US3340329A

US3340329A - Amine salts of oxyalkylenated hydroxyhydrocarbon thiophosphates

Info

Publication number: US3340329A
Application number: US330003A
Authority: US
Inventors: Anthony J Guarnaccio; Edwin J Latos
Original assignee: Universal Oil Products Co
Current assignee: Universal Oil Products Co
Priority date: 1963-12-12
Filing date: 1963-12-12
Publication date: 1967-09-05
Anticipated expiration: 1984-09-05

Description

United States Patent 3,340,329 AMINE SALTS 0F OXYALKYLENATED HY- DROXYHYDROCARBON THIOPHOSPHATES Anthony J. Guarnaccio, Niles, and Edwin J. Latos, Chicago, Ill., assignors to Universal Oil Products Company, Des Plaines, 111., a corporation of Delaware No Drawing. Filed Dec. 12, 1963, Ser. No. 330,003

11 Claims. (Cl. 260-925) This application relates to novel compositions of matter comprising amine salts of oxyalkylenated hydroxyhydrocarbon thiophosphates and to the use thereof as additives to organic substrates.

As will be set forth in detail hereinafter, the novel compound of the present invention is particularly advantageous for use as an additive to lubricating compositions comprising a major proportion of an oil of lubricating viscosity. A specific example of such a lubricating composition is E.P. (extreme pressure) lubricating oil used, for example, in the lubrication of hypoid gears, in which service the oil must meet the severe requirements of high torque-low speed, low torque-high speed and high torque-high speed conditions. These requirements are even more severe because such oils must perform satisfactorily for long periods of time which may be as high as 100,000 miles or more and even for the life of the vehicle.

In a preferred embodiment the novel compound of the present invention is believed to be of the following formula:

where O is oxygen, P is phosphorus, S is sulfur, H in hydrogen, X is selected from the group consisting of oxygen and sulfur, n is an integer of from 1 to 40, R is a hydrocarbon group, R is alkylene, A is amine and B is selected from the group consisting of hydrogen, the same as the bracketed group and the same as A. When X is oxygen, B is the same as the bracketed group. When X is sulfur, B is hydrogen or the same as A-.

A preferred embodiment is illustrated in the formula set forth below:

where O is oxygen, P is phosphorus, S is sulfur, H .s hydrogen, N is nitrogen, B is the same as the bracketed group, n is an integer of from 1 to 40, R is a hydrocarbon group, R is alkylene, R" is hydrocarbon or substituted hydrocarbon group, and R' is hydrogen, hydrocarbon or substituted hydrocarbon group.

In a preferred embodiment, R is selected from alkylphenyl and aliphatic groups. In the alkylphenyl species, 1, 2 or 3 alkyl groups of from 4 to 30 and, more particularly, from 6 to 15 carbon atoms each, will be attached to the phenyl ring. Illustrative preferred alkylphenyl groups include hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, tridecylphenyl, tetradecylphenyl, pentadecylphenyl, etc., dihexylphenyl, diheptylphenyl, dioctylphenyl, dinonylphenyl, didecylphenyl, diundecylphenyl, didodecylphenyl, etc., trihexylphenyl, triheptylphenyl, trioctylphenyl, trinonylphenyl, tridecylphenyl, etc. It is understood that the alkyl groups attached to the phenyl group may be of 3,340,329 Patented Sept. 5, 1967 primary, secondary or tertiary configuration, the primary and secondary configurations generally being preferred. In another embodiment the alkylphenyl radical may contain one or more alkyl groups containing 4 to 30 carbon atoms and one or more alkyl groups containing less than 4 carbon atoms and selected from methyl, ethyl and propyl. When one alkyl group is attached to the phenyl ring, it preferably is in the position para to the oxygen. When two alkyl groups are attached to the phenyl ring, they preferably are in the 2,4- or 3,5-positions.

Where R is an aliphatic group, it preferably contains from 6 to 40 carbon atoms and, more particularly, from 10 to 30 carbon atoms. Illustrative preferred aliphatic groups include decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, oc-tadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, etc. In general, it is preferred that the aliphatic group is saturated. In another embodiment, the aliphatic group may be unsaturated and will be selected from olefinic radicals corresponding to the saturated radicals hereinbefore specifically set forth. The aliphatic group may be straight chain or may contain branching in the chain.

R in the above formula is an alkylene group and may contain from 1 to 10 and preferably from 2 to 4 carbon atoms per group. The preferred alkylene radicals thus are ethylene, propylene and butylene. As hereinbefore set forth, n is an integer of from 1 to 40 and preferably of from 2 to 15.

As hereinbefore set forth, the novel additive of the present invention is an amine salt of an oxyalkylenated hydroxyhydrocarbon thiophosphate. Referring to the above general formula, when X is sulfur and B is hydro: gen or the same as A, the additive comprises the amine salt of the mono-(oxyalkylenated hydroxyhydrocarbon) thiophosphate. When X is oxygen and B in the above formula is the same as the bracketed group (oxyalkylenated hydroxyhydrocarbon), the additive of the present invention comprises the amine salt of the di-(oxyalkylenated hydroxyhydrocarbon)thiophosphate. It is understood that a mixture of the amine salt of the mono= (oxyalkylenated hydroxyhydrocarbon) thiophosphate and of the amine salt of the di-(oxyalkylenated hydroxy-. hydrocarbon) thiophosphate may be employed and also that a mixture of difierent amines may be used in preparing these additives.

Any suitable amine may be used and contains from 2 to 50 carbon atoms or more and preferably from 8 to 20 carbon atoms. The amine may be a monoamine or polyamine. Preferred monoamines include octyl amine, nonyl amine, decyl amine, undecyl amine dodecyl amine, tridecyl amine, tetradecyl amine, pentadecyl amine, hexaa decyl amine, heptadecyl amine, octadecyl amine, nonadecyl amine, eicosyl amine, etc. The amines may be prepared from fatty acid derivatives and, thus, may comprise tallow amine, hydrogenated tallow amine, lauryl amine, stearyl amine, oleyl amine, linoleyl amine, coconut amine, soya amine, etc.

Of the polyamines, N-alkyl diaminoalkanes are prea ferred. A particularly preferred amine of this class comprises an N-alkyl-1,3-diaminopropane in which the alkyl group contains from about 8 to about 25 carbon atoms. A number of N-alkyl diaminoalkanes of this class are available commercially, such as Duomeen T and Diam 26 in which the alkyl group is derived from tallow and contains from about 12 to about 20 carbon atoms per group and mostly 16 to 18 carbon atoms. Other N-alkyL 1,3-diaminopropanes may be prepared to contain any number of carbon atoms desired in the alkyl group and thus the alkyl group is selected from hexyl, heptyl, octyl,

nonyl, decyl, unclecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc.

