US3691077A

US3691077A - Lubricant composition

Info

Publication number: US3691077A
Application number: US123091A
Authority: US
Inventors: Robert Earl Wann; Denzel Allan Nicholson; Ted Joe Logan
Original assignee: Individual
Current assignee: Individual
Priority date: 1968-09-26
Filing date: 1971-03-10
Publication date: 1972-09-12
Anticipated expiration: 1989-09-12

Abstract

LUBRICANT COMPOSITIONS COMPRISING A MAJOR AMOUNT OF A LUBRICATING BASE FLUID AND A MINOR AMOUNT OF EXTREME PRESSURE ADDITIVES WHICH CONTAIN EITHER A METHYLENE, MONOHALOMETHYLENE OR DIHALOMEHYLENE GROUP BETWEEN TWO MOIETIES, SELECTED FROM THE GROUP CONSISTING OF PHOSPHONO, DIHYDROCARBYLPHOSPHORYL, PHENYL, SUBSTITUTED PHENYL, KETO, CYANO, AND CARBOXYLATE ESTER MOIETIES.

Description

United States Patent O U.S. Cl. 25254.6 6 Claims ABSTRACT OF THE DISCLOSURE Lubricant compositions comprising a major amount of a lubricating base fluid and a minor amount of extreme pressure additives which contain either a methylene, monohalomethylene or dihalomethylene group between two moieties, selected from the group consisting of phosphono, dihydrocarbylphosphoryl, phenyl, substituted phenyl, keto, cyano, and carboxylate ester moieties.

REFERENCE TO RELATED APPLICATIONS This application is a divisional of copending application Ser. No. 762,966, filed Sept. 26, 1968, and now U.S. Patent 3,579,449.

BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to lubricant compositions which contain a lubricating base fluid and an additive to increase the load-bearing properties of the base fluid. These additives are generally referred to as extreme pressure additives. Ideally, the additives should improve the loadbearing properties of the base fluid without causing excessive corrosion problems, should be reasonably effective within their level of solubility or dispersability in the base fluid, and should be relatively easy to prepare.

(2) Prior art Halogen substituted compounds having phosphonate ester and carboxylate ester moieties are known as additives for lubricant compositions. See, for example, U.S. Patents 2,275,359; 2,599,761; 3,296,138; 2,225,366; 2,882,303-316; 2,824,839; 2,993,859; 2,722,515; 2,767- 142; 2,882,228; and 2,848,475. However, the search has continued for effective extreme pressure lubricant additives and especially for such additives which are simple compounds that can be made economically and which do not cause excessive corrosion problems.

THE INVENTION This invention relates to lubricant compositions comprising (1) a major amount of a lubricating base fluid and (2) a minor amount suflicient to increase the loadbearing properties of said compositions of a compound having the formula:

wherein each X is selected from the group consisting of hydrogen, chlorine, iodine and bromine atoms, each Y is selected from the group consisting of moieties having the following formulas Patented Sept. 12, 1972 wherein each R is selected from the group consisting of alkyl, aryl, alkaryl, arylkyl, alkenyl, haloalkyl, haloaryl, haloalkaryl, haloaralkyl, haloalkenyl and nitroaryl moieties containing from 1 to about 22 carbon atoms and each R is selected from the group consisting of R, a halogen atom and a hydrogen atom, the above selections being made so that both Xs can be hydrogen atoms only when both Ys are and that one X can be hydrogen only when each Y is is selected from the group consisting of The lubricating base fluid The extreme pressure additives of this invention will impart improved load-bearing characteristics to a wide variety of base fluids which are used for a variety of purposes. Broadly, the base fluid can be either a petroleum hydrocarbon, a fatty acid triglyceride, a synthetic fluid, an aqueous based fluid, or mixtures thereof. Petroleum hydrocarbons include mineral oil (including light solvents, neutral oils, heavy, bright and refined stocks, and asphaltic residual stocks), greases and waxes. The lubricating base fluid can also comprise suspensions of graphite in oils. Synthetic fluids include such disparate materials as polymerized olefins, organic carbonates, organic esters and/or ethers, polyglycols, silicones, modified organic materials (halogenated, phosphates, sulfurized, etc.) polymers e.g., 'alkylmethacrylate polymers and synthetic resins, e.g., resins formed by esterification of polyhydric alcohols with polycarboxylic acids. Examples of base fluids which can be used in the practice of this invention include those disclosed in U.S. Patent 2,599,761, especially columns 9-11; U.S. Patent 2,725,359, especially columns 2, and 7-8; U.S. Patent 2,767,142 especially column 4; U.S. Patent 2,882,228, especially columns 6-7; U.S. Patent 2,956,952, especially columns 3-5; U.S. Patent 2,993,859, especially columns 2-3; U.S. Patent 3,296,- 138, especially columns 6-10 and 12-20; and U.S. Patent 3,357,920, especially columns 5-7. Other suitable lubricating base fluids are disclosed in Encyclopedia of Chemical Technology, Kirk-Othmer, second edition, volume 12, pages 557-616, especially pages 576-582, Interscience Publishers, 1967. More examples of metal working lubricant base fluids can be found in Metal Working Lubricants, E. L. H. Bastian, first edition, McGraW- Hill Book Co., Inc. 1951. All of the above patents and books including the references referred to therein are incorporated herein by reference.

