US 3775349 A
Description (OCR text may contain errors)
NOV. 27, 1973 TUVELL ET AL 3,775,34
DH'PI-JHUHN'I FOHMULA'IIUNS CONTAINING ALKYIJ POLYI'JIHOXY SUIJFA'II; MIX'IURFS Filed June 29, 1970 2 Sheets-Sheer 1 DISHWASHING PERFORMANCE O 5 l I 3O 4O 8O C AES, OF TOTAL ACTWE FIG. I
C ALKYL GROUPS 0 (AS SULFATES) LC /Q 23/32 v c ALKYL V c ALKYL GROUPS GROUPS AS SULFATES) (AS SULFATES) FIG. 2
Nov. 27, 1973 M. E TUVELL ET AL 3,775,349
DETERGENT FORMULATIONS CONTAINING ALKYL POLYETHOXY SULFATE MIXTURES Filed June 29, 1970 2 Sheets-$heet c ALKYL GROUPS (AS SULFATES) c ALKYL c ALKYL GROUPS e5 enoups (A8 SULFATES) (AS SULWES) FIG. 3
- wt v. ETHOXY SULFATES FOAM \DLUME (MI) 6 G o o fif/ 4 HARONESS I50 PPM ADDED sou. mcazusms (0.125
US. Cl. 252-547 21 Claims ABSTRACT OF THE DISCLOSURE It is disclosed that certain mixtures of alkyl sulfate and alkyl alkoxy sulfate detergents have superior properties when used in hard water where the alkyl groups of the sulfates range from about to about carbon atoms and wherein from about 10 to about 50 percent of the alkyl groups are decyl. It is disclosed that such sulfates are useful per se and in formulations with other adjuvants with or without other detergent active materials such as tertiary amine oxides, alkyl benzene sulfonates, linear alkyl benzene sulfonates, fatty acid ethanol amides, and fatty acid diethanol amides.
BACKGROUND OF THE INVENTION Field of the invention The invention relates to compositions of alkyl sulfate and alkyl alkoxy sulfate detergents of the formula where R is an alkyl group having from about 10 to about 20 carbon atoms; R is or mixtures; x is a number from 0 to about 6, averaging about 2-4; Me is selected from the group consisting of water soluble salt cations such as ammonium, lower alkanol ammonium and alkali metal cations.
Mixtures of alkyl sulfates and alkyl alkoxy sulfates are well known as having useful detergent properties. Where the alkoxy groups are ethoxy, the detergents are abbreviated AES (alcohol ethoxy sulfates). Typically, where R is dodecyl, OR is and Me is ammonium, the compound is Z-dodecyloxydiethoxyethyl ammonium sulfate.
DESCRIPTION OF THE PRIOR ART One of the typical uses of compounds of the foregoing general type is discussed in Us. Pat. 3,179,598. In that patent it is stated that the optimum chain length for the alkyl group of alkyl ethoxy sulfates is dodecyl. The preference is based largely upon the desirable properties of sudsing and detergency. The above-mentioned patent also indicates that alkyl ethoxy sulfates whose group has greater than 14 carbon atoms produce reduced quantities of suds. The typical prior art indicates a prefence for alkyl ethoxy sulfate detergents whose alkyl groups are based on mid-cut coconut alcohols which typically contain 2 percent decyl, 66 percent dodecyl, 23 percent tetradecyl, and 9 percent hexadecyl alkyl groups. The emphasis upon the dodecyl preference in the prior art is stated specifically andis also indicated by the general composition requirement that at least 50 percent of the alkyl groups of the alkyl ethoxy sulfate detergents be dodecyl groups.
"United States Patent 0 3,775,349 Patented Nov. 27, 1973 SUMMARY The invention is based on the discovery that in hard water the preformance of alkyl sulfate and alkyl alkoxy sulfate detergents is improved by employing mixtures containing substantial proportions of molecules in which the alkyl group is decyl. By substantial proportion is meant from about 10 to about '50 percent of the R alkyl groups in mixed alkyl alkoxy sulfate compositions as hereinafter defined.
The present invention is directed to compositions which are mixtures of alkyl sulfates and alkyl alkoxy sulfates of the formula:
wherein R is an alkyl group having from about 10 to about 20 carbon atoms, R is x is a number from O to about 6, averaging about 2-4; and Me is lower alkanol ammonium and alkali metal. Typical lower alkanol amonium cations are ethanol ammonium, diethanol ammonium and triethanol ammonium cations. Typical alkali metal cations are sodium and potassium. Said mixtures are characterized in that from about 10 to about 50 percent of the R alkyl groups are decyl.
Preferred sulfate compositions in accordance with the foregoing are those wherein the R alkyl groups are predominantly straight chain alkyl groups; that is, where molecules with branched chain R alkyl groups constitute no more than about 20 to 25 percent of the R alkyl groups present.
Particularly preferred compositions are those wherein the branched alkyl groups constitute no more than about 5 percent of the R alkyl groups present. A source of such is alcohols produced by the hydrolysis of aluminum alkoxides derived from the chain growth of ethylene on a lower alkyl aluminum compound as described in US. Pat. 3,415,861.
Preferred compositions are those wherein the alkoxy radicals are ethoxy because of the ready avaliability and low cost of ethylene oxide and the reactivity thereof with alcohols obtained as discused in the preceding paragraph to produce ethoxylated alcohols.
In one particular embodiment of the present invention, preferred mixtures of alkyl alkoxy sulfates contain the preceding highly preferred straight chain R alkyl groups of 10-16 carbon atoms per group wherein the branched chain R alkyl groups are in tow categories, a first category being those having more than 12 carbon atoms per group and which are limited to a maximum of about 4 percent and a second category wherein the compositions contain from about 2 to about 25 percent of branched primary R alkyl groups having 12 carbon atoms per group.
Typical branched primary R alkyl groups are 2-ethyl decyl-, 2-butyl octyl-, 2-methyl undecyland 2-methyl dodecyl-. The first is preferred for ease of production and low cost.
