US 3896057 A
Description (OCR text may contain errors)
United States Patent [1 1 Lindsay et al.
[451 July 22,1975
1 1 COMPOSITE OLEFIN SULFONATE  Inventors: Kenneth L. Lindsay; Gerhard O.
Kuehnhanss; Melvin E. Tuvell, all of Baton Rouge, La.
Related U.S. Application Data  Continuation-impart of Ser. No. 760,993, Sept. 19,
 U.S. CI. 252/555; 252/536; 252/546; 252/353; 252/556; 252/DIG. ll  Int. Cl ..Cl1d 1/12  Field of Search 252/353, 535, 536, 554, 252/555, 556, 546', 260/513 R  References Cited UNITED STATES PATENTS 3,332,880 7/1967 Kessler et a1. 252/555 3,367,987 2/1968 Walsh 260/677 R 3,544,475 12/1970 Tomiyama et a]. 260/513 A 3,565,809 2/1971 Sharman 252/555 X 3,708,437 l/1973 Sweeney 252/555 3,755,203 8/1973 Bentley et al.... 252/555 X 3,808.157 4/1974 Dewitt et al. 252/555 FOREIGN PATENTS OR APPLICATIONS 1,139,158 1/l969 United Kingdom 260/513 R OTHER PUBLICATIONS DeWitt, Performance of Alpha-Olefin Sulfonates J. Am. Oil Chem. Soc., Vol. 49. pp. 361-365, June 1972.
Primary Examiner-Stephen J. Lechert, Jr. Attorney, Agent, or Firm-Donald L. Johnson; John F. Sieberth; Shelton B. McAnelly  ABSTRACT It is disclosed that sulfonate materials corresponding to the products of SO sulfonation of composite mixtures of olefins which contain significant percentages of internal olefins and of vinylidene olefins in addition to vinyl olefins (COS) are superior in detergency to similar well-known materials obtained from sulfonation of substantially pure straight chain alpha olefins (AOS). A synergism is obtained with the COS materials in comparison to the ADS materials which is contrary to expectations based on numerous teachings that the products characteristic of those derived by sulfonation of non-vinyl olefins are inferior to the products characteristic of those derived by sulfonation of vinyl olefins. It is taught herein that the superior detergency mixtures rich in branched and internal structures (COS) have utility similar to the similar materials corresponding to sulfonation products of straight chain alpha olefins (A08).
7 Claims, No Drawings COMPOSITE OLEFIN SULFONATE CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of application Ser. No. 760,993, filed Sept. 19, 1968.
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a new class of materials known as composite olefin sulfonates (COS) having useful properties as cleaning and laundering active compositions. Such materials have utility as cleaning actives in detergent formulations similar to those of A05 materials. The word composite is used in an adjective sense relative to the word sulfonates." It is not intended to imply any particular method of production process or sequence of reacting and mixing or starting material.
2. Description of the Prior Art It will be evident that prior art olefin sulfonate materials as typified in U.S. Pat. No. 3,332,880 are those characteristic of the sulfonation of pure vinyl alpha olefins containing insignificant quantities of other types of olefins such as vinylidene olefins and internal olefins. The emphasis upon the placement of the sulfonate group in the terminal position is viewed as effectively a teaching that sulfonation compounds which do not have such a structural configuration are not only undesired as components of cleansing and laundering active compositions but may be actually deleterious with regard to adverse effect upon the desirable properties of the preferred essential critical compounds. It has long been recognized that vinylidene olefins can be present in amounts up to percent or even more in alpha olefin mixtures suitable for preparing alpha olefin sulfonate detergents. See for example British Pat. No. 1,072,601 and U.S. Pat. Nos. 3,488,384 and 3,531,518.
BRIEF DESCRIPTION OF THE INVENTION It has now been discovered that synergistic cleansing and laundering active compositions are produced by using olefin sulfonation compounds derived from internal olefins and vinylidene type of alpha olefins in ternary mixtures of such sulfonation compounds with the corresponding olefin sulfonation compounds of the vinyl alpha olefins. It is believed evident that the olefin sulfonation compounds derived from the internal and the vinylidene olefins are generally similar to those derived from the sulfonation of the vinyl alpha olefins; however, the essential requirement of prior art for location of the sulfonate groups on only terminal carbon atoms is now changed. The results of this change, particularly where sulfonation compounds that characterize the sulfonation of mixed olefins of the vinyl alpha, the internal, and the vinylidene type are involved, is a surprising synergism providing not merely similar results, not inferior results, but actually providing synergistic superior results with regard to cleaning properties for the most highly preferred compositions.
SUMMARY OF THE INVENTION Water soluble salts or acids of alkene sulfonates and hydroxy alkyl sulfonates (R-SO -D) containing some R groups of unbranched carbon skeleton and with the S0 linkage to non-terminal carbon atoms of the R groups, and some R groups of branched carbon skeleton and with the S0 linkage to terminal carbon atoms;
as well as some R groups of unbranched carbon skeleton and with the S0 linkage to terminal carbon atoms have excellent detergency properties. The foregoing materials are obtainable in several ways, as by coincidental sulfonation of the corresponding mixtures of olefins, by sulfonation of olefins individually or in various groups based on various factors such as source, molecular weight, carbon skeletal configuration etc., and then combining all or selected sulfonation products, or by producing the principal components in various other conventional ways and combining the products. It is to be understood that the term (COS), like the term (A05), is one of convenience for characterization of mixtures and does not necessarily require either an olefin history or a history of olefin sulfonation processing, even though COS products may, in some instances, be prepared preferably by olefin sulfonation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The COS materials useful contain from about 10 to about 24 carbon atoms per molecule and are preferably used in the form of water soluble salts containing a cation identified generally by D such as: alkali metals lithium, sodium, and potassium, (Li Na K alkaline earth metals magnesium and calcium, (V2 Mg, /2 Ca), and ammonium (HNl-If) including substituted ammonium compounds (HNRJ), for example, trialkyl ammonium and trialkanol ammonium compounds. Specific examples of substituted ammonium compounds are triethyl ammonium, trimethyl ammonium, and triethanol ammonium. The generic terms used for referring to these cation component structures conveniently lump together the ammonium cation and the substituted ammonium cation compounds in a single term called simply ammonium" which is intended to include the substituted forms. It is in this generic sense that the term ammonium is used in the appended claims.
