US3781339A - Sulfonate mixtures based on derivatives of olefins of the vinyl,vinylidene and internal types having from 12 to 16 carbon atoms per molecule - Google Patents

Abstract

IT IS DISCLOSED THAT OLEFIN SULFONATES OBTAINED BY SAPONIFYING THE REACTION PRODUCT OF SO3 AND OLEFINS HAVING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS PER MOLECULE PROVIDE EXCELLENT HARD WATER DETERGENT MATERIALS WHEN THE OLEFINS ARE PREDOMINANTLY UNBRANCHED ACYCLIC TERMINAL MONOOLEFINS IN ADMIXTURE WITH FROM ABOUT 3 TO ABOUT 30 MOL PERCENT OF BETA-BRANCHED TERMINAL OLEFINS AND FROM ABOUT 3 TO ABOUT 12 MOL PERCENT OF INTERNAL OLEFINS. PREFERRED OLEFIN SULFONATES ARE THE SODIUM AND POTASSIUM SLATS OF ALKENE SULFONIC ACIDS AND OF HYDROXY ALKANE SULFONIC ACIDS. THE MIXTURES OF THE PRESENT INVENTION INVOLVE SULFONATES WITH FROM ABOUT 64 TO ABOUT 97 PERCENT C16, FROM ZERO TO ABOUT 15 PERCENT C14 AND FROM ABOUT 3 TO ABOUT 33 PERCENT C12 CARBON ATOMS PER MOLECULE, IN PERCENT BY WEIGHT.

Description

Dec. 25, 1973 M TUVELL ETAL. 3,781,339

SULFONATE MIXTURES BASED ON DERIVATIVES OF OLEFINS OF THE VINYL, VINYLIDENE AND INTERNAL TYPES HAVING FROM 12 TO 16 CARBON ATOMS PER MOLECULE Filed Nov. 2, 1970 United States Patent O 260513 R 7 Claims 10 Us. Cl.

ABSTRACT on THE DISCLOSURE It is disclosed that olefin sulfonates obtained by saponifying the reaction product of S0 and olefins having from about 12 to about 16 carbon atoms per molecule provide excellent hard water detergent materials when the olefins are predominantly unbranched acyclic terminal morro olefins in admixture with from about 3 to about 30 mol percent of beta-branched terminal olefins and from about 20 3 to about 12 mol percent of internal olefins. Preferred olefin sulfonates are the sodium and potassium salts of alkene sulfonic acids and of hydroxy alkane sulfonic acids. The mixtures of the present invention involve sulfonates with from about 64 to about 97 percent C from zero to about 15 percent C and from about 3 to about 33 percent C carbon atoms per molecule, in percent by 'weight.

BACKGROUND OF THE INVENTION Field of the invention Description of the prior art Alpha olefin sulfonates are will known in the prior art as being readily produced by the reaction of alpha olefins with S0 or with compounds or complexes containing or yielding S0 Of particular interest is the reaction with uncomplexed S0 The reaction is followed by saponification with a caustic or alkaline substance such as a hydroxide, oxide or carbonate of the alkali or alkaline earth metals, such as NaOH and KOH, to produce water solu- .-'ble metal salts. These products have useful properties for various washing purposes such as cleansing fabrics, skin and dishes. The carbon skeletal structures of the sulfonates are basically isomeric unsaturated and hydroxy saturated isomers having carbon skeletons similar to the starting olefins. Typically, RCHgCH CH CH=CH reacte starting olefins. Typically, RCH CH CH CH=CH reacted with 80;, produces predominantly compounds of the formulas:

v j 'The prior art teaches generally that such sulfonates 70 ,can beproduced on a basis of olefins of various carbon skeletal configurations having 10 to 24, more or less, carbon atoms per molecule. For the most part, the prior art preference is for the use of olefins having a single molecular structural configuration, particularly straight chain olefins of the alpha type and for olefins that have 16 or more, preferably 18 or more, carbon atoms per molecule. Thus in the prior art, R of the foregoing formulae is generally a straight chain saturated alkyl group having 5 to 19', more or less, carbon atoms, particularly 11 or more, preferably 13. In some instances olefins have been used that were different .from such straight chain olefins. The plurally branched propylene tetramer, for example, has been mentioned. Internal olefins and vinylidene olefins, individually, have been mentioned in a general way but for the most part there is no teaching of synergism in sulfonate mixtures based on mixed olefins.

