US2448037A - Lubricating compositions - Google Patents

Description

Patented Aug. 31, 1948 r LUBRICATING COMPOSITIONS Bert H. Lincoln, Ponca City, and Gordon D. Byrkit, Niagara Falls, N. Y., asslgnors, by means assignments, to

The Lubrl-Zol Development Corporation, Cleveland, Ohio, a corporation of Delaware No Drawing.

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 lubricating oils of high film strength, of high oiliness characteristics, and of low tendency to oxidize during use. present-day 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 pressure, 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 coefficient of friction as low It has been found that the Application December 8, 1944, Serial No. 567,304 0 14 Claims. (Cl. 252-33.6)

is lubricated from a sump by pumping or circulating 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 during 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 suffer 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. v

This high oiliness film gives very even and smooth operation, which may be easily discerned by theexperienced operator or lubricatin englneer.-

When the hydrocarbon lubricants are diluted with unburned fuel or with other light hydroas 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 or at times totally under conditions of boundary or thin film lubrication, under which conditions the oiliness orunctuosity of the lubricant is the first and primary requisite of eflicient operation. Those skilled in the art of lubricant manufacture or machine manufacture will readily appreciate the value of an inventionthat will improve the oiliness 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 acid is particularly corrosive to hearing metals such as cadmium-silver, copper-lead, and the like.

In starting idle mechanical equipment which carbons, 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 hydroca'rbonlubricants 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 preemlnently satisfactory from the standpoint of oxidation in use, it is necessary to refine the oil thorclghly 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 subject to easy oxidation to form soluble acids and other corrosive materials. This can be prevented by the addition to the refined oil of small amounts of materials which either prevent the formation of these corrosive products or by some action render them inert. Furthermore, such well-refined oils are susceptible to the formation during use of lacquer-like materials which tend to stick'ringa This results in blow-by and hence loss of power, failure of lubrication, scratching, scoring, overheating, and eventually replacement of parts. It is practically impossible to refine a lubricant in such a. manner as to avoid all three invention and avoid these difilculties by this method.

Certain compounds are adsorbed or absorbed by metals thus forming tenacious films at the surface of rnetals:.these films are able to stand high pressures. X-ray diflraction methods 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 01' the molecules of hydrocarbon oil when added thereto. A metal immeroed 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. I

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 of oxidation and corrosion for addition to lubricants.

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

A further object of our invention is to provide a lubricant having detergent properties in addition to the above.

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

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 in which'C represents carbon, X represents either oxygen or sulphur (at least one of the X's must be sulphur) and R and R are organic radicles 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, sulphur, selenium, nitrogen, phosphorus, and metallic elements such as tin, arsenic, antimony, bismuth, aluminum, calcium, barium, magnesium, sodium, lithium, 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 tri-thiocarbonates as well as the di-thiocarbonates (xanthates).

The introduction of this characterizing element or elements 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 oxygen or sulphur in such active forms as. for example, halogenated carboxylic or thio-carboxylic acids, their esters, metal salts, ammonia, amine, or aniline salts, as shown in the following type formula:-

in which the substituted thiocarbonate radicle is as described above wherein, however, R's is fur- .ther defined as an organic radicle containing:

etc. c. an alkylated aryl radicle such as o, p-di'iso'emylphenyl cresyl, 2,4di-methylnaphthyl, etc.,

and

tetraaaaseezae eeee.s'ares; NHsRr, etc.; ASRr, PR; etc. where M is a monovalent metal, M is a divalent metal, andM" is a trivalent metal.

It is clear, from the above type formula, that the neutralized halogenated xanthated esters or salts of alkyl, arylalkyhor alkylated arylalkyl fatty acids are among the preferred forms of the additive.

In compounds of this type, we introduce additional active groups beyond the thiocarbonates previously described; thus by the use of halogenated fatty acid esters. we introduce high olliness and load-carrying capacity beyond that obtainable from the thiocarbonates or xanthates alone. Similarly, by the use of halogenated fatty acid or arylated fatty acid metal salts, we introduce detergency not otherwise obtainable from the thiocarbonates or xanthates alone.

