US2205948A - Primary alkyl phenol sulphonates - Google Patents

Description

Patented June 25, 1940 UNITED STATES "PATENT orrlcr.

PRDIARY PHENOI SULPHONATES Lawrence H. Flett, Hamburg, N. Y., assignor to National Aniline & Chemical Company, Inc., New York, N. Y., a corporation of New York No Drawing.

Application September 25, 1935,

Serial No. 42,157 1 Y 19 Claims. ('01. 260-512) I This invention relates to the production of chemical compounds useful as. detergents, wetting agents, emulsifying agents, foaming agents and the like. It relates more particularly to a 5. new class of compounds which are derivatives 0M B-CHrgroup and R represents an open-chain hydrocarbon radical (straight-chain or branchedchain, saturated or unsaturated) containing 11 or more (preferably 11 to 22, and especially 13 to 18) carbon atoms, and M represents hydrogen or a metal or" an ammonium or organic ammonium radical. For convenience they will be hereinafter referred to as primary alkyl phenol sulphonates, which term generically includes the phenol and cresol derivatives, in-the.

water or in acid treating baths or in salt baths.-

They have the further advantage of being in general better wetting agents and more soluble than the usual soaps, and of leaving the washed goods, with a soft feel. Inasmuch as water solutions of them in the form of their alkali metal salts are neutral in reaction, the latter may be safely used for the washing of delicate silks and 50 other flne fabrics as well as for personal toilet purposes. The said alkyl phenol sulphonates are also valuable wetting agents useful in the textile and related fields and as insecticidal, fungicidal, emulsifyin dispersing, and/or tanning agents. 7

are long chain alkyl derivatives of phenol and v in which A represents hydrogen or a methyl The compounds ofthe present invention can be prepared, in accordance with one method of procedure, by sulphonating the corresponding nuclear alkyl derivative of phenol (hydroxybenzene) or of a cresol (1.2-, 1.3- or 1.4-methyl-hydroxybenzene) having the general formula in which A represents hydrogen or a methyl group and Rrepresents an open-chain hydrocarbon radical (straight-chain or branchedchain,'saturated or unsaturated) containing 11 or more (preferably 11 to 22, and especially 13 to 18) carbon atoms. For convenience, such compounds are herein referred to as monoalkyl" phenol compounds, although they may contain a methyl group in addition when the phenol compound employed is a cresol. The said alkyl phenols and cresol can be prepared in the known manner, as for example, by condensing benzene or toluene with a fatty acid or acid'chloride containing the same number'of carbon atoms as the desired alkyl group,#reducing the resulting "alkyl keto benzene or toluene, for example, by

the Clemmensen method (cf. 8th ,Intemational Congress of Applied Chemistry, 6, 6 8-76 (1912) and Ber. 46, 183"! (1913)); sulphonating the resulting alkyl benzene or toluene, and fusing the resulting sulphonic acid with caustic alkali to form the corresponding alkyl phenol or cresol (cf.- Berichte der Deutschen Chemischen Gesellschaft 19 (1886) 2984); or by condensing a fatty acid or fatty acid chloride with phenol or a cresol to produce the corresponding alkyl keto phenol or cresol and reducing the resulting product to the alkyl phenol or cresol. Preferred alkyl phenol products for use in the preparation of alkyl phenol sulphonates in accordance with the present invention comprise the mixed alkyl phenol or cresol products which result from the employment in the above processes of a mixture.

of fatty acids obtained from naturally occurring vegetable and animal oils and waxes (such as the mixture of fatty acids obtainable from cocoanut oil, palm kernel oil, spermaceti, and the like).

, drate, oleum), chlorsulphonic acid, etc.

is preferably employed for sulphonation, especially when the product is to be used as a detergent, in view of the resulting superior detergent properties. Distillation is preferably carried out at a pressure not exceeding mm. to avoid decomposition.

The invention is of particular advantage in that it permits the production of products usein] as detergent, wetting, emulsifying, foaming agents, and the like from readily available higher fatty acids which in turn can be readily obtained from naturally occurring and relatively cheap fatty acid esters, for example, oils, fatsand waxes, such as cocoanut oil, stearin, palm kernel oil, olive oil, and the like. The invention is not limited, however, to the employment of higher fatty acids obtained from naturally occurring oils, fats and waxes, but includes other aliphatic carboxylic acids. 1

As sulphonating agents there may be employed sulphuric acids of various strengths (e. g.,

66 B. sulphuric acid, sulphuric acid monohy- The sulphonation may be carried out with the aid of heating or cooling, as required, depending upon the ease of sulphonation of the alkyl phenol or cresol and the sulphonating P wer of the sulphonating agents. The sulphonation of the alkyl phenol or cresol may be carried out to an extent such that mainly one, or more or less than one, sulphonic acid group is present in the final product (based on the alkyl phenol compound), it depending upon the properties desired of the final product, as will appear more fully hereinafter.