SUMMARY OF THE INVENTION The present invention provides synergistic compositions of olefin sulfonates of certain mixed structures and of a specific narrow range of molecular weights, expressed as a specific area on the proportions plot of the figure which have excellent detergent properties, particularly as regards solubility and cleaning ability even in hard water. The materials are useful for washing porous materials such as fabrics; surfaces of living organisms, typically the skin and hair of human beings or lower animals; and for washing materials having hard, comparatively impervious, surfaces such as sheet metal or plastics in various forms including but not limited to dishes and silverware. The materials are useful at intermediate temperatures at low temperatures such as 2030 C., as well as at hot water temperatures, typically to 100 C. or higher, and at atmospheric pressure or higher or lower pressures. Utility under such a wide variety of conditions permits a single composition to be used for most if not all cleaning applications for an entire family or business establishment, for example.

DESCRIPTION OF THE DRAWING The single figure of the drawing is a ternary diagram showing the properties of various olefin sulfonate compositions. Equal-effectiveness lines for various compositions are shown based on comparison with a standard detergent system. The present invention relates to the compositions in the area A-B-C-DEF-GA of the figure.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with the present invention, olefin sulfonates are provided which are based on the saponified products of sulfonation of monoolefin mixtures having from about 12 to about 16 carbon atoms per molecule and averaging from about 14.7 to about 15.9 carbon atoms per molecule. A narrower preferred range is based on the saponified product of the sulfonation of mixtures of monoolefins having mainly 12 and 16 carbon atoms per molecule containing from zero to about 15 wt. percent sulfonates having 14 carbon atoms per molecule. Preferred olefins range from about 60 to about 98 mol percent vinyl, from about 1 to about 30 mol percent vinylidene and from about 1 to about 15 mol percent "internal olefins. Olefins sulfonated may include C C C C C or mixtures provided that the mixtures meet the foregoing requirements. Of these, preferred olefins are those containing even numbers of carbon atoms per molecule.

Such olefins are preferably produced by chain growth with ethylene on triethyl aluminum.

In typical preferred olefin mixtures, the C olefins are from about to about 98 mol percent vinyl and from about 1 to about 7 percent each of vinylidene and internal olefins. The C olefins are from about 80 to about 90 mol percent vinyl, from about 5 to about 12% each of vinylidene and internal olefins. The C olefins are from about 60 to about 70 mol percent vinyl, from about 20 to about 30% vinylidene and from about 5 to about 15% internal olefins.

When such mixtures of olefins are reacted with S and saponified with NaOH, for example, the products are principally isomeric spectra of alkene sulfonic acid sodium salts, hydroxy alkane sulfonic acid sodium salts, alkene disulfonic acid disodium salts and hydroxy alkane disulfonic acid disodium salts. Similarly, Where the saponification is wtih caustic potash the products are potassium salts of these acids. These compounds are termed olefin sulfonates. They are exemplified (as sodium salts) by the basic formulas:

where R, R and R" are H or alkyl (C H and wherein the total number of carbon atoms in R, R and R" is predominantly 7, 9 and 11.

Additional components which may be present in trace amounts include trisulfonates and higher order sulfonates. The ratios of the various sulfonates of these categories normally present on a weight basis in the products of this invention are from about 30 to about 70 percent of alkene sulfonates, from about 20 to about 70 percent of hydroxy alkane sulfonates, from about 2 percent to about 15 percent of the disulfonates, and about 1 percent or less of trisulfonates, etc., such polysulfonates containing approximately equal amounts of alkane and hydroxy alkane compounds.

The foregoing sulfona-te compounds are believed to be the result of the formation and cleavage of sultone intermediates. Such sultone intermediates form preferentially as rings with a specific number of atoms per ring, typically 5. Ratings of other numbers of atoms such as 4 and 6 are formed generally in lesser proportions. On hydrolysis the sultones open to provide the alkene sulfonates and hydroxy alkane sulfonates where the location of the unsaturation and hydroxyl groups depend to a large extent upon the number of atoms in the rings of the intermediate sultones. Some further ramification of the distribution of the various forms arises through isomerization. Thus, it is characteristic of the alkane sulfonates that they have predominantly 2-3 unsaturation (30-70 percent) with some 1-2 unsaturation (10-25 percent), some 3-4 unsaturation (-25 percent), some 4-5 unsaturation (5- percent) and so on. Similarly, it is characteristic of the hydroxy alkane sulfonates that they are predominantly 3-hydroxy compounds (about 50-70 percent) with lesser amounts of 2-hydroxy, 4-hydroxy and S-hydroxy compounds. The disulfonates, trisulfonates may be regarded as the result of the reaction of a second molecule of S0 with the double bond of an alkene sulfonate precursor and hence involving further ramifications as several spectra based on the spectra of alkene sulfonates.