The most highly preferred mixtures are those which contain about percent or more of sulfate molecules of straight chain carbon-oxygen skeletal configuration; that is molecules whose alkyl alkoxy radicals R(OR) are 2-decyloxyethyl, Z-undecyloxyethyl, Z-dodecyloxyethyl, Z-tridecyloxyethyl, Z-tetradecyloxyethyl,
Z-pentadecyloxyethyl, 2-hexadecyloxyethyl, 2-decyloxyethyl, Z-undecyloxyethoxyethyl, 2-dodecyloxyethoxyethyl, 2-tridecyloxyethoxyethyl, 2-tetradecyloxyethoxyethyl, 2-pentadecyloxyethoxyethyl, 2-hexadecyloxyethoxyethyl, 2-decyloxydiethoxyethyl, Z-undecyloxydiethoxyethyl, 2-dodecyloxydiethoxyethyl, 2-tridecyloxydiethoxyethyl, 2-tetradecyloxydiethoxyethyl, 2-pentadecyloxydiethoxyethyl, 2-hexadecyloxydiethoxyethyl, 2-decyloxytriethoxyethyl, 2-undecyloxytriethoxyethyl, 2-dodecyloxytriethoxyethyl, Z-tridecyloxytriethoxyethyl, 2-tetradecyloxytriethoxyethyl, 2-pentadecyloxytriethoxyethyl, 2-hexadecyloxytriethoxyethyl, 2-decyloxytetracthoxyethyl, Z-undecyloxytetraethoxyethyl, 2-dodecyloxytetraethoxyethyl, 2-tridecyloxytetraethoxyethyl, 2-tetradecyloxytetraethoxyethyl, 2-pentadecyloxytetraethoxyethyl, 2-hexadecyloxytetraethoxyethyl.
Particularly preferred are mixtures which contain about 95 percent or more of straight chain R alkyl radicals having only even numbers of carbon atoms.
A preferred range for the percentage of decyl R alkyl groups in mixtures according to the present invention is from about 15 to about 40 percent. Such mixtures have the superior hard water performance discussed in the foregoing and additionally provide excellent performance over a wide range of hardnes of water, including soft water. Furthermore, mixtures containing tetradecyl R alkyl groups and hexadecyl R alkyl groups as essentially the only R alkyl groups in addition to decyl and dodecyl in ratios from about 1:1 to about 5:1 of tetradecyl to hexadecyl exhibit nearly uniform excellent washing effectiveness down to zero content of dodecyl R groups in the mixtures. In preferred compositions of this type, the total of decyl and dodecyl R alkyl groups is from about to about 65 percent, with the minimum percentage of decyl being about 10 percent and the minimum percentage for dodecyl R alkyl groups being about zero.
Typical preferred percentages of decyl R alkyl groups are 10 percent, 25 percent and 33% percent.
The number of alkylene oxide units in the preferred alkyl sulfates and alkyl ethoxy sulfates generally ranges from 0 for the alkyl sulfates up to about 6 ethylene oxide groups per molecule, with an average in given mixtures of about 2-4, preferably 3. An average of about 3 imparts a desired emulsification capability and a characteristic of mildness to the skin; however, molecules having more than about 3 ethylene oxide units are generally inferior in sudsing ability and may detract from the performance of mixtures, hence are less desired than those of about 2-4 ethylene oxide units per molecule.
The cations of the alkyl sulfates and alkyl alkoxy sulfates of the present invention are selected from a group which has the property of imparting a desired degree of water solubility to the resulting salts. Excellent cations for most instances are ammonium and alkanol ammonium radicals, and alkali metals, particularly sodium and potassium. The ammonium radical is most preferred because of solubility of the active in liquid dishwashing formulations. Of the alkali metals, sodium is usually preferred because 9f the 9 efiectivefless and of the ease of reaction of low cost NaOH with sulfuric acids produced from ethoxylated alcohols by reaction with chlorosulfonic acid. Potassium is similar to sodium.
Typical organic base cations are alkanol ammonium cations such as ethanol ammonium, diethanol ammonium and triethanol ammonium. All of these are useful, some being preferred in various circumstances.
The foregoing compositions are prepared in numerous ways individually and in various mixtures. The components may be prepared as individual compounds or mixtures of some or all of the compounds that go to make up a final composition and blended as necessary to form the compositions claimed. In many instances it is practical to employ mixtures of reactants to produce directly the claimed compositions desired. A particularly preferred process for producing the compositions employs as a starting feed retctant a mixture of synthetic or natural source primary alkanols ROH whose alkyl radicals R have a desired structural configuration and percentage distribution as set forth in the foregoing. In general, one prefers synthetic aluminum chemistry derived alcohols that have been treated to remove contaminants in accordance with processes of U.S. Pat. 3,468,965. This selected mixture of alcohols is then reacted with a lower alkylene oxide having from 2 to about 6 carbon atoms per molecule such as ethylene oxide or propylene oxide, pure or in mixtures in the desired molar proportions, generally typically about 3 molecules of alkylene oxide such as ethylene oxide per R alkyl radical in the starting alcohols to provide a desired average of 3 ethylene oxide units per molecule of ethoxylated alcohol intermediate product. For a different average unmber of alkylene oxide units per molecule in the product sulfates for specific purposes, a greater or lesser ratio of molecules of alkylene oxide is reacted per molecule of starting alcohol; for example, a lower average of 2.5 molecules of ethylene oxide per R alkyl group or a higher average of 3.5 mols of ethylene oxide per R alkyl group of the alcohol. In those instances where it is desired to produce only alkyl sulfates, the step of reaction of alcohols with the alkylene oxide is omitted.
The alcohols or alkoxylated alcohols are converted to the acid sulfate typically by reaction with chlorosulfonic acid or sulfur trioxide in accordance with well known processes such as U.S. Pat. 2,187,244.
In a typical procedure for producing the sulfate detergents, acid sulfate from the preceding paragraph is reacted with an appropriate compound containing the desired cations or their precursors. Thus, for example, the acid sulfates are reacted with ammonium hydroxide in approximately 1:1 molar proportions using an aqueous solution of about 1020 percent by weight ammonium hydroxide. This produces the water soluble salts with ammonium cations.
To produce the sodium salts, the acid sulfates are reacted with sodium hydroxide in approximately 1:1 molar proportions using an aqueous solution of about 5-10 percent by weight sodium hydroxide. Similar salts with potassium cations are produced by reaction with potassium hydroxide. Other alkali metal salts may be produced by similar procedures.
