Патент USA US2121617код для вставки
’ Patented June 21, 1938 ‘ 2,121,617 UNITED STATES ‘PATENT OFFICE , James ‘Herbert Werntz, Wilmington, Del_., as signor to E. I. du Pont de Nemours it Com _ nanmwi lmingto11, Del., a-corporation of Dela ware No Drawing. Application June 10, 192.7, Serial No. 147,486 17 Claims. (c1. zoo-99.12) ', This invention relates to new chemical com sodium sulphate, ?ltered, and the ether evapo pounds, their methods of production and their rated at room temperature. 19 parts by weight ' technical uses. and more particularly to the. of a light colored, syrupy, product was obtained manufacture-and utilization of secondary straight after drying over phosphorus pentoxide in a vac- 5 chain alkyl esters of mono-sulphato-polycarbox ylic acids wherein the alkyl groups contain 6 or more carbon atoms and the sulphato-poly carboxylic acids contain less than 15' carbon atoms and have no hydroxyl substituents. 10 This application is a continuation-in-part of my co-pending application, Serial Number 757, 465, ?led December 14, 1934, which became U. S. Patent No. 2,104,782 on January 11, 1938. . This invention has as an object‘the prepara 15 tion of a number of new chemical compounds which have surface active properties. A fur ther object is to manufacture these new chemi cal. compounds by novel and easily conducted processes from relatively inexpensive raw ma 20 terials. uum desiccator. , The sodium di(octyl-2) sul- 5 phato-succinate analyzed 6.4% sulphur indicat ing a purity greater than 92%. This’product was found to be a very e?icient wetting agent for cotton yarn. _ Example 2 - _ 10 Sodium di(octyl-3) sulphat0-succmate.-17.9 parts by weight'of di(octy1-3) malate was dis solved in '72 parts by weight of anhydrous ethyl ether and sulphated with 6.4 parts by weight of chlorosulphonic acid under the conditions de scribed in the. preceding example for the prep aration of sodium di(octyl-2) sulphato-succinate. 23 parts by weight of sulphated ester were ob‘ tained which analyzed 6.4% sulphur and indi- . A still further object is to apply these _ cated a purity greater than 91%. This'product new compounds in various connections wherein is an e?‘icient wetting agent for cotton textiles. surface active compounds are. commonly em The di(octyl-=3) malate was prepared by esteri ployed. Other objects will appear hereinafter. tying octanole'3 with malic acid using a catalytic These objects are accomplished by the follow amount of paratoluene sulphonic acid and ethyl 25 ing invention which relates generally to the - ene dichloride as the solvent for removing the 25 _ production of secondary straight chain dialkyl water liberated during the course of the reac-_ esters of aliphatic mono-sulphato-dicarboxylic tion. The product was puri?ed by washing the acids wherein the alkyl groups contain 6 or more ethylene solution with water and dis carbon atoms and the sulphato-dicarboxylic acids tilling oil?dichloride the ethylene dichloride. The product 30 contain less than 15 carbon-atoms and have was a water-white oil, and was therefore not dis- 3° no hydroxyl substituents. In the preferred em tilled prior to the sulphation. bodiment these objects are accomplished by the Example 3 production of esters oi’ aliphatic mono-sulphato- ' .s dicarboxylic acids having from 3 to 6 carbon 35 atoms and having no hydroxyl substituents with secondary straight chain aliphatic alcohols hav ing 6 or more carbon atoms. The following examples will serve to illustrate this invention. 4° ' Example 1 Sodium dKOCtl/l-Z) .iulphato-succinateL-l'ly parts by weight of di(octyl-2)_vmalate, which boiled at 170-173° C. at 3 mm., was dissolved 46 in 72 parts by weight of anhydrous ethyl ether, and \the solution placed in a reaction vessel ' Sodium di(he:cyl-3) sulphato-succinate.—15.l parts by weight of di(h’exyl-3) malate, which 35 distilled at 150-155° C. at 2 mm., was dissolved ' in 36 parts by weight of anhydrous ethyl ether, and the solution placed in a reaction vessel equippedwith an agitator, dropping funnel, and thermometer. A solution of 5.84 parts by weight 40 of chlorosulphonic acid was prepared by dissolv ing the acid. in 36 parts. by weight of anhydrous ethyl ether, and the acid solution allowed to drop slowly into the solution of the ester. After addition 01' the acid, the solution was stirred for 45 an additional 2 hours at about 0° C. It was then equipped with an- agitator, thermometer and I poured into 200 grams of ice and neutralized dropping funnel. 