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Publication numberUS2287639 A
Publication typeGrant
Publication dateJun 23, 1942
Filing dateApr 27, 1939
Priority dateApr 27, 1939
Publication numberUS 2287639 A, US 2287639A, US-A-2287639, US2287639 A, US2287639A
InventorsBennett Pings Wilbur
Original AssigneeDu Pont
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Lubricant composition comprising organic sulphonamides
US 2287639 A
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Description  (OCR text may contain errors)

lubricant compositions,

' tages.

Patented June23, 1942 "UNITED. smesa ATENT "OFFICE 2,287,639 r LUBRICANT COMPOSITION COMPRISING ORGANIC SULPHONAMIDES Wilbur Bennett Pings, Wilmington, Del, assignor to E. I. du Pont de Nemollrs & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application April 27, 1939,

Serial No. 270,423

18 Claims. This invention relates to methods of lubrication and lubricants and particularly to lubricant compositions comprising solutions or dispersions ofsulphonamides. More particularly it relates to lubricants comprising aqueous solutions or dispersions of sulphonamides' Still more particularly it relates to metal-working lubricants comprising aqueous solutions or dispersions of sulphonamides which contain halogen atoms'and to methods of lubricating involving the use of ing and cooling action. The beneficial cooling eflect of water has long'been made use of in they are accomplished. by the use as lubricants for metal-forming, shaping and machining operations-of aqueous solutions or dispersions of sulphonamides which contain combined halogen, preferably chlorine.

' In a more preferred embodiment of the invention they are accomplished by the use as lubricants of petroleum sulphonamides, e. g. sulphonamides obtained from'petroleum sulphonyl chlorides from non-gaseous petroleum fractions.

In a still more preferred embodiment-they are accomplished by the use of sulphonamides obtained from the' sulphonyl chloride reaction products obtained by reacting non-gaseous aliphatic or cycloaliphatic.hydrocarbons, and

especially saturated hydrocarbons with, admixed gaseous chlorine and gaseous sulphur dioxide after the manner set forth in Reed U. S. Patent many drawing and stamping operations by the use of aqueous emulsions of fatty oils, etc. How-.

ever, in certain operations, such as the deep drawing of sheet 'steel'and cutting of tough metals at high speeds, aqueous lubricants have been found to possess insumcient film strength I to withstand the pressures developed. It has been necessary to turn to the more expensive straightoils for such work, and to operate at reduced rates of speed in order to dissipate the heat developed.

This invention has for an object the preparation of stable aqueous lubricants of high filmstrength which overcome the above disadvan- Aiurther object is to provide a material which will reduce the friction between a metal being formed and the metal or other parts which contact with it during the drawing or stamping operation. A still further object is to provide a highly stable lubricant which not decom- When a non-gaseous aliphatic or cycloaliphatic hydrocarbon or a mixture of such hydrocarbons or predominating in such hydrocarbons is reacted with gaseous sulphur dioxide and gaseous chlorine, especially at a temperature below the decomposition point of the formed organic sulphonyl chlorides in the maner set forth in U. S. Patent 2,046,090, and Fox, Henke, Lockwood 8: Tinker application, Serial No. 216,838, filed June 30, 1938, a. rather complex mixture is formed, which usuall contains in varying proportions hydrocarbon monosulphonyl chlorides, chlorohydrocarbon monosulphonyl chloride,

, hydrocarbon polysulphonyl chlorides, chlorothe rate of flow, the intensity of the actinic 40- pose or separate under the conditions of shaping, forming or'machining metals. A still further object is to provide a metal-working lubricant combining the important features of eiiicient coolingand high film strength.

The above and other objects are accomplished and the described disadvantages obviated by the following. invention which comprises theuse in lubricant compositions, and particularly in aqueous lubricant compositions for metal-forming and machining operations of aliphatic, cycloaliphatic, or aromatic sulphonamides or mixtures thereof. v

In a' preferred embodiment of the invention hydrocarbon polysulphonyl chlorides and chlorohydrocarbons. The proportion of products in the mixture and the amount of chlorine substitution products can be varied somewhat by varying the proportions of sulphurdioxide to chlorine,

light used to. accelerate the reaction, pressure, and temperature conditions.

' In the case where the saturated open-chain hydrocarbons and derivatives thereof, e. g. nongaseous n-alkanes, iso-alkanes, chloroalkanes and mineral oil fractions are used as initial reactants the mixture are unusually complex since the sulphonyl chloride groups do not enter the same position in each molecule. Hence, the resulting sulphonamides are quite'complex when .the entire sulphonyl chloride reaction'product or. a portion or fraction thereof is' used for the,

amide reaction. I I The reaction products obtained from using saturated cycloaliphatic hydrocarbons, e'. g. I cyclohexane, menthane, camphane, etc. as initial reactants are not quite as complex and the sol-- phonamides prepared therefrom can in some instances be separated as pure compounds.