It is evident that the foregoing operations are amenable to the production of desired compositions in accordance with the present invention in a single sequence of reactions using mixed alcohols fed in the desired proportions; however, it is evident that individual alcohols may be produced or recovered from mixtures by distillation and that they may be individually treated with various proportions of various alkylene oxides to produce various mixtures of molecules which may be further ramified by using various cation materials and the like. Such individual mixtures are blended to produce final compositions in accordance with the requirements of the present claims. Typical alkyl sulfates and alkyl alkoxy sulfates decyl ammonium sulfate dodecyl ammonium sulfate tetradecyl ammonium sulfate hexadecyl ammonium sulfate 2-decyloxyethyl ammonium sulfate 2-dodecyloxyethyl ammonium sulfate Z-tetradecyloxyethyl ammonium sulfate 2-hexadecyloxyethyl ammonium sulfate Z-decyloxyethoxyethyl ammonium sulfate 2-dodecyloxyethoxyethyl ammonium sulfate 2-tetradecyloxyethoxyethyl ammonium sulfate Z-hexadecyloxyethoxyethyl ammonium sulfate 2-decyloxydiethoxyethyl ammonium sulfate Z-dodecyloxydiethoxyethyl ammonium sulfate Z-tetradecyloxydiethoxyethyl ammonium sulfate 2-hexadecyloxydiethoxyethyl ammonium sulfate 2-decyloxytriethoxyethyl ammonium sulfate 2-dodecyloxytriethoxyethyl ammonium sulfate 2-tetradecyloxytriethoxyethyl ammonium sulfate Z-hexadecyloxytriethoxyethyl ammonium sulfate Z-decyloxytetraethoxyethyl ammonium sulfate 2-dodecyloxytetraethoxyethyl ammonium sulfate 2-tetradecyloxytetraethoxyethyl ammonium sulfate 2-hexadecyloxytetraethoxyethyl ammonium sulfate 2-decyloxypentaethoxyethyl ammonium sulfate 2-dodecyloxypentaethoxyethyl ammonium ulfate 2-tetradecyloxypentaethoxyethyl ammonium sulfate 2-hexadecyloxypentaethoxyethyl ammonium sulfate 2-undecyldiethoxyethyl ammonium sulfate Z-tridecyloxydiethoxyethyl ammonium sulfate 2-pentadecyloxydiethoxyethyl ammonium sulfate Other typical compounds useful in accordance with the teachings of the present invention include:
2-decyloxydiethoxyethyl potassium sulfate 2-decyloxydiethoxyethyl sodium sulfate Z-decyloxydiethoxyethyl ethanolammonium sulfate 2-decyloxydiethoxyethyl diethanolammonium sulfate 2-decyloxydiethoxyethyl triethanolammonium sulfate 2-dodecyloxydiethoxyethyl potassium sulfate 2-dodecyloxydiethoxyethyl sodium sulfate 2-dodecyloxydiethoxyethyl ethanolammonium sulfate 2-dodecyloxydiethoxyethyl diethanolammonium sulfate 2-dodecyloxydiethoxyethyl triethanolammonium sulfate 2-tetradecyloxydiethoxyethyl potassium sulfate 2-tetradecyloxydiethoxyethyl sodium sulfate Z-tetradecyloxydiethoxyethyl ethanolammonium sulfate Z-tetradecyloxydiethoxyethyl diethanolammonium sulfate 2-tetradecyloxydiethoxyethyl triethanolammonium sulfate 2hexadecyloxydiethoxyethyl potassium sulfate 2hexadecyloxydiethoxyethyl sodium sulfate 2-hexadecyloxydiethoxyethyl ethanolammonium sulfate 2-hexadecyloxydiethoxyethyl diethanolammonium sulfate 2-hexadecyloxydiethoxyethyl triethanolammonium sulfate Z-undecyloxydiethoxyethyl potassium sulfate 2-decyloxydiethoxyethyl lithium sulfate 2-undecyloxydiethoxyethyl sodium sulfate Z-decyloxyisopropoxythoxyethyl ammonium sulfate 2-undecyloxydiethoxyethyl ethanolammonium sulfate Z-decyloxydiethoxyethyl sulfuric acid 2-undecyloxydiethoxyethyl diethanolammonium sulfate Z-undecyloxydiethoxyethyl triethanolammonium sulfate 2-tridecyloxydiethoxyethyl potassium sulfate Z-tridecyloxydiethoxyethyl sodium sulfate 2-tridecyloxydiethoxyethyl ethanolammonium sulfate 2-tridecyloxydiethoxyethyl diethanolammonium sulfate 2-tridecyloxydiethoxyethyl triethanolammonium sulfate 2-pentadecyloxydiethoxyethyl potassium sulfate 2-pentadecyloxydiethoxyethyl sodium sulfate 2-pentadecyloxydiethoxyethyl ethanolammonium sulfate 2-pentadecyloxydiethoxyethyl diethanolammonium sulfate 2-pentadecyloxydiethoxyethyl triethanolammonium sulfate Other typical compounds useful in accordance with the teachings of the present invention include:
Z-decyloxyisopropyl ammonium sulfate 2-dodecyloxyisopropyl ammonium sulfate 2-tetradecyloxyisopropyl ammonium sulfate Z-hexadecyloxyisopropyl ammonium sulfate 2-decyloxyisopropoxyisopropyl ammonium sulfate 2-dodecyloxyisopropoxyisopropyl ammonium sulfate 2-tetradecyloxyisopropoxyisopropyl ammonium sulfate 2-hexadecyloxyisopropoxyisopropyl ammonium sulfate 2-decyloxydiisopropoxyisopropyl ammonium sulfate Z-dodecyloxydiisopropoxyisopropyl ammonium sulfate 2-tetradecyloxydiisopropoxyisopropyl ammonium sulfate 2-hexadecyloxydiisopropoxyisopropyl ammonium sulfate 2-decyloxytriisopropoxyisopropyl ammonium sulfate 2-dodecyloXytriisopropoxyisopropyl ammonium sulfate 2-tetradecyloxytriisopropoxyisopropyl ammonium sulfate Z-hexadecyloxytriisopropoxyisopropyl ammonium sulfate 2-decyloxytetrapropoxyisopropyl ammonium sulfate 2-dodecyloxytetrapropoxyisopropyl ammonium sulfate Z-tetradecyloxytetrapropoxyisopropyl ammonium sulfate 2-hexadecyloxytetrapropoxyisopropyl ammonium sulfate 2-decyloXypentapropoxyisopropyl ammonium sulfate 2-dodecyloxypentapropoxyisopropyl ammonium sulfate 2-tetradecyloxypentaisopropoxyisopropyl ammonium sulfate 2-hexadecyloxypentaisopropoxyisopropyl ammonium sulfate Z-undecyldiisopropoxyisopropyl ammonium sulfate 2-tridecyloxydiisopropoxyisopropyl ammonium sulfate Z-pentadecyloxydiisopropoxyisopropyl ammonium sulfate 2-decyloxydiisopropoxyisopropyl potassium sulfate 2-decyloxyethoxyisopropoxyisopropyl ammonium sulfate 2-decyloxydiisopropoxyisopropyl sodium sulfate 2-decyloxydiisopropoxyisopropyl ethanolammonium sulfate 2-decyloxydiisopropoxydiisopropyl diethanolammonium sulfate Z-decyloxydiisopropoxytriisopropyl triethanolammonium sulfate 2-dodecyloxydiisopropoxyisopropyl potassium