US2061619A - Sulphonated aliphatic hydrocarbon - Google Patents

Description

Patented Nov. 24, 1935 DERIVATIVES, USEFUL AS WETTING AND CLEANSING AGENTS Frederick Baxter Downing, Carney: Point, N.

and Richard Gesse Clarkson, Wilmington. DeL, assignors to E. I. du Pont de Nemonrs 8: Co

pany, Wilmington, Del., a corporation of Delaware No Drawing- Anpucauon May as, 1932,

Serial No; 814,290

15 Claims. (01. 260-156) This invention relates to chemical compounds, more particularly surface active substances and a process for the manufacture thereof.

As is well known, surface active compounds which possess cleaning, wetting and dispersing properties may be advantageously used in the various industries, for example, the textile and a leather industries, for a wide variety of purposes.

Thus, surface active compounds such as soaps, that is, the sodium salts of the higher fatty acids, find a wide application in the laundering, dyeing and finishing of textiles. Soaps are characterized by the disadvantage, however, that they are not soluble in acidic solutions since-the alkali metal salts of the fatty acids are converted into the insoluble fatty acids. Soaps are also precipitated in strongly alkaline solutions. Furthermore, in hard water the alkali metal salts of fatty acids are precipitated as the insoluble alkaline earth metal salts, such as those of calcium, magnesium and the like.

While other surface active substances have been prepared such as, for example, the Turkey red oils (that is, the reaction products of castor oil with concentrated sulphuric acid at relatively low temperatures) which are more soluble than soaps in the presence of mineral acids and hard water, these substances are generally much less effective detergents than the soaps they are designed to replace.

It is an object of the present invention to produce new chemical productswhich are highly surface active, are water soluble, and possess good wetting and detergent power even in relatively strongly alkalineor acidic solutions. A further object is the production of surface active compounds having relatively soluble alkaline earth metal salts and which, therefore, are adapted foruse in hard water. A still further object of the invention is the provision of a new and improved process for producing the above described compounds. Another object is the production of these surface active compounds directly in a high state of purity. A further object is the production of compounds. of the character described by a process involving a series of reactions which proceed with great smoothness and almost theoretical I yields. Further objects will appear hereinafter.

These objects are accomplished according to this invention whereby products especially useful as detergent, wetting and dispersing agents are produced by reacting unsaturated aliphatic hydrocarbons, containing 8 or more carbon atoms and having a double bond at the end of the chain,

witha halogen sulphonlc acid in the presence of a halogenating catalyst and treating the reaction product with a hydrolyzlng agent.

While the invention is subject to considerable variation and modification in the manner of its practical application, particularly as regards the kind and proportions of the reactants and the exact method of procedure, the following examples, in which the parts are by weight, will serve to illustrate some of the products falling within the invention and how they may be prepared.

Example I Twenty parts 1-2-octadecylene obtained by dehydrating primary n-octadecyl alcohol were dissolved in about 80 parts of carbon tetrachloride. Approximately one-tenth part of pyrolusite was suspended in the solution which was then cooled to about -5 G. Twelve parts of chlorsulphonic acid were added slowly to the mixture with agitation, the resultant mixture being maintained at the above low temperature for a period of about two more hours. At the end of this time the temperature was allowed to rise to about 20-25 C. After standing at this temperature for 12-14 hours the liquid was poured into water, neutralized with 20% sodium hydroxide solution and about 6 parts of excess sodium hydroxide added. The product was boiled for an hour to hydrolyze it and to remove carbon tetrachloride. The resultant solution was neutralized with sulphuric acid solution and then evaporated to a small volume. The product was isolated by precipitating the inorganic salts with an excess of ethyl alcohol, filtering the alcohol solution and evaporating off the alcohol and water. The resultant product was a light brown 011, clearly soluble in water, possessing high surface activity.

and characterized by unusual stability in combination with marked wetting, cleaning, and dispersing power even in strongly acid or alkaline solutions. The weight of product obtained in this way was 32.5 parts.

Example I! more than 10% of hydrochloric acid and in solutions containing more than 10% of sodium hydroxide. In fact no tendency towards instability was noticed in any alkaline, neutral or acidic aqueous solutions.