The finished lubricant composition containing the above lubricating base fluids and the extreme pressure additives disclosed hereinbefore and specifically described hereinafter, can be used for lubricants for automobiles, aircraft, etc. as gear and bearing lubricants; as industrial metal working lubricants, e.g., for metal cutting and extrusion of steel, aluminum, titanium and its alloys, etc. (cutting fluids, drawing fluids, drawing compounds, extrusion lubricants, forging lubricants, rolling oils, machine tool lubricants, and other similar lubricants); and as fluids for the transmission of power, e.g., in car transmissions or hydraulic systems.

THE EXTREME PRESSURE ADDITIVE The extreme pressure additives of this invention when added to the lubricating base fluids hereinbefore described,

improve the load-bearing properties of said lubricating base fluids.

The extreme pressure additives of this invention are characterized by the presence of a methylene or halo (chloro, iodo, or bromo) substituted methylene group. This methylene group is attached to two other groups, each of which can be either a phosphono (phosphonate diester), carboxylate ester, keto, cyano, phosphoryl (e.g., dialkylphosphine oxide), phenyl or substituted phenyl group. These groups are essential to the good performance of the extreme pressure additives. These groups are also important in modifying the solubility of the extreme pressure additives in various lubricating base fluids. For example, those groups which contain alkyl groups can, by selecting the length of the alkyl groups, be modified to give various hydrophilic and hydrophobic properties to the extreme pressure additives. It will be noted that there is an optimum chain length for each extreme pressure additive for each lubricating base fluid.

The dihalo and monohalo extreme pressure additives of this invention can, in general, be prepared by reacting the non-halogenated compounds with the desired sodium hypohalite. See, e.g., O. T. Quimby et al., J. Organometallic Chemistry, 13, 199. (1968). The methylene diphosphonate esters can be prepared according to the teaching of US. Pat. 3,251,907. The dihalodicyanomethane extreme pressure additives can be prepared by reaction of the dicyanomethane with molecular halogen and subsequent decomposition of the alkali metal halide complex according to the teaching of Organic Synthesis, vol. 39, page 64, M. Tishler, Ed. and L. Ramberg and S. Widequist, Arkiv Kemi, Mineral. Geol., 12A, No. 22 (1937). The dihalodiphenylmethane compounds are available commercially. All of the extreme pressure additives can be prepared by known or analogous methods. The iodo compounds are generally a mixture of monoand diiodo compounds however.

