US2283214A - Washing, wetting, and emulsifying agent - Google Patents

Description

Patented May 19, 1942 Lucas P. Kyrldes, Webster Groves, Mm, assignor to Monsanto Chemical Comp ny, St. Louis, Mo., a corporation of Delaware No Drawing. Application December 24, 1937, Serial No. 181,597

' 16 Claims. (01.252-89) The present invention relates to wetting agents, emulsifying agents, textile assistants, detergents and similar agents and refers particularly to new agents of this class. The agents are the salts of acids resulting from the reaction of unsaturated hydrocarbons, alkyl chlorides or alcohols with maleic anhydride and similar aliphatic carboxylic acids or anhydrides containing the' alpha-betaenal grouping,

-c=cc=o l 'l I The present invention is based upon my discovery that alkali metal salts of the carboxylic acids obtained by the addition or condensation of mono-olefins, alkyl chlorides and alcohols containin from five to sixteen carbon atoms in the molecule, such as diisobutylene and triisobutylene, with various unsaturated aliphatic acids possessing the alpha-beta-enal grouping are characterized by pronounced wetting action. These compounds are comparable in their surface activity to similar well-known wetting agents such as the sulfated alcohols and the sulfonated alkyl aromatic hydrocarbons commonly used for this purpose, especially in their action in hard water, but many of them do not foam or lather as readily when mixed in water in the manner that is typical of known wetting agents. This failure to foam is a definite advantage for certain purposes, and does not detract from their desirability as wetting agents or detergents.

The condensed acids which I have found desirable for use in my invention are those derived from the reaction of unsaturated carboxylic acids containing the alpha-beta-enal grouping with mono-olefins containing about five to sixteen carbon atoms per molecule. Such olefins are the various amylenes, hexylenes, heptylenes or mixed olefins which result as by-products in petroleum cracking operations or as by-products in the chlorination of saturated aliphatic hydrocarbons. The olefins may be polymers of lower hydrocarbons, for example, diisobutylene or mixed isomeric triisobutylenes, which result from polymerization of isobutylene with sulfuric acid or metallic halides or result from simultaneous dehydration and polymerization of tertiary-butyl alcohol by concentrated sulfuric acid.

The olefins are added to or condensed with aliphatic carboxylic acids or anhydrides containing the alpha-beta-enal grouping. Unsaturated acids of this type are fumarlc or maleic acid, HO0C-CH=CHCOOH, itaconic acid, CHz=C(COOI-I)CH:COOH, citraconic acid, CHaClCOOH) =CHCOOH, acrylic acid,

and crotonic acid, CHaCH=CH-COOH. Because of their case of condensation and since they are readily obtainable, the anhydrides of dicarboxylic acids of this series are preferred as the starting materials for the addition or condensation reaction to produce the compounds contemplated in the invention. Maleic anhydride is the most common and most readily available acid anhydride of this series and hence is particularly considered throughout this specificaton. Aromatic acids such as phthalic acid, in which the reactive portion of the alpha-beta-enal grouping is partly incorporated in the phenyl nucleus, are not operative.

The reaction by which the compounds of the invention are obtained is considered to take place by addition of the'olefin at the double bond of the unsaturated dicarboxylic acid. As far as can be determined, the unsaturation of the original olefin reacted is preserved. The reaction of maleic anhydride withdiisobutylene and its subsequent hydration with water is representable as:

The product is an octene-succlnic acid, viz., dilsobutylene-succinic acid, or, when other olefins are used, in general, an alkene-succinic acid.

The reaction itself is referred to herein either as an addition or condensation reaction, since, as will be pointed out hereinafter, alkyl halides yield products by elimination of hydrogen chloride that are substantially identical with those obtained from olefins. Alcohols undergo a similar reaction by addition of'the alcohol at the double bond ofthe acid. The reaction of olefins and unsaturated acids is described in U. S. Patent' 2,055,456;

The condensation of the olefin with the unsaturated acid containing the alpha-betaqenal grouping can be conducted with stirring under {reflux or pressure to avoid any loss of volatile materials. sBy conducting the reaction under pressure the period of heating can be somewhat reduced. At atmospheric pressure periods as long as 48 hours or more of heating at a temperature sufficient to maintain a gentle reflux are required. Of course, with amylene and similar low-boiling olefins the temperature required to maintain a reflux is too low to produce any appreciable reaction, hence autoclaving or pressure treatment is desirable. However, refluxing at atmospheric pressure can be used with mixtures that reflux at about 150 C. or above. For example, in heating triisooutylene with maleic anhydride, gentle refiuence at the beginning of the reaction can be maintained by keeping the mixture at about 156 C. As reaction progresses higher temperatures are required to maintain the reflux. By conducting the reaction in this manner, viz.,.by raising the temperature of heating just sufficient to maintain a gentle reflux, the end of the reaction can be judged as that point at which no further rise in temperature of the mass is required to maintain refluence. No such guide is available, of course, when the reaction is conducted in an autoclave under pressure and in that case some preliminary experimentation is required with each individual reaction mixture to determine the optimum period of reaction under the particular conditions. The period of reaction will be dependent upon the pressure maintained as well as the temperature and -can be controlled'by varying both.