While the N-alkyl-l,3-diaminopropanes are preferred, it is understood that other suitable N-alkyl diaminoalkanes may be employed. Illustrative examples include N-alkyl- 1,2-diaminoethane, N-alkyl-1,2-diaminopropane, N-alkyl- 1,2-diaminobutane, N-alkyl-l,3-diaminobutane, N-alkyl-l, 4-diaminobutane, N-alkyl1,2-diaminopentane, N-alkyl-l, B-diaminopentane, N-alkyl-l,4-diaminopentane, N-alkyl-l, S-diaminopentane, N-alkyl-1,Z-diaminohexane, N-alkyl-l, 3-diaminohexane, N-alkyl-1,4-diaminohexane, N-alkyl-l, S-diaminohexane, N-alkyl-l,6-diaminohexane, etc. Other polyamines include ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, heptylenediamine, octylenediamine, etc., diethylenetriamine, dipropylenetriamine, dibutylenetriamine, dipentylenetriarnine, dihexylenetriamine, dipheptylenetriamine, dioctylenetriamine, etc., triethylenetetraamine, tripropylentetraamine, tributylenetetraamine, tripentylenetetraamine, trihexylenetetraamine, triheptylenetetraamine, trioctylenetetraamine, etc., tetraethylenepentaamine, tetrapropylenepentaamine, tetrabutylenepentaamine, tetrahexylenepentaamine, tetraheptylenepentaamine, tetraoctylenepentaamine, etc., pentaethylenehexaamine, pentapropylenehexaamine, pentabutylenehexaamine, pentapentylenehexaamine, pentahexylenehexaamine, pentaheptylenehexaamine, pentaoctylenehexaamine, etc.

In other embodiment the amine is an aromatic amine. Aromatic monoamines include aniline, toluidines, xylidines, etc., naphthylamine, anthracylamine, rosin amine, etc., as well as the N-monoand N,N-di-alkylated aromatic amines in which the alkyl group or groups contain from 1 to carbon atoms or more. Illustrative examples of such compounds include N-methylaniline, N,N-di-methylaniline, N-ethylaniline, N,N-di-ethylaniline, N-propylaniline, N,N-di-pyropylaniline, N-butylaniline, N,N-dibutylaniline, N-amylaniline, N,N-di-amylaniline, N-hexylaniline, N,N-di-hexylaniline, N-heptylaniline, N,N-diheptylaniline, N-octylaniline, N,N-di-octylaniline, N-nonylaniline, N,N-di-nonylaniline, N-decylaniline, N,N,-didecylaniline, N-undecylaniline, N,N-di-undecylaniline, N- dodecylaniline, N,N-di-dodecylaniline, etc., as Well as the corresponding substituted toluidines, xylidines, naphthylamines, anthracylamines, etc.

In still another embodiment the amine may contain halogen as, for example, in compounds such as chloroaniline, 2,3-dichloroaniline, 2,4-dichloroaniline, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, bromoaniline, 2,3-dibro-moaniline, 2,4-dibromoaniline, 2,5-dibromoaniline, 2,6-dibromoaniline, 3, 4-dibromoaniline, 3,5-dibromoaniline, etc.

In another embodiment the aromatic amine is a diarylamine including, for example, diphenylamine, aminodiphenylamine, diaminodiphenylamine, dinaphthylamine, aminodinaphthylamine, diaminodinap-hthylamine, etc. In the polyamino aromatic compounds, the nitrogen atoms may be in the position ortho-, metaor parato each other. The amino or diaminodiphenylamines may contain alkyl groups attached to one or both nitrogen atoms and the alkyl groups may contain from 1 to or more carbon atoms each. Illustrative compounds include p,p-di-methylaminodiphenylamine, p,p'-di-ethylaminodiphenylamine, p, p di propylaminodiphenylamine, p,p'-di-butylaminodiphenylamine, p,p'-di-amylaminodiphenylamine, p,p'-dihexylaminodiphenylamine, p,p' di-heptylaminodiphenylamine, p,p-di-octylaminodiphenylamine, p,p'-di-nonylaminodiphenylamine, p,p di-decylaminodiphenylamine, etc., o,p'-di-methylaminodiphenylamine, o,p'-di-ethylaminodiphenylamine, o,p'-di-propylaminodiphenylamine, o, p-di-butylaminodiphenylamine, -o,p'-di-amy1aminodiphenylamine, o,p'-di-hexylaminodiphenylamine, o,p'-di-heptylaminodiphenylamine, o,p'-di-octylaminodiphenylamine, o, p di-nonylaminodiphenylamine, o,p-di-decylarninodiphenylamine, etc., N-alkyldiaminodiphenylamine, N,N,N-

trialkyldiaminodiphenylamine, N,N,N',N-tetralkyldiaminodiphenylamine, etc.

In still another embodiment the amine comprises such compounds as aminodiphenyl ether, N-alkylaminodiphenyl ether, N,N-dialkylaminodiphenyl ether, N,N,N'-trialkyl aminodiphenyl ether, N,N,N'N'-tetralkylaminodiphenyl ether, aminodiphenyl sulfide, N-alkylaminodiphenyl sulfide, N,N-dialkylaminodiphenyl sulfide, N,N,N'-trialkylaminodiphenyl sulfide, N,N,N,N'-tetralkylaminodiphenyl sulfide, aminodiphenylmethane, N-alkylaminodiphenylmethane, N,N'-dialkylaminodiphenyhnethane, N,N,N'- trialkylaminodiphenylmethane, N,N,N',N-tetralkylaminodiphenylmethane, aminodiphenylethane, N-alkylaminodiphenylethane, N,N-dialkylaminodiphenylethane, N,N,N'- trialkylaminodiphenylethane, N,N,N,N'-tetralkylaminodiphenylethane, aminodiphenylpropane, N-alkylaminodiphenylpropane, N,N'-dialkylaminodiphenylpropane, N,N, N trialkylaminodiphenylpropane, N,N,N',N'-tetralkylaminodiphenylpropane, aminodiphenylbutane, N-alkylaminodiphenylbutane, N,N'-dialkylaminodiphenylbutane, N,N,N' trialkylaminodiphenylbutane, N,N,N',N-tetralkylaminodiphenylbutane, etc., in which the alkyl group or groups contain from 1 to 20 or more carbon atoms each.

In still another embodiment the amine may contain other substituents and particularly sulfur. The additional sulfur in the amine and, accordingly, in the final product may be of advantage when the product is used as an additive in lubricating oil or other substrate in which additional sulfur is desired. In one embodiment the sulfurcontaining amine is prepared by reacting carbon disulfide with the amine, and particularly with an N-alkylated or N,N-di-alkylated alkylene polyamine. Particularly preferred substituted amines in this embodiment include the product formed by reacting carbon disulfide with N,N'- dialkyl-ethylenediamine or with N ,N -dialkyl-diethylenetriamine. The reaction is effected by dissolving the amine in a suitable solvent such as benzene, toluene, etc., pentane, hexane, heptane, etc., cooling the solution to about 50 F. or lower and gradually adding an equal mole ratio of carbon disulfide dissolved in a suitable solvent and preferably the same solvent as used to dissolve the amine. The reaction is highly exothermic and the temperature is controlled by cooling in an ice bath or otherwise. In most cases the reaction mixture solidifies, apparently forming an inert salt. The reaction mixture is heated to a temperature of from about 300 to about 350 F. to remove the solvent and to eliminate hydrogen sulfide, resulting in the formation of the corresponding imidazolidinethione. The product is recovered as an amber clear liquid. It is understood that other sulfur-containing amines which react with the oxyalkylenated hydroxyhydrocarbon thiophosphate may be used in accordance with the present invention.

