Sulphuric derivative of higher alcohols

Patented July 31, 1934

1,968,797

UNITED STATES PATENT OFFICE

1,968,797

SULPHURIC DERIVATIVE OF HIGHER ALCOHOLS

Heinrich Bertsch, Chemnitz, Germany

No Drawing. Application January 4,1933, Serial No. 650,203. In Germany March 30, 1928

Claims. (Cl. 260—99.12)

This invention relates to soap-like products and to the manufacture of soaps, detergents, and the like, and to improvements in treatment liquids for use in the textile, leather, and allied in₅ dustries. It is the primary object of the invention to produce new soap-like materials and other . substances of this character having greater wetting, cleansing, dispersing, and foaming properties than the agents heretofore used.

Water-soluble sulphuric esters produced by the action of sulphuric acid on fatty materials, including both fatty acids and esters of fatty acids, containing double linkages and/or hydroxyl groups, are widely employed as wetting, cleans₁₅ ing, and dispersing agents in the textile and related industries. Thus a sulphuric acid ester of the hydroxy stearic acid may be produced by treating oleic acid with sulphuric acid, and a sulphuric acid ester of a dihydroxy stearic acid may 20 be obtained by the treatment of ricinoleic acid with sulphuric acid. These agents are not entirely satisfactory, since sulphated fatty materials heretofore available contain carboxyl groups—either free or combined with alkali, de2g pending upon the proportion of alkali used for neutralization after sulphation—and in consequence are capable of forming insoluble alkali earth salts. For instance, the difficultly soluble lime salts of these esters produce deleterious ef30 fects in the textile industry.

In accordance with the present invention, this defect is in large measure avoided if, instead of fatty acids or the esters of these acids, the corresponding alcohols obtained therefrom by re35 placement in effect of the carboxyl group whether free or combined with the CH2OH group are treated with sulphuric acid or with other sulphating or sulphonating agent. Commercial fats are essentially mixed glycerides of the various 40 higher fatty acids, and the higher alcohols obtainable therefrom are mixtures of alcohols of the general formula CxHy—CH2OH. These mixtures consist predominantly of alcohols having 10 or more carbon atoms per molecule, corre⁴⁵ sponding to the molecular weight of the fatty acids, free or combined, contained in the natural fats and fatty oils and the other commercially available fatty materials derived therefrom. ₆θ I have found that products soluble in water and valuable for use as wetting, cleansing, dispersing, and foaming agents can be obtained by treating such alcohols with sulphuric acid or with other sulphating or sulphonating agent. These 55 alcohols may be referred to collectively as nor mal primary alcohols having more than eight carbon atoms to the molecule.

Thus the invention contemplates the conversion of the free or combined fatty acids of fatty -materials, i. e. animal and vegetable fats and _Moils, and manufactured derivatives such as oleic acid or ethyl oleate, into the corresponding alcohols, and the treatment of these alcohols with a sulphating or sulphonating agent such as sulphuric acid. Usually it is also advisable to neutralize the reaction product with a base, for example sodium hydroxide or ammonia to form a water soluble soap-like salt, as is common practice in the case of sulphated fatty acids or sulphated fatty oils, such as Turkey red oil.

The precise nature Of the method selected to * convert the fatty material to the alcohol may be varied. For instance, a well-known method is that of Bouveault and Blanc, in accordance with which an alkyl ester of a fatty acid, e. g. »an ethyl oleate, is reduced by sodium or other ’ alkali metal and a lower aliphatic alcohol such as butyl alcohol, or the improved method described in my application for Letters Patent Serial No. 472,764 may be used. Numerous processes are known for preparing the alkyl esters ⁰from fats and fatty acids.

The Bouveault and Blanc process is of general application for the preparation of both unsaturated and saturated alcohols. For instance, by _g_ this process oleic alcohol (C17H33—CH2OH) may ⁸be prepared from esters of oleic acid (C17H33COOH). An octodecyl alcohol (C17H35—CH2OH) may be formed from esters of stearic acid (C17H35—COOH). Mixed saturated and unsaturated alcohols result when the unfractionated esters of the fatty acids of most natural fats, for example, tallow, are reduced according to the Bouveault and Blanc process.