It is evident that the hydrocarbon structures of the various compounds exemplified are principally constituted by a ramified substituent containing portion or radical having about 5 carbon atoms connnected to a long unsubstituted hydrocarbon radical. In general, the length variation of the unsubstituted radical is small over the range of 12-16 total carbon atoms per molecule, thus it is not essential that the relative proportions of vinyl, vinylidene and internal olefin structures be the same for all starting olefins or the resultant products. Although such similarity of distributions for the various molecular weights is preferred in some instances, it is preferred in some instances that there be a higher percentage of non-vinyl molecular structures in the C starting olefins than in the C starting olefins thereby maintaining a greater degree of similarity in the number of carbon atoms in the long unsubstituted hydrocarbon radical. Y

Examples of typical compounds in the mixtures 'described herein include the following.

tetradec-1,2-ene-1-sulfonic acid sodium salt hexadec-1,2-ene-l-sulfonic acid potassium salt dodec-1,2-ene-1-sulfonic acid sodium salt tetradec-2,3-ene-l-sulfonic acid sodium salt hexadec-2,3-ene-l-sulfonic acid sodium salt tetradec-3,4-ene-1-sulfonic acid potassium salt hexadec-3,4-ene-l-sulfonic acid sodium salt dodec-3,4-ene-1-sulfonic acid sodium salt tetradec-4,5-ene-l-sulfonic acid sodium salt hexadec-4,5-ene-l-sulfonic acid sodium salt 2-ethyl-dodec-1,2-ene-1-sulfonic acid sodium salt Z-butyl-decyl-1,2-ene-1-sulfonic acid sodium salt Z-hexyl-oct-l,2-ene-1-sulfonic acid potassium salt Z-ethyI-tetradec-1,2-ene-1-sulfonic acid sodium salt Z-butyl-dodec-1,2-ene-1-sulfonic acid sodium salt Z-hexyl-dec-l,2-ene-l-sulfonic acid sodium salt tetradec-3,4-ene-3-sulfonic acid sodium salt hexadec-3,4-ene-3-sulfonic acid sodium salt tetradec-6,7-ene-6-sulfonic acid sodium salt hexadec-6,7-ene-6-sulfonie acid potassium salt 4-ethyl-dodec-3,4-ene-3 sulfonic acid sodium salt 4-ethyl-tetradec-3,4-ene-3-sulfonic acid sodium salt undec-7,8-ene-5-(1'-ethyl methylene sulfonic acid potassium salt) tridec-7,8-ene-5-(1-ethyl methylene sulfonic acid sodium salt) tetradec-3,4-ene-1,2-disulfonic acid-disodium salt hexadec-3,4-ene-1,2-disulfonic acid-disodium salt undec-6,7-ene-5-sodium sulfonate-S- l-ethyl-methylene potassium sulfonate) tridec-6,7-ene-5-sodium sulfonate-5-(1-ethyl-methylene sodium sulfonate) tetradec-4,5-ene-1,2-disulfonic acid-disodium salt Examples of other typical compounds in the mixtures described herein include the following.

tetradec-Z-ol-l-sulfonic acid sodium salt hexadec-Z-ol-l-sulfonic acid sodium salt tetradec-3-ol-1-sulfonic acid sodium salt hexadec-S-ol-l-sulfonic acid sodium salt tetradec-4-ol-l-sulfonic acid potassium salt hexadec-4-ol-1-sulfonic acid sodium salt tetradec-S-ol-l-sulfonic acid sodium salt hexadec-S-ol-l-sulfonic acid sodium salt 2-ethyl-dodec-2-ol-l-sulfonic acid sodium salt 2-butyl-decyl-3-ol-l-sulfonic acid sodium salt 2-hexyl-oct-4-ol-l-sulfonic acid potassium salt 2-ethyl-tetradec-3-ol-l-sulfonic acid sodium salt 2-butyl-dodec-2-ol-l-sultonic acid sodium salt 2-hexyl-dec-3-ol-l-sulfonic acid sodium salt tetradec-4-ol-3-sulfonic acid sodium salt hexadec-5-ol-3-sulfonic acid sodium salt tetradec-7-ol-6-sulfonic acid sodium salt heXadec-7-ol-6-sulfonic acid potassium salt 4-ethyl-dodec-4-ol-3-sulfonic acid sodium salt 4-ethyl-tetradec-4-0l-3-sulfonic acid sodium salt' undec-8-ol-5-(1'-ethyl methylene sulfonic acid sodium salt) tridec-8-ol-5-(1'-ethyl methylene sulfonic acid sodium salt) i tetradec-4-ol-1,2-disulfonic acid-disodium salt hexadec-4-ol-1,2-disulfonic acid-disodium salt undec-7-ol-5-sodium sulfonate-5-(1'-ethyl-methylene sodium sulfonate) The sulfonate compositions are useful as detergents per se and in combination with other detergent active compounds, builders and adjuvant compounds. These materials are well known in the art.