Compounds illustrative of these oxygen or sul- I phur containing halogen substituted thiocarbonates are:

. Methyl ethylxanthyl-chlorostearate Barium ethyixanthyl-chlorostearato C alcium amylxanthyl-phenyl chlorostearate in butylxanthyl- .-chlorophenyl chloroecetate zthium ethylxant yl-o. .-di-isoamylphenylchloracetate hiophenyl ethylxanthy chlorostearate 7. Barium amylxanthyl-naphthyl chloromono-thioacetate The additional inhibiting action of phosphorus, nitrogen, or other inhibiting groups may be added to the molecule to produce an extremely effective inhibitor of oxidation and/or corrosion.

Thus nitrogen and/or phosphorus may be introduced as the salt-type compound of the thiooarbonate substituted halogenated fatty acids described above or as otherwise substituted in the molecule. For example, when nitrogen is present in the molecule, it may be present in combination with the halogenated aliphatic or aryl-aliphatlc acid as:

a. Amide, anilide, hydrazide, etc.

are

and Q, is a nitrogen conem having R groups of alkyl, aryl, cycloalkyl, or heterocycllo nature 6. Ammonium salts c. Other salt-type compounds oi the xanthated, halogenated acid and nitrogen bases such as pyridine, quinoline, nitrogen bases from coal tar or petroleum fractions, natural alkaloids, and the like.

The newly introduced element or elements in addition to halogen have a considerable eflect on the activity of the thiocarbonate sulphur and it may be activated or depressed by the use oi. suitable groups in the R's or our thiocarbonates. 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 chlorostearic acid ester group shows a greater eflect as an oiliness agent than the chlorostearate group in, say, methyl chlorostearate plus the same xanthate without the chiorostearate group. Similar unexpected results are obtained on the introduction of metal salts as a detergency factor in addition to halogen, oxygen and/or sulphur and the like as film strength or inhibiting factors.

The particular thiocarbonates of this invention 2 have a multiple action in a lubricant. One action involves increased load-carrying ability and/or oiliness, while other actions are directed to detergency and the stability of the lubricant. For load-carrying capacity, quantities ranging from 0.1 per cent to about per cent may be added. As an anti-corrosive agent and/or an anti-sluding 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 diflicult 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 synthetically 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. it

In practice, it is better to employ compounds whose boiling point is above 225 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 or 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. It 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 comthiocarbonates may be of various types as shown in the following classification. Each of the following organic, or organo-metallic radicles may be combined with mono-, diand tri-thiocarbonateradicles as further examples or our invention.

I. Aliphatic ty as A. Contain goxygen a. Alchohois 4 l. Hydrqxyethyl ethylxanthate 2. Reaction product of potassium laurylxanthate and ilygeirol monochlorohydrin or glycerol dichloroy r n 3. Reaction roduct of potassium ethoxyethylxanthate with ch orinatcd, hydroxylated paraiiln wax which has been chlorinated to 20 per cent chlorine and had half the chlorine removed by treatment with aqueous caustic under pressure to form the hydroxy 8. Reaction product of potassium amylxanthate with chloroacetone 9. Reaction product of potassium amylxanthate with symmetrical dichloroacetone so as to form di(amylxanthylmethybketone 10. Reaction product of potassium amylxanthate withsymmetrical dichloroacetone so as to form amylxanthylmethyl chloromcthyl ketone 11. Unsaponiiiable oxidation products of parailln wax chlorinated and Earl: of the chlorine removed by condensation wit sodium ethylxanthate d. Aldehydes 12. Alpha-butylxanthylbutyraldehydc l3. Alpha-ethoxylethylxanthyloenanthaldehyde e. Acids and salts 14. Alpha-amylxauthylchlorostearic acid 15. Calcium amylxantliylchlorostearate l6. Tin amylxanthylchlorostearate l7. EthoxyethylxanthylBhcnylchlorostearic acid 18. Aluminum ethoxyet ylxanthylphenylchlorostearate Esters l9. n-Butyl ethylxanthylchloroacetate. A mixture oi 65 parts of finely powdered potassium ethylxanthate. 65 parts of n-butyl chloroacetate, and 200 parts of acetone was agitated and heated (or live hours. The acetone solution was drawn oil, concentrated, and the residual oil distilled at 128-135 at one mm. pressure. The product is then halogenated to produce the halogenated additive.