Within the scope of the definition of the extreme pressure additives of this invention, there is a considerable variation in effectiveness with respect to extreme pressure properties and there is considerable variation with respect to other properties such as corrosivity, antiwear properties and, of course, solubility or dispersability. The non-halogenated methylenediphosphonate esters are the least corrosive of the additives. However, in general, they are also the least effective with respect to the extreme pressure properties. In general, the most effective extreme pressure additives are those which contain a dibromomethylene group. However, they tend to be more corrosive than the other additives. Among the more effective extreme pressure additives are the dichloro-, diiodoand dibromomethylenediphosphonates, the dibromomalonates, dibromomalononitrile, the tetrabromoglutarates, diphenyldichloromethane, dibenzolyldibromomethane, and the dibromoand dichlorophosphonoacetates. The dichlorophosphonoacetates are equal to or slightly better than the dibromophosphonoacetates. This is a surprising reversal of the general trend in which the dibromo compounds are more effective than the dichloro compounds. In general, the alkyl groups should contain from 1 to about 6 carbon atoms. However, in the case of the malonates, it is preferred that the alkyl groups contain at least about carbon atoms since the malonates containing alkyl groups with less than about 5 carbon atoms tend to be more corrosive.

Certain of the extreme pressure additives have a different primary activity. For example, when the alkyl groups contain from about 7 to about 22 carbon atoms, they are effective antiwear additives. This is especially true of the methyleneand halomethylenediphosphonate esters.

Although the additives which contain long chain alkyl groups are more effective as antiwear additives, they also are as effective as the shorter chain compounds, on a molar basis, as extreme pressure additives and the longer chains are quite often more compatible with lubricants which are greases and waxes.

The iodo compounds, which are normally a mixture of monoand diiodo compounds, are good additives for metal working lubricants, especially lubricants which are used in the working of titanium and titanium alloys.

In general there will be from 1% to about 20% of the additive, preferably from about 2% to about 10% in the lubricant composition.

Mixtures of extreme pressure additives can also be used. A synergistic mixture of tetraalkyl dichloromethylenediphosphonate and tricresyl phosphate, a well-known extreme pressure and anti-wear additive, is also preferred and is claimed in the application of Robert E Wann, Ser. No. 763,006, filed Sept. 26, 1968, and now abandoned.

Finished lubricant compositions containing the extreme pressure additives of this invention can also contain other known additives, e.g., antioxidants, corrosion inhibitors, metal deactivators, viscosity index improvers, dispersing materials, dyes, thickeners, etc. Examples of antioxidants include 2,6-ditertiarybutyl-4-methylphenol; 2,6-ditertiarybutyl phenol; 2,6-ditertiaryamyl-4-methylphenol; 2,6-diisopropyl-4-methylphenol; phenylnaphthylamine; phenylenediamine; and diphenylamine.

This invention can be better understood by reference to the following examples which should not be taken as limiting the scope of the invention.

Example I.The following compositions were tested in a standard four ball tester for Weld point (extreme pressure test) and wear scar (wear test). The weld point is defined as that pressure where the balls weld together in two successive runs of one minute under the indicated pressure. The wear scar is the average, based on three balls, of the average of both length and width of the scars when the balls are run under a 40 kg. load for one hour at 1200 rpm. and at a temperature of F.

All of the indicated additives in the following table were added to a Kendall SAE 10, paraffin base, additive free oil (lubricating base fluid) at the indicated level.

Percent Weld Wear Compoy point scar sition Additive weight (kg) (cm.)

1 (base oil) 130 0. 82 2 Sulfur, chlorine and lead naph- 5 240-260 0. 76

thenate in fish oil (SCL).

L 2 216 0. 68 1 180 0. 70 5 0. 63 5 340 0. G4 5 210 0. 64 5 200 0. 70 Trichloroacetio acid L. 5 70 1.01 10. Randomly chlorinated paraffin. 5 210 0.62 11 Lead naphthenates 5 230 0. 72 12 Molybdenum disulfide 5 140 0.80 13 Tetraisepropyl dichlorometh- 10 468 ylenediphosphonate (iPnOlzMDP) 5 390 1. l8 2. 5 300 iPnClzMDP- 1 270 0. 94 Tetraethyl dichloromethyl- 5 500 1.16

enediphosphonate (EtiClzMDP). l8- EtiClgMDP 2.5 460 1.06 19 ElZgClzMDP 1 270 0.94 20 Tetramethyl diehloro- 5 400 methylenediphosphonate (MmClzlWDP). 21 Tetrakis(decy1)diehlorometh- 5 210 0. 49

