US2088020A - Secondary alkyl sulphates as wash - Google Patents
Secondary alkyl sulphates as wash Download PDFInfo
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- US2088020A US2088020A US2088020DA US2088020A US 2088020 A US2088020 A US 2088020A US 2088020D A US2088020D A US 2088020DA US 2088020 A US2088020 A US 2088020A
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- sulphate
- water
- carbon atoms
- esters
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- -1 alkyl sulphates Chemical group 0.000 title description 36
- 125000004432 carbon atoms Chemical group C* 0.000 description 58
- 239000003599 detergent Substances 0.000 description 32
- 229910052799 carbon Inorganic materials 0.000 description 30
- 239000000243 solution Substances 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 26
- 239000000203 mixture Substances 0.000 description 22
- 238000005406 washing Methods 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000011780 sodium chloride Substances 0.000 description 18
- 239000001117 sulphuric acid Substances 0.000 description 18
- 235000011149 sulphuric acid Nutrition 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000006260 foam Substances 0.000 description 14
- 150000002576 ketones Chemical class 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 14
- 239000004753 textile Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 12
- 230000001804 emulsifying Effects 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 12
- 150000001298 alcohols Chemical class 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 230000001264 neutralization Effects 0.000 description 8
- 239000000344 soap Substances 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 6
- 125000003172 aldehyde group Chemical group 0.000 description 6
- 230000000881 depressing Effects 0.000 description 6
- 239000008233 hard water Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 150000003333 secondary alcohols Chemical class 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical class CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N Manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- ALSTYHKOOCGGFT-KTKRTIGZSA-N Oleyl alcohol Chemical class CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 4
- 210000002268 Wool Anatomy 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 125000004429 atoms Chemical group 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000875 corresponding Effects 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 159000000003 magnesium salts Chemical class 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000009991 scouring Methods 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FTASCHGWCDZHSK-UHFFFAOYSA-M sodium;nonadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCOS([O-])(=O)=O FTASCHGWCDZHSK-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 210000001736 Capillaries Anatomy 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N Phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory Effects 0.000 description 2
- 239000001187 sodium carbonate Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- HHURSJAUVYNJBT-UHFFFAOYSA-M sodium;heptadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCOS([O-])(=O)=O HHURSJAUVYNJBT-UHFFFAOYSA-M 0.000 description 2
- UPUIQOIQVMNQAP-UHFFFAOYSA-M sodium;tetradecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCOS([O-])(=O)=O UPUIQOIQVMNQAP-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 101700054498 such-1 Proteins 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- URLJMZWTXZTZRR-UHFFFAOYSA-M tetradecyl sulfate Chemical class CCCCCCCCCCCCCCOS([O-])(=O)=O URLJMZWTXZTZRR-UHFFFAOYSA-M 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/03—Organic sulfoxy compound containing
Definitions
- This invention relates to washing and emulsi-- tying operations; and more especially it concerns the utilization therein of water-soluble inorganic salts, and amine or substituted amine salts, of the half esters of sulphuric acid with saturated secondary branched-chain alcohols having at least 8 carbon atoms in the molecule.
- the invention is of special utility in the preparation and use of liquors employed in the treat- I 10 ment of textiles and fibrous substances, such as in wool scouring, and in the washing of cotton, wool, and silk textiles.
- the present invention is based in important part uponthe discovery that salts of monoesters of sulphuric acid derived from saturated secondary branched-chain alcohols having 8 or more carbon atoms inthe molecule are highly eflicient cleansing agents and emulsificants, either when used alone, or with other detergents such as soap and sodium carbonate, in solutions in water or the usual volatile solvents.
- alkali metal salts and substituted amine salts of the half esters of sulphuric acid with secondary branched-chain aliphatic alcohols having 8 or more carbon atoms in the molecule possess in common strong detergent and emulsifying properties well adapting them for use in the preparation of cleaning, scouring, and emulsifying compositions.
- those derived, in the manner hereinafter indicated, from secondary aliphatic alcohols having 14 or more carbon atoms in the molecule are especially efiective in cleaning and washing operations conducted under neutral or alkaline conditions, reducing greatly the interiacial tension between the washing fluid and any oily or other materials presen in the material to be cleaned.
- sulphate esters of the higher secondary aliphatic alcohols exist as colorless, amorphous waxes, completely soluble in organic solvents such as alcohols, esters, ketones, and hydrocarbons; and they are much more soluble in water than are sulphuric acid esters of corresponding carbon content, derived from primary alcohols or those having straight carbon chains.
