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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/43—Solvents

Definitions

• ABSTRACT Compositions which contain isopropylamine salts of a mixture of linear alkylbenzene sulfonic acids in which the alkyl groups contain 7 through 14 carbon atoms, a predominant amount of the mixture containing from 11 through 12 carbon atoms, from about 19 to about 24 numerical percent of linear alkylbenzene sulfonic acid salts having the benzene sul fonic acid group located on the two position of the alkyl group and an organic solvent which is preferably Stoddard Solvent or 1 1 ,2-trichloro- 1 ,2 ,2- trifluoroethane or trichloromonofluoromethane.
• Such compositions have a high tolerance for water even in the presence of inorganic salts and are useful for solvent cleaning of textiles and machinery.
• Solvent cleaning solutions widely used in the past have embodied one or more of a variety of volatile solvents which have the capacity for removing stains and soils from textiles, machinery and other objects, without wetting the object to be cleaned and thus avoiding the drying step in the case of textiles and the potential corrosion in the case of machinery, attendant upon aqueous cleaning methods.
• the volatile solvent dry cleaning fluids however, often proved less than satisfactory in failing to remove water soluble soils.
• small quantities of water are usually incorporated with the solvent cleaning fluid together fluids a water and oil soluble emulsifying detergent such a long branchedchain alkylbenzene slufonate, to form water-in-oil emulsions.
• Such emulsions provide improved water soluble soil removal, but suffer from the drawback that only minor amounts of water can be incorporated while maintaining the water-in-oil character of the emulsion. Attempts at increasing the water content often produce either separation of the emulsion into two phases, water and oil, or inversion of the emulsion to an oil-inwater type emulsion. In either case, the advantages of the solvent type cleaning composition are lost, and the disadvantages of the aqueous cleaning agents reappear. Additionally, since such branched-chain alkylbenzene sulfonates are not completely biodegradable, their disposal after use adds to the stream pollution problem.
• cleaning solvents having either a high initial water content or a high water tolerance, i.e., an ability to hold, in emulsion form, large quantities of water, either present in the solvent initially or absorbed into the solvent system from the object to be cleaned such as, for example, water-wet textiles or water-wet machinery and the like, to leave the object dry and substantially free of moisture. It is especially desirable that in the solvent cleaning of textile fabrics, machine parts and the like, high water tolerances be present in the detergent-containing solvent cleaning solvent.
• an object of the present invention to provide an initially substantially anhydrous solvent cleaning emulsifier composition which is capable of tolerating and/or absorbing significantly larger proportions of water in relation to the amount of emulsifier present than has been possible in the past.
• compositions capable of forming stable emulsions with water which compositions comprise from about 0.2 to about 91% by weight of a detergent having novel characteristics which detergent comprises a mixture of linear alkylbenzene sulfonic acid isopropylamine salts, the alkyl groups of which contain from 7 through 14 carbon atoms, a predominant amount and preferably at least 75 weight percent of the alkyl groups in the linear alkylbenzene isopropylamine salt containing 1 1 through 14 carbon atoms, from about 19 to about 24, preferably from about 20 to 23.5 and more preferably from about 21.5 to 23 numerical percent of the linear alkyl benzene sulfonic acid, isopropylamine salts having the benzene sulfonic acid group located on the two position (second carbon atom phenyl; 2q5) of the linear alkyl group; and at least 9 percent by weight of the composition being essentially an organic solvent selected from ali
• the water tolerance of our novel compositions may vary somewhat with the detergent used, (Le. these mixtures alkyl aryl sulfonate salts in which the range of C and C alkyl group moieties varies and as the numerical percent of benzene sulfonic acid group located on the two position varies as indicated herein), with the concentration of the detergent present and also with the organic solvent used.
• the relationship of weight percent of the detergent required in the compositions to emulsify the maximum amount of water that can be emulsified in the composition is relatively constant and is a ratio of about 1:4. In other words, about 25% of the detergent by weight of water emulsified in the composition is required to obtain maximum water tolerance in the composition. About 25% as used herein means 25% i 7%. Larger percentages of the detergent while sometimes creating a small increase in stability generally do not increase water tolerance. For example it has been found that a maximum of water by weight of composition can be emulsified when 25% of the detergent by weight of emulsified water is present in the composition when Stoddard Solvent is used as the organic solvent.