ylenediphosphonate. 22 Tetrakis(stearyl)dichloro- 5 0. 345

mesylenediphosphonate. 23 Tetraethyl dibromomothylene- 5 800 1.10

diphosphonate (Et BnMDP). 24 Et BrzMDP 2. 5 660 1.12 25 ElisBlzMDP 1 250 0. G0 26 Tetraisopropyl dibromomethyl- 5 400 1. 12

enediphosphonate (iPnBnMDP). 27 Tetraisopropyl monobromo- 5 270 l. 14

methylenediphosphonate. 28 Tetraisopropyl monoehloro- 5 280 1.07

methylenediphosphonate. 20 Tetraisopropyl methylone- 5 260 1. O2

diphosphonate. 30 Tetraethyl methylenedi- 5 phosphonate. 31 Tctrukis(stearyl)mctl1ylene- 5 140 0.375

(liphosphonate (C MDl). 32 Diethyl trichlor0mcthyl- 5 800 0. 90

phosphonate.

d 44 Dl(isopentyl) dibromomalonate (lc BrzMal). 45 do 40 do 47 do 48 Diethyldlbromomalonate 4 (Et BnMal).

Trls(deeyl) dibromophosphonoacetate (CmBl'zPA). 63 Triethyl chlorophosphonoacetate (E1; 01 PA). 54 Trlethyl phosphonaeetate (Et PA). 55 Tetrakis(decyl) methylenediphosphonate (CmMDP). 56 Tetrabenzyl methylenediphosphonate (Benzyl MD]? 57 Tetrabenzyl dlchloromethylenedlphosphonate (Benzyl ClzMDP). 58...... Tetraisopropyl diiodomethylenediphosphona Dlmethyl 3-keto-2,2,4,4-tetrabromoglutarate. Dibromomalononitrile 61 Dibenzoyl dlbrornmethane on an O! m or mum-N OH-IMOS cur-now mamfllm 1 Very corrosive.

Compositions 2-12 and 32 demonstrate the efiectiveness of certain representative prior art extreme pressure additives. It should be noted that, with the exception of the trichloroacetic acid and the diethyl trichloromethylphosphonate, the weld points are well under 400 kg. at an additive level of about 5%. The trichloroacetic acid and trichloromethylphosphonate, however, are quite corrosive.

Compositions 13-19, 23-25, and 40-51 show the effect of varying the level of six representative extreme pressure additives of this invention. At a level of only about 1% they are still better than most conventional additives at a level of 5%.

Compositions 22 shows the effect of changing the length of the alkyl chain. The longer alkyl chains merely dilute the extreme pressure additive eifect, since on a molar basis the' improvements of the additives of compositions 20-22 are about the same. There is a major difference however in anti-wear properties since the tetrakis(decyl) and tetrakis(stearyl) additives provide a major improvement as demonstrated by the wear scar. The tetramethyl additive does not help the antiwear properties of the base fluid.

A comparison of Compositions 17 and 23; 14 and 26; and 37 and 38 shows that, in general, the dibromo additives are more effective than the dichloro additives. This is especially true with the malonates. Similarly, a comparison of Compositions 14, 26 and 58 shows that for the particular tetraisopropyl methylenediphosphonate additives the diiodo derivative is beter than the dibromo derivative which is better than the dichloro derivative. However, the ranking of the diiodo compound is undoubtedly affected by the fact it contained a substantial amount of monoiodomethylenediphosphonate.

A comparison of Compositions 2'6, 27 and 29; 14, 28 and 29; 17 and 30; 21 and 55; 23 and 30; 37 and 39; 38 and 39; and 34, 53 and 54 shows the eifect of going from a nonhalogenated to a monohalogenated to a dihalogenated extreme pressure additive having the same basic structure. In general the nonhalogenated compounds are not effective extreme pressure additives. However,

surprisingly, the methylenediphosphonate esters have substantial extreme pressure activity. The monohalogenated compounds in general are not much better than the nonhalogenated compounds as extreme pressure additives and it is only with the dihalogenated compounds that the best extreme pressure activity is achieved. It is surprising that the change from monohalogenated to dihalogenated compounds would give such a tremendous increase in extreme pressure activity.

