Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
  • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/02—Preparations for cleaning the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q9/00—Preparations for removing hair or for aiding hair removal
  • A61Q9/02—Shaving preparations
• • 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
  • C11D10/00—Compositions of detergents, not provided for by one single preceding group
  • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
  • D06P1/628—Compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides

Definitions

• This invention relates to improvements in the production of amide-type anionic surface active sulfonates, more particularly N-higher acyl taurine salts.
• Patent 1,932,180 several processes are described for the preparation of such surface active materials, but the only process which has up to the present been employed commercially is that wherein an acid chloride is reacted in aqueous medium with a Z-aminoalkane of aliphatic and alicyclic carboxylic acids of at least 8 carbon atoms with one mole of a taurine salt of the formula wherein R is selected from the group consisting of H and hydrocarbon radicals of 1 to carbon'atoms, R is selected from the group consisting of H and lower alkyl, and M is a salt-forming radical selected from the group consisting of alkali metals and alkaline earth metals, in an inert atmosphere at a temperature of about 200 to 320 C. while removing the water formed during the reaction.
• the reaction which takes place may be illustrated by the following equation wherein stearic acid is employed as the acylating agent and the sodium salt of N-methyl sulfonic acid in the presence of an acid neutralizer such t as caustic soda.
• an acid neutralizer such t as caustic soda.
• the preparation of the .acid chloride. employed as an intermediate is not only hazardous but time-consuming and costly, since it employs phosphorus trichloride and requires at least one additional step.
• an anionic surface active agent is obtained containing a considerable quantity of salt, e.g. sodium chloride, which is highly undesirable when said surface active agent is employed in detergent and built soap formulations. such formulations imparts thereto an unduly high bygroscopicity and its removal therefrom is very expensive.
• the process of this invention eliminates the necessity for first preparing the'fatty acid chloride as a step preliminary to its subsequent reaction with the taurine, and It has also been found that this process requires a much shorter reaction time, and makes possible the attainment of excellent yields of a product in the form of a solid instead of a slurry or dilute solution.
• the product thus obtained is, further, of excellent quality relative to purity and lack-of discoloration and odor. While the exact reason for theimproved results is not known, it is thought that the excess free carboxylic acid in the reaction mixture stabilizes the taurine salt, minimizing its decomposition, increasing yields and reducing the formation of odoriferous and discolored by-products. In most cases, the use of the excess carboxylic acid acylating agent simultaneously effects a highly desirable reduction in the viscosity of the reaction mixtures.
• the duration of the reaction is generally inversely proportional to the temperature employed, the rate of reaction increasing as the temperature increases.
• the temperature employed in any particular instance will be limited by the acid employed, particularly its molecular weight, degree of unsaturation, and reactivity.
• lower temperatures may be employed where lauric acid is the acylating agent than where stearic acid is employed.
• the maximum temperature is defined by the relationship between taurine decomposition (darkening, odor, etc.) and yield. In general while 200 to 320 C. define the extreme limits of operation, a range of 200 to 260 C.
• an inert atmosphere such as nitrogen or vacuum should be maintained over the mixture during. the reaction.
• an inert atmosphere such as nitrogen or vacuum
• 10 to 200 mm. mercury absolute pressures are preferred. Pressures less than 10 mm. mercury may be employed if the acid is not too volatile. The extent of vacuum will therefore depend on the volatility of the acid and the reaction temperature.
• the inert atmosphere is maintained by use of an inert gas such as nitrogen, the gas is preferably passed in continuous manner over the reaction mixture to assist in removal of the water formed during the reaction.