Other actives useful in conjunction with the present compositions include anionic, nonionic, ampholytic and zwitterionic synthetic detergents individually and in various combination. Typical other actives include alkali metal and ammonium salts of higher fatty acids, alcohol sulfates, linear alkyl sulfonates, alkali metal, alkaline earth metal and ammonium alkaryl sulfonates and fatty alcohol alkoxy sulfates. Typical specific compositions include sodiumdodecylbenzenesulfonate, sodium xylene sulfonate, sodiumnonylphenol ether sulfate (40 percent ethylene oxide).

Builders are ordinarily used such as water soluble inorganic alkaline builder salts, water soluble organic alkaline 'builder salts, and mixtures thereof. The proportions of builders to such sulfonate compounds generally range from about 10:1 to about 1:10 by weight, with about 5:1 to about 1:2 being preferred.

Typical builders for use with olefin sulfonates are well known as, for example, set forth in U.S. Pat. 3,332,880. They include ammonium or alkali metal borates, carbonates, and phosphates; ammonia or alkali metal polycarboxylates, alkali metal polyphosphates. Typical builders are sodium tripolyphosphate, tri-sodium nitrolotriacetate, potassium ethane-l-hydroxy-l,l-diphosphate.

The following examples indicate preferred embodiments of the present invention.

EXAMPLE I Vinyl olefins 93.0 Vinylidene olefins 3.7 Internal olefins 3.3

The dodecene was reacted in a laboratory falling film sulfonation reactor system similar to that described in Soap and Chemical Specialty 43, 122 (May 1967) using an S olefin molar feed ratio of 1.04. The reactor was a jacketed tube of mm. internal diameter and 75 cm. length. S0 and nitrogen (5 mol percent S0 were fed as a gaseous phase at the top. The olefin was also fed at the top and in a liquid phase. The reactor temperature was 38 to 40 C. The olefin feed rate was 24 grams per hour per millimeter of internal periphery of the vertically disposed tubular reactor.

The sulfonation efliuent was saponified by reaction at reflux for eight hours with l-normal NaOH solution fed at 50-60 C. The NaOH was used in about 25 percent excess above the stoichiometric. After saponification, residual oil phase material was removed, then the mixture was cooled and back titrated to neutrality with 1- normal H SO to form product olefin sulfonates.

EXAMPLE II Example I was repeated using a high purity tetradecene cut containing 98.0 weight percent C olefins, 1.3 weight 6 percent C olefins and traces of C and other olefins and paraflins. The olefin mixture contained an overall distribution (mol percent) on a basis of molecular structure as determined by nuclear magnetic resonance (NMR) as follows:

Vinyl olefins v 82.0 Vinylidene olefins 10.9 Internal olefins 7.1

The olefins were sulfonated and the product saponified as in Example I, all conditions being the same, with the exception of the olefin feed rate which in this instance was 28 grams per hour per millimeter of internal periphery of the vertically disposed tubular reactor.

EXAMPLE III Vinyl olefins 63.0 Vinylidene olefins 27.2 Internal olefins 9.8

The olefins were sulfonated as in Example I, all conditions being the same, with the exception of the olefin feed rate which in this instance was 32 grams per hour per millimeter of internal periphery of the vertically disposed tubular reactor. The sulfonation product was converted to alkali metal salts as in Example I.

