US3676372A - Hydrogenated olefin sulfonate-fatty acid amide detergent compositions - Google Patents

Abstract

High performance detergent compositions comprise a mixture of hydrogenated olefin sulfonates and a selected amide or substituted amide.

Description

United States Patent Shannan [451 July 1 1, 1972 s41 HYDROGENATED OLEFIN [56] References Cited glkgONATE-FATIY ACID AMIDE UNITED STATES PATENTS RGENT C0 SITIONS 3,332,878 7/ 1967 Coward et al ....252/ l 52 [72] Inventor: Samuel H. Shannan, Berkeley, Calif. 3,345,301 10/ I967 Stein et al ..252/ l 52 Assignee: Chevron p y San Fran BEN-158811811 l 3 cisco, n 3,428,654 2/ 1969 Rubmfeld et a1. ..260/ 327 3,444,087 5/1969 Eccles et al ..252/138 [22] Flledz Oct. 24, 1968 [2]] Appl. No.: 770,415 Primary Examiner-Leon D. Rosdol Assistant ExaminerP. E. Willis [52] U S Cl 252/525 252/535 252/536 AtI0mey--A. L. Snow, F. E. Johnston and John Stoner, Jr.

252/544, 252/554, 252/555 511 men ..Clld3/066,Clld 1/12 [571 ABSTRACT [58] held of Search ..252/l 37, 138, 161, 125626255? High performance detergent compositions comprise a mixture of hydrogenated olefin sulfonates and a selected amide or substituted amide.

7 Claims, No Drawings HYDROGENATED OLEFIN SULFONATE-FATIY ACID AMIDE DETERGENT COMPOSITIONS BACKGROUND OF INVENTION Recent concern over water pollution has resultedfin significant changes in the active ingredient of modern detergents. Extensive and expensive research has been directed at discovering suitable detergent compounds which are both readily biodegradable and possess highdetersive properties.

Heretofore, however, known commercial detergent compounds which possessed high detersive properties were not as- DESCRIPTION OF INVENTION It has now been found that superior detergent compositions comprise a mixture of straight-chain hydrogenatedolefin sulfonates containing from 10 to 24 carbon atoms, and selected substituted and unsubstituted amides. In particular, the performance of the described mixture is significantly greater than would be predicted from a knowledge of the performance of the individual components as well as other compounds.

The term hydrogenated. olefin sulfonates as used in the present invention defines the complex mixture obtained by the S sulfonation of straight-chain olefins containing to 24 carbon'atoms and subsequent neutralization, hydrolysis and hydrogenation of the sulfonation reaction product. This complex mixture may contain hydroxyalkane, alkane and alkene sulfonates as its major components and a lesser proportion of disulfonated product.

While the general nature of the major components of the complex mixture is known, the specific identity and the relative proportions of the various hydroxy, sulfonate and disulfonate radicals and double bond locations are unknown. Accordingly, a determination of the entire chemical makeup is exceedingly difficult and has not heretofore been successfully accomplished. The mixture is best defined by the process used for producing it.

Optimum detergent characteristics are exhibited by a hydrogenated olefin sulfonate obtained by SO -air sulfonation of C F24 straight-chain olefins with an SO;,:air volume ratio of about 1 to 50-100 and SO :olefin mol ratio of 0.95 to 1.15; neutralization and hydrolysis of the sulfonation reaction product at temperatures of 145 to 200 C. using one equivalent of base per mol of S0 consumed in the sulfonation step; treatment of the sulfonate product with air, oxygen, or hydrogen peroxide; and hydrogenation in the presence of Raney nickel or palladium on carbon catalysts at temperatures of from 70 to 120 C.

In addition to the preferred straightchain alpha-olefins from wax cracking suitable olefin starting materials include straight-chain alpha-olefins produced by Ziegler polymerization of ethylene, or internal straight-chain olefins prepared by catalytic dehydrogenation of normal paraffins or by chlorination-dehydrochlorination of normal paraffins. The olefins may containfrom 10 to 24 carbon atoms, usually 13 to 22 carbon atoms, and preferably 15 to 18 carbon atoms per molecule. Olefin mixtures should have an average molecular weight of at least about 200.

