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Publication numberUS2088019 A
Publication typeGrant
Publication dateJul 27, 1937
Filing dateDec 29, 1934
Priority dateDec 29, 1934
Publication numberUS 2088019 A, US 2088019A, US-A-2088019, US2088019 A, US2088019A
InventorsWickert Jacob N
Original AssigneeUnion Carbide & Carbon Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Secondary alkyl sulphates as wetting agents
US 2088019 A
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Description  (OCR text may contain errors)

Patented July 27, 1937 2,088,019

UNITED STATES PATENT OFFICE SECONDARY ALKYL SULPHATES AS we'r- TING AGENTS Jacob N. Wickert, Charleston, W. Va., assignor, by

mesne assignments, to Union Carbide and Carbon Corporation, a corporation of New York No Drawing. Application December 29, 1934,

Serial No. 759,739

9 Claims. (Cl. 252-4) The invention relates to the manufacture of pletely soluble in organic solvents, such as the improved products having properties adapting lower alcohols, esters, ketones, ether and hydrothem for use as wetting, penetrating, scouring, carbons; and they are readily soluble in water, dye-levelling, and softening agents, especially in the solubility decreasing with increasing molec- 5 connection with treatment liquors employed in ular weight. They are somewhat less soluble in the textile, leather, and related industries. dilute acid than in neutral or dilute alkaline solu- Among the more important objects of the intions. vention is the provision of treating agents of the The high wetting power of these sulphates of above type which have unusually high penetrating secondary alcohols makes them highly active power, and which are much more soluble in water when present in treating liquors in very small 10 than are sulphate esters of corresponding carbon amounts; and concentrations thereof as low as content, but which have a primary alcohol group 0.02% have effected the desired wetting out of on a straight carbon chain; and the former are textile materials. especially adapted for use in relatively high con- The secondary alkyl sulphates of the present centrations, either in dilute alkaline solutions as invention may be prepared by sulphating, at low 15 in wool scouring; in dilute acid solutions, as in temperatures, preferably around 0 to 10 C., a wool carbonlzing; or in simple aqueous solutions. saturated secondary branched-chain monohydric Water-soluble sulphuric acid esters formed by alcohol having at least 8 carbon atoms in its reacting sulphuric acid with fatty substances, molecular structure. Such a secondary alcohol fatty acids, esters, or with primary alcohols demay be formed by hydrogenating an unsaturated 2O rived from such fatty substances, are now widely ketone at temperatures up to around 150 C. and used as textile wetting, and penetrating agents. at pressures around 800 to 1000 pounds per square The sulphate esters produced from the fatty alinch. The latter may be formed by the removal cohols have the important advantage over those of elements of water from the product of the V produced from the fatty substances, fatty acids conjoint condensation of a primary or secondary 25 and esters in that the tendency of the former to aliphatic aldehyde having at least 4 carbon atoms form insoluble alkaline earth soaps is very much in its molecule, with a ketone, such as acetone, less marked than that of the sulphate esters promethylethyl ketone, or a ketonic derivative of duced from the fatty substances and esters. either, in the presence of an alkaline catalyst.

However, the utility of these sulphate esters of By the term secondary aldehyde" is meant an 30 the primary, fatty alcohols having a straight-caraldehyde in which the carbon atom connected to i bon chain structure is limited by such factors as the aldehyde group is also directly connected the rather low solubility in water of the neutral with two and only two other carbon atoms. alkali salts of these higher sulphate esters. The secondary branched-chain alcohols may be In accordance with the present invention, treatconverted to the corresponding acid sulphate 35 mg compositions having extremely high-wetting, esters by any of the usual sulphating methods. penetrating, softening, and emulsifying powers According to one such method, the secondary are produced by adding thereto a product formed alcohol is reacted with approximately an equivby sulphating a saturated secondary branchedalent amount of equimolar proportions of 96% chain high aliphatic monohydric alcohol having 8 sulphuric acid and acetic anhydride, at low tem- 40 or more carbon atoms in its molecular structure. t res, referably around 0 to 10 C.