sulfate 2-dodecyloxydiisopropoxyisopropyl sodium sulfate 2-d0decyloxydiisopropoxyisopropyl ethanolammonium sulfate 2-dodecyloxydiisopropoxydiisopropyl diethanolammonium sulfate 2-dodecyloxydiisopropoxytriisopropyl triethanolammonium sulfate 2-tetradecyloxydiisopropoxyisopropyl potassium sulfate Z-tetradecyloxydiisopropoxyisopropyl sodium sulfate Z-tetradecyloxydiisopropoxyisopropyl ethanolammonium sulfate 2-tetradecyloxydiisopropoxydiisopropyl diethanolammonium sulfate 2-tetradecyloxydiisopropoxytriisopropyl triethanolammonium sulfate 2-hexadecyloxydiisopropoxyisopropyl potassium sulfate 2-hexadecyloxydiisopropoxyisopropyl sodium sulfate Z-hexadecyloxydiisopropoxyisopropyl ethanolammonium sulfate Z-hexadecyloxydiisopropoxydiisopropyl diethanolammonium sulfate Z-hexadecyloxydiisopropoxytriisopropyl triethanolammonium sulfate 2-undecyloxydiisopropoxyisopropyl potassium sulfate Z-undecyloxydiisopropoxyisopropyl sodium sulfate 2-undecyloxydiisopropoxyisopropyl ethanolammonium sulfate 2-undecyloxydiisopropoxydiisopropyl diethanolammonium sulfate 2-undecyloxydiisopropoxytriisopropyl triethanolammonium sulfate Z-tridecyloxydiisopropoxyisopropyl potassium sulfate 2-tridecyl0xydiisopropoxyisopropyl sodium sulfate Z-tridecyloxydiisopropoxyisopropyl ethanolammonium sulfate 2-tridecyloxydiisopropoxydiisopropyl diethanolammonium sulfate Z-tridecyloxydiisopropoxytriisopropyl triethanolammonium sulfate 2-pentadecyloxydiisopropoxyisopropyl potassium sulfate 2-pentadecyloxydiisopropoxyisopropyly sodium sulfate 2-pen;adecyloxydiisopropoxyisopropyl ethanolammonium sul ate 2-pentadecyloxydiisopropoxydiisopropyl diethanolammonium sulfate Z-pentadecyloxydiisopropoxytriisopropyl triethanolammonium sulfate Other typical compounds useful in accordance with the teachings of the present invention include: 2-(2-ethyldecyloxydiethoxyethyl) ammonium sulfate 2-(2-propylnonyloxydiethoxyethyl) ammonium sulfate 2-(2 butyloctyloxydiethoxyethyl) ammonium sulfate 2-(2-ethyldecyloxydiethoxyethyl) ethanolammonium sulfate 2-(2-propylnonyloxydiethoxyethyl) ethanolammonium sulfate 2-(2-butyloctyloxydiethoxyethyl) ethanolammonium sulfate 2-(2-ethyldecyloxydiethoxyethyl) diethanolammonium sulfate 2-(2-propylnonyloxydiethoxyethyl) diethanolammonium sulfate 2(Z-butyloctyloxydiethoxyethyl) diethanolammonium sulfate 2-(2-ethyldecyloxydiethoxyethyl) triethanolammonium sulfate 2-(fi zropylnonyloxydiethoxyethyl) triethanolammonium s ate 2-(2-butyloctyloxydiethoxyethyl) triethanolammonium sulfate 2-(2-ethyldecyloxydiethoxyethyl) sodium sulfate 2-(2-propylnonyloxydiethoxyethyl) sodium sulfate 2-(2-butyloetyloxydiethoxyethyl) sodium sulfate 2-(2-ethyldecyloxydiethoxyethyl) potassium sulfate 2-(2-propylnonyloxydiethoxyethyl) potassium sulfate 2-(Z-butyloctyloxydiethoxyethyl) potassium sulfate 2-(2-methyldecyloxydiethoxyethyl) ammonium sulfate 2-(2-methylundecyloxydiethoxyethyl) ammonium sulfate 2-(2-methyldodecyloxydiethoxyethyl) ammonium sulfate 2-(2-methyltridecyloxydiethoxyethyl) ammonium sulfate 2-(2-methyltetradecyloxydiethoxyethyl) ammonium sulfate 2-(2-methylpentadecyloxydiethoxyethyl) ammonium sulfate 2-(Z-methyldecyloxydiethoxyethyl) ethanolammonium sulfate 2-(2-methylundecyloxydiethoxyethyl) ethanolammonium sulfate 2-(2-methy1dodecyloxydiethoxyethyl) ethanolammonium sulfate 2-(Z-methyltridecyloxydiethoxyethyl) ethanolammonium sulfate 2-(2-methyltetradecyloxydiethoxyethyl) ethanolammonium sulfate 2-(Z-methylpentadecyloxydiethoxyethyl) ethanolammonium sulfate 2-(2-methyldecyloxydiethoxyethyl) diethanolammonium sulfate 2-(Z-methylundecyloxydiethoxyethyl) diethanolammonium sulfate 2-(Z-methyldodecyloxydiethoxyethyl) diethanolammonium sulfate 2-(2-methyltridecyloxydiethoxyethyl) diethanolammonium sulfate 2-(2-methyltetradecyloxydiethoxyethyl) diethanolammonium sulfate 2-(2-methylpentadecyloxydiethoxyethyl) diethanolammonium sulfate 2-(2-methyldecyloxydiethoxyethyl) triethanolammonium sulfate 2-(2-methylundecyloxydiethoxyethyl) triethanolammonium sulfate 2-(Z-methyldodecyloxydiethoxyethyl) triethanolammonium sulfate 2-(2-methyltridecyloxydiethoxyethyl) triethanolammonium sulfate 2-(2-methyltetradecyloxydiethoxyethyl) triethanolammonium sulfate 2-(2-methylpentadecyloxydiethoxyethyl) triethanolammom'um sulfate 2-(Z-methyldecyloxydiethoxyethyl) sodium sulfate 2-(2-methylundecyloxydiethoxyethyl) sodium sulfate 2-(Z-methyldodecyloxydiethoxyethyl) sodium sulfate 2-(Z-methyltridecyloxydiethoxyethyl) sodium sulfate 2-(2-methyltetradecyloxydiethoxyethyl) sodium sulfate 2-(2-methyldecyloxydiethoxyethyl) potassium sulfate 2-(2-methylundecyloxydiethoxyethyl) potassium sulfate 2-(Z-methyldodecyloxydiethoxyethyl) potassium sulfate 2-(Z-methyltridecyloxydiethoxyethyl) potassium sulfate 2-(2-methyltetradecyloxydiethoxyethyl) potassium sulfate Although the alkyl sulfates and alkyl alkoxy sulfates described in the foregoing have useful detergent properties per se, it is generally preferred to use them in combination with other detergent active compounds and With various adjuvants such as hydrotopes, typically cumene, xylene and toluene sulfonates, perfumes, pH modifiers, inorganic salts, bacteriastats, dyes, solvents such as alkanols and carbitols, typically ethanol, isopropanol, methyl carbitol and ethyl carbitol, and the like. A particularly effective combination of active detergent compounds includes the ammonium salt form of the present alkyl sulfates and alkyl alkoxy sulfates plus amine oxide detergents. Such combinations of detergent actives are employed in conjunction with various adjuvant materials such as those set forth in the foregoing or with various adjuvants specific to desired applications such as carboxymethyl cellulose, optical brighteners, corrosion inhibitors, alkaline builders, and the like.
