|||||||||||||| USOO530852A United States Patent (19) 11 Patent Number: 5,308,512 Stoll et al. 45 Date of Patent: May 3, 1994 54 THIODIGLYCOLALKOXYLATE 4010606 10/1991 Fed. Rep. of Germany. DERIVATIVES, A PROCESS FOR THEIR 0213067 12/1983 Japan. PRODUCTION AND THEIR USE AS FABRIC 153309 3/1984 Japan. SOFTENERS 1097396 1/1968 United Kingdom . (75) Inventors: Gerhard Stoll, Korschenbroich; OTHER PUBLICATIONS Peter Daute, Essen; Ingo Wegener; Trofimov, Zh. Prikl. Khim., vol. 48, pp. 626-628 1975. Faize Berger, both of Duesseldorf, all Vogel & Krissman & Seifen, Öle, Fette, Wachse, vol. of Fed. Rep. of Germany 115, 1989, pp. 3-8 Article Unavailable. (73) Assignee: Henkel Kommanditgesellschaft auf J. Falbe, Surfactants in Consumer Products, Springer, Aktien, Duesseldorf, Fed. Rep. of 1987, pp. 87-90. Germany Vogel & Krussmann, Seifen, Öle, Fette, Wachse, vol. (21) Appl. No.: 961,683 III, 1985, pp. 567-574 1985. Primary Examiner-Paul Lieberman (22) PCT Filed: Jun. 28, 1991 Assistant Examiner-Michael P. Tierney 86) PCT No.: PCT/EP91/01213 Attorney, Agent, or Firm-Ernest G. Szoke; Wayne C. S371 Date: Mar. 5, 1993 Jaeschke; Real J. Grandmaison S 102(e) Date: Mar. 5, 1993 57) ABSTRACT The process of producing alkoxylated thiodiglycol sulf 87). PCT Pub. No.: WO92/00959 oxide derivatives and thiodiglycol sulfone derivatives PCT Pub. Date: Jan. 23, 1992 corresponding to formula I (30) Foreign Application Priority Data Jul. 7, 1990 (DE) Fed. Rep. of Germany ....... 402,694 CH-CH-O-CH-CHR)-o-x, (I) (O)S 51) Int. Cl. ............................................ D06M 10/08 N 52 U.S.C. ...................................... 252/8.7; 252/8.6; CH-CH2-(O-CH-CHR)-O-X 252/8.9; 568/27; 568/28; 554/227; 560/263; 560/264 wherein X1 and X2 may be the same or different and 58 Field of Search ................ 560/263,264; 554/227; represent a hydroxyl-substituted aklyl radical contain 568/27, 28; 252/8.6, 8.7, 8.9 ing 8 to 30 carbon atoms, an acyl radical of an alkyl 56) References Cited monocarboxylic acid containing 8 to 30 carbon atoms, U.S. PATENT DOCUMENTS and X or X2 may be hydrogen, R represents hydrogen or methyl, z is 1 or 2, n is 0 to 25 and m is 1 to 25, by 4,830,636 5/1989 Horodysky ............................. 44/70 reacting an alkoxylated thiodiglycol with a C814 C30 FOREIGN PATENT DOCUMENTS a-olefin expoide or a C8-C30 monocarboxylic acid in a 0176797 4/1986 European Pat. Off. molar ratio of about 1:1 to about 1:2, and oxidizing the 2334899 1/1974 Fed. Rep. of Germany . mono- and bis- ethers or mono- and bis- esters formed to 3604039 8/1987 Fed. Rep. of Germany . the sulfoxide or sulfone derivatives. 3833076 4/1989 Fed. Rep. of Germany . 3936862 5/1991 Fed. Rep. of Germany . 6 Claims, No Drawings 5,308,512 1. 2 THIODIGLYCOLALKOXYLATEDERIVATIVES, A CH-CH2-(O-CH2-CHR)-O-X (I) PROCESS FORTHEIR PRODUCTION AND THEIR / USE AS FABRIC SOFTENERS (Os, CH-CH2-(O-CH2-CHR)-O-X BACKGROUND OF THE INVENTION in which X1 and X2 may be the same or different and i. Field of the Invention have the following meanings: This invention relates to new thiodiglycol alkoxylate hydroxyl-substituted alkyl radicals containing 8 to 30 derivatives, to their production by reaction of thiodi 10 carbon atoms, glycol with alkylene oxides, subsequent reaction with acyl radicals of alkyl monocarboxylic acids contain a-olefin epoxides or monocarboxylic acids and oxida ing 8 to 30 carbon atoms; tion with hydrogen peroxide to form the corresponding one of the substituents X1 or X2 may be hydrogen, mono- and/or bis-ethers or mono- and/or bis-esters of R is hydrogen and/or methyl, thiodiglycol alkoxylate sulfoxides or sulfones and to the 5 z is the number 1 or 2, use of the thiodiglycol alkoxylate sulfoxides or sulfones n is a number of 0 to 25 and as fabric softeners. m is a number of 1 to 25. Hitherto, considerable practical significance has been The thiodiglycol alkoxylate compounds of general attributed to quaternary ammonium compounds, partic formula (I) according to the invention are a hitherto ularly dimethyl distearyl ammonium chloride, in the unreported class of compounds. They are prepared by field of domestic and institutional fabric softeners (see reaction of alkoxylated thiodiglycol compounds with P. Vogel and H. Kruemann, Seifen, ole, Fette, a-olefin epoxide compounds containing 8 to 30 carbon atoms in the molecule or by the corresponding reaction Wachse, Vol. 111, pages 567 to 574, 1985 and L. Gode of alkoxylated thiodiglycol compounds with alkyl froy and H. Hein, Seifen, ole, Fette, wachse, Vol. 115, 25 monocarboxylic acids of comparable chain length and pages 3 to 8, 1989). subsequent oxidation with hydrogen peroxide to the In view of the increasing consideration being given to corresponding sulfoxides or sulfones. the storability and viscosity characteristic and also to According to the invention, the alkoxylated