Example III The process of Example I was carried out in the presence of about one-tenth part of cuprous chloride instead of pyrolusite; The yield of prodnot obtained by extraction with alcohol was about 25.5 parts and its properties were similar to those of the substances produced as described in Examples I and II.

For comparison, the procedure described in Examples I, II and III was carried out a number' of times without a catalyst, all other conditions of operation and proportions of materials being the same. In marked contrast with the reaction where a catalyst was used, it was observed that after hydrolysis and neutralization of the hydrolyzed product with the 10% sulphuric acid solution an oily liquid formed in the reaiction mixture. This oily substance was removed and the remaining liquid evaporated to a small volume and extracted with alcohol as described in Example I. The average yield-of product was about 23.0 parts. This product likewise was soluble in water and possessed good wetting, cleaning and dispersing powers. even in relatively strongly acidic or alkaline solutions. As will be apparent, however, the yield was not so high as that obtained from the reaction with a catalyst. Thus the increase of yield obtained by the procedure of Example I, was about 41%. Actually the increase in yield wasprobably greater than this since the products obtained by the use of catalysts' were purer than those obtained without catalysts. This was shown by the fact that the aqueous solutions of the products obtained with catalysts were perfectly clear while solutions of the products obtained without a catalyst were cloudy, the cloudiness probably indicating incomplete removal of the by-product oily material formed during the hydrolysis. Furthermore, the products'obtained from the reaction with a catalyst were more effective-wetting agents than the products obtained without-catalysts.

The unsaturated hydrocarbons employed in drocarbonsmay-be of the straight or branched chain type.

Generally. speaking, the straight chain hydrocarbons having a single double bond at the end of the chain are preferred. Hydrocarbons of this kind may be obtained in any suitable manner, 'for-- example, by dehydrating the primary alcohols obtained by hydrogenating fatty 'acids or their esters, .e. g. those contained in palm oil, tallow, coconut oil and olive oil. Branched chain unsaturated hydrocarbons falling within the invention may likewise be obtained in any desirable manner, for example, by, polymerizing relatively short chain olefines or by dehydrating synthetic higher alc0h91$ or mixtures tion.

thereof, e. g. those-produced by the hydrogenation of carbon oxides under elevated temperatures and pressures. Where branched chain hydrocarbonsare employed the better results are obtained the shorter the side chain.

In practicing the invention the halogen sulphonic acids preferably employed are chlorsulphonic acid and bromsulphonic acid. The proportions of halogen sulphonic acid employed may vary within relatively wide limits dependinglargely upon the nature of the unsaturated hydrocarbon treated and the products desired. In general, it is preferable to employ about l-2 moles of halogen sulphonic acid for each double bond per mole of an unsaturated hydrocarbon. In certain cases, however, it may be desirable to use larger or smaller proportions of the halogen sulphonic acid} it being understood that the desired reaction proceeds whether. a small or large amount of sulphonic acid is employed.

' As indicated by the examples, the reaction of the halogen sulphonic acid with the unsaturated hydrocarbon is preferably effected in a suitable liquid medium, that is to say, a medium which is liquid at the temperature of the reaction and is inert to the reactants and products or does not affect, the reaction unfavorably. It may or may not be a solvent for the reactants and/or products. As examples of such mediamay be mentioned carbon tetrachloride, ethylene-dichloride, trichlorethylene, tetrachlorethane, chloroform,

liquid sulphur dioxide, diethyl'ether, acetic anhydride, propionic acid and propionic'anhydride. Generally speaking, we prefer to employ solvent or suspension media having a boiling point below about 100 C., and especially desirable results have been obtained with carbon tetrachloride.