The alkyl phenol sulphonates may be prepared in accordance with the present invention in the form of their free sulphonic acids or in the form of salts of metals (as for example, of the alkali metals) or of organic bases, or of ammonia, etc.

The salts may be obtained in any suitable manner, for example by reacting the sulphonated product, either in the crude form resulting from the sulphonation or in a purified form, with a metal oxide or hydroxide, ammonia or an organic base, or a suitable salt of one of these, in an amount adapted to form a neutral product. Among the bases, oxides and salts which may be combined with the sulphonated products to produce salts useful as detergents and otherwise are, for example sodium, potassium and ammonium hydroxides; sodium, potassium and ammonium carbonates and bicarbonates; ammonia; magnesium oxide? ethylamine; pyridine; triethanolamine; propanolamines; butanolamine's; diamino propanol; ethylenediamine; triethylene tetramine, etc.

The invention will be illustrated by the following specific examples. It will be realized by those skilled in the art that the invention is not limited thereto, however, except as indicated in the appended patent claims. The parts are by weight and temperatures are in degrees centigrade.

Emmple 1.-Acetic anhydride (20 parts) is mixed with 100 parts of para normal cetyl phenol (resulting from the condensation of 1 mol of palmitic acid with 1 mol of phenol in the presence of zinc chloride and reduction of the resulting palmitoyl phenol by the Clemmensen method; or by condensing 1 mol of palmitoyl chloride with 1 mol of benzene in the presence of aluminum chloride, reducing the corresponding ketone by the Clemmensen method, sulphonating and fusing the sulphonic acid with caustic alkali in the usual manner; or by condensing n-cetyl alphahalide withl benzene, fractionating the resulting product, sulphonating the primary cetyl benzene and fusing the sulphonic acid with caustic alkali in the usual manner). To this agitated mixture, '75 parts of 25% oleum are added at such a rate that the temperature of the mix does not exceed 50. The mix is warmed to 85 and held at this temperature until a sample is completely soluble in neutral, acid and alkaline aqueous solutions,

'and a 0.2 per cent neutral solution does not precipitate any calcium salts "from a solution of a soluble calcium salt containing the equivalent of 0.224 gram calcium oxide per liter. When the sulphonation is completed, the reaction mass is diluted with water to 450 to 600 parts and neutralized with alkali; as for example, caustic soda, potash, soda ash, etc., or their equivalents. The neutral solution is clarified, if desired, by filtration and the solution or filtrate is evaporated to dryness.

The sulphonate thus obtained may be represented in the form of the free acid by the probable formula CmHaa-CsHa-(OH)-SO:H, or more particularly as .orawrmuoHQon oiH Example. 2.-100 parts of the mixed normal alkyl phenols obtained by condensing phenol with the mixture of free acids produced by saponifying cocoanut fat, to form the mixed ketone phenols, and reducing the ketone phenols by the well known Clemmensen method to the normal alkyl phenols, and 20 parts of acetic anhydride are mixed, and to this agitated mixture 80 parts of 26% oleum are added at such a rate that the temperature of the mix does not exceed 50". The mix is heated to 80 and held at this temperature until the desired degree of sulphonation has been attained. The mass is diluted with water, neutralized, filtered and evaporated to dryness.

The sulphonated product thus obtained comprises, chiefly, a mixture of normal primary alkyl phenol sulphonates in which the alkyl groups consist of straight (normal) saturated aliphatic chains containing mainly from 12 to 18 carbon atoms. In the form of the freeacids the latter may be represented by the following general probable formula in which Rn=a normal alkyl group from CHI-I25 to Cid-I31, inclusive.

It will be realized by those skilled in the art that changes may be made in the products, and in the processes of preparing them, hereinbefore described, without departing from the scope of the invention. I

The sulphonation may be carried out in the presence or absence of an inert organic solvent or diluent and in the presence or absence of a sulphonation assistant. As solvents or diluent there may be employed any inert organic liquid which is not readily sulphonated, such as halogenated hydrocarbons of the aliphatic and aromatic series, as for example, carbon tetrachloride, dichlorethane, tetrachlorethane, dichlorbenzene, etc. When an-inert solvent or diluent is used, it may be separated from the alkaline aqueous solution of the sulphonic acid salt of the alkyl phenol which results upon diluting the sulphonation mass with water and neutralizing or it may be separated in the process of drying said salt.

As sulphonation assistants there maybe employed' the lower organic acids and/or their anhydrides, as for example, acetic acid, acetic anhydride, etc.