- sulphate esters of the invention having less than 15 carbon atoms in the molecule are completely soluble in water, yielding a clear solution at 0.25% concentration at room temperature.
- Those having 15 or more carbon atoms in the molecule form faintly cloudy solutions which do not settle out upon standing; whereas soaps and other detergent solutions under similar conditions of concentration are very cloudy, and in many instances precipitate a solid after several days.
- the neutral secondary alkyl sulphates of the present invention may be produced by condensing an aliphatic primary or secondary aldehyde having at least 4 carbon atoms in its molecule, with acetone, methylethyl ketone, or a ketone derivative of either, in the presence of an alkaline catalyst.
- secondary aldehyde is meant an aldehyde in which the carbon atom connected with the aldehyde group is also directly connected with 2, and only 2, other carbon atoms.
- the resultant reaction mixture is made slightly acid to phenolphthalein by means of a suitable acid, and the acidified mixture is heated to its boiling point, thus converting the ketol present as a result of the condensation of the aldehyde and ketone, into an unsaturated ketone.
- the mixture is fractionally distilled under vacuum to separate the unreacted starting materials and water from the ketone; and to isolate the ketone from the said mixture.
- This ketone is hydrogenated under superatmospheric pressure, preferably around 800-1000 pounds per square inch, and at temperatures up to around C., in the presence of a hydrogenation catalyst such as active nickel.
- the saturated secondary alcohol thus formed is then recovered by fractional distillation of the reaction mixture under vacuum, and is converted to its acid sulphate by any of the usual sulphating methods.
- the secondary alcohol is reacted with approximately an equivalent amount of equimolar proportions of 96% sulphuric acid and acetic anhydride, at low temperatures maintained preferably from around 0 to around 10 C.
- concentration of the sulphuric acid can vary considerably: or this acid or sulphuric anhydride can be used alone;
- Table I t Apparent formula of inter- Substance mediate alcohol ga atoms 1.
- Sodiumnonyls phate..- 3,ethylheptanol-6 9 3.
- Sodium docylsufphata--- 2methylnonanol-4. 10 4.
- Sodiumundecylsulphato. 5ethyln0nan0l-2 11 5.
- Sodiumdodecylsulphate, 3,ethyl-8-methylnona l2 6.
- the power of depressing the interfacial tension between water and hydrocarbons is one of the properties possessed to a remarkable degree by the sulphate esters of secondary branchedchain alcohols of the invention. Evaluation of this power may beobtained by drop number measurements. Those recorded in Table I consist in counting the number of drops formed by a plane-ground capillary tip when a fixed volume (10 c. c.) of an aqueous solution containing 25% by weight of the sample is allowed to flow slowly into a body of kerosene maintained at 30 C. The tip is of such size that the fixed volume of water, selected as a standard, will be divided into about 25 drops. The rate of flow is so regulated that the drops will form distinctly and can be counted conveniently.
- the number of drops observed may vary somewhat from one sample to another, particularly when the number is in excess of 100. Therefore, the values here recorded are in some cases the average of those found for several samples.
- This depressing power is measured directly by the number of drops formed. It is closely related to the detergent power, and particularly to the emulsifying power, of the sample.
- Example 1 A soiled white silk cloth impregnated with carbon black, mineral oil, manganese dioxide, and carbon tetrachloride, was agitated for five minutes in a .25% aqueous solution of sodium nondecyl sulphate (see Table I) The cloth was then rinsed with water and dried. Practically all of the color imparted by the impurities was removed in the washing, and the white color of the cloth restored. Similarly, the monoand triethanolamine heptadecyl and nondecyl sulphates were highly effective detergents in washing silk.
- Example 2 A soiled white cotton cloth stained with mineral oil, carbon black, and manganese compounds, was treated with an aqueous solution of sodium heptadecyl sulphate, following the procedure described in Example 1. After rinsing the washed cloth in water and drying it, the color imparted by the impregnating materials had been in main part eliminated.
- Unboiled cotton yarn was soaked in a dilute aqueous solution of the sodium nondecyl sulphate, and when dried was very appreciably whiter and softer, indicating a strong cleaning action.
- the higher members of the series of sulphate esters those having 14 or more carbon atoms in the molecules, have a detergent power superior to the lower members of the series; although it has been discovered that blends of the compounds of higher carbon content than 14 carbon atoms with those of lower carbon content are eificient cleansers in certain instances, and have better hard water and sea water solubility than those of the higher carbon content alone. Blends of one or more of these sulphate esters with ordinary soaps also are good detergents.