The amount of SO utilized in the sulfonation reaction may be varied but is usually within the range of 0.95 to 1.25 mols of SO per mol of olefinand preferably in in the range 1:1 to 1:1.15. Greater formation of disulfonated products is observed at higher sO zolefin ratios. Disulfonation may be reduced by carrying the sulfonation reaction only to partial conversion of the olefin, for example by using so zolefin ratios of less than 1 and removing the unreacted olefins by a deoiling process. The unreacted olefins may be removed by extracting the reaction product with a hydrocarbon such as pentane.

In order to obtain a product of good color, the employed in the sulfonation reaction is generally mixed with an inert diluent or with a modifying agent. Inert diluents which are satisfactory for this purpose include air, nitrogen, 50;, dichloromethane, etc. The volume ratio of $0 to diluent is usually within the range of 1:100 to l l.

The reaction product from the sulfonation step may be neutralized with aqueous basic solutions containing compounds such as hydroxides, carbonates and oxides of the alkali metals, alkaline earth metals and ammonium. 1n the preferred method, sufficient neutralizing solution may be added to provide for neutralization of the hydroxyalkane sulfonic acids formed by sultone hydrolysis. Generally, one equivalent of base for each mole of S0 consumed in the sulfonation reaction is added to the sulfonation reaction product.

The proportion of hydroxyalkane sulfonates to alkene sulfonates in the hydrolyzed neutralized product may be varied somewhat by the manner in which neutralization and hydrolysis are carried out. Thus, reduced amounts of hydroxyalkane sulfonates are obtained by carrying out the neutralization and hydrolysis at temperatures in the range of l45-200 C. while higher yields of hydroxy sulfonate are favored by carrying out the neutralization and hydrolysis at temperatures below C. Suitable hydrolysis temperatures range from about 100 to 200 C.

Amides suitable for producing the excellent detergent compositions of the present invention may be represented by the formula 0 Il -C NHR:

wherein R is a straight-chain alkyl radical containing from 10 to 17 carbon atoms and R is hydrogen or an alkyl radical containing from 1 to three carbon atomsv The amide component of the detergent composition need not be limited to compounds containing alkyl radicals of a single set carbon number, but may include mixtures thereof, such as found in coconut amide.

In addition, when substituted amides are utilized. they likewise need not be of the same type of substitution. For example, a mixture of SOpercent coconut amide and SOpercent of N-methylhexadecanarnide is within the scope of the present invention.

Specific examples of amides suitable for use in the present invention, but by no means an exhaustive list include: dodecanamide, tridecanamide, tetradecanamide, pen tadecanamide, hexadecanamide, heptadecanamide, octadecanamide, N-methyldo-decanamide, N-methyltridecanamide, N-methyltetradecanamide, N-methylpentadecanamide, N-methylhexadecanamide, N-methylhepta'decanamide and N-methyloctadecanamide, etc.

The selected amides or mixtures thereof may comprise from 5 to 35 parts per hundred parts by weight of hydrogenated olefin sulfonate of the detergent composition. The most desirable ratio is usually from 10 to 20 parts per hundred parts by weight of olefin sulfonate.

The following examples describe the preparation of hydrogenated olefin sulfonates, their precursor olefin sulfonates and the novel detergent compositions of the present invention.

EXAMPLE 1 Preparation of Olefin Sulfonates The reactor used for this sulfonation consisted of a continuous falling film-type unit in the form of a vertical waterjacketed tube. Both the olefin and the S air mixture were introduced at the top of the reactor and flowed concurrently down to the reactor. At the bottom the sulfonated product was separated from the air stream.

