CA2189208C

CA2189208C - Antiwear enhancing composition for lubricants and functional fluids

Info

Publication number: CA2189208C
Application number: CA 2189208
Authority: CA
Inventors: James L. Sumiejski
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1996-07-17
Filing date: 1996-10-30
Publication date: 2000-05-30
Anticipated expiration: 2016-10-30
Also published as: CA2189208A1

Abstract

This invention relates to a composition, comprising: (A) a boron-containing overbased material; (B) a phosphorus acid, ester or derivative thereof; and (C) a borated epoxide or borated fatty acid ester of glycerol. In one embodiment the inventive composition further comprises (D) a thiocarbamate. These compositions are useful in providing lubricants and functional fluids, particularly automatic transmission fluids, with enhanced anitwear properties. In one embodiment these compositions also provide such lubricants and functional fluids with enhanced extreme-pressure and/or friction-modifying.

Description

27088-02 (CIA
Title: ANTTWEAR ENIiANCING COMPOSITION FOR LUBRICANTS
AND :FUNCTIONAL FLUIDS
Technical Field_ This invention relates to additive compositions that are useful for enhancing the antiwear properties of lubricants and functional fluids, especially automatic transmission fluids.
Background of the Invention ~s is a contunuing demand in the automotive and truck markets for automatic transmissions that can operate under more severe conditions and for longer periods of time than was previously acceptable. The automatic transmissions that meet these standards require improved automatic transmission fluids that are characterized by enhanced antiwear properties. The present invention fulfills this need.
Summary of the Invention This invention relates to a composition, comprising: (A) a boron-containing overbased material; I;B) a phosphorus acid, ester or derivative thereof; and (C) a borated epoxide or t~orated fatty acid ester of glycerol. In one embodiment, the inventive composition. further comprises (D) a thiocarbamate. These compositions are u~~l in providing lubricants and functional fluids, particularly automatic transmission fluids, with enhanced antiwear properties. In one embodiment these compositions also provide such lubricants and functional fluids with enhanced extreme-pressure and/or friction-modifying properties.
Description of the Preferred Embodiments As used in this specification and in the appended claims, the term "hydrocarbyl" denotes a group having a carbon atom directly attached to the remainder of the molecule and having a hydrocarbon or predominantly hydrocarbon character within the context of this invention. Such groups include the following:

(1) Hydrocarbon groups; that is, aliphatic, (e.g., alkyl or allo~yl), alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatio- and alicyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic groups, and the like, as well as cyclic groups wherean the ring is completed through another portion of the molecule (that is, any two indic~te<i substituents may together form an alicyclic group). Such groups are lrnown to those sin the art. Examples include methyl, ethyl, octyl, decyl, octadecyl, cyclohexyl, phenyl, etc.
(2) Substituted hydrocarbon groups; that is, groups containing non-hydrocarbon subst~ts which, in the context of this invention, do not alter the predominantly hydrocarbon c~arac~ of the group. Those sla'lled in the art will be aware of suitable substituents. Examples include halo, hydroxy, vitro, cyano, alkoxy, aryl, etc.
C3) o groups; that is, groups which, while predominantly hydrocarbon in character within tile context of this invention, contain atoms other than carbon in a chain or ring o~wise composed of carbon atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen and sulfur.
In geneaal, no more than about three substituents or het~o atoms, and preferably no more than one, will be preset for each 10 carbon atoms in the hydmcar byl group.
Teams such as "alkyl-based", "aryl~asad", and the like have meanings analogous to the above with respect to alkyl groups, aryl groups and the like.
The teen "hydrocarbon-based" has the same meaning and can be used interchangeably with the terrri hydrocarbyl when referring to molecular groups having a carbon atom attached directly to the nnmainder of a molecule.
The germ "lower" as used herein in conjunction with farms such as hydrocarbyl, alkyl, alkenyl, alkoxy, and the like, is int~ded to desctbe such groups which contain a total of up to 7 carbon atoms.
The term "oil-soluble" refeas to a material that is soluble in mineral. oil to the extent of at least about one gram per liter at 25°C.