- a voluminous foam is produced which has over 15 times the volume of the foam produced under similar conditions using a sulphation product now on the market for the purpose and made from technical oleyl alco-' hols.
- the foam produced by the said sulphate esters of the present invention persisted for over two hours after agitation had ceased, the foam produced by the oleyl alcohol derivatives lasted but six seconds.
- the step which comprises agitating the same while immersed in a solution of a neutral water-soluble salt of a sulphuric acid ester derived from a saturated secondary branched-chain monohydric aliphatic alcohol, and having at least 14 carbon atoms in its molecular structure.
- a detergent and emulsifying composition which comprises a solution of a water-soluble sulphuric acid ester of a saturated secondary branched-chain -monohydric aliphatic alcohol containing at least 8 carbon atoms in its molecule and having two branched-chain alkyl groups respectively connected directly to the carbon atom to which the sulphuric acid group is attached.
- a detergent and emulsifying composition which comprises a solution of' a water-soluble salt of a sulphuric acid ester of a secondary branched-chain monohydric aliphatic alcohol containing at least 14 carbon atoms in its molecule.
- a detergent and emulsifying composition which comprises a solution of a water-soluble salt of a sulphuric acid ester of a secondary branchedchain monohydric aliphatic alcohol containing from 14 to 19 carbon atoms in its molecule.
- a detergent composition comprising a solution of a water soluble sulphate ester of a saturated secondary branched-chain monohydric alcohol, which ester has at least 8 carbon atoms in its molecule and has at least one alkyl sidechain directly connected with the third carbon atom of the main chain spaced from that carbon atom to which the sulphate group is attached.
- the step which comprises contacting the same with a solution of a water-soluble sulphate ester of a satu: rated secondary branched-chain monohydric aliphatic alcohol having at least 8 carbon atoms in its molecule and having two branched-chain alkyl groups respectively connected directly to the carbon atom to which the sulphate group is attached.
- the step which comprises contacting the said materials with a solution of a water-soluble sulphate ester of a saturated secondary branched-chain monohydric aliphatic 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 chain spaced from that carbon atom to which the sulphate group is attached.
Description
UNITED STATES PATENT oFFici:
SECONDARY ALKYL SULPHATES AS WASH- ING AND EMULSIFYING 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 January 10, 1935, Serial No. 1,172
8 Claims.
This invention relates to washing and emulsi-- tying operations; and more especially it concerns the utilization therein of water-soluble inorganic salts, and amine or substituted amine salts, of the half esters of sulphuric acid with saturated secondary branched-chain alcohols having at least 8 carbon atoms in the molecule. The invention is of special utility in the preparation and use of liquors employed in the treat- I 10 ment of textiles and fibrous substances, such as in wool scouring, and in the washing of cotton, wool, and silk textiles.
Heretoiore, there have been employed as detergents certain half sulphuric esters of primary l5 alcohols'or amines containing straight chains of 10 to 20 and more carbon atoms, and derived from the soap-forming fatty acids.
The present invention is based in important part uponthe discovery that salts of monoesters of sulphuric acid derived from saturated secondary branched-chain alcohols having 8 or more carbon atoms inthe molecule are highly eflicient cleansing agents and emulsificants, either when used alone, or with other detergents such as soap and sodium carbonate, in solutions in water or the usual volatile solvents.
The alkali metal salts and substituted amine salts of the half esters of sulphuric acid with secondary branched-chain aliphatic alcohols having 8 or more carbon atoms in the molecule possess in common strong detergent and emulsifying properties well adapting them for use in the preparation of cleaning, scouring, and emulsifying compositions. However, those derived, in the manner hereinafter indicated, from secondary aliphatic alcohols having 14 or more carbon atoms in the molecule are especially efiective in cleaning and washing operations conducted under neutral or alkaline conditions, reducing greatly the interiacial tension between the washing fluid and any oily or other materials presen in the material to be cleaned.
These sulphate esters of the higher secondary aliphatic alcohols exist as colorless, amorphous waxes, completely soluble in organic solvents such as alcohols, esters, ketones, and hydrocarbons; and they are much more soluble in water than are sulphuric acid esters of corresponding carbon content, derived from primary alcohols or those having straight carbon chains.