Various methods for the preparation of the preferred sulphonamides used according to this ganic primary or secondary amine with the reaction products obtained by reacting a saturated hydrocarbonor a derivative thereof with gaseous sulphur dioxide and gaseous chlorine; the first-mentioned reaction being carried out under sulphonamide-forming conditions.

The lubricants of this invention may be prepared by incorporating the desired sulphonamide or mixture of sulphonamides in a suitable carrying medium such as water or an aqueous solution to form emulsions or dispersions. Other aqueous lubricant constituents may be incorporated if desired with the sulphonamides.

The primary and secondary sulphonamides which represent the preferred embodiments of the invention may be easily incorporated into water or aqueous solutions in the form of'their ment of the reaction product of cetane, sulphur' alkali metal, e. g. sodium and potassium, salts,

thus providing a solution suitable for use in the machining or forming of metals. Tertiary sulphonamides may also be used in neutral and alkaline solutions and dispersions, but it is sometimes advisable to use emulsifying and dispersing agents.

The invention will be further illustrated, but is not intended to be limited by the following examples in which the parts stated are parts by weight.

Example I A solution containing 45 parts of a sulphonamide prepared by reacting a. No. 40 viscosity paraflin base white oil substantially free from unsaturates with a gaseous mixture of chlorine and sulphur dioxide and a further reaction of the sulphonyl chloride product with liquid ammonia, 3.6 parts of sodium hydroxide and 131.4 parts of water was tested for film strength in a Cornell (Faville-Levally) friction testing machine. This machine consists of a small steel rod held in position by a soft brass pin and rotating at a speed of about 325 R. P. M. against the flat surfaces of two fixed cylindrical test blocks which are set in frames attached to two lever arms. Increasing load is applied uniformly and automatically through the arms to these test pieces by means of a ratchet and screw operated from an eccentric on the drive shaft. Torque and load are registered simultaneously. Failure of the lubricating film is indicated by seizure and consequent shearing of the brass .pin, or by a squealing with a sharp and persistent rise in torque although the bearing continues to turn withoutactual seizure. The solution of the viscosity 40 white oil sulphonamide stood a Cornell load of 3750 pounds, with a torque reading at this load of 46 pound inches.

Example II low-carbon deep-drawing steel through highcarbon steel dies. The lubricant was fed by positive forced feed circulation. With the customary lubricant, failure was usually apparent after No. 40 white oil has the following analytical characteristics: A. S. '1. M. distillation range:

200-300 draws, but using the sulphonamide lubricant 800 cups were drawn before definite scratching was noticed, and even after 1200 draws there was not a severe pick-up of metal on the dies. The drawn cups were also found to be quite resistant to corrosion, samples examined after about 6 months showing only slight rusting, although they had been stored without removal of the lubricant.

Example III A solution containing 10 parts of-the sodium salt of cetanesulphonamide (prepared by treatdioxide and chlorine with liquid ammonia in the manner described above) carried a load of3500 pounds on the Comeli machine without failure.

' Example IV- An aqueous solution containing 100 parts" of water, 2.5 parts sodium hydroxide, and 25 parts of the sulphonamide obtained from paraflin wax sulphonyl chloride andliquid ammonia prepared by a procedure similar to that described above, when tested in the Cornell machine carried a load of 4250 pounds without failure, with a-torque value of 26 pound inches.

Example V An aqueous solution containing 25 parts of propanesulphonamide derived from propanesulphonyl chloride and liquid ammonia, and 100 parts of water, failed when tested in a Cornell machine after the manner of Example I at a load of 750 pounds, with a torque reading of 42 pound inches at this load.

Example VI Example VII An aqueous solution containing 10 parts of the sodium salt of cyclohexanesulphonamide and 100 parts of water was prepared. It withstood a Cornell load of 2750 pounds when tested in the manner set forth in Example I, but gave some evidence of rupture of the film at 'a load of about 1000 polmds.

Example VIII An aqueous solution containing 5 parts of sodium hydroxide, 25 parts N-phenylcyclohexanesulphonamide, and 100 parts of water was prepared. It showed evidence of film rupture at 750 pounds load on the Cornell machine after the manner set forth in Example I, but a load of 1750 pounds was reached before complete failure was observed.

