkane reactants that are useful in the preparation of the hydroxy ether sulfonates of the present invention can be any epoxy alkane having a terminal group i.e., an epoxy alkane having the structure:
• R is as defined above.
• R comprises a straight or branchedchain alkyl. radical of from about six to about 30 carbon atoms.
• Illustrative examples of some suitable alkyl radicals include:
• n-hexyl iso-hexyl iso-heptyl n-octyl iso-octyl n-nonyl iso-nonyl n-decyl n-dodecyl tertedodecyl 2-propylheptyl S-ethylnonyl 2-butyloctyl n-undecyl n-tridecyl n-tetradecyl n-pentadecyl tert-octadecyl 2,6,8-trimethylnonyl v 7-ethyl-2-methy1-4-undecyl n-hexadecyl n-octadecyl eicosyl docosyl tricosyl pentacosyl triacontyl etc.
• the alkyl radicals may also include unsaturated alkyl radicals such as hexenyl, oleyl, dodecenyl, hexadecenyl, and the like.
• Illustrative examples of some epoxy alkanes which can be employed as reactants in the process of the present invention to produce the novel hydroxy ether sulfonates of the present invention include:
• Exemplary hydroxy ether sulfonates in accordance with the present invention include:
• R is as defined above; and R is C to C which together with CH-CH forms an unsaturated group within the scope of R,,.
• Reaction 1 above is preferably catalyzed by the employment of sodium, preferably dissolved in the alcohol reactant.
• sodium preferably dissolved in the alcohol reactant.
• any catalyst material capable of effecting the condensation of the alcohol and longchain epoxide with the opening of the epoxy ring can be successfully employed in the process of the present invention.
• Such exemplary catalysts include for example BF BF -dialkyl etherate, etc.
• the reaction of the long-chain epoxide and alcohol is not critically dependent upon the choice of temperature, pressure or amount of reactants, thus, while the epoxide and alcohol react in substantially stoichiometric proportions, it is possible to employ a relatively large excess of either the long-chain epoxide or the alcohol reactant without adversely effecting the reaction system. in this respect, it has been shown that the employment of such a relatively large excess of either reactant merely necessitates removal of the excess reactant from the reaction system and does not adversely efiect the product or yield thereof.
• reaction of the present invention can be suitably run at ambient pressure or under increased pressure conditioi'is, the pressure of the system having relatively little effect upon the yield and purity of the intermediate product and final product produced. For economic purposes however, it has been found most suitable to run the reaction under atmospheric pressure conditions.
• the temperature at which the reaction is run is not critical with respect to the purity and yield of both the intermediate product and the final product in accordance with the process of the present invention.
• temperatures ranging from ambient temperatures up through approximately 150 C. have been found suitable in accordance with the process of the present invention, although any temperature may be used provided the reactants are stable thereat.
• the selection of any particular temperature will be dependent, inter alia, upon the specific reactants and the selection of catalyst, if any, employed.
• Suitable catalysts include any basic or acidic material.
• Illustrative catalysts are alkali metals, alkalihydroxides, Lewis acids such as boron trifluoride, aluminum chloride, etc.
• the catalyst concentration is not critical, and as little as 0.001 percent may be used; the upper limit may be 10 percent.
• aqueous alcohols e.g., aqueous methanol, ethanol, n-propanol, isopropanol, butanol, pyridine, etc.
• novel unsaturated hydroxy ether intermediate prepared by the reaction of the long-chain epoxide and unsaturated alcohol can be sulfonated to produce the novel detergent and 0 fabric-softening compounds of the present invention in any suitable conventional manner.
