US2368670A

US2368670A - Lubricating composition

Info

Publication number: US2368670A
Application number: US298337A
Authority: US
Inventors: Bert H Lincoln; Gordon D Byrkit
Original assignee: Lubrizol Development Corp
Current assignee: Lubrizol Development Corp
Priority date: 1939-10-06
Filing date: 1939-10-06
Publication date: 1945-02-06
Anticipated expiration: 1962-02-06

Description

Patented Feb. 6, 1945 LUBRICATING COMPOSITION Bert H. Lincoln and Gordon D. Byrkit, Ponca City, Okla, assignors, by mesne' assignments, to The Lubri-Zol Development Corporation,

- Cleveland, Ohio, a corporation of Delaware No Drawing. Appllcation October .6, 1939, Serial No. 298,337

1 Claim.

This invention relates to lubricating oils and more particularly to improved lubricating oils of high film strength, high resistance to oxidation, and markedly reduced formation of corrosive products during use.

Present-day 'mechanical devices require lubri eating oils of high film strength, of high oiliness characteristics, and of low tendency to oxidize during use. It has been found that the presentday hydrocarbon lubricants of the very highest quality are deficient in these very important characteristics. These three properties are of vital importance under conditions of thin film lubrication where the lubricant has been squeezed from between the friction surfaces because of high pres-l sure, slow speeds, and other causes. In modern engines, large surfaces of oil are exposed to the action of atmospheric oxygen, promoting rapid oxidation. It is readily seen ,that the viscosity or the body of the lubricant plays no part in thin film lubrication and that the remaining film of oil must have a very high film strength and be of high oiliness value to prevent rupture of the film of the lubricant, which would cause seizure. The oil film must tend to keep the coefilcient of friction as low as possible. The oil must resist oxidation when these thin film are heated in the presence of atmospheric oxygen as they are in use.

Mechanical devices are being designed for higher pressure operation, and the film strength of the best quality straight hydrocarbon lubricant has been found to be too low for satisfactory service. It will be obvious that an invention which provides a means of improving the film strength of these lubricants is of great-importance to the art of lubricant manufacture and to the designer and fabricator of mechanical devices.

Substantially all machines operate in part orat times totally under conditions of boundary or thin film lubrication, under which conditions the oiliness or unctuosity of the lubricant is the first and primary requisite of efiicient operation. Those skilled in the art of lubricant manufacture or machine manufacture will readily appreciate the value of an invention that will improve the oi iness of these otherwise high-quality lubricants. Furthermore, sludge and acid are especially deleterious under conditions of thin film lubrication. The sludge is not a lubricant in any sense of the word, and the soluble acidis particularly corrosive to bearing metals such as cadmium-silver, copperlead, and the like.

In starting idle mechanical equipment which is lubricated from a sump by pumping or circulatin the lubricant, there is always a short period of time in which the rubbing surfaces must operate under conditions of dry friction if ordinary hydrocarbon lubricants are used. With dry friction, the wear on friction surfaces is extreme; and durin cold weather when the lubricant is sluggish or during periods when the lubricating system is not functioning properly for one reason or another, rubbing surfaces may not only sufier considerable wear but may be damaged to the point where they must be replaced. The product of our invention has a very important property of reacting with the metal surfaces, penetrating or adsorbing on the metal surfaces, and leaving a film of lubricant with high oiliness character, which remains on the metal surface irrespective of the length of time the machine has been idle.

This high oiliness film gives very even and smooth operation, which may be easily discerned by the experienced operator or lubricating engineer. 7

When the hydrocarbon lubricants are diluted with unburned fuel or with other light hydrocarbons, the small degree of oiliness of the original hydrocarbon lubricant is greatly decreased. We have found that the addition of the products of our invention to hydrocarbon lubricants more than compensates for the loss in oiliness and load-carrying ability from dilution.

It is well known that, in order to obtain lubricants which are preeminently satisfactory from the standpoint of oxidation in use, it is necessary to refine the oil thoroughly and then to add an inhibitor of oxidation. The thorough refining may consist of more and heavier acid treatments or solvent treating so as to remove a considerable part of the oil and leave only the most stable portion. Such drastic refining is necessary in order to obtain stability with respect to sludge formation, but the oil is then a manner as to avoid all three of these dimculties, namely, soluble, corrosive products, sludge, and lacquer. It is considerably more advantageous to add the materials of our invention and avoid these difficulties by this method.

