US2785135A

US2785135A - Method of preparing dry cleaning compositions

Info

Publication number: US2785135A
Application number: US317571A
Authority: US
Inventors: Martin B Mathews; Charles E Stauffer
Original assignee: RR Street and Co Inc
Current assignee: RR Street and Co Inc
Priority date: 1952-10-29
Filing date: 1952-10-29
Publication date: 1957-03-12
Anticipated expiration: 1974-03-12

Description

METHOD OF PREPARING DRY CLEANING COMPOSITIONS Martin B. Mathews, Chicago, and Charles E. Stautfer, River Forest, 111., assignors to R. R. Street & Co., Inc., Chicago, 111., a corporation of Illinois No Drawing. Application October 29, 1952, Serial No. 317,571

9 Claims. (Cl. 252-161) Our invention relates to the cleaning or detergent field, and, more especially, the dry cleaning field, and is particularly concerned with new and improved methods of simply and directly producing compositions containing, as essential ingredients thereof, an inert high boiling organic liquid solvent having a boiling point or an initial boiling point not substantially below 200 degrees C. in which are dissolved certain oil-soluble esters of sulfopolycarboxylic acids, said compositions being substantially free of inorganic salts and, preferably, also being substantially free from water as prepared.

The compositions of matter which are prepared in accordance with our present invention are highly useful, among other purposes, as dry cleaning detergents and dry cleaning emulsifying agents and are adapted to be admixed with hydrocarbons, chlorinated hydrocarbons, and other organic solvents. They are highly effective in the production of emulsion wherein the external phase is an organic water-insoluble liquid, the internal phase being water or aqueous material or other liquids which are insoluble in the organic phase. In order to be fully effective for use in the dry cleaning field, it is important that such compositions be substantially free of inorganic salts, generally below about 0.1% by weight, and it is also highly desirable, at least in most case, that, as prepared, they be substantially free of water.

Oil-soluble esters of sulfopolycarboxylic acids are, per se, not new, being shown, for instance, in U. S. Patents Nos. 2,028,091; 2,176,423; 2,315,375 and 2,345,041. Moreover, they have heretofore been disclosed for use in dry cleaning liquid organic solvents as well as in conjunction with paraflin oils or parafiin hydrocarbons. Said esters have heretofore been prepared, for example, by reacting a maleic acid alcohol diester, for example, dicaprylmaleate, with .sodium bisulfite in an aqueous medium. The resulting reaction mixture is then dried and, where it is desired that said mixture be free of inorganic salts, this has been accomplished by dissolving the reaction mixture in an organic solvent such as benzene, filtering, and evaporating the benzene. This procedure is a costly and cumbersome one in that it requires, among other things, the preliminary drying of the reaction mixture and this, in itself, presents a number of difliculties because various of the sulfopolycarboxylic acid esters are of a gummy nature and present serious problems with respect to the handling and drying thereof.

In accordance with our invention, compositions having marked efficacy in the dry cleaning field, which compositions contain an inert high boiling organic liquid solvent having a boiling point or an initial boiling point not substantially below 200 degrees C., in which are dissolved oil-soluble esters of sulfopolycarboxylic acids, are prepared in such a manner as to offer marked advantages over earlier methods heretofore suggested. As indicated, the compositions are directly prepared in a form wherein they are-readily adapted for use in the dry cleaning field and form highly useful dry cleaning compositions. When added in small amounts to dry cleaning water-immiscible Patented Mar. 12, 1957 organic solvents, such as naphtha, Stoddard solvent, carbon tetrachloride, trichlorethylene, benzene, gasoline, and the like, they enable substantial amounts of water to be taken up by the organic solvents and largely retain such water during the dry cleaning operation, the water being so finely dispersed in the organic solvent that the clarity of the latter is not visibly afiected.

In the practice of our invention, the inorganic salts and moisture are removed after the reaction is essentially completed without requiring the handling of the product in the form of a solid or semi-solid gummy mass and without requiring expensive drying operations followed by extraction with organic solvents. By proceeding in accordance with our invention, these latter expensive and cumbersome steps are avoided and, at the same time, reduction of the inorganic salt content in the final product to the desired degree is readily effected in an inexpensive and simple manner.