• a bisulfite e.g., sodium bisulfite
• Suitable initiators include peroxide initiators include for example tertiary butyl perbenzoates, di-tbutyl peroxide, dibenzoyl peroxide, dilauryl peroxide, etc.'(' Another initiator system is the nitrate/oxygen system eg potassium nitrate, lithium nitrate ammonium nitrate, alkaline earth nitrates and others, whichdo not accelerate bisulfite oxidation to sulfate in the presence of oxygen, preferably at a partial pressure of from I to 1.5 psi)
• nitrate/oxygen system eg potassium nitrate, lithium nitrate ammonium nitrate, alkaline earth nitrates and others, whichdo not accelerate bisulfite oxidation to sulfate in the presence of oxygen, preferably at a partial pressure of from I to 1.5 psi
• novel hydroxy ether sulfonates of the present invention in addition to possessing excellent detergency and fabric-softening properties, have been found to be compatible with the various detergent builders and other additives conventionally employed in detergent compositions. Accordingly, it is possible to formulate a detergent composition based upon the hydroxy ether sulfonate as the detergent and fabric softener. Because of the unusual compatibility of the hydroxy ether sulfonates of the present invention with the various detergent builders, it is possible to prepare both solid-phase detergent compositions and single-phase liquid detergent compositions which could not be suitably prepared with the employment of conventional linear alkyl benzene sulfonates.
• the new compounds of this invention and the new mixtures containing such compounds may be employed in a wide variety of detergent compositions, including light-duty liquid detergent formulations and granular compositions such as spray-dried built detergent powders. They may be used in toilet bars for washing the hands, face and body (here, as in other formulations, their unexpected germicidal properties are highly advantageous) or in laundry detergent bars, containing appreciable amounts of builder salts, for washing clothes. They may also be used in hair-shampooing, hair-dyeing or other hair-treating or hair-conditioning compositions. They may also be used in dental creams or other dentifrices and in skin care preparations such as creams and lotions.
• novel detergent compounds of this invention may be used as such or as mixtures with other surface-active detergents.
• the added surfaceactive detergents may be of the anionic, nonionic, cationic or amphoteric types, or mixtures thereof.
• the anionic surface active agents include those surface active or detergent compounds which contain an organic hydrophobic group and an anionic solubilizing group.
• anionic solubilizing groups are sulfonate, sulfate, carboxylate, phosphonate and phosphate.
• Suitable anionic detergents which fall within the scope of the invention include the soaps, such as the water-soluble salts of higher fatty acids or rosin acids, such as may be derived from fats, oils and waxes of animal, vegetable or marine origin, eg the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof; and the sulfated and sulfonated synthetic detergents, particularly those having about eight to 26, and preferably about 12 to 22, carbon atoms to the molecule.
• soaps such as the water-soluble salts of higher fatty acids or rosin acids, such as may be derived from fats, oils and waxes of animal, vegetable or marine origin, eg the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof
• sulfated and sulfonated synthetic detergents particularly those having about eight to 26, and preferably about 12 to 22, carbon atoms to the molecule.
• suitable synthetic anionic detergents there may be cited the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from to 16 carbon atoms in the alkyl group in a straight or branched chain, e.g., the sodium salts of higher alkyl benzene sulfonates or of the higher alkyl toluene, xylene and phenol sulfonates; alkyl napthalene sulfonate, ammonium diamyl napthalene sulfonate, and sodium dinonyl napthalene sulfonate.
• the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from to 16 carbon atoms in the alkyl group in a straight or branched chain, e.g., the sodium salts of higher alkyl benzene sul
• composition there is used a linear alkyl 1 sulfonate having a high content of 3-(or higher) phenyl isomers and a correspondingly low content (well below 50 percent of 2-( or lower) phenyl isomers; in other terminology, the benzene ring is preferably attached in large part at the 3 or higher (e.g. 4, 5, 6 or 7) position of the alkyl group and the content of isomers in which the benzene ring is attached at the the 2 or 1 position is correspondingly low.
• Particularly preferred materials are set forth in US. Pat. No. 3,320,174, May 16, 1967, OH. Rubinfeld.
• mixtures containing linear alkylbenzene sulfonates and the detergent compounds of this invention have unexpectedly good properties, particularly with respect to softening power. These mixtures are the invention of Harold Wixon.
• olefin sulfonates including long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkenesulfonates and hydroxyalkanesulfonates
• These olefin sulfonate detergents may be prepared, in known manner, by the reaction of 80;, with long chain olefins (of 8 to 25, preferably 12-21 carbon atoms) of the formula R'CH-CHR", where R is alkyl and R" is alkyl or hydrogen, to produce a mixture of sultones and alkenesulfonic acids, which mixture is then treated to convert the sultones to sulfonates.