(A) Boron-Containing Overbased Material.
Overbased products are metal salts or complexes characterized by a metal content in excess of that which would be present according to the stoichiometry of the metal and the particular acidic organic compound read with the metal, e.g., a sulfonic acid. The term "metal ratio" is used herein to designate the ratio of the total chemical equivalents of the metal in the ova material (e.g., a metal sulfonate or carboxylate) to the chemical equivalents of the metal in the product which would be expected to result in the reaction between the organic material to be overbased (e.g., sulfonic or carboxylic acid) and the metal-containing rea~ant (e.g., calcium hydroxide, barium oxide, etc.) according to the Irnown cheanical reiuxivity and stoichiometry of the two rea~nts.
The boron-containing overbased material (A) of this invention typically has a metal ratio in excess of 1 and generally up to about 40 or more. In one embodim~t, the metal ratio for component (A) is from an excess of 1 up to about 35, and in one embodiment from an excess of 1 up to about 30. The metal ratio generally ranges from about 1.1 or about 1.5 to about 40, and in ~e embodiment about 1.1 or about 1.5 to about 35, and in one embodiment about 1.1 or about 1.5 to about 30, and in one embodiment about 1.1 or about 1.5 to about 26. In one embodiment the meal ratio is from about 1.5 to about 30, and in one embodim~t about 6 to about 30, and in one embodiment about 10 to about 30, and in one embodiment about 15 to about 30.
In one embodiment, the meal ratio is from about 20 to about 30. Here, as well as throughout the specification, the range and ratio limits may be combined.
In one embodiment, the borated ovesbased material (A) is prepared by first Preparing an overbased material then contacting that overbased material with at least one boron compound. The overbased material is prepared by contacting a reason mixture comprising at least one organic material to be overbased, a reaction medium consisting essentially of at least one inert, organic solvent/diluent for said organic material to be overbased, a stoichiometric excess of at least one metal base and at least one promoter, with at least one acidic material. Methods for preparing the overbased materials as well as an extremely diverse group of overbased materials are well Irnown in the prior art and are disclosed, for example in the following U.S. patent 3,492,231.
The organic; material to be overbased is generally at Ieast one cuboxylic acid, sulfur-containing <~cid, phosphorus-containing aad, hydroxyammatic compound, precursor of any of the foregoing compounds, or mixture of two or more of any of the foregoing compounds or precursors.
u~ AGds The carboxylic acids useful as the organic ma~ial to be overbased may be aliphatic or aznmatic, mono- or polycarboxylic acid or acid~roducing compounds.
Throughout this spcxificabion and in the appended claims, any reference to ca~oxylic acids is intended to include the acid producing derivatives thereof such as anhydrides, esters, (lower, e.g. Cl~, alkyl esters), aryl halides, lactones and mixriues thereof unless otherwise spEx~ffically stated.
These carboxylic acids can have at least about 8, or at least about 12 carbon atoms, or at least albut 16 carbon atoms, or at least about 20 carbon atoms, or at least about 30 carbon atoms, or at least about 50 carbon atoms. Generally, these carboxylic acids do not contain more than about 400 or about 500 carbon atoms per molecule.
The monoc~rboxylic acids contemplated herein include and unsaturated ;acids. The monocarboxylic acids include fatty acids having from about 8 to about 30, or fiom about 10 to about 24 ca~fion atoms. F~camples of such useful monocarboxylic acids include dodecxnoic acid, palmitic acid, decanoic aciy, oleic acid, lauric acid, stearic acid, myristic acid, Iinoleic acid, linolenic acid, naphthenic acid, chlorostearic acid, tall oil acid, etc.
Anhydrides amd lower alkyl esters of these acids can also be used. N~ues of two or more such agents can also be used. An extensive discussion of these acids is found in Kirk-0thmer "Encyclopedia of Chemical Technology" Third Edition, 19733, John Whey & Sons New York, pp. 814-871 .
The monocarboxylic acids include isoaliphatic acids, i.e., a;cids having one or more lower acyclic F~endant alkyl groups. Such acids often contain a principal chain 2 o~2oa _5-having from about 14 to about 20 sat<uated, aliphatic carbon atoms and at least one but usually no more than about four pendant acyclic alkyl groups. The principal chain of the acid is exemplified by groups derived from tetradecane, pentadecane, heRadecane, heptadecane, octadecane, and ei~e. The pendant group is preferably a lower alkyl group such as methyl, ethyl, n propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, or other groups having up to about 7 carbon atoms. The pendant group may also be a polar-substituted alkyl group such as chloromethyl, bromobutyl, methoxyethyl, or the like, but it preferably contains no more than one polar substituent per group.
Specific examples of such isaaliphatic acids include 11-methyl-pentadecanoic acid, 3-ethyl-hexaderanoic acid, 6-methyl-octadecanoic acid, 16-methyl-odadecanoic acid, l5~thy1-heptxdecanoic acid, 3-chloromethyl-nonad~anoic acid, 7, 8,9,10-tetramethyl-octadecanoic acid, and 2,9,10-trimethyloctadecanoic acid.
The isoaliphatic acids include mixt<ues of branch-chain acids prepared by the isomerization of commercial fatty acids of, for example, about 16 to about 20 carbon atoms. A useful method involves heating the fatty acid at a temperature above about 250°C and a pressure between about 200 and 700 psi, distilling the cxude isomeaized acid, and hydrogenating the disttllate to produce a substantially saturated isomeaized acid. The isomerization can be promoted by a catalyst such as mineral clay, diatomaceous earth, aluminum chloride, zinc chloride, ferric chloride, or some other Friedel-Crafts c~lyst. The oonoentration of the catalyst may be as low as about 0.01 % , but more often from about 0.1 % to about 3 % by weight of the isomerization mixture. Water also promotes the isomerization and a small amount, from about 0.1 %
to about 5 % by weight, of water may thus be advantageously added to the isomerization mixture. 1fie unsat<uated fatty acids from which the isoaliphatic acids may be derived include oleac acid, linoleic acid, linolenic acid, and commercial fatty acid mixtures such as tall oil acids.
In one embodim~t the carboxylic acid is at least one hydrocarbyl-substituted carboxylic acid or anhydride. In one embodiment, die hydrocarbyl group has at least about 8 carbon atoms up to about 400, preferably at least about 12 to about 300, more preferably at least about 16 to about 200 carbon atoms. In one embodiment, the '~ 2189208 hydrocarbyl substituted carboxylic acid or anhydride is derived from the reaction of an w~riuated carboxylic reagent and a polyalkene. The unsa~uated carboxylic reagent includes mono, di , tri or tetracaiboxylic reagents. Specific examples of useful mono-basic unsaturated carboxylic acids are acrylic acid, methacrylic acid, cinnamic acid, S crotonic acid, 2 ph~ylpropenoic acid, and Iower alkyl esters thereof.
Exemplary polybasic acids include malefic acid, malefic anhydride, fumaric acid, mesaconic acid, itaconic acid and citraconic acid. Genially, the unsaturated carboxylic neag~t is malefic anhydride, acid or lower ester, e.g. those containing less than eight carbon atoms.
14 The polyalinclude homopolymers and interpolymers of olefins having from 2 to about 20 carbon atoms. The olefins include ethylene, Propylene, 1-but~e, isobutylene, I-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, i-heptene, 1-octene, styrene, 1-none, 1-deoene, 1-iuideoene, 1-dodeoene, 1-trideoene, 1-tetradeceene, l~enta;deoene, 1-hexadene, 1-heptadeoene and 1-ocxadecene.
ITigh~
15 olefin mixt<ues such as olefins in the range of about 18 to about 24 carbon atoms can be used. The hydrorarbyl group, R, can be derived from at least one alpha-olefin fraction selecr~ from the group consisting of Cu.ia alpha-olefins, Clm6 alpha-olefins, Clø16 alpha-olefins, Cløl8 alpha-olefins and Clms alPha.~lefins. In one embodiment, R is an alkyl or an alkenyl group. Examples of polyalkenes include polybutene, 20 polyisobutylene, ethylene-propylene copolymer, polypropylene, and mixtures of two or more of any of these. Included in this group are those derived finm polybut~e in which at least about 50% of the total units derived from butenes is derived from isobutylene.
In one embodiment, the polyalkene is characterized by an Mn (number average 25 molecular weight) of at least about 200 or at least about 400. Generally, the polyalkene is characterized by having an Mn finm about 500 up to about 5000, or from about 700 up to about 3000, or from about 800 up to 2500, or from about 900 up to about 2000. In another embodiment, Mn varies from about 500 up to about 1500, or from about 700 up to about 1300, or from about 800 up to about 1200. In another 30 embodiment, the polyalkenes have an Mn from about 1300 up to about 5000, or from _7_ about 1500 up to about 4500, or from about 1700 up to about 3000. In one embodiment, the Fblyal~s have an Mw/Mn from about 1 to about 10, or from about 1.5 to about :S, or from about 2.5 to about 4.
In another embodiment, the acylating agents may be prepay by rig one or more of the ab~we described polyallcenes with an excess of maleac anhydride to provide substituted sua,~inic acylating agents wherein the number of succinic groups for each equivalent weight of substituent group, i.e., polyallaenyl group, is at least 0.9.
The maximum number will generally not exceed 4.5. A suitable range is from about 1.3 to 3.5 and or from about 1.5 to about 2.5 suaxnic groups per equivalent weagllt of substituent groups.
In one embodiment, the carboxylic acid is at least one substituted suocinic acid or anhydride, said substituted succanic acid or anhydride has a polybuteayl group characterized by an Mn value of about 1500 to about 2000 and an Mw/Mn value of about 3 to about 4. These acids or anhydrides are characterized by the presence within their structure of ~~n aveaage of about 1.5 to about 2.5 succlnic groups for each equivalent weight of substituent groups. In another embodiment, the carboxylic acid or anhydrideis a polybutenyl suocinc anhydride wherein the polybutenyl group has an Mn value of about 1300 to about 1200; an Mw/Mn value of about 2 to about 3;
and is characterized by the presence within their stru~u~e of an average of about 0.9 to about 1.2 succinic groups for each equivalent weight of substituent groups.
Hydmcarbyl-substituted carboxylic acids suitable for use as the organic material to be overbasad are described in detail in the following U.S. Patents: U.S.
Patents 3,219,666; and 4,234,435.
A useful group of carboxylic acids are the aromatic carboxylic acids. These acids can be represented by the formula Xi II
(R).-(~') - C - X~i b (n 2. i 89208 wherein R is an aliphatic hydmcarbyl group of preferably-about 4 to about 400 carbon atoms, a is a number in the range of zero to about 4, Ar is an aromatic group, Xl and X2 are independently sulfur or oxygen, and b is a number in the range of from 1 to about 4, with the proviso that the sum of a and b does not exceed the number of unsatisfied valences of Ar. Preferably, R and a are such that there is an average of at least about 8 aliphatic carbon atoms provided by the R groups. The aromatic gmups Ar that are useful include the polyvalent aromatic gmups derived from benzene, naphthalene, anthracene, phenanthrene, indene, fluorene, biphenyl, and the like.
Generally, the Ar groups used herein are polyvalent nuclea derived from beazene or naphthal~e such as pheuyl~es and naphthylene, e.g., methylph~ylenes, ethoxyphenylenes, nitrophenylenes, isopmpylphenylenes, hydroxyphenylenes, merraptophenylenes, N,N-diethylaminophenylenes, chlor~ophenylenes, dipropoxy-naphthylenes, taethylnaphthylenes, and similar tri-, tetra , pentavalent nuclei thereof, etc. These Ar groups may contain non~ydmcarbon substituents, for example, such diverse substihients as lower alkoxy, lower alkyl m~apto, vitro, halo, alkyl or alkenyl groups of less than about 4 carbon atoms, hydroxy, memapto, and the lie.
F.xacnples of the R groups include butyl, isobutyl, pentyl, octyl, ~ nonyl, dodecyl, dooosyl, tetzacontyl, 5-chlomhexyl, 4-ethoxypmtyl, 4-hexenyl, 3-cyclohexyloctyl, 4-~P-~°~Ph~Y'~ 2,3,5-tdrnethylhept~rl, 4~xhy15-methylodyl, and substituents derived from polymerized olefins such as polychlomprenes, polyethylenes, PoIYP~PYl~es, polyisobutylenes, ethylenepropylene copolymers, chlorinated olefin polymers, oxidized ethylene-propylene copolymers, and the like.
A group of useful carboxylic acids are those of the formula Xi ~ I
~c-x~,, wherein R, Ar, Xl, X2, a and b are as defined in Formula I, X3 is oxygen or sulfur, and c is a number in the range of 1 to about 4, usually 1 to about 2, with the proviso that the sum of a, b and c does not exoead the unsatisfied-valences of Ar.
Within this group are the carboxylic acids of the formula (COOI~b (OHM
wherein R is an aliphatic hydrocubyl group preferably containing from about 4 to about 400 carbon atoms, a is a number in the range of from zero to about 4, preferably 1 to about 3; b is a number in the range of 1 to about 4, preferably 1 to about 2, c is a number in the range of 1 to about 4, preferably 1 to about 2, and more preferably 1;
with the proviso thax the sum of a, b and c does not exceed 6. Preferably, R
and a are such that the acrd rnolecules contain ax least an average of about 12 aliphatic carbon atoms in the aliphatic hydr~arbon substituents per acid molecule. Also useful are the aliphatic hydmru~~n-substituted salicylic acids wherein each aliphatic hydrocarbon substituent contains an average of at Ieast about 8 carbon atoms per substituent and 1 to 3 substituents per molecule. Salts prepared from such salicylic acids wheaein the aliphatic hydrocarbcm substitue~rts are derived from polymerized olefins, particularly polymerized lower 1-mono-olefins such as polyethylene, polypropylene, polyisobutylene, etlrylenelpropylene copolymers and the like and having average carbon contearts of about 30 to about 400 carbon atoms are particularly useful. The aromatic carboxylic acids corresponding to the above formulae are well known or can be prepared according to procedures known in the art. Carboxylic adds of the type illustrated by these l:ormulae and processes for preparing their neutral and basic metal salts are well lrnown and disclosed, for example, in U.S. Patents 2,197,832;
2,197,835; 2,252,6ti2; 2,252,664; 2,714,092; 3,410,798; and 3,595,791.