• the solvent is selected from l,l,2-trichloro-l,2,2-trifluoroethane, sym. and assym. tetrachlorodifluoroethane, trichloro-monofluoromethane and mixtures thereof
• the maximum amount of water which can be tolerated in the composition is about 10% and again this maximum amount is reached where the detergent is present in an amount of about 25 percent by weight of water in the composition. Further increases in detergent do not further increase water tolerance.
• the relationship between the amount of detergent required to emulsify less than the maximum possible amount of Water with the particular organic solvent if more detergent were used, to the amount of water which can be emulsified with the amount of detergent actually used is not necessarily a constant relationship.
• compositions containing 0.5 weight percent of a detergent which is a mixture of the isopropylamine salts of a mixture of linear alkylbenzene sulfonic acids containing about weight percent of linear alkylbenzene sulfonic acid salts having alkyl groups which are l l or 12 carbon atoms in length and containing about 23 numerical percent linear alkylben zene sulfonic acid salts having the sulfonic acid group on the second carbon atom in the alkyl chain in Stoddard Solvent will form a stable emulsion with up to 1 gram of water
• a similar composition containing 2.0 weight percent of the detergent will form a stable emulsion with 3 to 5 weight percent of water.
• the percentages of the benzene sulfonic acid groups located on the two position of the linear alkyl group are by number (100 times the number of molecules having the benzene sulfonic acid group on the second carbon atom of the alkyl group divided by the total number of linear alkyl benzene sulfonic acid isopropylamine salt molecules in the mixture) and remaining percentages are by weight.
• compositions of this invention with respect to water tolerance may vary and will depend not only on the concentration, the nature of the alkyl side chains of the mixture of linear alkylbenzene sulfonate salts and the percentage of benzene sulfonic acid groups located on the two position of the alkyl group, but also upon the organic solvent which serves as the oil phase of the resultant emulsion.
• compositions of our invention possess certain valuable advantages over prior art compositions of U.S. Pat. No. 3,336,232, which are compositions of isopropylammonium dodecylbenzenesulfonate (Emcol P 10-59), a branched chain alkyl aryl sulfonate salt, in 1,1,2-trich1oro-l,2,2-trifluoroethane. It has been found that our compositions comprising the isopropylamine salts of a mixture of linear alkylbenzene sulfonic acid, are substantially more effective than the compositions of U.S. Pat. No. 3,336,232.
• compositions of our invention comprising the isopropylamine salts of a mixture of linear alkylbenzene sulfonic acids are substantially more effective with respect to their water tolerance.
• compositions retain their emulsifying character even in the presence of inorganic salts, e.g., sodium chloride, to a surprising degree in view of the reported sensitivity to such salts of the compositions of U.S. Pat. No. 3,336,232.
• inorganic salts e.g., sodium chloride
• compositions contain salts of linear alkylbenzene sulfonic acids which are completely biodegradable whereas the prior art compositions, since they contain a branched chain alkylbenzene sulfonate salt, are not completely biodegradable and hence, upon disposal after use, would contribute to the pollution problem.
• Stoddard Solvent is a commercially available water white petroleum distillate having a boiling range between about 154C. and about 202C. and a flash point not lower than 100F. (38C.). (Dept. of Commerce Bulletin CS 3-28).
• the detergent salts of the above compositions can be prepared by incrementally adding a linear alkylbenzene sulfonic acid mixture, which may contain up to about 10% free sulfuric acid, to a mixture of an organic solvent such as Stoddard Solvent or l,l,2-trichloro-l,2,2- trifluoroethane with isopropylamine, preferably in a ratio of about 0.5 part of about 1 part by weight of solvent to 1 part by weight of amine, the amine being present in an amount at least substantially sufficient to neutralize both the sulfonic acids and the free sulfuric acid in the linear alkylbenzene sulfonic acid mixture, adding additional amine if the resulting mixture is acidic, and then heating or blowing air through the resultant mixture to volatilize excess amine.
• an organic solvent such as Stoddard Solvent or l,l,2-trichloro-l,2,2- trifluoroethane with isopropylamine
• the resulting solution of isopropylamine salts of linear alkylbenzene sulfonic acids and isopropylamine sulfate is, at this point, substantially anhydrous, containing not more than about 3% water, usually between about 0.5 and 2.5%.
• This solution is a detergent concentrate suitable for sale and shipment in its concentrated'form.
• the salt may be prepared by addition of isopropylamine to a solution of the linear alkylbenzene sulfonic acids in the desired solvent.