The proportions of reacting materials may be varied. Theoretically, equimolecular quantities of the acid and olefin combine. Generally when equimolecular quantities are used the reaction does not proceed to completion and to facilitate it, it is preferable to add an excess of one reactant. When reacting the mass under pressure I prefer to use an excess of olefin since it is easily recoverable but when conducting the reaction under atmospheric pressure I prefer to use an excess of the acid to permit maintaining a higher temperature during the heating of the reaction mass.

From the resulting reaction mixture, for example, that resulting from triisobutylene and maleic anhydride, which is a viscous fluid mass, the unreacted olefin or acid may be recovered by any of the usual methods. After reacting maleic anhydride With triisobutylene, I prefer to add to the mass a solution of sodium hydroxide, whereupon the excess olefin separates as a supernatant layer. The acid that has formed dissolves in the aqueous layer in the form of the respective sodium salt. The aqueous layer after separation is then acidified to precipitate the triisobutylene-succinic acid formed as a result of the reaction while the unreacted maleic aci'd remains in solution. Be-

1 fore separating the precipitated acid mass from the aqueous solution it is advantageous to add a water-immiscible solvent such as chloroform to the mixture to reduce the viscosity and take up the triisobutylene-succinic acid remaining dissolved in the maleic acid aqueous layer. The two layers are then separated, the acid product is recovered from the chloroform layer, and the products in the aqueous layer also are recovered. Obviously, other methods may be used for the separation.

The separation may be dispensed with after merely removing unreacted olefin, for example, by distillation in vacuum or with steam, inasmuch as small amounts of unreacted maleic or other from the decomposition of alkyl chlorides.

acid which may be present generally have no detrimental effect in the particular contemplated use.

Instead of using diisobutylene, triisobutylene and, similar olefins resulting from polymerization of refinery waste gases, I may use olefins resulting Thus, decyl chloride, dodecyl chloride and tridecyl chloride obtained by chlorinating the corresponding paraflin hydrocarbons or petroleum fractions rich therein can be converted to the corresponding olefinsby heating. This decomposition may be advantageously facilitated by catalysts. The decomposition to olefins may be eifected in the reaction mixture with the maleic anhydride, that is, instead of reacting the olefin and the maleic anhydride, the alkyl chloride may be reacted directly with the maleic anhydride. The products correspond in formula and properties to those obtained from the respective olefins.

The resulting triisobutylene-succinic acid or similar acid product is then converted to the sodium salt or other alkali-metal salt by means of sodium hydroxide or other alkali hydroxide. The potassium salts of the compounds of the invention possess the same general characteristics as the sodium salts. Alkali-metal salts of the acids are replaceable by the free acids themselves or by salts of the acids'with ammonia or organic bases. Thus, salts with ammonia, triethanolamine, mono-, di-, or tri-ethyl amine, etc., pyridine, nicotine and the like, can be prepared. The salts with nicotine are insecticidal in nature and permit the use of this material in aqueous media and furthermore, provide compositions of increased spreading power. The alkene-dicarboxylic acid may also be partially esterified, for example, the monoethyl ester of triisobutylene-succinic acid, and the salt of the partially esterified acid used in a similar manner.

Instead of reacting anhydrides of dicarboxylic acids I may use the acids themselves, but in this event the addition or condensation reaction proceeds somewhat more slowly than with the anhydrides. With monocarboxylic acids and acids that do not form anhydrides no choice'in this regard exists. Maleic acid may be replaced by its isomeric form, fumaric acid.

To the salts of the invention various adjuvants or builders may be added, for example, such materials as sodium carbonate, sodium sulfate, magnesium sulfate, etc., particularly when the products are to be used as detergents. When sodium carbonate is used in this manner the free acid instead of its sodium salt may be incorporated into the composition, since the sodium carbonate converts the acid to the salt in aqueous solution and thus obviates the step of converting the free acid to the salt.