Methyl ethylxanthylchlorostearate. A mixture of 48 parts of ilnely powdered otassium ethylxanthate, 102.5 parts 0! methyl dich orostearate, and parts of acetone was similarly refluxed and separated. The residual oil contained 4.05 per centsulphur. A one per cent blend of this material in a SAE 30 mineral oil showed a Timken film strength of 28 pounds on the arm. The mineral oil alone had a Timken film strength of only 9 pounds on the arm. 0. Amides 2i. Amylxanthylchloro-succindiamide 22. Laurylxanthylchloro-lauramide Containing sulphur a. Mercaptans 23. Mercaptoamyl butoxyethoxyethylxanthate 24. Amylxanthyl mercaptomethylchlorostearate b. sulphides and polysulphides 25. Reaction product of sodium laurylxanthate with beta,

beta prime-dlchloroethyl sulphide v 26. Reaction product of sodium amyltrithiocarbonate with dichloroamyl trisulphide c. Thioacids and derivatives 27. Reaction product of sodium amylmonothiocarbonate with methyl alpha di-chlorothiostearate 0. Containing nitrogen a. Amines 84. Beta-aminochloroethyl ethylxanthate 86. Reaction product potassium octadecyixanthate with :i-amino-Q-ohlcropentano so. Reaction product oi potassium amylxanthate with s-dimethylamino-z-ohloropentane b. Nitro compounds 31. Omega-nitroamyl amylxanthate 38. Reaction roduct oi potassium hutylxanthate with nitro-ch oroaraifln wax c. Cyanidas, isccyan dos, thioc ides, cyanates 39. 'lhloc ate-ethyl laury thate 40. React on roduct oi sodium ethoxyethylxanthate with dic loroacetonitrlle 41. Reaction product oi sodium propylxanthate with omega-chloroamyl isocyanide 42. Reaction product oi sodium amylxanthate with omega-chloroamyl cyanate Containin hosphorus 43. 'Iri et oxyethylxanthyl phosphate 44. Tri ethoxyethylxanthyl phosphite 45. Tri ethox ethylxanthyl thioiihosphate 46. Methyl utoxyethylxanthy phosphlnochlorosteare 47. Diethylphosphinoethyl amylzanthate Containin metals a. Group V 48. Triethylstannylam lamyixanthate 49. Triethylplumb let ylamyltrithiooarbonste b Triarfnylstanny ethy ethoxycthyixanthatc map 61. Diethylarsenylamyl ethylxanthate 52. Diethylantimonylamyl ethylmonothiooarbonate 63. Dieth lblsmuthylamyl ethylxanthat'e c. GroupV s4. Amylseleniumethylethox ethylxanthale 65. Amyltelluriumethyl buty anthate II. Carbocyclic types A. Containing oxygen is Phenols 56. Hydro henylethylxanthate 57. Omegaydroxyphenylamylamylxanthate 58. Reaction product oi potassium amylxanthate with chlororesorcinol 69. Reaction product oi potassium amylxanthate with halogenated paraiiin wax substituted phenol b. Alcohols 60. Reaction groduct oi sodium butoxyathylxanthate witho-c lorobenzyl alcohol 01. Reaction roduct oi sodium but lxanthate with hydroxy ated, halogenated pheny ated wax c. Eth rs 70. Reaction product oi sodium ethoxyethylxanthate with omega-chlorotolualdehyde f. Acids and salts 71. Reaction product oi potassium amylxanthate with cinnamic acid dichloride 72. Reaction roduct oi sodium cthylxanthate with chlorineearing dinaphthylstearic acid 73. Calcium salt of the reaction product oi sodium lauryl E he xanthate with o,p-dichlorobenr.oylbensoic acid a. s rs 74. Reaction product of potassium amylxanthatc and chlorinated phenyl bensoate 76. Phenyl ethoxyethylxanthyl henyichlorostcarate 76. Chlorinated wax condensed (Friedel-Craits) with phenyl bentoatc and sodium amylxsnthatc It. Amides 77. Potassium butoxyethylxanthate condensed with dichloro-stearanilide 78. Amylxanthylchlorosteartoluidide Containing suliur o. Mercaptans and thggghenols 79. Mercapto-dode ydro-diphenylethylxanthate 80. Reaction product of potassium butyl-monothiocarbonate and ogr-dlchlorophenyi ethylmercaptan b. Suliides and polysulfl es 81. Reaction product of dichlorobonzyldisulflde and potassium hexyltrithlocarbonate 82. Reaction roduct oi sodium amyltrithlocarbonate and dich orophenylethyl dlsulilde 83. Reaction Product oi sodium amlyl-monothio-carbonate w th dlchlorodiphenyltris tide 84. Reaction product of tassium amyixanthate with dichlorodi henylsu flde c. 'Thioacids and erivatives 85. Reaction product oi sodium laurylxanthate with omega-d chlorothlotoluic acid 86. Reaction product of sodium benzylxanthate with alphadibromothiobutyramide d. Suliones and sulioxldes 87. Reaction groduct oi potassium octadecylxanthate with dic lorodipheuylsulione' 88. Reaction product of potassium cthyltrithiocarbonate with dichlorodibentylsulions 89. Reaction product oi sodium etliiygmonothiocarbonate with dichiorodibentyisulioxi O. Containlngnitrogon a. Amines 00. Reaction groduct oi lithium butylxanthate with nylamine o,p-dieh orodimcthylaniline pounds 92. Nitrocrasyl thiocarbonste 93. Amyinitrobensylxanthate 0. Aso compounds 94. Reaction product oi potassium am i the roduct oi oouplin diamt roan ine with alpha-nap thol Containing phosphorus thate with o,p'dichlo- 05. Reaction product oi sodium othoxyethyl trithio-- When the end-product contains no halogen, or when the end-product contain less than one atom of chlorine per molecule the product may be subsequently halogenated to preferably contain not less than one atom of chlorine per molecule.