• the reaction may under certain circumstances be conducted in a suitable high boiling solvent such as chlorobenzene, dichlorobenzene, nitrobenzene, chlorinated paraifins, tetrachloroethylene, trichloroethane, ethylene dichloride, propylene dichloride, toluene, xylene, alkyl benzenes, alkyl naphthalenes and the like.
• a suitable high boiling solvent such as chlorobenzene, dichlorobenzene, nitrobenzene, chlorinated paraifins, tetrachloroethylene, trichloroethane, ethylene dichloride, propylene dichloride, toluene, xylene, alkyl benzenes, alkyl naphthalenes and the like.
• a suitable high boiling solvent such as chlorobenzene, dichlorobenzene, nitrobenzene, chlorinated paraifins, tetrachlor
• the use of at least 1.2 moles of the carboxylic acid acylating agent for each mole of taurine salt is essential to the attainment of the desired results in carrying out the process of this invention. In general, proportions of about 1.5 to 2 moles of the acid per mole of taurine salt have been found sufficient in most instances.
• the reaction mixture may contain a larger excess of the acid, such as up to 6 to 10 moles or more per mole of taurine salt, where a product containing a higher free carboxylic acid content is desired. Treatment of such a product with caustic soda or potash, or an organic base, to 'saponify the free carboxylic acid would then yield in situ a detergent mixture containing soap and N-higher acyl taurine in any desired proportions.
• any increase in the amount of excess carboxylic acid employed in the reaction mixture, while to some extent aiding in stabilizing the taurine salt, at the same time tends to increase the cost of the product due to greater heat requirements and increased carboxylic acid losses.
• carboxylic acid acylating agents of at least 8 carbon atoms which may be employed in the instant invention, those preferred are of the aliphatic or alicyclic type although aromatic acids may be used. Particularly preferred are the higher fatty acids.
• carboxylic acid acylating agents of at least 8 carbon atoms which may be employed in the instant invention, those preferred are of the aliphatic or alicyclic type although aromatic acids may be used. Particularly preferred are the higher fatty acids.
• caprylic acid pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, undecylenic acid, tall oil acid, acid mixtures from various natural plant and animal oils such as olive, tallow, castor, peanut, coconut, soybean, cotton seed, ucahuba, linseed, cod, herring, menhaden, neats-foot, sperm, palm, corn, butter, ba
• alkyl benzoic acids such as dodecyl benzoic acid, nonyl benzoic acid, octyl benzoic acid, alkyl naphthoic acids such as nonyl naphthoic acid, and the like.
• R may represent hydrogen, methyl, ethyl, isopropyl or the like; R may represent either hydrogen or a hydrocarbon radical of 1 to 20 carbon atoms such as methyl, ethyl, isopropyl, butyl, heptyl, isooctyl, dodecyl, pentadecyl, stearyl, abietinyl, oleyl, cyclohexyl, phenyl, or the like, and M may represent an alkali metal such as sodium, potassium, or lithium, an alkaline earth metal such as calcium, magnesium, barium, or the like, or a tertiary or hindered amine such as dicyclohexyl amine, tributyl amine, trioc'tyl amine, triethanolamine, N,N-diphenyl methylamine, N,N-dimethyl octadecy
• the following specific 2-aminoalkane sulfonic acids may be employed in the form of their salts with a saltforming group having one of the values given above for M: taurine, ditaurine, N-methyl taurine, N-methyl ditaurine, N-ethyl taurine, N-propyl taurine, N-isopropyl taurine, N-butyl taurine, N-isobutyl taurine, N-tertiary butyl taurine, N-arnyl taurine, N-hexyl taurine, N-cyclohexyl taurine, N-phenyl taurine, N-methyl-2-methyl taurine, N-methyl-Z-ethyl taurine, N-methyl-l,2-dimethyl taurine, N-octyl taurine, N-dodecyl taurine, N-stearyl taurine, and the like.
• the taurine salts are preferably employed in the form of dried powders, but they may also be employed as aqueous solutions since the water is removed during the reaction.
• Tritaurine, Na salt In view of the high yields obtained by the process ofv the instant invention, the following reactions are also CHICHISOINB an -h-on HN cmomsoma Ditaurine impurity in taurine O CH2CHzSO
• the products obtained by this process are valuable anionic surface active agents and have many varied commercial uses.