The compounds of the invention are of value in the preparation of detergents, polishes, wax and hydrocarbon oil emulsions, insecticidal emulsions, cold water paints and as thickening agents for rubber latex, as flotation reagents, as pigment treating agents to improve dispersibility and grinding properties, as rubber compounding ingredients and the like. They are of especial value i or the preparation of detergents for use in hard water, for which purpose they are equal to or superior to sulfonated detergents such as alkylbenzenesulfonic acids. The calcium salts of the compounds are soluble in water, and the compounds are well-adapted for use in alkaline Washing operations. By the term wetting agent" as used in the specification and claims is to be understood an agent suitable for use as adetergent, emulsifying agent, textile assistant, dispersing agent, etc., or, in general, agents whose properties of reducing surface tension of liquids make them eminently desirable for many applications dependent upon their surface activity.

In place of alkene-substit'uted acids resulting from condensation of an olefin with an unsaturated aliphatic carboxylic acid containing the alpha-enalgrouping (as shown below as Formula I) I may use similar compounds which are satu-, rated alkoxy-substituted acids, for example, lauroxy-succinic acid, or in general, as typified by Formula II hereinbelow:

Alkenyl-H (J-C O O H I. Alkene-acids Alkanyl-O-H(i3COOH II. Alkoxy-acids In both these formulae the grouping -HCC OH must correspond to that which would result from an unsaturated aliphatic acid containing the essential alpha-beta-enal grouping, for example, the grouping may be that found in succinic acid (resulting from saturation of the maleic acid double bond), propionic acid (saturation of acrylic acid double bond), or pyrotartaric acid or methyl succinic acid (saturation of double bonds in itaconic or citraconic acids). These alkoxy-acids are considered as condensation products of an alcohol and an'unsaturated aliphatic carboxylic acid characterized by the presence of the alpha-beta-enal grouping. The wetting properties of the alkoxy-acids, like those of the alkene-acids are dependent upon the length of the chain, and alkoxy-acids having chains containing from five to sixteen carbon atoms are effective wetting agents.

In preparing the alkoxy-acids represented above in the general Formula II, various methods are available. In my preferred methods, however, I prefer to start with an alcohol and an ester of the unsaturated acid, that is, to prepare lauroxy-succinic acid, lauryl alcohol and diethyl maleate are condensed in the presence of metallic sodium under anhydrous conditions. The resulting diethyl ester of lauroxy-succinic acid is saponified and thesalt formed after saponification is then converted to the acid.

Instead of starting with diethyl maleate I may start with the half ester, monoethyl maleate, by forming the sodium salt-of the half ester and reacting this salt with lauryl alcohol under anhydrous conditions with metallic sodium. Saponification of the resulting salt and recovery as before, yield lauroxy-succinic acid.

Alcohols containing from five to sixteen carbon atoms can be thus reacted to product salts of acids having efiective wetting properties. Such alcohols include amyl alcohols, hexyl alcohols, heptyl alcohols, octyl alcohols, decyl alcohols, dodecyl (lauryl) alcohols and hexadecyl (palmityl) alcohols.

The following examples are illustrative of the method of preparing the compounds of the invention:

EXAMPLE l.-Triisobutylene-succinic acid.- Two hundred fifty-two grams of triisobutylene (B. P.165-1'75" C.) were refluxed with 98 grams of maleic anhydride while agitating. Refiuence started at a temperature of 157 and was maintained by gradually increasing the temperature over a period of 80 hours to 193 C. An additional 20 hours of heating failed to produce any further elevation of the temperature of refiuence. The reaction product was dissolved in 5% sodium hydroxide solution and the unreacted olefin was separated. The remaining liquid was made acid to Congo red indicator by the addition of 1% hydrochloric acid solution. Extraction of acid and water layers with chloroform and subsequent evaporation of the solvent yielded triisobutylenesuccinic acid. The product was in the form of a dark, gummy, resinous mass. The approximate content of the desired product can be determined by titrating a sample of the product to a thymol blue end-point with N/2 sodium hydroxide solution and calculating on the assumption that all titratable material is triisobutylenc-succinic acid. The salt was prepared by adding sodium hydroxide solution in quantity just sufficient to neutralize the acid, according'to the titration results. By dilution with water, solutions of the sodium salt of desired concentration may beprepared for use or the sodium salt may be recovered by evaporation or other suitable methods.