5.84 parts by weight of chloro sulphonic acid were added slowly to the ether 50 solution maintained at 0° C. by means of an ice bath. The reaction mixture was stirred 2% hours, then poured intb' ice water, and neutral ized with a 4% aqueous sodium hydroxide solu tion. The aqueous solution was extractedwith so ether, the ether extract dried with anhydrous with a 4% aqueous sodium hydroxide solution. The sulphated ester was only-sparingly soluble in ethyl ether, so the ether layer was removed 50 and the sulphated ester in the aqueous solution evaluated as a‘wetting agent. It displayed wet ting properties for cotton textiles but in this respect was inferior to sodium di(octyl-3) sul phato-succinate. 55 2,121,817 2 ‘ The esters which are to be sulphated may be prepared from any secondary straight chain aliphatic alcohol containing 6 or more. carbon atoms. Such secondary aliphatic alcohols may be obtained by hydrating straight'chain olefin! such as those produced by the cracking of pe troleum products followed by separation of the branched chain olefins. vA few of the secondary normal secondary alcohol containing 6 or more carbon atoms and the other carboxyl group with a dissimilar alcohol such as ethanol, butanol, cyclohexanol, normal octanol, 2-ethylhexano1-l, 4-methyl hexanol-l, etc. I at present prefer to prepare the esters which are to be sulphated by esterifying both of the carboxyl groups of a monohydroxy dicarboxylic acid containing from 3 to 6 carbon atoms-especially malic acid— with a secondary straight chain aliphatic alcohol 10 ' straight chain aliphatic alcohols which are use 10 ful in this connection are the various isomeric containing? or more carbon atoms. normal secondary hexanols, heptanols, octanols, nonanols, decanols, undecanols, dodecanols, tri , Estersprepared as indicated in the preceding paragraph or by any other suitable method may decanols, ~tetradecanola, pentadecanols, hexane- canols, heptadecanols, and octadecanols, speci?c be sulphated by means of such sulphating agents 15 as concentrated sulphuric acid, oleum, chloro 15 examples of which are hexanol-3, ,heptanol-Z. v‘sulphonic acid, pyridine sulphuric’ acid, etc. > octanol-2, octanoL-S, nonanol-ii, nonanol-4. non Sulphation may be carried out in the presence of anol-5, decanol-5, undecanol-Ii, undecanol-G, tri or'diluents, such as water, aliphatic-hy decanol-‘7, pentadecanol-B, heptadecanol-_4, etc. solvents In the preparation of wetting agents for cotton drocarbons, ethyl ether, carbon tetrachloride, ni 20 trobenzene, trichloroethylene, symmetrical di 20 textiles, it‘is preferred to prepare the esters which chloro-ethyl ether, etc. ' Sulphation is advisably '_are to be sulphated from straight chain second carried out within the temperature range of from .. ary alcohols containing from 6 to 10 carbon atoms. Starting out in this manner, there may -20° C. to 35° C. in order to avoid-the formation ‘of sulphonic acids. As indicated by the above examples, it is preferred to carry out the sulpha 25 be obtained secondary straight chain dialkyl 25 esters of sulphatosuccinic acid wherein the alkyl tion in dry ether solution by meansToI chloro sulphonic acid at a temperature of about 0° C. Sulphated'esters produced in accordance with the ‘foregoing directions are usually neutralized groups contain from 6 to 10 carbon atoms. In place of individual alcohols, mixtures thereof may be used, the various components of which may vary from traces to major fractions. While the esters which are to be sulphated may be made from any monohydroxy polycar boxylic acid which contains less than 15 carbon atoms,'lt is preferred to use acids having from 3 to 8 carbon atoms. Aromatic acids, such as 3 35 with salt-forming compounds or bases, which 30 may be inorganic or organic. .All of the free acid groups present in the molecule may be reacted with such bases, although it is contemplated that products containing a'free ‘sulphate or carboxyl group may be produced and utilized. It is gen-‘ 35' hydroxy crthophthalic and 4-hydroxy ortho erally preferred to