It is understood that a mixture of amines may be employed and that the different amines are not necessarily equivalent, but all of them will serve to produce effective additives.

The compound of the present invention is prepared in any suitable manner. In a preferred method, the hydroxyhydrocarbon, including particularly alkylphenol or aliphatic alcohol, is oxyalkylenated by reacting with alkylene oxide, including particularly ethylene oxide, in the molar ratios to produce. an oxyalkylenated hydroxyhydrocarbon containing the oxyalkylene group in the desired proportion. As hereinabove set forth, in a preferred embodiment the additive contains from 2 to 15 oxyalkylene groups. The oxyalkylenation is effected in any suitable manner and generally will be conducted at a temperature of from about room temperature to about 350 F. and more particularly from about 200 to about 300 F. When polyoxyalkylenation is desired, the reaction is effected in the presence of a catalyst such as sodium hydroxide, potassium hydroxide, tertiary amine, quaternary hydroxide, etc. When the oxyalkylenation is to be limited to the addition of one oxy group, the catalyst is used with the alkanols but may be omitted with the alkylphenols. Superatmospheric pressure may be employed, which may range from to 1000 pounds or more.

The oxyalkylenated hydroxyhydrocarbon then is reacted in any suitable manner with phosphorus pentasulfide or other suitable phosphorus sulfide to form the desired phosphate. At the present time there are different schools of thought as to the structure of phosphorus pentasulfide. It is believed to be P 8 but also has been expressed as P 8 Various structures have been proposed including a polymeric cage-like configuration. Regardless of the exact structure of this compound, phosphorus pentasulfide is available commercially and is used for reaction with the oxyalkylenated hydroxyhydrocarbon in the manner herein set forth. In the interest of simplicity, phosphorus pentasulfide is also referred to in the present specifications as P 8 with the understanding that this is intended to cover the phosphorus pentasulfide available commercially or prepared in any suitable manner.

In a preferred embodiment the compound of the present invention is an amine salt of a di-(oxyalkylenated hydroxyhydrocarbon)-dithiophosphate (B in the above formula corresponding to the bracketed group) and is prepared by the reaction of four mole proportions of the oxyalkylenated hydroxyhydrocarbon with one mole proportion of P 8 Generally, an excess of P 5 is used in order to insure complete reaction, which excess usually will not be above about 25% by weight of the stoichiometric amount of P 8 The reaction conveniently is effected by heating the oxyalkylenated hydroxyhydrocarbon and, with intimate stirring, adding the P 8 thereto, preferably in in cremental portions. The reaction is effected by refluxing the mixture of reactants to effect formation of the di-(oxyalkylenated hydroxyhydrocarbon) dithiophosphate with the liberation of one mole proportion of hydrogen sulfide.

The reaction preferably is effected in the presence of a solvent and the temperature of refluxing accordingly will depend upon the specific solvent used. Any suitable solvent may be employed. Preferred solvents comprise aromatic hydrocarbons and include particularly benzene. When using benzene as the solvent, the refluxing temperature will be in the order of 175 F. Other aromatic solvents include toluene, xylene, ethyl benzene, cumene, etc., or mixtures thereof. In another embodiment the solvent may comprise a paraflinic hydrocarbon or mixtures thereof which preferably are selected from hexane, heptane, octane, nonane, decane, undecane, dodecane, etc. As herein before set forth, the refluxing temperature will depend upon the particular solvent employed and thus may range from about 140 and preferably should not exceed about 215 F. The reaction maybe effected at atmospheric pressure or, when desired, at subatmospheric pressure or superatmospheric pressure.

Hydrogensulfide is formed in the above reaction and preferably is continuously removed from the reaction zone. After completion of the reaction, the reaction mass may be filtered to remove unreacted P 8 if any. In one embodiment the product may be recovered in solution in the benzene or other solvent or, when desired, the benzene solvent may be removed in any suitable manner such as by distillation, preferably under vacuum. The di- (oxyalkylenated hydroxyhydrocarbon)-dithiophosphate is recovered as a liquid of medium viscosity.

While the di-(oxyalkylenated hydroxyhydrocarbon)-dithiophosphate is a preferred reactant for forming the amine salt, it is understood that the use of the mono- (oxyalkylenated hydroxyhydrocarbon) dithiophosphate also is comprised Within the scope of the present invention, as well as the monoand/or di-(oxyalkylenated hydroxyhydrocarbon)-monothiophosphate. The latter compound may be prepared, for example, by reacting di- (oxyalkylenated hydroxyhydrocarbon)-phosphite or the sodium salt thereof with free sulphur.

As hereinbefore set forth, the novel additive of the present invention is the amine salt. The amine salt is prepared in any suitable manner and is readily prepared by slowly adding the amine to the free acid form of the thiophosphate with intimate stirring. When the amine is a solid, it may be heated to melt the same. The reaction is effected at any suitable temperature, and preferably as low as practical. The temperature, therefore, preferably is within the range of from room temperature to 250 F. and more particularly to 150 F. In general, the neutral salt is preferred and is prepared by using equivalent amine and acid groups. Accordingly, this will depend upon whether a monoamine or polyamine is used and whether the monoor di (oxyalkylenated hydroxyhydrocarbon) thiophosphate is used in preparing the .salt. When the basic salt is desired, an excess of amine per acid group will be used and, when the acid salt is desired, a deficiency of amine per acid group is employed in forming the salt. Generally the amine salt will be recovered as a viscous liquid.

Illustrative preferred compounds of the present invention include the amine salts of di-(oxyethylenated alkylphenol)-dithiophosphates containing from 2 to 15 oxyethylene groups. The preferred amines include stearyl amine and oleyl amine as illustrative of the fatty acid amines, N-tallow-1,3-diaminopropane as illustrative of the N-alkyl-diaminoalkanes, and the reaction products of carbon disulfide with N,N-dioctyl-ethylenediamine, with N ,N -dioctyl-diethylenetriamine or with N ,N -triethylenetetramine as illustrative of the carbon disulfideamine reaction product. Preferred di-(oxyethylenated alkylphenol)-dithiophosphates for use in preparing the amine salts include di-(oxyethylenated octylphenol)-dithiophosphate containing from two to fifteen oxyethylene groups, di (oxyethylenated dioctylphenol) dithiophosphate containing from two to fifteen oxyethylene groups, di (oxyethylenated nonylphenol) dithiophosphate containing from two to fifteen oxyethylene groups, di-(oxyethylenated dinonylphenol) -dithiophosphate containing from two to fifteen oxyethylene groups, di-(oxyethylenated decylphenol)-dithiophosphate containing from two to fifteen oxyethylene groups, di-(oxyethylenated didecylphenol)-dithiophosphate containing from two to fifteen oxyethylene groups, di-(oxyethylenated undecylphenol)- dithiophosphate containing from two to fifteen oxyethylene groups, di-(oxyethylenated diundecylphenol)-dithiophosphate containing from two to fifteen oxyethylene groups, di (oxyethylenated dodecylphenol) dithiophosphate containing from two to fifteen oxyethylene groups, di (oxyethylenated didodecylphenol) dithiophosphate containing from two to fifteen oxyethylene groups, etc., corresponding di (oxypropylenated alkylphenol)-dithiophosphates, etc. As hereinbefore set forth, the alkyl group or groups attached to the phenyl ring preferably are of primary or secondary configuration.