Those sulphate esters of the invention having less than 15 carbon atoms in the molecule are completely soluble in water, yielding a clear solution at 0.25% concentration at room temperature. Those having 15 or more carbon atoms in the molecule form faintly cloudy solutions which do not settle out upon standing; whereas soaps and other detergent solutions under similar conditions of concentration are very cloudy, and in many instances precipitate a solid after several days.
These new sulphate esters yield voluminous foams when shaken with warm water. The calcium and magnesium salts present in moderately hard waters are not precipitated by these compounds in dilute solutions, since their calcium and magnesium salts are almost as soluble as the sodium salts. Dilute aqueous solutions of the alkali metal sulphate esters when slightly acidified still retain a large proportion of their detergent properties. Such solutions evidently contain some alkyl hydrogen sulphate.
The neutral secondary alkyl sulphates of the present invention may be produced by condensing an aliphatic primary or secondary aldehyde having at least 4 carbon atoms in its molecule, with acetone, methylethyl ketone, or a ketone derivative of either, in the presence of an alkaline catalyst. By the term secondary aldehyde is meant an aldehyde in which the carbon atom connected with the aldehyde group is also directly connected with 2, and only 2, other carbon atoms.
The resultant reaction mixture is made slightly acid to phenolphthalein by means of a suitable acid, and the acidified mixture is heated to its boiling point, thus converting the ketol present as a result of the condensation of the aldehyde and ketone, into an unsaturated ketone. The mixture is fractionally distilled under vacuum to separate the unreacted starting materials and water from the ketone; and to isolate the ketone from the said mixture. This ketone is hydrogenated under superatmospheric pressure, preferably around 800-1000 pounds per square inch, and at temperatures up to around C., in the presence of a hydrogenation catalyst such as active nickel. The saturated secondary alcohol thus formed is then recovered by fractional distillation of the reaction mixture under vacuum, and is converted to its acid sulphate by any of the usual sulphating methods. According to one method, the secondary alcohol is reacted with approximately an equivalent amount of equimolar proportions of 96% sulphuric acid and acetic anhydride, at low temperatures maintained preferably from around 0 to around 10 C. The concentration of the sulphuric acid can vary considerably: or this acid or sulphuric anhydride can be used alone;
and other anhydrides of organic acids, or the acids themselves, or their chlorides, may be substituted for the acetic anhydride; or chlorsulphonic acid dissolved in a suitable diluent such 1 as detergents in the washing of textiles and other materials soiled with grease, paint, carbon, and other objectionable substances, are those listed in Table I.
Table I t; Apparent formula of inter- Substance mediate alcohol ga atoms 1. Sodium octylsulufhato.-- 3, methylheptanol-2 s 2. Sodiumnonyls phate..- 3,ethylheptanol-6 9 3. Sodium docylsufphata--- 2methylnonanol-4. 10 4. Sodiumundecylsulphato. 5ethyln0nan0l-2 11 5. Sodiumdodecylsulphate, 3,ethyl-8-methylnona l2 6. Sodiumtridecylmlphate- 3,ethylundecanol-6 l3 7. Sodignze tetradecyl sul- 7,ethyl-2-methylundecanol- 14 8 8. sm l m pantadecyl sul- 3,9 diethylundecanol-o.- 15
p e 9. Scul pentadecyl sul-' 5,ethy ltrldecanol-8 15 p l0. Sodiglrn hexadecyl sul- 9, ethyl-o-methyltridecanol- 16 D 11. Sodiggi haptadecyl 8111- 3,9 diethyltridecanol-G. 17 '12. Sotfign; nondecyl sul- 5,11 diethylpentadecanolt..- 19
p a o 13. 'MJtfiAt. tetradecyl sul- 7,ethyl-2rnethy1undecanol- 16 p a e 14. 'M.E Aieheptadecyl sul- 3,9 diethyltridecanol-fi. 19
a 15. nondecyl sul- 5,11 diethylpentadecanol-8 21 p e 16."T.E.A. tetradecyl sul- 7, 2thyl-2-methylundecanol- D 9 l7."'-T.E.A. heptadecyl sul- 3,9 diethyltridecanol-fl 23 p 18. "T.E.A. nondecyl-sulphate- 5,11 diethylpentadecanol-S.-. 25
Table II 0.25% aqueous solution Intel-facial Numbers cones. to substance] Drop mum tension bar at dynes per 0. cm. at 26 Water 22 43. 3
atom of the main chain spaced from that carbon atom to which the sulphate group is attached; and that many of the alkyl sulphates have two branched-chain alkyl groups respectively connected directly to the carbon atom to which the sulphate group is attached. These structural characteristics possessed by so many compounds of this class examined appear to have an important bearing on the emciency of such compounds as detergents and emulsifying agents in the compositions employed.