' EXAMPLE 2. DecyZene-succinic acid-Onefifth mol (35.3 grams) of decyl chloride obtained by chlorinating a commercial petroleum decane fraction washeat-ed under reflux with one-fifth mol grams) of maleic anhydride. 'Evolution of hydrogen chloride started at 176 C. Refluxing started at 178 C. The vapor temperature did not gradually "rise as observed when condensing olefins with maleic anhydride. Heating was discontinued at the end of 50 hours, at which time evolution of hydrogen chloride had practically ceased. The reaction product was made alkaline with 5%sodium hydroxide solution ands the light, oily fraction of decyl chloride was separated. The sodium salt solution was made acid to Congo red with 10% hydrochloric acid solution and the precipitated acid was separated from the aqueous solution. The acid and water layers were thoroughly extracted with chloroform. Evaporation of the chloroform extracts yielded a dark, gummy mass. This product assayed decylene-succinic acid by the method described in Example 1. The sodium salt or its solution can be prepared by the method described in Example 1.

EXAMPLE 3.Triisobutylene-succi1iic acid.- Into a one-liter steel autoclave were charged 500 grams of triisobutylene and 150 grams of maleic anhydride. The mixture was heated to 208 C. for 3 hours with agitation. The pressure developed ranged from to pounds per square inch. The products were treated with a 5% excess of dilute sodium hydroxide solution over that required to neutralize the maleic anhydride charged. This solution was refluxed for 2 hours and subsequentlycooled. Two layers of liquids resulted,the supernatent layer of triisobutylene was separated and discarded. The aqueous layer was made acid to Congo red paper with concentrated hydrochloric acid. The acid and water portions were extracted with chloroform. The free triisobutylene-succinic acid obtained on evaporation of the chloroform can be converted to the sodium salt as described in Example 1.

EXAMPLE 4.Lauroa:y-succinic acid. -Three hundred forty-four grams of diethyl maleate (approximately 2 mols) and 410 grams of lauryl alcohol (approximately 2.2 mols) were placed in a conditions.

flask provided with a reflux condenser. Approximately 5 grams (0.2 gram atoms) of sodium metal (in small pieces or in rolled form) were then continuously added. Reaction started immediately and the mixture became warm- The mixture was allowed to stand until the initial reaction. subsided and was thereupon heated on a steam bath for several hours. To the mixture was then added alcoholic sodium hydroxide in quantity suflicient to .saponify the ester and the mixture was subjected to refluxing. After saponification was complete the mixture was cooled, ethyl alcohol w'asgdistilled from the mixture and unreacted lauryl alcohol was extracted from the alkaline solution with a non-aqueous solvent. The reaction mixture was then made acid with hydrochloric acid and the precipitated lauroxysuccinic acid was removed by extraction with chloroform. The residual solution contained maleic acid resulting from unreacted diethyl maleate. The lauroxy-succinic acid was converted to its sodium salt and recovered as such.

The free lauroxy-succinic acid is a solid of waxy appearance and its sodium salt is a mass resembling soap in appearance and feel.

Wetting tests-The sodium salt of triisobutylene-succinic acid formed in Example 1 was dissolved in water to make solutions of varying dilutions. Similarly, solutions of a commercial wetting agent know n to thetrade under the mark Santomerse, which is a sodium sulfonate, were made. These solutions were tested for wettability by placing a cotton thread in each and determining the period it took for the thread to become completely wetted by the solution. In some cases a small proportion of hydrochloric acid was added to the solution. The tests with both materials were conducted under exactly comparable The periods required for'wetting at the various dilutions are as indicated in the table:

Sodium salt Standard soil launderometer tests-Standard soil launderometer tests were made with the sodiumsalts of triisobutylene-succinic acidpre pared in Example 1 and the lauroxy-succinic acid prepared in Example 4, in comparison under identical conditions with the commercial detergent Santomerse. Thestandard soil washing test is conducted as follows: To a desired cotton fabric is applied under controlled conditions a standard soil solution. This solution is composed or a suspension'of carbon black, vegetable oils and mineral oils in water. The fabric is then aged for a predetermined period. The aging of the fabric is important because the soil is more difficult to remove as it becomes older; 'I'he'soiled fabric is then washed in a launderometer and each sample is tested in triplicate at various wash intervals 10, 20, 30 and 40 minutes are suitable).

The washed sample is then dried and the lightening of the fabric is'determined, using a Pulfrich photometer. v The relative detergency is then established.