• paraffin sulfonates such as the reaction products of alpha olefins and bisulfates (e.g. sodium bisulfate), e.g., primary paraffin sulfonates of about 10-20, preferably about 15-20 carbon atoms; sulfates or higher alcohols; salts of a-sulfofatty esters (e.g. of about 10-20 carbon atoms, such as methyl a-sulfomyristate or a-sulfotallowate).
• alpha olefins and bisulfates e.g. sodium bisulfate
• a-sulfofatty esters e.g. of about 10-20 carbon atoms, such as methyl a-sulfomyristate or a-sulfotallowate.
• sulfates of higher alcohols are sodium lauryl sulfate, sodium tallow alcohol sulfate, Turkey Red Oil or other sulfated oils, or sulfates of monoor diglycerides of fatty acids (e.g.
• alkyl poly (ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and lauryl alcohol (usually having one to five ethenoxy groups per molecule); lauryl or other higher alkyl glyceryl ether sulfonates; aromatic poly (ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and nonyl phenol (usually having one to six oxyethylene groups per molecule).
• the suitable anionic detergents include also the acyl sarocosinates (e.g. sodium lauroylsarcosinate) the acyl esters (e.g. oleic acid ester) of isethionates, and the acyl N-methyl taurides (e.g. potassium N-methyl lauroylor oleyl tauride).
• acyl sarocosinates e.g. sodium lauroylsarcosinate
• acyl esters e.g. oleic acid ester
• acyl N-methyl taurides e.g. potassium N-methyl lauroylor oleyl tauride
• the most highly preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono-, diand triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts or the higher alkyl benzene sulfonates, olefin sulfonates, the higher alkyl sulfates, and the higher fatty acid monoglyceride sulfates.
• alkali metal such as sodium and potassium
• alkaline earth metal such as calcium and magnesium
• the particular salt will be suitably selected depending upon the particular formulation and the proportions therein.
• Nonionic surface-active agents include those surface-active or detergent compounds which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amide or amino with ethylene oxide or with the polyhydration product thereof, polyethylene glycol.
• nonionic surface-active agents which may be used there may be noted the condensation products of alkyl phenols with ethylene oxide, e.g., the reaction product of isooctyl phenol with about six to 30 ethylene oxide units; condensation products of alkyl thiophenols with [0 to 15 ethylene oxide units; condensation products of higher fatty alcohols such as tridecyl alcohol with ethylene oxide; ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol monooleate and mannital monopalmitate, and the condensation products of polypropylene glycol with ethylene oxide.
• Cationic surface-active agents may also be employed. Such agents are those surface-active detergent compounds which contain an organic hydrophobic group and a cationic solubilizing group. Typical cationic solubilizing groups are amine and quaternary groups.
• suitable synthetic cationic detergents there may be noted the diamines such as those of the type RNHQl-LNH wherein R is an alkyl group of about l2 to 22 carbon atoms, such as .N-Z-aminoethyl stearyl amine and N-2- aminoethyl myristyl amine; amide-linked amines such as those of the type RCONHC l-LNH where R is an alkyl group of about nine to 20 carbon atoms, such as N-2-amino ethylstearyl amide and N-amino ethyl myristyl amide; quaternary ammonium compounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group of about 12 to l8 carbon atoms and three of the groups linked to the nitrogen atom are alkyl groups which contain one to three carbon atoms, including such one to three carbon alkyl groups bearing inert substituents, such as phenyl groups
• Typical quaternary ammonium detergents are ethyl-dimethylstearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, trimethyl stearyl ammonium chloride, trimethyl-cetyl ammonium bromide, dimethyl-ethyl dilauryl ammonium chloride, dimethyl-propylmyristyl ammonium chloride, and the corresponding methosulfates and acetates.