neutralize the sulphated esters phthalic, and tricarboxylic acids, such as citric, may be used in this connection, but generally 40 with an alkali metal hydroxide, such as sodium hydroxide, in order to obtain their alkali metal they are notv to be preferred; For instance, a salts. I may also use inorganic bases such as di(octyl-2) hydroxy phthalate-may be prepared 'soda ash, ammonium hydroxide, potassium hy from one of the hydroxy phthalic acids and con I vertedwith ,chlorosulphonic acid to a di(octyl-2) vsulphato-phthalate. , ,droxide', lithium hydroxide, magnesium hydrox It is generally preferred, however, to make the ‘esters which are to be sulphated from aliphatic monohydroxy dicar-z ide, calcium hydroxide, and barium hydroxide for neutralizing the sulphated esters. Amines such as aniline, toluidine, cyclohexyl amine, pyridine, piperidine, dim'ethyl amine, ethyl amine, di 45 boxylic acids containing from 3 to 6 carbon atoms _ ethanol amine, butyl amine, triethanol amine, ' such as tartronic, malic‘, methyl tartronic, ethyl tartronic, beta-methyl‘malic, alpha-hydroxy glu-> taric, beta-hydroxy glutaric, alpha-hydroxy adipic, beta-beta-dimethyl malic, beta-ethyl 60 malic, etc. . At present I prefer to use malic acid for preparing the esters to be sulphated above any of the other acids mentioned'in this para graph. - ’ , Esters which are to be sulphated may be pre pared by any method known to the art, e. g., by reacting the alcohol or the alkali metal alcoholate with the acid, acid chloride, or acid anhydride, or by ester interchange. Usually the esters to 45 glucamine, methyl glucamine, etc. may also be used for'neutralizing, these sulphated esters. When in the claims I refer to esters of mono sulphato-polycarboxylic acids, it is to be under stood that such an expression generically de notes the sulphated esters comprehended by the present invention irrespective of whether or how the sulphated esters may be neutralized.’ By the expression “ester of a mono-sulphate polycarboxylic acid", I refer to esters in which be‘ sulphated are prepared by csterifying all'of 60 the carboxyl groups of the particular polycar boxylic acid employed with a secondary straight chain aliphatic alcohol containing 6 or more carbon atoms. Esters which are to be sulphated may also be made in which only one of the 65 carboxyl groups is esteri?ed with a secondary , straight chain alcohoLhaving 6 or more car bon atoms. Each of the carboxyl groups of a dicarboxylic acid may be esteri?ed with the same . or with different alcohols. In the case of the 70 esters employed for making the products de ' scribed in‘ the above examples, both of the car boxyl groups of the acid have been esteri?ed with ‘the same secondary alcohol. Esters to be sul phated may also be obtained by esterifying one ‘75 carboxyl group of a dicarbom'iic acid with a , 55 one neutralized or unneutralized sulphate group is attached to a carbon atom on the acid residue. The new compositions covered in this case be-, long to the class of surface active or capillary’ active materials in that they have colloidal prop erties and may, therefore, be advantageously used in any '.process involving ‘wetting, penetrating, deterging, dispersing, emulsifying, frothing, foam ing and kindred phenomena. These composi tions may be employed in pure or standardized "form, and, if desired, in conjunction with mown processing or treating agents. ‘They may be used so by themselves or in combination with‘ other sur face active agents in any relation in which sur 70' face active agents having colloidal properties have heretofore been used. _ Many uses of these new compositions are con nected with treatments ‘forxprocessing and im proving natural and synthetic textile materials. .it. . ‘ 7 ~ _ ' 2,121,017 . . 