The power of depressing the interfacial tension between water and hydrocarbons is one of the properties possessed to a remarkable degree by the sulphate esters of secondary branchedchain alcohols of the invention. Evaluation of this power may beobtained by drop number measurements. Those recorded in Table I consist in counting the number of drops formed by a plane-ground capillary tip when a fixed volume (10 c. c.) of an aqueous solution containing 25% by weight of the sample is allowed to flow slowly into a body of kerosene maintained at 30 C. The tip is of such size that the fixed volume of water, selected as a standard, will be divided into about 25 drops. The rate of flow is so regulated that the drops will form distinctly and can be counted conveniently. The number of drops observed may vary somewhat from one sample to another, particularly when the number is in excess of 100. Therefore, the values here recorded are in some cases the average of those found for several samples. This depressing power is measured directly by the number of drops formed. It is closely related to the detergent power, and particularly to the emulsifying power, of the sample.
Reference to the table will show the greatly increased effectiveness of the neutral alkyl sulphates having 14 or more carbon atoms in their molecules over those of lower molecular weight for depressing the interfacial tension between aqueous solutions and hydrocarbons.
The following examples will serve to illustrate the invention:
Example 1 A soiled white silk cloth impregnated with carbon black, mineral oil, manganese dioxide, and carbon tetrachloride, was agitated for five minutes in a .25% aqueous solution of sodium nondecyl sulphate (see Table I) The cloth was then rinsed with water and dried. Practically all of the color imparted by the impurities was removed in the washing, and the white color of the cloth restored. Similarly, the monoand triethanolamine heptadecyl and nondecyl sulphates were highly effective detergents in washing silk.
Example 2 A soiled white cotton cloth stained with mineral oil, carbon black, and manganese compounds, was treated with an aqueous solution of sodium heptadecyl sulphate, following the procedure described in Example 1. After rinsing the washed cloth in water and drying it, the color imparted by the impregnating materials had been in main part eliminated.
Unboiled cotton yarn was soaked in a dilute aqueous solution of the sodium nondecyl sulphate, and when dried was very appreciably whiter and softer, indicating a strong cleaning action.
The higher members of the series of sulphate esters, those having 14 or more carbon atoms in the molecules, have a detergent power superior to the lower members of the series; although it has been discovered that blends of the compounds of higher carbon content than 14 carbon atoms with those of lower carbon content are eificient cleansers in certain instances, and have better hard water and sea water solubility than those of the higher carbon content alone. Blends of one or more of these sulphate esters with ordinary soaps also are good detergents.
Hands soiled with grease, fresh paint, and other forms of dirt readily are washed clean .with water containing any of the sulphate esters of the invention. A copious lather is obtained, and the soil is removed as completely and efliciently as with special pumice-base soaps and others.
'Ifieggtiles readily may be washed clean in aqueous or solvent solutions containing hardness-1m parting ingredients or acidic substances, by the employment of a small amount of the sulphate esters of one of the secondary alcohols produced in the manner herein described. voluminous suds or froth which are relatively stable are formed r upon shaking dilute solutions of these sulphate esters. For example, upon agitating a .25% aqueous solution of the sodium tetradecyl sulphate, or of the corresponding monoor triethanolamine salt thereof, in hard water containing 400 parts per million of CaClz, a voluminous foam is produced which has over 15 times the volume of the foam produced under similar conditions using a sulphation product now on the market for the purpose and made from technical oleyl alco-' hols. Moreover, whereas the foam produced by the said sulphate esters of the present invention persisted for over two hours after agitation had ceased, the foam produced by the oleyl alcohol derivatives lasted but six seconds.
When sea water .was substituted for the hard water mentioned above, the tetradecyl sulphates of this invention gave foams which persisted for over two hours, whereas the oleyl alcohol derivatives produced but from one-third to one-half as much foam, which vanished in eight seconds after discontinuing the agitation.
The invention -is susceptible of modification within the scope of the appended claims:
I claim:
1. In the process of washing textiles, the step which comprises agitating the same while immersed in a solution of a neutral water-soluble salt of a sulphuric acid ester derived from a saturated secondary branched-chain monohydric aliphatic alcohol, and having at least 14 carbon atoms in its molecular structure.