'' 2.189208 -lo-Sulfur-Containing Acids The sulfur-containing acids include the sulfonic, sulfamic, thiosulfonic, sulfinic, sulfenic, partial ester sulfuric, sulfurous and thiosulfuric acids.
The sulfonic acids include the mono- or polynuclear aromatic or cycloaliphatic compounds.
The sulf°n~c adds and sulfonates can be represented for the most part by the following formulae:
~1s T-(s~~~'ta or (RZ-(S~~°Ma In the above formulae, T is a cyclic nucleus such as, for example, b~zene, naphthalene, anthraoene, pheaanthrene, diphenyl~e oxide, thianthrene, phenothioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, Biphenyl sulfide, diphenylamine, cyclohexane, petroleum naphth~es, decahydronaphthalene, cyclopentane, etc.; Rl is an aliphatic group such as alkyl, allacnyl, allcoxy, aIkoxyalkyl, carboallooxyallcyl, etc.;
a is at least 1, and Ri,+T contains a total of at least about 15 carbon atoms.
R2 is an aliphatic hydrocarbyl group containing at least about 15 carbon atoms.
Faamples of R2 ~ ~Yh ~Yh ~xY~y~ ~'boalkozyalkyl, etc. Specific examples of R2 are groups derived from petrolatum, saturated and unsaturated paraffin wax, and polyolefins, including polymeaized C.i, C3, C4, C5, C6, etc., olefins containing from about 15 to 7000 or more carbon atoms. The groups T, Rl, and R2 in the above formulae can also contain other inorganic or organic substituents in addition to those enumerated above such as, for example, hydroxy, m~capto, halog~, nitm, amino, nitroso, sulfide, disulfide, etc. M is hydrogen or a metal ration (e.g., alkali or allcaline earth metal), and a, b, c and d are each at least 1.
The following oil soluble sulfonic acids are useful: mahogany sulfonic acids;
bright stock sulfonic acids; sulfonic acids deaived from lubricating oil fiactions having a Saybolt viscosity from about 100 seconds at 100°F to about 200 seconds at 210°F;
petrolatum sulfonic acids; mono- and poly-wax-substituted sulfonic and polysulfonic acids of, e.g., benzene, naphthalene, phenol, Biphenyl ether, naphthalene disulfide, diphenylamine, thiophene, alpha~hlomnaphthalene, etc.; other substituted sulfonic '' ?_.187208 acids such as alkyl benzene sulfonic acids (where the alkyl group has at least 8 car-bons), cetyiphenol mono-sulfide sulfonic acids, dicetyl thianthrene disulfonic acids, dilauryl beta naphthyl sulfonic acids, dicapryl nitronaphthal~e sulfonic acids, and alkaryl sulfonic acids such as dodecyl beazene "bottoms" sulfonic acids.
The latter are acids derived from benzene which has been alkylated with propylene tetramers or isobutene trims to introduce l, 2, 3, or more branched-chain C12 substifuents on the b~zene ring. Dodecyl benzene bottoms, principally miztures of mono- and di-dodecyl b~z~,s, are available as by-products from the manufa~ure of household detergents. Similar products stained from alkylation bottoms formed during manufacture of linear alkyl sulfonates (LAS) are also useful. in malting the sulfonates used in this inv~tion.
Also included are aliphatic sulfonic acids such as paraffin wax sulfonic acids, undated paraffin wax sulfonic acids, hydrozy-substituted para~n wax sulfonic acids, hexapropylene sulfonic adds, tetra amyl~e sulfonic acids, polyisobutene sulfonic acids wherean the polyisobutene contains from 20 to 7000 or more carbon atoms, chlorn-substituted paraffin waz sulfonic acids, nitroparafhn wax sulfonic acids, etc.; cycloaliphatic sulfonic acids such as petroleum naphth~e sulfonic acids, cetyl cyclop~tyl sulfonic acids, lauryl cyclohearyl sulfonic acids, bis-(di-isobutyl) cyclohezyl sulfonic acids, mono- or poly wax substituted cyclohezyl sulfonic acids, etc.
With respect to the sulfonic acids or salts thereof described herein and in the appended claims, it is intended herein to employ the term "petroleum sulfonic acids" or °petroleum sulfonates" to cover all sulfonic acids or the salts thereof derived from petroleum products. A useful group of petroleum sulfonic acids are the mahogany sulfonic acids (so called because of thear reddish-brown color) obtained as a by~r~oduct from the manufacbue of petroleum white oils by a sulfuric acid process.
PhoSphOrus-Con aininø
The phosphorus-containing acids can be represented by the formula Rl~l~a P_X4H
R2~2 wherein Xi, X2, X3 and X4 are independently O, S or NR3 wh~~ein R3 is hydrogen or a hydrocarbyl group, preferably hydrogen or a lower alkyl group; a and b are independently zero or one, and Ri and R2 are independently hydrogen or hydmcarbyl groups. These phosphorus~ontaining acids include the phosphorus- and sulfur-oon-taming acids. They include those acids wherein at least one X3 or X4 is sulfur, and more preferably both X3 and X4 are sulfur, at least one Xl or X2 is oxygen or sulfur, more preferably both X' and X2 are oxyg~, and a and b are each 1. ~xhues of these acids may be employed in aooordance with this invention. Rl and RZ are independently hY~°g~ °r hydmcarbyl groups that are preferably free from acetylenic unsatiuation and usually also from ethyl~ic un~adon. The total number of c~bon atoms in Rl and R2 must be sufficient to render the compound soluble in the reaction medium.
Generally this total is at least about 8 carbon atoms, and in one embodim~t at least about 12 carbon acorns, and in one embodiment at least about 16 carbon atoms, and in one embodiment at least about 20 carbon atoms. In one embodiment, Rl and R2 independ~tly have up to about 400 or about 500 carbon atoms. Each Rl and R2 can be the same as the other, although mey may be different and either or both may be mixtures. Examples of useful Rl and RZ groups include t-butyl, isobutyl, amyl, isooctyl, dacyl, dodecyl, eicosyl, dodec~yl, naphthyl, alkylphenyl, alkylnaphthyl, ph~Y~3'~ ~PhmY~3'1~ ~ylphenylalkyl, alkylnaphthylalkyl, and the like.
The phosphorus~ontaining acids can be at least one phosphate, phosphonate, phosphinate or phosphine oxide. These pentavalent phosphorus derivatives can be represented by the formula ~- 2189208 Ry(O~ _ Rz-(O~ ~ P~
R3 -(Ok wherein Rl, . RZ and R3 are independently hydrocarbyl groups, or hydrogen and a, b and c are independently zero or 1. The phosphorus-containing acid can be at least one phosphite, phosphonite, phosphinite or phosphine. These trivalent phosphorus derivatives can be repres~ted by the formula R -(O) Rz-(Oh, P
R3 -(Ok wherein Rl, R2 and R3 are independently hydrocarbyl groups, and a, b and c are independently zerio or 1. The total number of carbon atoms in Rl, R2 and R3 in each of the above formulae must be sufficient to render the compound soluble in the reaction medium. Geneaally, the total number of carbon atoms in RI, R2 and R3 is at least about 8, and in one embodiment at least about 12, and in one embodiment at least about 16. There is no limit to the total number of carbon atoms in Rl, R2 and R3 that is required, but a practical upper limit is about 400 or about 500 carbon atoms. In one embodiment, Rl, R2 and R3 in each of the above formulae are independently hydrocarbyl groups of preferably 1 to about 100 carbon atoms, or 1 to about 50 carbon atoms, or 1 to about 30 carbon atoms, with the proviso that the total number of carbons is at least about 8. Fach Rl, R2 and R3 can be the same as the other, although ~eY ~Y ~ ~~t. Examples of useful Rl, R2 and R3 groups include hydrogen, t butyl, oisobutyl, amyl, isooctyl, decyl, dodecyl, eicosyl, 2-pentenyl, dodeoenyl, phenyl, naphthyl, alkylphenyl, alkylnaphthyl, pher~ylalkyl, naphthylalkyl, alkylphenylalkyl, alkY~Ph~Y~YI~ ~d the like.
In another embodiment, the phosphorus acid is characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the treatrnent of an olefin polymer, such as one or more of the above polyalkenes (e.g., polyisobut~e 21~920~