In the practice of our invention, an alcohol ester of an unsaturated polycarboxylic acid, for example, lauryl fumarate, is reacted with an alkali bisulfite, particularly sodiumbisulfite, in the presence of water and in the additional presence of an inert high boiling organic liquid solvent, for example, a petroleum hydrocarbon fraction having an initial boiling point, at atmospheric pressure, not substantially below 200 degrees C., such fraction being exemplified by a mineral oil having an initial boiling point of the order of 200 to 220 degrees C. or more. In general, we prefer to utilize petroleum fractions having a boiling point range, at atmospheric pressure, between about 200 and 400 degrees C. or, still more preferably, between about 260 and 350 degrees C. Other high boiling organic liquid solvents include esters of the type which are commonly used as plasticizers, polyglycols, etc. which are inert under the conditions of the reaction. The mixture is reacted, under conditions of agitation, at somewhat elevated temperatures, usually of the order of degrees C. to somewhat in excess of degrees C. until the reaction is essentially completed, that is, the production of the sulfopolycarboxylic acid ester is achieved. This usually takes at least several hours. It is preferred to carry out the reaction'at atomspheric pressure but, if desired, the reaction can be performed at greater pressures in which event the reaction conditions may be somewhat modified. The mineral oil or other inert high boiling organic liquid solvent serves, among other things, to maintain the reaction mixture in a state where it can be handled as a liquid, particularly toward the end of the reaction Where, if it were not present, a gummy reaction mixture would usually result which could not be stirred or satisfactorily handled.

At the completion of the reaction, there is then particularly advantageously added to the reaction mixture 21 further quantity of a mineral oil or similar petroleum fraction or the like having an initial boiling point not substantially below 200 degrees C. and, in addition, it, is especially desirable to add a volatile organic solvent which is distillable together with water to assist in the subsequent elimination of water from the mixture. Typical examples of such latter agents are carbon tetrachloride, trichlorethylene, benzene, perchlorethylene, and toluene. The mixture is then heated to distill therefrom water and the added volatile organic solvent. In the usual case, the temperature to which the mixture is heated to effect removal of water and organic solvent will fall Within the range of about to about degrees C. Thereafter, to the residual mass it is particularly desirable to add a petroleum fraction having an initial boiling point not substantially below 200 degrees C., for example, a mineral oil, or a volatile organic solvent such as Stoddard solvent, trichlorethylene or benzene or the like, after which the mixture is cooled and filtered. The final product is a isu iifim. t tstant allx reapt .in r aa asdo.ant

au yl su q u cinete. 21. usu l. ase, Wc., fi '1d; tTPar-:

ticularly satisfactory to, produce compositionspcontaining about;40% to about 65 preferably about 55 to 60%,

weight, of the esters of sulfopolycarboxylic,acidsin the mineraloil or like or'other petroleum hydrocarbon fraction. V p v For particularly elfectiye'use in the dry cleaning industry, in connection withthe production of oil-soluble e en n a h rm t on. Qf: t -.in-oi1 emu sio s, the alcohol radical of the sulfosuccinic acid esters should, be of aliphatic character. and contain; from 6-toabout 10 carbon atoms. For othendetergent and allied uses, the

alcohol maybe of aromatic or hydroaromatic oraromatic aliphatic character and may contain up to 22 but preferably from Sto 18 carbon atoms. Typical examples of such alcohols are, therefore, n l1exyl. alcohol, ,isohexyl.

alcohol, n-heptyl alcohol, n-octyl alcohol, Z-ethylhex'yl alcohol, mixtures of dimethyl hexanols, n nonyl alcohol,

isononyl alcohol, isomeric nonyl alcohols, decylalcohol, undecyl alcohol, dodecyl alcohol, tetradecyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, cyclohexanol, phenylethyl alcohol, benzyl alcohol,cresols,:jnaphthols,

etc. Reference may be had, for example, to the afore-..

mentioned patents for other alcohols whose esters with sulfopolycarboxylic aids are oil-soluble; It will be understood that mixtures of anytwo or more of suchalcohols can also effectively be utilized, Those of the esterswhich.

are utilized in accordance with the present invention are, as'pointed out above, the sulfopolycarboxylic acid esters inwhich one or all of the carboxyl groups of the polycarboxylic acid are esterified with the aforesaid alcohols. While, in the usual case, where all of the carboxyl groups of the sulfopolycarboxylic acid are esterified they'will be.

esterified with the same alcohol or alcohols, it will be understood that the production -of compositions within the scope 'of our. invention also comprises such mixed esters wherein, for instance, one of the carboxyl groups may be esterified with, for example,.one aliphatic alcohol such as hexyl alcohol, and the, other or others of the carboxyl groups may be esterified with another aliphatic alcohol such as octyl alcohol] Among the unsaturated polycarboxylicacids Whose alcohol esters are utilized as one of the reactants in accordance with the present invention are, by way of example,"dicarboxylic acids such as maleic acid (or maleic anhydride'), iumaric acid, glutaconic acid, mesaconic acid,

itaconic' acid, citraconic acid, and tricarboxylicacids such as aconitic acid, and others which may be disclosed, for instance, in the aforementioned patents.