Certain compounds are adsorbed or absorbed by metals thus forming tenacious films at the surface of metals; these films are able to stand high pressures. X-ray dill'ractionmethods have shown that compounds containing highly polar molecules, that is, molecules of unsymmetrical electrical character containing an atom or group of atoms exhibiting a secondary or residual valence, tend to produce regimentation of the molecules of hydrocarbon oil when added thereto. A metal immersed in a strongly polar compound will show a film of the compound in which there is a regimentation of molecules oriented with respect to the surface of the metal by which they are adsorbed or absorbed.

Many of our additive materials are effective when added to poorly refined or even wholly unrefined lubricants. The addends may thus be substituted in whole or in part for the usual refining processes.

In the prior art of applying these principles to the manufacture of lubricants, many diverse types of materials have been suggested to be added to obtain improvement in various characteristics. It has been found that the addition of various compounds frequently improves film strength, oxidation resistance, noncorrosiveness, and other characteristics.

One object of our invention is to provide improved inhibitors ofoxidation and corrosion for addition to lubricants.

Another object of our invention is l'oprovide film strength improving addition agents suitable for use in lubricants and especially in crankcase lubricants.

Other and further objects of our invention will appear in the course of the following description. I

To the accomplishment of the foregoing and related ends, said invention, then, consists of the means hereinafter fully described and particularly pointed out in the claims.

In general, our invention contemplates an oil of lubricating viscosity having added thereto a small amount of an organic thiocarbonate of the general formula axoxa' in which represents carbon, X represents either oxygen or sulfur (at least one of the'Xs must be sulfur) and R and R are organic radicals one or both of which contain carbon, hydrogen, and at least one other element besides halogen. Halogen may 'be present in the R's but in that case another characterizing element must also be present. The elements which we refer to here as characterizing elements" include oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus. arsenic, and metallic elements, such as, tin, antimony, bismuth, and the like. The R's may be aliphatic, carbocyclic, or heterocyclic in character. It will be apparent that by thiocarbonate in the appended claims we mean to include monoand trithiocarbonates as well as the dithiocarbonates (xanthates) The introduction of this characterizing element into our thiocarbonates'permits of an extraordinary flexibility in the design of the addend for a particular use. Thus it permits the introduction of additional sulfur if the sulfur in the thiocarbonate is insufiicient in amount or the introduction of other forms of sulfur if the thio- .tion have a dual action in a lubricant. ,action involves increased load-carrying ability carbonate sulfur is too stable or too unstable. The additional inhibiting action of phosphorus. nitrogen, or organo-mctallic groups may be added to the molecule to produce an extremely effec tive inhibitor of oxidation and/or corrosion. Furthermore the newly introduced elements have a considerable effect on the activity of the thio carbonate sulfur and it may be activated or depressed by the use of suitable groups in the R's of our thiocarbonatcs. Chlorine may in turn have an activating effect on the characterizing element or elements,

The substituted thiocarbonates of our invention show an unexpected improvement over the corresponding unsubstituted thiocarbonates and even over mixtures of the unsubstituted thiocarbonates with other compounds having the same substituting groups. Thus a xanthate containing a triphenyltin group in the organic radical shows a greater effect as an antioxidant than the triphenyltin group in. say, tetraphenyltin plus the same xanthate without the triphenyltin group Similar unexpected results are obtained on the introduction of oxygen as an oiliness factor, halogen, nitrogen, phosphorus, sulfur metal and the like as film strength or inhibiting factors.