having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride.
Iivdroxyaromatic Compounds The organic material to be overbased can be at least one hydroxyaromatic compound represented by the formula: Ra Ar-(~,, , wheaean R is an aliphatic hydrocarbyl group of generally about 4 to about 400 carbon atoms;
Ar is an aromatic group; X is O, S, CH20 or CHzNRI, wherean RI is hydrog~ or a hydrocarbyl group (preferably alkyl yr allaenyl) of generally 1 to about 30 carbon atoms, and in one embodiment 1 to about 20 carbon atoms, and in one eanbodimeut 1 to about 10 carbon atoms; a and b are independently numbers of at least one, the sum of a and b being in the range of two up to the number of displaceable hydrogens on the aromatic nucleus or nuclei of Ar. Generally, a and b are indep~dently numbers in the range of 1 to about 4, and in one embodiment 1 to about 2. R and a are such that them 1 S is a sufficient number of aliphatic carbon atoms in the R groups to render the compound soluble in the reason medium. Generally, there is an average of at least about 8 aliphatic carbon atoms, and in one embodiment at least about 12 carbon atoms, provided by the R groups.
In one embodim~t, X is O and the fiuxfiionally-substituted aromatic compound is a phenol. With such phenols, however, it is to be understood that the aromatic group Ar is not a limited benzene, as discussed below.
The R group is a hydrocatbyl group that is directly bonded to the aromatic group Ar. R generally contains about 6 to about 80 carbon atoms, and in one embodiment about 6 to about 30 carbon atoms, and in one embodiment about 8 to about 25 carbon atoms, and advantageously about 8 to about 15 carbon atoms.
Examples of R groups include butyl, isobutyl, pentyl, oclyl, nonyl, dodecyl, dodecosyl, tetracontyl, 5-chlorohexyl, 4~thoxypentyl, 4-hexenyl, 3-cyclohexyloctyl, 4-(p~hlorophenyl)-octyl, 2,3,5-trimethylheptyl, 4-ethyl-5-methyloctyl, and substituents derived from polymerized olefins such as polychloroprenes, polyethylenes, polypropylenes, polyisobutylenes, ethylene-propylene copolymers, chlorinated olefin 218~2~8 polymers, oxidized ethylene-propYl~e copolymers, - PmPYlene tetramer and tri(isobutene). In one embodiment, R is a hydrocarbyl group as defined above for caboxylic acids.
As will be appreaated from inspearon of the above formula, these compounds contain at least one R group, as defined above, and at least one functional group XH.
Each of the foregoing must be ato a carbon atom which is a part of an aromatic nucleus in the Ar group. They need not, however, each be attached to the same aromatic ring if mom than one aromatic nucleus is present in the Ar group.
It is to be undeastood that ~e aromatic group as represented by "Ar" in the above formula, as well as elsewhea~e in other formulae in this specification and in the app~ded claims, can be mononuclear such as a ph~yl, a pyridyl, a thieayl, or polynuclear. The polynuclear groups can be of the fused type wherein an aromatic nucleus is fused at two points to ano~er nucl~s such as found in naphthyl, anthranyl, azanaphthyl, etc. The polynuclear group can also be of the linked type wherein at least two nuclei (either mononuclear or poiynuclear) are linked through bridging linkages to each other. These bridging linkages can be chosen from the group consisting of ~bon-to-carbon single bonds, ether linkages, keto linkages, sulfide linkages, polysulfide linkages of 2 to about 6 sulfur atoms, sulfinyl linkages, sulfonyl linkages, alkylene linkages, alkylid~e linkages, lower alkylene ether linkages, alkylene keto linkages, lower alkylene sulfur linkages, lower allrylene polysulfide linkages of 2 to about 6 carbon atoms, amino linkages, polyamino linkages and mixtures of such dival-ent bridging linkages. In certain insmnoes, more than one bridging linkage can be Present in Ar between two aromatic nuclei; for example, a fluor~e nucleus having two benzene nuclei linked by both a methylene linkage and a covalea~t bond. Such a nucleus may be consid~ea~ed to have three nuclei but only two of them are aromatic.
Normally, however, Ar will contain only carbon atoms in the aromatic nuclei per se (plus any alkyl or alkoxy substituent present).
The number of aromatic nuclei, fused, linked or both, in Ar can play a role in determining the integer values of a and b in the above formula. For example, when Ar contains a single aromatic nucleus, the sum of a and b is from 2 to 6. When Ar 2 ~ ~~2oa contains two aromatic nucl~, the sum of a and b is from -2 to 10. With a tri-nuclear Ar moiety, the sum of a and b is from 2 to 15. The value for the sum of a and b is limited by the fact that it cannot exceed the total number of displa~oeable hydrogens on the aromatic nucleus or nuclea of Ar.
In one embodiment, the organic material to be overbased is at least one phenol represented by the formula Oyy'b v l1~ c wherein R is a hydmcarbyl group of about 4 to about 400 carbon atoms; R1 is a lower alkyl, lower alkoxyl, amino, aminomethyl, mercapto, amido, thioamido, vitro or halo group; a is a number in the range of 1 to about 3; b is 1 or 2; and c is 0 or 1. Usually R is derived from a homo- or int~polymer of monoolefins having from 2 to about carbon atoms and is in a position para to the -0H group. In one embodiment, R
is one or more of the above polyalkene groups. Specific examples of the substituent R
are a polypropylene group of about 60 too about 340 carbons, a poly(ethylenelpropyl~e) group of about 110 to about 260 carbons (equimolar monomer ratio), a poly(isobutene) group of about 70 to about 320 carbon atoms, and a poly(1-hexe~nell-ocxenell-dame) group of about 400 to about 750 carbons (equimolar monomer ratios).
Reaction Medium The reaction medium used to prepare the overbased product (A) is a substantially inert, organic solvent/diluea~t for the organic material to be overbased.
Examples include the alkanes and haloalicanes of about 5 to about 18 carbons, alkyl ethos, alkanols, alkylene glycols, alkyl ethers of allrylene glycols and polyalkyl~e glycols, dibasic alkanoic acid diesters, silicate esters, and mixtures of these. Specific examples include pentane, hexane. octane_ cvl'.lnnPntanP r~vnlnt,AV",o isopropylcyclohexane, cyclooctane, halobenzenes such as mono- and polychlorobenzenes, mineral oils, isobutylether, methyl-n-amylether, methoxybenzene, 2~'.'92~8 p-methoxytoluene, methanol, ethanol, propanol, isopropanol, hexanol, alkylene glycols such as ethylene glycol and propylene glycol, diethyl lcetone, methylbutyl laetone, dimethylformamide, dimethylacetamide, diisocxyl azelate, polyethyl~e glycols, PoIYP~PYIene glycols, etc.
From the standpoint of availability, cost, and performance, the allcyl, cycloalkyl, and aryl hydrocarbons represent a useful class of reaction mediums. Liquid petroleum fiactions represent another useful class. Included within these classes are benzenes and alkylated benzenes, cycloal>mnes and alkylatsd cycloalkanes, cycloalkenes and alkylated cycloal>ornes such as found in naphthene_based petroleum fractions, and the alkanes such as found in the par~f n-based petroleum fractions.
Petroleum ether, naphthas, mineral oils, Stoddard Solvent, toluene, xylene, etc., and mixtures thereof are examples of economical sources of suitable inert organic liquids which can function as the reaction medium. Particularly useful are those containing at least some mineral oil as a component of the reaction medium.
Meal Base The metal base used in preparing the oveabased products is selected from the group consisting of alkali metals, alkaline~arth metals, titanium, zirconium, molybdenum, iron, copper, zinc, aluminum, mixttue of two or more thereof, or basically reacring compounds thereof. The mdal can be an alkali metal, alkaline-earth metal, zinc, aluminum, or a mixdire of two or more thereof. Lithium, sodium, Potassium, magae~um, calcium and barium are useful. The metal bases include alkoxides, nitrites, carboxylates, phosphites, sulfites, hydrog~ sulfites, carbonates, hydrog~ carbonates, borates, hydroxides, oxides, alkoxides, and amides of one or more of the above metals. The nitrites, carboxylates, phosphites, alkoxides, carbonates, borates, hydroxides and oxides are useful. The hydroxides, oxides, alkoxides and carbonates are especially useful.

