US2255316A - Aromatic sulphocarboxylic esters - Google Patents

Description

"for" use as detergents, wetting, penetrating, 4 v emulsifying, lathering, flotation and anti-spat- 5 L used in relatively small quantities but capable oi cipally the'result of a wetting action such as at p o a water-oil interface. In 'the'text'ile and dyeing Blow-43111! .-m'dustries, for example, there are many'situal v tlons where a wetting or "detergent action is im- 4H 0c-C -s=o 5 perative as, .for example, in laundering,'bleach J; I \oom v produced calculated to reduce surface tension Oil! .use of prior art substances has not been attended v lowing detailed description;

Patented Sept 9,1941 I 2 255 315 UNITED; STATES PATENT OFFICE Q U 550mm SUIJZZtiliZQXYHC nsrsn Ghicsmlil. t

lvo nrawing tg i a pg igaglgiail me 24, 1939, 1 claims; roman-40o) inventionrelates to a new'class of chemiwithin the scope oi my invention are as follows: cal substances, and more'in particular to anew l class 01;,chemical substances particularly adapted tering' agents, and for frothili pllrposes. A a) In certain classes of industries, there is a need i for a certain class of chemical substances usually g use inlarger quantities to secure an eflect'prini0 ing, mercerizing, dyeing or otheroperations, and

many different chemical substances have been 3' 0-08-08 and promote wetting in these industries.- The 0 with unqualified success'in all instances. j 3, ,',g,, 'bg, The principal object or my present invention t i f is the provision oi. a new class of chemical substances capable of satisfactory use in connection with the problems hereinabove discussed. 0 Another object is the provision of a new class 0 v otchem-ical substances which are in generalot (4) emu-c '8 u relatively simple structure and can be cheaply made in commercial quantities.

- Another object is the provision of a new class 30 or chemical substances having improved wetting mc-o-t'z-cm; characteristics. a

Other objects and features of the invention H -040m: will be apparent from a consideration of the fola The substances of my invention are, in general, sulpho-carboxylic acid esters of higher molecular v weight alcohols, the estletrs containing an aroma 0 group. More pa 'icularly, most of the compounds are esters of aliphatic polyhydroxy (6) mo 0 some derivatives or lipophile materials containing at H least iour carbon atoms and preferably from mc-o-o eight to eighteen carbon atoms with aromatic sulphonic carboxylic acids. In. general, the com- I pounds include both aromatic and aliphatic I c groups. Certain of the substances comprise aro- 0 1:

matic sulpho-carboxylic acid esters of aliphatic on: son: q polyhydroxy substances, at least one hydroxy 7 group of the aliphatic polyhydroxy substance be- 50 (8) cE-cH-'c -0-cm-O ing esteriiied with a carboxylic acid containing O'K Ad a v at least four carbon atoms and preferably of aliphatic or cycloaliphatic character and containin (9) from eight to eighteen carbon atoms. CHr-Cm-CHJH-CmcME-o-cHPO Illustrative examples of compounds falling j m our cm-o-c -cunn tnorr So far as the aromatic sulphp-carboxylic esters are concerned which are derivatives of polyhydroxy substances, I may select many difierent types of compounds as lipophile groups which are to be esteriiied with the rpoly ydroxy substances, principally compounds having lipophile radicals of relatively high molecular weight. For example, the following materials may be utilized as sources of lipophile groups: straight chain and branched chain, saturated and unsaturated, carboxylic, aliphatic (including cycloaliphatic), fatty, aromatic, hydroaromatic, and araliphatic acids including butyric acid, caprylic acid, heptylic acid, caproic acid, capric acid, pimelic acid, sebacic acid, behenic acid, arachic acid, cerotic acid, erucic acid, melissic acid, stearic acid, oleic acid, riclnoleic acid: ricinelaidic acid, ricinostearolic acid, linoleic acid, linolenic acid, lauric acid, myristic acid, palmitic acid, mixtures of any two or more of the above mentioned acids or other acids, mixed higher fatty acids derived from animal or vegetablesources, for example, lard, coconut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soya bean oil, peanut oil, castor oil, seal oils, whale oil, shark oil and other fish oils, partially or completely hydrogenated acid, alpha-hydro arachidic acid, and the like; fatty and similar acids derived from various waxes such as beeswax, spermaceti, montan wax, coccerin, and carnauba wax and higher molecular weight carboxylic acids derived, by oxidation and other methods, from paraflin wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids such as hexahydrobenzoic acid, naphthenic acids may contain substituent groups such as sulanimal and vegetable oils such as those men- 7 tioned; oxidized and/or polymerized higher fatty acids or higher fatty acids derived from oxidized and/or polymerized triglyceride oils; hydroxy and alpha-hydroxy higher carboxylic, aliphatic and fatty acids such as i-hydroxy stearic acid, dihydroxypalmitic acid, dihydroxystearic acid, dihydroxybehenic acid, alpha-hydroxy capric acid, alpha-hydroxy stearic acid, alpha-hydroxy diethylene glycol; pentaerythritol; quercitol; di-