• amphoteric detergents are those containing both an anionic and a cationic group and a hydrophobic organic group, which is advantageously a higher aliphatic radical, e.g. of 1020 carbon atoms.
• suitable amphoteric detergents are those containing both an anionic and a cationic group and a hydrophobic organic group, which is advantageously a higher aliphatic radical, e.g. of 1020 carbon atoms.
• N- longchain alkyl aminocarboxylic acids e.g. of the formula the N-long-chain alkyl iminodicarboxylic acids (e.g. of the forwhere R is a long-chain alkyl group, e.g. of about -20 carbons, R is a divalent radical joining the amino and carboxyl portions of an amino acid (e.g.
• M is hydrogen or a salt-forming metal
• R is a hydrogen or another monovalent substituent (e.g. methyl or other lower alkyl)
• R and R are monovalent substituents joined to the nitrogen by carbon-to-nitrogen bonds (e.g. methyl or other lower alkyl substituents).
• amphoteric detergents are N-alkyl-betaaminopropionic acid; N-alkyl-beta-iminodipropionic acid, and N-alkyl, N,N-dimethyl glycine; the alkyl group may be, for example, that derived from coco fatty alcohol, lauryl alcohol, myristyl alcohol (or a lauryl-myristyl mixture), hydrogenated tallow alcohol, cetyl, stearyl, or blends of such alcohols.
• the substituted aminopropionic and iminodipropionic acids are often supplied in the sodium or other salt forms, which may likewise be used in the practice of this invention.
• amphoteric detergents examples include the fatty imidazolines such as those made by reacting a long chain fatty acid (e.g. of 10 to carbon atoms) with diethylene triamine and monohalocarboxylic acids having two to six carbon atoms, e.g. l-coco-S- hydroxethyl-S-carboxymethylimidazoline; betaines containing a sulfonic group instead of the carboxylic group; betaines in which the long-chain substituent is joined to the carboxylic group without an intervening nitrogen atom, e.g. inner salts of Z-trimethylamino fatty acids such as Z-trimethylaminolauric acid, and compounds of any of the previously mentioned types but in which the nitrogen atom is replaced by phosphorus.
• a long chain fatty acid e.g. of 10 to carbon atoms
• diethylene triamine and monohalocarboxylic acids having two to six carbon atoms e.g. l-coco
• Water-soluble builder salts may also be present, in the usual proportions, in the detergent formulations when heavy-duty cleaning is desired.
• These salts include phosphates and particularly condensed phosphates (e.g. pyrophosphates orv tripolyphosphates), as well as organic builders such as salts of nitrilotriacetic acid or ethylene diamine tetracetic acid.
• Sodium and potassium salts are preferred. Specific examples are sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, sodium tetraborate, sodium silicate, salts (e.g.
• Na salt of methylene diphosphonic acid, trisodium nitrilotriacetate, or mixtures of such builders, including mix tures of pentasodium tripolyphosphate and trisodium nitrilotriacetate in a ratio, of these two builders, of 1:10 to 10:1, e.g. 1:1.
• the proportions of builder salt may be, for example, 50 parts or more (e.g. 50 to 1,000 parts) per 100 parts of detergent.
• the detergent formulation may also contain other ingredients.
• soil-suspending agents such as sodium carboxymethyl cellulose or polyvinyl alcohol, preferably both, or other soluble polymeric materials, such as methyl cellulose (the amount of suspending agent being, for example, in the range of about 1/20 percent to 2 percent); antioxidants such as 2,6-di-tert-butylphenol, or other phenolic antioxidant materials (e.g. in amounts in the range of about 0.001 to 0.1 percent); coloring agents and optical brightening agents or fluorescent dyes in amounts in the range of, for example, about 1.20 percent to 1/2 percent.
• the optical brightening agents are such compounds as the fluorescent dyes of the stilbene type, e.g.
• hydrotropic materials such as lower alkyl aryl sulfonates, e.g.
• sodium tolueneor xylene-sulfonate may be used where desired or necessary; in general, these materials are present in minor amounts, usually in the range of about l/2 to 15 percent (e.g. 10 percent) of the total liquid' composition.