3 ‘A few representative uses of these new products in the manufacture of cosmetic preparations as textile assistants will be mentioned in order' such as'cold creams and lip sticks. They maybe that the importance and widespread applicability employed’for preparing emulsions of the water of these new products in the textile industries may be fully appreciated. They may be used in-oil type such as emulsions of water in such‘ organic solvents as, are used in the dry cleaning alone or in combination withsuitable detergents industry. I g for cleansing and scouring vegetable and animal These compositions may also be used alone as fibers when removing fatty or oily materials. contact insecticides and for enhancing the ‘ When added to ?ax retting baths, they function spreading and penetrating power of other para 10 as wettingand penetrating agents. They may be siticides. They may be employed in agricultural 10 employed as assistants in .fulling and felting sprays in combination with the ordinary insecti processes. They may be used‘ in sizing prepara cides and fungicides. They are useful for pro tions in combination with the usual materials. mating the penetrating power of wood preserva such as starches or gelatine or their equivalents, 15 clays, talcs, weighting salts such‘ as magnesium , sulphate or calcium ‘chloride, oils and oils processed by oxidation, polymerization, sulphona tion, etc. The penetrating power of these new compositions is utilized with advantage when 20 they are added to baths containing starch fer ments which are employed _for removing sizing from textile materials. These products function as useful wetting, cleansing, and penetrating agents in bleaching liquors such as those used in as the kier boiling of cotton goods. They may be added to the lye liquors used for mercerizing cotton goods. _They improve" the absorption capability 'of ?brous materials when such ma tives. ' - In the paper industry these products may be 15 used as penetrants in the‘liquors used-for cook ing rags and pulp, and. as assistants in paper softening, ?lling, and processes to increase ab sorbency. These compositions may be employed as deter gents in several different relations. They may be _ used in the washing of fruits and vegetables for spray residue removal. They may be used in combination with metal cleaning compounds in neutral, slightly acid, or slightly alkaline liquors. 25 They may be used for paint, varnish, and lacquer cleaners. They may advantageously be employed _as cleansing'agents in hard water and where a terials are subjected to treatments for ?nishing, ‘ fatty or oily ?lm resists the ordinary cleansing 30 softening, stiffening, coloring, impregnating, water-proo?ng,-and mildew-proo?ng. They may . be- used alone or in combination with other ma terials for lustering or delustering fabrics. They may be employed to oil or lubricate textile ma 35 terials and as' assistant'siin processes of weight ing' or loading fabrics. They may be used as media. They may be added to soap in hard 80 water baths, since these compositions do not form precipitates so readily in hard waters as soaps and Turkey red oils. ‘ These compositions may be used as aids in var ious chemical reactions. They may be used to 35 control particle size and shape during precipita assistants in‘ silk .degumming liquors ‘and silk > tion or crystallization of compounds from reac I tion mixtures. They may be used to decrease the Another important class of uses of these new particle size of insoluble amine hydrochlorides 40 compositions is as assistants in the preparation ‘just before these amines are to be diazotized. _ and application of dyestuffs. >Th'ey may be used These compositions also have several miscel in the‘ preparation of dyestuffs in readily dis laneous uses. They may be employed as foam 'persible form and for the production of inor stabilizing agents, .especially for use in air-foam soaking solutions. ‘ganic pigments-or pigments of azo, basic, acid, vat, and sulphur dyes in a ?nely divided con; ,dition. As penetrants ~and wetting agents they assist in producing level dyeings in neutral, acid, or alkaline dyeing baths. They facilitate dyeing with developed dyes, the _dyeing of animal ?bers 50 with vat dyes, ‘the dyeing of cellulose acetate ?bers with insoluble dyes, dyeing and printing with aniline black, and-the dyeing of leather. In ‘printing pastes they assist in the dispersion 55 of the dye or dyefcomponent and facilitate its penetration into the natural or synthetic ?ber. Inv the leather industry these compositions function as useful wetting agents in soaking, de liming, bating, tanning, and dyeing baths. They are useful in softening and‘treating baths for 60 hides' and skins, particularly in baths used for ?re extinguishing‘ compositions. They may be used to stabilize rubber latex. They may also be used as frothing and collecting agents in ore ' flotation processes, and in other processes such as the recovery of ?xed oil from the oil sands. These compounds may be used in toothpaste, non spattering margarins and may be employed-es emulsifying agents for synthetic rubber latex such as neoprene. ‘ - The above description and examples are in tended to be illustrative only and not to limit the scope of the invention. Any departure therefrom 651 which conforms to ‘the spirit of the invention is intended to be included within the scope of the appended claims. I claim: . 