As compositions 22 and 31 show the antiwear properties are aifected only slightly by the presence or absence of the halogen atoms on a compound. Also, in composition 33 a mixture of a extreme pressure additive and an anti-wear additive (C MDP) gives both good eX- treme pressure activity and anti-wear activity.

A comparison of the above composition shows that the dichloroand dibromomethylenediphosphonates, the dichloroand dibromophosphonoacetates, the dibromomalonates, the dibromomalononitrile, and the tetrabromoglutarates give the best extreme pressure activity. The dichloromalononitrile and the tetrachloroglutarates are also good. The diiodomethylenediphosphonates, dibenzoyldibromomethane, and the diphenylmethylene dichloride are also very good extreme pressure additives. These compounds, in general, will give a weld point in the four ball test of at least about 400 kg. when used at the 5% level in this base fluid.

The dimethyl 3-keto-2,2,4,4-tetrabromoglutarate (Composition 59) is a difuctional dibromomethylene compound which shows that more than one YCX Y group can be present in a molecule of the extreme pressure additives of this invention.

Tetrabenzyl methylenediphosphonates are not very soluble in the base fluid of this example and accordingly are not as effective in this fluid as some of the other extreme pressure additives.

The diethyl dibromomalonates, e.g., compositions 37 and 48-51 are extremely corrosive. The dipentyl and diisopentyl esters of the dichloroand dibromomalonates, e.g., compositions 40-47 are not corrosive.

In the following compositions, a comparison has been made between a base oil containing only the additives of this invention (Kendall base oil) and an oil containing a complete additive package including a corrosion inhibitor (Havoline). The corrosion inhibitor apparently has an adverse effect upon the extreme pressure activity, but the extreme pressure activity is still very good and the corrosiveness is minimized. Tetraisopropyl dichloromethylenediphosphonate is not as corrosive to steel as the other three additives and is included for comparison.

In the following compositions the base fluid was water.

Weld

point Percent point Additive by weight (kg) MelChMDP 5 Example II.The following compositions are excellent lubricants having better extreme pressure characteristics than the lubricating base fluid.

Additive, percent Extreme pressure additive Lubricating base fluid by weight Allyllaurate- Dibromodicyanomethane..-

Diehlorodieyanomethane Dibrornocyano (diethylpl1osphono)methane Dibromo(phcnylmethyl) (dimethylphosphoryhn Dichloro (diisopropylphosphono) decanoylmethane Ethyl diehlorocyanoacetate Dibromocyanooctanoylmethane Dichlcro(butylmethylphosphoryl)cyanomethane Dichiorodiphenylmethane Dibromo(mcthyiphenyl)(dodecylphenyDmethane Bromocliloro (dccylphenyl) (dicth ylpheny Dmethaue Dicl1l0r0(biphenyl) (naphtliyDmethane Dibrom(chlorophcnyl) (3,4-dinitrophenyl)methane DibromoblS(butylcthylphosphoryDmetliane t Dibutyl ether of ethylene glyco Glycerol OW IOUh-LOJMl- Paraffin wax 1:1 mixture of naphthalene and xylene.

z eww-e e'es ew-ee w t OOOOO QOQOQOQQQI Dibro nO di(ethylbutylphosphoryl)mcthane Methyl ethyl ketone Chlorobromo(tetrachlorostearylmethylphosphonio)-tctrafluorostearylmethylphosphonio)methane. Carnuba Wax Dichltt aro( iuitrophenyl) (methyl dichlorooctylphosphonio) Tallow 5 H16 lane. Ethyl dibromo(dlmethylphosphonio)acetate Sterayl alcohol 5 Dil2-iodoneetyl)dibromomethane emulsion of tallow in water. 10 Di(aeetyl)dlehlor0methane Octyl tripropylene glycol cther 5 Dipentyl moneehlorornalonate Mineral oil S.A.E. 10 5 Di(methylbenzoyl)dibromomethane Rosin 4 1:1 phenol-iormadchyde resin (M.W. Grease (lubricating oil thickened with soap) Isopropyl laurate 1:1 mixture of isopropyl and alcohol. Kerosene Broniostearyl bromomethyl bromomalonate Stcaryl behenyl dichloromalonate Dodeeenyl bromobenzyl dibromomalonate Iodobenzoyl (diiodoethylphcsphono)dichloromethane Biphenylnaphthyldibromomcthane Dihexyl ehlorornalonatc W. Turbine oil Iodomestyl iodobenzyl dibromomalonate. soybean oil in water emulsion li(2-etl1ylhexyl) dibromomalonate Di (Zethylhexyhsebacate 10% suspension of graphite in mineral oil SAE 10 Polyethyleneglycol (M.W. 1,800)

