Патент USA US2110281код для вставки
2,110,281 Patented Mar. 8, 1938 UNITED. STATES PATENT‘ oFFicE ‘ j 2,110,281 _ PURE oomoimns A8 LUBRIO ' Elmer Wade m and George in. annuity. Hammond, Ind., .assignon to Standard Oil Company, GhicaIm-IIL, a corporation of Indi ana No ' Application March '31, 1934; \ Serial N0. 718,438 12 Claims. . This invention relates to an improved lubricant for use .on bearing surfaces which are subjected to high. pressures and high rubbing velocities during use. - ' Y ‘ ~ ' ' 5 v The present day trend in automotive design toward smaller rear axles and consequently smaller gears. On account of the small gears, tooth pressures and rubbing velocities are rapidly (cl. va'z-o) of vthe lubricant. ' These extreme-pressure lu bricants have substantially no corrosive action upon metal surfaces. . added to mineral lubricating o?s or greases to impart, extreme-pressure lubricating properties thereto are as follows: - - mineral lubricating oils. 15 ' ' 20 ' ' approaching a point where rear axles cannot 10 be lubricated satisfactorily with the. ordinary v V The sulfur-bearing compounds which may be - , ~\ - I ' R,—s—s—1_2, 10 Buliideo The trend toward in-_ ' wherein R and R1 represent alkyl groups‘ con- . creasing loads on gear teeth in other ?elds has developed an urgent need for special lubricants. When hypoid gears, worm gears, heavy duty taining at least 5 carbon atoms each gr aromatic under those conditions of use. The object of our invention is to .provide a lu disul?des are ethyl disul?de, n-propyl disul?de, n-butyl disul?de, secondary butyl .disul?de, ter groups such as phenyl radicals and tolyl radicals, - however, when It ‘represents a phenyl group, R1, bearings, planetary automatic shifts, and the - may represent any alkyl group; and. R2 and Rs 15 like are used under conditions of high pressure represent alkyl groups or phenyl groups. ‘The and high rubbing velocities, special types of ex term‘ alkyl is intended to include the saturated treme-pressure lubricants must be provided in - cyclic radicals also, such as the cyclohexyl group. order to reduce the wear upon such moving parts. Examples of the sul?des are amyl sul?de, hexyl Extreme-pressure lubricants are likewise im sul?de, cyclohexyl ‘sul?de, phenyl sul?de, ethyl 20 portant in cutting and drawing operations where phenyl sul?de, methyl phenyl sul?de, tolyl. sul the 011 must withstand high pressures encountered ?de, and butylphenyl sul?de. Examples of the 25 bri’cant which will give satisfactory lubrication to bearing surfaces which are subjected to high pressures and/or high rubbing velocities. A fur ' ther object is to provide a lubricant which will tiary butyl disul?de, cyclohexyl disul?de, ethyl propyl disul?de, amyl disulfide, heptyl disul?de, tolyl disul?de, and phenyl disul?de. II ' maintain a lubricant ?lm on bearing surfaces at 30 all times. We have found that if small amounts of certain types of organic sulfur compounds are added to theJubn'cating oils and, soft greases, the lubricant will enable the bearing surfaces to withstand the high pressures and high rubbing velocities witho-ut- noticeable wear. Similarly, these sulfur compounds may be incorporated into drawing lubricants and cutting oils. , We have found that the extreme-pressure lu bricants can be prepared by adding a small 40 _quantity of ‘an alkyl disul?de, high molecular weight alkyl sul?des, aryl thiocyanates and aryl isothioc'yanates, xanthic disul?des, or xanthates to mineral lubricating oils, preferably, those lu bricating oils having aviscosity from about 90 25 R4—S—C E N Aryl thiocyanic esters R4-—N=C=S 30' ‘ fAryl isothiocyanic esters wherein R4 represents’ aryl groups such,as_ phenyl, tolyl and naphthyl groups. Examples of the aryl thiocyanic esters are phenyl thiocyanic ester, tolyl thiocyanic ester, and naphthyl thio cyanic ester. Examples of the aryl isothiocyanic esters or aryl isosulphocyanic esters are?phenyl isos'ulphocyanic ester, tolyl isosulphocyanic esters, and naphthyl isosulphocyanic‘ester. The