thiodi the biodegradability of highly concentrated fabric soft glycol compounds are obtained by the base-catalyzed eners, numerous proposals for replacing these compo 30 reaction of thiodiglycol with alkylene oxides. The al nents by nitrogen-free substitute compounds or corre koxylation is generally carried out by the method sponding systems have been published. These proposals known from the literature for alcohols at a reaction encompass both inorganic components, more particu temperature in the range from about 100 to 200 C., larly inorganically insoluble components, such as layer 35 under a pressure of 1 to 50 bar and in a nitrogen atmo silicate compounds (see for example DE-PS 23 34899), sphere. and also selected organic components, for example dis In one preferred embodiment of the invention, a cata alts of long-chain a-sulfofatty acids and combinations of lytic quantity of methanolic potassium hydroxide solu such systems (see DE-PS36 04039). tion is added to the thiodiglycol in an autoclave and the 40 thiodiglycol is reacted with ethylene oxide at 140 to 2. Discussion of Related Art 150° C. to form the ethoxylated thiodiglycols, the pres Thiodiglycol derivatives, a process for their produc sure not exceeding 5X 10. Pa. tion and their use as fabric softeners are already known According to the invention, the molar ratio of thiodi from the teaching of applicants' German patent applica glycol to alkylene oxide is between 1:1 and 1:25 and tion P 39 36862.9. However, in view of their limited 45 preferably between 1:1 and 1:10. The expert knows that solubility in water and their high melting points, the the alkoxylation reaction can result in a homolog distri compounds in question can only be formulated as ex bution with a varying distribution of the EO degree (see pensive mixtures in stable dispersions. J. Falbe, "Surfactants in Consumer Products", Springer Accordingly, the problem addressed by the present 1987, pages 87 to 90). In addition to basic catalysts, such invention was to provide a hitherto unreported class of 50 as preferably potassium hydroxide or sodium methano nitrogen-free inorganic compounds for use as rinse late, the cationic layer compounds known from DE-OS cycle fabric softeners which, on the one hand, would be 38 33 076 and DE 40 10 606.3 may also be used as al easier to formulate through greater dispersion stability koxylation catalysts. and, on the other hand, would be distinguished by bet In one important embodiment of the invention, the corresponding mono- and/or bis-ethers of the alkoxyl ter feel behavior compared with the compounds de-55 ated thiodiglycol compounds corresponding to general scribed above. formula (I) with g-hydroxyalkyl groups in X1 or X2 are DESCRIPTION OF THE INVENTION formed by opening of the epoxide ring, depending on the molar ratio between the thiodiglycol alkoxylates Other than in the operating examples, or where oth 60 and the a-olefin epoxide compound (1:1 to 1:2). By erwise indicated, all numbers expressing quantities of contrast, another route to the bis-ether derivatives of ingredients or reaction conditions used herein are to be thiodiglycol is described in GB-PS 1,097,396. The start understood as modified in all instances by the term ing compounds used there are divinyl sulfones and alco "about'. hols which do not lead to the g-hydroxyalkyl group In a first embodiment, therefore, the present inven according to the invention in the corresponding bis-(2- tion relates to new alkoxylated thiodiglycol sulfoxide alkoxyethyl-sulfones. derivatives or thiodiglycol sulfone derivatives corre In one preferred embodiment of the invention, the sponding to general formula I thiodiglycol alkoxylates are reacted with the C8-30 a 5,308,512 3 4 olefin epoxide compound in the desired molar ratio (1:1 molecule, fall within the scope of the present invention. to 1:2) by addition of a typical basic catalyst, such as for Structurally the same and, if desired, structurally differ example an alkali metal hydroxide and/or alkali metal ent radicals may be present in X1 and X2. For reasons of alcoholate, in a quantity of at least 0.05% by weight to easier accessibility alone, preference is attributed to about 5% by weight and preferably in a quantity of 5 structurally the same radicals which, in the case of about 0.1 to 1% by weight, based on the total quantity compounds containing mixed radicals X1 and X2, will weighed in. contain, for example, corresponding radicals differing The actual reaction takes place at temperatures of at in their chain length. least 100 C. to about 200 C. and preferably at tempera Thiodiglycol derivatives corresponding to general tures of about 160 to 170° C. over a period of about 3 to 10 formula (I) which contain uniform radicals and, in par 6 hours to an epoxide oxygen content below 0.5% and ticular, the same radicals, i.e.