Chloroeyano (diisopropylphosphono)methane Oetylether of polyethyleneglyeol (M.W. 4,000).

Bromocyano(cetylmethylphosphoryl)methane Dw e t hy lgganoate of 1:1 ethylene glycol propyle glycol Octadccenyl (dibromobutyloetadecenylphosphoryDaeetate Stearyl stearatc Diehloro(din'ietliylphosphonio) (dimcthylphosphono)methane 20% cottonseed oil in water emulsion with 5% lkyl u-15) poly ethoxylate (9 moles) emulsifier.

Dibromodl (3,4-diiodopl1enyl)methane winterized and hardened (LV. 8) soybean oil Tri benzyl bromochlorophosphonaeetate Naphthenie hydrocarbon oil Tetra (tetrafiuorostearyl) dibromomethylcne diphosphonate Fluorinated polypropylene (M.W. 1,000)

Bromodicyanomethanm Chlorodicyanomethane. Ethyl ehlorocyanoacetat Dichloro dl(3,4,5-trlchlorophenyl)methane Di-n-butylphthalate Dibromoaeetoylpropionoylrnethanc 1:1 mixture of di-(Zbutoxyethyl) azelate and di(mcthyleyclohexyDadipate. 3-bromopropyl dibrolno(4,5-dichlorodeeanoyl) acetate The condensation product of propylene glycol, ethylene glycol,

phthalic acid and sebacic acid in a 322:1:1 ratio (M.W. 2,000).

Dibromo hexanoyl (butylpropylpliosphono)methane. The Cg-Cm oxo alcohol esters of phthalic acid Dichlorobenzoyl(ditolylphosphono)methane Butyl ether of polyethylene glycol (M.W. 1,000)

4 A 5:2 mixture of tr1(decylphenyl) dichlorophospliono acetate and A 3:1 mixture of butyl ether of polypropylene glycol N-phenyl-a napht yl m and diisooctyl adipate. Bromochloro(decylphenyl)deeanoylmethane Dioetylpentadeeandicarboxylate Dimethyldibutyl methylene diphosphouate Dimethylsiiicone polymer (M.W. 3,000)

Ethyldecylhoxyl dibromophosphouoaeetate Mineraloil SAE 30 Dibron10[(2,3-dichlor0hexylphenyl) (3,4-difluorobcnzyDphos- Petroleum wax phone] [(5,6-dibromo2-deeenyl) methylphosphono]methane.

1:1 mixture of b1s(2-ethylhexyl)dibromo-malonatc and tetra- Kendall base oil (SAE 10) mcthyldichloromcthylcnediphosphonate.

1:1:1 mixture of tetraisopropyl dibromomethylencdiphosphonate, do

triethyl dichlorophosphonoacetate, and bis (ZethylhexyDdichloromalonate. Diaeetyldibromomethane Kendall base oil (SAE 20) Dibenzoyldiiodomethane Cotton seed oil l V l Bis(2chlorocthyl)dlehloromalonat Bis(2-ethy1hexyl)sebacate. Dihexyl dibromomalonate Kendall base oil (SAE 10). Dibromomalononltrlle l Bis(2-ethyl hexyl) adipate.

n-Dccyl dlbromocyanoacetate Deeyl deeanoate Tetrabenzyl diehloromcthylenediphosphonatc Tris(p-nitrobenzyl) diiodophosphonoacetate 6l Bis[bis(fiuoromethyl) phosphorylkiichloromdthana 62 Bis(2,4-dichlorobeuzoyl) dibromomethane 63 Dioleyldibromomalonate te 6l Bis(p-dodeeylbcnzoyl) dichloromethane 1 65 l3romoiodomalononitrile u 1 66..." Tetraisopropylbromoiodomethylenediphosphonate Polypropylene glycol (M.W.