The table illustrates the improvement in whiteness expressed as per cent baryta white units obtained with the detergents when used in both hard and in soft water.

fi lfi it? sa r ss 0 55259, isobutyllauroxyene supcinic suocimc acid acid 8 5 9 l5 7 ll 18 9- 13 21 l1 14 Hard water (300 PPM):

1st wash min.) 13 12 2nd wash min.) l7 l8 3rd wash min.) 18 21 4th Wash min.) 20 24 from the invention, which is defined in the ap pended claims. Iclaim: 1. A washing, wetting and emulsifying agent comprising a water-soluble salt of a condensation product of an unsaturated aliphatic carboxylic acid containing the alpha-beta-enal grouping with a compound selected from the group consisting of aliphatic mono-olefins and alkyl chlorides containing at least five and less than seventeen carbon atoms'in the molecule.

2. A-washing, wetting and emulsifying agent comprising an alkali-metal salt of the condensation product of maleic anhydride and an aliphatic monoolefin containing from five to six- I teen carbon atoms in the molecule.

-3. A washing; wetting and emulsifying agent comprising an alkali-metal salt of the reaction product of maleic anhydride and an alkyl chloride containing from five to sixteen carbon atoms in the molecule.

' 4. A washing, wetting and emulsifying agent comprising a water-soluble salt of a condensation productiof an unsaturated aliphatic carboxylic acid containing the alpha-beta-enal grouping with a compound selected from the group consisting of aliphatic mono-olefins and alkylchlorides containing at least five and less than seventeen carbon atoms in the molecule, which'condensation product consists of a carboxylic acidcorresponding to the general formula in which 'R is selected from the group consisting of hydrogen, carboxyl and lower alkyl radicals and in which the alkenyl group containsat least five and less than seventeen carbon atoms in the molecule.

5. A washing, wetting and emulsifying agent comprising a water-soluble salt of a condensation product of an unsaturated aliphatic carboxylic acid containing the alpha-beta-enal grouping with diisobutylenawhich condensation product consists of a carboxylic acid corresponding to the general formula H Alkenyl-(k-C O OH 9. A wetting and detergent composition for the treatment of textiles, which comprises an aqueous solution of more than about 0.125 part of a water-soluble salt of a condensation product as 5 defined in claim l per hundred parts of water. R-C-R 10. A' washing, wetting and emulsifying agent comprising the sodium salt of the condensation in which R. is selected from the group consisting of hydrogen, carboxyl and lower alkyl radicals and in which the alkenyl radical is that resulting from diisobutylene.

6. A washing, comprising a water-soluble salt of a condensation product of an unsaturated aliphatic carboxylic acid containing the alpha-beta-enal grouping with triisobutylene, which condensation product consists of a carboxylic acid corresponding to the general formula wetting and emulsifying agent product of maleic anhydride and diisobutylene. 11. A washing, wetting and emulsifying agent comprising the sodium salt of the condensation product of maleic anhydride and triisobutylene.

12. The process of washing textiles which comprises agitating said materials while they are immersed in an aqueous solution of a watersoluble salt of a condensation'product as defined in claim 1.

13. The process of washing textiles which comprises agitating said materials while they are immersed in an aqueous solution of an alkali- H 20 metal salt of the condensation product defined in Alkenyi-l-COOH claim 14. The process of washing textiles which comprises agitating said materials while they are sation product of maleic anhydride and diisobutylene.

8. A washing, wetting and emulsifying agent comprising an alkali-metal salt of the condensation product ofmaleic anhydride and triisobutylene.

Patent No. 2,283,211,-

LUCAS 'P KYRIDES immersed in an aqueous solution of an alkalimetal salt of the condensation product defined in claim 8.

prises agitating said materials while they are immersed in an aqueous solution of the sodium salt of a condensation product as defined in claim 11.

.LUCAS, P. KYRIDES.

CERTIFICATE 6F (JGRREEIT 0N M y s 9 m.

It is hereby-certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page l,- second column, line 55, for"C H read -C H page}, first column, line 614., for "product" read --produco--; and that the said Letters Patent should be read with this correction therein that the same may conformto the rec ord of the case in the Patent Office.

Signed. and. sealed this 50th day of June, A. D. 19Li2.

' Henry Van Ar'sdale, Acting commissioner of Patents.

(Seal) Patent No. 2,283,21Lp

CERTIFICATE dF'cdmc'rct'on.

. May 19 1913, LUCAS P. mamas.

It is hereby-certified that error appears in the printedepecificatioa of the above numbered patent requiring correction as follows: Page 1, second column, line 55, for"'C H read --C H page 5, first column, line I for "product" read --produce-- and that the said Letters Patent -should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed. andsealed this 30th day of June, A. n. 1912.

. Henry Van Arsdale, (Seal) Acting Commissioner of Patente.