The particular thiocarbonates of this inven- One and/or oiliness, while another action is directed to the stability of the lubricant. For load-carrying capacity, quantities ranging from 0.1 per cent to'about 10 per cent may be added. As an anticorrosive agent and/or an anti-sludging agent, much smaller amounts may be required ranging from approximately 0.001 to 1.0 per cent. The action of our thiocarbonates is specific but dinicult to understand. These compounds may be added to any type of hydrocarbon lubricants but show an unusual value in highly refined and solvent treated lubricants. By oil having lubricating viscosity in the appended claims, we mean to include the so called mineral oils and various hydrogenated. polymerized and otherwise syn-- thetically treated oils such as voltolized oils. aluminum chloride treated oils, and the like. Furthermore the lubricating oil may consist in .whole or in part of shale oil, animal or vegetable oils such as castor oil, lard oil, corn oil, cottonseed oil, and the like. I

In practice, it is better to employ compounds whose boiling point is above 2 -'5 F. in order that the addition'compound will not be evaporated or distilled in use. The selection of a particular ,compound or compounds to be used as an addition agent to the hydrocarbon or other oil is to be made considering the physical and chemical properties of the various compounds and the use to which the blend is put. Thus, if water is likely to be present during use, a salt or combination of salts is selected which is not affected by water. If a particular added compound proves too volatile for its application, a higher boiling material should be used and the more volatile compound used for blending in an oil intended for duty at lower temperatures. In general, for automotive crankcase lubricants, we prefer to use compounds having vapor pressures of less than atmospheric at 250 F.

The following compounds may be used in accordance with our invention. All and each 'of mono-, di-, or trithiocarbonates may be of various types as shown in the following classifiestion. Each of the following organic, or organeinetallic radicals may be combined with mono-,

diand trithiocarbonate radicals as further examples of our invention.

I-Aliphatic types Reaction product of potassium amyltrithiocarbonate with paraiiin wax chlorinated to 23 per cent chlorine and treated with sodium butylate to re move about one-third of the chlorine to make the butyl ether 6. Reaction product of potassium amylxanthate with beta, beta prime-dichloroethyl ether.

7. Methyl ethoxyamylxanthate c. Ketones 8. Reaction product of potassium amylxanthate with chloroacetone 9. Reaction product of potassium amylxantliate with symmetrical dichloroacetone so as to form di(amylxanthylmethyl) ketone.

10. Reaction product of potassium amylxantllate with symmetrical dichloro acetone so as to form amylxanthylmethyl chloroinethyl ketone 11. Unsaponifiable oxidation products of parafiiii wax chlorinated and part or all of the chlorine removed by condensation with sodium ethylxanthate d. Aldehydes 12. A1pha-butylxanthylbutyraldehyde 13. Allphz ethoxylethylxanthyloenanthaldey 9 e. Acids and salts 14. Alpha-amylxanthylstearic acid 15. Calcium amylxanthylchlorostearate 15a. Tin amylxanthylchlorostearate 16. Ethoxyetliylxanthylphenylstearic acid 17. Aluminum ethoxyethylxanthylphenylstearate f. Esters 18. n-Butyl ethylxanthylacemte A-mixturc of 65 parts of finely powdered potassium ethylxanthate, 65 parts of n-butyl .chloroacetate. and 200 parts of acetone was agitated and heated for five hours. The acetone solution was drawn off, concentrated, and the residual oil distilled at 128-135 at one mm. pressure.