Any of these compounds or other members of the classes represented may be used within the scope 0! our invention.

The thiooarbonates 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 term colloidal suspensions oi. the compound in 011. 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 eirective. 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 suillcient extent to be satisfactory for our purpose. In general, more than 0.001 per cent or our addition agents are used, and we may add one, two, or even five per cent or more. 1 Furthermore, it is well known that diil'erent types. of oils have different capabilities or 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 thiocerbonates in permanent suspension.

Many of the more difllcultly soluble materials are rendered more soluble by the introduction 0! alkyl groups, particularly those containing tour or more carbon atoms. The isoamyl, octyl. lauryl, and octadecyl radicals and radicals from paraflln 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 hydro- 75 carbon oil or by blending one in the hydrocarbon oi sodium benzyixanthate with ano es? v 9 oil, blending the second into this mixture, and so on until the composition is complete.

The .various thiocarbona-tes 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 ieature contributed to lubricants by some of our compounds.

It may be desirable toinclude in one and the some blend, in addition'to the addends scribed, 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 phosphate esters in addition to our thiocarbonates. Furthermore, various metallic compounds may be added to the blend without 1 interfering with the action of our ingredients.

Indeed, in some cases it is advantageous to comblue with our compounds in a hydrocarbon oil blend such materials as calciumdichlorstearate. sodium stearate, sodium oleate, sodium chloroleate, tin oleate, sodium naphthenates, tin naphthenate, chromium oleate, aluminum stearate, aanld other metallic soaps or inorganic-organic 5 ts.

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

compounds, such as halogenated:

Benzene and related compounds each as: (i) Heiogeneted benzene, e. g.