Preferred COS materials on a molecular weight basis are sulfonates containing from about 14 to 20 carbon atoms per molecule. A preferred restricted range for light duty applications is mixtures or individual components having from about 12 to about 16 carbon atoms per molecule. A preferred restricted range for heavy duty applications is mixtures or individual components having from about 16 to about 20 carbon atoms per molecule.
In general, the COS material sulfonates are repre sented by the formula R-SO -D.
In the fundamental aspect of the present invention the preferred components for R are mixtures consisting essentially of three principal components on a basis of various Rs identified as component A, component B and component C.
In another coincidental aspect the preferred components for R in the foregoing formula are mixtures containing mainly about equal amounts of alkene radicals and hydroxy alkyl radicals in several types characteristic of the principal products of sulfonation of olefins and which will be described in greater detail subsequently. In particular as to the coincidental latter aspect, the COS materials of components A, B and C each consist essentially of three principal sub-groups or types 1, 2 and 3 which types designation corresponds generally to the categories of U.S. Pat. No. 3,332,880 which were therein referred to as components A, B and C; however, minor proportions of more complicated molecules are present which form a spectra proposition. The distinction between the components of this application and the components" of U.S. Pat. No. 3,332,880 must be emphasized to avoid the possibility of confusion. The higher orders above about disulfonic acids are similar enough in properties and are present in such minor amounts as to be of comparatively insignificant effect upon the overall properties of the materials. A typical composition mole percent is 44 percent alkene sulfonates, 44 percent hydroxy alkyl sulfonates, 5 percent alkene disulfonates, 5 percent hydroxy alkyl disulfonates and about 2 percent miscellaneous higher order sulfonates.
COMPONENT A, B AND C DETAILS Component A represents sulfonate materials of the foregoing formula having types 1, 2 and 3 aspects whose R radicals are unbranched carbon skeletal structures wherein the linkage between the R radical and the S is to a primary carbon atom of the R radical. Such structures are those characteristic of the sulfonation of straight chain alpha olefins (vinyl olefins).
Component B represents sulfonate materials of the foregoing formula having types I, 2 and 3 aspects whose R radicals are unbranched carbon skeletal structures wherein the linkage between the R radical and the S0 is via a secondary carbon atom of the R radical and free of S0 linkage to a primary carbon atom of R, Such structures are those characteristic of the sulfonation of straight chain internal olefins.
Component C represents sulfonate materials of the foregoing formula having types 1, 2 and 3 aspects whose R radicals are of branched carbon skeletal structures wherein the linkage between the R radical and the S0 is via a primary carbon atom of the R radical. Such structures are those characteristic of the sulfonation of branched chain alpha olefins (vinylidene olefins).
The preferred distribution among components A, B and C on a molar basis is wherein from about 20 to about 95 percent of the molecules are component A materials, from about 2 to about 75 percent of the molecules are component B materials, and from about 4 to about 40 percent of the molecules are component C materials.
A preferred restricted composition range for the components A, B and C materials is wherein from about 60 to about 80 percent of the molecules are component A materials, from about 2 to about l0 percent of the molecules are component B materials, and from about 5 to about 40 percent of the molecules are component C materials. In general, this composition relates to compositions having a high molecular ratio of A to B.
Another preferred restricted composition range for component A. B and C materials is one of a somewhat lower ratio of A molecules to B molecules wherein from about 40 to about 60 percent of the molecules are component A materials, from about to about 35 percent of the molecules are component B materials and from about 5 to about 40 percent of the molecules are component C materials.
Another composition of still higher percentage of component B materials is one wherein the distribution of components on a molecular percent basis is from about to about 40 percent of the molecules are component A materials, from about 35 to about 75 percent of the molecules are component B materials and from about 5 to about 40 percent of the molecules are component C materials.
EVEN" NUMBERS OF CARBONS PREFERRED Compatibility with natural organisms provides a basis for the preference of COS materials of even number or numbers of carbon atoms per radical. As a general proposition, it is desirable to have a predominance of molecules of even number or numbers of carbon atoms per molecule. On the other hand, random, or 50-50 odd-even mixtures or predominantly or exclusively odd, though less desired, are not excluded.
SIMPLE BRANCHING PREFERRED Similarly, some forms of branching in the R radicals provide an obstacle to biodegradability so that where this is important the preference is for the branched R radicals to have single branching with short side chains located close to the primary carbon atom linked to the S0 Thus, the preference in branched structures is for those of beta-ethyl, beta-propyl and beta-butyl configuration; that is those having the short branch such as ethyl on a carbon atom adjacent to the primary carbon atom having the S0 linkage.
TYPES DISCUSSED lN PRIOR ART in addition to the foregoing classification as to components on a basis of carbon skeletal structure and dis tribution of the linkage to the $0 which form the principal feature of the present invention, the COS materials are classified as to the fundamental type distributions (1, 2 and 3) which characterize the A05 materials and which are discussed in numerous reference works such as US. Pat. No. 3,332,880.
A typical type distribution 1, 2 and 3 useful herein corresponds generally to the distribution of US. Pat. No. 3,332,880 therein called components A, B and C, respectively, which are not to be confused with components A, B and C of the present description.
Fundamentally, thte type distributions in the AOS materials arise because of the formation of unstable ring structures in initial phases of the overall reaction and rearrangements of at least some of the rings with a preference for structures of five member and six member make-up. In addition to this, the products of decomposition of the ring materials in subsequent phases of the overall reaction result in the production of two fundamental classes of sulfonate materials, one being alkene materials, the other being hydroxy alkyl materials. Thus, COS materials, like the ADS materials described in US. Pat. No. 3,332,880, are by weight about 30 percent to about percent of alkene sulfonates (Type I), about 20 percent to about 70 percent hydroxy alkyl sulfonates (Type 2) and 2-15 percent of alkene disulfonates and hydroxy disulfonates (grouped together as Type 3).