• halogenated carbanilides e.g. trichlorocarbanilide
• halogenated salicylanilide e.g. tribromosalicylanilide
• bisphenols e.g. hexachlorophene
• halogenated trifluoromethyldiphenyl urea zinc salt of lhydroxy-Z-pyridinethione and the like (e.g. in amounts in the range of about l/50 percent
• Opacifiers, perfumes, and antitarnishing agents may also be included in the detergent compositions containing the novel products of this invention, as may oxygenand chlorinereleasing bleaches, such as sodium perborate or sodium or potassium dichloroisocyanurate.
• Heavy-duty detergent compositions containing the new products may also contain sodium bromide (e.g. in amount of 0.1 to 1 percent) to improve the bleaching effect of sodium hypochlorite present in the wash water.
• the detergent compositions containing the novel products of this invention may also contain enzymes to assist in the removal of stains.
• enzymes particularly important among these are the proteolytic enzymes which such materials as pepsin, trypsin, chymotrypsin, papain, bromelin, colleginase, keratinase, carboxylase, amino peptidase, elastase, substilisia and aspergillopepidase A and B.
• the proteolytic enzymes which such materials as pepsin, trypsin, chymotrypsin, papain, bromelin, colleginase, keratinase, carboxylase, amino peptidase, elastase, substilisia and aspergillopepidase A and B.
• Alcalcase and Maxatase are commercially available enzymes.
• the enzyme is preferably present in powered form and is admixed into the detergent formulation, typically in amount of
• the novel materials of this invention may be incorporated in toothpastes, dental creams, tooth powders, liquid dentifrices, mouth washes or rinses, dental chewing gums, lozenges or troches.
• the composition may comprise some 20-75 percent of dental polishing agent, together with water.
• a humectant such as glycerol
• a gelling agent such as sodium carboxymethyl cellulose.
• Fluorides such as stannous fluoride may be present.
• the novel hydroxy ether sulfonate compounds of this invention may each be substituted for the olefin sulfonates in each of the general and specific formulations set forth in the applications of Bouchal and Salzmann, Ser. No. 579,497 and of Rubinfeld and Levinsky, Ser. No. 579,524 now abandoned, each filed Sept. 15, 1966.
• Shampoo formulations may comprise simple dispersions of the new detergent materials of this invention in water, e.g. in the form of alkanolammonium salts thereof, or combinations containing minor proportions of foam-boosting agents such as fatty acid (e.g. lauric/myristic) monoor di-ethanolamides or the corresponding isopropanolamides, or amine oxides such as lauryl dimethylamine oxide.
• foam-boosting agents such as fatty acid (e.g. lauric/myristic) monoor di-ethanolamides or the corresponding isopropanolamides, or amine oxides such as lauryl dimethylamine oxide.
• Other surface active detergents such as soaps and sodium lauryl sulfate may also be present.
• the original epoxide appears as a peak after 6.6 minutes in the column. After 3.5 hours of reflux the epoxide peak has almost disappeared, while the formation of the product can be seen as a strong peak that appears after 9 minutes in the column. After 4.5 hours of reflux the epoxide peak has disappeared completely.
• the unsaturated hydroxyether produced above is sul-- fonated by dissolving 15 grams of the unsaturated intermediate compound (0.05 moles) in 25 milliliters of methanol, adding 5.2 grams of sodium bisulfite dissolved in milliliters water, and adding 0.5 milliliters of tertiary butyl perbenzoate as a catalyst. This mixture is stirred at 75 C., and the reaction is followed by gas phase chromatography as above, this time by watching the disappearance of the peak at 9 minutes which is due to the unsaturated hydroxyether. After 3 hours at 75 C., most of the unsaturated hydroxyether has reacted.
• This product decomposes at about 1 75 C.
• Example 1V is repeated except that the two isomeric alcohols are separated by the chromatographic procedure described in example 1V and the pure primary unsaturated alcohol product is sulfonated as in example 1V.
