Classifications

• • 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
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

• the present invention relates to detergent compositions comprising a mixture of higher linear alkyl benzene sulfonate detergents having particular characteristics as hereinafter described which exhibit a high level of performance.
• the detergent material of the type described in this invention remedies the foregoing problem because it is readily removed by degradation or adsorption on the sludge and when processed in a sewage plant produces an etlluent from said plant having little or no tendency to foam and furnishes a high level of performance as herein described.
• the present invention relates to detergent compositions comprising essentially a mixture of higher alkyl benzene sulfonates, the alkylated benzene content of said sulfonates having an average molecular weight within the range of 250 to 270, and particularly from 252 to 266, said alkyl groups being essentially linear and containing a minimum of about 85% and particularly 90% of alkyl groups having 12 to 14 carbons with at least about 10% and particularly at least about 15% each of dodecyl, tridecyl and tetradecyl groups, said alkyl benzene sulfonates having a minimum of about 37% of S-phenyl and higher phenyl isomers and a maximum of 27% of 2-phenyl isomers, said :amounts being by weight.
• a feature of the present invention resides in detergent compositions comprising a minor proportion of said sulfonates admixed with a major amount of water-soluble inorganic builder salts, particularly alkaline builder salts.
• the detergent compositions of the present invention are characterized by many desirable properties.
• the particular linear alkyl benzene sulfonate salts result in detergent compositions which exhibit optimum cleansing and foaming properties, particularly in admixture with neutral detergent builder salts or alkaline builder salts.
• the use of the particular blends or mixtures of linear "ice sulfonates herein described result in built detergent compositions which exhibit over-all superior characteristics as compared with the standard polypropylene derived tridecyl benzene sulfonate under the same conditions.
• the claimed linear alkyl benzene sulfonates having the desired structural characteristics exhibit markedly superior properties as compared with other linear alkyl benzene sulfonate mixtures not having the specified structural properties evaluated under the same conditions.
• the detergent compositions exhibit superior foaming properties in the presence of greased soil in the dishpan and a high level of washing power in the laundering of soiled textiles.
• the foaming power is enhanced in hard water where washing conditions are most demanding.
• the improved foaming, detergency and emulsification properties of the specific linear alkyl benzene sulfonates in heavy duty detergent compositions in both hard and soft water is particularly significant in comparison with the other linear phenyl alkane sulfonate detergents.
• the desired linear alkyl benzene materials should be characterized by the proper relationship and integration of various factors to provide for optimum performance of the corresponding sulfonate detergents. It has been found that the molecular Weight, the proportion of ndodecyl, tridecyl and tetradecyl alkyl groups and character of the isomer content such as the phenyl position isomers mutually affect one another and provide a criterion for the determination and selection of those sulfonate materials which result in superior performance of the ultimate detergent composition. For convenience of illustration, these factors are discussed individually below to some extent, but the desired properties result from the proper integration thereof. As indicated, the molecular weight is an important consideration.
• the linear alkyl benzene portion of said sulfonates should have a mean molecular weight within the range of 250- 270, preferably 252266, and particularly from 255 to 262 for optimum effects.
• the distribution of the carbon chains in the linear alkyl benzene structure is another important consideration.
• structures within the specified molecular weight range should contain at least about and preferably at least about of carbon chains as C C and C with less than 15% and preferably less than 10% of other alkyl chains such as C and lower and C and higher chains.
• the minimum proportion of each of the dodecyl, tridecyl and tetradecyl alkyl chains should be about 10%, and preferably 15%.
• a preferred distribution of carbon chains is about 2040% C about 30-50% C and about 20-40% of C alkyl chains.
• a third factor to be considered in optimizing the performance characteristics of the corresponding sulfonates is the distribution of phenyl isomers. For example, it has been found that the mixed chain linear alkyl benzene sulfonate materials containing particular proportions of internal 5- and 6'phenyl isomers are better foaming materials under a variety of conditions than mixtures containing predominately the 2, 3 and 4 phenyl isomers.