The disulfonates arise at least in part through further reaction of alkene sulfonic acids produced during the course of the overall reaction. Such acids represent material having olefinic linkages which can participate in further addition reaction with S0 The result of this is the conversion of some of the alkene mono-sulfonates into disulfonate and higher order materials which contain, in addition to the single functional group linkage to $0 mentioned in the foregoing paragraph, a second functional group linkage to another structure. Be-
cause of the aforementioned ring instability, the position of the unsaturation in the alkene mono-sulfonate molecules which react to disulfonates is subject to considezable variety. Thus, compounded variety is present in the resulting alkene disulfonates and hydroxy alkyl disulfonates.
To expand on the implications involved in the formation of ring structures in which certain arrangements are more stable than others, the stability of the fivemembered and six-membered rings results in preferentiality in the formation of isomeric mixtures of alkenyl sulfonates and hydroxy alkyl sulfonates. On a weight basis, the alkene sulfonates of the chosen range are characterized by about to about 25 percent alphabeta unsaturation, about 30 to about 70 percent betagamma unsaturation, about 5 to about 25 percent gamma-delta unsaturation, about 5 to about 10 percent delta-epsilon unsaturation, and about 5 to 10 percent of isomers containing even more remote positioning of the double bond relative to the sulfonate-carbon linkage of the molecule. A similar distribution as to the hydroxy group positions exists on the hydroxy alkyl sulfonate isomers. Of the hydroxy sulfonates, one obtains a high proportion of 3-hydroxy-, 4-hydroxy-, and 5- hydroxy-sulfonates which are useful detergent materials. Of course, it is evident that higher positional orders such as 6-hydroxy-, 7-hydroxy-, and so forth, are obtained in measureable quantities; however, in general, like the more remotely positioned isomers, they are sufficiently uniform in comparison to the other materials, performance-wise, and present in such small quantities, as to be safely ignored either in detailed discussion of sulfonation products or in synthesis of substantial equivalents from individual components. One should note. however, that these materials are present in sulfonation production of COS materials and A08 materials as well despite the fact that many references, such as US. Pat. No. 3,332,880, do not usually go into such minute detail.
To expand on the disulfonate structures, these are produced as discussed in US. Pat. No. 3,332,880 in a significant percentage such as from about two to about fifteen percent by weight of the sulfonation products and they are distributed between alkene disulfonate and hydroxy alkyl disulfonates in proportions of about 3 to 90 percent to about 5 to 75 percent, respectively. Again it is characteristic of these materials that they are of an isomeric nature as to location of the unsaturation and OH groups based upon the reaction of an isomeric spectrum of olefinic double bond materials to produce or form intermediate ring materials which prefer fiveand six-member rings and that they in turn decompose to produce isomeric materials of further variety as regards the location of the unsaturate linkage of the alkene disulfonates or the location of the hydroxy component of the hydroxy alkyl disulfonates.
From the foregoing, it is evident that double bonds in alkene disulfonic acids present in the sulfonation environment are in turn subject to further reaction to produce additional spectra, such as, trisulfonates of both the alkene and hydroxy alkyl varieties as well as similar tetrasulfonates and so forth. Again it is pointed out that most discussions do not dwell on such details and generally ignore the high order materials normalizing the monosulfonates (Types 1 and 2) to 100 percent frequently even without the disulfonates (Type 3) particularly in conjunction with consisting essentially of Ianguage so as to permit appropriate generalization in such regard. In general, limited contact devices such as falling-film reactors have some capability for minimizing the formation of the higher order materials. This capability arises, for example, through recirculation with saponification and separation of acid materials from the recirculation stream prior to reentry.
From the foregoing discussion relative to the various isomers that result from the sulfonation of olefins, generally, and of vinyl olefins particularly, one sees that various additional spectra result from the sulfonation of vinyl olefins, internal olefins and vinylidene olefins. The various spectra for these different types of olefins are generally similar, particularly in regard to the variety such as the percentages of the individual isomers, and the location of the internal double bonds and hydroxyl groups relative to the locations of the sulfonate group (S0 linkages as determined by ring stability, and the like, for the ranges of components A, B and C specified herein.
VARIETY IN E AND C COMPONENTS The position of the double bond in the internal olefins that produce component B of the COS materials and the location and length of the branching in the vi nylidene olefins that produce component C of the COS materials will influence to some degree the distributions of the isomers but this does not affect properties of the complex mixtures to any unpredictable adverse extent, and in fact, appears to be a factor in synergism. Thus, certain highly unsymmetrical internal olefins such as beta-gamma olefins will, in general, appear to have the statistical opportunity to produce somewhat larger quantities of isomers wherein the double bond of the alkene radicals and the hydroxy group of the hydroxy alkyl radicals are close to the position of the S0 linkage.
What this would mean at first glance as a matter of possible expectation based on the prior art is that there would appear to be produced a higher quantity of the supposedly undesired beta-hydroxy alkyl sulfonante materials, particularly if the olefins are rich in betagamma internal olefins and in closely branched short side chain olefins of the vinylidene type such as beta methyl vinylidene olefins. Again, despite this seemingly adverse factor, excellent results are obtainable with sulfonate mixtures characteristic of the reaction products of random internal olefins and of highly nonsymmetrical vinylidene olefins such as beta-ethyl vinylidene olefins of the ranges of carbon atoms per molecule herein specified.