mo The promoters, that is, the materials which permit the incorporation of the excess metal into the overbased product, are also quite diverse and well lrnown in the art as evidenced by the cited patents. These materials must be less acidic than the acidic material usa3 in roiling the oveabased products. A particularly oowe discussion of suitable promoters is found in U.S. Patents 2,777,874;
2,695,910; and 2,616,904. These iinclude the alcoholic and phenolic promoters which are preferred.
The alcohol promoters include the alkanols of one to about 12 carbon atoms.
Examples of the alcohols include methanol, ethanol, isopropanol, amyl alcohol, cyclohexanol, octanol, dodecanol" decanol, behenyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, monomethylether of ethylene glycol, trimethylene glycol, hexamethylene glycol, glycerol, pentaerythritol, benzyl alcohol, phenylethyl alcohol, sorbitorl, nitropropanol, chloroethanol, aminoethanol, cinnamyl alcohol, allyl alcohol, and the like. Phenolic promoters include a variety of hydroxy-substituted benzenes and ~phthalenes. A particularly useful class of phenols are the alkylated phenols, such as heptylphenol, octylphenol, nonlyphenol, dodecyl phenol, propylene tetramer phenol, etc.
Mixtures of various promoters can be used.
Acidic Material Suitable acidic materials are also disclosed in the above cited patents, for example, U.S. Patent 2,616,904. Included within the lrnown group of useful acidic materials are c~rbamic acid, acetic acid, formic acid, boric acid, trinitromethane, SCE, C41, sources of said acids, and mixtures thereof. COi and SCE, and sources thereof, are useful. Usefrd sources of COi include urea, carbamates and ammonium carbonates. Useful. sources of S02 include sulfurous acid, thiosulfuric acid and dithionous acid. CC~ is especially preferred.
Preparation of the Overbased Material In one embodiment, the overbased materials are prepared by contacting a mixture of the orgarnc material to be overbased, the reaction medium, the metal base, and the promoter, ~avith the acidic material. The tempera>xue at which the acidic ..-- 2189208 material contacts the remainder of the reacrion mass depends to a large measure upon the promoter that is used. With a phenolic promoter, the temperature usually ranges from about 60°C to about 300°C, and often from about 100°C to about 200°C. When an alcohol or m~tan is used as the promoter, the temperature usually does not exceed the reflux teznpezxri~re of the reaction mixture and preferably does not exceed about 100°C. The exact nature of the resulting overbased mad is not known.
However, it can be adequately deb for purposes of the present specification as a single phase homogeneous mixt<me of the reaction medium and (1) either a metal.
complex formed from the metal base, the acidic mateaial, and the organic material to be overbased and/or (2) an amorphous metal salt formed from the reaction of the acidic material with the metal base and the organic material to be overbased. Thus, if mineral ofi is used as the reaction medium, p~sulfonic acid as the organic material which is ov~based, Ca(OH~ as the metal base, and carbon dioxide as the acidic mateaiai, the resulting overbased mad ~n be described for purposes of this 1 S invention as an oil solution of either a metal containing complex of the acidic material, the metal base, and the petrosulfonic acid or as an oil solution of amorphous calcium carbonate and calcium petmsulfonate. Since ~e overbased materials are well known and as they are used merely as intermediates in the preparation of ~e boron-containing overbased rnateaials (A) employed herean, the exact nature of these materials is not critical to the present inv~tion.
Preparation of the Boron-Containing Overbased Materials The boron-containing overbased mateaial (A) can be prepared by contacting at least one overbased material with ~ l~ one boron compound. The boron compound ~ ~ b°~ °~de~ boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boron acids such as boronic acid r.e., alkyl-B(OH)2 or aryl-B(OH~, boric acid ('~.e., H3B03), tetraboric acid ~.e., H2B40~), metaboric acid (i.e., HBO, boron anhydrides, and various esters of such boron acids. The use of complexes of boron irihalide with ethers, organic acids, inorganic acids, or hydro carbons is a convenient means of introducing the boron reac~nt into the reaction 218~2Q~
-20.
The boron acid esters include especially mono-, di-, and tri-organic esters of boric acid with alcohols or phenols such as, e.g., methanol, ethanol, isopropanol, cyclohexanol, cyclopentanol, 1-~odanol, 2-octanol,. ~yl alcohol, 2-butyl cyclohex-anol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 2,4-hexanediol, glycerol, triethylene glycol, tripropylene glycol, phenol, naphthol, p-butylphenol, o,p-diheptylpheaol, n-cyclohexylphenol, 2,2~is-(p-hydroxyphenyl~
propane, o-chlorophenol, m-nitrophenol, 6-bmmooctanol, and 7 keto-decanoi.
Lower alcohols, 1,2-glyools, and 1-3-glycols, i.e., those having less than about 8 carbon atoms are especially useful for preparing the boric acid esters for the purpose of this invention.
Methods for preparing the esters of boron acid are lrnown and disclosed in the ~ (~~ ~ "c~ ~," pp. 959-1064, Vol. 56). Thus, one method involves the reaction of boron tachloride with 3 moles of an alcohol or a phenol to result in a tri-organic borate. Another method involves the reaction of boric oxide with an alcohol or a phenol. Another method involves the direct esterification of tetra boric acid with 3 moles of an alcohol or a phenol. Still another method involves the direct esterification of boric acid with a glycol to form, e.g., a cyclic alkylene borate.
The contacting of the overbased mat~iai with the boron compound can be effected using smndard mixing techniques. The ratio of equivalents of the boron compound to equivalents of the overbasad material can range up to about 40:1 or higher, and is typically in the range of about 0.05:1 to about 30:1, and is often in the range of about 0.2:1 to about 20:I. Equivalent ratios of about 0.5:1 to about 5:1, or about 0.5:1 to about 2:1, and often about 1:1 can be used. For purposes of this invention, an equivalent of a boron compound is based upon the number of moles of boron in said compound. Thus, boric acid has an equivalent weight equal to its molar weight, while tetraboric acid has an equivalent weight equal to ona-fourth of its molar weight. An equivalent weight of an overbased material is based upon the number of equivalents of metal in said overbaseri material available to react with the boron. An equivalent of a metal is dependent upon its valence. Thus, one mole of a monovalent metal such as sodium provides one equivalent of the metal, whereas two moles of a 21 ~9~i~8 divalent metal such as calcium are inquired to provide one equivalent of such metal.
This number can be measured using standard techniques (e.g., titration using bromophenol blue as the indicator to measure total base number). Thus, an overbased material having one equivalent of metal available to react with the boron has an equivalent weight equal to its actual weight. An overbasad material having two equivalents of metal available to react with the boron has an equivalent weight equal to one-half its actual weight.
The temperature can range from about room temperature up to the decomposition tempeaa~ue of the rea~nts or desired products having the lowest such temperature, and is generally in the range of about 20°C to about 200°C, and in one embodiment about 20°C to about 150°C, and in one embodiment about 50°C to about 150°C, and in one embodiment about 80°C to about 120°C.
The contacting time is the time required to form the desired conc~tration of metal borate (e.g., sodium borate) in the boron-containing oveabased material (A).
This concentration can be measured using standard techniques (e.g., measurement of the concentration of dissolved solids when the boron compound is a solid, measurem~t of the water of reaction formed by the borating process, measurem~t of the displacement of acidic material , e.g., COi, from the overbased product (A), etc.
Generally, the contacting time is from about 0.5 to about 50 hours, and often is from about 1 to about 25 hours, and in one embodiment about 1 to about 15 hours, and in one embodim~t about 4 to about 12 hours.
The following Example A illustrates the preparation of a boron-containing over-based material (A) that is useful in accordance with the invention. Unless otherwise indicated in the examples as well as throughout the specification and the appended claims, all parts and percentages are by weight, all temperatures are in degrees centigrade, and all pressures are atmospheric.
Example A-1 Fart I:
A mixture of 1000 parts of alkyl benzene sulfonic acid in oil (24. 8 % oil), parts of o-xylene, and 75.2 parts of polyisobutenyl (number average molecular weight = 950) suocinic anhydride is charged to a reaction vessel and the temperature is adjusted to 31.9°C. 87.3 parts magnesium oxide are added to the mixture. 35.8 parts of acetic acid are then added to the mixture. 31.4 parts of methanol and 59 parts of water are added to the mixture. The mixture is carbonated, the temperature of the mixture being 34.7-40.2°C. 87.3 parts of magnesium oxide, 31.4 parts of methanol and 59 parts of water are added to the mixture, and the mixture is again Carbonated.
87.3 parts of magnesium oxide, 31.4 parts of methanol and 59 parts of water are again added to the mixture, and the mixtiue is again carbonated. The total amount of carbon dioxide added is 232 parts. Methanol, o-xyl~e, and water are removed by atmospheaic and vacuum flash stripping. The reaction mixture is cooled and filtea~ed to provide the de,9red overbased magnesium sulfonate having a metal ratio of 14.7 and a diluent contest of 42~ by w~ght.
Part II:
A mixture of 5580 parts of the product from Part (n and 2790 parts of tolu~e are charged to a r~ion vessel. A slow nitrogen purge is started. The mixture is stuTed and die t~pe~at<ue is adjusted to 45°C. 1395 parts of boric acid are added to the miztiu~e over a period of IO minutes. The mixture is heated from 45°C to 96°C
over a peaiod of 4.5 hours. The mixture is maintained at 80-96°C for 16 hours. The mixture is heated from 80°C to 102°C over a period of 3 hours.
The mixtiu~e is the heated from 102°C to 120°C over a peaiod of 5 hours. 310 parts of water distillate are removed. The toluene phase of the distillate is added back to the reaction vessel. The mixture is heated to 148°C ova a 5-hour period with full distivate removal. 296 parts of diatomaceous earth are added to the mixture and the mixture is filtered over a two-~Y period. The resulting product has a sulfur content of 1.29 qb by weaght, a magnesium content of 8.28% by weaght, and a boron content of 4.66 by weight.
B) Phasnhorus Acid Fster or Derivative.
The lubricating compositions include at least one phosphorus acid, phosphorus acid ester or phosphorus acid salt or derivatives thereof. The phosphorus acids, esters, salts or derivatives thereof include compounds selected from the group consisting of phosphorus acid esters or salts thereof, phosphites, phosphorus containing amides, phosphorus-containing carboxylic acids or esters, phosphorus containing ethers and mixtures thereof. lfncluded in this Section (B) are the phosphorus~ontaining acids listed above in Section (A).
The phosphorus acids include the phosphoric, phosphoric, phosphinic and thiophosphoric acids including dithiophosphoric acid as well as the monothiophosphor-ic, thiophosphinic and thiophosphoric ands. Included in this group are the phosphorus-containing ands desc~ed above under the subtitle 'Phosphorus Containing Acids." Phosphosc aad is a preferred component of the compositions of this invention.
Eighty five peroeut phosphoric acid is the preferred compound for addition to the fully formulated ATF package and is included at a level of about 0.01-0.3 weight percent based on the weaght of the ATF.
The phosphorus acid esters can be prepared by reacting a phosphorus acid or anhydride with an alcohol containing from 1 or about 3 carbon atoms up to about 30, 1 S yr about 24, or about 12 carbon atoms. The phosphorus acid or anhydride is generally an inorganic phosphorus reagent such as phosphorus pentaoxide, phosphorus trioxide, phosphorus tetraoxide, phosphorus acid, phosphorus halide, or lower phosphorus esters, and the like. Lower phosphorus acid esteas contain from 1 to about 7 carbon atoms in each ester group. The phosphorus acid ester may be a mono, di- or triphosphoric acid estea.
Alcohols used. to prepare the phosphorus acid esters include butyl, amyl, hexyl, octyl, oleyl, and cresol aloohols. Higher synthetic monohydric aloohols of the type formed by Oxo process (e.g., 2-ethylhexyl), the Aldol condensation, or by organo aluminum catalyzed oligomerizabion of alpha-olefins (especially ethylene), followed by oxidation and hydrolysis, also are useful. Examples of some preferred monohydric alcohols and alcohol mixtures include the commercially available "Alfol~
aYcohols marketed by Continental Oil Corporation. Alfol 810 is a mixture of alcohols containing primarily straight chain, primary aloohols having from 8 ' to 10 carbon atoms. Alfol 12 is a mixture of alcohols containing mostly C12 fatty alcohols.
Alfol 1218 is a mixture of synthetic, primary, shaight-chain alcohols containing primarily 12 ,I"'"", to 18 carbon atoms. The Alfol 20+ aloohols are mixt<u~es-of Cls-C~ primary aloohols having mostly, on an alcohol basis, Cm alcohols as determined by GLC
(~-~1~-~oaphY)~ The Alfol 22+ aloohols are Cls-C~ Primary aloohols containing primarily, on an alcohol basis, C~ aloohols. These Alfol aloohols can contain a fairly large percentage (up to 40% by weight) of para~nic oompowrds which can be removed before the reaaron if deared.
Another example of a commerraally available alcohol mixriu~e is ~ 60 which comprise',s about 75% by weight of a straight chain C~ primary alcohol, about 15% of a Cio primary alcohol and about 8 % of Cl8 and Cu alcohols. Adol 320 comprises predominantly oleyl alcohol. The Adol alcohols are marketed by Ashland Chemical.
A of mixtures of monohydric fatty aloohols deaived from naturglly ooauting t~iglYand ranging in chain length of from Cs to Cls are available from Pmctor & Gamble Company. These mixtures contain various amounts of fatty aloohols containing mainly 12, 14, 16, or i8 carbon atoms. For example, CO-1214 is a fatty alcohol mixriu~e containing 0.5% of Clo alcohol, 66.0% of C12 alcohol, 26.0%
of C14 alcohol and 6.5% of C16 alcohol.
Another grcxip of commercially available mixtures include the "Neodol'~
products available from Shell Chemical Co. For example, Neodol 23 is a mixtiue of C12 ~d C13 ~hols; Neodol 25 is a mixture of C12 and Cu aloohols; and Neodol 45 is a mixture of Cl~ to C~ linear aloohols. Neodol 91 is a mixture of Cg, Clo and Cu alcohols.
Fatty vicinal diols also are useful and these include those availabhe from Ashland Oil under the general trade designation Adol 114 and Adol 158. The former is derived from a straight chain alpha ole5n fiaction of Cn-Ci4, and the latter is derived from a Cu-Cl$ fiction.
Examples of useful phosphorus acid esters include the phosphoric acid esters prepared by reacting a phosphoric acid or anhydride with cresol alcohols. An example is tricresol phosphate.
In one ~nbodiment, the phosphorus acid ester is a monothiophosphoric acid ester or a monothiophosphate. Monothiophosphates are pre~red by the region of a sulfur source and a hydrorubyl or aryl substituted phosphites. The sulfur source may be elemental sulfur;, a monosulfide, such as a sulfur coupled olefin or a sulfur coupled dithiophosphate. ):~emental sulfur is a prefeared sulfur sourre. The preparation of monothiophosphate;; is disclosed in U.S. Patent 4,755,311 and PCT Publication WO
87/07638. A preferred monothiophosphate is triphenyl monothiophosphate.
Monothiophosphates may also be formed in the lubricant blend or functional fluid by adding a hydrocarbyl or aryl phosphite to a lubricating composition or functional fluid conniving a sulfur source. The phosphate may react with the sulfur source under blending conditions ('Le., temperatures from about 30°C.
to about 100°C. or higher) to form the monothiophosphate.
In one embodiment, the phosphorus acid is a dithiophosphoric acid or phosphorodithioic acid. The dithiophosphoric acid can be read with an e~OZide or a glycol to form an ir~te~mediate. The intermediate is then reacted with a phosphorus acid, anhydride, or :lower ester. The epoxide is generally an aliphatic epoxide or a styrene oxide. Examples of useful epoxides include ethylene oxide, propylene oxide, butene oxide, octene: oxide, dode~cane oxide, styrene oxide, etc. Propylene oxide is preferred. The glyoc~ls may be aliphatic glyools having from 1 to about i2, preferably about 2 to about 6,. more preferably 2 or 3 carbon atoms, or aromatic glycols.
Aliphatic glyools include e~ylene glycol, propylene glycol, triethylene glycol and the like. Aromatic glycols include hydroquinone, cate~hol, resorcinol, and the IilGe.
These are din U.S. patent 3,197,405.
When the phosphorus acid esters are acidic, they may be read with an amine compound or metallic; base to form the corresponding amine or metal salt. The salts may be formed separ,~tely and then the salt of the phosphorus acid ester is added to the lubricant or functional fluid composition. Alternatively, the salts may also be formed when the phosphorus acid ester is blended with other components to form the lubricating composition. The phosphorus acid ester could then form salts with basic mateaials which am in the lubricant or functional fluid composition such as basic nitrogen containing compounds (e.g., carboxylic dispersants) and overbased ~.
The amine s;~lts of the phosphorus acid esters may be formed from ammonia, or a primary, secondary or tertiary amine, or mixtures thereof. Useful amines include those amines disclosed in U.S. Patent 4,234,435 at Col. l, line 4, to Col. 27, line 50.
The metal salts of the phosphorus acid esters are prepared by the reaction of a metal base with the ;phosphorus acid ester. The metal base may be in aay oomrenient form such as oxide, hydroxide, carbonate, sulfate, borate, or the line. The metals of the metal base include Group IA, IIA, IB through VI>B and VI>I metals (CAS
version of the Periodic Table: of tile Elements). These metals include the alkali metals, alkaline earth metals and transition metals. In one embodiment, the metal is a Group IIA meal such as calcium or magnesium, Group IIB metal such as zinc, or a Group V~
metal such as manganese. Preferably the metal is magnesium, calcium, manganese or zinc, more preferably mal~esium, calcium or zinc, more preferably magnesium or zux.
Specific examples of useful metal bases include those dabove under the heading "Metal Base ".
The phosphorus acid ester can be a phosphite. In one embodiment, the phosphite is a di- or trihydrocarbyl phosphite. Each hydrocarbyi group can have from 1 to about 24 carbon atoms, or from 1 to about 18 carbon atoms, or from about 2 to about 8 carbon atoms. Each hydrocarbyl group may be independently alkyl, alkrnyl or aryl. When the hydrncarbyl group is an aryl group, then it contains at least about 6 carbon atoms; and in one embodiment about 6 to about 18 carbon atoms. Examples of ~e ~yl or alkenyl gmups include propyl, butyl, hexyl, heptyl, octyl, oleyl, linoleyl, stearyl, etc. Eacamplex of aryl groups include phenyl, naphthyl, heptylphenol, etc. In one embodiment each hydrocarbyl group is independently propyl, butyl, pentyl, hexyl, heptyl, oleyl or phenyl, more preferably butyl, oleyl or phenyl. Phosphites and their preparation are knovm and many phosphites are available commercially. Useful phosphites are dr'butylhydrogea phosphite (DBPH), trioleyl phosphite and triphenyl phosphite with DBPH being a preferred component.
In one embodiment, the phosphorus acid derivative is a phosphorus-containing amide. The phosphorus~ontaining amides may be prepared by the reaction of a phosphorus acid (e.g., a dithiophosphoric acid as described above) with an unsaturated amide. Examples of unsaturated amides include acrylamide, N,N methylene bisacrylamide, metlaacrylamide, crotonamide, and the like. The reaction product of the phosphorus acidl with the unsaturated amide may be further reacted with linking or coupling compounds, such as formaldehyde or paraformaldehyde ,to form coupled compounds. The plhosphorus-containing amides are known in the art and are disclosed in U.S. Patents 4"876,374, x,770,807 and 4,670,169 .
In one embodiment, the phosphorus acid ester is a phosphorus~ontaining carboxylic ester. The phosphorus-containing carboxylic esters may be prepared by reaction of one of the above~iescribed phosphorus acids, such as a dithiophosphoric acid, and an unsatur,at~ed carboxylic acid or ester, such as a vinyl or allyl acid or ester.
If the carboxylic edict is used, the ester may then be formed by subsequent ruction with an alcohol. _ The vinyl ester of a ~rboxylic acid may be represented by the formula RCH=CH-0(O)CR~ wherein R is a hydrogen or hydmcarbyl group having from 1 to about 30 carbon atoms, preferably hydrogen or a hydroc~rbyl group having 1 to about 12, more preferably hydrogen, and Rr is a hydmrarbyl group having 1 to about carbon atoms, or 1 to about 12, or 1 to about 8. Examples of vinyl esters include vinyl acetate, vinyl 2.-ethylhexanoate, vinyl butanoate, and vinyl crotonate.
In one embodiment, the unsahrrated carboxylic ester is an ester of an unsaturated carboxylic acid, such as malefic, fumaric, acrylic, mettlacrylic, itaconic, citrioonic acids and the like. The ester can be represented by the formula RO-(O)C-HC=CH-C(O)OR v~rher~ein each R is independently a hydrocarbyl group having 1 to about 18 carbon atoms, or 1 to about 12, or 1 to about 8 carbon atoms.