• a minimum of 37% of 5-, 6- and higher phenyl isomers and a maximum of 27% of the 2-phenyl alkane should be present for the proper performance characteristics.
• Preferred phenyl alkane distributions should contain the maximum 5-, 6- and higher phenyl alkane and the minimum 2- phenyl alkane consistent with economic production techniques. From the practical manufacturing stand-point, such mixtures can be made on a particularly economic basis with a 5-, 6- and higher phenyl content within the range of 3760% and the 2-phenyl content within the range of 5 to 27%.
• particularly suitable linear alkyl benzene materials have the following approximate chemical characteristics:
• Carbon chain content is expressed as mole percent.
• the products are sulfonated in known manner with a sulfonating agent, such as 20% oleum or sulfur trioxide at 90 F., and neutralized with alkali to form the corresponding water-soluble higher alkyl benzene sulfonate detergent salts.
• a sulfonating agent such as 20% oleum or sulfur trioxide at 90 F.
• alkali such as the sodium, potassium and lithium salts although other highly soluble salts such as the ammonium, and lower alkylolamine, e.g. monoand tri-ethanolamine, salts may be employed also.
• the corresponding calcium and magnesium salts are prepared similarly.
• the product may contain varying amounts of water-soluble inorganic sulfate salts resulting from the neutralization of any excess sulfuric acid employed in the sulfonation reaction.
• the linear alkyl chain may be derived from kerosene by distillation to yield a fraction containing C -C hydrocarbons, such as containing about 34% dodecyl, 43% tridecyl and 17% tetradecyl alkyl chains.
• the desired linear alkyl fraction may then be reacted with a halogen in a monohalogenation reaction process to yield a mixture of kerosene and monohalogenated kerosene which can be separated in a subsequent distillation.
• the halogenated kerosene fraction contains the halogen randomly distributed along the alkyl chain and is generally alkylated with benzene in the presence of aluminum chloride catalyst.
• the typical product of such alkylation reaction consists of an isomeric mixture of phenyl alkanes of the desired chain length containing usually a relatively high proportion of 2-phenyl alkane and relatively low proportions of other isomers as analyzed by mass spectrometry. Because the linear alkyl benzene product from this reaction contains generally a high content of the 2-phenyl alkane, it is necessary to carry out a blending operation or additional processing operations in order to reduce the 2-phenyl isomer concentration to the desired level. For example, subsequent distillation concentrates the Z-phenyl isomer in the bottoms with simultaneous increases in the higher phenyl isomers. The concentrated 2-phenyl alkane material can be then recycle to the alkylation reactor wherein rearrangement of the phenyl position occurs during the subsequent equilibrium alkylation reaction in the presence of the aluminum chloride catalyst.
• alpha olefins having the desired distribution of carbon chains in the alkylation reaction with benzene in the presence of hydrogen fluoride catalyst under proper conditions may have certain advantages.
• the hydrogen fluoride catalyst is a rate controlling catalyst 4 and the resulting product contains generally a mixture of 2-, 3-, 4-, 5-, 6- and 7-phenyl alkane which can be treated to obtain a final product of any desired proportions.
• Alkylation processes involving use of sulfuric acid catalyst result in mixtures of isomeric phenyl alkanes containing usually a high predominance of 2-phenyl alkane, and lesser amounts of the other isomers. Therefore, this product generally requires additional processing operations analogous to the aluminum chloride catalyzed alkylation product such as by blending or distillation to reduce the 2-phenyl alkane to the desired level.
• these new alkyl aryl sulfonate detergent mixtures are advantageously used in combination with detergent builders.
• Such builders are generally watersoluble inorganic salts which may be neutral builder salts such as sodium sulfate, alkaline builder salts such as sodium tripolyphosphate or mixtures of the neutral builder salts and alkaline builder salts.