• the linear alkylbenzene sulfonic acid intermediates necessary for preparation of the detergent solvent compositions of this invention may be manufactured by sulfonating a mixture of linear alkyl benzenes which mixture contains from about 19 to about 24 numerical percent 24) content, (the numerical percent of molecules having the benzene group located on the second carbon atom of the alkyl group).
• a predominant portion of the linear alkyl benzenes in the mixture in addition have alkyl groups with 11 or 12 carbon atoms.
• linear alkyl benzenes having the desired properties are generally obtained from petroleum fractionation or alternatively 211) linear alkyl benzenes can be synthesized by known procedures.
• n-dodecyl alcohol (lauryl alcohol) is prepared by catalytic reduction of lauric acid or by the alfol process using air oxygenation of metal alkyls formed from ethylene using the Ziegler-Natta process.
• the n-dodecyl alcohol is then treated with HCl and ZnCl to form l-chloro-n-dodecane.
• the l-chloro-ndodecane is then treated with benzene and AlCl by Friedel Crafts alkylation to form a product containing 2 benzene sulfonate which can be removed from other reaction products by high efficiency fractionation.
• the above detergent solution in solvent is useful per se as an emulsifier of, or additive to, various non-aqueous liquids, e.g., herbicide or insecticide sprays, gasoline, etc. It is capable of infinite dilution with additional solvent, or other conventional dry cleaning solvents and, in diluted form, is useful for a variety of applications, for example for textile dry cleaning, for scouring textiles to remove oily extruding and weaving lubricants, including graphite, from the fibers, for cleaning oil soluble and water soluble stains from machinery, glass and the like.
• solutions have outstanding water tolerance even in extremely dilute solutions; solutions containing only about 0.20% by weight of the detergent mixture being capable of emulsifying up to 15 times as much water as the weight of detergent without breaking the water-in-oil emulsion or inverting it to an oil-inwater type.
• Detergent solutions containing 1% or more of detergentmixture are capable of emulsifying water in an amount of up to times or more the weight of isopropylamine salts of the mixture of linear alkylbenzene sulfonic acids.
• the surprisingly high water tolerance of our composition appears to be due in part to the character of the detergent mixture, i.e., to the nature and mixture of the alkyl groups of the linear alkylbenzene sulfonic acids and in part to the combination of this mixture with a particular solvent.
• compositions contemplated herein will consist essentially of the following (by weight): from O to 70% of water w from 0.2 to 91% of linear alkyl benzene sulfuric acid isopropylamine salt detergent and at least 9% of solvent.
• compositions may also contain up to '60 percent by weight of total detergent of isopropylamine salts of alkyl benzene sulfonic acids having a branched chain C H to C, alkyl group in a mixture with the linear alkyl benzene sulfonic acid salts, minor amounts of other detergents, textile lubricants brightening agents, water-proofing agents and the like adjuvants conventionally added to augment the performance of solvent cleaning solutions.
• compositions may contain small quantities of non-ionic and/or anionic surfactants such as polyethoxylated phenols, alkali metal salts of complex polyphosphoric ester acid anhydrides, ethoxylated alcohol sulfates and alpha olefin sulfonates.
• non-ionic and/or anionic surfactants such as polyethoxylated phenols, alkali metal salts of complex polyphosphoric ester acid anhydrides, ethoxylated alcohol sulfates and alpha olefin sulfonates.
• our invention includes both the detergent concentrate and the diluted forms thereof.
• the detergent concentrate the form of which is suitable for shipment and sale to the ultimate user, will normally be substantially anhydrous, i.e., it may contain from 0 to about 3.0% water and may contain from about 50 to 90% by weight of the isopropylamine salts of the linear alkylbenzene sulfonic acids, the balance being essentially all organic solvent.
• Such compositions will vary from clear solutions to thick pastes.
• these detergent concentrates Upon delivery to, and prior to use by, the ultimate user, these detergent concentrates usually will be diluted to the desired strength of detergent with organic solvent, water, and auxiliary agents of the type indicated above, as suits said ultimate users purpose.
• such diluted compositions will contain: from about 0 to 10% of water from about 0.2 to 57% detergent and the balance essentially organic solvent.
• the amount of water will vary depending upon the ultimate use of the diluted emulsion, that intended for cleaning metals will contain a lesser amount (since the purpose here is mainly to remove oil soluble soils) while that intended for cleaning textiles will contain a larger amount of water (since the purpose here is to remove water soluble soils as well as oil soluble soils).