The amine oxide detergents preferred include tertiary amine oxide detergents, particularly those with two short and one long chain alkyl R, oxy alkyl R(OR') or hydroxy alkyl groups R"(CH(OH) (CH bonded to the nitrogen atom. In such representation, R, R and x are as heretofore defined and R" plus x plus it is equal to the number of carbon atoms in R. Amine oxides having one long chain alkyl group containing for each nitrogen atom from about 10 to about 20 carbon atoms and two short chain alkyl groups containing from about 1 to about 4 carbon atoms per group are particularly preferred because of good effectiveness and low cost. Of these, compounds having methyl, plus decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl alkyl groups are most preferred, such compounds being used individually as well as in various mixtures. Thus, typical highly preferred amine oxide detergents are dimethyl dodecyl amine oxide, dimethyl tetradecyl amine oxide and dimethyl hexadecyl amine oxide, pure and in various mixtures. Such compounds are described in US. Pat. 3,001,945. A mixture based on center cut coconut oil derived natural source long chain alcohols is coconut dimethyl amine oxide. Such mixtures of dimethyl tertiary mono amine oxides are molecules with various long alkyl chains with a usual distribution of about 2 percent C 66 percent C 23 percent C and 9 percent C Such amine oxides are described in US. Pat. 3,086,943 as are compositions based on whole coconut fatty acids.
Typical hydroxy amine oxides (mono) are described in US. Pat. 3,202,714 as including bis(2-hydroxy ethyl) dodecyl amine oxide, bis(2-hydroxyethyl)-2-hydroxy tetradecyl amine oxide, and the like.
Other typical tertiary amine oxides include those wherein the long radical contains ether linkages and hydroxy groups such as 1-stearoxy-2-hydroxy-3-dimethyl amino propane-N-oxide according to US. Pat. 3,499,930. Other typical tertiary amine oxides include compounds containing ether linkages (oxy alkyl) in either or both short radicals with or without the ramification of ether linkages or hydroxyl groups in the long chain radical. Such are shown in British Pat. 1,053,278.
Other amine oxides are the poly amine oxides such as N,N-dimethyl-1,1-dihydrogen perfluoro octyl amine oxides and related compounds described in US. Pat. 3,194,- 767.
Other useful amine oxide compounds include amine oxides wherein the short chain aliphatic groups are ethyl, propyl or butyl or are mono nuclear aromatic groups or which together form heterocyclic structures as described in US. Pats. 3,317,430 and 3,324,183. Such materials are exemplified by N-benzyl-N'-methyl dodecyl amine oxide, by the mono dodecyl ether of diethanol amine oxide,
by N,N-bis(2-hydroxy ethyl) dodecyl amine oxide, and by dodecyl morpholine oxide.
Included also in the amine oxide compounds generally within the scope of the present invention are diamine dioxide compounds such as described in US. Pat. 3,234,139. Such compounds are exemplified as N,N-trimethyl-n-decyl trimethylene diamine-N,N'-dioxide and N,N',N-triethyl-n-dodecyl ethylene diamine-N,N'-dioxide.
When the present alkyl sulfate and alkyl alkoxy sulfate detergents are used with amine oxides such as those typified in the foregoing, useful light duty liquid dishwashing concentrates are produced. Such concentrates contain generally from about 3 to about 10 parts by weight of the alkyl sulfate or alkyl alkoxy sulfate detergents per part of amine oxide. A preferred narrower range is from about 7 to about 3 parts of said sulfates per part of amine oxide with a ratio of about :1 being most highly preferred. For amine oxides with more than one nitrogen oxide group per molecule the weight of amine oxide used is generally inversely proportional to the number of nitrogen atoms in the molecule. Thus, for example, with diamine dioxides, the foregoing ratios may be advantageously doubled.
Another typical light duty dishwashing concentrate formulation in which the alkyl sulfate and alkyl alkoxy sulfate detergents of the present invention are of value is in admixture with alkyl benzene sulfonate detergents (ABS or LAS) and fatty acid mono or diethanol amides. In such mixtures, linear alkyl benzene sulfonates (LAS) are generally preferred, particularly where the alkyl groups have from about 10 to about 13 carbon atoms. Such LAS detergents are generally preferred types of ABS detergents because of biodegradability properties.
Typical LAS compounds useful in the present formulations include dodecyl benzene sodium sulfonate, undecyl benzene ammonium sulfonate, and tridecyl benzene potassium sulfonate. Included as typical are both the low and the high Z-phenyl isomers. A typical ABS detergent is tetrapropylenebenzene sodium sulfonate.