These alkyl su pha s of secondary branched- The acid alkyl sulphate formed is neutralized, chain higher alcohols not only are little if at all eferably with caustic alkali, or ammonia, i afiected by alkaline earth salts in moderately with an organic amine such as one of the ethanolhard waters, since their alkahne earth salts are amines yielding the corresponding salt of the 45 soluble in water, but, moreover, they are much ondary alkyl sulpham more soluble in water than are substances of corresponding carbon content having a primary ah thg gvgg gg n examples will serve to illustrate cohol group on a straight-carbon chain. Conse- Emmple 1 quently, these secondary alkyl sulphates can be 50 employed conveniently in many operations where 0.5 mol. of 7-ethyl-2-methylundecanol-4 was it is necessary to use such wetting agents in relareacted with a mixture of 0.58 mol. acetic antively high concentrations. hydride and 0.58 mol. concentrated (95%) sul- The said secondary alkyl sulphates are amorphuric acid, at temperatures between 0 C. and phous waxy solids, colorless or nearly so, com- 10 C. The reaction mixture was then neu- 55 tralized with caustic soda, thus forming the sodium sulphate ester of this tetradecyl secondary, branched-chain alcohol. This is removed from the inorganic compounds present by extraction with ether and evaporation of the extract.

The ethylmethylundecanol used was produced by hydrogenating at 100 to 125 C. under pressures of 900 to 1000 pounds per square inch, the 14-carbon atom unsaturated ketone boiling at 256 C. under atmospheric pressures, formed by condensing ethylhexaldehyde with methylisobutyl ketone, at a temperature around 25 C., in the presence of a methanolic solution of caustic soda, and removing elements of water from the resultant ketol.

A 1% solution of this secondary tetradecyl sulphate wetted cotton yarn at 80 F. in onefourth the time required by a well known alkylated naphthalene sulphonic acid salt now widely used as a wetting agent; and, in a. 0.5% solution, the former wetted the cotton yarn in one-tenth the time required by the latter. Alt 212 F, the secondary tetradecyl sulphate required for wetting cotton but one-fortieth of the time required by the sulphonate.

Example 2 absolute pressure, and hydrogenating the latter under pressures of 800 to 1000 pounds per square inch, and at temperatures around 150 C. This secondary branched-chain heptadecyl alcohol was sulphated by reacting at about 10 C. a 50% solution thereof in pp'dichlorethyl ether with'a 25% solution of chlorsulphonic acid in the said ether. The reaction product was cooled, diluted, and neutralized with caustic soda. This salt was extracted from the ether solution by washing with water, separating the liquid layers which formed, and evaporating to dryness the aqueous layer under reduced pressure at temperatures below 100 C. The residue was extracted with methanol to dissolve the alkyl sulphate, and the extract, upon evaporation to dryness under reduced pressure, yielded the neutral secondary heptadecylsulphate. v

Asolution of this secondary heptadecyl sulphate containing 0.5% oi the latter, at F. efiectively wetted cotton yarn in one-seventh the time required for the purpose by a solution of like strength of a well known alkylated naphthalene sulphonic acid salt now in commercial use as a wetting agent. At 212 F., a solution containing 0.25% of the former wetted the cotton yarn in about one-hundredth the timerequired by a solution of the latter of the same strength.

Wool yarn was wetted by a 0.5% aqueous solution of secondary heptadecyl sulphate in from about one-third to about one-fiftieth of the time required for the purpose by similar solutions of various well known wetting agents in commercial use in the textile industry, certain of which had been derived from primary alcohols prepared from fatty materials. The secondary sulphate is still more efiective than the other wetting agents, when used in more dilute solutions, and is from.- around twenty to around two hundred times as rapid a wetting agent for wool in concentrations of 0.25% in water. l

Example 3 the thus-formed unsaturated tridecyl ketone,

boiling at 258 C. at atmospheric pressure, was sulphated at around 0 to 10 C. with chlorsulphonic acid in solution in fip'dichlorethyl ether.