The feed was a straight-chain l-olefin blend produced by cracking highly paraffinic wax and having the following composition by weight: lpercent tetradecene, 27percent pentadecene, 29percent hexadecene, 28percent heptadecene, l4percent octadecene and lpercent nonodecene. This material was charged to the top of the above described reactor at a rate of 206 pounds/hour. At the same time 124.2 pounds/hour of SO diluted with air to 3percent by volume concentration of 80;, was introduced into the top of the reactor. The reactor was cooled with water to maintain the temperature of the effluent product within the range of 4346 C. The average residenee time of the reactants in the reactor was less than 2 minutes.

After passing out of the reactor the sulfonated product was mixed with 612 pounds/hour of 11.2percent aqueous caustic and heated to l45l50 C. in a tubular reactor at an average residence time of 30 minutes. This step neutralized the sulfonic acids contained in the sulfonation reaction product, hydrolyzed the sultones to hydroxy sulfonic acids and neutral ized the hydroxy sulfonic acids. Olefin sulfonates were produced at the rate of 463 pounds per hour as an aqueous solution having a 45percent by weight solids content and a pH of 10.8.

A portion of this product was analyzed and shown to be made up of the sodium salts of alkene sulfonic acids, hydroxy alkane sulfonic acids, and disulfonic acids. These three major components were present in a weight ratio of about 50/35/15.

EXAMPLE 2 Preparation of C1540 Olefin Sulfonates A straight-chain l-olefin mixture produced by cracking a highly paraffinic wax and containing lpercent tetradecene, l8percent pentadecene, l7percent hexadecene, l6percent heptadecene, l6percent octadecene, l4percent nonadecene, l3percent eicosene and percent heneicosene was processed following the procedure in Example 1.

EXAMPLE 3 Preparation of Hydrogenated Olefin sulfonates The apparatus for this hydrogenation consisted of a l-liter Magne-Drive autoclave equipped with an accumulator, a constant pressure regulator, and a temperature recording means. The product of Example 1 was diluted with water to a 26percent solids concentration and was filtered to remove a trace amount of insoluble material. The pH was adjusted to a value of 6.5-7.5 by neutralizing the slight excess of NaOH used in the neutralization and hydrolysis step with H SO and 100 parts of 30percent hydrogen peroxide was added to 3,850 parts of the filtered 26percent solution in an open glass vessel. This mixture was heated to 80 C. and stirred for 1 hour at this temperature, after which time no hydrogen peroxide remained. After cooling this solution to room temperature, 650 g. of it was charged to the previously described autoclave along with 8.5 g. of Raney nickel. The system was purged with nitrogen and then with hydrogen. It was then pressured with hydrogen to 50 psig. The autoclave was warmed to 100 C. at which temperature hydrogen was again introduced to bring the pressure up to 100 psig. The hydrogen pressure was maintained constant at 100 psig. throughout the run. After 1% hours of stirring at this temperature and pressure, and at which time there was no additional hydrogen uptake, the solution was cooled to about 70 C., filtered and then allowed to cool.

EXAMPLE 4 Preparation of Hydrogenated Olefin Sulfonates The product of Example 2 was reduced as in Example 3 to give a substantially l00percent reduction of double bonds in the olefin sulfonate.

The hydrogen peroxide treating step prior to hydrogenation increases hydrogenation efficiency. The olefin sulfonate prior to such treatment contains unidentified compounds which poison hydrogenation catalysts. Without the hydrogen peroxide pretreat catalyst consumption is much higher. Other oxidizing agents may be used instead of hydrogen peroxide in the pretreating step, preferably oxidizing agents which leave no solid residues in the product such as elemental oxygen or air.

in addition to the Raney nickel exemplified, a wide variety of known hydrogenation catalysts may be used in the hydrogenation step. These include the noble metals and various forms of nickel other than Raney nickel such as nickel on kieselguhr, and other supported nickel catalysts. Palladium on carbon and ruthenium on alumina are effective noble metal catalysts, although Raney nickel and palladium on carbon are preferred catalysts.