19. Methyl etliylxanthylchlorostearate A mixture of 48 parts of finely powdered potassium ethylxanthate, 102.5 parts of methyl dichlorostearate, and 100 parts of acetone was similarly refluxed and separated. The residual oil contained 4.05 per cent sulfur. A one per cent blend of this material in a S. A. E. 30 mineral 011 showed a Timken film strength of 28 poundspn the arm. The mineral oil alone had 9. Timken film strength of only 9 pounds on the A iii" Y ru es g 20. Amylxanthylsuccindiamide 21. Laurylxanthylauramide B. Containing sulfur a. Mercaptans 22. Mercaptoamyl a e 23. Amylxanthyl mercaptomethylstearate b. Sulfldes and polysulfides 24. Reaction product of sodium laurylxanthate with beta, beta primedichloro- 25 R t il t r sodium amyltri eac ion ro no thiocarbgnate with dichloroamyl' tributoxyethoxyethylxansul e c. Thloacids and derivatives 26. Reaction product of sodium amylmonothiocargiimatte with methyl .alphas eara e chlomt o lithium isobutyl- R ct'on roduct of 27 an that with alphabromothiovalerthate w th omega-chloroamy'lsulfoxide pentane 35. Reaction product of potassium amylxanthate with 3-dimethylainino-2- chloropentane b. Nltro compounds 36. Omega-nitroamyl amylxanthate 37. Reaction product of potassium buiylxanthate with nitrochloro parailin wax c. Cyanides, isocyanides, thiocyanides, cyanates 38. Thiocyanato-ethyl laurylxanthate 39. Reaction product of sodium ethoxyethylxanthate with chloroacetonitrile' 40. Reaction product of sodium propylxanthate with omega-chloroamyl isocyam e 41. Reaction product of sodium amylxanthate with omega-chloroamyl cyanate. D. Containing phosphorus 42. Tri (etlioxyethylxanthyl) phosphate 43. Tri(ethoxyethylxanthyl)phosphite 44. Tri (ethoxyethylxanthyl) thiophosphate 45. Methyl butoxyethylxunthyl phosphinostearate 46. Diethylphosphinoethyl amylxanthate E. Containing metals a. Group IV 47. Triethylstannylarnyl amylxanthate 48. Triethylplumbylethyl amyltrithiocarbonate 49. Triamylstannylethyl ethoxyethylxani thate 1:. Group V 50. Diethylarsenylamyl ethylxanthate 51. Diethylantimonylainyl ethylnionothiocarbonate I 52. Diethylbismuthylamyl ethylxanthate 0. Group VI 53. Amylseleniumethyl ethoxyetliylxanthate 54. Amyltelluriumethyl butylxanthate IICarbocyclic types A. Containing oxygen a. Phenols 55. Hydroxyphenyl ethylxantliate 56. omielga-hydroxyphenylamyl 57. Reaction product of potassium amyl xanthate with chlororesorcinol 58. Reaction product of potassium amylxanthate with halogenated parafiin wax substituted phenol b. Alcohols 59. Reaction product of sodium butoxyethylxanthate with o-chlorobenzyl alaniylxancohol 60. Reaction product of sodium butylxanthate with hydroxylated, halogenated phenylated wax c. Ethers 61. Anisyl laurylxanthate 62. Omega-phenoxyamyl amylxanthate 63. Phenoxyphenyl laur lxanthate 64. Reaction product 0 potassium benzylxanthate with chlororesorcinol d1- methyl ether d. Ketones 65. Reaction product of sodium ethylxanthate with chlorobenzophenone' 66. Omega-amylxanthylacetophenone 67. Reaction product of potassium isobutylxanthate with chlorostearoyltetralin e. Aldehydes 68. Reaction roduct of sodium benzylxanthate w th 'o-chlorobenzaldehyde 69. Reaction product of sodium ethoxye' ethyixanthate with omega-chlorotolualdehyde f. Ac gs and salts thate with cinnamic acid dichloride Reaction product of sodium ethylxam thate with chlorine-bearing dinaphth lstearic acid sodium laurylxanthate with o-chlorobenzoylbenzoic acid a. Esters .73. Reaction product of potassium amylxanthate and chlorinated phenyl ben- Reaction product of potassium amylxan- Calc umsalt of the reaction product of 75. Chlorinated wax condensed (Frledel- Crafts) with phcnyi beuzoate and sodium nmylxonthate h. Amides 70. Potassium butoxyethylxanthnte doused with chloro-stearanii ide 77. Chloro-amyixunthylstcnrtoiuidido B. Containing sulfur a. Mcrcuplans and thiophenols 78. Mercapto-dodccahydro-diphenyl xunlhatc 79. Reaction product oi potassium butylmoaothiocarbonate and o-chlorophcnyl ethyhuerca tan and polysu tides b. Sulildes a 85. Reaction product of sodium benzylxanthate with aipliabromothiobutyramidc (l. Sulfones and sulfoxides 86. Reaction product oi potassium octadecylxunthate with chiorodiphenylsullone 87. Reaction product of potassium ethyltrithiocarbonate with chlorodibenzylsulone 88. Reaction product of sodium ethylmono thlocarbonate with chlorodibenzylsulfoxide (l. Containing nitrogen a. Amines 89. Reaction Product of lithium butylxauthate w th chlorodipheuylaminc 90. Reaction product of sodium benzylxair thatc with o-chlorodimethylanilinc h. Nitro compounds 91. Nitrocrosyl thiocarbonate 92. Amyl nitrobenzylxanthato c. Azo compounds 93. Reaction product of potassium amylxanthate with the product of coupling diazotized p-chloroaniline with alphanaphthol I). Containing phosphorus 94. Reaction product of sodium ethoxycthyl trlthiocarbonate with chlorophosphazobenzenc 95'). Reaction product of sodium hutoxyethoxycthylxanthaie with p-chlorophosphinobenzene l'l. Containing metals 06. Reaction product of tri henyl-oniegachloroamyitin with 501 iuui aiuyltrithiocarbonaie 97. Triethylstannyiphenyl bcnzylxanthate 98. Triethylplumbylphenyl ainylxnnthate 99. Ethylmercuriphenyl amylxanthate lib-Heterocyclic types A. Containing oxygen 100. Reaction product of potassium butylxanthate with chlorodioxanc lOl. Reaction product of potassium ethylxandlhutc with chlorodiphenylcne ox: e I02. Reaction product of chlorohydroxythiophene with sodium butoxyethylxanthate B. (Iontaining sulfur 103. Reaction product of potassium ethoxyethylxanthate with chlorothianthrcnc C. Containing nitrogen 104. Reaction product of potassium amyl- -xanthate with nlpha-chloropyridine Any of these compounds or other members of the classes represented may be used within the scope of our invention.