aryl 40 esters of isothiocyanic acid impart excellent ex treme-pressure lubricating properties to mineral to 200 seconds Saybolt at 210° F. These com pounds may be used in oils designated as S. A. E. 45 20, 30, 40, 50, and 60 oils. These sulfuricom pounds are ‘added in quantities ranging from V2 to 7%, but generally amounts ranging from‘ 1 to 5% are satisfactory. The organic sulfur com pounds may be dissolved in the oil .by any con-> ventional mixing means. If desired, calcium and aluminum soaps or other soaps of high molecular weight fatty acids may be added to the com 55 position to increase the viscosity or consistency Wherein R5, R6, and R11 represent alkyl groups. Examples of the xanthic esters are ethyl xanth 50 ate ethyl'ester, methyl xanthate ethyl ester, ethyl . ~ ‘ xanthate methyl ester, ethyl xanthate butyl ester and ethyl xantha-te propyl ester. Examples _'of the xanthic disul?des are methyl xanthic disul ?de and ethyl‘ xanthic disul?de. ' ’ 2 The load-carrying capacity of extreme-pres captans in the petroleum distillate. Generally sure lubricants may- be determined by the ex-' this temperature is below 80 to'100" C. Other oxidinng agents such as hydrogen peroxide or potassium permanganate may be used instead of treme-pressure testing machines such as the "Almen extreme-pressure lubricant testing ma chine" described by Wolf and Mougey in their paper on extreme-pressure lubricants'given at the 13th annual meeting of the A. P. I. at Hous ton, Texas, November 17, 1932. The following table gives the. load-carrying ca pacity of extreme-pressure lubricants as deter mined by an extreme-pressure lubricant twting the oxygen. Also the high molecular. weight alkyl disulfldes maybe prepared by treating hydro carbon distillates with sodium plumbite solution and sulfur, separating the plumbite solution from the oil containing the dissolved disuliide and re6 covering the alkyl' disul?des by distilling the hy drocarbon oil from~ the dissolved disul?des. _ machine designed and operated on the same prin While we have described our invention with ciple as the Almen extreme-pressure lubricant 'reference to particular ‘examples, it should be ‘ i testing machine. 'lhose lubricants withstanding , understood that our invention is not limited a bearing pressure of 20,000 pounds per sq. inch thereby,‘ except as set forth in thefollowing are satisfactory. ‘ ' ' , Table I ' We claim: - ' / ' _ ‘ , > 1. An extreme-pressure lubricant comprising, a mineral lubricating oil and from $5 to 5% of a - Sample: 5% of the following compounds dissolved in zero bright stock (mineral oil having a vis cosity of 150 Saybolt at 210° F.) .> disuliide having the following general formula: R+B—8—R1, wherein R and R1 represent sub 'Speedofpin:150R.P.M. stituents selected from the group consisting of alkyl groups or hydrocarbon phenyl vgroups. - 2. An extreme-pressure lubricant comprising, a mineral lubricating oil and from ya to 5% of an alkyl disulflde having the following general formula: R-B-S-Ri, wherein R and R1 repre sent substituents selected from the class consisting Compounds of methyl, ethyl, propyl, butyl, amyl, hexyl, and Control 30 Am lsulil cyclohexyl groups. ‘ 80 g ‘ 3. An extreme-pressure lubricant comprising, a mineral lubricating oil having a viscosity from 90 to 200 seconds Saybolt at 210° F. and from y sulii $5 to 5% of a butyl disul?de. ................ .. ' . 4. An extreme-pressure lubricant comprising, a mineral lubricating oil and from $5 to 7% of an Bntyl sulfide--.‘ ....... -_ n-Hoptyl mercaptsnnn Eth benzene sulionate. 7 Met yl p-toluane sulicnatc. organic sul?de having the following general formula: RPS-R1, wherein R and R1 represent alkyl groups containing at least 5- carbon atoms As stated hereinbefore, the sulfur compounds may be added to the viscous mineral oil by any each. 40 - suitable means. Generally the sulfur compounds 5.7An extreme-pressure lubricant comprising, are added to the mineral oil and stirred until a a mineral lubricating oil having a viscosity from 90 to 200 sec. Saybolt at 210° F. and from 1 to 5% homogeneous mixture is obtained. Example I ~ of an organic sul?de having the following general formula: R—S--R1, wherein R and R1 represent _ Extreme-pressure lubricants for use under con substituents selected from the class consisting of - ditions of 'high- rubbing velocities and pressures V amyl. hexyl, and cyclohexyl groups. 