• Suitable inorganic builder salts preferably alkali metal salts
• alkali metal salts are sodium and potassium carbonate, tetrasodium pyrophosphate, trisodium phosphate, sodium and potassium tripolyphosphate, sodium hexametaphosphate and sodium and potassium silicates, such as sodium metasilicate (Na O:SiO and alkaline sodium silicates (Na O:2SiO and Na O:3SiO It is in many cases advantageous to add one or more phosphates and one or more silicates in combination.
• compositions according to the invention may also contain other detergent adjuvant materials.
• Soilsuspending agents which are usually cellulosic or starch derivatives may be used, preferably the sodium salt of carboxymethylcellulose.
• Other components which may be added as desired in suitable amounts to the compositions according to the invention are bleaching agents, i.e., agents which have an oxidizing effect, and optical bleaching agents, the effect of which is due to fluorescence.
• peroxygen compounds such as persulfates, perborates and percarbonates, for example, are suitable as chemical, i.e., oxidizing, bleaching agents.
• Various organic materials intended to modify the foaming or cleansing power may be added such as lauric or coconut diethanolamide, monoethanolamide, isopropanolamide and ethylene oxide derivatives thereof, fatty alcohols such as lauryl or cetyl alcohol, amine oxides such as dodecyl dimethyl amine oxide, and the like. Solubilizing agents such as the commercial sodium and potassium Xylene and toluene sulfonates may also be included where desired.
• the new compositions can also contain other surfaceactive agents besides the alkyl aryl sulfonates of the invention. More preferably, these may be of the anionic and/ or nonionic type. Alkyl sulfonates and alkyl sulfate salts having alkyl chains of 8 to 2-0 carbon atoms are typical of the anionic surface-active agents which can be used as well as alkyl aryl sulfonates which do not have the advantageous structure of the new compounds. Other suitable anionic materials are the sulfated higher alkyl phenol-ethylene oxide condensates and the sulfated higher alkyl ethylene oxide sulfates, preferably containing an average of about 1-10 moles of ethylene oxide. Polyethylene glycol ethers and esters are examples of suitable nonionic surface-active agents which can be advantageously used in the new compositions.
• Formulations containing these specific linear alkyl benzene sulfonate salts in combination with inorganic detergent builder salts may be of the light duty type containing only neutral builder salts or of the heavy duty type containing a substantial amount of alkaline builder salts, or mixtures of alkaline and neutral builder salts.
• the proportions of the various components can be varied depending upon the type of washing formulation. Generally, both types of composition will contain a minor proportion, e.g. 150'%, usually 5 to 50% by weight and preferably 1535% by weight, of the specific linear alkyl benzene sulfonate surface active agent and a major proportion, e.g.
• the inorganic builder salts may consist of the inorganic polyphosphates such as sodium tripolyphosphate. The above amounts are by weight of the specified mixture of ingredients.
• linear alkyl benzene sulfonates represent optimum foaming performance properties in varying water hardnesses as compared with other linear alkyl benzene sulfonate mixtures under similar washing conditions when admixed with either neutral inorganic builder salts or alkaline builder salts.
• the built detergent composition within the described proportions also exhibits more foam in hard than in soft water.
• the detergent composition may be prepared in any suitable form, either as liquids, pastes or as solid product in cake (e.g. bar or tablet) or in particulate form.
• the described linear alkyl benzene sulfonates may be the sole active ingredient or admixed with other suitable materials as indicated. It is prepared preferably in particulate form by the application of known heat-drying procedures on an aqueous mixture of the sulfonate salts with or without the presence of the inorganic builders.
• an aqueous mixture of the sulfonates may be roll-dried, drum-dried or spray-dried in known manner at a temperature above 212 F. to produce particles in the form of flakes or beads.
• the materials in substantially solid form may be admixed mechanically in known manner to form a uniform mixture.
• the ingredients in solid form may be admixed with sufficient water which will be absorbed by hydratable inorganic salts to form a substantially dry product which can then be ground or sieved to size as desired.