phate, sulphonic, nitrile, thiocyanogen, carbonyl, amide, amine or substituted amine, halogen, ketone and other groups. The acids may be employed as such or in the form of their anhydrldes, esters including mono-, di-, tri-glycerides and the like, amides and acyl halides.

The polvhydrow substances which provide the linkage between the lipophile group and the 910- matic sulpho-carboxylic acid radical may be selected from a large class and include,among those mentioned, glycerol; glycois such as ethylene glycol, propylene glycol, trimethylene. glycol, butyiene glycol and'the like; polygl'ycols such as hydroxy acetone; triethanolamine; tripropanol. amine; polyglycerols such as di-glycerol, triglycerol, tetragiycerol and the like including mixtures thereof; carbohydrates and sugars including mono-, diand polysaccharides such as dextrose, sucrose, xylose, arabinose, galactose, fruc tose, maltose, mannose, dextrin, starch, and the like; the natural and synthetic simple and com.- plex glucosides; sugar alcohols such as arabitol, mannitol, sorbitol and dulcitol; and polyhydroxycarboxylic acids such as tartaric acid, mucic acid, saccharic acid, gluconic acid, glucuronic acid, gulonic acid, mannonic acid, trihydroxyglutaric acid, glyceric acid, carboxylici oxdation products of polyglycerols, others of similar character, and hydroxyethyl and hydroxlpropyl ether derivatives of the above, as, for example:

cn,-o-omcmon cm-o-cm-cmon H-O-GHrCHiOH CHO-CHz-CH2OH CH-.O-CH:CH:OH

CH-OCH:CHOH

CHOCH:CH:OH

CH:OCH:CH:0H (For convenience, all hydroxyl groups are written facing one way.)

In general, this type of alcohol may be represented by the formula (R0) v-X-(OH) 20 wherein R is a radical selected from the group therein.

. acyl, and substitution products thereoi', X is the residue of' the aliphatic-polyhydroxy substance.

. and v and w are small whole numbers.

Froma study of the compounds which I list hereinabove, those skilled in the art will understand that I mayuse many diflerent expedients for forming the compounds in so far as the dominant lipophile groupand the aromatic sulphonic acid group are concerned. As stated, however, ester linkages are utilized between these two portions of the compound-and the skilled chemist will .understand in general the most approved practices -in securing this .result. Numerous methods are also available for the introduction of the sulphonic acid group. In the case of aromatic sulphonic acids, of course, standard sjulphonation procedures employed. for producing aromatic sulphonic acids may be used and if desired the lipophile group may be introduced subsequently.

My preferred process comprises reacting one or more free or esteriflable hydroxy groups of a polyhydroxy substance or derivative of a polyhydroxy substance, with a sulpho-aromatic carboxylic anhydride and then converting the resulting ester into the desired salt by neutralization The following examples are illustrative of the preparation of compounds falling withinthe scope of my invention. It will be understood that said examples are given only by way of illustration and are not to be considered in any way limitative of the true scope of my invention.