The reaction product was neutralized with caustic soda, and the secondary tridecyl sulphate was recovered, following the procedure described in Example 2.

Wool immersed in a wool-carbonizing bath containing a 5% aqueous solution of sulphuric acid and 0.25% of the above-mentioned secondary tridecyl sulphate satisfactorily wetted wool in about one-fourth the time required by a solution of like strength of another type of well known wetting-out agent now in commercial use.

When using 0.062% of the tridecyl sulphate in 5% aqueous sulphuric acid solution, the desired wetting-out is effected in less than one-twentyfifth the time required by a solution of like strength of the said other type of wetting agent.

Example 4 Cotton yarn, wound on packages, was dyed in a pressure-dyeing machine with a solution of a reduced dye color containing .18 pound of sodium secondary hexadecyl sulphate in 400 gallons of the dye solution. The said alkyl sulphate served to wet the yarn as effectively as did another and conmiercially known wetting agent used in six times the quantity of the former.

In Table 1, below, is listed a number of the sodium and other alkyl sulphates of secondary alcohols suitable for use with the present invention. The table also specifies the secondary a1- cohol from which each alkyl sulphate is produced.

, However, a wide variety of other alkali metal salts and other salts of the secondary alkyl sulphates likewise may be employed.

Table I Derivation of wetting agents Sodium nondecyl sulphate Monoethanolamine tetradecyl sulphate. Triethanolamine hept adecyl 5 ul phate 5,11 diethylpentadecanol-8 7, ethyl-Z-methylundecanol- 3,9 diethyltridecanol-(i Obviously, inplace of the sodium salt of the alkyl sulphates, other salts thereof may be utilized in the process, such as those produced by neutralizing the alkyl hydrogen sulphate, from the sulphation step, with another alkali such as potassium, or with ammonia, or an organic amine such as triethanolamine, as indicated in Table 1.

Secondary alkyl sulphates may be used which contain one or more methyl, ethyl, or other alkyl, aryl, or aralkyl groups so attached to the main carbon chain as to provide compounds having a branched-chain or chains in their structure. These secondary alkyl sulphates in a number 0 instances have at least one 1%,. 27a) rib group directly connected with the third carbon atom of the main chain spaced from that carbon atom to which the sulphate group is attached, as clearly indicated in Table I. As further shown in the said table, many of the higher secondary alkyl sulphates particularly adapted for use in neutral and dilute alkaline solutions have two branched-chain alkyl groups respectively connected directly to the carbon atom to which the sulphate group is attached.

The secondary alkyl sulphates having from 8 to 13 carbon atoms in their molecular structure generally are preferred for use in acid solutions, such as the usual aqueous wool-carbonizing baths. Under such conditions they are very active wetting-out agents. Alkali metal salts of the secondary undecyl and dodecyl sulphates are particularly well adapted for'service as wettingout agents in dilute acid solutions.

Those secondary alkyl, branched-chain sulphates above pentadecyl sulphate in molecular weight preferably are used in neutral solutions. The secondary tridecyl and tetradecyl sulphates serve effectively as wetting-out and penetrating agents for general use in water, in dilute alkaline solutions, and in acid solutions. Especially suitable in the preparation of textile treatment liquors are mixtures of the secondary tridecyl sulphates and the secondary tetradecyl sulphates. A treating liquor containing equal parts of sodium secondary tridecyl sulphate and sodium secondary tetradecyl sulphate has high wetting and penetrating powers for textiles.

The solubilities of the secondary alkyl sulphates decrease with increase of molecular weight; and those above the secondary pentadecyl sulphate are relatively insoluble in dilute acid, though they are very highly effective in neutral solution for wetting-out textiles, even when used in very small amounts, ranging as low as from .02% to 1%. I

Textiles and fibrous materials which are heavily starch-sized may be penetrated and wetted in accordance with the present invention. The secondary hexadecyl, heptadecyl, and higher sulphates appear particularly efficient for the wetting of such materials.