EXAMPLE IV The sulfonate products of Examples I, II and III were combined in various proportions by weight to provide various sulfonate mixtures for testing for washing performance. Data based on the results are tabulated in the figure. The curves for the various performance percentages from 30 percent to percent inclusive are based upon the results obtained when using the sulfonate products of the Examples I, II and HI in the approximate proportions mdicated, considering the deoiled sulfonate portion of the product of Example I as all C that of Example H as all C and that of Example III as all C The data for the percent line of the figure is corrected for the actual proportions of the starting olefins, considering olefins lower than C as C and those higher than C as C The 90 percent line represents from about 4 to about 33 Wt. percent C sulfonates, from 0 to about 18 percent C sulfonates and from about 60 to about 96 percent C sulfonates. The corrected compositions for the points A through G of the 90 percent line of the figure are as folows:

Wt. percent The difference between the approximate proportions and the actual proportions is small for the 90 percent performance data and negligible for the 35-85 percent data. The 30-85 percent data is readily converted to an acgial basis using the analysis given in Examples I, II an III.

The olefin sulfonate mixtures were tested using a standard comparative Dishwashing Test (J.A.O C.S. 43, 576 (1966)) to achieve a standard performance evaluation. This testing involves comparison to the performance of a representative standard washing preparation similar to commercial light duty dishwashing concentrates containing 60 percent LAS (linear alkyl benzene sulfonate, Ultrawet K), 30 percent AES (alcohol ethoxy sulfate, Steol 4N) and 10 percent LDEA (lauryl diethanol amide, Ninol AA62 extra). Tests were with water of 50-150 p.p.m. hardness at a temperature of 49 C. using active concentration of 0.045 wt. percent.

The olefin sulfonates (sodium salts) were formulated with a monoethanol amide (Stephen LMMEA) in a ratio of about 4 parts by weight of olefin sulfonates and 1 part of amide.

Results of the test are plotted in the figure, the performance lines indicating percentage based on number of plates washed by the test composition relative to the number of plates similarly washed by the standard composition.

EXAMPLE V The foregoing experiments are repeated with other sulfonation systems and conditions, including pot type reactors, sprayed chamber reactors, and the like, using saponification under various conditions of temperature and with various arrangements for immediate and delayed neutralization or hydrolysis of the sulfonation efiluent as a separate step before complete saponification and using various proportions of caustic or alkaline substance ranging from about stoichiometric (1:1) based on the number of moles of sulfonic acid radicals or precursors present in the sulfonation efiluent to about a 50 percent excess of mols of caustic or alkaline substance. Olefins sulfonated include substantially pure olefins with respect to molecular weight as well as carbon skeleton structure, as well as sub combinations, for subsequent blending, and also include total compositions for use without requiring subsequent blending.

We claim:

1. A mixture of water soluble olefin sulfonate salts which results from saponifying the reaction product of S and olefins having from about 12 to about 16 carbon atoms per molecule, the proportions of C C and C 8 olefin sulfonates being within the area defined by the points ABCDEFGA of the figure.

2. The sulfonates of claim 1 further characterized as having from about '12'to about 16 carbon atoms per molecule, averaging from about 14.7 to about 15.9 carbon atoms per molecule, and containing from 0 to about 15 wt. percent of sulfonates having 14 carbon atoms per molecule.

3. The sulfonates of claim 1 further characterized as having from about 4 to about 33 percent C sulfonates, from 0 to about 18 percent C sulfonates, and from about to about 96 percent C sulfonates. 1

4. The composition in accordance with claim 1 wherein the olefin sulfonate salts aresalts of sodium. 1 p

5. The composition in accordance with claim 1 wherein the sulfonates are salts of sodium or potassium.

6. The sulfonates of claim 1 further characterized as being derived from mixed olefins containing from about 60 to about 98 mol percent vinyl olefins, from about 1 to about 30 mol. percent vinylidene olefins and from about 1 to about 15 mol percent internal olefins.

7. The sulfonates of claim 1 further characterized as being derived from mixed olefins wherein: v V

(a) the C olefins are from about 90 to about 98 mol percent vinyl olefins, from about 1 to about 7 percent vinylidene olefins and from about 1 to about 7 percent internal olefins,

(b) the C olefins are from about to about mol percent vinyl olefins, from about 5 to about 12 percent vinylidene olefins and from about 5 to about 12 percent internal olefins, and

(c) the C olefins are from about 60 to about 70 mol percent vinyl olefins, from about 20 to about 30 percent vinylidene olefins and from about 5 to about 15 percent internal olefins. I

References Cited UNITED STATES PATENTS 3,409,637 11/1968 Eccles et a1 260-513 R FOREIGN PATENTS 1,961,963 12/1969 Germany 260-513 R DANIEL D. HORWITZ, Primary Examiner

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