The thiocarbonates have varying degrees of solubility in hydrocarbon and other oils. In some cases it is necessary to.use a solvent for the compound or to form colloidal suspensions of the compound in oil. While some of these compounds have only limited solubility in hydrocarbon oils, it is to be remembered that because of their great efllciency extremely small amounts are often effective. Thus we may use as little as 0.001 'per cent of some of these compounds, and it will be seen that a fairly insoluble material may dissolve to a sufficient extent to be satisfactory for our purpose. In general, more than 0.001 per cent of Reaction product of chlorobouzyldisul-.

omega-,chloroihiotoluic our addition agents are used, and we may add one, two, or even five per cent or more.

Furthermore, it is well known that different types of oils have different capabilities of dissolving a given material. For some purposes therefore, we prefer parafllnic, for other purposes, asphaltic, and for still other purposes, naphthenic or mixed ,base lubricants. Another method of obtaining a satisfactory mixture of addition agent with the hydrocarbon oil is the use of a mutual solvent to bring the addend into solution. Alternatively, peptizing agents may be added to maintain the thiocarbonates in permanent suspension.

Many of the more diillcultly soluble materials are rendered more soluble by the introduction of alkyl groups, particularly those containing four or more carbon atoms. The isoamyl, octyl, lauryl, and octadecyl radicals and radicals from paraffin wax greatly increase the solubility of organic compounds in oil. One or more of such groups may be introduced as required.

It is'sometimes advantageous to combine more than one of these compounds in a blend to obtain particular properties. We accomplish this by mixing two or more of these compounds together and blending the mixture with the hydrocarbon oil or by blending one in the hydrocarbon oil, blending the second into this mixture, and so on until the composition is complete.

The various thiocarbonates usually improve both the film strength and oxidation characteristics of the hydrocarbon oil. For example, the sludging tendencies may be decreased by as little as 0.001 per cent of our thiocarbonates. The

oxidation characteristics of lubricants are very important, and these are markedly improved by our compounds. The ability to reduce friction is another feature contributed to lubricants by some of our compounds.

It may be desirable to include in one and the same blend, in addition to the midlands here described, other addends for specific purposes. Thus, we may add a pour point depressor such as a naphthalenechlor wax condensation product, a viscosity index improver such as certain resins or polymerized hydrocarbons, and sulfur or phosphorus containing inhibitors, such as alkyl and aryl phosphite esters and alkyl and aryl phosphate esters in addition to our thiocarbonates. Furthermore, various metallic compounds may be added to the blend without interfering with the action of our ingredients. Indeed, in some cases it is advantageous to combine with our compounds in'a hydrocarbon oil blend such materials as calcium dichlorstearate, sodium stearate, sodium oleate, sodium chloroleate, tin oleate, sodium naphthenates, tin naphthenate, chromium oleate, aluminum stearate, and other metallic soaps or inorganic-organic salts.