• solubilizing materials in suitable amounts such as ethanol, propylene glycol, urea, hydrotropic salts such as sodium and potassium commercial xylene and toluene sulfonates, added foaming modifiers such as the higher fatty acid alkylolamides, builder salts in suitable proportions such as tetrapotassium pyrophosphate, other compatible detergents, etc.
• Trideeylbenzene sulfonate from polypropylene 20 20 It is to be noted that all of the linear alkyl benzene sulfonates gave substantially poorer performances than the standard tridecylbenzene sulfonate and also that the molecular weight is not a sufficient criterion per se of products exhibiting optimum performance.
• gredient as sodium salts about 35% sodium tripolyphosphate, about 7% sodium orthosilicate, about 29% sodium sulfate and about 5% moisture.
• the sulfonate in rolldried form was mixed with the other ingredients and dissolved in water to form aqueous washing solutions which were subjected to foam stability tests in a practical dishwashing procedure. In this test, all products are examined at 0.15% concentration, at 115 F. and at 50 and 150 ppm. hardnesses, employing a layer of hydrogenated vegetable oil type of soil on each plate.
• the importance of the phenyl isomer distribution namely minimizing the amount of 2-phenyl and maximizing the amount of 5-, 6- and higher phenyl in the linear alkyl benzene sulfonates, is illustrated again in the following table.
• the linear alkyl benzene sulfonates containing only 4- and higher phenyl isomers and having the desired molecular weight and phenyl isomer distribution were evaluated in the described heavy duty detergent formulation using the described dishwashing test.
• Example I Preparation of the sodium linear alkyl benzene sulfonates
• the sodium linear alkyl benzene sulfonates above-described are prepared by the following typical procedure.
• the selected alkylates are reacted with benzene using aluminum chloride or hydrogen fluoride catalyst in known manner to obtain the desired alkylated benzene product.
• These materials are sulfonated using a standard oleum batch sulfonate technique wherein 525 grams of oleum are added to 500 grams of linear alkyl benzene with agitation over the period of about 30 minutes while maintaining the temperature of the reaction at 90:5 F. using a cold water bath.
• the sulfonation reaction mixture is then heated to 120122 F.
• the acid mixture is then diluted with distilled water in a ratio of 10.8 parts of water per 100 parts of acid mix while agitating the mixture and cooling to maintain the temperature at about 130135 F.
• the diluted acid mix is then allowed to separate by gravity into a sulfonic acid rich upper layer and a sulfuric acid rich lower layer while maintaining the temperature at about 135i5 F. or centrifuged into tWo layers.
• the sulfonic acid layer containing about 88% sulfonic acid, 7% sulfuric acid and 5% water is then neutralized by adding slowly to 15-20% sodium hydroxide solution while maintaining the temperature at 120:5 F.
• the alcoholic layer containing the sulfonate is then drum dried to yield a sulfonate of 98% purity.
• the sodium linear alkyl benzene sulfonates of the present invention such as mixtures A-E in Table II above exhibit a high level of cleansing and foaming ability in dishwashing and laundering and have been found to be biodegradable.
• the aqueous slurries may be neutralized with alkali other than caustic soda in known manner to form the potassium, ammonium, triethanolamine, calcium and magnesium salts of said linear alkyl benzene sulfonates and mixtures thereof which are effective detersive materials also.
• Examples 11-111 The sodium linear alkyl benzene sulfonates in flake form are admixed with inorganic salts according to the following formulations to form light-duty product 11 and heavy-duty product III:
• the sulfonates in roll-dried form are blended with the solid powdered inorganic builder salts to yield a particulate solid product.
• Example IV The neutralized aqueous slurry of sodium linear alkyl benzene sulfonate C was prepared in spray-dried form having the following composition:
• the above ingredients are mixed at about 160 F. in a soap crutcher to form an aqueous slurry of about 60% solids.
• This slurry is submitted to spray-drying with heated air at a temperature of about 650 F. with a resultant moisture loss of almost 35%.