Preferred di-(oxyalkylenated aliphatic alcohol)-dithiophosphates for use in forming the amine salts include di (oxyethylenated decanol) dithiophosphate, di-(oxyethylenated undecanol)-dithiophosphate, di-(oxyethylenated dodecanol) dithiophosphate, di (oxyethylenated tridecanol)-dithiophosphate, di-(oxyethylenated tetradecanol)-dithiophosphate, di-(oxyethylenated pentadecanol)- dithiophosphate, di-(oxyethylenated hexadecanol)-dithiophosphate, di-(oxyethylenated heptadecanol)-dithiophosphate, di-(oxyethylenated octadecanol)dithiophosphate, di-(oxyethylenated nonadecanol) dithiophosphate, di- (oxyethylenated eicosanol) -dithiophosphate, di-(oxyethylenated heneicosanol)-dithiophosphate, di-(oxyethylenated docosanol) dithiophosphate, di (oxyethylenated tricosanol) dithiophosphate, di (oxyethylenated tetracosanol) dithiophosphate, di (oxyethylenated pentacosanol) dithiophosphate, di (oxyethylenated hexacosanol) dithiophosphate, di (oxyethylenated heptacosanol) dithiophosphate, di (oxyethylenated octacosanol) dithiophosphate, di (oxyethylenated nonacosanol)-dithiophosphate, di- (oxyethylenated triacontanol)-dithiophosphate, etc., corresponding di-(oxypropylenated alkanol)-dithiophosphates, etc.

Conveniently the final product is recovered as a solution in a suitable solvent and is used in this manner as an additive to an organic substrate. However, when the product is recovered in the absence of a solvent or when the product is not sufficiently soluble in the substrate, the desired solubility may be obtained by dissolving the compound in a mutual solvent. Suitable solvents for this purpose comprise phenols and particularly alkylphenols or 'ployalkylphenols in which the alkyl groupor groups contain from six to twenty carbon atoms. The phenol may be used in a concentration from from about and preferably from about 25% to about 500% by weight, and more particularly from about 30% to about 200% by weight of the product of the present invention.

The amine salt of the oxyalkylenated hydroxyhydrocarbon thiophosphate will have varied utility and is useful as an additive to organic substrates which undergo oxidative deterioration. In addition, the additive serves as a detergent-dispersant, peroxide decomposer, etc. Organic substrates includes gasoline, naphtha, kerosene, jet fuel, lubricating oil, diesel fuel, fuel oil, residual oil, drying oil, grease, wax, resin, plastic, rubber, etc.

The amine salt of the oxyalkylenated hydroxyhydrocarbon thiophosphate is advantageously used as an additive in lubricating oil, particularly when the lubricating oil is subjected to extreme temperature conditions. The lubricating oil may be of natural or synthetic origin. The mineral oils include those of petroleum origin and are referred to as motor lubricating oil, railroad type lubricating oil, marine oil, transformer oil, turbine oil, differential oil, diesel lubricating oil, gear oil, cylinder oil, specialty products oil, etc. Other natural oils include those of animal, marine or vegetable origin.

The lubricating oils generally have a viscosity Within the range of from SUS at 100 F. to 1000 SUS at 210 F. (SAE viscosity numbers include the range from SAE 10 to SAE 160). The petroleum oils are obtained from parafiinic, naphthenic, asphaltic or mixed base crudes. When highly paraflinic lubricating oils are used, a solubilizing agent also is used.

Synthetic lubricating oils are of varied types including aliphatic esters, polyalkylene oxides, silicones, esters of phosphoric and silicic acids, highly fluorine-substituted hydrocarbons, etc. Of the aliphatic esters, di-(Z-ethylhexyl) sebacate is being used on a comparatively large commercial scale. Other aliphatic esters include dialkyl azelates, dialkyl suberates, dialkyl pimelates, dialkyl adipates, dialkyl glutarates, etc. Specific examples of these esters include dihexyl azelate, di-(Z-ethylhexyl) azelate, di-3,5,5-trimethylhexyl glutarate, di-3,5,5-trimethylpentyl glutarate, di-(2-ethylhexyl) pimelate, di-(Z-ethylhexyl) adipate, triamyl tricarballylate, pentaerythritol tetracaproate, dipropylene glycol dipelargonate, 1,5-pentanedioldi-(2-ethylhexanonate), etc. The polyalkylene oxides include polyisopropylene oxide, polyisopropylene oxide diether, polyisopropylene oxide diester, etc. The silicones include methyl silicone, methylphenyl silicone, etc., and the silicates include, for example, tetraisooctyl silicate, etc. The highly fluorinated hydrocarbons include fluorinated oil, perfluorohydrocarbons, etc.

Additional synthetic lubricating oils include (1) neopentyl glycol esters, in which the ester group contains from three to twelve carbon atoms or more, and particularly neopentyl glycol propionates, neopentyl glycol butyrates, neopentyl glycol caproates, neopentyl glycol caprylates, neopentyl glycol pelargonates, etc., (2) trimethylol alkanes such as trimethylol ethane, trimethylol propane, trimethylol butane, trimethylol pentane, trimethylol hexane, trimethylol heptane, trimethylol octane, trimethylol decane, trimethylol undecane, trimethylol dodecane, etc., as well as the esters thereof and particularly triesters in which the ester portions each contain from three to twelve carbon atoms and may be selected from those hereinbefore specifically set forth in connection with the discussion of the neopentyl glycol esters, and (3) tricresylphosphate, trioctylphosphate, trinonylphosphate, tridecylphosphate, as well as mixed aryl and alkyl phosphates, etc.

The present invention also is used in the stabilization of greases made by compositing one or more thickening agents with an oil of natural or synthetic origin. Metal base synthetic greases are further classified as lithium grease, sodium grease, calcium grease, barium grease, strontium grease, aluminum grease, etc. These greases are solid or semi-solid gels and, in general, are prepared by the addition to the lubricating oil of hydrocarbon soluble metal soaps or salts of higher fatty acids as, for example, lithium stearate, calcium stearate, aluminum naphthenate, etc. The grease may contain one or more thickening agents such as silica, carbon black, talc, organic modified bentonite, etc., polyacrylates, amides, polyamides, aryl ureas, methyl N-n-octadecyl terephthalomate, etc. Another type of grease is prepared from oxidized petroleum wax, to which the saponifiable base is combined with the proper amount of the desired saponifying agent, and the resultant mixture is processed to produce a grease. Other types of greases in which the features of the present invention are usable include petroleum greases, whale grease, wool grease, etc., and those made from inedible fats, tallow, butchers waste, etc.