• EXAMPLE VI The general procedure of example 1V is followed using 8.6 g. (0.1 mole) of l-pentene-S-ol containing 2 drops of boron trifluoride etherate (diethyl), and adding dropwise while stirring, 18.4 g. (0.1 mole) of dodecane-1,2-epoxide. Two main products are formed (Le. a primary and a secondary alcohol) as shown by the gas chromatogram. The products are isomeric and have the structures:
• the mixture produced above is sulfonated using g. of
• the sulfonated mixture contains:
• the Spangler Soil test is carried out using cotton percale swatches (3 inches by 6 inches) soiled with synthetically prepared sebum soil employing 1.5 g. of test detergent and 1 liter of water; the wash cycle is 10 minutes at 100 c.p.m. agitation followed by 5 minutes rinse in same water used in wash.
• the test detergent is comprised of:
• the previous example IS repeated using 0.15 moles of the alcohol and 0.1 mole of hexadecane-l,2-epoxide.
• the isolated unsaturated alcohol mixture has a boiling point range of 178184 C. at 0.6 mm. Hg.
• the molecular weight is 326.
• the product is a liquid at room temperature and contains:
• EXAMPLE X The hydroxy ether sulfonate produced in example 1 is tested for fabric-softening ability in a towel tests.
• the water employed in the foregoing softening test is l20 F., New Brunswick, N..l., tap water.
• a controlled detergent composition is prepared by combining 40 grams of sodium tripolyphosphate and I grams of active ingredient of linear dodecyl benzene sulfonate. Ten grams of the hydroxy ether sulfonate produced in example I is also added to 40 grams of the detergent builder sodium tripolyphosphate.
• the hydroxy ether sulfonate is prepared by reacting the corresponding long-chain epoxide with allyl alcohol to form the unsaturated hydroxy ether intermediate with sulfonation of the unsaturated intermediate with sodium, potassium, or ammonium bisulfite to produce the desired hydroxy ether sulfonate.
• EXAMPLE XV Example I is repeated except that the final product is acidified in water, the aqueous solution extracted with alcohol and the acid form neutralized with triethanolamine. Isolation is done similarly as in example I by precipitation with acetone.
• R is a straight or branched higher alkyl group of C to C 2.
• Rz is a straight or branched alkylene of C,, to C 3.
• R to R are, independently, hydrogen, straight or branched alkyl of C, to C,,,;
• Z is oxygen or sulfur
• R is C, alkylene.
• R is C, alkylene.
• R is C, alkylene.
• R is C,, alkylene.
• a process for producing the compounds of claim 1 which comprises reacting a 1,2-epoxy C to C alkane with a C to C, olefinically unsaturated alcohol or thiol and thereafter sulfonating the resultant product with sodium bisulfite in the presence of a peroxide initiator.

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Families Citing this family (3)

Citations (9)

Family Cites Families (1)

• 0
  • NL NL132430D patent/NL132430C/xx active
• 1968
  • 1968-11-29 US US780276A patent/US3627822A/en not_active Expired - Lifetime
  • 1968-11-29 US US780172A patent/US3609090A/en not_active Expired - Lifetime
• 1969
  • 1969-11-15 NO NO694539A patent/NO132430C/no unknown
  • 1969-11-17 SE SE7207263A patent/SE371837B/xx unknown
  • 1969-11-17 SE SE15779/69A patent/SE370070B/xx unknown
  • 1969-11-19 ES ES373687A patent/ES373687A1/es not_active Expired
  • 1969-11-21 FR FR6940067A patent/FR2024489A1/fr not_active Withdrawn
  • 1969-11-24 BE BE742104D patent/BE742104A/xx unknown
  • 1969-11-24 GB GB57348/69A patent/GB1286860A/en not_active Expired
  • 1969-11-25 DE DE19691959103 patent/DE1959103A1/de active Pending
  • 1969-11-26 CH CH211073A patent/CH567096A5/xx not_active IP Right Cessation
  • 1969-11-26 CH CH1765869A patent/CH539009A/de not_active IP Right Cessation
  • 1969-11-28 NL NL6917975A patent/NL6917975A/xx unknown

Patent Citations (9)

Non-Patent Citations (2)

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