The temperature at which the sulphonation is carried out may vary within wide limits. For example, temperature as low as about 0 and as high as about 140 C. may be employed. v In general the more vigorous the sulphonating agent the lower is the preferred temperature. Ordinarily the completion of the sulphonation is carried out at a temperature in the neighborhood of about 25 to about 80 C. The ratio of sulphonating agent employed with respect to the alkyl phenol also may be varied. While the preferred amounts are given in the above examples, an amount of sulphuric acid or other sulphonating agent equivalent to from 1 to about 5 parts by weight of sulphuric acid monohydrate per part by weight of the alkyl phenol may be employed.

The extent to which the sulphonation is carried out may vary with the individual material being sulphonated and the use to be made of the sulphonated product. In general the extent of the sulphonation of the alkyl phenol treated is such as to form chiefly the monosulphonic acid of the alkyl phenol, and to sulphonate impurities as well, if present.

The reaction mixtures resulting from the sulphonation of the alkyl phenol or cresol may also be directly employed for the formation of mixed products, as for example mixtures of salts of the alkyl phenol sulphonic acid and of other acids present in said reaction mixtures, which mixtures of salts are also useful as such. Thus. the sulphonation reaction mixture resulting from the treatment of the alkyl phenol or cresol with an amount of sulphonating agent in excess of that theoretically required to effect the desired degree of sulphonation maybe treated with a suitable inorganic or organic base or basic salt (as for example, one'of those hereinbefore mentioned) and the resulting mixture of the salt of the suiphonated allgvlphenol or 'cresol and the salt of the other acid (as for example, sodium sulphate) may be jointly isolated from the reaction mixture and employed as such. when it is desired to produce a salt of the sulphonated alkyl phenol or cresol in a form substantially free from inorganic salts (for example, inorganic sulphates) the alkyl phenol sulphonic acids may be recovered in the free form by any well-known method for recovering aromatic sulphonic acids. They may also be obtained from the mixed products produced by such processes as are given in the above specific examples by taking advantage of the solubility of the alkyl phenol sulphonates in the salt form in alcohol and other organic so1- vents. Thus a mixture of a salt of the alkyl phenol sulphonate and an-inorganic sulphate,-

such as the mixed products resulting from the processes of Examples 1 and 2} may be extracted with alcohol; and the resulting extract may be evaporated to leave a residue of the purified salt of the sulphonated product, as illustrated by the following specific example:

Example 3.-,-The neutralized solution of normal cetyl phenol sulphonic acid prepared in Example I (or the equivalent aqueous solution prepared from the dry sulphonate) is diluted with an equal volume of denatured alcohol, thoroughly mixed for several hours, a decolorizing charcoal is added, and the solution is filtered and evaporated to dryness. Alternatively thedry prodbe extracted with successive portions of denatured alcohol, the total amount of'alcohol used for-this extraction being preferably approximate- 1y four times the weight of the dry unextracted sulphonate, the combined extracts are mixed witha small amount of animal charcoal, filtered and evaporated to dryness. The residue obtained in either case is n-cetyl phenol sulphonate practicallyfree from inorganic salts of mineral acids. It is preferable to add a small amount of alkali to the alcoholic extract before drying. If'thecrude product before extraction is dark colored, the purified sulphonate is lighterin color. The product dissolves very readily in neutral, acid and. alkaline aqueous solutions.

The alkyl phenol sulphonates may also be prepared by employing benzene sulphonic acid, a toluene sulphonic acid, a phenol sulphonic acid, or a crescl sulphonic acid-instead of the benzene,

uct resulting from the process of Example 1 may toluene, phenol and cresol in the processes hereinbefore described, followed byreduction of the alkyl keto compound at any stage in the process. The processes hereinbefore described, in which the unsulphonated alkyl phenol is first-prepared and then sulphonated are preferred, however.

The sulphonated products in the form of metallic salts or salts of inorganic bases are usually,,,. yellowish to white, friable solids; and in the form.

of salts or organic bases vary from viscous oils to semi-solids to solids. are readily soluble in water and in aqueous (neutral, acid or alkaline) solutionsto form solutions which are faintly colored brown or yellow, which are of a soapy nature and which foam readily. Certain of the salts, such as the salts of the aromatic monoamines and the aliphaticand-aromatic polyamines, are oils which generally are insoluble in water but soluble in organic solvents (as for example, benzene, gasoline, etc.) and in aqueous solutions of alkalis (presumably by conversion-to the salts of the alkalis).

It is to be understood that the invention includes products containing a plurality of alkyl phenol sulphonic acid nuclei linked together through the sulphonic acid groups by a polyvalent metal or organic basic radical, as well as products in which an alkyl phenol sulphonic acid is linked through the sulphonic acid groupto a different acid compound by a polyvalent metal or organic basic radical.

Thus the invention comprehends compounds of the type (X) n'Z(X')1. and (X)n-Z (Y)n, wherein X and X each represent the radical.

wherein X and B. have the meaning defined above,

- and W represents a radical containing an acid In general, the salts group at least one of which is a radical of the type represented by X.