• the final product is recovered in the form of beads and possesses a high degree of detersive and foaming properties in both soft and hard water in dishwashing and laundering and is biodegradable after use.
• Example VIl.Abrasive cleanser Ingredients Percent Spray-dried detergent particles of Ex. IV l0 Silica (fine particle size of less than 200 mesh) 90 Minor amounts of suitable bleaching agents such as 0.25% of trichlorocyanuric acid or chlorinated trisodium phosphate or 0.5% of oxalic acid as an oxidizing agent may be added in powdered form.
• a detergent composition consisting essentially of a mixture of higher alkyl benzene sulfonates, the alkylated benzene content of said sulfonates having an average molecular weight within the range of 250 to 270, said alkyl groups being linear and containing a minimum of about 85% of alkyl chains of 12 to 14 carbons with at least about having 12 carbon atoms, at least about 10% having 13 carbon atoms and at least about 10% having 14 carbon atoms, said alkyl benzene sulfonates having phenyl isomers in at least one of the 2- and higher positions of said alkyl groups, said phenyl isomers being a minimum of about 37% of S-phenyl and higher phenyl isomers and a maximum of about 27% of 2-phenyl isomers, said amounts being by weight.
• a detergent composition consisting essentially of a mixture of Water-soluble higher alkyl benzene sulfonates, the alkylated benzene content of said sulfonates having an average molecular weight within the range of 252 to 266, said alkyl groups being linear and containing a minimum of about 90% of alkyl chains of 12 to 14 carbons with at least about 15% having 12 carbon atoms,
• said alkyl benzene sulfonates having phenyl isomers in at least one of the 2- and higher positions of said alkyl groups, said phenyl isomers being a minimum of about 37% of 5-phenyl and higher phenyl isomers and a maximum of about 27% of 2-phenyl isomers, said amounts being by weight.
• a detergent composition in accordance with claim 2 wherein said alkyl groups of 12 to 14 carbon has a carbon chain distribution of about 20-40% of 12 carbon, about 30 to 50% of 13 carbon and about 20 to 40% of 14 carbon alkyl chains.
• a detergent composition in accordance with claim 2 having a 5-phenyl and higher isomer content from 37-60% and a 2-phenyl content from 5 to 27%.
• a spray-dried detergent composition consisting essentially of about 150% of sodium higher alkyl benzene sufonates, the alkylated benzene content of said sulfonates having an average molecular weight within the range of 250 to 270, said alkyl groups being linear and containing a minimum of about of alkyl chains of 12 to 14 carbons with at least about 10% having 12 carbon atoms, at least about 10% having 13 carbon atoms and at least about 10% having 14 carbon atoms, said alkyl benzene sulfonates having phenyl isomers in at least one of the 2- and higher positions of said alkyl groups, said phenyl isomers being a minimum of about 37% of S-phenyl and higher phenyl isomers and a maximum of about 27% of 2-phenyl isomers, and 5099% of water-soluble inorganic builder salts selected from the group consisting of neutral builder salts, alkaline builder salts an mixtures thereof, said amounts being by

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Citations (4)

• 1964
  • 1964-04-20 US US361289A patent/US3320174A/en not_active Expired - Lifetime
• 1965
  • 1965-03-03 ES ES0310058A patent/ES310058A1/es not_active Expired
  • 1965-03-10 DE DEC35269A patent/DE1281087B/de active Pending
  • 1965-03-11 SE SE3220/65A patent/SE303168B/xx unknown
  • 1965-03-12 CH CH346465A patent/CH481213A/de not_active IP Right Cessation
  • 1965-03-12 GB GB10707/65A patent/GB1087337A/en not_active Expired
  • 1965-04-12 BE BE662407D patent/BE662407A/xx unknown
  • 1965-04-15 OA OA51591A patent/OA01693A/xx unknown
  • 1965-04-20 DK DK198265AA patent/DK117311B/da unknown
  • 1965-04-20 NL NL6504957A patent/NL6504957A/xx unknown

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