The following examples are illustrative of the practice of our invention. It will be understood that these examples are not to be construed in any way as limitative of the dull scope of our invention since dififerent alcohols oan be utilized, the proportions of the ingredients can be varied, the reaction temperatures and times are likewise variable, within limits, and other modifications can be made, all within the spirit and guiding principles of the teachings herein. All parts stated are by weight.

Example 1 additional'parts of mineral oil is addedand, after cooling to room temperature, or somewhat therea-bove, the mixture Example 2 Q 300 parts of dibenzyl. maleate, prepared by esterification of maleic anhydride with benzyl alcohol, is admixed with 35 partsminer'al oil (initialB. P. 245 degrees C.), 105 parts of water and 105 parts of sodium bisulfite, and the mix-ture is heated, with agitation, at about 100 degrees C. dor about .20 hours. Then additional parts of mineral oil and 90 parts of perchlorethylene are added and the mixture is heated and allowed to distill until the tempera ture of the mixture reaches 180 degrees C. To the residual mass, additional parts of mineral oil is added and, after cooling to. about room temperature, the

mixture is. filtered whereupon a clear composition is ob-. tainedcontaining a.high percentage of sodiurndibenzyl zou a'a's' of tri-n-hexyl aconitate' is admixed with 16 parts mineral oil (initial B. P. 235 degrees C.), 60 parts wa-ter 'and .60 parts sodium bisulfite, and the mixture is heated, with agitation, at about 100v degrees C. for about 24 hours whereby sodium trin-hexyl sulfotricarballylate is produced in the reactionmixture. Then 50 additional parts of mineral oil and 50 parts of perchlorethylene are added and the mixture is heated and allowed to distill until the temperature of the mixture reaches, about 185 degrees C. To the residual mass 65 additional parts of mineral oil is added and, after cooling to room temperature or somewhat thereab'ove, the mixture is filtered whereupon a clear composition is obtained containing in excess of 50%, by weight, of sodium tr-i-n-hexyl sulfotricarballylate,

mineral oil (initial B. R245 degrees C.), 60 parts of water and 65. parts of ammonium bisulfite, and the mixture is heated, with agitation, at about 100 degrees C. forabout 18 hours. Then 50 additional parts of mineral oiland'50 parts of perchlorethylene are added and the mixture is heated and allowedto distill until the temperature of the mixture reaches degrees C. To the residual mass, 60 additional parts of mineral oil is added and, after cooling to about room temperature, the mixture is filtered whereupon a clear composition is obtained containing a high percentage of ammonium trioctyl sulfotricarballylate, said composition being substantially free of inorganic salts.

Example 5 200 parts of triphenylethyl aconitate is admixed with 20' parts mineraloil (initial B. P. 225 degrees C.), 60 parts water and 6O parts sodiumbisulfite and the mixture' is heated,with agitation, at about 100 degrees C. for about 16 hours whereby sodium triphenylethylsulfotricarballylate is produced in the reaction mixture. Then 50 additional parts of mineraloil and 50 parts of perchlorethylene 'areadded and the mixture is heated and allowed to distilluntil thetemperature of the mixture relation to Example 1, comprises, based on the use of 320 parts of dilauryl maleate, from about to about 35 parts of mineral oil, from about 80 to about 110 parts of water, and from about 80 to about 110 parts of sodium bisulfite in the reaction proper to produce the diester of sulfosuccinic acid. A good average reaction temperature is from about 95 to about 110 degrees C. and a good average reaction time is from several hours to about 24 hours. The amount of mineral oil or the like which is added initially after the completion of said reaction is from about 70 to about 100 parts and the amount of volatile organic solvent, such as perchlorethylene, utilized will ordinarily vary from about 50 to about 150 parts. These illustrative figures will serve as guides to enable those versed in the art readily to select suitable operating con ditions and proportions of ingredients etfectively to carry out the teachings of our invention.

Where reference is made in the claims to the boiling point of the inert organic liquid solvent, it will be understood to include the initial boiling point of such liquids Where the latter have a boiling point range as, for instance, in the case of petroleum hydrocarbons which contain mixtures of various fractions.

What we claim as new and desire to protect by Letters Patent of the United States is:

l. A method of preparing a dry cleaning composition, which comprises reacting, under agitation, an alcohol ester of a polycarboxylic acid, the alcohol radical of which contains at least 6 carbon atoms and the polycarboxylic acid radical of which contains a double bond, with an alkali bisulfite in aqueous solution and in a mineral oil having an initial boiling point not substantially below 200 degrees C., said polycarboxylic acid ester and said alkali bisulfite being present in proportions to produce the alkali salt of the sulfopo lycarboxylic acid ester of said alcohol, said mineral oil being present in amounts sufiicient to maintain the reaction medium in a liquid condition throughout said reaction, at the end of said reaction adding to the reaction mixture a liquid volatile organic solvent which is distillable together with water at a temperature below 190 degrees C., then heating the mixture to remove the water and at least most of the lastmentioned liquid volatile organic solvent but not said mineral oil, and filtering whereby to obtain a liquid composition substantially free of inorganic salts.