67 Dlpentyleyanodlbromomethylphosphonate Polyethylene glycol (M.W.QOO).

68"- Tetrakis(2,3-dibromopropyl) dibromomethylenediphosphonate Petroleum Wax 69 Bis(0,l0-diehlorostearyl)bromomalonate do 1 70 Tris(2,2,2-trlchloroethyl) dichlorophosphonoaeetate 1,1,2-triehlorothane.

71 Bromodicyanomethane K r en 72 Tetraetliyl diiodornethylencdiphosphonat 20% emulsion of tallow in water with 6% coconut alkyl polyethoxylate (15 moles ethylene oxide) emulsifier. Pentyl diehlorocyanoaeetate Kendall base oil (SAE 30) Dibromodiphenylmethane Kendall base oil (SAE 10) Bis(p-nitrophenyl) diiodomethane Cyanodibromophenylmethane Dicyclohexyl bromomalonate Ethyl (perfluorophenyl) dibromoaeetate. Tctramethyl diehloromethylencdiphosphonate BisQ-ethylhexyl) dibromomalonate Bis(2-mcthylbutyl) bromomalonate Bis(dioctylphospl1oryl) dichloronicthane. Dimethyl 3-keto-2,2,4,4-tetrabromoglutaratc flubcncacnoacnoomuvl czwcamoemmosoe 84. enzoyltrilluoroaeetyldibromomethane. Tetrapropylene glycol dioctyl ether- 8 Pentyl (trichloroacetyl) diehloroaeetate Kendall base oil (SAE 20) 5 86 Pcntachlorobenzoylcyanodibromomethane 9 87.... (Diphcnylphosplloryl) propionylehIoromethanc 12 83..-" DlplieiIylphosphoryleyzmoidonicthauc Naphthalene 3 TABLE--Continned Additive, percent Extreme pressure additive Lubricating base fluid by Weight 89. Dipropyl phenyidiehloromethylphosphonate Dioetyl phthalate 90 Tetrakis(decyl) brornochloromethylenediphosphonate Kendallbase oil (SAE 30)- 5 91.. Tetrakis(stearyl) broxnoiodomethylenediphosphonate. Tallow 5 92 Bisfloehenyl) dibromomalonate Behenyl behenate 20 93 Stearyl bromoiodocyannnretafe Stearyl acetate 94... Divinyl eyanodichloromethylphosphonate Kendall base Oil (SAE 10) 5 95.. Dichloromalononitrile 20% soybean oil in Water emulsion; 5% tallow fatty alcohol poly- 5 ethoxylate (45 moles) emulsifier. 96 Tetraethyl dibromomethylenediphosphonate Pentapropylene glycol diundecanoate 5 97.-- Tetra/ethyl dichloromethylenediphosphonate. Tripropylene glycol diderannate 5 98 Tetraisopropyl dibromornethylenediphosphonate- Havoliue oil. 5 99.-. Tetraisopropyl dichloromethylenediphosphonate. i hy yl) adipate 5 100. Tetraisopropyl methylenediphosphonate Tetrapropylene glycol d1d0decanoate- 5 101 Tetraisopropyl bromomethylenediphosphonate Kendall base oil (SAE 10) 5 102...- Diethyl dibromomalonate do 5 103. Bis(benzoyl) dibromomethane Cotton seed oil-.. 5 104-.-. Dipentyl diiodomalonate Soybea Oil 105 Pentyl3-keto-2,2-dibromobl1tyrate Kendall base oil (SAE 5 Example III.In the following test the following addi- What is claimed is: tives were added to the Kendall base oil of Example I to 1. A lubricant composition comprising give an additive level of about 5% by weight of the com- 20 (l) a major amount of a lubricating base fluid and position and coupons of the indicated metals were ex- (2) a minor amount suifieient to increase the loadposed to the oil/additive composition in air at a tembearing properties of said compositions of a comperature of about 275 F. for 100 hours at the rate of pound have the formula: 5 liters per hour. The numbers given are the weight 0 O chan es in milli ms uar entimeter 0 surface I areag gra per sq e c f l lt wherein one X is selected from the group consisting of hydrogen, atoms, the other X is bromine and wherein each R is selected from the group consisting (31 MDP 1P MDP of alkyl, aryl, alkaryl, aralkyl, alkenyl, haloalkyl, Magnesium M28 (L210 haloaryl, haloalkaryl, haloaralkyl, haloalkenyl and Aluminum 0, 0,0 mtroaryl moieties containing from 1 to about 22 Steel (soft)..- 0. 045 0. 173 Copper 1.876 0.105 carbon m Silver 0. 05a 0. 555 2. The eomposltion of claim 1 wherem component (2) 35 is a dibromomalonate.