Examples of unsaturated carboxylic esters that are useful include methyl-~Y~~ ~Y~Y~~ 2~thylhexylacrylate, 2-hydroxyethylacrylate, ethyl_ methacrylate, 2-hydroxyethylmetha~crylate, 2-hydroxypropYlmethacrylate, 2_ hydroxypropylacryiate, ethylmaleate, butylmaleate and 2-ethylhexylmaleate. The above Iist includes mono- as well as diesters of malefic, fumaric and citraconic acids.
In one embodiment, the phosphorus acid is the region product of a phosphorus acid and a vinyl ether. The vinyl ether is represented by the formula R
CH2=CH-0RI wherein R is hydrogen or a hydroc~rbyl group having 1 to about 30, preferably 1 to about 24, more preferably 1 to about 12 carbon atoms, and Rl is a hydmcarbyl group having 1 to about 30 carbon atoms, preferably 1 to about 24, more preferably 1 to about 12 carbon atoms. Examples of vinyl ethers include vinyl methylether, vinyl propylether, vinyl 2-ethylhexylether and the li'he.
(C) Borated Enoxide or Borated Fatty Acid Ester of G~cerol and other Fridaon Modifiers.
The borated epoxides are made by reacting at least one of boric acid or boron trioxide with at least one epoxide having the formula Ri \ / Rs C j C
RZ ~ ~ ~ ~ Ra wherein each of Rl, R2, R3 and R4 is hydrogen or an aliphatic radical, or any two thereof together with the epoxy carbon atom or atoms to which they are attached form a cyclic radical, said epoxide containing at least 8 carbon atoms. In one embodiment this reaction is conduc~eti in the presence of a minor amount of a heel of a previously obtained oil-soluble boron-containing composition prepared by reacting the foregoing reagents.
The boric acid that can be used can be any of the various forms of boric acid, including metaboric acid (HBO, orthoboric acid (H3B03) and tetraboric acid (HZB40.r). Boric acid and orthoboric acid are preferred.