Typical fatty acid ethanol amides are center cut coconut acid monoethanol amide, whole cut coconut acid 'diethanol amide, lauric acid diethanol amide, myristic acid monoethanol amide, palmitic acid diethanol amide, capric acid monoethanol amide.
In such ternary detergent active mixtures of: (1) alkyl benzene sulfonate detergents, (2) fatty acid mono or diethanol amide detergents and (3) the present alkyl sulfates or alkyl ethoxy sulfates, the weight proportions used range from about 3 to about 10 parts of ABS per part of aimde, and from about 2 to about 10 parts of the present sulfates per part of amide. This is expressed as: 10- 3:1:10-2. Typical proportions are 10:1:2, 10:1:3, 3:1:2, 321:3, 5:1:3, and 6:1:3, said proportions so expressed being of the components 1, 2 and 3, respectively.
10 In general the preferred weight ratio of ABS relative to the present sulfates in such mixtures is from about 1:1 to about 3:1 while the preferred weight ratio of the sum of the ABS and the present sulfates relative to the amide is from about 5:1 to about 10:1.
BRIEF DESCRIPTION OF THE DRAWING FIG. 1 is a plot of dishwashing performance as a function of the amount of decyl sulfates (including decylalkoxy sulfates) in typical sulfate mixtures, the balance of which typically consist essentially of dodecyl, tetradecyl and hexadecyl sulfates wherein the ratio of ethoxy units to alkyl units is an average of about 3:1 as obtained from ethoxylating alcohols with about 3 mols of ethylene oxide per mol of alcohol. For convenience, with the numerous experiments required, the data are based on experimentation wherein the proportions of the components were based on wt. percent of the ammonium salts used. This results in a slight variation of the distributions on a basis of alkyl groups. For example, a 12 percent C alkyl corresponds to a 10 percent by weight as the ammonium sulfate. A 60 percent C alkyl corresponds to 50 percent by weight as the ammonium sulfate. The compositions tested in deriving FIG. 1 contained lauryl dimethyl amine oxide in an amount of about 16.7 percent by weight (sulfate/LDMO weight ratio=5/ 1). The information presented by FIG. 1 was derived in accordance with the Miniplate dishwashing tests described in detail hereinafter in the examples. Active matter concentration was 0.45 gram per liter at a temperature of about F. Comparative dishwashing performance is shown ranging from about 40 to about 90 percent against a standard commercial dishwashing detergent to facilitate reproducibility of results over a prolonged period of testing. The two curves of FIG. 1 show the performance in soft water of 0 part per million hardness, Curve A, and the performance in water of p.p.m. hardness, Curve B. Data for other hardness amounts are not plotted in FIG. 1; however, in general, the curves for hardness down to as low as 50 p.p.m. lie intermediate Curves A and B, close to and approximating the general shape of Curve B.
Curve B shows the superiority of present sulfate compositions containing from about 10 percent to about 50 percent decyl alkyl groups (about 8 percent to about 42 percent on the basis of the curves). It is noteworthy that a significant drop in performance is shown where the percentage of decyl alkyl groups is below about 10 percent (about 8 percent on the Curve B). Curve A shows that the high percentages of decyl are less effective with soft water than with hard water providing a basis for the preferred upper limit of about 40 percent for the amount of decyl alkyl groups present in the mixtures (about 32 on the basis of the curves). It is believed evident from the Curves A and B that within the region of from about 15 to about 35 percent decyl akyl groups, (about 12.5 to 29 on the curves) high performance is obtained with soft water as well as with hard water.
It is emphasized that the dishwashing performance data shown in FIG. 1 are on a comparative basis and do not necessarily represent an optimum with respect to composition formulations. Nevertheless, the performance, particularly that in hard water, is extremely good representing excellent preferred formulations.
FIG. 2 is a ternary diagram showing 70, 80, and 90 percent comparative performance lines for various proportions of dodecyl, tetradecyl, and hexadecyl alkyl groups in mixtures containing about 12 percent decyl groups. The upward curvature of the performance curve in approaching the C and C base line from the pure C apex at the lower left is highly desired. The straight line between the C apex and the C -C base indicates performances where the C -C ammonium sulfate ratio is 23/32 which approximates the typical center cut coconut alkyl distribution. It represents exchanging C C ammonium sulfates in 32/32 ratio for C at a fixed percent of C It is note- 1 1 worthy that the performance along this 23/32 slope line is almost uniform, about 85-87, for a ratio of dodecyl ammonium sulfate ranging from O to about 65 percent.
The significance of this uniformity is that, for similar ratios of C to C one can produce mixtures of decyl, tetradecyl and hexadecyl sulfates of the present type which compare quite favorably with mixtures of dodecyl, tetradecyl and hexadecyl sulfates over a very wide range. In fact, improved performance is shown in many instances. The curvatures provide nearly uniform performance for C /C ammonium sulfate ratios extending from about I/ 1 to about 1. This is despite the prior art preference for dodecyl.
FIG. 3 is similar to FIG. 2 showing the comparative performance of detergents evaluated as discussed in connection with FIGS. 1 and 2; however, in this instance, the performance lines shown for 60, 70, 75, 80 and 85 percent are derived when using ammonium sulfates containing substantially no decyl alkyl groups. In other words, the data of FIG. 3 represent the performance of ternary mixtures of dodecyl, tetradecyl and hexadecyl sulfates (3 :1 ethoxy unit average) wherein the only additional active material present is lauryl dimethylene oxide in an amount of about 1 part of a total of 6 by weight. In FIG. 3, it is considered significant that the comparative performance curves bend downward in progressing from the C apex to the C /C base line rather than upward as in FIG. 2. Thus when a C /C line for a typical ratio of 23/32 is placed upon the ternary diagram, a pronounced drop in comparative performance is shown for compositions that have the smaller quantities of dodecyl. Comparative performance on the typical 23/32 ratio of C /C drops from about 84 percent for the 65 percent dodecyl ammonium sulfate composition to about 80 percent for 42 percent dodecyl ammonium sulfate composition, to about 75 percent for a dodecyl ammonium sulfate content of about 21 percent, to about 70 percent for a dodecyl ammonium sulfate content of about 19 percent and reaches an estimated 66 percent for 0 dodecyl ammonium sulfate content.
It is evident that similar rapid deterioration in comparative performance figures is attained for all 0 C ratios between 0 percent C and 0 percent C The effect of the combined consideration of FIGS. 2 and 3 is to show that in general the effect of increased amounts of decyl alkyl groups beyond the 12 percent level of FIG. 1 will result in at least equivalent performance to that at the 12 percent C alkyl level.