3. The composition of claim 1 wherein each R is an alkyl group containing from about 5 to about 22 carbon Example IV.The following table compares the base atoms.

oil of Example I with compositions containing the indi- 4. The composition of claim 1 wherein there is from cated amounts of the indicated additives in a four ball about 1% to about 20% of component (2). tester, a Timken tester, and a Falex tester. All three tests 5. The composition of claim 1 wherein there is from should be used to determine if the extreme pressure addiabout 2% to about 10% of component (2). tive has wide utility. The representative additives of this 6. The composition of claim 2 wherein each R is an invention are all clearly superior to the commercially alkyl group containing from about 5 to about 22 caravailable additives. bon atoms.

Base 5 2.5 5 7 2.5 7 2.5 2.5

oil 5% TOP 5% soL iPnChMD? iPnClzMDl EnChMDr EncnMfiP iPriBrrM P EtiBHMD Z Four Ball:

Load wearindex.. 18.4 20.0 02.0 50.3 105.0 Weld point or 112 112 355 251 502 gillnkenz (Beam load in lb.) 3 12 65 z rload1n1b.)..-; 500 1,250 4, 500 4,500 4, 500 (Torque in 1b.- (65 (54) (60) 1 Capacity of instrument.

No'rE.--All parts, percentages, and ratios herein are by weight unless otherwise specified. The tour ball results in Example IV were obtained on a different testing machine than the results in the other examples which caused the discrepancy.

References Cited UNITED STATES PATENTS 3,181,992 5/1965 Michalski et ai 106-45 FOREIGN PATENTS 785,198 10/ 1957 Great Britain.

DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner TED wires mrrm OFFEQE CERTEHUUEFE Oi @ORREUHON pa e Ne, 3,691,077 Dated September 12, 1972 t fl Robert Earl Wann, Denzel Allan Nicholson & Ted Joe Logan It is certified thater'ror appears in the above-idntified patent and that: said Lstters Z'etent are hereby corrected as shown below:

Wage 1, Column l, in the heading after Cincinnati, Ohio, add a? ---'-j--' Assignors to the Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio I Col. 1, line l9, after "moieties" a'ndbefore "selected" delete I II,

Col. 1, line 45, "delete' "2,275, 359" and insert therefore 2,725,359 1 1 Col, 2, line 2, delete "arylkyl" and insert therefore aralky l v Col. line '35; delete "Phosphates" ai insert therefore Col. ,3, line: 2l6,i delete "teaching" and insert therefore teachings g 'Col. 4, line '47, (In the Table under Weld Point (kg. number 9 delete "Q70" and insert therefore 4,700

CoL- 6, line 72, delete second. occurrence of "point" Col, 8, Example 29 under "additive percent by weight delete O and insert therefore 10 Col 10, I line 27, after the first comma and before "atoms" insert and bromine Col., 10, line 27, after "bromine" and before "and" insert Signed and sealed this 19th day- 0f November 1974.

l (SEAL) Attest:

MCCOY M. GIBSDN JR, C, MARSHALL DANN Arresting Officer Commissioner of Patents