• a satisfactory solvent cleaning solution for laundering textiles materials may contain:
• the linear alkyl benzenesulfonic acids in the above composition has an alkyl carbon distribution from C to C with 79.9 weight percent ofsuch linear alkyl benzene sulfonic acids containing C and C groups, a molecular weight of about 237 and 22.6 numerical percent of the salts havingthe -benzene sulfonic acid group located on the 2 positionof the alkyl group.
• the resulting solution is somewhat acidic and is adjusted to pH of 7.5 with 93.5 additional parts of isopropylamine.
• the reaction mass is heated to 3540C. to flash off excess isopropylamine (b.p. 34C.).
• the resulting alkylbenzene isopropylamine sulfonate solution has the following analysisz EXAMPLEQ I The substantially anhydrous Stoddard solvent so1u.-. tion of the alkylbenzene isopropylamine 'sulfonate of.
• Example 1 is tested for water emulsifying properties by first diluting portions of the concentrate of Example 1 with sufficient additional Stoddard solvent to provide solutions-of amine salts of linear alkylbenzene sulfonic 8 agitated mixture was maintained at below C. An additional 6.0 parts of isopropylamine arerequired to adjust the pH of the mass to about 7.5. The mass was warmed to about C. to remove unreacted isopropylamine.
• the resultant composition weighs 903 parts and containsabout 0.4% water and about 54% solids of which about 98%is the isopropylamine salt of the mixture of linear-alkylbenzene sulfonic acids, the balance being isopropylamine sulfate. 1
• EXAMPLE 3 A mixture of 408 parts of a mixture of linear alkylbenzene .sulfonate acids containing about 80 weight percentof linear alkyl benzene sulfonic acids having a C or C alkyl group and containing about 22.6, nilmerical percent of 211) linear alkyl benzene sulfonic. acids (linear'alkyl benzene sulfonic acids having the sulfonic acid group on the second carbon atomof the alkyl group), and 415 parts of 1,1,2-trichloro-l.2.2-trifluoroethane is cooled to about 10C.
• EXAMPLE 5 The procedure of Example 4 is followed except to make a series of linear alkyl benzene sulfonic acid salts l.l.2-trichloro-l.2,2-trifluoroethane water mixtures using a series on linear alkyl benzene sulfonic acids having 17. 21.5. 226,230. 24.5, 32.0 and 36.4 numerical percent of the sulfonic acid groups located on the second carbon atom (l2 phenyl) of the alkyl group.
• the resulting mixtures are tested for stability at C. as in Example 1. The results of such tests are shown in Table III below:
• Table I 5 The strips are then placed in 100 ml. beakers with v twenty times their weight of wash liquor which is a 4% 3 Swill solution of the isopropylamine salt of a mixture of lin- (7 day ear alkylbenzene sulfonic acids in l.l.2-trichloro-l .2.2- i trifluoro-ethane prepared as described in Example 3 4: 5510 so airy; l9 above (IPA). As a control.
• EXAMPLE 7 To illustrate the use of the substantially anhydrous isopropylamine mixed salt solution in Stoddard solvent. as an emulsifier for petroleum fractions. grams of White Oil. a colorless distillate of high boiling (330 to 390C.) petroleum fractions. are placed in a container and to this oil is added slowly with rapid agitation a 3 solution of 6.25 grams of the isopropylamine salt Stodstirring for 15 minutes. Thereafter. the cloth strips are put through a wringer and immediately weighed The washer strips are then rinsed in an amount of rinse liquor equivalent to twenty times the dry weight of the strip by stirring the strip immersed in the rinse liquor for 15 minutes. The rinsed strips are put through a wringer and weighed. The strips are dried in air and then reweighed to determine the amount of residual water.
• the strips are then immersed in l()() ml. of distilled water and titrated with ().l N silver nitrate solution using potassium chromate as an indicator to determine residual sodium chloride.
• salt solution for impregnating cloth was of 2.5; concentration "2 water added to wash liquor 4'; isopropylamine salt in
• EXAMPLE 8 This example illustrates the use of our isopropylamine salt solution in the solvent cleaning of textiles containing sodium chloride.
• a set of six 6 X 3 inches strips of cotton sheeting are weighed separately and then submerged in a 10% aqueous sodium chloride solution. The thoroughly wetted strips are removed and the excess salt solution removed by passing the wet strips through a clothes wringer.
• EXAMPLE 9 6.0 parts of water. in a separatory funnel. To this solution, 5 parts of 2.0% aqueous sodium chloride are added and the mixture is shaken 30 times. The mixture is permitted to stand for at least 4 hours and the layers which form are drawn off into graduated cylinders and the volumes recorded.