An important example of a method for pre- „ paring predominantly saturated alcohols is catalytic hydrogenation of esters under high pressure, as described in the application for U. S. Letters Patent of Wilhelm Normann, Serial No. 510,326, filed January 21, 1931, and assigned to _10flthe assignee of the present application. This ¹method may be applied directly to the conversion of the natural glycerides, such as coconut oil, to primary alcohols for use in accordance with the present invention. ₁₀₅

Fatty alcohols obtained from the source described are next treated with a sulphating agent having water-binding properties. Ordinary concentrated sulphuric acid may be used, or stronger reagents such as anhydrous sulphuric acid, no

1,968,797 chlorsulphonic acid, or fuming sulphuric acid. The principal reaction occurring is the formation of sulphuric esters, frequently called alkyl sulphuric acids, for instance, as follows:

CxHy-CH₂OH-|-H₂SO4=

CxHyCH₂-SO4H+H2O

In the case of an unsaturated alcohol, some addition of sulphuric acid at the double bond also occurs, so that complete reaction of sulphuric acid with oleic alcohol would be according to the equation:

CH3.(CH₂) 7CH=CH.(CH₂) 7CH2OH+2H₂SO4= H₂O+CH3.(CH₂) 7.CH₂.CH.OSO3H.(CH₂) 7 CHu.OSOsH sulphuric ester of 1, 9-octodecanediol.

Unless a higher temperature is required to melt the alcohol, I prefer to effect sulphation in the cold within the range of ordinary room temperature or lower, down to about 0° C. However, higher and lower temperatures can be used, and my invention is not restricted to a particular range of temperature of sulphation.

Under almost any practical condition of sulphation, there may be formed at least traces of sulphonic acids, the proportion of which may be increased by choice of sulphating medium and other conditions of reaction, for instance, by high reaction temperatures and by the use of highly concentrated energetically acting reagents such as fuming sulphuric acid. While these are not my preferred reaction conditions, it should be understood that the sulphation products made in accordance with the present invention are not purely esters, but may contain also appreciable amounts of sulphonic acids or sulphonates. For convenience, the products resulting from the treatment with sulphuric acid or other agent hereinbefore mentioned will be referred to generically as “sulphuric reaction products”.

One method of sulphating which is of fairly general application to different alcohol mixtures is to treat the alcohol just above its melting point with 100%-110% of the theoretical quantity of chlorsulphonic acid required according to the equation

CxHy-CH₂OH+C1SO3H=

CxHy-CH₂-SO4H+HC1

The acid reaction products obtained as described above are preferably carefully neutralized, for instance, with sodium hydroxide. Neutralization should be carried out at relatively low temperatures, preferably in a vessel fitted with a means for cooling. The resulting organic salts such as sodium lauryl sulphate may be separated from inorganic components such as sodium sulphate and sodium chloride by known methods, for instance, by dissolving in ethyl alcohol, decanting or filtering, and evaporating off the solvent. With or without this purification, the products obtained are in general readily soluble in water, possess marked wetting, cleansing, dispersing, and foaming properties, and may be employed for manifold textile purposes. In a general way, they resemble the ordinary commercial sulphuric esters of the fats and fatty acids, but are greatly superior in resistance to precipitation by lime salts and the other characteristic constituents of hard water.

The sulphated products of oleic alcohol are particularly resistant to hardness and are highly suitable for use in the textile and related industries.

Likewise a high resistance to the action of hard water is shown by the sulphated products of lauryl alcohol, which is the principal con- 80 stituent of the mixed alcohols obtained by reduction of coconut, palm kernel and similar oils, or by reduction of the alkyl esters or the free fatty acids of these oils. Sulphated alcohols of this class have remarkable cleansing and foam- 85 ing properties, and are valuable as soap substitutes, especially for use in hard water.

The sulphuric reaction products derived from lauryl alcohol, especially the esters and salts thereof, are also found to be particularly effec- 90 tive in the textile industry. Thus when starting from the fatty alcohols made from free fatty acids of the coconut oil or palm seed oil in a manner known per se by esterifying the fatty acids of the same with lower aliphatic alcohols 95 and reducing the mixture of esters by means of sodium, it is advantageous to distill the reduction product and to use only the first 50% to 60% of the distillate. The product thus obtained consists mainly of lauryl alcohol, the somewhat less 100 suitable higher fractions which contain principally myristyl alcohol and octodecyl alcohol being substantially eliminated. It should be understood, however, that the presence of the sulphuric derivatives of lower or higher alcohols, such as 105 of myristyl alcohol with the lauryl alcohol derivatives does not materially decrease the efficiency of the final product.

Various other higher alcohols may be produced and converted into wetting and cleansing 110 agents, substantially according to the procedure indicated in the above examples, for instance the following:

Alcohols obtained by catalytic hydrogenation of the free fatty acids of coconut oil and compris- 115 ing mainly lauric alcohol, myristic alcohol, cetyl alcohol, and stearic alcohol or the single alcohols separated from each other by fractional distillation.

Alcohols obtained by catalytic hydrogenation 120 of palm kernel oil or of the free fatty acids of palm kernel oil comprising similar constituents as the alcohols obtained from coconut oil.

Alcohols obtained by saponification of spermaceti, sperm oil, beeswax and distillation accord- 125 ing to Axelrad and Hochstadter (U. S. A. Patent 1,290,870).