(a) chlorinated benzene, e. g.

the dichlorbenaenes, notably the ortho oom- Cyclic pound (b) brominated benzenem. g. ortho-dibrom benzene (c) fluorinated bensene (2) Halogenated derivatives of benzene such as:

(a) Halogenated bomologs oi benzene, e. g.

mono-chlor toluene mono-chlor xylene mono-chlor c ene ethyl mono-c lor benzenes prop lmono-chlor benzenes diet 1 dichlor benzenes prop dichlor benzenes di-et yl tetrachlor benaenes (h) Halogenated amino derivatives .oi benzene, e. g.

chlorinated aniline mono-chlor aniline (preferably the ortho compound) mono-chlor di-methyl aniline chlorinatedtoluidines chlorinated xylidines chlorinated diphenylamine (c) Halogenated hydrobenzenes, e. g.

hydrogenated dichlor-benzenes dichlorhexahydrobenzene (dichlor cyclohexane) Yolyphenyls, and related compounds, including diphenyl,

diphenyl benzenes, eto., such as: I (l) Halozenated diphenyl, e. g.

(a) Chlorinated diphenyl, e. g.

mono-chlor. diphenyls iii-chlor diphenyls tri-chlor diphenyls (b) Brominated diphenyl. e. g.

the mono-brorn diphenyls (c) Fiuorinated diphenyl (2) Halogenated derivatives of diphenyl, such as:

(a) Halogenated homologs of diphenyl, e. g. chlorinated phenyl-toluenes ethfiated, or propylated, chlorinated dip enyl, e. g. di-ethyl tetrachlor diphenyl (b) Halogenated amino derivatives of diphenyl 0.3.

chlorinated phenyl-amlines chlorinated phenyl-toluidines chlorinated diphenyl amines (xenyl amines) (c) Halogenated hydrodiphenyls, e.g.

chlorinated phenyl hexahydrobenzene chlorinated dodecahydrodiphenyl III. Naphthalene and related compounds, such as:

lease (0) Halozeneted amino derivatives oi naphthalene, e. g.

chlorinated naphthylamines mono-chlor naphthyl amine (c) Halogenated ligdronaphthalenes, e. g.

chlorinate docahydronaphthalene chlorinated tetrahydronaphthelene IV. Phenanthrene and anthracene and related compounds, such as. (1) Chlorinated phenanthrene, chlorinated anthrecene (2) Halogenated derivatives of cone, such as: (a) Halogenated homologs, e. chlorinated i-methylp enanthrene chlorinated 3-methyl phenanthrene chlorinated 9,10 dirnethyl phenanthrene chlorinated progyl and isopropyl derivatives oi p enanthrene such asretene chlorinated dimethyl anthraoenes ohlorinated-methy anthracene chlorinated propyl and isopropyl derivatives oi anthracene (b) Hal ated amino derivatives, 0. g.

c lorinated phenanthrylamines chlorinated anthramines (c) Halogenated hydrophenenthrenes and halogenated hydroanthracenes, e. g.: chlorinated retene oil (contains hydro retene) V. Ohrysene picene and related compounds, ncluding their derivatives, such as homologs, amino derivatives and other substitution products. VI. Bridged ring compounds, such as the ter ass and related compounds, and their derivatives, e. g. c lorinated plnene. VII. Heterooyclic compounds, such as yridine, quinoline, pyrrole glililophene, and derivatives oi t em, e. g. monoohior pyri- VIII. Nitriles derived from any oi the above compounds, 0. g.

Chlorinated benwnitrlle tolunitriles bentyl cyanide naphthyl nlde xenyl cyan de eyclohexyl cyanide from any oi the above compounds, e. g.

irom any of the above compounds, as g.

meroa tan benzy meroaptans mercaptans merceptans x! Tm t mercaptan ana es, e. g. C lorinated:

benzyl thioc anate phenyl ethy thiooyanate phenyl propyl thiocyanate cyclohexyl thiocyanate Halogen-bearing aliphatic compounds:

i. Hydrocarbons, e. g.