SIMILAR HYDROPHOBES Another consideration in connection with the identification of the components A, B and C is that in many instances where control of such is possible as in blending operations, there are advantages in seeking to maintain similar hydrophobes in the components B and C relative to the components A. What is meant by this statement is that, with internal olefins and branched olefin structures, the hydrophobic portion of the resulting molecule or longest carbon chain from the point of attachment of S0 is, in general, inherently shorter in terms of numbers of carbon atoms than in a structure derived from a vinyl alpha olefin. In those instances where uniformity is not specifically desired, one can easily obtain a suitable olefin feedstock for sulfonation by a simple distillation which will provide controlled molecular weight ranges to provide sulfonation feed mixtures whose molecules have generally similar numbers of carbon atoms in the R radicals regardless of whether the olefins sulfonated are vinyl, vinylidene, or internal. On the other hand. where one seeks uniformity of h drophobes, as for example where specialized cleaning properties are desired. it is advantageous to employ higher molecular weight olefins to provide the components B and C of the COS materials in comparison to the olefins employed to provide components A of the COS materials. Such a situation provides an exemplification of advantages that can arise in blending feed olefins or using corresponding feed materials for other reaction or in blending of various molecular weight sulfonates themselves to achieve compositions of the present invention.
Thus, it is seen that, from a uniformity of hydrophobe viewpoint, a preferred class of compositions in accordance with the present invention is one wherein the components B and C have a greater number of carbon atoms per molecule, on the average, than the components A. An illustration of such is one wherein the components B and C have from about two to about six carbon atoms per molecule more, on an average, than the components A. Typical specific examples are those wherein the components B and C have two, four or six carbon atoms per molecule more than the molecules of component A.
R RADICAL DETAILS For the purposes of the present discussion, the R radicals are discussed on an analogy basis relative to olefins used as feed for typical S sulfonation. The structures are described in three principal categories.
The first category of R radicals (component A) corresponds to vinyl olefins which is intended to define unbranched or straight chain" or normal alpha olefins broadly characterized on a basis of molecular sizes as having from about to about 24 carbon atoms per molecule. The characteristic of the vinyl olefins is that they are straight chain structures and may be identified by a structural formula RCH=CH wherein R is normal alkyl of 822 carbon atoms. Although the term is broader, for the most part, when reference is made to alpha olefins generally it is this type of olefins that is meant unless some further characterization is made. Olefins of this type are readily produced in several ways as by chain growth with ethylene via the Ziegler techniques of US. Pat. No. 2,826,598 together with a displacement of the grown" higher alkyl residues liberating the corresponding higher olefins and producing ethyl aluminum compounds, In general, it is regarded that this is the most preferred process for producing long chain even olefins of high vinyl purity. The olefins derived by that process possess the further highly desired characteristic that they can be of exclusively even" numbers of carbon atoms per molecule since they are produced by the addition of units of ethylene to triethyl aluminum starting material.
The Ziegler chain growth process is not limited to the production of olefins of even carbon numbers per molecule. When starting with a lower trialkyl aluminum compound having an odd number of carbon atoms per molecule such as tri-n-propyl aluminum, it is possible to build up in units of two carbon atoms so as to produce molecules having odd numbers of carbon atoms.
One factor that is characteristic of the Ziegler process, however, is that the chain growth operation is a combination of splitting off, substitution and synthesis. One cannot prevent the splitting-off of alkyl residues from aluminum. The result is that even when starting with a pure tri-n-propyl aluminum, one will usually evolve a mixture approaching 50 percent evens, particularly in the upper molecular weight range in the region of 18-24 carbon atoms per molecule.
A second type of R radical, (component B) is discussed in the present connection as identified with internal olefins that can be used to produce component B materials by $0 sulfonation. This particular cate' gory of olefins as the connection is made herein is characterized by essentially mono-unsaturated unbranched carbon skeletal configurations which differ from the vinyl alpha olefins primarily only in the position of the double bond or unsaturate linkage. For this type of olefins, the general formula is RCl-l=Cl-lR wherein R and R are n-alkyl totalling from about eight to about 22 carbon atoms. From hydrophobe considerations, the general preference for the purposes of the present invention is that the groups R and R be predominantly considerably different. On the other hand, random internal olefins produced, for example, by halogenation and dehydrohalogenation of n-alkanes are suitable. In general, a non-symmetry preference for R and R extends to a point at which there is a preference for predominantly highly unsymmetrical structures such as gamma-delta olefins, beta-gamma olefins and deltaepsilon olefins. Although some internal olefins may arise in the Ziegler chain growth processes as by side reactions such as isomerization, normally that process is performed so as to avoid such side reactions and ma terials to the greatest possible extent so that a deliberate variation such as the use of severe conditions as in U.S, Pat. No. 3,451,861 by W. T. Davis and C. L. Kingrea, or mixing of streams, is normally required. For purposes of elaboration where desirable, the teachings of that patent are thus incorporated herein by reference.
A third category of R radicals (component C) involved in the present invention is identified in relationship to vinylidene olefins that can be used to produce component C materials by S0 sulfonation. A principal distinction of this type of olefins from the previously described two types vinyl and internal is that, although they are alpha or terminal in a broad sense, they are characterized by branching of the carbon skeletal chain. The branching of this type of olefins generally imparts different chemical and physical properties in comparison to vinyl and internal olefins of similar molecular weights. The general formula for vinylidene olefins is given as R R C==Cl-l where R and R are nalkyl. in the preferred exemplification for the present invention, the broad range of molecular weight of these olefins is similar to that of the other olefins ranging from a total of about 10 to about 24 carbon atoms per molecule which means that the sum of R and R ranges from about eight to about 22. in general, a nonsymmetrical distribution for R 3 and R is preferred even to the extent that a preference is for one of the groups to be ethyl. Other alkyl groups such as butyl are suitable.
ln addition to the foregoing three principal categories of olefins discussed, there are several composite types that can be mentioned in part in passing to show considerations involving them. In general, in the mixture contemplated for the present invention the quantity of these other types of olefins is preferably held low such as less than 2 percent. These olefins are largely the products of isomerization or methathesis and are difficult to avoid completely in olefins systems. In general, it can be said that the desire to avoid such structures makes it undesirable to produce mixtures of vinyl, vinylidene and internal olefins by isomerization of mixtures of vinyl and vinylidene olefins. The olefins in question are identified first as the tri-substituted olefins which are a combination of features of internal olefins and vinylidene olefins in some respects identified by the general formula R R C=CHR A metathetical variation of this is of the form R R C=CRR where R, R R and R are n-alkyl. Another olefin form involved in the present discussion is the plurally branched vinylidene olefin which is similar to the simple vinylidene olefin described in the foregoing differing primarily in that one or both of the R groups is branched alkyl. A generalized representation for such an olefin is R"(CH ),,R "CI-I(CI-I CR =CI-I where R", R and R are n-alkyl. The subscripts n and m in the above formula provide for variations in the positions of R between the extremes where n or m is zero. The various Rs above are similar or different. These branched vinylidene olefins and the COS structures that result from them, while usually not so highly desired as the others from biodegradability considerations, are acceptable in small quantities such as up to about 5 percent.