7 can be prepared satisfactorily by mixing 5% by _ ‘ 6.‘ An extreme-pressure lubricant comprising, a weight of ethyl disulflde with a mineral oil hav ing a viscosity of about 150 to -l60 Saybolt at 210° F.. Coastal mineral oils, Mid-Continent oils and para?in mineral oils may be used'as the base mineral oil having a viscosity from 90. to 200 sec onds Saybolt at 210° F. and from 1/2 to 5% of an organic disulfide selected from the group consist ing of n-propyl disulfide, and n-butyl disul?de. 7. An improved liquid lubricant composition comprising a mineral lubricating oil and from $9 to 7% of a disul?de having the following general formula R—S-_—S—Ri, wherein R and R1 repre for these extreme-pressure lubricants, Any of the hereinbefore mentioned compounds may. be used in the preparation of extreme-pressure lubri cants instead of ethyl disul?de as set forth in Example I. v . . sent substituents selected from the group con The alkyl disul?des may be prepared by any conventional means‘ but if desired, they may be prepared from" the ~mercaptans occurring in petroleum distillates boiling within the gasoline 1 or kerosene-range. A petroleum distillate, pref sisting of alkyl groups and hydrocarbon phenyl . groups. 8. An improved lubricant composition compris ing a mineral lubricating oil and from 55 to 7% of an alkyl disul?de'having the following general - I erably one containing a high percent of mercap formula R--S—S-R1, wherein R and R1 repre tansis agitated with caustic. The caustic solu - tion is separated from. the hydrocarbon material sent substituents selected from the group con by decantation and then oxidized with any suit-' sisting of ‘methyl, ethyl, propyl, ‘butyl, amyl, ' .able chemical reagent, for. example air, or ongen. hexyl and cyclohexyl groups.~ 9. An improved lubricant composition com The alkyl disul?des are then removed from the prising a mineral lubricating oil and from $6; to oxidized caustic solution by boiling and are col lected by absorption in a mineral oil solution; if 7% of~ an organic compound selected from the ‘ desired, they may be absorbed in the mineral oil ‘group consisting of organic sul?des having thew , _ 70 used in the preparation of the extreme-pressure formula R—S--R1, wherein R and R1 represent lubricant. phenyl groups or alkyl groups containing from 5 ' toB carbon atoms each; and- disulfides having the ‘ The-oxidation with air or oxygen is preferably performed under pressure and ,at a temperature below the boiling point of the mer general formula Re-S—S—Ra, wherein R: and u . , 2,1 10,9131 ' ,_ 3 ‘R: represent alkyl groups and hydrocarbon '> 'rosive action upon metal surfaces, selected from phenyl groups. p 10. An extreme-pressure lubricant comprising a mineral lubricating oil and from % to'7% of an organic compound selected from the group con sisting of organic sul?des having the formula R—,-S-R1 wherein R and Ru represent alkyl groups containing from 5 to 6 carbon atoms each the group consisting of organic, sul?des having the formula R'—.S--R1 wherein R and’ R1 repre sent alkyl groups containing at least ?ve carbon atoms each. and di-sul?des having the general formula Rg'-s'_s‘-_Ra wherein R2 and R: repre ' sent alkyl-f'groups. and di-sul?des having the general formula prising mineral lubricating oil and from % to_‘: groups. formula R-S-S-R', wherein Band B’ repre 10 Rz-S-S-R: wherein R: andR; represent alhi ~ _ ' ~ 11. An improved lubricant composition com prising a mineral lubricating oil and from lé to 7% of an organic compound, which has no cor 5% of a 'disul?de having‘ ‘e following general sent alkyl groups. ' GEORGE M. McNUL'lg'llf." '.