Each of the R groups in the above formula are most often hydrogen or an aliphatic group with at least one beang an aliphatic group containing at least 6 carbon atoms. The term "aliphatic group" includes aliphatic hydrocarbon groups (e.g., hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, stearyl, hexenyl, oleyl), preferably free from acetylenic unsaturation; substituted aliphatic hydrocarbon groups including substituents such as hydroxy, ni>ro, c~rballcoxy, alkoxy and alkylthio (especially those containing a lower alkyl group; i.e., one containing 7 carbon atoms or less); and hetero atom-containing groups in which the heteno atoms may be, for example, oxygen, nitrog~ or sulfur. The aliphatic gmups are geneaally alkyl groups, and in one embodiment those containing from about 10 to about 20 carbon atoms. It is within the scope of the invention to use commercial mixtures of epoxides; for example, commercial mixtures of CIøis or Cløis epoxides and the like, wherein Ri is a mixture of alkyl radicals having two less carbon atoms than die epoxide.
In one embodim~t the borated epoxide (C) is a borated alpha-olefin epoxide having about 10 to about 20 carbon atoms, and in one embodim~t about 14 to about 18 carbon atoms.
Also within the scope of the invention is the use of epoxides in which any two of the R groups together with the epoxy carbon atom or atoms to which they are attached, form a cyclic group, which may be alicyclic or heterocyclic.
Examples include n~utylcyclopentene oxide, n hexylcyclohex~e oxide, methyl~ecyclooctene oxide and 2-methyl~~3-n-hexyltetcahydrofuran oxide.
The boratsd epoxides may be prepared by merely bleeding the boric acid or boron trioxide and the epoxide and heating them at a temperature from about 80°C to about 250°C, and in one embodiment fmm about 100°C to about 200°~, for a period of time sufficient for ration to rake place. If desired, the reaction may be effected in the presence of a substantially inert, normally liquid organic diluent such as toluene, xylene, chlorobenzene, dimethylformamide or the like, but such diluents are usually unnecessary. During the reaction, water is frequently evolved and may be removed by distillation.

~- 2189208 The molar ratio of the boric acid or boron trioxide to the epoxide is generally between about 1:0.25 and about 1:4. Ratios between about 1:1 and about 1:3 are useful.
In o~ embodiment it is advantageous to employ a catalytic amount of an alkaline reagent to facilitate the reaction. Suitable allmline reagents include inorganic bases and basic salts such as sodium hydroxide, potassium hydroxide and sodium ~; ~ des such as sodium methoxide, potassium t-butoxide and calcium edioxide; heterocyclic amines such as piperidine, morpholine and pyridine;
and aliphatic amines such as n-butylamine, di-n-hexylamine and tri n-butylamine.
Useful allmline reagents are the aliphatic and heterocyclic amines and especially tertiary amines.
The preparation of a borated epoxide useful in this inv~tion is illustrated by the following example.
)~ramnle C-1 Part I:
A mixtin~e of 1500 parts (6.25 moles) of 1-hexade~ne oxide and 1 part of td-n-butylamine is heated to 100-lI0°C under nitrogen, with stirring.
Boric acid, 193 parts (3.13 moles), is added incrementally over 15 minutes. Why boric acid addition is complete, the reaction mixture is heated to 185°C as water is removed by distillation. When water evolution ceases, the mixture is filtered while hot, and the filtrate is allowed to cool to a waxy solid melting at 60-65°C. This solid is the product; it contains 2.7% boron.

21 ~ 9 2 ~~~

Part II:
A blend of 193 parts (3.13 moles) of boric acid, 1 part of tri-n-butylamine and a "heel" comprising 402 parts of the product prepared as in Part I is heated to 188°C, with stirring, as volatiles are removed by distillation. After 8.5 hours, 1500 parts (6.25 moles) of 1-hexa~deceae oxide is added over 5.5 hours at 186-195°C, with storing. Heating and storing are continued for 2 hours as volatiles are removed. The material is then vacuum shipped and filtered at 93-99°C. The filtrate is the desired product; it contains 2.1 % boron.
The borated fatty acid esters of glycerol are prepared by reacting a fatty acid ester of glycerol with a boric acid (e.g., boric acid, metaboric acid, orthoboric acid, tetraboric acid) with m~noval of the water of reaction. In one embodiment there is sufficient boron present such that each boron will react with from about 1.5 to about 2.5 hydroxyl groups present in the ration mixture.
The reaction may be out at a tempeiatme in the range of about 60°C
to about 135°C, in the absence or presence of any suitable organic solvent such as methanol, b~ze~e, xylenes, toluene, neutral oil and the like.
Fatty acid esters of glycerol can be prepared by a variety of methods well known in the art. Many of these esters, such as glycerol monooleate and glycerol tallowate, are manu~ured on a commercial scale. The esters useful for this invention are oil soluble and are preferably prepared from C8 to C~ fatty acids or mixtures thereof such as are found in natural products. The fatty acid may be saturated or unsaturated. Certain compounds found in acids from natural sources may include licanic acid which contains one laeto group. Useful C8 to C~ fatty acids are those of the formula R-COOH wherein R is alkyl or alkenyl.
The faay acid monoester of glycerol is useful. M~xhues of mono and diesters may be used. Nfixtures of mono- and diester can contain at least about 40% of the monoester. Mixtures of mono- and diesters of glycerol containing from about 40 % to about 60% by weight of the monoester can be used. For example, commercial glycerol monooleate containing a mixture of from 45 % to 55 % by weight monoester 3 0 and from 55 % to 45 % diester can be used.

Useful fatty acids are oleic, stearic, isostearic, palmitic, myristic, palmitoleac, linoleic, lauric, lin~~lenic, and eleostearic, and the acids from the natural products tallow, palm oil, olive oil, peanut oil.
Friction modifiers are also well known to those skilled in the art. A useful list of friction modifiers are included in U.S. Pat. No. 4,792,410 . U.S. Patent 5,110,488 discloses metal salts of fatty .acids and especially zinc salts. Said list of friction modifiers includes:
fatty Phosphates fatty acid amides fatty epoxides borated fatty epoxides fatiy amines ~Y~
borated glycerol esters allooxylated fatty amines borated alhoxylated fatty amines metal salts of fatty cads strlfurrzad olefins fatty imidazolines and mixtures thereof.
The preferred friction modifier is a borated fatty epoxide as previously mentioned as being included for its boron content. Friction modifiers are included in the compositions in the amounts of 0.1-10 weight percent and may be a single fricxion modifier or mixtures of two or more.
Friction modifiers also viclude metal salts of fatty acids. Preferred rations are zinc, magnesium, calcium, and sodium and_ any other alkali, or alkaline earth metals may be used. The salts may be overbased by including an excess of rations per equivalent of amine. The excess rations are then treated with carbon dioxide to form the carbonate. The metal salts are prepared by reacting a suitable salt with the acid to 21892~~8 form the salt, and where appropriate adding carbon dioxide to the reaction mixture to form the carbonate of any canon beyond that needed to form the salt. A
preferred friction modifier is zinc oleate.
(D) lbiocarbamate.
The thiocarbamates (D) are compounds represented by the formula RIRZN-C(X)S-(CR3R~,Y
where Rl, RI, R3 and R4 are independently hydrogen or hydrocxrbyl groups, Provided that at least one of Rl or RI is a hydrocarbyl group; X is oxygen or sulfur; a is 1 or 2;
and Y is a hydrocarbyl group, a heteao group (that is, a group attached through a heteroatom such as O, N, or S), an additional -SC(X) NR1R2 group, or an aarvating group.
When a is 2, Y is an activating group, in describing Y as an "activating 1 S group, ° what is meant is a group which will activate an olefin to which it is attached toward nucleophilic addition by, e.g., CSI or COS derived inteamediates. (This is reflective of the method by which this material is normally prepared, by reaction of an activated olefin with CSI and an amine.) The activating group Y can be, for instance, an ester group, typically but not necessarily a c~boxylic ester group of the struchme -COORS. It can also be an ester group based on a non-carbon acid, such as a sulfonic or sulfinic ester or a phosphoric or phosphinic ester. The activating group can also be any of the acids corresponding to the aforementioned esters. Y can also be an amide group, that is, based on the condensation of an acid group, preferably a carboxylic acid group, with an amine. In that case the -(CR3R~,Y group can be derived from acrylamide. Y can also be an ether group, -ORS; a carbonyl group, -C(O)-, that is, an aIdehyde or a Icetone group; a cyano group, -CN, or an aryl group. In one embodiment Y is an ester group of the structure, -COORS, where RS is a hydrocxrbyl group. RS can comprise 1 to about 18 carbon atoms, and in one embodiment 1 to about 6 carbon atoms. In one embodiment RS is methyl so that the activating group is -COOCH3.