PROPERTIES OF COS MATERIALS The class of materials termed Composite Olefin Sulfonates (COS) is generally similar in properties and uses to the well known Alpha Olefin Sulfonates (AOS); however, the COS materials are characterized by a synergism that provides improved detergency relative to the AOS materials and by a lower cost for many of the compositions. Thus they provide a double application of the important cost-effectiveness consideration.
In general, the prior art emphasis with regard to AOS materials has been toward products characteristic of the S0 sulfonation of straight chain alpha olefins on the basis of a belief that such vinyl olefin derived materials are superior to similar materials derived from internal olefins or from branched alpha olefins. This strong emphasis is shown by Marquis et al. in Journal of the American Oil Chemists Society 43, p. 607 (November 1966). In addition, such emphasis is further typified by the concentration on alkene-l-sulfonic acid structures throughout US. Pat. No. 3,332,880 where statements are made as to the criticality of position of the sulfonate radical as always on the terminal carbon, and the like. Perhaps this criticality and superiority is readily shown with regard to individual comparisons of: A vinyl olefin sulfonation characteristic materials, B internal olefin sulfonation characteristic materials, and C vinylidene olefin sulfonation characteristic materials; however, it has been discovered that when materials of the three types are combined in certain proportions that a synergism is obtained wherein the detergency of cleansing and laundering formulations produced from mixtures is superior to the detergency of similar products of the type that characterize the sulfonation products of exclusively straight chain alpha olefins.
FORMULATIONS OF COS MATERIALS Formulations of COS materials have utility in light duty and in heavy duty applications. These terms as applied to detergency have acquired fairly definite meanings in the art. The term light duty generally refers to detergents used under mild conditions, particularly with regard to low temperatures such as situations involving the presence of the hands as in dishwashin g and washing of delicate fabrics. They are frequently produced as liquid concentrates with K or ammonium cations or as bars with Na or K cations.
The classification heavy duty generally applies to materials predominantly used in cleaning situations involving higher temperatures and mechanical agitation. They are used with more durable fabrics such as cottom, particularly where the amount and nature of the foreign material to be removed characterized the situation as a difficult cleaning operation.
These materials are generally produced as Na or K cation powders. In various situations to achieve various improved properties at lower cost, the COS materials are usable in admixture with other cleansing and laundering actives such as amides, alkyl aryl sulfonates, alkyl ether sulfonates, coconut alkyl glycerol ether sulfonates, alkali metal sulfuric acid esters of alkyl ethoxylates, zwitterionic quaternary ammonium compounds, and the like in various binary and ternary actives compositions. Some such combinations are typified by those used for AOS materials in U.S. Pat. Nos. 3,332,874; 3,332,876; 3,332,877; 3,332,878; and 3,332,879.
FORMULATIONS BUILDERS The COS actives with or without other actives normally are accompanied by builders, sequestering agents and soil suspending agents. Where employed, builders are used in a ratio of active detergent to builder of from about 10:1 to about 1:10. A preferred ratio is from about 2:1 to about 1:5.
Useful builders for COS materials are generally the same as for AOS materials, LAS materials and ABS materials and include a water soluble inorganic alkaline material, such as alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Typical specific examples of such builders are sodium tripolyphosphate, potassium tripolyphosphate, sodium carbonate, potassium carbonate, sodium tetraborate, potassium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, sodium hexametaphosphate, sodium sesquicarbonate, sodium monoand diorthophosphate and potassium carbonate.
Another class of typical builders includes materials of organic nature. Typical organic builders are amino polycarboxylates of alkali metals, as well as of ammonium compounds including substituted ammonium compounds as mentioned in the foregoing relative to cations. Other typical organic builders are sodium n-( 2- hydroxy ethyl)-ethylene diamine triacetate, potassium n(2-hydroxy ethyl)-ethylene diamine triacetate, sodium nitrilotriacetate, potassium nitrilotriacetate, sodium triethanol ammonium-N-(2-hydroxy ethyl)- nitrilodiacetate, potassium triethanol ammonium-2-(2- hydroxy ethyl)-nitrilodiacetate. Other typical organic builders are the sodium and potassium salts of poly maleate, of poly itaconate and of poly acrylate.
Other typical organic builders are the alkali metal salts of phytic acid and the like, for example, sodium phytate. Other suitable builders are the sodium and potassium salts of ethane-l-hydroxy-l,l-diphosphonate, the sodium and potassium salts of methylene diphosphonate, the sodium and potassium salts of ethylene diphosphonate, and sodium and potassium salts of ethane-l ,l ,Z-triphosphonate.
Other suitable builders include the alkali metal salts of ethane-Z-carboxy-l,l-diphosphonic acid, hydroxy methane diphosphonic acid, carbonyl diphosphonic acid, ethane-l-hydroxyl ,l,2-triphosphonic acid, ethane-2-hydroxy-l ,Z-triphosphonic acid, propane- 1,1 ,3 ,3-tetraphosphonic acid, propanel ,l ,2,3-tetraphosphonic acid and propane-l,2.2,3-tetraphosphonic acid.
FORMULATIONS MISCELLANEOUS COMPONENTS Another class of components useful in detergent for mulations is called hydrotopes' These components are used to increase the compatibility of the ingredients of solid and liquid formulations. Preferred hydrotope anions are benzene sulfonate, xylene sulfonate, and toluene sulfonate. Preferably, such hydrotopes are used as their soluble salts such as ethanol ammonium, diethanol ammonium, and triethanol ammonium, and especially as the alkali metal salts, particularly those of potassium or sodium. In the salt form, toluene sulfonates are especially preferred, particularly those of sodium and of potassium. The hydrotopes are added at levels up to about 15 percent by weight of the total composition. Amounts in excess of this usually are not desired since such provides undesired content of inerts.