Oils of lubricating viscosity also are used as transmission fluids, hydraulic fluids, industrial fluids, etc., and the novel features of the present invention are used to further improve the properties of these oils. During such use the lubricity properties of the oil are important. Any suitable lubricating oil which is used for this purpose is improved by incorporating the additive of the present invention.

Oils of lubricating viscosity also are used as cutting oils, rolling oils, soluble oils, drawing compounds, etc. In this application, the oil is used as such or as an emulsion with water. Here again, it is desired that the oil serves to lubricate the metal parts of saws, knives, blades, rollers, etc., in addition to dissipating the heat created by the contact of the moving metal parts.

Oils of lubricating viscosity also are used as slushing oils. The slushing oils are employed to protect finished or unfinished metal articles during storage or transportation from one area to another. The metal articles may be of any shape or form including steel sheets, plates, panels, coils, bars, etc., which may comprise machine parts, engines, drums, piston rings, light arms, etc., as well as farm machinery, marine equipment, parts for military or other vehicles, household equipment, factory equipment, etc. A coating which may be visible to the eye, or not, as desired, covers the metal part and protects it from corrosion, etc.

The concentration of the amine salt of the oxyalkylenated hydroxyhydrocarbon thiophosphate to be employed as an additive will depend upon the particular substrate in which it is to be used. In general, the additive is used in a concentration of from about 0.001% to about 25% by weight of the substrate and preferably within the range of from about 0.01% to about 5% by weight of the substrate. When used in conventional lubricating oil, the additive generally may be employed in a concentration of from about 0.01% to about 2% by weight of the oil. When used in lubricating oil for more severe operations, such as hypoid gear oil, the additive is used in a concentration of from about 1% to about 20% or more by weight of the oil. In general, substantially the same range of additive concentration is employed when the oil is used as transmission fluid, hydraulic fluid, industrial fluid, etc. When the oil is used in the formulation of a grease, the additive is used in a concentration of from about 0.5% to 5% by weight of the oil. When used in cutting oil, rolling oil, soluble oil, drawing compound, etc., the additive may be used in a concentration of from about 0.1% to about 10% by weight of the oil. When used in slushing oil, the additive may be used in a concentration of from about 0.1% to about 15% by weight or more of the oil.

It is understood that the additive of the present invention may be used along with other additives incorporated in the organic substrate. The other additives will depend upon the particular organic substrate. For example, in lubricating oil, the additional additives may comprise one or more of viscosity index improver, pour point depressor, anti-foam additive, detergent, corrosion inhibitor, additional antioxidant, etc. Preferred additional antioxidants are of the phenolic type and include tertiarybutylcatechol, 2,6-ditertiarybutyl-4-methylphenol, 2,4-dimet-hyl-6-tertiarybutylphenol, etc., 2-tertiarybutyl-4-methoxyphenol, 2- tertiarybutyl-4-ethoxyphenol, etc.

The amine salt of the present invention is an emulsifying agent and, therefore, will serve to emulsify water and oil of lubricating viscosity for use as lubricating oil, slushing oil, cutting oil, rolling oil, soluble oil, drawing compound, etc. When desired, an additional emulsifying agent may be employed. Any suitable emulsifying agent can be used, including alkali metal sulfonates of petroleum sulfonic acids, mahogany sulfonates, naphthenic acids, fatty acids, etc., fatty alcohol sulfonates, pentaerythritol oleates, laurates, etc. The amount of water used in the emulsified oils will depend upon the particular use of the emulsion and may range from 0.25% to 50% or even up to 98% by weight of the composition.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

Example I The compound of this example is the N-tallow-1,3-diaminopropane salt of di-(oxyethylenated nonylphenol)- dithiophosphate containing one oxyethylene group per each nonylphenyl group. The di-(oxyethylenated nonylphenol)-dithiophosphate was prepared by charging 528 g. (2 moles) of oxyethylenated nonylphenol containing one oxyethylene group and benzene into a reaction flask and then stirring and heating the mixture to 140 F. At this temperature and with stirring, 111 g. (0.5 mole) of P S were added gradually over a period of 2.5 hours. During the addition of the P 8 the temperature rose slowly to about 165 F. Stirring and heating to about 195 F. were continued for an additional two hours. Following completion of the reaction, the reaction flask was cooled and then filtered to remove any unreacted P S The filtrate was then distilled under vacuum to remove the benzene solvent. The di-(oxyethylated nonylphenol)-dithiophosphate was recovered as a liquid of medium viscosity. Analyses showed a sulfur content of 9.28% which corresponds to the theoretical sulfur content of 10.3% and a phosphorus content of 4.12% which corresponds to the theoretical phosphorus content of 5%.

The amine salt of the dithiophosphate prepared as described in the previous paragraph was formed by mixing, on an equivalent weight basis, 75 g. of the di-(oxy- Example II The compound of this example is the oleyl amine salt of the di-(oxyethylenated nonylphenol)-dithiophosphate containing one oxyethylene group per each nonylphenyl group. The di-(oxyethylenated nonylphenol)-dithioph0sphate was prepared as described in Example I. This reaction was effected by mixing equivalent weights of the reactants which, in this case, were 25 g. of this dithiophosphate and 11.7 g. of oleyl amine. The reactants were mixed at room temperature and the oleyl amine salt of di-(oxyethylenated nonylphenol)-dithiophosphate was recovered as a viscous liquid of amber color having a viscosity of 4400.3 centistokes at F. measured according to ASTM method D445.

Example III The compound of this example was prepared using an amine formed by reacting N ,N -bis-(1-ethyl-3-methylpentyl)-diethylenetriamine with carbon disulfide and then reacting the resultant amine with the di-(oxyethylenated nonylphenol)-dithiophosphate prepared in the manner described in Example I. The reaction of the N ,N -bisdiethylenetriamine with carbon disulfide was effected by dissolving 327 g. (1 mole) of the triamine in 500 cc. of xylene and slowly adding 76 g. (1 mole) of carbon disulfidethereto with vigorous stirring. The mixture then was stirred and heated to refluxing until the evolution of hydrogen sulfide ceased. After completion of the reaction, the solvents were removed by vacuum distillation. The product had a neuralization equivalent of 359.7 which corresponds to the calculated neutralization equivalent of 369.7.

The amine salt was prepared by mixing, on an equivalent weight basis, 15.6 g. of the triamine-carbon disulfide reaction product and 25 g. of di-(oxyethylenated nonylphenol)-dithiophosphate prepared as described in Example I. The mixing was effected at room temperature, but heat was generated due to the exothermicity of the reaction. The amine salt was recovered as a viscous liquid of amber color having an index of refraction 11 of 1.53807.