• the most conspicuous property of these products is their great activity at surfaces and interfaces which promotes their use in a large field of the technical arts. For instance, they can be .used as wetting, frothing, or washing agents in the treating and processing of textiles; for converting liquid or solid substances which per so are insoluble in water (such as hydrocarbons, higher alcohols, oils, fats, waxes, and resins) into creamy emulsions, clear solutions or fine stable dispersions; for carbonizing, for dyeing; for the pasting of dyestuffs; for fulling, sizing, impregnating and bleaching treatments; as cleansing agents in hard water; in tanning and mordanting processes; for dyeing acetate with isoluble dyestuffs; for the preparation of dyestuffs in finely divided form; for dispersible dye powders; for producing foam for fire extinguishers; as a means for improving the absorp
• these products are valuable emulsifiers, wetting agents and dispersants for agricultural compositions containing insecticides, fungicides, bactericides, or other pesticidal substances, herbicides, plant growth regulators, fertilizers and/or soil conditioners, or the like, or mixtures thereof, in solid or liquid form.
• metal cleaning compositions dry cleaning compositions; additives for rubber latices; foam inhibitors for synthetic rubber latex emulsions; froth flotation agents; additives for road building materials; as air entraining agents for concrete or cement; additives to asphalt compositions; plasticizers and modifiers for vinyl plastics, alkyl resins, phenolformaldehyde resins and other types of polymeric-type plastic materials; for incorporation into adhesives, paint, linoleum; for use in bonding agents used in various insulating and building materials; as refining aids in wood digesters to prepare pulp, as additives to pulp slurries in beating operations to prevent foaming and also to aid the heating operation in paper-making; and as aids in the preparation of viscose dope.
• the products are also useful as emulsifiers for emulsion polymerization, as mercerizing assistants, wetting agents, rewetting agents, dispersing agents, detergents, penetrating agents, softening agents, lime soaps dispersants, dishwashing agents, anti-static agents, disinfectants, insecticides, moth-proofing agents, bactericides, fungicides and biocides. They are valuable as anti-fogging agents for use on glass and other surfaces where the accumulation of an aqueous fog is detrimental. They are useful in the rayon industry as additives to the dope or to the spinning bath-and as aids in clarifying viscose rayon. They are of value in hydraulic fluids to improve viscosity characteristics.
• the products are especially useful in breaking petroleum emulsions. They may be used to break emulsions of crude petroleum and salt water as obtained from oil wells, or to prevent water-in-oil emulsions resulting from acidization of oil wells by introducing the agent into the well, or to break or prevent emulsions which would result from a water flooding process for recovering oil from oil-bearing strata. Theymay also be used to break emulsions encountered in a petroleum refining process.
• Theproducts may be employed in the preparation of skin creams, lotions, salves and other cosmetic preparations such as home hair-wave sets, shaving creams, shampoos, toothpastes, etc. They may also be employed in food products as foaming agents, emulsifying agents, and softening agents.
• They may be used as aids in conditioning of soil; as aids in the grinding, milling or cutting of metals either in aqueous solution, emulsions or in oils; as aids in the fixing of dyes to leather and natural or synthetic fibers; as aids in level dyeing of fibers; as aids in stimulating plant growth; as an additive to cement to improve the strength of the resulting concrete or to improve its hardening time or its resistance to freezing and thawing or scaling; and as curing aids and penetrants for use in fertilizer.
• EXAMPLE 1 In a 250 cc. 3-neck flask equipped with a mechanical stirrer, stopper and exit to aspirator vacuum, were placed 11.8 g, dry sodium salt of N-methyl taurine (85% purity; .062 mole), and 35.2 g. stearic acid (.124 mole). The flask was then placed in an oil bath which was thermostatically controlled at 220 C. and held there for 10 hours under aspirator vacuum (approximately 15 to 20 mm. of mercury pressure), while the mixture was stirred.
• aspirator vacuum approximately 15 to 20 mm. of mercury pressure
• the product (molten at 220 C.) was cooled and the' resultant brittle waxy tan mass chipped out. This product had the odor of stearic acid, but no objectionable amine odor was noticed.
• Stearic acid .do 2:1 220 10 94 1 In this example the reaction was carried out at atmospheric pressure under nitrogen which was passed through the flask in a slow stream during the heating period. I 1.5 free acidtl.