From the foregoing recitations, it is evident that some adjuvant materials may have plural functions or capabilities and that there can be some duplication of terminology, result, etc. Other terms used to describe similar or different components of formulations include materials which emphasize esthetic or other characteristics or definitions such as opassifiers, buffering agents, pH control agents, anti-corrosion agents, perfumes, antiredeposition agents, resin stabilizers, dyes, pigments, germicides, anti-bacterial agents, softness control, viscosity control agents, and the like.
In addition to the foregoing in certain instances, advantages are achieved in some formulations wherein additives which increase the apparent hardness of the water are deliberately used such as magnesium or calcium sulfate or chloride, or the like.
Formulations such as the foregoing are generally used in water at a concentration from about 0.01 to about 0.50 percent by weight based on the cleaning actives present. In computing this percentage, the builders and the other adjuvants such as hydrotopes are not considered as actives.
PREPARATION OF COS COMPOSITIONS The novel compositions of the present invention can be prepared in any suitable manner so long as the above teachings are adhered to. For instance, each of the ingredients can be synthesized separately and then mixed according to the stated proportions.
If it is desired to synthesize separately the individual components of the novel mixture, it is possible to do so according to the procedures in the following discussion which are, in general, well known and described in issued patents referred to herein. Any other suitable methods can be used.
The symbol R as used in the following equation represents an aliphatic hydrocarbon radical that would allow for a total of carbon atoms in the molecule between about IO and about 24. The alpha-beta unsaturated sulfonate containing aliphatic compounds of Type 1 can be prepared readily by dehydrochlorinating a Z-chlorosulfonic acid derivative. A fairly detailed discussion of a suitable preparation route appears in an article in the Journal of Organic Chemistry, Vol. I949, page 46, written by .I. D. Rose and A. Lambert. The starting step for this synthesis is a reaction between a long chain epoxide and sodium bisulfite to produce a Z-hydroxy-l-sulfonate derivative of the particular long chain epoxide used. This reaction product is condensed with PCl to prepare the aforementioned 2- chlorosulfonic acid derivative which in turn is reacted with sodium carbonate to yield an alpha-beta unsaturated compound. The particular carbon skeletal structures for the epoxides are selected to provide the component A, B and C structures desired.
The other preferred double-bond positional isomers of Type 1, i.e., the beta-gamma, gamma-delta, and delta-epsilon alkene sulfonates can be prepared by the thermal dehydration of hydroxy alkyl sulfonates. Again materials of appropriate carbon skeletal configuration are selected to provide the desired component A, B and C structures. According to the following reaction, the thermal dehydration of the sodium salt of 3-hydroxysulfonate results in the preparation of a reaction mixture containing the beta-gamma isomer and the gamma-delta isomer.
Similarly a reaction mixture of a gamma-delta and a delta-epsilon double-bond isomer compound can be prepared by using a 4-hydroxysulfonate of appropriate carbon skeletal configuration as a starting material:
The foregoing synthesis of the double-bond positional isomers follows closely the well known dehydration of an organic alcohol as is mentioned in such standard texts as Whitmores Organic Chemistry, second edition, pages 39-41.
There is no need to separate the reaction product of the two illustrated dehydration reactions. The reaction product can be formulated directly into a detergent composition according to the present invention. If, for some reason, it is desired to work with pure ingredients, they can be separated into pure forms.
The hydroxy alkyl sulfonates of Type 2, such as the preferred 3-, 4-, and S-hydroxy compounds, can be prepared by the free radical addition of sodium bisulfite to the corresponding 3-, 4-, or S-hydroxy-i-olefin, respectively:
Free Radical RCH(OH)CH=CH NaHSO; RCH( OH )CH CH SO Na Sodium 3-hydroxyalkane sulfonate RCH(OH)CH CH=CH NaHSO RCH(OH )CH CH CH so Na Sodium 4-hydroxyalkane sulfonate The hydroxy olefin for use as starting materials in the preceding free radical addition reaction can be prepart by well known organo-metallic reactions, e.g., involvin g an aldehyde and a Grignard reagent in which R and R" are organic radicals and X is a halogen. For example:
Aldehyde Grignard 3-hydroxyl -olefin Aldehyde Grignard 4-hydroxyl -olefin Reagent A discussion of the conversion of hydroxyolefins produced by preceding equations (a) and (b) to hydroxy alkyl sulfonates appears in an article written by J. Willens. Bulletin of the Chemical Society of Belgium, Vol. 64. page 427 (1955).
It is to be understood that other hydroxy alkyl sulfonates as desired can be prepared by using different Grignard reagents in the reaction equation set forth above.
The alkene disulfonates and the hydroxy alkyl disulfonates of the Type 3 may also be prepared separately by any known manner. For instance, the hydroxy alkyl disulfonates may be prepared by epoxidizing appropriate olefin sulfonic acid isomers, and then opening the epoxide ring with sodium bisulfite by standard reaction techniques. The hydroxy alkyl disulfonates may then be dehydrated by reactions known to those skilled in the art to yield the corresponding isomeric alkene disulfonates.
EXAMPLE 1 An olefin sample was sulfonated in accordance with the following batch technique and tested for detersive efficiency in accordance with a standard procedure for comparison as hereinafter described.
A. One mol of olefin containing on a mol percent basis 75 percent hexadecene-l, 5 percent random internal hexadecenes and percent 2-ethyl-tetradecene-l was charged into a well-agitated one-liter creased flask equipped with a fritted glass bubbler and provided with a condenser-vent system. With the olefin at C, a mixture of 600 liters of nitrogen and 60 grams (0.75 mole) of sulfur trioxide was added through the bubbler over a period of about 1% hours allowing excess nitrogen to escape through the vent.