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

hexachlor ethane pentachlor ethane chlor ropane chlor utane chlor tane iluor decane tetrachlor ethylene hexachlor propylene chlor butylenes chlor pontenes chlorinated unsaturated hydrocarbons obtained from Broducts of partial pyrolytic decomposition of high oiling petroleum hydrocarbons.

chlorinated petroleum wax chlorinated paraiiln wax chlorinated petrolatum chlorinated aliphatic fractions of mineral oil 11. Amines, e. g.

Primary, secondary, and tertiary, e. g.

fluorinated tri-bptyl amines iiuorinated tri-amyl amines iiuorineted hexyl amines III. Nitriles, e. g.

Chlorinated or fiuorinated ethyl cyanide butyl cyanide oetyl cyanide lauryl nitrile stearyl nitrile phenanthrene and anthra- The halogen bearing compounds which maythus be advantageously employed in combination with the sulphur compounds of the type above identified may also desirably contain oxygen and Halogen and oxygen-bearing organic ring compounds Oiiygen-bearing derivatives of:

. "Carbon ring" type compounds (1) of the aromatic, or allied type, including oxygen-bearing derivatives of benzene, naphthalene. anthracene, etc., also compounds! the bridged ring type, such as the terpenes, and related compounds.

(2) of the class including the cycloparaflflns, cyclo-olelines, etc. Examples of this class are oxygen-bearing derivatives of the iollowing:

(a) Hydrogenation products oi benzene (e. g. cyclohexane, cyclohexene, cyclohexadiene), such as hydrogenated phenol, notably cyclohexenol di-hydro phenol tetra-hydro phenol (b) Hydro enation products of naphthalene (e. g., decahydronaphthalene, tetra-hydronaphthalene, etc), such as the hydrogenated naphthols.

(c) Naphthenes, such as naphthenic acid, etc. (3) oi mixed type such as derivatives of indene, hydrindene,

hydranthracene, etc. B. "Heterocyclic" type compounds (l) of the aromatic or allied type including derivatives of pyridine, quinoline, etc. (2) other types such as iurane and its derivatives and derivatives oi thiophene, pyrrole, etc.

Halogen and oxygen-bearing aliphatic compounds Alcohols (mono-, di-, and tri-hydric) e. g.

ethylene chlorhydrin glyceryl monochlorhydrin 1 fluorinated octyl alcohol lluorinated decyl alcohol fluorinated lauryl alcohol chlorinated cctadecyl alcohol Esters and salts, e. g.

methyl chlorpropionate ethyl chlorlaurate methyl dichlorstearete chlorinated monoand di-glycol esters oi propionic, lauric,.and

stearic acids chlorinated mono-, di-, and tri-glyceroi esters of propionic, lauric,

and stearic acids methyl dichlorpaimitate sodium chlorhydroxy stem-ate calcium di-chloro stearate aluminum di-chloro stearate Ethers, e. g.

chlormethyl propyl ether chlor butyl ether chlor amyl ether chlor methyl lauryl ether Keto as, e. g.

:ormethyl ethyl ketone ordibutyl ketone or almitone chlor aurone chlor stearone Aldehydes, e. g.

chlorbutanal chlorpentanal Acids, e. g.

chlorpropionic acid chlorlauric acid chlormyristic acid chlorpalmitic acid chlorsteeric acid chlorricinoleic acid chlor crotonic acid chlor acrylic acid chlor oleic acid (5 O or an:

Other halogen containing compounds which may be employed to advantage in lubricating compositions along with the previously identified sulphur compounds are as follows:

Halogenated aliphatic hosphorus-contalning compounds chlor-lauryl hosp ine chlor-octyl p osphine chlor-di-ethyl di-thiophosphine sulfide chlor-amyl phosphite chlor-butyl phosphate chlor-lauryl phosphite chlor-leuryl thiophosphate chlor-lauryl tliiophosphite Halogenated aliphatic compounds containing sulfur and nitrogen chlor-lauryl thiocyanide chlor-butyi thiocyanate Halogenated aliphatic compounds containing sulfur chlor-amyl sulfide chlor-butyl disulflde 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 halogen in 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 disulflde and a. caustic metal hydroxide. Furthermore it'will be obvious that in order to come within the scope of our claims the halogenated hydrocarbons listed above may be used only with such alkali thiocarbon ates as contain in the first R group one of the characterizing elements.