This application is a continuation-in-part of applications Serial Nos. 691,081 and 691,082, filed September 26, 1933.

I claim:

1. A sulphonated nuclear monoalkyl derivative of phenol and its mono-methyl derivatives, useful as a detergent, wetting agent, emulsifying agent and the like, having at least 11 carbon atoms in an alkyl radical linked to the phenol nucleus by a methylene group.

2. A sulphonated nuclear monoalkyl derivative of phenol and its mono-methyl derivatives, useful as a detergent, wetting agent, emulsifying agent and the like, having at least 11 carbon atoms in a straight-chain alkyl radical linked to the phenol nucleus by a methylene group.

3. A sulphonated nuclear monoalkyl derivative of phenol and its monomethyl derivatives useful as a detergent, wetting agent, emulsifying agent and the like, having at least 11 carbon atoms in a straight-chain saturated hydrocarbon radical linked to the phenol nucleus by a methylene group.

4. A sulphonated nuclear monoalkyl derivative of phenol and its mono-methyl derivatives, useful as a. detergent, wetting agent, emulsifying agent and the like, having 11 to 22 carbon atoms in an open-chain hydrocarbon radical linked to the phenol nucleus by-a methylene group.

5. A sulphonated nuclear monoalkyl derivative of phenol and its mono-methyl derivatives, useful as a detergent, wetting agent, emulsifying agent and the like, having 13 to 18 carbon atoms in an open-chain hydrocarbon radical linked to the phenol nucleus by a methylene group.

6. A sulphonated nuclear monoalkyl derivative of phenol and its mono-methyl derivatives, useful as a detergent, wetting agent, emulsifying agent and the like, having 11 to 22 carbon atoms in a straight-chain hydrocarbon radical linked to the phenol nucleus by a methylene group.

7. A sulphonated nuclear monoalkyl derivative of phenol and its mono-methyl derivatives, useful as a detergent, wetting agent, emulsifying agent and the like, having 15 carbon atoms in a straight-chain saturated hydrocarbon radical linked to the phenol nucleus by a methylene group.

8. A phenol sulphonate having a single openchain hydrocarbon radical containing at least 11 carbon atoms linked so the phenol nucleus by a methylene group.

9. 'A phenol sulphonate having a single straight-chain saturated hydrocarbon radical containing at least 11 carbon atoms linked to the phenol nucleus by a methylene group.

10. A phenol sulphonate having a single openchain hydrocarbon radical containing 11 to 22 carbon atoms linked to the phenol nucleus by a methylene group.

11. A phenol sulphonate having a single openchain hydrocarbon radical containing 13 to 18 carbon atoms linked to the phenol nucleus by a methylene group.

12. The method of making a sulphonated nuclear alkyl derivative of phenol useful as a detergent, wetting agent, emulsifying agent, and the like, which comprises sulphonating a nuclear monoalkyl derivative of phenol and its monomethyl derivatives, having at least 11 carbon atoms in an open-chain hydrocarbon radical linked to the phenol nucleus by a methylene group.

13. The method of making a sulphonated nuclear monoalkyl derivative of phenol useful as a detergent, wetting agent, emulsifying agent, and the like, which comprises sulphonating a nuclear alkyl derivative of phenol and its monomethyl derivatives having 11 to 22 carbon atoms in a single open chain hydrocarbon radical linked to the phenol nucleus by a methylene group and resulting from the reduction of the corresponding alkyl keto phenol followed by fractional distillation of the reduction product and collection of a fraction of purified alkyl phenol.

14. Compounds having in the form of the free sulphonic acids the following general formula I on RCHr' BOaH wherein.R represents a straight chain alkyl group containing from 11 to 17 carbon atoms.

15. Compounds having in the form of the free sulphonic acids the general formula RCHs- OaH in which R. represents an alkyl hydrocarbon radical containing 11 to 22 carbon carbon atoms, the alkyl radicals represented by B being derived from a mixture of fatty acids obtained from a natural product.

19. Primary dodecyl phenol monosulphonate.

jLAwRnNcE H. mm.

. v CERTIFICATE OF CORRECTION. Patent No. 2,205,9 L8- June 25; I9LLO.-

LAWRENCE H. FLETT. g

It is hereby certified that error appears in. the printed specification of the above numbered patent requiring correction as follows: Page )4, first column, linef55', claim8, for the word "so" read --to--; and second column, line 111., claim 15, for "monoalky1"' read --alkyl--; line 1?, same claim, for "alkyl' read -monoalky lL- line 57, claim 18, for "carbon carbon atoms" read -carbon atomsand that the said Letters Patent shouldbe read with this correction therein that thesame may conform to the record of the case in the Patent Office.

Signed and sealed .this 5rd day of September, A. D. 191p.

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