FIG. 4 shows a plot of dishwashing performance using the compositions and procedure of Example III. The dotted line shows the performance of the C1244 AES as inferior to the mixtures containing C1042 AES. Superior performance is shown by the dash and dot-dash lines with the solid line showing a limitation on the amount of C1042 present.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The following examples indicate preferred embodiments of the present invention and are presented by Way of exemplification and not limitation.
Example I A group of standard alkoxy alkyl ammonium sulfate samples were prepared from alkanols as hereinafter described and blended in various proportions to provide compositions which were tested to derive the data for FIGS. 1, 2 and 3 of the drawing and to define the limits for the compositions claimed herein. Normal indicates alcohol with unbranched carbon skeleton structure having only a single hydroxyl group attached to only one terminal carbon atom. Branched alcohols are similar to the normal alcohols with the exception of having one hydrogen atom on the second carbon atom of the carbon skeleton substituted by a short chain alkyl group such as methyl, ethyl, propyl or butyl. In the particular alcohols chosen the substitution consists essentially of ethyl and butyl groups, with ethyl predominating at least about 3: 1.
Fatty alcohols used had the following compositions:
The four alcohol mixtures were individually reacted with ethylene oxide using sodium hydroxide as a catalyst to give an alcohol polyoxyethylene containing an average of 3 moles of ethylene oxide. The ethylene oxide adducts were analyzed according to a procedure described in J. Am. Oil Chem. Soc., 46, 289 (1969).
The alcohol ethoxylates were sulfated with sulfamic acid in trichlorofiuoromethane using a urea catalyst. The
molar ratio of alcohol ethoxylate to sulfamic acid was 1:1.05. About 0.13 g. of urea per one gram of sulfamic acid was used as a catalyst. The reactants Were heated in an autoclave to 120 C. and this temperature Was maintained for 30 minutes before cooling the reactor with an ice-water mixture. The pH of the mixture was adjusted to 9.5 with ammonia and then the mixture was filtered with the aid of Filter Aid. The filtrate was evaporated to leave a solid ammonium alcohol ethoxy sulfate which was dissolved in a mixture of percent ethanol and water. This solution was deoiled with petroleum ether (B.P. 36-57 C.). The oil content of the final product was about 0.2-0.5 percent (58 percent active basis) (Analytical Method described in ASTM Standards, Part 22, D1570-63, 1968). The concentration of alcohol ethoxy sulfates was determined by cationic titration procedure (ASTM Standards, Part 22, D1681-62, 1968).
The alcohol ethoxy sulfates were also prepared from the alcohol ethoxylate and chlorosulfonic acid. In this case the alcohol ethoxylate and chlorosulfonic acid (1:1.03 ratio) were reacted in trichlorofluoro methane in a glass reaction vessel fitted with a stirrer, Dry Ice condenser and addition funnels blanketed with nitrogen. The chlorosulfonic was added at such a rate as to maintain a moderate reflux. When the addition was complete, the mixture was refluxed for about one hour. Solvent and dissolved HCl were then evaporated. The resulting acid sulfate was neutralized with about 20 percent ammonium hydroxide solution. Ethanol was added to increase solubility. The neutralized product was deoiled and analyzed as described above.
The individual alcohol ethoxy sulfate was tested in pure form and in various combinations in formulations using a Dishwashing Test (I. Am. Oil Chem. Soc., 43, 576 (1966)) to achieve a standard performance evaluation. To minimize problems of reproducibility from day to day and with different operators, this performance was compared to that of a representative standard commercial light duty dishwashing concentrate based on alcohol ethoxy sulfate and lauryl dimethyl amine oxide. Tests were with water of 50-300 p.p.m. hardness (Ca/ M'g==60/ 40) at a temperature of 49 using active concentration of 0.045 wt. percent.
Lauryl dimethylamine oxide 17 Performance of various combinations of Claims with 10 percent C AES (12 percent C alkyl group content) at 150 p.p.m. water hardness as a percent of the commercial standard are shown in FIG. 1. Synergism of C AES is seen when comparing similar performance without C10 i.e., percent 3 4 AES B, C, D and percent lauryl dimethylamine oxide (see FIG. 2). A similar synergistic effect was observed with C ABS at 50 and 300 p.p.m. water hardness.
Example II The following alkanol mixture was ethoxylated, sulfated and neutralized with ammonium hydroxide according to procedures outlined in Example I.
Weight percent Normal Branched alcohol Carbon No. alcohol Formulations were made containing a 5/ 1 ratio alcohol "ethoxy sulfate (ABS) to lauryl dimethylamine oxide Example 111 Using procedures outlined in Example I, the ammonium salt of the 3-mole ethoxylate was prepared from an alcohol having the following composition:
Weight percent Normal Branched Carbon N 0. alcohol alcohol The branched alcohols consisted essentially of 2-ethyl and 2-butyl branched alcohols.
This C1042 ethoxy sulfate was used as a partial replacement of C1244 ethoxy sulfate in the following active:
'Wt. percent Linear alkyl (-C benzene sulfonate, sodium salt 69.8
C1244 alcohol (55 percent C 45 percent C ethoxy sulfate, ammonium salt 23.2 Laurie diethanol amide 7.0
The Dynamic Foam Dishwashing Test was used (J. Am. Oil Chem. Soc. 31 (1954)). Active concentration was 0.2 wt. percent. Added increments of soil of 0.125 gram were used in place of 0.1 gram as described in the reference. The C1244 ethoxy sulfate was replaced with up to 40 percent of the C1042 ethoxy sulfate. The dishwashing results at 150 p.p.m. water hardness are shown in FIG. 4. The beneficial effect of C alcohol ethoxy sulfate on dishwashing performance is shown by this data. Improved performance due to C AES was also observed at 25, 50 and 300 p.p.m. water hardness.
Weight percent ethoxy sulfates Composition Example IV Preceding examples are repeated with other compositions of sulfates and ethoxy sulfates described in the foregoing. Similar desirable results are obtained. Those materials under test include alkanol ammonium and alkali metal sulfates such as the ethanol ammonium, diethanol ammonium, triethanol ammonium, sodium and potassium sulfates described. Other tests employ various numbers of alkoxy units of the identity and ratio per molecule herein defined. Proportions covered include the ranges set forth in the appended claims for compositions and formulations of those compositions with other detergent actives and adjuvants discussed herein.