The catalyst employed in accordance with.the invention may be any catalyst favoring the halogenation of carbon compounds. By' halogenation is meant the action of a free halogen on a hydrocarbon whereby a hydrogen atom in the hydrocarbon is replaced bya halogen atom. The catalyst should preferably be soluble in the reaction mixture and, furthermore, should preferably be a compound which does not give rise to oxidation reactions. As examples of halogenating catalysts may be mentioned antimony trioxide, antimonypentoxide, antimony trichloride, antimony pentachloride, antimony sulphate,

cuprous chloride, cupric oxide, cuprous oxide,

cupric sulphate, cupric acetate, manganese dioxide. pyrolusite, manganous sulphate, manganese oxide, ferric chloride. ferrous sulphate.

ferric sulphate, ferric o'xide, ferrous oxide, magnetite, vanadium pentoxide, sodium vanadate, vanadyl sulphate, aluminum chloride, aluminum sulphate. cuprous iodide, sodium iodide, potassium iodide and free iodine. It will berecognized that the results obtained with the foregong catalysts'may differ widely depending largely upon thespecific reactants and conditions of opera- We have found that the reaction proceeds very smoothly and the final products are exceptionally light in color when unsaturated hydrocarbons of the character herein described are reacted with chlorsulphonic acid in the presence of a chlorinating catalyst. Of the various chlorlnating catalysts with which we have practiced this-preferred embodiment of the invention, the

results obtainedwith pyrolusite and iodine have been very-highly advantageous. The amount of catalyst employed may vary considerably depending more or less upon the.

nature thereof and that of the reactants, but as a general rule desirable results have been obtained by the addition of catalysts to the reaction mixture in proportions corresponding to about (Ll-5.0%- by weight of the reacting substances.

The time allowed for the reaction between the halogen sulphonic acid and the unsaturated hydrocarbon to take place will depend largely upon the nature of the reactants, the catalysts and theconditions oi temperature. Under ordinary operating conditions it may vary from about 2 to 48 hours. In practice, however, this reaction is ordinarily allowed to proceed until a sample of the product boiled with a hydrolyzlng agent is soluble in water.

While the temperature maintained in effecting the reaction with the halogen sulphonic acid may vary within relatively wide limits, the temperature employed should preferably be below that giving rise to decompositiomresiniflcation or polymerization of the reactants and products. In general, it is preferable to maintain the temperatures in this. step of the process below about 50 C. and preferably within the range of about 10-+35 C. Ordinarily, higher temperatures tend to yield darker product a The hydrolysis of the product resulting from the reaction of the halogen sulphonic acid and the unsaturated hydrocarbon may be effected in a number 01 ways. Thus, water may be added until the acid concentration is relatively low and the resultant product boiled: or the sulphonated product may be neutralized and then heated with a hydrolyzing agent. In some cases it may be possible to effect hydrolysis, at least in part, by merely neutralizing the reaction product of the halogen sulphonic acid and unsaturated hydrocarbon with an aqueous alkaline reagent and then boiling the resultant product. Hydrolyzing agents which are suitable for the process. of the invention are mineral acids, e. g. hydrochloric, sulphuric and the like, or alkaline reagents, e. g., alkali metal and alkaline earth metal hydroxides. In practice, we prefer to neutralize the sulphonated product with an aqueous solution of an alkali metal hydroxide, preferably sodium hydroxide, and heat ,the product with a further quantity of the alkali metal hydroxide to eflect hydrolysis.

Thev amount of alkaline reagent employed for neutralization and hydrolysis of the sulphonation product should preferably correspond to at least one equivalent for every equivalent of halogen sulphonic acid used. Thus, if the reaction with the unsaturated hydrocarbon is carried out by means ofone mole of chlorsulphonic acid.

neutralization and hydrolysis of the product may be effected with two moles of sodium hydroxide.

- In general, it is preferable to use an excess of the alkaline reagent over the amount required for neutralization and hydrolysis.

The amount of water present during the hydrolysis,may vary widely, Very satisfactory resuits are obtained, however, when the suphonated product is heated with solutions of mineral acids, alkali metal hydroxides or akaline earth metal hydroxides having concentrations of about 2-20%.

The temperature of the hydrolysis is subject to considerable variation but should preferably be above 50 C. and below the temperature at which the reactants or products decompose. A temperature of about 100 C. is normally satisfactory for carrying out the hydrolysis. If a solvent-or suspension medium is used in the first step of the process, it is preferably removed prior to or during hydrolysis by evaporation, steam distillation or in any other suitable manner. .The time allowed'ior the hydrolysis is preferably determined by allowing the hydrolytic action to proceed until a sample of the product dissolves in water.

Products of some value as emulsifying agents may be obtained by reacting the unsaturated aliphatic hydrocarbons with a halogen sulphonic acid in the presence of a halogenating catalyst as above described, and then merely neutralizing the reaction product without hydrolyzing it. These intermediate products may also possess some wetting and detergent power, particularly it relatively short chain unsaturated hydrocarbons are employed. In general, however, these products are insoluble or only slightly soluble in water.

The final products produced in accordance with the invention, on the other hand, are soluble in water. Furthermore, they are highly surface active and possess excellent cleaning, wetting-and dispersing properties. They are particularly valuable from a commercial standpoint because of their stability in all kinds of acidic, alkaline and neutral aqueous media and are distinguished from any products previously preparedby their stability in strong acids and alkalies. Because of these characteristics our new products have an unusually wide application for industrial purposes. Since they may be used in acid, neutral or alkaline baths they are especially well adapted for the laundering, dyeing, bleaching. carbonizing, mercerizing and finishing of textiles. They are also well adapted for use as emulsifying and solubilizing agents for water immiscible or only slightly miscible solvents. They'may be employed assuch or in combination with water miscible or immiscible alcohols, ketones or other additional materials, such as washing, cleansing, emulsifying and wetting agents, e. g. trisodium phosphate, Turkey red oils, soaps, aliphatic or aromatic sulphonic acids, such as alkylated naphthalene sulphonic acids, mineral oil sulphonic acids, sulphonated derivatives of abietic acid, sulphuric esters, saponin and aliphatic and aromatic acid amides, such as sodium taurocholate or sodium salts of analogous acid amides. When employed alone or in combination with other materials such as those mentioned above they find wide application as pasting, cleansing, lathering, wetting or fulling agents in the dye, paper, textile and leather industries. The products of the invention may also be employed in combination with neutral, acid or basic salts which serve to increase their emulsifying, wetting and dispersing power, such as, for example, sodium sulphate. sodium chloride. sodium acetate. monodiand tri-sodium phosphates, sodium carbonate, sodium b carbonate. and similar compounds of the other alkali metals or of ammonium. Other additional materials with which the products of the invention may be combined are bleaching and disinfectant agents such as persulphates, percarbonates and perborates: filling materials such as talc, marbe-dust, and starch:' adsorbing materials such as suitable clays, e. g. i'ullers' earth; protective colloids or dispersing agents such as gum tragacanth, gall acids and their derivatives, agar-agar, glue, metlwl cellulose, sulphite cellul"se lyes, sodium cellulose phthalate, calcium saccharate, albumin. sodium cellulose glycollate, gelatin, natural and artificial resins, derivatives of chloresterine; phosphatides. geloses, natural and artificial waxes, wool waxes, solvent and softening sulphonlc acid derivatives.

agents, organic bases and their salts such as alkylolamine salts and-quaternary ammonium compounds, inorganic colloids, and alkalies; and scouring materials such as kieselguhr, powdered pumice, sulphur, flour, china-clay salt and the like. Desirable results for many purposes may also be obtained by employing the sulpho acids or salts thereof produced as herein described in combination with the various acyclic, monocyclic, or complex cyclic terpenes or derivatives thereof such as, for example, limonene, dipentene, terpinolene, terpinene, phellandrene, sylvestrene, .pinene, 'bornylene, sabine and their alcoholic, ketonic and aldehydic derivatives. It will be apparent, furthermore, our new products may be combined with a wide variety of other additional materials which possess washing, cleansing,

emulsifying, wetting, dispersing, adsorbing, lathering. bleaching, germicidal and bactericidal powers. They may likewise have incorporated therewith artificial or natural perfuming substances, many of which in themselves may possess detergent properties of some value.

In addition to the' advantages above enumerated the invention is further advantageous in that it offers a large outlet for cheap raw material such asoils and fats from natural sources and those obtainable in large quantities as byproducts from the textile, and leather industries, from fish oils, and a large number of other sources. Moreover, many' of these by-products have been of relatively little value or usefulness heretoforebecause of the bad odor asso-' ciated therewith. By converting these raw materials to olefines for use in the present process odor ceases to be a serious factor.

In the practical application of the products of the invention it has been noted that as a general rule their wetting properties increase with the number of carbon atoms in the unsaturated hydrocarbon employed up to about 18 carbon atoms and thereafter decrease. It has also been noted that the detergent properties of the product may vary within a relatively wide range depending largely upon the number of carbon atoms therein and the nature of the liquid in which they are employed. Thus, in soft water the detergent power increases with the number of carbon atoms in the starting material and the products prepared from unsaturated hydrocarbons containing about 20-30 carbon atoms are especially desirable. In hard water, on the other hand, products prepared from unsaturated aliphatic hydrocarbons containing less than 20 but more than about carbon atoms are preferred from the standpoint of detergent power, and those preparedfrom the unsaturated straight chain hydrocarbons containingabout 14 to 16 carbon atoms are particularly advantageous.

The chemical constitution of the products produced in accordance with the invention has not been definitely determined and therefore we do not wish to be limited by any theory in this regard or in regard to the mechanism of the reactions. In view of the enhanced wetting and. detergent power of these products, however, and their greater stability in strongly alkaline and acidic solutions than products previously prepared, it appears that they are most probably true As previously pointed out, the products obtained by reaction of the unsaturated hydrocarbon with chlorsulphonic acid in the presence of a chlorinating catalyst and then hydrolyzing are somewhat better than those obtained by a similar procedure without a catalyst.

the catalyst causes one reaction to occur to the exclusion or practically to the exclusion of others. A probable course of the reactions occurring when chlorsulphonic acid is reacted upon a higher oleflne having a single double bond at the end of the chain in the presence of a chlorinating catalyst may be illustrated by the following equations, in which R represents a saturated hydrocarbon radical containing at least six carbon atoms:

Sulionation SOaH Hydrolysis H H Hydrolysing H H agent )3 I. R- H R- -11 where M is 9H, or a metallic radical such as -Na, -K, or thelike, depending upon the hydrolyzing agent used.

Another probable course of the reactions is as follows? Sulionation H n H H n. 'n-c=c-n+cisotn i iim OaH J1 Hydrolysis "dominated, or occurred practically to the exclusion of the other, it would seem that Reaction I would be favored in view of the tendency of chlorine, in the presence of a chlorinating catalyst, to attach itself to the alpha carbon atom.

If the radical R of the unsaturated hydrocarbon contains an unsaturated bond, similar reactions 'would probablyoccur at this bond. As previously indicated, these products are usually less desirable for the purposes of the invention.

As many apparent and widely different embodiments of this invention may be made without departing from the spirit thereof, it is to be understood that we do not limit ourselves to the foregoing examples or description except as indicated in the following claims.

We claim:

1. In a process for preparing surface active substances, the step which comprises V reacting an aliphatic unsaturated hydrocarbon, containing at least 8 carbon atoms and having a double bond at the end of the chain, with a halogen sulphonic acid in the presence of a halogenating catalyst.

2. A process for preparing surface active substances, which comprises reacting an aliphatic unsaturated hydrocarbon, containing at least 8 carbon atoms and having a double bond at the end of the chain, with a halogen sulphonic acid in the presence of a halogenating catalyst, and hydrolyzing the reaction product.

3. A process for preparing surface active substances, which comprises reacting an aliphatic unsaturated hydrocarbon, containing at least 8 carbon atoms and having a double bond at the end of the chain, with chlorsulphonic acid in the presence of a chlorinating catalyst, and treating the reaction product with a hydrolyzing agent whereby the chlorine is removed from the hydrocarbon molecule.

4. A process for preparing surface active substances, which comprises reacting an aliphatic unsaturated hydrocarbon, containing at least 8 carbon atoms and having a double bond at the i end of the chain, with chlorsulphonic acid at a relatively low temperature, in the presence of a chlorinating catalyst, and heating the resultant product with a hydrolyzing agent.