• the cycle is repeated. after dilution of the oil layer to its original volume. with sufficient water, until no further emulsion forms on addition of the aqueous sodium chloride.
• the number of cycles which the detergent. solution can withstand is a measure of the sensitivity of the solution to salts. the more cycles, the less sensitive.
• an analogous detergent solution containing 2.5 parts of Emcol P -59 branch chain alkyl benzene sulfonic acid isopropylamine salt was tested similarly.
• a detergent solvent composition comprising from about 0.2 to about 91% by weight of composition of a detergent comprising a mixture of linear alkylbenzene sulfonic acid isopropylamine salts, the alkyl groups of which contain from 7 through 14 carbon atoms, a pre dominant amount of the alkyl groups in said linear alkylbenzene isopropylamine salts containing 1 1 through .12 carbon atoms.
• said linear alkylbenzene sulfonic acid isopropylamine salts having the benzene sulfonic acid group located on the two position of the linear alkyl group; and at least 9 percent by weight of said composition being essentially an organic cleaning solvent selected from the group consisting of Stoddard solvent; l.l.2-trichlor0-1,2,2-trifluoroethane; sym. or assym. tetrachlorodifluoroethane; trichloromonofluoromethane; and mixtures thereof.
• compositions asdescribed in claim 1 wherein the organic solvent is Stoddard Solvent additionally comprises up to about by weight of water and contains at least 25 percent of said detergent by weight of water when about 70 weight percent water is present in the composition.
• composition as described in claim 1 wherein the detergent consists essentially of linear alkylbenzene sulfonic acid isopropylamine salts, at least weight percent of said linear alkylbenzene sulfonic acid salts containing alkyl groups having 11 through 12 carbon atoms.
• composition as described in claim 1 in which from about 20 to about 23.5 numerical percent of the isopropylamine salts have the benzene sulfonic acid group located on the two position of the linear alkyl group.
• composition as described in claim 1 in which from about 21.5 to 23 numerical percent of the isopropylamine salts have the benzene sulfonic acid group located on the two position of the linear alkyl group.
• composition as described in claim 1 wherein said composition is substantially anhydrous.
• composition as described in claim 1 wherein the composition contains from about 0 to about 3.0 weight percent water, from about 50 to about weight percent of said linear alkyl benzene sulfonic acid isopropylamine salts. the balance being said or ganic solvent.
• compositionas described in claim 1 wherein the composition contains from about 0 to about 10 weight percent of water and 0.2 to about 57 weight percent of linear alkyl benzene sulfonic acid isopropylamine salts.
• a detergent solvent composition comprising from about 0.2 to about 91 percent by weight of composition of a detergent comprising a mixture of linear alkyl benzene sulfonic acid isopropyl amine salts. the alkyl groups of which contain from -7 through 14 carbon atoms, a predominant amount of the alkyl groups in said linear alkyl benzene isopropyl amine salts containing l1 through 12 carbon atoms-from about 19 to about 24 numerical percentof said linearalkyl benzene sulfonic acid isopropyl amine salts having the benzene sulfonic acid group located on the two position of the linear alkyl group; and at least 9 percent by weight of said composition being essentially organic solvent selected from the group consisting of Stoddard solvent; 1, 1,2 trichloro-1,2.2-trifluoroethane; trichloromonofluoromethane andmixtures thereof.
• a process for cleaning comprising washing an object with a detergent solvent composition comprising 14 sulfonic acid group located on the two position of the linear alkyl group; and at least 9 percent by weight of said composition being essentially an organic solvent selected from the group consisting of Stoddard solvent; l,2,2-trichloro-l,2,2-trifluoroethane; sym. or assym. tetrachlorodifluoroethane; trichloromonofluoromethane; and mixtures thereof.

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• 1973
  • 1973-04-16 US US351201A patent/US3926862A/en not_active Expired - Lifetime
• 1974
  • 1974-04-05 CA CA196,929A patent/CA1014445A/en not_active Expired
  • 1974-04-10 IT IT68143/74A patent/IT1024541B/it active
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  • 1974-04-13 DE DE2418178A patent/DE2418178C2/de not_active Expired
  • 1974-04-16 FR FR7413214A patent/FR2225511B3/fr not_active Expired
  • 1974-04-16 JP JP49041855A patent/JPS5746479B2/ja not_active Expired

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