1 straight chain neutral alkylv fat-liquoring leather. Solutions of these com-7 ester of a mono-sulphato-polycarboxylic acid ' 1. A secondary pounds are useful for pretreating leather prior wherein the alkyl group contains at least 6 car to dyeing. bon atoms and the sulphato-polycarboxylic acid , , ’ , The dispersing‘ and emulsifying powers of these contains less than 15 carbon atoms and has no 65 new-compositions give rise to many.‘ interesting - hydroxyl substituents. uses. They may be utilized for converting liq ‘ uid or solid substances normally‘insoluble in _ 2. A secondarystraight chain dialkyl ester of an aliphatic mono-sulphato-dicarboxylic acid' water, such as hydrocarbons, higher alcohols, wherein the alkyl groups contain at least 6 ‘car ' pitches, and pitchy substances into clear solutions‘ bon atoms and the sulphato-dicarboxylic acid 70 or stable-emulsions or dispersions. They are use- ' contains ‘less than 15 carbon atoms and has no ful in preparing emulsions of wax and wax-like hydroxyl substituents. . . _ . compositions which are used as leather dressings 3. An alkali metal salt of a secondary straight or ?oor polishes. _They_may be used to prepare chain dialkyl ester of\an aliphatic mono-‘sub arti?cial dispersions of crude,_vulcanized. or re phato-dicarboxylic acid whergn the alkyl groups 75 claimed rubber. They may be used as emulsi?ers contain at least‘ 6 carbon atomsand the sulphate 70" I ' ‘ ‘2,121,617 atoms and has no hydroxyl substituents. ' - 9. An alkali metal salt of a secondary straight chain dialkyl ester or sulphato-succinic acid dicarboxylic acid contains from 3 to 6 carbon ' wherein the alkyl groups contain from 6 to 10 4. A process of making the products de?ned in claim 3 which comprises sulphating a secondary straight chain dialkyl ester of an aliphatic mono carbon atoms. / ‘ 10. A process of making the products defined in claim 9 which comprises sulphating a secondary straight chain dialkyl ester of malic acid wherein hydroxy dicarboxylic acid wherein the alkyl groups contain at least 6 carbon atoms and the dicarboxylic acid contains from 3 to -6 carbon atoms, and neutralizing the sulphated ester with an alkali metal hydroxide. the alkyl groups contain from 6 to 10 carbon atoms by reacting an ether solution of said ester with chlorosulphonic acid, and neutralizing the sulphated ester with an aqueous solution of an 5. A secondary straight chain dialkyl esterof sulphato-succinic acid wherein the alkyl groups alkali metal hydroxide. ‘ 11. A>di(octyl-3) sulphato-succinate. contain at least 6 carbon atoms. 6. An alkali metal salt of a secondary straight / 12. Sodium di(octyl-3) sulphato-succinate. 13. A process of making sodium di(octyl-3) 15 sulphato - succinate which comprises adding wherein the alkyl groups contain at least 6 car ' chlorosulphonic acid to a dry ether solution of bon atoms. 7. .A process of making the products defined in di(octyl-3) malate, stirring the reaction mixture, claim 6 which comprises sulphating a secondary and’ neutralizing the sulphated malate ester with 20 straight chain dialkyl ester of malic acid wherein - an aqueous solution of sodium hydroxide. 14. A di(octyl-2) sulphato-succinate. the alkyl groups contain at least 6 carbon atoms, chain dialkyl ester of sulphato-succinic acid and neutralizing the sulphated malate ester with an alkali metal hydroxide. 8. A secondary straight chain dialkyl ester of sulphato-succinic acid wherein the alkyl groups contain from 6 to 10 carbon atoms. ‘ 15. Sodium di(octyl-2) suiphato-succinate. 16. A di(hexyl-3) sulphato-succinate. 17. Sodium di(hexyl-3) sulphato-succinate. 25 JAMIES HERBERT WERNTZ.