Of the S0 admitted, 54.3 grams (0.68 moles) reacted providing 278.7 grams of crude sulfonation product.
About one third of the crude solfonation product (72.9 grams) was saponified by reacting with 10.9 grams of NaOH in 351 ml of water at a temperature of 200C for 60 minutes.
The unsaponifiables (mainly residual olefin) were removed by extraction of the saponified mixture with a 50-50 mixture of methyl ethyl ketone and pentane. The extraction removed 26.2 grams of unsaponified material.
The remaining sodium sulfonate materials were evaporated to apparent dryness using a rotary vacuum evaporator.
The partially dried residue was then held at l 15C for 48 hours at a pressure of about 50 mm Hg yielding a dried product weighing 71.8 grams.
The dry materials were then further purified to remove inorganic materials such as Na SO by treatment according to ASTM Method 855-56.
The product material was mainly mixed alkenyl sulfonates, hydroxy alkyl sulfonates in the usual proportions containing components A, B and C in relative proportions of /5/20. This material was tested for Detersive Efficiency giving a value of 117. Like the other materials hereinafter described, this material was used as a blending stock with them in various ratios to provide mixtures of various proportions of A, B and C components.
B. Using the foregoing procedure, another sample was prepared using 95 percent hexadecene-l and 5 percent Z-ethyI-tetradecene-l. The product was primarily component A material but included 5 percent component C material. The Detersive Efficiency was 109.
C. Using the foregoing procedure another sample was prepared using Z-ethyI-tetradecene-l in percent purity prepared by the Ziegler synthesis reaction of triethyl aluminum with l-tetradecene. The product was essentially component C material. The Detersive Efficiency was 98.
D. Using the foregoing procedure a mixture rich in component B materials was prepared using as olefin feed, the percent hexadecene-l partially isomerized by passage over A1 0 impregnated with H PO A first such olefin sample contained 55 percent hexadecene, 40 percent straight chain internal hexadecenes and 5 percent Z-ethyI-tetradecene-l. The product corresponding to a mol percent distribution of 55/40/5 of A, B and C components, respectively, provided a Detersive Efficiency of 113.
E. Using the foregoing procedure another isomerization derived olefin mixture similar to the preceding but even richer in component B material was reacted. The distribution of olefins was 15 percent hexadecene-l 80 percent internal hexadecenes, and 5 percent Z-ethyI-tetradecene-l. The product sulfonates corresponding to a mol percent distribution of 15/80/5 of A, B and C components, respectively, provided a Detersive Efficiency of 108.
F. Another sulfonation process employs complexation, for example, with a dioxane-SO complex. The products from this sulfonation generally have proportionate characteristics but the Detersive Efficiency factors are generally lower. For example, the sulfonation products of the olefins of Example l-B when derived through the SO -complexed process provide a D. E. factor of 101. This general relationship must be recalled in comparing situations where the only data given are for the complexed process. In general, one experiences a product D. E. of about when using the olefin mixtures of l-A above in a complexation process so when making comparisons one must be certain that the bases are the same.
G. Another aspect of comparison of data, particularly where different sources are involved, is molecular weight. Frequently, one encounters situations where olefins used in sulfonation are not limited to materials of a single number of carbon atoms per molecule. For comparative purposes as to percentages of components A, B and C it is generally preferable to minimize the variables by using the pure olefins as has been done to a significant extent herein; however, mixtures provide somewhat higher Detersive Factors and are usually preferred in actual operation. Thus mixtures with regard to molecular weight; such as, C C and CH4; C C,,,, r: and m; C13, C14- C15, C161 C17 and m; and C13 C14, C C and C in equal proportions of the components as well as peaked as with a 2:1 to 3:l mol ratio of the middle components to the terminal components with in-betweens about proportionate are useful. Similarly skewed mixtures, i.e., those with a peaking at or near one end are useful. The point that must be observed with regard to such mixtures, generally, is that they produce higher D. E. factors. Thus. a typical mixture produced by procedure 1 -A containing about equal proportions of sulfonates having l4, l5, l6, l7 and 18 carbon atoms per molecule of essentially 100 percent vinyl olefin derivation (essentially all component A), produced D. E. factors of 113-1 16. In summary of this point, one must be careful in comparisons of data from different sources to make certain that there is a real basis for comparison.
EXAMPLE 2 Detersive Efficiency Factors reported in Example 1 were measured in accordance with a Launder-Ometer multiple wash technique as described by .I. C. Harris, Detergency Evaluation and Testing, lnterscience 1954, page 94. The materials were used in water in a typical weight concentration of 0.20 percent of active. Temperature of the wash was 120F. The washing solutions were adjusted with NaOH to a pH of 9.5-10.0 prior to testing. A standard soiled cotton cloth sample designated EMPA (lOl) produced by Testfabrics, Inc. was used.
The samples were washed for a period of 10 minutes, then dried and exposed to reflectance measurement using a Photovolt reflectometer Model No. 610. Prior to cleaning, a typical soiled sample had a reflectance value of 30 percent based on 100 percent reflectance for pure magnesium oxide, MgO. After cleaning with material of l-A, for example, the reflectance value increased to 75 percent.
For convenience in expression of comparative results on a near lOO percent basis, the results of the foregoing tests were related to an arbitrarily selected standard, commercial linear alkyl benzene sulfonate (abbreviated LAS in the trade). The reflectance increase provided by this material was arbitrarily assigned a D. E. of 100. Thus, materials which clean better than the standard have D. E. values higher than the standard (100) and those inferior to the standard such as that of Example l-C have values lower. In general, different soiled cloth standards, and a different washing standard will change the absolute values of the D. E. Factors and must be considered in comparing data from different sources but within a standard framework of testing operations, meaningful comparisons are obtained.
All data given in Example 1 and subsequent examples are based on an average of the value of eight separate washes following the foregoing procedure.
EXAMPLE 3 An alternate procedure for reacting oleflns with 50;, to produce COS materials uses a falling film reactor. This is generally similar to a falling film distillation system, structural apparatus details being well known. The
principal advantages of falling film reactor for the present usage are adaptability to a continuous operation, excellent temperature control, and through conventional expedients such as staging, an additional measure of control over side reactions such as minimizing the production of higher order sulfonates where such is desirable.