The amount of catalyst employed in the hydrogenation of olefin sulfonates may vary in a range from about 0.05 to 30percent by weight based on the olefin sulfonate present. Increasing the amount of catalyst will usually result in a shortening of the time necessary for complete hydrogenation.

The hydrogenation reaction is usually carried out at temperatures from about 20 C. to about 200 C. and preferably 70 C. to C. At temperatures appreciably above 200 C. unnecessary hydrogenation of hydroxyalkane sulfonates and hydrogenative degradation of the product tend to occur.

Hydrogen pressure during the reaction is not a critical variable. Reduction may be carried out at pressures varying from less than atmospheric to 5,000 psig, but preferably from 30 to 200 psig.

In Examples 3 and 4 above hydrogenation of the alkene sulfonate component of the neutralized sulfonation reaction mixture to alkane sulfonate was essentially complete. Partial hydrogenation of the olefin sulfonate to the extent that at least SOpercent of the alkene sulfonate is converted to alkane sulfonate yields a hydrogenated olefin sulfonate suitable for use in producing high quality non-soap detergent bars. Partial hydrogenation may be accomplished by proceeding as in Example 3 but discontinuing the hydrogenation reaction before hydrogen take-up ceases. Partial hydrogenation can also be carried out by subjecting the olefin sulfonate to hydrogenation after neutralization but prior to hydrolysis.

EXAMPLE 5 Preparation of Partially Hydrogenated Olefin Sulfonate The procedure of Example 3 was followed except that reduction was allowed to continue for only 30 minutes. The product was worked up as before. Analysis of a small aliquot by bromine number titration showed that 55percent of the double bonds originally contained had been saturated.

EXAMPLE 6 Hydrogenation of an Unhydrolyzed Olefin Sulfonate l-Hexadecene was sulfonated in a continuous falling-film reactor with SO /olefin mo] ratio of about 1.2. The product from this reaction, 184 g. was dissolved in 198 g. of dioxane to give a 48percent solution.

Fifty g. of this 48percent solution was heated with stirring to 60 C. Then 2.1 g. of 34percent hydrogen peroxide was added. Stirring was continued at this temperature for 1 hour. The solution was allowed to cool to room temperature.

Of the hydrogen peroxide treated material, 17.3 g. was diluted to 50 ml. with dioxane and charged to a 200 ml.

F ischer-Porter bottle along with 0.80 g. of Spercent palladium on carbon hydrogenation catalyst. The mixture was heated to 24-26 C. and pressured to 50.5 psig with hydrogen. After 30 minutes of reaction, the pressure had dropped 18.4 psig. No further drop in pressure occurred after this time. This pressure drop corresponds to hydrogenation of 3 lpercent of the original olefin-S reaction product.

The hydrogenated material was filtered to remove the catalyst. The dioxane was removed by evaporation at temperatures below 40 C. under reduced pressure. In this way, there was obtained 8.3 g. of a low melting solid. A portion of this solid, 6.4 g. was mixed with 2.0 g. of 50percent aqueous sodium hydroxide in 35 ml. of water and heated at 150155 C. for 2 hours. The water was then removed by evaporation. A bromine number analysis of the final product indicated that about 25percent of the product was unsaturated. Accordingly, the calculated weight ratio of hydroxyalkane, alkene and a1- kane sulfonates would be 44/25/31, respectively.

EXAMPLE 7 Preparation of Detergent Composition A sample of hydrogenated olefin sulfonates produced in accordance with Example 4 was formulated with an amide and other ingredients into a household detergent composition. The percentages of the various ingredients based on the total weight of the formulation were:

Hydrogenated olefin sulfonate 21 Coconut amide 4 Sodium tripolyphosphate 40 Carboxy methyl cellulose 1 Sodium silicate 7 Sodium sulfate 19 Water 8 Total 100% Mixed amide having 8% C 7% C 49% C 17%C 9% C and 10% c The detergent formulation was dissolved in water to a 0.lpercent by weight concentration and evaluated by use of the Hand Dishwashing Test". The Hand Dishwashing Test isan effective means for evaluating the detersive characteristics of detergent compositions and is based on a procedure presented at the ASTM D-12 Subcommittee on Detergents, Mar. 10, 1949, New York, New York. The test measures under simulated home washing conditions the number of plates or dishes washed before foam collapses.