Linoleic alcohol obtained by reduction of linoleic acid by means of sodium and ethyl alcohol. 130

Alcohols obtained by catalytic reduction of tallow or the free fatty acids of tallow.

Alcohols obtained by catalytic hydrogenation of the free fatty acids of coconut oil.

Alcohols obtained by catalytic hydrogenation of 135 the free fatty acids of palm kernel oil;

Alcohols obtained by reducing olive oil by means of metallic sodium and butyl alcohol.

Alcohols obtained by reducing the ethyl esters of tallow fatty acids by means of metallic sodium ¹⁴⁰and butyl alcohol.

Alcohols obtained by catalytic hydrogenation of the ethyl ester of commercial stearic acid.

Ricinoleic alcohol obtained by reduction of ricinoleic acid by means of sodium and ethyl alcohol.

The following examples are given to illustrate the manner in which the process may be carried out: 150

1,868,707

Example 1

Example 6

100 kgs. of a mixture of fatty alcohols mainly consisting of lauryl alcohol, and obtained from coconut oil by esterification of the fatty acids ⁰ with ethyl alcohol, reduction of the ethyl ester, distillation of the product of the reduction and collection of the first 50% to 60% of the distillate, are heated to melting temperature about 30’ C. and treated at . this temperature with 50 kgs. of chlorstilphonic acid.

The foregoing reaction may be represented by the following formula:

CHstCHs) i!)CH2OH+ClSO2OH=

CH₃(CH₂)ii-O-SO2OH+HC1

100 kgs. of pure lauryl alcohol would require for best results a higher proportion of chlorsulphonic acid about 60 kgs.

Example 2

100 kgs. of the same mixture of fatty alcohols is sulphonated with 70 kgs. of fuming sulphuric acid 10% SO₃ at the temperature of 50° C.

The products of the reaction are directly neutralized by means of soda lye and separated by known methods from inorganic components such as sodium sulphate or sodium chloride.

Example 3

100 kgs. of a mixture of fatty alcohols obtained by catalytic reduction of spermaceti with hydrogen and a copper catalyst at a temperature between 300 and 350° C. and a pressure of ₃₅ 150-200 atmospheres until the acid number has wholly disappeared, are sulphonated at a temperature of 35° C. with 60 kgs. of chloro-sulphonic acid. The product is poured in 200 kgs. of ice water and is then neutralized by means of a 40 potassium hydroxide solution. There results a white paste readily soluble in water.

The reactions occurring can be represented by the following equations:

CH3.(CH₂) i4.CH₂OOC.(CH₂) i4.CH₃+2H₂=

2CH3. (CH2) 14.CH2OH

CH3.(CH2) 14.CH₂OH+C1SO3H=

CH3.(CH2) 14.CH2SO4H+HCI

Example 4

100 kgs. of oleic alcohol are sulphated at 25° C.

with 80 kgs. of concentrated sulphuric acid. The mixture is poured into 150 kgs. of ice water and is neutralized by means of piperidine.

The reaction may be represented by the fol55 lowing equations:

CH₃.(CH₂) 7.CH=CH.(CH₂) 7.CH2OH +H2SOi=

CH3.(CH2> 7.CH=CH.(CH2) 7.CH2SO4H

4-H2O CH3.CCH2) 7.CH=CH.(CH2) 7.CH2OH +2H₂SO4= CH₃.(CH2) 7.CH₂-CHSO4H.(CH2) 7.CH2SO4H

Example 5

100 kgs. of the mixture of unsaturated and saturated fatty alcohols obtained by reduction of coconut oil by means of an alkali metal and butyl alcohol, adding water, separating the re_yo culting watery alkali hydroxide solution and removing the butyl alcohol by distillation, are treated with 80 kgs. of chlorosulphonic acid at 35° C. The product is worked up as described in Example 3, neutralized with sodium hydrox-- ide solution to form a white, readily water-soluble paste.

(1)

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(2)

100 kgs. of ricinoleic alcohol obtained by reduction of ricinoleic acid by means of sodium and amyl alcohol, adding water, separating the wa- gg tery alkali hydroxide solution and removing the amyl alcohol by distillation are treated with 150 kgs. of concentrated sulphuric acid at a temperature between 10 and 20° C. The product is worked up as described in Example 3 and neu- §5 tralized by means of equal parts of sodium hydroxide solution and potassium hydroxide solution. An oily product readily soluble in water is obtained. The main reaction is probably represented by the following equation:

CH₃. (CH2) 5.CHOH.CH₂.CH=CH.(CH2) 7.CH2OH +3H2SO4= CH₃. (CH2) 5.CH.SO4H.CH2.CH2CH.SO4H.(CH2) 7.CH2.SO4H

Besides this reaction there may be also a reaction of only two or only one of the free groups (two hydroxyl groups and one double linkage) capable of reaction with sulphating means. These reactions yield for example the following products ^w