Example IV The compound of this example is the N-tallow-1,3- diaminopropane salt of di-(oxyethylenated nonylphenol)- dithiophosphate containing five oxyethylene groups per each nonylphenyl group. The di-(oxyethylenated nonylphenol)-dithiophosphate was prepared in substantially the same manner as hereinbefore described and was recovered as a fluid oil having a refractive index n of 1.5055 and a sulfur analysis of 4.29% by weight which corresponds to the theoretical sulfur content of 4.62%.

The amine salt was prepared by mixing 1.8 g. (0.01 mole) of the N-tallow-1,3-diarninopropane with 8.6 g. (0.01 mole) of the di-(oxyethylenated nonylphenol)- dithiop=hosphate at room temperature. The salt was re covered as a viscous liquid of amber color.

Example V The compound of this example is the N-tallow-1,3-diaminopropane salt of di-(oxyethylenated nonylphenol)- dithiophosphate having an average of 12 to 13 oxyethylene groups per each nonylphenyl group. The salt was prepared by the room temperature mixing of 1.8 g. (0.01 mole) of N-tallow-1,3 diaminopropane with 15.9 g. (0.01 mole) of di-oxyethylenated nonylphenol)-dithiophosphate having an average of 12 to 13 oxyethylene groups. The salt was recovered as a viscous liquid of amber color having an index of refraction 11 of 1.49725.

Example VI The oleyl amine salt of di-(oxyethylenated nonylphenol dithiophosphate containing five oxyethylene groups per each nonylphenyl group was prepared in substantially the same manner as described herein-before by intimately mixing, at room temperature, 2.7 g. (0.01 mole) of oleyl amine with 8.6 g. (0.01 mole) of the di- (oxyethylenated nonylphenol)-dithiophosphate. The salt was recovered as a viscous liquid of amber color having an index of refraction n of 1.51173.

1 1 Example VII The oleyl amine salt of di-(oxyethylenated nonylphenol)-dithiophosphate, containing an average of 12 to 13 oxyethylene groups per each nonylphenyl group, was prepared in substantially the same manner as described hereinbefo're by intimately mixing, at room temperature, 2.7 g. (0.01 mole) of oleyl amine with 13.2 g. (0.01 mole) of the di-(oxyethylenated nonylphenol)-dithiophosphate. The salt was recovered as a viscous liquid of amber color.

Example VIII The amine salt of this example is prepared by mixing, at room temperature, 3.6 g. (0.01 mole) of the triaminecarbon disulfide reaction product, prepared as described in Example III, with 8.6 g. (0.01 mole) of di-(oxyethylenated nonylphenol)-dithiophosphate containing five oxyethylene groups per each nonylphenyl group. The salt is recovered as a viscous liquid of amber color having a refractive index 11, of 1.52372.

Example IX The compound of this example is the triamine-carbon disulfide salt of di-(oxyethylenated nonylphenol)-dithiophosphate having an average of 12 to 13 oxyethylene groups per each nonylphenyl group. The triamine-carbon disulfide reaction product was prepared as described in Example III. This salt was prepared by mixing, at room temperature, 3.6 g. (0.01 mole) of the triamine-carbon disulfide reaction product with 15.9 g. (0.01 mole) of the di-(oxyeth'ylenated nonylphenol)-dithiophosphate. The salt was recovered as a viscous liquid of amber color.

Example X The compound of this example is the N-tallow-1,3-diaminopropane salt of di-(oxyethylenated octylphenol)- dithiophosphate having an average of 9 to 10 oxyethylene groups per each octylphenyl group. This salt was prepared by mixing, at room temperature, 1.8 g. (0.01 mole) of N-tallow-1,3-diaminopropane with 13.2 g. (0.01 mole) of the di-(oxyethylenated octylphenol)-dithiophosphate. The resulting salt was recovered as a viscous liquid of amber color having a refractive index 11 of 1.50806.

Example XI The oleyl amine salt of the di-(oxyethylenated octylphenol)-dithiophosphate, having an average of 9 to 10 oxythylene groups per each octylphenyl group, was prepared by mixing, at room temperature, 2.7 g. (0.01 mole) of oleyl amine with 13.2 g. (0.01 mole) of the di-(oxyethylenated octylphenol)-dithiophosphate and recovering the resultant salt as a viscous liquid of amber color having a viscosity of 990.9 centistokes at 74 F. measured in accordance with ASTM method D445.

Example XII The amine salt of this example was prepared by mixing, at room temperature, 3.6 g. (0.01 mole) of the triamine-carbon disulfide reaction product described in Example III with 13.2 g. (0.01 mole) of di-oxyethylenated octylphenol)-dithiophosphate having an average of 9 to 10 oxyethylene groups per each octylphenyl group. The resulting salt was recovered as a viscous liquid of amber color having a viscosity of 2223.3 centistokes at 76 F. measured in accordance with ASTM method D445.

Example XIII The compound of this example is the oleyl amine salt of di-(oxyethylenated dinonylphenol) dithiophosphate having eight oxyethylene group per each nonylphenyl group. This salt was prepared by mixing, at room temperature, 2.7 (0.01 mole) of oleyl amine with 14.1 g. (0.01 mole) of di-(oxyethylenated dinonylphenol)-dithiophosphate having eight oxyethylene groups, and recovering the salt as a viscous liquid of amber color.

12 Example XIV The compound of this example is the N ,N -bis- (1-ethyl-3-methylpentyl) -diethylenetriamine salt of di- (oxyethylenated nonylphenol) dithiophosphate having four oxyethylene groups per each nonylphenyl group. This salt was prepared by mixing, at room temperature, 9.6 g. (0.1 mole) of di-(oxyethylenated nonylphenol)- dithiophosphate having four oxyethylene groups with 10.86 g. (0.033 mole) of the N ,N -dioctyl-diethylenetriamine. The temperature of mixing rose to a maximum of about F. and the salt was recovered as a viscous liquid of medium amber color.

Example XV The N ,N -dioctyl-diethylenetriamine salt of di-(oxyethylenated nonylphenol)-dithiophosphate having eight oxyethylene groups per each nonylphenyl group was prepared by mixing, at room temperature, g. (0.1 mole) of the di-(oxyethylenated nonylphenol)-dithiophosphate with 10.86 g. (0.033 :mole) of the N ,N dioctyl-diethylenetriamine. The temperature rose to a maximum of about 115 F. and the salt was recovered as a heavy viscous liquid having a slight amber color. The N ,N -dioctyl-diethylenetriamine used in this example is the same as described in Example XIV.

Example XVI The compound of this example was prepared by mixing at room temperature, 10.86 g. (0.033 mole of the N ,N dioctyl-diethylenetriamine, described in Example XIV, with 169.4 g. (0.1 mole) of di-(oxyethylenated nonylphenol)-dithiophosphate having an average of 12 to 13 oxyethylene groups per each nonylphenyl group. The temperature rose to a maximum of about 108 F., and the salt was recovered as a heavy viscous liquid having a slight amber color.