2. A method of preparing a dry cleaning composition, which comprises reacting, under agitation, an alcohol ester of a dicarboxylic acid, the aliphatic alcohol radical of which contains from 6 to about 22 carbon atoms and the dicarboxylic acid radical of which contains a double bond, with sodium bisulfite in aqueous solution and in a mineral oil having a boiling point between about 260 and 350 degrees C., said dicarboxylic acid ester and said sodium bisulfite being present in proportions to produce the sodium salt of the sulfodicarboxylic acid ester of said alcohol, said mineral oil being present in amounts sufiicient to maintain the reaction medium in a liquid condition throughout said reaction, at the end of said reaction adding to the reaction mixture a mineral oil having a boiling point between about 260 and 350 degrees C. and also adding a liquid volatile organic solvent which is distillable together with water at a temperature below degrees C., then heating the mixture to remove the water and at least most of the last-mentioned liquid volatile organic solvent but not said mineral oil, and filtering whereby to obtain a liquid composition substantially free of inorganic salts.

3. A method of preparing a dry cleaning composition, which comprises reacting, under agitation, an alcohol ester of a tricarboxylic acid, the alcohol radical of which contains from 6 to about 22 carbon atoms and the tricarboxylic acid radical of which contains a double bond, with an alkali bisulfite in aqueous solution and in a mineral oil having an initial boiling point not substantially below 200 degrees C., said tricarboxylic acid ester and said alkali bisulfite being present in proportions to produce the alkali salt of the sulfotricarboxylic acid ester of said alcohol, said mineral oil being present in amounts sufficient to maintain the reaction medium in a liquid condition throughout said reaction, at the end of said reaction adding to the reaction mixture a liquid volatile organic solvent which is distillable together with water at a temperature below 190 degrees C., then heating the mixture to remove the water and at least most of the lastmentioned liquid volatile organic solvent but not said mineral oil, cooling the residual product, and then filtering whereby to obtain a liquid composition substantially free of inorganic salts and water.

4. A method in accordance with claim 1, wherein the alcohol is phenylethyl alcohol.

5. A method in accordance with claim 3, wherein the alcohol is oleyl alcohol.

6. A method in accordance with claim 3, wherein the tricarboxylic acid is aconitic acid.

7. A method in accordance with claim 6, wherein the alcohol is tetradecyl alcohol.

8. A method in accordance with claim 6, wherein the alcohol is lauryl alcohol.

9. A method in accordance with claim 6, wherein the alcohol is cetyl alcohol.

References Cited in the file of this patent UNITED STATES PATENTS 2,028,091 Jaeger Jan. 14, 1936 2,315,375 Nawiasky et al Mar. 30, 1943 2,327,183 Flett Aug. 17, 1943

Claims

1. A METHOD OF PREPARING A DRY CLEANING COMPOSITION, WHICH COMPRISES REACTING, UNDER AGITATION, AN ALCOHOL ESTER OF A POLYCARBOXYLIC ACID, THE ALCOHOL RADICAL OF WHICH CONTAIN AT LEAST 6 CARBON ATOMS AND THE POLYCARBOXYLIC ACID RADICAL OF WHICH CONTAIN A DOUBLE BOND, WITH AN ALKALI BISULFITE IN AQUEOUS SOLUTION AND IN A MINERAL OIL HAVING AN INITIAL BOILING POINT NOT SUBSTANTIALLY BELOW 200 DEGREES C., SAID POLYCARBOXYLIC ACID ESTER AND SAID ALKALI BISULFITE BEING PRESENT IN PROPORTIONS TO PRODUCE THE ALKALI SALT OF THE SULFOPOLYCARBOXYLIC ACID ESTER OF SAID ALCOHOL, SAID MINERAL OIL BEING PRESENT IN AMOUNTS SUFFICIENT TO MAINTAIN THE REACTION MEDIUM IN A LIQUID CONDITION THROUGHTOUT SAID REACTION, AT THE END OF SAID REACTION ADDING TO THE REACTION MIXTURE A LIQUID VOLATILE ORGANIC SOLVENT WHICH IS DISTILLABLE TOGETHER WITH WATER AT A TEMPERATURE BELOW 190 DEGREES C., THEN HEATING THE MIXTURE TO REMOVE THE WATER AND AT LEAST THE LASTMENTIONED LIQUID VOLATILE ORGANIC SOLVENT BUT NOT SAID MINERAL OIL, AND FILTERING WHEREBY TO OBTAIN A LIQUID COMPOSITION SUBSTANTIALLY FREE OF INORGANIC SALTS.