The composition of Example 7 gave an excellent rating of 30 plates by this test. In comparison a sample of olefin sulfonates prepared in accordance with Example 1 was formulated as above and tested, but gave a rating of only 25 plates.

EXAMPLE 8 A sample of hydrogenated olefin sulfonates was prepared in accordance with Example 4 and separated into two portions. The first portion, 25 parts, was dissolved in 75 parts of water. This solution was evaluated at 0.l5percent concentration in the dishwashing test and gave a low rating of only six plates. A similar solution of olefin sulfonates prepared in accordance with Example 1 was dissolved in water for a rating of 20 plates.

EXAMPLE 9 The second portion from Example 8 was combined with 19 parts of coconut amide per hundred parts of hydrogenated olefin sulfonate, and 25 parts of this mixture was dissolved in 75 parts of water. Evaluation of this composition at 0.l5percent concentration gave a rating of 16 plates, an improvement of over 250percent.

Detergent compositions were prepared in accordance with Example 7 except that different amounts and amides were substituted for coconut amide. The results obtained in the dishwashing test are shown in Table l.

TABLE I I Ex. Amide Amount Plates 7 Coconut amide 20/105 30 10 Docosanamlde 20/ 105 12 l 1 Dodecanarnlde 20/ 105 28 12 Coconut Amide 30/95 30 13 Decanomlde 20/105 24 14 None 24 Parts of amide per/parts of hydrogenated olefin sulfonate.

Another effective means for measuring the properties of 'detergent compositions is known as the Bench Foam Test. In a representative test series solutions of 0.0Spercent by weight concentration of formulations were prepared in aliquots of 1,000 ml. The test consisted of mechanically stirring the test solutions, after heating to 120 i 10 F in a 2,000 ml. beaker for 1 minute, and measuring the foam height in mm. at 0, and after 10 minutes. Foam heights of ll and 8 mm. at 0 and 10 minutes are considered satisfactory.

EXAMPLE 15 The Bench Foam Test correlates well with the dishwashing test. For example, a test on a sample prepared in accordance with Example 8 gave foam heights of 9 and 7 mm. at 0 and 10 minutes respectively. Foam heights of 14 and 13 mm. were observed for a sample prepared in accordance with Example 9 in a ratio of 20 parts of coconut amide per parts of hydrogenated olefin sulfonate.

A sample prepared in accordance with Example lo in a ratio of 10 parts of docosanamide per parts of hydrogenated olefin sulfonate gave foam heights of 7 and 6 mm. respectively.

Similar tests were run on various amides and the results are given in Table II.

Made to 0.05% by weight concentration in water. Parts of amide/per parts of hydrogenated olefin sulfonate.

Additional compatible ingredients may be incorporated into the detergent compositions prepared in accordance with the present invention to enhance their detergent properties. Particularly effective is the incorporation of certain pentavalent phosphoric acid salts. For example, suitable phosphates would include, but are not limited to: sodium tripolyphosphate, potassium tripolyphosphate, ammonium tripolyphosphate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, trisodium phosphate, tripotassium phosphate, ammonium phosphate, sodium hexametaphosphate, potassium hexametaphosphate, ammonium hexametaphosphate, monosodium orthophosphate, monopotassium orthophosphate, disodiurn orthophosphate, dipotassium orthophosphate and the like.

An effective amount of alkali pentavalent phosphoric acid salt usually comprises from about 0.2 to 3 parts per parts by weight of hydrogenated olefin sulfonate. Preferably, the ratio is l to 2 parts per part by weight of hydrogenated olefin sulfonate.