Example XVII The compound of this example is the N-soya-1,2-diaminoethane salt of di-(oxypropylenated dodecylphenol)- dithiophosphate containing two oxypropylene groups per each dodecylphenyl group. The amine salt is prepared by commingling, at room temperature, equal mole proportions of the N-soya-1,2-diaminoethane and di-(oxypropylenated dodecylphenyl)-dithiophosphate. The resulting salt is recovered as a viscous liquid of amber color.

Example XVIII The salt of thi example is prepared by mixing, at room temperature, equal mole proportions of N,N'-dioctylamino-diphenylmethane with di (oxyethylenated decanol)-dithiophosphate having an average of six oxyethylene groups per each decyl group. The salt is recovered as a viscous liquid of amber color.

Example XIX As hereinbefore set forth, the compounds of the present invention are of especial utility as additives in lubricating oils. One method of evaluating lubricating oils is by the Falex machine. This procedure is described in detail in a book entitled Lubricant Testing authored by E. G. Ellis and published by Scientific Publications (Great Britain) Limited, 1953, pages -154. Briefly, the Falex machine consists of a rotating pin which runs between two V shape bearings which are spring loaded against the pin and provided with means for varying the load. The oil to be tested is poured into a metal trough in which the pin and bearings are partly submerged. The machine was operated for five minutes each at 250 and 500 pound loads and then forty-five minutes at 750 pound load and, in some evaluations, up to 1000 pound or 1500 pound loads. The data collected includes the temperature of the oil at each of the loads and the torque in pounds per square inch at each load, as well as the wear which is determined by a ratchet wheel arrangement in which the teeth are advanced in order to maintain the desired load. Each tooth is equivalent to approximately 0.000022 inch. Preferred additives are those 14 as Games 340 White Oil. Typical specifications of this oil include the following:

which impart low temperature, low torque and low wear Distillation range, F. 740-975 t the l- Specific gravity at 60 F 0.8836

'In another series of tests the machine was operated for Vi i five minutes at each load from 250 pounds to seizure 100 F 360 at 250 pound increments. The maximum load and the 210" 52.2 time in minutes at this load to seizure are reported, as Fl h point, OG 440 well as the temperature of the oil. In this case the higher p point, a 2 temperature is preferred because it means that the oil R f a ti index at 1,4805 1s operatmg sa tlsfactonly at a hlgher temperature saybolt 1 +30 The lubricatmg oil used 1n this example is dioctyl iz zgg gz 011 marketed under the trade some of the additives were not readily soluble in the Run 1 in the following table is a run made using white 011 and, accordingly, were solublhzed by cornmm- Plexol not containing an additive and thus is the blank ghng. nonylphenol therewlth and heatmg and Surfing as or control run. requlred' Run 2 is a run made using another Sample of Run No. 7 1n the followmg table s a run made us1ng 3 5 to which had been added two percent by Weight the white 011 not conta1n1ng an add 1t1ve and thus 1s the of the N-tallow-1,3-diaminopropane salt of di-(oxyethylblank or enated nonylphenol)-dithiophosphate containing one oxy- R N 8 a run made another Sample Of the ethylene. group prepared as described in Example 1, white 011 to which had been added two percent by welght Run No. 3 is a run made using another sample of the i i' g i g salt xyethyl- Plexol to which had been added two percent by weight enated nony pheno lthlop osphate contammg an y of the oleyl amine salt of di-(oxyethylenated nonylphe- W of 12 to 13 oxyethylene groups Prepared as descnbed nol)-dithiophosphate containing one oxyethylcne group In Example prepared as described in Example IL Iiun No. 9 1s a run made using another sample of the Run No. 4 is a run made using another Sample of whlte 011 to wh1ch had been added two percent by welght to which had been added two percent by Weight of the oleyl amlne salt otdi-(oxyethylenated nonylphenol) of the N ,N -diaminopropane salt of di-(oxyethylenated dlthlophosphate con/taming an aveiage 9 12 to 13 nonylphenol)-dithiophosphate containing five oxyethylcne ethylene groups Prepared as descnbed m Example groups prepared as d ib d i E l 1V Run No. 10 is a run made using another sample of the {Run N0, 5 is a run made using another ample of White Oil to which had been added tWO percent by weight P161101 to which had been added two percent by eight 0f the triamine-carbon disulfide salt Of til-(OXYfithYlEl'lZtfid of the oleyl amine salt of di-(oxyethylenated nonylnonylphenol)-dithiophosphate containing an average of phenol)-dithiophosphate containing five oxyethylcne 12 to 13 oXyethylene groups P p as described in groups prepared as described in Example VI. Example IX.

Run No. 6 i a run made using another sample of Run No. 11 is a run made using another sample of the Plexol to which had been added two percent by weight white oil to which had been added two percent by weight of the N-tallow-1,3-diaminopropane salt of di-(oxyethylof the N-tallow-1,3-diaminopropane salt of di-(oxyenated octylphenol)-dithiophosphate containing an averethylenated octylphenol)-dithiophosphate containing an age of 9 to 10 oxyethylcne groups prepared as described average of 9 to 10 oxyethylcne groups prepared as dein Example X. scribed in Example X.

TABLE I Temperature, F. Torque, lbs. Wear, Teeth Seizure Conditions Run No.

250 500 750 1,000 250 500 750 1,000 250 500 750 1,000 Load Time Tempera ture, F-.

SSeizure.

From the data in the above table, it will be seen that Run No. 12 is a run made using another sample of the the dioctyl sebacate without additive (Run No. 1) underwhite oil to which had been added two percent by weight went seizure at a load of 750 pounds. In contrast, seizure of the oleyl amine salt of di-(oxyethylenated octylphenol) conditions for the samples of the dioctyl sebacate condithiophosphate containing an average of 9 to 10 oxytaining the compounds of the present invention were ethylene groups prepared as described in Example XI.

Run No. 13 is a run made using another sample of the from 1250 to 1500 pounds.

Example XX lubricating oil was a mineral oil marketed commercially white oil to which had been added two percent by weight of the triamine-carbon disulfide salt of di-(oxyethylenated octylphenol)-dithiophosphate containing an average of 9 to 10 oxyethylcne groups prepared as described in Example XII.

TABLE II Temperature, F. Torque, lbs. Wear, Teeth Seizure Conditions Run No.

250 500 750 250 500 750 250 500 750 Load Time Temperature, F.

172 350-8 5-6 30-S S 425 0.1 275 192 278 364 4-6 10-15 13-18 0 0 31 1, 325 0v 1 450 185 265 375 4-5 10-11 13-17 0 0 33 1, 500 0. 5 450 164 264 388 4-5 -11 -20 0 0 6 1, 250 0. 1 400 175 285 375 3-5 10-13 12-20 0 0 22 1, 250 0. 4 425 164 267 357 4-5 10-13 13-17 0 O 37 1, 225 0. 1 400 180 285 405 5 11-12 14-18 0 0 30 1, 250 2. 2 435 SSeizure.

From the above data, it will be noted that the oil without additive (Run No. 7) underwent seizure at a load of 425 pounds. In contrast, the white oil containing the additive of the present invention did not undergo seizure until loads of from 1225 to 1500 pounds.