Example A 7.5 grams of commercial monostearinv (washed and dried) were heated to 100degrees C. and 4.0

"grams of powdered sulpho-benzoic acid anhydride II CHKCHzM-C-O-CH;

HOH

o s ox could be powdered. It dissolved to form a clear solution in hot water and foamed excellently It possessed good surface tension reducing properties and also functioned effectively in proportions of the order of 0.5% to reduce the spattering of margarine.

. Example B --5.8 grams of the monolauric acid ester of diethylene glycol were heatedto 90 degrees C. and 4.0 grams of powdered sulpho-benzoic acid anhydride were added thereto.. The temperature dropped to 80 degrees C. but, on continued stirring, it again rose to 90 degrees C. Aiter minutes the reaction-mixture was heated to 100 degrees C. for 2 to 3 minutes andwas then allowed The product was a white powder, dissolved in water and foamed readily. It functioned to reduce the spattering of margarine andalso effectively reduced the surface tension of water.

Example C 6.5 grams of the monostearic acid ester. of ethylene glycol were heated to 100 degrees C. and 4.0 grams of powdered sulpho-benzoic acid anhydride were added, the mixture being stirred for a period of about 10 minutes, the mass becoming V a homogeneous syrup. It was dissolved in '75 cc. of iso-propyl alcohol and then there was added thereto sufiicient alcoholic potassium hydroxide to neutralize the product to phenolphthalein. A

precipitate formed and the clear alcoholic solution which contained the unreacted matter was decanted. The resulting product contained a substantial proportion of a compound having the following structural formula:

KO-S

The product was soluble in warm water and had I foaming and surface tension reducing properties.

i The product was an ivory colored solid which Example D 11.6 grams of coconut oil mixed fatty acid mono esters of diethylene glycoiand 9.2 grams of sulpho-phthalic anhydride were heated to degrees C, with stirring. after which the temperature spontaneously rose to about degrees C., at which temperature the mass was kept for about 5 minutes. On cooling, it became a brown viscous liquid which dissolved in water and showed good foaming properties. To the resulting product 100 cc. of isopropyl alcohol were added and then, in order to neutralize the same tophenolphthalein, cc. of 0.5 N alcoholicpotassi'um hydroxide were added. The precipitate which formed was filtered from the solution and dried. On being crushed, it was an ivory colored powder which had goodsurface reducing properties. It contained a, substantial proportion of a compound having the formula:

Example E 12.8 grams of the mono stearic acid. ester of ethylene glycol and 9.2 grams of sulpho-phthalic anhydride were heated to 85 deg ees C. after which the temperature spontaneously rose to aboutlOO degrees 0., the mass being retained at such temperature for about 5 minutes. It was then cooled to 40 degrees C.-50 degrees C. and then 100 cc. of isopropyl alcohol were added thereto. 150 cc. of 0.5 N alcoholic potassium hydroxide were then added andthe precipitate which formed was filtered off and dried. It was a cream colored product, dissolved in warm water, exhibited foaming properties, and contained a substantial proportion of a compound having the following formula:

Example F propyl alcohol were added and the mass boiled and then filtered on the Buchner filter. To the precipitate there were added 100 cc. of ether and the mass wasfiltered again. The final product was a cream colored solid which dissolved in warm water and exhibited foaming properties. It contained a substantial proportion of a compound having the formula:

Those of my substances which are freely soluble in water may be recovered from their solutions and from their water solutions in the customary manner by concentrating and crystallizing. As stated hereinabove, as the mass of the lipophile radical increases, solubility decreases and affinity for water is manifested by the dispersibility in water. From these dispersions, my substances may be readily recovered by salting out with suitable soluble electrolytes. Common salt is very satisfactory for this purpose in most cases. When salted out of an aqueous dispersion at temperatures ranging from 60 to 95 degrees C., the substances are obtained in the form of a paste with a water content ranging from approximately 25 to 75%. The more hydrophillic the substance, the greater the water content,

and, of course, the salt is present in the water of the paste in approximately the same concentration in which it existed in the dispersion from which the paste was salted out.

As I have indicated hereinabove, the lipophile or oleophile group may be of widely varied character and may be selected from an extensive class of available materials. The lipophile groups are of generally fatty or oleaginous character or are characterized by an amnity for oils and fats and comprise, for example, alkyl, aralkyl, aryl, ether, amide, ester and like groups containing preferably at least eight carbon atoms. These lipophile groups, which, in general. possess predominantly hydrocarbon characteristics. are most frequently derived from triglyceride oils and fats, higher fatty acids, waxes, mineral'oils and other hydrocarbons and the like. As indicated, such lipophile groups may contain nitrogen. oxygen, sulphur or phosphorus as exemplified, for example, by the higher carboxylic and fatty acid amides of alcohol amines such as caproic, lauric, myristic and stearic acid amides of monoethanolamine, diethanolamine, monopropanolamine, and

' the like; the caproic, lauric, stearic, oleic and similar mono-esters of the glycois such as ethylene glycol and diethylene glycol; the caprolc, lauric, myristic. palmitic, stearic and similar fatty acid mono-esters of thiodiglycol, thiodiglycerol, and the like. In all cases, such lipophile materials may be reacted to produce therewith esters of aromatic sulpho-earboxylic acids which fall within the broad scope of my invention.

Many of the compounds of my invention may be represented by the following general formula acid group of my compounds is concerned, I may employ a sulpho-benzoate, sulpho-phthallate, sulpho-salicylate, suIpho-naphthenate, anthraquinone-, anthracene-, and phenanthrene-sulphocarboxylic acids, or other similar groups containing an unesterified sulphonic acid radical. The aromatic sulDho-carboxylic acid may contain one or more sulphonic groups and one or more carboxylic groups. In other words, the aromatic sulpho-carboxylic acids may be mono-, di-, or poly-sulpho in character and they may be mono-, di-, or poly-carboxylic. In many cases, the sulpho-aromatic acid' radical may contain substituent groups such as N02, CN, N=C0, halogen, OH", NHz, COOI-I, alkyl, aralkyl and the like.

The chemical compounds are preferably used in the form of their salts in which case the acid derivatives may be neutralized, in whole or in part, with suitable anti-acid materials. In this connection, considerable latitude and modifies.- tion may be exercised. In general, inorganic as Well as organic anti-acid agents may be em- Dloyed. Examples of such agents which may be used satisfactorily are bicarbonates of the alkali metals, potassium hydroxide, potassium car- :di'ethanol amine, diethanol cyclohexylamine, aniline, alkylol' polyamines such asalkylol derivatives, of ethylene 'diamine, mono-methyl 2 assasie" :5

Y bonate, sodium hydroxide, sodium oxide, sodium carbonate, hydroxide,ammonia gas, calcium, magnesium, ammonitum, and zinc'oxides, hydroxides, and salts. po-

t'assium stearate, sodium stearate, and the like:

' organienitrogenous bases suchas primary, secondary and tertiary aminesincl'uding alcohol-,

' alwlob, and aralkylol-amineaincluding monoethanolamine, diethanolamine, trietha'nolamine, propanolamines, butanolamines, pentanolamines,

hexanolamines, glycerolamines, sugar 'alkylol- -amines and sugar alcohol alkylolamines such as those of dextrose, sucrose, s'orbitol, mannitol and the like; dimethyllmonoethanolamine, diethyl monoethanolamine, dibutyl; mono-ethanolamin'e,

Y diethanol methyl amine, diethanol ethyl amine,

butanol amine, cyclohexyl ethanolethanol.

monoethanolamine, diethyl: monoethanolamine,

1- am'ino-2, S-propaned-iol, 1 ,2-diamino-propanol; v

allwlamines'such as 'ethylamihe, propylamine,

' laurylamine, cetylamine, but'ylamine, hexylamine, cyclohexylamine, aniline,toluidines, di-

methylamine, diethylamine, N-methyl-rN-ethyl amine, triethylamine, trimethylamine, ethylene diamine, diethylene triamine, triethylene tetraamine, betaine, mono-methyl ethylene diamine,

T monoethyl diethylene tetra-amine, monoaliy so .amine, hydrazine \and substituted hydrazine, aromatic and heterocyclic basesand cyclic nitrogenous substances such. as benzylamine, cy-

clohexylethyl aniline, morpholine, pyridine, dimethylaniline, ethyl- N-naphthyl amine, quinoline, quinaldine, piperidine, alkyl pyridines suchas methylpyridine, pyrrolidines, nicotine, and homologues'and derivatives or substitution products thereof, and, 1

in general, primary, secondary and tertiary 40 amines substituted or not with other radicals,

' suchas hydroxy, alkyl, aryl, cyclo-alkyl groups and the like; quaternary ammonium bases or v hydroxides such, as tetra-methyl ammonium hydroxide, tetra-ethyl ammonium hydroxide,

quaternary ammonium bases with dissimilar .alkyl radicals such as methyl-triethyl ammonium hydroxide, propyl trimethyl ammonium hydroxide; mixtures of any two or more of said bases as, for example, in the case o1. commercial trl- 5o ethanolamine which contains minor proportions of monoand di-ethanolamine. It will be understood that these substituted ammonium compounds or organic nitrogenous bases may. be utilized in pure, impure, or commercial form.

The compounds of my invention haye utility in various arts in which interface modifying agents are employed. Many of them are resistant-to precipitation by calcium and magnesium salts and are compatible with acid and alkali media. They may be utilized in washing and laundering and in the textile and related industrieswhereln they function for wetting, lathering, detergent, emulsifying, penetrating, softening, finishing,

dispersing, frothing and foaming purposes. The as textiles, various treatmentsof which in the presence of the agents of the present invention is rendered effective, comprise natural products. such as cotton,.-.wool, linen and the like as well as the artiflcially-produced-fibres, (and fabrics) such as rayon, cellulose acetates, cellulose ethers and similar artificial silk fabricsand silk-and wool substitutes. It will be understood,'of course, that the agents may be used in aqueous and other media either alone or in combination with N-methyl-N-benzyl amine, N- 35 other suitable salts of organic or inorganic 'a'cter or with other interface modifying agents.

Inthe dyeing of textiles'many of them may be employed as assistants in =orilerto bring about even level shades. -Many oi them also may be used in the leather industry as wetting agents in soaking, dyeing, tanning and .the softening and other treating baths for hides and skins. Their 1 utility as emulsifying agents enables them to be employed for the preparation of emulsions which may be used for insecticidal, fungicidal and for similar agriculture purposes. They have utility in the preparation of hair washes and hair shampoos, 'dentifrices of liquid, cream and -.powdertype, cosmetic creams such as cold creams, vanishing creams, tissue creams, shaving creams of the brushless and latherins type'and similar cosmetic preparations; Another use to which many of the agents of my invention may be placed is for the treatment of paper or paperpulp or the like. Their capillary or interfacial tension reducing properties enables them to be employed in the fruit andvegetableindustryin order to effect the removal fromfruits and the like of arsenical and similar sprays. They possess. utility in the ore dressing industry wherein they function effectively. in. frothflota- I tion and agglomeration processes. Their interface modifying properties alsopermit their use in lubricating oils and. thelike enabling the production of effective boring oils, cutting, oils, drilling .oils', wire drawing oils, extreme pressure lubricants and the like. Many of them may also be used with effect in the preparation of metal and furniture polishes, shoe polishes, in rubber compositions, for breaking or demulsifylns petroleum emulsions suchas those of the water-in-oil type which are encountered in oil-field operations, as well as in paints and the like, and for various other purposes which will readily occur to those versed in the art in the light .of my dis closure herein.