Our invention also contemplates the use in lubricating compositions comprising a major proportion of lubricating oil of minor amounts of the previously identified sulphur compounds with a separate organic halogen compound. The halogen compounds which may thus be employed may be classified as follows:

Cyclic compounds, such as halogenated I-Bcnzeue and related compounds such as:

(1) Halo cnated benzene, e. g.

(a) hlorinated benzene, e. g.

The dlcglorbenzenes, notably the ortho compoun (b) Bromlnated benzene, e. g. Ortbo-dlbrom benzene (0) Fluorinated benzene assassin (2) fialoenated derivatives of benzene such as:

. (o) alogenated homologs of benzene, e. g.- Mono-chlor toluene Mono-chlor xylene Mono-chlor gmene Ethyl monolor benzenes Propvl mono-chlor benzenes Di-ethyl dichlor benzenes Propyl dichlor benzenes Di-ethyl tetrachlor benzenes Halogenated amino derivatives of henzene, e. g. Chlorinated aniline Mono-chlor aniline (preferably the orthocompound) Mono-chlor di-methyl aniline Chlorinated toluidines Chlorinated xylidines Chlorinated diphenylamine Halogenated hydrobenzenes, e. g.

Hydrogenated dichlor-benzenes Dlchlorhexahydrobenzene (Dichlor cyclohexane) iii-Polyphenyls, and related compounds, including diphenyl, diphenyl henzenes, etc., su as (1) Halogenated diphenyl, e. g.

(a) Chlorinated dinhenyl, e. g.

Mono-chlor diphenyls Di-chlor diphenyls Tri-chlor diphenyls (h) Brominated diphenyl, e. g.

The mono-brom diphenyls (c) Fluorinated diphenyl (2) Halogenated derivatives of diphenyl, such as,

(a) Halogenated homologs of dlphenyl, e. g.

Chlorinated phenyl-toluenes Ethylated, or propylnted. chlorinated di phenyl, e. g. (ii-ethyl tetrachlor diphenyl (b) Halogenated amino dervlatives of diphenyl, e. g. Chlorinated phenyl-anilines Chlorinated nhenyl-toluidines Chlorinated diphenyl amines (xenyl amines) (c) Halogenated hydrodiphenyls. e. g.

Chlorinated phenyl hexahydrohenzene Chlorinated dodecahydrodiphenyl III-Naphthalene and related compounds, such as (1) Halogenated naphthalene (a) Chlorinated naphthalene. e. g. -mono-chlor naphthalene (b) Brominated naphthalenes, e. g. -mono brom naphthalene (c) Fluorinated naphthalene (2) Halogenated derivatives of naphthalenes, such as. (a) Halogenated homologs of naphthalenes, e. g. Chlorinated methyl naphthalenes, such as -methyl naphthalene Chlorinated ethyl, propyl, or isopropyl naphthalenes Halogenated amino derivatives thalene, e. Chlorinated nanhthylamines Mono-chlor naphthyl amine Halogenated hydronaphthalenes, e. g. Chlorinated decahydronaphthalene Chlorinated tetrahydronaphthalene IV-Phenanthrene and anthracene and related compounds,

on as:

(1) Chlorinated phenanthrene, chlorinated anthrac n (2) Halogenated derivatives of anthracene, such as: (a) Halogenated homologs, e. g.-

Chlorinated l-methyl phenanthrene Chlorinated 3-methyl phenanthrene Chlorinated 9,10 dimethyl phenanthrene Chlorinated propyl and isopropyl derivatives of phenanthrene such as retene Chlorinated dimethyl anthracenes Chlorinated -methyl anthracene Chlorinated propyl and isopropyl derivatives of anthracene Halogenated amino derivatives, e. g.