By the expression secondary alkyl sulphate", and similar terms used in the specification and claims, it is intended to designate an alkyl sulphate derived from a secondary saturated aliphatic alcohol containing 8 or more carbon atoms in its molecular structure.

The term higher branched-chain secondary alcohol, and similar terms herein used, are intended to designate those alcohols having more than 8 carbon atoms in their molecular structures, and in which at least one of the carbon for the impregnation of powdered materials, and

for the production of emulsions, homogeneous pastes and the like. Therefore, the expression "treating liquor and similar expressions appearing in the claims are intended to designate alkaline, acid, and neutral solutions or baths of the type ordinarily employed in the textile, leather, and related industries for the scouring,

dyeing, softening, or other treatment of textiles, leather, etc.

The invention is susceptible of modification within the scope of the appended claims.

I claim:

1. A treating bath having high wetting and penetrating properties, comprising a liquid treating agent and a neutral sulphate ester of a saturated higher branched-chain secondary monohydric alcohol having at least 8 carbon atoms in its molecule and having at least one alkyl side chain directly connected with the third carbon atom of the main carbon chain spaced from the carbon atom to which the sulphate group is attached.

2. A treating bath having high penetrating and.

wetting powers for textiles, the said bath containing an aqueous treating agent and a sulsaturated higher phuric derivative of a branched-chain secondary monohydric alcohol having at least 13 carbon atoms in its molecule and having at least one alkyl side chain directly connected with the third carbon atom of the main carbon chain spaced from the carbon atom to which the sulphate group is attached.

3. A treating liquor having high wetting and penetrating powers for textiles, said liquor containing an aqueous treating agent and a sulphate ester of a saturated higher branched-chain secondary monohydrlc alcohol having at least 8 carbon atoms in its molecule, the said alcohol being free from primary alcohol groups, and having two branched-chain alkyl groups respectively connected directly to the carbon atom to which the sulphate group is attached.

4. A penetrating and wetting composition which comprises a treating agent and a sulphate ester of a saturated secondary branched-chain monohydric aliphatic alcohol having two branched-chain alkyl groups respectively connected directly to the carbon atom to which the sulphate group is attached.

5. A penetrating and wetting composition, comprising an alkyl sulphate of a saturated secondary monohydric aliphatic alcohol having at least 13 carbon atoms in its molecular structure and having at least one alkyl side chain directly connected with the third carbon atom of the main carbon chain spaced from the carbon atom to which the sulphate group is attached.

6. A penetrating and wetting composition which comprises an aqueousliquid containing a sulphate ester of a saturated branched-chain secondary tridecyl alcohol having an alkyl side chain directly connected with the third carbon atom of the main carbon chain spaced from the carbon atom to which the sulphate group is attached.

7. A penetrating and wetting composition which comprises an aqueous liquid containing a treating agentand a sulphuric acid ester of a saturated branched-chain secondary tetradecyl alcohol.

8. A penetrating and wetting composition which comprises an aqueous liquid containing a sulphate ester of a saturated branched-chain secondary heptadecyl alcohol.

9. A penetrating and wetting composition which comprises an aqueous liquid containing a mixture of the respective neutral sulphuric acid esters of a saturated secondary branched-chain tridecyl alcohol and of a saturated secondary branched-chain tetradecyl alcohol.

JACOB N. WICKERT.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2423692 *May 26, 1943Jul 8, 1947Colgate Palmolive Peet CoNormal secondary nonadecyl sulphates
US2512435 *Jan 3, 1948Jun 20, 1950Shell DevEmulsions
US2531276 *Mar 6, 1946Nov 21, 1950Walter C KlingelMethod for killing weeds
US4249902 *May 30, 1978Feb 10, 1981Bayer AktiengesellschaftDyestuff formulations
US6288288 *Nov 25, 1998Sep 11, 2001Celanese GmbhProcess for preparing saturated alcohols
Classifications
U.S. Classification516/200, 558/38, 568/880
International ClassificationD06M13/00, D06M13/256
Cooperative ClassificationD06M13/256
European ClassificationD06M13/256