5. Aprocess for preparing surface active substances, which comprises reacting an aliphatic unsaturated hydrocarbon, containing at least 8 carbon atoms and having a double bond at the end of the chain, with chlorsulphonic acid in an inert liquid reaction medium, and in the presence of a chlorinating catalyst, and treating the reaction product with a hydrolyzing agent whereby .the chlorine is removed from the hydrocarbon molecule.

l 6. The process of producing a highly surface active substance, which comprises reacting an :aliphatic unsaturated hydrocarbon, containing at least 8 carbon atoms and having a double bond at the end of the chain, with chlorsulphonic acid at a temperature within the range of about -10-+85 C., in an inert liquid reaction medium which is asolvent for the unsaturated hydro- I carbgn, in the presence of a chlorinating catalyst,

then removing the reaction medium, heating the remaining product with a hydrolyzing agent, neutralizing the resultant product and recovering the neutralized product.

7. The process of preparing surface active substances, which comprises reacting a straight has chain unsaturated aliphatic hydrocarbon, containing at least 8 carbonatoms and having a single double bondat the end of the chain, with chlorsulphonic acid in proportionsmorresponding to about 1 to 2 mols of chlorsulphonic acid per mole of unsaturated hydrocarbon, in an inert solvent reaction medium boiling below about 100 C.,, at a temperature within the range of -'-10-+35?' C., in the presence of a,chlorinating catalyst, adding to the resultant product water and about one equivalent of alkali metal hydroxide for every equivalent ofchlorsulphonic acid used.

the proportions of water corresponding to an product.

aqueous solution of said alkali metal hydroxide having a concentration of about 2-20%, he the product obtained to a temperature of about 100 C. to effect hydrolysis thereof and at the same time to remove the reaction medium, neutralizing the hydrolyzed product with a mineral acid and recovering the neutralized product substantially free from inorganic salts.

8. In a process of preparing surface active substances, the step which comprises reacting an aliphatic unsaturated hydrocarbon containing 8 to 18 carbon atoms, inclusive, and having a double bond at the end of the chain, with chlorsulphonic acid in the presence of a chlorinating catalyst.

9. In a process of preparing surface active substances, the step which comprises reacting an aliphatic unsaturated hydrocarbon containing 20 to 30 carbon atoms, inclusive, and having a double bond at the end of the chain, with chlorsulphonic acid in the presence of a chlorinating catalyst.

10. In a process of preparing surface active substances. the step which comprises reacting branched chain aliphatic unsaturated hydrocarbons containing at least 8 carbon atoms and having a double bond at the end of the chain, with chlorsulphonic acid in the presence of a chlorinating catalyst.

11. In a process of preparing surface active substances, the step which comprises reacting an aliphatic unsaturated hydrocarbon containing at least 8 carbon atoms and having a double bond at the end of the chain, with chlorsulphonic acid in the presence of a chlorinating catalyst selected from the group consisting of inorganic oxides and salts of antimony, copper, manganese,

iron, vanadium, aluminum, alkali metal iodides and free iodine.

12. The process of claim 8 in which the reaction product is subsequently heated with a hydrolyzing agent selected from the class consisting of dilute acids and dilute alkalis under conditions adapted to replace chlorine atoms .by hydroxyl D 13. The process of claim 11 in which the reaction product is subsequently heated with a hydrolyzing agent selected from the class consisting of dilute acids and dilute'alkalis under con.- ditions adapted to replace chlorine atoms by hydroxyl groups.

14. The process of clam 8 in which the aliphatic unsaturated hydrocarbons correspond to the oleflnes obtainable by the dehydration -of alcohols from coconut oil. 1

15. The process which comprises reacting an aliphatic unsaturated hydrocarbon containing at least eight carbon atoms and having a double bond at the end of the chain with chlorsulphonic acid at'a temperature below about 50 C.,- in an inert solvent for the unsaturated hydrocarbon in the presence of a chlorination catalyst, then removing'the solvent, heating the. remaining product with a hydrolyzing agent, neutralizing the resultant product, and recovering the neutralized FREDERICK n. nownmo. RICHARD a. cmaxson.