O First drop 262 265 270-272 276-278 r- 87-29 :55 M 291-292 ry 6-31 carbon atoms. Primary and secondary suphonamides have the most utility and the primary sulphonamides are preferred. Additional suitable sulphonamides include n-heptane-, n-'octane-, ndodecane-, n-tetradecane-, n-hex-adecane-, noctadecane-, 2-ethylhexane-, menthane-, pinane-, camphane-, tetrahydronaphthalene'-, decahydronaphthalene-, p-toluene-, and 2-naphthalenesulphonamides. Thesecompounds may be substantially pure or in admixture with other sulphonamides. They may be substituted with halogen, amino-nitro,alkoxy, carboxy or ester groups. The sulphonamides may be substituted upon the nitrogen atom, e. g. N-octadecylparatoluenesulphonamide, N, N-dimethylhexadecanesulphonamide, N-methyl-N-phenyl-dodecanesulphonamide,.-etc. v

The above products as previously stated may be obtained from pure sulphonic acids'or sulphonyl chlorides or from the more complex sulphonyl chloride products obtained by reacting non-gaseous saturated hydrocarbons with gaseous i chlorine and gaseous sulphur dioxide; by an appropriate amide forming reaction. The sulphonyl chlorides obtained by reacting hydrogenated olefine polymers, e. g., di-, trior tetra-isobutylene, hydrogenated hexene-Zi-polymers, hydrogenated ethylene polymers, etc. with gaseous chlorine and gaseous sulphur dioxide are also useful as intermediates. scribed in Bruson et a1; 2,142,934 are useful as intermediates for sulphonamides. halides prepared by the method described in J ohnson'U. S. Pats. 2,146,744 and 2,147,346 may be converted to sulphonamides-which are useful in carrying out the invention. Additional useful sulphonamides are described in the above-identi fied case of A. L. Fox.

Among the amines which may be used for theamine component are primary and secondary mono-, diand poly-aliphatic, aromatic and heterocyclic amines. Suitable specific mines include primary amines such as methyl-, ethyl-, normaland isopropyl-, iso and secondary butyl-,

isoamyl-, 2-ethy1hexyl-, octy1-, dodecyl-, octadecyl-, etc. amines, ethylene-, propylene-', hexa- V methylene-, etc. diamines, aniline, toluidine, xylimetal and amine salts of long chain aliphatic carboxylic acids such as sodium oleate, sodium stearate, triethanolamine oleate, amine and alkali metal salts of higher aliphatic alcohol sulphates, mineral Oil sulphonic acids, sulphonated oils, alkyl naphthalene sulphonates, casein, glue, starch, dextrin, pectin, gum Arabic, gum ghatti and polyvinyl alcohol. Combinations of the surface active type with colloidal dispersing agents may be used.

The aqueous solutions and dispersions described herein are suitable for lubrication per se in applications which will permit of a low-boiling lubricant, or they may be used for improving the lubricating qualities of other aqueous solutions or emulsions, e. g., of metal-working lubricants. The liquid sulphonamides may be used as special The petroleum sulphonyl chlorides depurpose oils, e. g., in the machining of tough metals.

Solutions or dispersions containing about 25 to about 50 of the sulphonamides have been found to be generally useful, but up to 80% of the sulphonamide may be used with success. In the case of aqueous lubricants used for light drawing operations, for example, for drawing readily workable metal such as brass, tin, or copper, for

. lubricants described possess excellent cooling action by virtue of their water content and in addition have greater film strength than .it has heretofore been possible to obtain in such aqueous lubricants.

The compounds which contain chlorine possess high film strength. Since the compounds are preferably used in the form of their salts, or in an alkaline solution, they will not tend to become The sulphonyl corrosive, as has been the case with chlorinated oils, which constitutes a distinct advantage. These materials possess the further advantage of a stably bound sulphur atom which cannot separate or form corrosive substances such as are often encountered in the use of sulphurized oils. Another advantage of the materials of the present invention is that they. do not corrode metal, but in fact tend to prevent corrosion, and therefore aid in obtaining and maintaining bright finishes.

As many apparently widely difierent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that wev do not limit ourselves to the specific embodiments hereof except as defined by the appended claims.

I claim:

1. A lubricant composition comprising an aqueous carrying medium containing from 10% to of a sulphonamide having an organic radical attached to the sulphur atoms,

2. A lubricant composition comprising an aqueous alkaline solution containing a sulphonamide having an organic radical attached to the sulphur atom. I

3. A lubricant composition comprising an aqueous carrying medium containing from about 25% to 80% of a. sulphonamide having an organic radical of at least 6 carbon atoms attachedto the sulphur atom.

4. A lubricant composition comprising an aqueous alkaline solution containing a sulphonamide having an organic radical of at least 6 carbon atoms-attached to the sulphur atom.

5. A metal-working lubricant compositioncomprising an aqueous carrying medium containing from 10% to 80% of a sulphonamide having a hydrocarbon radical of at least 6 carbon atoms attached-to the sulphur atoms, said sulphonamide having at leastone hydrogen atom attached to the nitrogen atom thereof.