• Examples 3, 13 and 16 are included in the table to illustrate the importance of employing an excess of the carboxylic acid acylating agent in the instant process.
• Example 5 is included to illustrate the importance of operating within the range of temperature disclosed hereinabove.
• Examples 13, 14 and 16 additionally show the importance of employing the acylating agent in the form of its free carboxylic acid, in excess of the amount of taurine salt, instead of in the form of its sodium salt.
• Examples 15 and 16 show that the sodium salt of the fatty acid does not interfere with the reaction as long as there remains the required amount of excess free carboxylic acid in the reaction mixture.
• Example 17 is included to illustrate the importance in employing the taurine in the form of its salt instead of in the form of the free sulfonic acid inner salt.
• the product of Ex ample 8 was converted to an excellent liquid shampoo by saponifying the excess laurice acid with triethanolamine.
• the product of Example 9 was a good cotton detergent when the excess oleic acid was saponified with caustic. It foamed well in a Maytag agitator type washing machine. It also formed a soap-detergent bar with excellent lathering and lime soap dispersing properties.
• EXAMPLE 22 Using equipment described in Example 1, 92 g. (0.324 mole) of oleic acid was mixed With 30 g. (0.162 mole) of 87% N-methyl taurine, sodium salt. The mixture was stirred and heated in an oil bath at 220 C. for 4 hours. Moderate foaming was observed during the first part of the heating period due to the evolution of water. The opaque slurry gradually changed to a clear, yellow melt. The melt was cooled to 95 C. and the excess 3 0.5 free acrdzl.
• a process comprising heating at least 1.2 moles of an acylating agent selected from the group consisting of free aliphatic and alicyclic carboxylic acids of at least 8 carbon atoms with one mole of a taurine salt of the formula wherein R is selected from the group consisting of H and hydrocarbon radicals of 1 to 20 carbon atoms, R is selected from the group consisting of H and lower alkyl, and M is a salt-forming radical selected from the group consisting of alkali metals and alkaline earth metals, in an inert atmosphere at a temperature of about 200 to 320 C. while removing the water formed during the reaction.
• taurine salt is the sodium salt of taurine.
• taurine salt is the sodium salt of N-methyl taurine.
• a process comprising heating at least 1.2 moles of an acylating agent selected from the group consisting of free aliphatic and alicyclic carboxylic acids of at least 8 carbon atoms with one mole of a taurine salt of the formula wherein R is selected from the group consisting of H and hydrocarbon radicals of 1 to 20 carbon atoms, R is selected from the group consisting of H and lower alkyl, and M is a salt-forming radical selected from the group consisting of alkali metals and alkaline earth metals, in an inert atmosphere at a temperature of about 200 to 320 C. while removing the water formed during the reaction, and then saponifying the excess acylating agent in the reaction product in situ.
• an acylating agent selected from the group consisting of free aliphatic and alicyclic carboxylic acids of at least 8 carbon atoms with one mole of a taurine salt of the formula wherein R is selected from the group consisting of H and hydrocarbon radicals of 1 to 20 carbon atoms,
• a process as defined in claim 11 acylating agent is palmitic acid.
• acylating agent is oleic acid.
• a process as defined in claim 11 acylating agent is lauric acid.
• acylating agent is tallow acid.
• a process as defined in claim taurine salt is the sodium salt of taurine.
• taurine salt is the sodium salt of N-methyl taurine.
• McCutcheon Synthetic Detergents, 1950, p. 207.

Landscapes

• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Veterinary Medicine (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Textile Engineering (AREA)
• Oral & Maxillofacial Surgery (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Dermatology (AREA)
• Organic Chemistry (AREA)
• Birds (AREA)
• Epidemiology (AREA)
• Detergent Compositions (AREA)
• Cosmetics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (3)

Applications Claiming Priority (1)

Publications (1)

Family

ID=23867882

Family Applications (1)

Country Status (2)

Cited By (24)

Citations (2)

• 0
  • NL NL95122D patent/NL95122C/xx active
  • NL NL202017D patent/NL202017A/xx unknown
• 1954
  • 1954-11-22 US US470509A patent/US2880219A/en not_active Expired - Lifetime

Patent Citations (2)

Also Published As

Similar Documents