Other compatible ingredients which may be incorporated C. of the sultone content of said mixture;and into the detergent compositions of the present invention in- 3. neutralization of said mixture; and clude anticorrosion, antiredeposition, chemical bleaching and B. an amide, of the formula sequestering agents; optical whiteners and certain inorganic salts other than phosphate, such as inorganic sulfates, car- 0 bonates or borates. The appropriate quantities and compositions of these additives, agents and builders are well described Bro in the art. NHR;

Iclaim: 1. A detergent composition having improved detersive wherein R, is a straight-chain alkyl radical containing from characteristics consisting essentially of 10 to 17 carbon atoms and R is hydrogen or an alkyl A. a mixture of hydrogenated olefin sulfonates obtained by radical Containing from one to three Carbon atoms, in a sulfonating straight-chain olefins containing from 10 to io f 5 i0 35 parts per hundred parts by weight of 24 carbon atoms with S0 wherein the amount of S0,, is y g n Olefin sulfonatewithin the range of 0.95 to 1.25 mols of so per mol of A detergent Composition as in Claim 1 wherein the olefin, and wherein said sulfonated olefins are sub- Straight-chain Olefin-5 are alpha'olefinssequently subjected to, in any desired sequence, the steps A detergent composition as in Claim 2 where!" the f; straight-chain olefins contain from 15 to carbon atoms.

1. treating with an oxidizing agent selected from the A detergent composition as in claim 3 wherein the amide group consisting of hydrogen peroxide, elemental 20 is present in an amount of from 10 to 20 parts per hundred ygen, and air in an amount sufficient to improve the Parts Ofhydrogenated Olefin Q hydrogenatability th f and hydmgenating Said 5. A detergent composition as in claim 4 wherein from 75 to treated sulfonated olefins with a conventional 100 Percent of carbon'cal'bon double bonds are hydrogenation catalyst at a temperature of from about hydrogenated- 20 to 200 C" said catalyst being employed in an 6. A detergent composition as in claim 4 wherein R conamount of from about 0.05 to percent by weight tams from 11 to 13 Carbon atoms nd R lS hydrogen.

based upon the olefin sulfonate content, the 7. A detergent composition of claim 1 which contains as an hydrogenation being allowed to proceed until f 50 additional adjuvant an alkali metal pentavalent phosphoric to lOO percent of the unsaturated carbon-carbon douacid salt In an amount of from to 3 Pans by of ble bonds therein are saturated; 30 hydrogenated olefin sulfonate- 2. hydrolysis at a temperature of from about 100 to 200

Claims (8)

1. 2. A detergent composition as in claim 1 wherein the straight-chain olefins are alpha-olefins.
2. 2. hydrolysis at a temperature of from about 100* to 200* C. of the sultone content of said mixture; and
3. 3. neutralization of said mixture; and B. an amide, of the formula wherein R1 is a straight-chain alkyl radical containing from 10 to 17 carbon atoms and R2 is hydrogen or an alkyl radical containing from one to three carbon atoms, in a ratio of 5 to 35 parts per hundred parts by weight of hydrogenated olefin sulfonate.
4. 3. A detergent composition as in claim 2 wherein the straight-chain olefins contain from 15 to 20 carbon atoms.
5. 4. A detergent composition as in claim 3 wherein the amide is present in an amount of from 10 to 20 parts per hundred parts of hydrogenated olefin sulfonates.
6. 5. A detergent composition as in claim 4 wherein from 75 to 100 percent of carbon-carbon double bonds are hydrogenated.
7. 6. A detergent composition as in claim 4 wherein R1 contains from 11 to 13 carbon atoms and R2 is hydrogen.
8. 7. A detergent composition of claim 1 which contains as an additional adjuvant an alkali metal pentavalent phosphoric acid salt in an amount of from 0.2 to 3 parts by weight of hydrogenated olefin sulfonate.