Chlorinated phenanthrylamines Chlorinated anthramines (c) Halogenated hydrophenanthrenes and Halogenated hydronnthracenes. e. g. Chlorinated retene oil (contains hydro retene) \Chrysene, picene, and related compounds, including their derivatives. such as homologs, amino derivatives and other substitution 'products.

VL-Bridged' ring compounds, such as the terpenes and related compounds, and their derivatives, 9. g. chlorinated pinene.

VIIHeterocyclic'compounds, such as pyridine, quinoline,

pyrrole,'th ophene, and derivatives of them, e. g. monochlor pyridine.

VIII-Nitriles derived from any of the above compounds, e. g.

Chlorinated:

Benzonitrile Tolunitriles Benzyl cyanide Naphthyl cyanide Xenyl cyanide Cyclohexyl cyanide (b) of 'naph (c) is phenanthrene and ill.

' XMercaptans derived from any oi? the above compounds, e. g.

Chlorinated:

Benzy" mercaptan Pheny beuzyl mercaptans Naphthyl mercaptans Phenyl propyl mercaptans Cyclohexyl mercaptan XL-Thiocyanates, e. g.

Chlorinated Benzyl thiocyanate Phenyl ethyl thiocyanate Phenyl propyl thiocyanate Cyclohexyl thiocyanate Halogen-bearing aliphatic compounds I. Hydrocarbons, e. g. I

Chlorinated or fiuorinated hydrocarbons which contain from four to ten or more carbon atoms and certain others containing less than four carbon atoms, e. g.

Hexachlor ethane Pentachlor ethane Chlor propane Chlor butane Chlor. pentune Fiuor hexane Fluor octane Fluor decane Tetrachlor ethylene 'Hexachlor propylene Chlor butylenes Chlor pentenes Chlorinated unsaturated hydrocarbons obtained from products of partial pyrolytic decomposition of high boiling petroleum hydrocarbons. Chlorinated petroleum wax Chlor nated paraffin wax Chlorinated petrolaturu Chlorinated aliphatic fractlons of mineral oil II. Amines, e. g.

Primary, secondary, and tertiary, e. g. Fluorinated tri-butyl amines Fluorinated tri-amyl amines Fluorinated hexyl amines III. Nitriles, e. g.

Chlorinated or fluorinated Ethyl cyanide Butyl cyanide Octyl cyanide Lauryl nitrile Stearyl nitrile The halogen bearing compounds which may thus be advantageously employe in combination with the sulphur compounds of the type above identified may also desirably containoxygen and such halogen and oxygen bearing organlc compounds may be classified as follows:

Halogen and oxygen-bearing organic ring compounds Oxygen-bearing derivatives of A. Carbon ring" type compounds (1) of the aromatic, or allied type, including oxy en-bearing derivatives of benzene, naphtha ene. anthracene, etc., also compounds of the bridged ring type, such as the terpemes, and related compounds.

(2) of the class including the cycloparaflins, cyclo-olefines, etc. Examples of th1s class are oxygen-bearing derivatives of the following:

(a) Hydrogenation products of benzene (e. g. cyclohexane, cyclohexene, cyclo hexadiene), such as hydrogenated phenol, notably Cyclohexanol Di-hydro phenol Tetra-hydro phenol (b) Hydrogenation products 0 aphthalene (e. g., decahydronaphthalen' tetrahydronaphthalene, etc.), such as the hydrogenated naphthols.

(c)tNaphthenes, such as naphthenic acid,

(3) of'mixed type such as derivatives of indene, hydrindeue, hydranthracene, etc. B. Heterocyclic type compounds (1) of the aromatic or alliedjype including derivatives of pyridine, quinolme, etc. (2) other types such as furane and its derivatltves and derivatives of thiophene, pyrrole, e c.

Alcohols (mono-, di-, and tri-hydric) e. g.

Ethylene chlorhydrin Glyceryl monochlorhydrin Fluorinated octyl alcohol Fluorinated decyl alcohol Fluorinated lauryl alcohol Chlorinated octadecyl alcohol Esters and salts. e.

g. Methyl chlorpropionate Ethyl chlorlaurate Methyl dichlorstearate Chlorinated monoand di-glycol esters of propionic.

lauric, and stcaric acids Chlorinated mono-, di-, and tri-glycernl esters of propionlc, lauric, and stearic acids Methyl dichlorpalmiiate Sodium chlorhydroxy stearate Calcium di-chloro stearate Aluminum di-chloro stcarate l lthers. e. g.