What is claimed is:
1. A mixture of water soluble alkyl ethoxy sulfates in which the alkyl groups have from about 10 to about 20 carbon atoms and in which the average number of ethoxy groups present is from about 2 to about 4 per molecule, from about 10 to about 50 percent of the alkyl groups being decyl groups.
2. The composition of claim 1 wherein from about 15 to about 40 percent of the alkyl groups are decyl.
3. The composition of claim 1 wherein the average number of ethoxy groups present is about three per molecule.
4. The composition of claim 1 wherein from about 15 to about 40 percent of the alkyl groups are decyl, wherein the average number of ethoxy groups present is about tlgfee per molecule, and Where the sulfates are ammonium s ts.
5. The composition of claim 1 wherein about 25 percent of the alkyl groups are decyl.
6. The composition of claim 1 wherein about one-third of the alkyl groups are decyl.
7. The composition of claim 1 wherein the sulfates are ammonium salts.
8. The composition of claim 1 wherein the sulfates are ethanolammonium, diethanolammonium, or triethanolammonium salts.
9. The composition of claim 1 wherein the sulfates are alkali metal salts.
10. The composition of claim 1 wherein the sulfates are sodium salts.
11. The composition of claim 1 wherein the total of decyl and dodecyl alkyl groups is from about 10 to about 65 percent and wherein the minimum percentage of decyl alkyl groups is about 10 percent, the balance up to percent consisting essentially of tetradecyl and hexadecyl alkyl groups in ratios of tetradecyl to hexadecyl from about 1:1 to about 5:1.
12. A light-duty detergent composition consisting essentially of alkyl benzene sulfonate detergent, fatty acid mono or diethanol amide and alkyl ethoxy sulfates as defined in claim 1, the proportions ranging from about 3 to about 10 parts by weight of alkyl benzene sulfonate detergent per part of fatty acid mono or diethanol amide, and from about 2 to about 10 parts by weight of said sulfates per part of fatty acid mono or diethanol amide.
13. A composition in accordance with claim 12 wherein the weight ratio of the alkyl benzene sulfonate detergent relative to said sulfates is from about 1:1 to about 3:1 and wherein the weight ratio of the sum of the alkyl benzene sulfonate detergent and the said sulfates relative to the amide is from about 5:l to about 10:1.
14. A composition in accordance with claim 12 wherein the weight ratio of alkyl benzene sulfonate detergent relative to fatty acid mono or diethanol amide relative to said sulfates is about 6: 1 :3.
15. A light duty detergent composition consisting essentially of: (a) alkoxy ethoxy sulfates as defined in claim 1, and (b) tertiary amine oxide detergent having two short and one long chain alkyl R, oxy alkyl R('OR),, or hydroxy alkyl groups R"(CI-I(OH) ),,(C3H bonded to the nitrogen atom wherein R is an alkyl group having from about 10 to about 20 carbon atoms; R is -cH,cH,) or (-H-CH: or mixtures; x is a number from to about 6, averaging about 2-4, R"+x+n is equal to the number of carbon atoms in R, the proportions on a weight basis ranging from about parts of said sulfates per part of amine oxide to about 3 parts of said sulfates per part of amine oxide.
16. The composition of claim wherein the weight ratio of said sulfates per part of amine oxide detergent is from about 7 to 1 to about 3 to l.
17. The composition of claim 15 wherein the tertiary amine oxide detergent contains one long chain and two short chain alkyl, oxy alkyl or hydroxy alkyl groups, the long chain group having from about 10 to about carbon atoms, the short chain groups having from 1 to about 4 carbon atoms.
18. The composition of claim 15 wherein the amine oxide detergent has one long chain alkyl group containing from about 10 to about 20 carbon atoms and two short chain alkyl groups containing from about 1 to about 4 carbon atoms.
19. The composition of claim 15 wherein the tertiary amine oxide detergent contains one long chain alkyl group having from about 10 to about 20 carbon atoms and two methyl groups.
20. The composition of claim 15 wherein the tertiary amine oxide detergent contains one long chain alkyl group having from about 10 to about 16 carbon atoms and two methyl groups.
21. The composition of claim 15 wherein the tertiary amine oxide detergent is dimethyl decyl amine oxide, dimethyl undecyl amine oxide, dimethyl dodecyl amine oxide, dimethyl tridecyl amine oxide, dimethyl tetradecyl amine oxide, dimethyl pentadecyl amine oxide or dimethyl hexadecyl amine oxide, and mixtures thereof.
References Cited UNITED STATES PATENTS OTHER REFERENCES Matson, T. P.: Use Evaluation of Alcohol Derivatives in Detergent Formulations, J. Am. Oil. Chem. S0c., vol. 40, 'November 1963, pp. 636-640.
LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner US. Cl. X.R.
33 3 2 UNITED STATES PATENT armor CERTIFICATE OF QURRECTWN Patent No. 5,775,549 Dated November 27, 1975 Inventor(s) Melvin E. Tuvell, Charlie F. Yancey and Richard D. Gorslch It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 2, line 2, reads "preformance", should read performance .--5 line 2%, reads "amonium", should read ammonium line H, reads "avaliability", should read availability -5 line +6, reads "discused", should read discussed line 52, reads "tow", should read two Column 3, line 59, reads "hardnes", should read hardness Column t, line 17, reads "retctant", should read reactant line 52, reads "unmber", should read number Column 5, line 61, reads "decyloxyisopropoxythoxyethyl", should read dec loxyisopropoxyethoxyethyl Column 9, line 71, reads "aimde should read amide Column 10, line 55, reads "akyl", should read alkyl -3 line 72, reads "25/52", should read 25/9 line 75,
reads "52/5 2", should read 25/9 Column ll, line 1,
reads "25/32", should read 25/9 --5 line 29, reads "25/52", should read 25/9 line 52, reads "25/52",
should read 25/9 Column 15, line A, reads "Fla. 1',
should read FIG. 2 5 line 7, reads "FIG. 2", should read FIG. '3 5 line 5 reads "FIG. 5", should read FIG. 1
FIG. 2. The le end "0 /0l 25/52" at the right hand side of the Figure should read O /C 25/9 FIG. 5. The le end "0 /0 25/52" at the ri ht hand side of th Fi ure should read e /cl 25/9 Signed and sealed this 31st day of December 1974.
(S AL) Attest:
McCOY M. GIBSON. JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents