The present invention relates to washing, wetting and emulsifying agents which are also known as textile assistants and detergents and refers particularly to new agents of this class. The new agents are derived from alkenyl-substtuted polycarboxylic acids resulting from the reaction of unsaturated...

Example 1 herein- salts of partial esters whose u Teh. according to the present in The compoinds of the invention can also be salts of partial esters of ac made by condensing an ester of the unsaturated 65 condensation or reaction of m acid, such as the dihexyl ester of maleic acid chlorides having from five with triisobutylene or other olefln or alkyl halide, atoms, inclusive, with unsaturt and thereafter partially hydroly~ ng or saponify- acids containing the alpha-b ing the resulting diester of the alkenyl-subeti- The alkenyl groups repres tuted acid, for example, dihexyl ester of trilso- 70 going formulae are those coi butenyl-succinic acid(cas:110-15-6), to obtain the acid or salt to sixteen carbon atoms, incl of the monoester of the alkenyl-substituted acid, range compounds having the -for example, sodium salt of the monohexyl ester ting, washing and emulsifyln of trilsobutenyl-suceinic acid. This method is Preferred alkenyl groups ai illustrated in Example 2. Ts from polymerized oleflns uc egoing. significance' a carboxyl group.

a--COOH e previous formula, lensation with oleg most probably to sponds to the genm which the comntion are derived) w: Alkenyl--CH HE-COOH H2--COOH" Formula H bstituted polyearondensation of the rboxylic acids, will corresponding satyl-substituted acids with maleic acid or ifc acids, whereas or citraconic acids ds (methylsuccinic ompounds that the Isaturated polycarubstituted acid be 6toms, as shown in mulae. These forlered as exemplary iclude most of the boxylic acids conouping and the alrllc acids resulting More generally, the se Is contemplated vention, are those Ids resulting from onooleflns or alkyl to sixteen carbon ated polycarboxylic eta-enal grouping.entedin the forentalning from five isive, vithin which nost desirable wetg properties occure those resulting Sas diisobutylene, triisobutylene and tetraisobutylene; and triisobutylene is a preferred species.

The salts of partial esters of alkenyl-substituted polycarboxylic acids described herein are comparable in their surface activity to wellknown wetting agents and detergents such as the sulfated alcohols and the sulfonated alkyl aromatic hydrocarbons commonly used for this purpose, but many of them do not foam or lather as readily when added to water in the manner that is typical of other wetting agents and detergents. This failure to foam is a definite advantage for certain purposes, and does not detract from their desirability as wetting agents or detergents. They compare favorably with the salts of unesterified alkenyl - substituted carboxylic acids which are specifically claimed in my prior copending application, Serial Number 181,597, and exhibit somewhat faster wetting action. Alkenyl-substituted acids, whether monocarboxylic or polycarboxylic, such as described in my prior copending application, Serial Number 181,597 and herein, when completely esterifled so that a solubilizing unesterified carboxyl or metal-substituted carboxyl group, such as COONa, that is capable of yielding positive ions, is absent, lack both solubility and other properties which make for good wetting and detergent action.

In the examples which follow the various alkenyl-substituted polycarboxylic acids or anhydrides of such acids which are specified may be made by the methods described in U. S. Patent No. 2,055,456, or as more particularly described in my prior applications, Serial Numbers 181,597 and 430,633. For the preparation of anhydrides of these alkenyl-substituted polycarboxylic acids the following procedures, exemplified by the preparation of diisobutenyl-succinic and triisobutenyl-succinic anhydrides, may be used: Preparation 1.-Triisobutenyl-succinic anhydride Into a rotating steel autoclave are charged 330 grams (about 3.37 mols) of maleic anhydride and 45 600 grams (about 3.56 mols) of triisobutylene (boiling range 173°-1750 C.) The autoclave is sealed and agitated and the charge is then heated at 207 to 210° C. (405* to 410* F.) for a period of about 5 hours. The product is removed from the autoclave and subjected to vacuum distillation. The unreacted maleic anhydride and triisobutylene distill first and they are substantially removed when the distillation conditions reach a temperature of about 1250 C. at a pressure of about 185 mm. of mercury. The pressure is then slowly decreased until a pressure of 2 mm. is reached. The distillation is then taken to a temperature of 140° C. at 2 mm. The triisobutenyl-succinic anhydride which remains as the residue may be used without additional purification or it may be purified by further distillation at a higher vacuum, for example, a vacuum of the order of about 1 mm.

The distilled product, having a boiling range of about 1350 to 1450 C. at a pressure of about 1 mm., which is obtained according to this preparation, amounts to about 545 grams, which is about 60% of the yield theoretically possible from the amount of reactants charged to the autoclave. The distilled product obtained as above described had a neutralization equivalent of 132.1, as determined acidimetrically. The molecular weight of triisobutenyl-succinic acid(cas:110-15-6) anhydride is 266, and its theoretical neutralization equivalent is therefore 133. The proportions of reactants used may be varied, as is obvious.

Preparation 2.-Diisobutenyl-succinic anhydride Into a rotating steel autoclave are charged 392 grams (about 4.0 mols) of maleic anhydride and 750 grams (about 6.7 mols) of diisobutylene. The autoclave is sealed and, while it is rotated, it is gradually heated to 207° C. (4050 F.) during the course of about 11/ hours and maintained at about that temperature for an additional period of about 212 hours. The recovery of the product is made by the general method of distillation in vacuum used in Preparation 1.

The boiling range of diisobutenyl-succinic anhydride is approximately 132° to 134° C. at a pressure of 1 mm. of mercury. The yield is about 608 grams of product, which is about 72% of that theoretically obtainable from the charge used. The neutralization equivalent of diisobutenyl-succinic acid(cas:110-15-6) anhydride that has been distilled within the range described is 103.0. The molecular weight of diisobuteryl-succinic acid anhydride is 210 and the theoretical neutralization equivalent is therefore 105.

The washing, wetting and emulsifying agents of the invention, which consist. of water-soluble metal salts of partial esters of the alkenyl-substituted polycarboxylic acids, may be produced from the alkenyl-substituted polycarboxylic acids or anhydrides according to general procedures illustrated in the examples which follow: Example 1.-Sodium salt of mono-n-amyl triisobutenyl-succinate Into a flask provided with a stirrer and thermometer are charged 266 grams (about 1 mol) of triisobutenyl-succinic anhydride, prepared, for example, as described in Preparation 1 above, and 88 grams (about 1 mol) of n-amyl alcohol.

The charge is heated with stirring to about 100° to 1100 C. and maintained at that temperature for a period of about three hours. The resulting product is cooled, any insoluble oil which separates is discarded, and the product is then poured into a solution of 53 grams ('/2 mol) of anhydrous sodium carbonate (Na2CO3) dissolved in 2 liters of water. The product may be recovered as a solid from the solution by drying on a drumdrier.