CH₃. (CH2) 5.CH.SO4H.CH2.CH=

CH. (CH2) T.CH2.SO4H CH3.(CH2) 5.CHOH.CH2.CH=CH. (CH2) 7.CH.SO4H

Example 7

100 kgs. of stearic alcohol are treated at 40-50° C. with 50 kgs. of chlorosulphonic acid. The product is worked up as described in Example 3. A white paste is obtained. The reaction can 110 be represented by the following formula:

CH₃.(CH2) ie.CH₂OH+ClSO₃H=

HC1+CH₃(CH2) 16.CH2SO4H

Example 8 115

100 kgs. of a mixture of the alcohols obtained by saponification of spermaceti oil by means of caustic lime and distillation of the saponification product according to U. S. A. Patent 1,290,870, ,90 said alcohols having an iodine number of about ¹50 and consisting mainly of cetyl alcohol and oleic alcohol, are mixed with 100 kgs. of concentrated sulphuric acid at 40° C. The mass is then poured into 200 kgs. of ice water. The mixture is neutralized by adding sodium hydroxide solution of 28° Be. The resulting solution containing 15-20% calculated on free fatty alcohol, is introduced in a spraying dryer of the Krause system and dried at a temperature between 75-80° C., the temperature of the hot air entering at the bottom of dryer being about 170° C.

Before or after the drying operation such quantities of Glauber’s salt may be added to the solution or to the dried product respectively, that the final product contains for example 35% calculated on free fatty alcohol.

Example 9

100 kgs. of linoleic alcohol obtained by reduction of linoleic acid by means of an alkali metal and ethyl alcohol in a manner known per se, are dissolved in 50 kgs. of water free ethyl ether and treated with 200 kgs. of concentrated sulphuric acid at a temperature between 0 and 5° C. for several hours. The product is mixed with 300 kgs. chopped ice and 50 kgs. ethyl ether, washed with saturated Glauber’s salt solution and neutralized by means of triethanolamine.

The reaction is probably represented by the following equation:

125

130

135

140

145

150

1,968,797

CH3.(CHj)4.CH==CH.CHa.CH= to the corresponding higher alcohols by treatCH.(CH2)7.CHaOH+H2SO4=CH3.(CHa)4.CH=« ment with an alkali metal and a lower alcohol, CH.CH2.CH=CH.(CH2)7.CHaSO&lt;H+H2O and thereafter* sulphating the resulting higher stlcoliols thA The process of manufacturing wetting and 80 addition of sulphuric acid to one or both of the _{cleansing agents} which comprises reducing a fatty double linkages may occur. ,., . material to form higher alcohols corresponding

The following fatty materials have been found _{t t acid rad}j_Pal- corT-impd therein sulparticularly suitable for conversion to alcohols phating'said higher alcohols to form alkyl suland thence to sulphuric acid derivatives: tallow, _hu*_{ic acids}^d_a„_{d neutrali7}5_ng with a base to yield ^^rd^^an^ei^Op;X°nn νη,ΓΛ OU Lⁿu nU water-soluble salts of said alkyl sulphuric acids, oil, olive oil, castor oil, Lnseed oil, tall oil, tech- θ _{A composition of ma}tter having soap-like meal stearic acid, technics cleic acid and ncm- _properties consisting essentially of sulphuric esters oleic acid, paimitic acio, tallow fatty acids Japan _{of aliphatic alcoho}._{ls havlng more} than 8 carbon 3^a*· X^elT^Cn hv 1^PXT k^{atoms obtained from fatty material by} ^liminatwax. methyl, ethyl, propyl and butyl enters oi _{ing carboxy] groups} from the carboxyl containing technical fatty acid mixtures such as stearic acids, _nnnstit_1]prit&lt;MV.M—, LU11U,'.' i , —,L’J : 'AU1V.U, ,1.

acids and whale oil fatty acids.

, material to form higher alcohols corresponding tecnnicai iauLy aciu. miXLures sucn as stearic acias, constituents ^{liQSeed od iatty} 1®· Sulphated mixture of primary alcohols oband v/nale o..l fatty a-ids. tained by conversion, of fatty materials containThe present invention is disclosed in my prior _{ing fatty acids tocludtag combined} fatty acids _9fiM-roh'fi Vqw^ShAb ^{having more than 8 carbon} atoms in the chain.

19-3, and 433,815 filed Mai ch 6, 1930, of whiUi _{n A} wetting _and cleansing agent comprising the present application is a continuation in part _{a su]phaUon product} of an unsaturated alcohol sssajasr¹*...

disclosed, but that it includes all modifications _{12 Th}J _{process of producin}g wetting and ¹⁰⁰ing within the terms of the claims and the scope sShThavin^more thTn°8 clrbon SS comSS or the tenor of the specification. ,,. ing producing alcohols from a fatty material con-