Example XXI Example XXII Because the amine salts of the present invention are more thermally stable than the dithiophosphates, another series of evaluations were made in substantially the same manner as described in Example XIX, except that the machine was operated for five minutes each at 250, 500,

Run No. 16 is a run made using another sample of the Hercules J64 oil to which had been added two percent by weight of the oleyl amine salt of di-(oxyethylenated nonylphenol)-dithiophosphate containing five oxyethylene groups prepared as described in Example VI.

Run No. 17 is a run made using another sample of the Hercules J64 oil to which had been added two percent by weight of the triamine-carbon disulfide salt of di-(oxyethylenated nonylphenol)-dithiophosphate containing five oxyethylene groups prepared as described in Example VIII.

Run No. 18 is a run made using another sample of the Hercules J64 oil to which had been added two percent by weight of the oleyl amine salt of di-(oxyethylenated octylphenol)-dithiophosphate containing an average of 9 to 10 oxyethylene groups prepared as described in Example XI.

Run No. 19 is a run made using another sample of the TABLE III Temperature, F. Torque, lbs. Wear,Teeth Run No.

750, 1000 and 1250 loads and then for forty-five minutes at 1500 load. It is readily seen that this is a much more severe evaluation than those reported in the previous examples. Also, these evaluations were made using pentaerythritol ester lubricating oil which is marketed commercially as Hercules J64.

When evaluated in the manner previously described, the Hercules J64 oil without additive had a seizure load of 1000 pounds. Results of various runs using other samples of this oil Containing additives of the present invention are reported in the following table.

Run No. 14 is a run made using another sample of the Hercules J 64 oil to which had been added two percent by weight of the N-tallow-1,3-diaminopropane salt of di-(oxyethylenated nonylphenol)-dithiophosphate containing five oxyethylene groups prepared as described in Example IV.

Run No. 15 is a run made using another sample of the Hercules J64 oil to which had been added two percent by weight of the N-tallow-l,3-diaminopropane salt of di-(oxyethylenated nonylphenol)-dithiophosphate containing an average of 12 to 13 oxyethylene groups prepared as described in Example V.

From the data in the above table, it will be seen that the additives of the present invention were effective in inhibiting seizure even at the high load of 1500 pounds when evaluated in this oil.

Example XXIII The N-tallow-1,3-diaminopropane salt of di-(oxyethyla.

enated nonylphenol)-dithiophosphate containing five oxyethylene groups, prepared as described in Example IV, is used in a concentration of 0.5% by weight as an additive in grease. The additive is incorporated in a commercial Mid-Continent lubricating oil having an S.A.E. viscosity of 20. Approximately 92% of the lubricating oil then is mixed with approximately 8% by weight of lithium stearate. The mixture is heated to about 450 F., with constant agitation. Subsequently, the grease is cooled, while agitating, to approximately 250 F., and then the grease is further cooled slowly to room temperature.

The stability of the grease is tested in accordance with ASTM D-942 method, in which method a sample of the grease is placed in a bomb and maintained at a temperature of 250 F. Oxygen is charged to the bomb, and the time required for a drop of five pounds pressure is taken as the induction period. A sample of the grease without additive will reach the induction period in about eight hours. On the other hand, a sample of the grease containing 0.3% by weight of the additive of the present invention will not reach the induction period for more than 100 hours.

We claim as our invention:

1. Amine salt of oxyalkylenated hydroxyhydrocarbon .thiophosphate containing one or two oxyalkylenated hydroxyhydrocarbon radicals per molecule, said radical or radicals containing a chain of from 1 to 40 oxyalkylene groups linking the hydroxyhydrocarbon with the phosphorus atom.

2. Amine salt of oxyalkylenated hydroxyhydrocarbon dithiophosphate containing one or two oxyalkylenated hydroxyhydrocarbon radicals per molecule, said radical or radicals containing a chain of from 1 to 40 oxyalkylene groups linking the hydroxyhydrocarbon with the phosphorus atom.

3. Amine salt of oxyalkylenated alkylphenol dithiophosphate containing one or two oxyalkylenated alkylphenol radicals per molecule, said radical or radicals containing a chain of from 1 to 40 oxyalkylene groups linking the alkylphenol With the phosphorus atom.

4. Amine salt of di-(oxyalkylenated alkylphenol)dithiophosphate, each of the two oxyalkylenated alkylphenol radicals containing a chain of from 1 to 40 oxyalkylene groups linking the alkylphenol with the phosphorus atom.

5. Amine salt of di-(oxyethylenated alkylphenol)dithiophosphate, each of the two oxyethylenated alkylphenol radicals containing a chain of from 1 to 40 oxyethylene groups linking the alkylphenol with the phosphorus atom.

6. N-alkyl-diaminoalkane salt of di-(oxyalkylenated alkylphenol)-dithiophosphate, each of the two oxyalkyl- 18 enated alkylphenol radicals containing a chain of from 1 to oxyalkylene groups linking the alkylphenol with the phosphorus atom.

7. N-tallow-1,3-diaminopropane salt of di-(oxyethylenated octylphenol)-dithiophosphate, each of the two oxyethylenated octylphenol radicals containing a chain of from 1 to 40 oxythylene groups linking the octylphenol with the phosphorus atom.

8. N-tallow-1,3-diamin-opropane salt of di-(oxyethylenated nonylphenol)-dithiophosphate, each of the two ox'yethylenated nonylphenol radicals containing a chain of from 1 to 40 oxyethylene groups linking the nonylphenol with the phosphorus atom.

9. Fatty amine salt of di-(oxyalkylenated alkylphenol)- dithiophosphate, each of the two oxyalkylenated alkylphenol radicals containing a chain of from 1 to 40 oxyalkylene groups linking the alkylphenol with the phosphorus atom.

10. Oleyl amine salt of di-(oxyethylenated octylphenol)-dithiophosphate, each of the two oxyethylenated octylphenol radicals containing a chain of from 1 to 40 oxyethylene groups linking the octylphenol with the phosphorus atom.

11. Oleyl amine salt of di-(oxyethylenated nonylphenoD-dithiophos-phate, each of the two oxyethylenated nonylphenol radicals containing a chain of from 1 to 40 oxyethylene groups linking the nonylphenol with the phosphorus atom.

References Cited UNITED STATES PATENTS 3,002,014 9/ 1961 Dinsmore et al 260-925 CHARLES B. PARKER, Primary Examiner.

BERNARD BILLIAN, Assistant Examiner.

Claims

1. AMINE SALT OF OXYALKYLENATED HYDROXYHYDROCARBON THIOPHOSPHATE CONTAINING ONE OR TWO OXYALKYLENATED HYDROXYHYDROCARBON RADICALS PER MOLECULE, SAID RADICAL OR RADICALS CONTAINING A CHAIN OF FROM 1 TO 40 OXYALKYLENE GROUPS LINKING THE HYDROXYHYDROCARBON WITH THE PHOSPHOROUS ATOM.