Our addends are admirably adapted for use in lubricating oils of all types including these 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 metals such 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 lubricating gasoline, we blend 0.5 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 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.

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 claims. It is further obvious that various changes may be made in details within the scope of our claims 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.

This application is a continuation-in-part of our copending application Serial No. 298,337, fiied October 6, 1939, now Patent No. 2,368,670 dated February 6, 1945.

Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of the following claims or the equivalent of such be employed.

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

1. A lubricant comprising in combination a major amount of oil of lubricating viscosity and from 0.001% to 10% of an oil-soluble neutralized organic carboxylic acid bearing a thiocarbon'ate radicle having theformula:

where C represents carbon; X is an element se lected from the class consisting of oxygen and sulphur, at least one X is sulphur; Y is a halogen; R is an organic radicle; and Q is one hydrogen equivalent of a sole-forming radicle.

2. A lubricant comprising in combination a major amount of oil of lubricating viscosity and from 0.001% to 10% of anoil-soluble compound having the formula:

in which C represents carbon; X is an element selected from the class consisting of oxygen and sulphur, at least one X is sulphur; Y is a halo- ,gen; It is an organic radicle, and Q is a'radicle containing trivalent nitrogen.

3. A lubricant comprising in combination a major amount of oil of lubricating viscosity and 1rom 0.001% to 10% of an oil-soluble compound having the formula:

in which C represents carbon; X is an element selected from the class sulphur, at least one X is sulphur; Y is a halogen; R is an organic radicle; and Q" is a radicle containing pentavalent nitrogen.

4. A lubricant comprising in combination a major amount of an oil of lubricating viscosity and a minor amount, suflicient to improve the extreme pressure characteristics of the oil, of an oil soluble neutralized organic carboxylic acid bearing a thio-carbonate radicle having the formula: I

where 0 represents carbon; X is an element selected from the class consisting of oxygen and sulphur, at least one X is sulphur; Y is a halogen; R is an organic radicle; and Q is one equivalent ot a metal.

5. A composition in accordance with claim 1 in which Q is one equivalent of a non-metallic salt-iorming radicle.

consisting of oxygen and,

' Number 6. A composition in accordance with claim 1 in which Q is one equivalent of an organo-metallic radicle.

7. A composition in accordance with claim 1 in which at least one X in the grouping BX'(3X is sulphur.

8. A composition in accordance with claim 1 in which Q is an organo-metallic radicle and at least one X in the grouping R-X("3X is sulphur.

9. A composition in accordance with claim 1 in which at least two X's in the grouping R-X-("JX are sulphur.

10. A composition in accordance with claim 1 in which Q is an organo-metallic radicle and at least two Xs in the grouping 11. A composition in accordance with claim 1 in which at least 3 XS in the grouping R-X("3X- are sulphur.

12. A composition in accordance with claim 1 in which Q is an organo-metallic radicle and at least 3 X5 in the grouping n-x-tr-xare sulphur.

13. A composition in accordance with claim 1 in which R is aliphatic.

-14. A composition in accordance with claim 1 in which R is aliphatic and Q is an organo-metallic radicle.

BERT H. LINCOLN.

GORDON p. BYRKIT.

REFERENCES CITED The following references are of record in the iile of this patent:

UNITED STATES PATENTS Name Date I 2,153,496 Berger Apr. 4, 1939 2,158,668 Rosen .May 16, 1939 2,197,835 Reifl Apr. 23, 1940 2,257,750 Lincoln Oct. '7, 1941 2,288,238 Lincoln June 30, 1942 2,289,795 McNab July 14, 1942 2,320,287 Lieber May 25, 1943 2,365,011 Rosen Dec. 12, 1944 2,368,670 Lincoln. et al Feb. 6, 1945 2,369,150 Lincoln et a1. Feb. 13, 1945