6. A metal-working lubricant composition comprising an aqueous alkaline solution containing a sulphonamide having an organic radical of at least 6 carbon atoms attached to the sulphur 3 atom.

7. A metal-working lubricant composition comprising an aqueous alkaline solution containtaining an aliphatic primary sulphonamide having at least six carbon atoms and containing combined chlorine attached to carbon.

10. A metal-working lubricant composition comprising an aqueous alkaline solution containing a sulphonamlde obtained from the sulphonyl chlorides produced by reacting a no'ngaseous saturated hydrocarbon with a gaseous mixture of chlorine and sulphur dioxide.

11. A metal-working lubricant composition comprising an alkaline aqueous solution containing a sulphonamide obtained from the sulphonylchlorides produced by reacting a nongaseous petroleum hydrocarbon with a gaseous mixture of chlorine and sulphur dioxide.

12. A lubricant composition comprising an aqueous alkali metal hydroxide solution containing 0.5 to 80% -by weight of a cetane sulphonamide,

13. A lubricant composition comprising an aqueous alkali metal hydroxide solution containing 0.5 to 80% by weight of a mixture of aliphatic sulphonamides wherein the hydrocarbon radicals attached to the sulphur atoms correspond to thehydrocarbons present in petroleum white oils,

said hydrocarbon radicals containing chlorine attached to carbon atoms.

14. A lubricant composition comprising an aqueous alkali metal hydroxide solution containing 0.5 to by weight of a mixture of aliphatic sulphonamides wherein the hydrocarbon radicals attached to the sulphur atoms correspond to the hydrocarbons present in a paraflin wax, said hydrocarbon radicals containing chlorine attached to carbon atoms.

15. A lubricant composition comprising an aqueous carrying medium containing from 10% to 80% of a-sulphonamide having a hydrocarbon radical attached to the sulphur atom and an emulsifying agent.

16. A lubricant composition comprising an aqueous carrying medium containing as an essential lubricant thereof a. sulfonamide having an organic radical attached .to the sulphur atom and being further characterized in that the groups attached to the nitrogen contain hydrogen and carbon atoms only.

17. A lubricant composition comprising an aqueous carrying medium containing as an esmntial lubricant thereof an aliphatic sulphonamide having an aliphatic hydrocarbon radical of at least 6 carbon atoms attached to the sulphur atom,

18. A lubricant composition comprising an aqueous carrying medium containing as an-essential lubricant thereof an aliphatic primary sulphonamide having an aliphatic hydrocarbon radical of at least 6 carbon atoms attached to the sulphur atom.

WILBUR BENNETT PINGS.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2533300 *Dec 31, 1945Dec 12, 1950Sinclair Refining CoMorpholine mahogany sulfonate as a rust inhibitor for petroleum oils
US2560240 *Apr 12, 1949Jul 10, 1951Oppenauer RupertProcess for preparing sulfonamides
US2658916 *Jun 10, 1950Nov 10, 1953Colgate Palmolive Peet CoPreparation and purification of higher alkyl aryl sulfonamides and their salts
US2748082 *Aug 18, 1953May 29, 1956Shell DevLubricating compositions
US2956951 *Oct 26, 1956Oct 18, 1960Exxon Research Engineering CoWater base lubricant containing dimethyl sulfoxide
US3038857 *Nov 10, 1958Jun 12, 1962Sun Oil CoLubricants containing additives
US3238257 *Oct 10, 1960Mar 1, 1966Du PontN-tertiary-alkyl alkanesulfonamides
US3287267 *Dec 28, 1964Nov 22, 1966 Antirust oil
US3325418 *Sep 23, 1964Jun 13, 1967Chevron ResPolychlorosulfonated polymers as viscosity index improvers and lubricating oil detergents
US4122266 *Dec 29, 1975Oct 24, 1978Chevron Research CompanyReaction of aryl sulfonic acid ester and amines
US4447348 *Mar 4, 1982May 8, 1984The Lubrizol CorporationCarboxylic solubilizer/surfactant combinations and aqueous compositions containing same
US4448703 *Mar 4, 1982May 15, 1984The Lubrizol CorporationSolubilizer is reaction product of polycarboxylic acid acylation agent with hydroxyl acrylic amine
US4666620 *Mar 13, 1986May 19, 1987The Lubrizol CorporationCarboxylic solubilizer/surfactant combinations and aqueous compositions containing same
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USRE36479 *Oct 4, 1996Jan 4, 2000The Lubrizol CorporationAqueous compositions containing nitrogen-containing salts
DE977492C *Sep 25, 1952Aug 18, 1966Bataafsche PetroleumOElfreie, waesserige Schmier-, Schneid- und Kuehlfluessigkeit fuer die spanabhebende Metallbearbeitung