The falling film reactor used is a vertically oriented two pipe device employing an inner stainless steel tube of 4.85 cm OD. and an outer glass tube of 10.2 cm ID. The tubes are approximately cm long with appropriate closures and ports at the ends for feed and withdrawal of materials.
The olefin feed is provided at the top providing a downward flow stream on the outer surface of the inner tube. The SO -N feed mixture is fed at the bottom of the annular space as a gas or vapor phase stream. Nitrogen, incompletely reacted sulfur materials, and any other vapors are removed at the top of the annular space. Reacted liquid product is removed at the bottom of the annular space.
A heat transfer medium such as water, oil or Dowtherm is circulated through the interior of the inner tube providing excellent control for bringing the system up to temperature and for heat removal.
Operation of the falling film reactor is typified for separate preparation of the component A, B and C materials for subsequent blending. Operation is at 40C and atmospheric pressure. The preparation of component A materials is described in detail, the preparation of the component B and component C materials being similar. The results of a combined feed reaction are similar; however, for experimental purposes the prepa' ration of large separate batches of component A, B and C materials facilitates studies of the effects of variations in the proportions of the three components.
A liquid recycle system was provided for this run wherein liquid material obtained at the bottom of the reactor was fed back to the top. A run based on 1 mole of hexadecene-l with a liquid recycle flow rate of 170 ml/minute lasted for 3 hours. During this time the nitrogen was fed continuously for a total of 1200 liters, reduced to standard conditions, carrying a total of 88 grams (1.1 moles) of vaporized $0 at a uniform feed rate.
A viscous reaction product was obtained which contained 70.3 grams of reacted $0 A [00 gram portion of the crude product was saponitied with NaOH. This was accomplished with 12 grams of NaOH in 388 ml water at a reaction temperature of 200C, a pressure of l80-200 psig with a treatment time of minutes.
Phase separation by decantation provided an aqueous sulfonate system which was evaporated to dryness with a spray dryer producing 86.5 grams of a nearly colorless powder.
Other similar powders with various numbers of carbon atoms in the radicals R are produced individually and in various combinations.
Other similar compositions of the components are prepared using other saponification cation systems including calcium, magnesium, potassium, lithium, ammonia and substituted ammonium compounds particularly the mono and dialkanol amines such as diethanol amine and monoethanol amine.
A further class of cation materials is produced by reaction of compositions of the foregoing paragraph with mineral acid. Of this large group a typical system is the reaction of stoichiometric quantities of the sodium cation salt of the component A C radical material with an excess of concentrated HCl at 20C to produce the corresponding l-l cation composition, a mixture of alkenyl sulfonic acid and hydroxy alkyl sulfonic acid.
EXAMPLE 4 Various ones of the foregoing materials, such as the component A C powder whose production is described in detail in Example 3, and appropriate component B and component C materials, are blended in various combinations within the ranges specified in the claims and in the foregoing and succeeding portions of the specification.
The blends and compositions are tested in formulations with adjuvants such as the builders recited herein. Various proportions of A, B and C components are made and tested in proportions ranging from 100 percent of individual components to 0 percent. Good results are obtained for the ranges claimed.
EXAMPLE Compositions of the foregoing specific distributions of R radicals as to total carbon atoms per R group are further exemplified with regard to average distributions between component A, B and C materials (in mol percent) as follows.
Component A B C 94 2 4 94 1 5 93 2 5 92 2 6 90 1 9 90 2 8 85 3 12 83 3 14 82 3 15 80 3 17 8O 4 16 75 5 20 70 20 6O 10 30 6O 35 5 50 10 40 Compositions of the foregoing proportions are tested providing desirable results in accordance with the foregoing teachings.
EXAMPLES 6-7 Distribution of Olefins Used on Basis of Number of Carbon Atoms per Molecule (Wt Component C Materials Wt of Starting Olefins of Preceding Table Example 6 Example 7 C 7.9 1.5 C 17.3 2.7 C 33.6 6.0 C 43.6 12.1
Average Composition of A, B, C Components Wt of Starting Olefins Vinyl (Component A) 77.3 93.6 Internal (Component B) 3.7 2.4 vinylidene (Component C) 19.0 4.0
The materials are tested for cleaning properties as in preceding examples. The results are superior to those obtained from materials corresponding to similar products of the sulfonation of pure alpha olefins of similar distribution as to number of carbon atoms per molecule.
1. The composite olefin sulfonate product obtained by sulfonating with gaseous uncomplexed S0 a mixture of olefins having from about 12 to about 16 carbon atoms per molecule and the following mol percent composition:
vinyl olefins from about 40 to about 60 percent internal olefins from about 10 to about 35 percent vinylidene olefins from about 5 to about 40 percent,
saponifying the sulfonated olefins with NaOH, and removing the unsaponified material from the saponified mixture.
2. The composite olefin sulfonate product obtained by sulfonating with gaseous uncomplexed S0 a mixture of olefins having from about 14 to about 20 carbon atoms per molecule and the following mol percent composition:
vinyl olefins from about 40 to about 60 percent internal olefins from about 10 to about 35 percent vinylidene olefins from about 5 to about 40 percent,
saponifying the sulfonated olefins with NaOl-l, and removing the unsaponified material from the saponified mixture.
3. The composition of claim 2 wherein said mixture of olefins has from about l6 to about 20 carbon atoms per molecule.
4. The composition of claim 2 wherein the longest carbon chain from a point of attachment of the S0 radical is from about l6 to about 18 carbon atoms.
5. The composition of claim 2 wherein the olefins are predominantly olefins having an even number of carbon atoms per molecule and wherein the vinylidene olefins are predominantly olefins having a maximum of per molecule. one branch per molecule. 7. The composition of claim 2 wherein the sulfona- 6. The composition of claim 2 wherein substantially tion is performed in a falling film reactor. all of the olefins have an even number of carbon atoms