Chlormethyl propyl ether Chlor butyl ether Chlor amyl ether Chlor methyl lauryl ether lxetones, e. g.

Chlormet'nyl ethyl ketone Chlordibutyl ketone Chlor palmitone Chlor laurone Chlor stearone Aldehydes. e. g.

Chlorbutanal Chlor'pentanal Acids. e. g.

Chlornropionic acid Chlorlauric acid Chlormyrisfic acid Chlorpalmitic acid Chlorstearic acid Chlorhydrostearlc acid Chlorricinoleic acid Chlor crotonic acid Chlor acrylic acid I Chlor oleic acid Other halogen containing compounds which may be employed to advantage in lubricating compositions along with thepreviously identified sulphur compounds are as follows:

Halogenated aliphaticoompounds containing sulfur and nitrogen Chlor-lauryl thiocyanide Chlor-butyl thiocyanate I Halogenated aliphatic compounds containing sulfur Chlor-amyl sulfide I Chlor-butyl disulfide While the above compounds have been disclosed primarily as separate halogen compounds which may be used in conjunction with our thiocarbonates, they may also serve another use.

Many of them may be used to react with alkali metal thiocarbonates to. form the substituted thiocarbonates which are the principal products of our invention. For these secondary uses, the halogenin these compounds may be replaced in whole or in part. It will be obvious to those skilled in the art that most .of these compounds,

are useful only, in introducing the second R of ,our thiocarbonates since the first is derived from an alcoholic compound, carbon bisulfide and-a caustic metal hydroxide. Furthermore it will be obviousthat in order to come within the scope of our claims the halogenated hydrocarbons listed above may be used only with such alkali thiccarbonates as contain in the first B group one of the characterizing elements.

Our addends are admirably adapted for use in lubricating oils of all types including those designed for use in automotive crankcases, Diesel oils, and any other .oils of lubricating viscosity. Certain lubricating compositions containing certain of the addition agents above mentioned will 'be found particularly useful in the lubrication bearings formed of cadmium or lead containing bearing metalssuch as, for example, cadmiumsilver and copper-lead bearings. Furthermore, our addends are' advantageously blended in gasoline and other petroleum fuels either directly or after being blended first in a lubricating oil and then added to the fuel. Soap-thickened mineral oils of all types ranging from those showing only a slight increase in viscosity over that, of the mineral oil alone to the semi-solid and solid greases containing fifty per cent or more of soap are amenable to treatment according to our invention. In making these greases,

the usual soaps such as sodium stearate, aluminum stearate, calcium soaps of beta fat, and the like may be used to form the large part of the necessary soap. Various other thickening ingredients or materials for other purposes may be added. These include yarn, hair, graphite, glycerol, water, lampblack, mica, zinc, dust, litharge, and the like,

In making a per cent of the product of Example 19 with gasoline. It is to be understood, however, that. the

hydrocarbon oil in the treated fuels may be of a viscosity of from about 35 seconds at 100,F. S. S. U. to 350 seconds or more and the amount of oil blended with the thiocarbonate to form the fuel addend may vary between 0%.to 99.5%. In some cases the 'fuel may be prepared without adding any. hydrocarbon oil. The quantity of thiocarbonate in the final blended fuel may vary from 0.0001 to 1.0% or slightly more. I

It will be understood that certain features-and sub-combinations may be employed without reference to other species or combinations. This is contemplated by and is within the scope of our claim. It is further obvious that various changes may be made in details within the scope of our claim without departing from the spirit of our invention. It is therefore to be understood that our invention is not to be limited to the details described.

Other 'forms may be employed embodying the features of our invention instead of the one here explained, change being made in the form or construction, provided the elements stated by the following claim or the equivalent of such stated elements be employed.

We therefore particularly point out and distinctly claim as our invention:

A lubricant comprising in combination a major proportion of an oil of'lubricating viscosity and a minor proportion of methyl ethylxanthyl lubricating gasoline, we blend 0.5