2. The process forcleaning textile materials,
which comprises contacting the said materials with an aqueous solution having therein a watersoluble salt of an acid sulphuric ester of a saturated secondary branched-chain monohydric aliphatic alcohol having at least 14 carbon atoms in its molecular structure.
3. A detergent and emulsifying composition, which comprises a solution of a water-soluble sulphuric acid ester of a saturated secondary branched-chain -monohydric aliphatic alcohol containing at least 8 carbon atoms in its molecule and having two branched-chain alkyl groups respectively connected directly to the carbon atom to which the sulphuric acid group is attached.
4. A detergent and emulsifying composition, which comprises a solution of' a water-soluble salt of a sulphuric acid ester of a secondary branched-chain monohydric aliphatic alcohol containing at least 14 carbon atoms in its molecule.
5. A detergent and emulsifying composition, which comprises a solution of a water-soluble salt of a sulphuric acid ester of a secondary branchedchain monohydric aliphatic alcohol containing from 14 to 19 carbon atoms in its molecule.
6. A detergent composition comprising a solution of a water soluble sulphate ester of a saturated secondary branched-chain monohydric alcohol, which ester has at least 8 carbon atoms in its molecule and has at least one alkyl sidechain directly connected with the third carbon atom of the main chain spaced from that carbon atom to which the sulphate group is attached.
7. In the process of washing textiles, the step which comprises contacting the same with a solution of a water-soluble sulphate ester of a satu: rated secondary branched-chain monohydric aliphatic alcohol having at least 8 carbon atoms in its molecule and having two branched-chain alkyl groups respectively connected directly to the carbon atom to which the sulphate group is attached.
8. In the process of washing textiles, the step which comprises contacting the said materials with a solution of a water-soluble sulphate ester of a saturated secondary branched-chain monohydric aliphatic 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 chain spaced from that carbon atom to which the sulphate group is attached.
JACOB N. WICKERT.
CERTIFICATE OF CORRECTION.
' Patent No. 2,088,020.
July 27, 1937.
JACOB N. WICKERT.
It is hereby-certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line 49, inthe table, strike out "Table II"; 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 and sealed this 21st day of September,A. D. 1937.
Henry Van Arsdale
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2088020A true US2088020A (en) | 1937-07-27 |
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ID=3428815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2088020D Expired - Lifetime US2088020A (en) | Secondary alkyl sulphates as wash |
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| Country | Link |
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| US (1) | US2088020A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2480730A (en) * | 1949-08-30 | Method of producing a free-flowing | ||
| US2571689A (en) * | 1946-11-01 | 1951-10-16 | Dobbelman N V | Process for the preparation of strongly lathering and purifying agents, shampoos, and the like |
| DE767428C (en) * | 1940-12-12 | 1952-08-07 | Maerkische Seifen Ind | Process for the preparation of sulfonates of secondary alcohols |
| US2606874A (en) * | 1947-06-23 | 1952-08-12 | Shell Dev | Water in oil emulsions containing 1, 2-alkanediols as coupling agents |
| US2612477A (en) * | 1945-03-29 | 1952-09-30 | Shell Dev | Emulsifier compositions |
| US2633473A (en) * | 1948-01-07 | 1953-03-31 | Du Pont | Sodium sulfate of highly branched primary heptadecanol |
| US3468805A (en) * | 1965-10-22 | 1969-09-23 | Gaf Corp | Detergent composition |
-
0
- US US2088020D patent/US2088020A/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2480730A (en) * | 1949-08-30 | Method of producing a free-flowing | ||
| DE767428C (en) * | 1940-12-12 | 1952-08-07 | Maerkische Seifen Ind | Process for the preparation of sulfonates of secondary alcohols |
| US2612477A (en) * | 1945-03-29 | 1952-09-30 | Shell Dev | Emulsifier compositions |
| US2571689A (en) * | 1946-11-01 | 1951-10-16 | Dobbelman N V | Process for the preparation of strongly lathering and purifying agents, shampoos, and the like |
| US2606874A (en) * | 1947-06-23 | 1952-08-12 | Shell Dev | Water in oil emulsions containing 1, 2-alkanediols as coupling agents |
| US2633473A (en) * | 1948-01-07 | 1953-03-31 | Du Pont | Sodium sulfate of highly branched primary heptadecanol |
| US3468805A (en) * | 1965-10-22 | 1969-09-23 | Gaf Corp | Detergent composition |
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