As detergents, they'may in general be dissolved in water or aqueous media and utilized in sodium sulphate, alums, perborates such as so-.

dium perborate, and the like" Many of said products may be utilized in alkaline oracid media/in the presence of sodium carbonate, so-

dium bicarbonate, dilute acids such as. hydrochloric. sulphurous, acetic and similar inorganic and organic acids. They may also be employed in the presence of such diverse substances as hydrophillic gums including'pectin, tragac'ant-h, karaya, locust bean, gelatin, arabic and the like,

glue, vegetable, animal, fish and mineral oils,

solvents such as carbon tetrachioride,monoethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, monoethyl and monobutyl ethers' of diethylene glycol, cyclohexanol, and the like. They may be used together with wetting, emulsifying, frothing, foaming, penetrating and detergent agents such as the higher molecular weight alkyl sulphates, phosphates, pyrophosphates and tetraphosphatcs as, 'ior example, lauryl sodium sulphate, myristyl sodium pyrophosphate, cetyl sodium tetraphosphate, octyl sodium sulphate, oleyl sodium sulphate, and the like; higher molecular weight sulphonic acid derivatives such as cetyl sodium sulphonate and lauryl sodium sulphonate; sulphocarboxylic acid esters of higher molecular weight alcohols such as lauryl sodium sulphoacetate, dioctyl sodium 'sulphosuccinate, dilauryl potassium sulphoglutarate, lauryl monoethanolamine sulphoacetate, and thelike; sulphuric and sulphonic derivatives of condensation products of alhlolamines and higher fatty acids; reaction products of phosphoric, pyrophosphoric, meta-phosphoric, tetraphosphoric, and polyphosphoric acids with higher molecular weight alcohols; Turkey red oils; compounds of the type of isopropyl naphthalene sodium sulphonate, and other classes of wetting agents.

Itwill be understood that the compounds need not be utilized in the pure state. Indeed, in most instances it will be found to be more convenient and commercially desirable to employ them in the form of their reaction mixtures with or without the addition of diluents. It will also be understood that mixtures of anyone or more of the reacting constituents may be employed in producing the products hereof and this is par-.

ticularly the case where commercial supplies of the chemicals are utilized.

It will be understood that the term lipophile group," as employed herein, is intended to cover any radical containing at least four carbon atoms and having an amnity {or oleaginous material such as oils, fats, hydrocarbons and the like and may comprise radicals such ashydrocarbon radicals, acyl or alkyl groups derived from allphatic or fatty acids or their corresponding alcohols, and the like.

Unless otherwise indicated, the term higher, wherever employed in the claims, will be understood to mean at least eight carbon atoms and, concomitantly, the term lower will mean less than eight carbon atoms.

When the term aromatic sulpho-carboxylic ester or the like expression is employed in the claims, it will be understood to cover the compounds irrespective of whether the hydrogen of the sulphonic acid is present as such or replaced by another cation.

My present application is acontinuation-inpart of my prior application, Serial No. 827,096, filed July 30, 1932, now Patent No. 2,190,921.

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

1. A carboxylic ester of an aliphatic polyhydroxy substance containing a higher molecular weight aliphatic radical with sulphonated benzoi acid.

2. A. derivative of an aliphatic polyhydroxy substance, the hydrogen of at least one hydroxyl group oi. whichis substituted by a sulpho-aromatic carboxylicacid acyl radical, and the hydrogen of at least one hydroxyl group of the polyhydroxy substance is substituted by an aliphatic radical containing from eight to eighteen carbon atoms.

3. A derivative of an aliphatic polyhydroxy substance, the hydrogen of at least one hydroxyl group of whichis substituted by a sulpho-aromatic carboxylic acid acyl radical, and the hydrogen of at least one hydroxyl group of the polyhydroxy substance is substituted by an allphatlc carboxylic acid acyl radical containing at least eight carbon atoms.

4. A sulpho-aromatic carbonlic acid ester of a. higher fatty acid ester of an aliphatic polyhydric alcohol.

5. A sulpho-aromatic carboxylic acid ester of a higher fatty acid ester of glycerol.

6. A sulpho-aromatic carboxylic acid ester of glycerol wherein the hydrogen of 'at least one hydroxyl group of the glycerol is substituted by a higher molecular weight aliphatic radical.

7. A sulpho-aromatic carboxylic acid ester of a glycol wherein the hydrogen oi. one hydroxyl group of the glycol is substituted by a higher molecular weight aliphatic radical.

BENJAMIN R. HARRIS.