When a is 1, Y need not be an activating group, because the molecule is generally prepared b;y methods, descn'bed below, which do not involve nucleophilic addition to an activated double bond.
R3 and R4 can be, independently, hydrogen or methyl or ethyl groups. When a is 2; at least one of R3 and R4 is normally hydrogen so that this compound will be R'R2N-C(S)S-CR3R4~CR3HCOORS. In one embodiment most or all of the R3 and R4 groups are hydrogcxi so that the thiocarbamate will be R1R2N-C-(S),S =CH2 CH2COOCH3. (These materials ran be derived from methyl methacrylate and methylacrylate, respectively.) These and other materials containing appropriate activating groups are; disclosed in greater detail in U.S. Patent 4,758,362.
The substituer~ts Rr and R2 on the nitrogen atom are li>cewise hydrogen or hydrocarbyl groups, but at least one should be a hydrocarbyl group. It is generally believed that at least one such hydmcarbyl group is desired in order to provide a measure of oil-solubility to the molecule. However, Rl and R2 cxn both be hydrogen, pm~~ ~e other R groups in the molecule provide sufficient oil solubility to the molecule. In practice; this means that at least one of the groups R3 or R4 should be a hydrocarbyl group of at least 4 carbon atoms. R' or R2 are preferably alkyl groups of 1 to about 18 cari~on atoms, and in one embodiment alkyl groups of 1 to about carbon atoms. In one embodiment, both Rl and R2 are butyl groups. Thus, in one embodiment, the thi~x~rbamate (D) is S-carbomethoxyethyl-N,N-dibutyl dithiocar-bamate which can be represented by the formula S O
~ N-C-S-CH2CH2C-0CH3 Briefly, these materials are prepared by reacting an amine, ~rbon disulfide or carbonyl sulfide, or source materials for these reactants, and a reactant containing an activated, ethylenically-unsatural~ed bond or derivafives thereof. These rea~ants are charged to a reactor and stirred, generally without heating, since the reaction is norn~ally exothermic. Once the reaction reaches the teriiperature of the exotherm (typically 40-65~G~, the reaction mixture is held at the temperature to insure compleae reaction. After a reaction tune of typically 3-5 hours, the volatile materials are removed under reduced pressure and the residue is filtered to yield the final product.
The relative ~~rnounts of the reactants used to prepare these compounds are not critical. The charge :ratios to the reactor can vary where economics and the amount of the product desued are controlling factors. Thus, the molar charge ratio of the amine to the CSl or COS rent to the ethylenically unsaturated reactant may vary in the ranges 5:1:1 to 1:5: I to 1:1:5. :(n one embodiment, the charge ratios of these rea~nts is 1:1:1.
In the case v~rhere a is I, the activating group Y is separated from the sulfur atom by a methylen~e group. hsaterials of this type can be prepared by reaction of sodium dithiocarbamate with .a chlorine-substituted material. Such ~ are descn'bed in great,~a detail in U.S. Patent 2,897,152, .
U. S. Patents 4,758,362: and 4,997,969 describe dithiocubamate compounds and methods of mating the same.
Concentraty, lubricating Comnos~itions and Flunctional Fluids.
The lubricant and functional fluid compositions of the present invention are based on diverse oils of lubricating viscosity, including natural and synthetic lubricating 0~ ~d ~e~f. The lubricating compositions may be lubricating oils and greases usefiil in industrial applications and in automotive engines, transmissions and axles. These lubricating compositions are effective in a variety of applications including crankcase lubricating ails for spark ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-cycle engines, a~fion piston e:ngin.es, marine, and low-load diesel engines, and the like.
Also, automatic transmission fluids, >ransaxle lubricants, gear lubricants, metalworking lubricants, hydraulic fluids, and other lubricating oil and grease compositions can benefit from the ina>rporation of the compositions of this invention. The inventive functional fluids are particularly effective as automatic -transmission fluids having enhanced aniiwear properties.
The lubricants and functional fluid compositions of this invention employ an oil of lubricating viscosity which is g~eaally present in a major amount (i.e. an amount than about 50~ by weaght). Generally, the oil of lubricating vis~ity is present in an amount greater than about 60%, or greater than about 709&, or greater than about 80~ by weight of the composition.
The natural oils useful in malting the inventive lubricants and functional fluids include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as mineral lubricating oils such as liquid petroleum oils and solvent treated or acid treated mineral lubricating oils of the parafbnic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating viscosity delved from coal or shale are also useful. Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymetized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutyleae copolymers, chlorinated polybutylenes, etc.); polY(I
hexes), poly-(1-octenes), polY(1-decenes), etc. and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzenes, tebra~decylbe~zenes, dinonylbenzenes, di-(2-ethylhexyl~benzenes, etc.); PoIYPh~Y~ (e.g., bipherlyls, teaphenyls, allcylated polyphenyls, etc.);
alkylated Biphenyl ethers and alkylated Biphenyl sulfides and the derivatives, analogs and homologs thereof and the h'ke.
Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have beg modified by esterification, etheaification, etc., constitute another class of known syn~etic lubricating oils that can be used.
These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl polyisopropylene glyovl ether having an average molecular weight of about 1000, Biphenyl ether of polyethylene glycol having a molecular weight of about 500-1000, diethyl ether of polypropylene glycol having a molecular weight of about 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed Cj.$ fatty acid esters, or the C~Oxo acid diester of tettaethylene gym.
Another suitable class of synthetic lubricating oils that can be used comprises the esters of dicarboxylic acids (e.g., phthalic acid, sucxinic acid, alkyl succinic acids, alkenyl succinic acids, malefic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propyl~e glycol, etc.) Specific examples of these esters include dibutyl adipate, di(2-ethylheacyl) sebacate, di n hexyl fumarate, dioclyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didacyl phthalate, dieicosyl sebacate, the 2-exhylhexyl diester of linoleac acid dimer, the complex ester formed by reacting one mole of sW acic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid and the lilae.
Esters useful as synthetic oils also include those made from CS to Cla monocarboxylic acids and polyols and polyol ethers such as neap~tyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, txipentaerythritol, etc.
Silicon-based oils such as the polyalkyl-, polyaryl , polyalkoxy-, or polyaryloxy-siloxane oils. and silicate oils comprise another useful class of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-hexyl)silicate, tetra-(p-tert-butylphenyl) silicate, hexyl-(4-methyl-2-pentoxy~isiloxane, poly(methyl) siloxanes, poly-(methylph~yl)siloxanes, etc.).
Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, tiiocxyl phosphate; diethyl ester of decane phosphoric acid, etc.), polymeric tetrahydrofmans and the like.
Unrefined, refined and rerefined oils, either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove can be used in the lubricants of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification trealznent~
For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly ~1~92~~

from primacy distillation or ester oil obtained directly from an esterification process and used without further treaanent would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques are lrnown to those skilled in the art such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also lmown as reclaimed or reprocessed oils and often are a~itionally processed by techniques directed to removal I O of spent additives and oil breakdown products.
In one embodiment, me oil of lubricating viscosity is a poly alpha-olefin (PAO). Typically, the polyalpha-olefins are derived from monomers having from about 4 to about 30, or from about 4 to about 20, or from about 6 to about 16 carbon atoms. Examples of useful PAOs include those deaived from dec~e. These PAOs may have a viscosity firm about 3 to about 150, or from about 4 to about 100, or from about 4 to about 8 cSt ax 100°C. Examples of PAOs include 4 cSt poly alpha~lefins, 6 cSt, poly-alpha-olefins, 40 cSt poly-alpha-olefins and 100 cSt poly-alpha~lefins.
Mixtures of mineral oils with the foregoing poly-alpha-olefins can be useful.
Generally, the lubricants and functional fluids of the present invention contain 2o an effective amount of the inv~tive composition ~.e., components (A), (B), (C), and (D)) to provide said lubricants and functional fluids with enhanced antiwear pmpesties.
Normally the compositions of the present invention will be employed in such lubricants and functional fluids at a level in the range of about 0.01 % to about 20 % by w~ght, and in one embodim~t about 0.05 ~6 to about 10 % by weight of the total weight of the lubricant or functional fluid. The weight of substituents added to an oil to form a lubricant or functional fluid is given on a chemical basis. That is, the composition or component thereof is given on an oil-free basis.
The ranges for weight percents on an oil-free basis of components of the inventive composition are given below on the basis of total weight of the lubricant/functional fluid:

2.1 ~92.'~

(A)0.05-3.0 a boron-containing oveabased material;

tB)0.05-2.5 a phosphorus acid, ester or derivative;

(C~0.05-1.0 a borated epoxide or borated fatty acid of glycerol;

tD)0.05-1.0 a thiocarbamate.

The inv~tion also contemplates the use of lubricants and functional fluids containing other additives in addition to the compositions of this inv~tion.
Such additives include, for example, detergents and dispersants, ion-inhibiting agents, antioxidants, visoosuy index improving agents, extreme pressure (E.P.) agents, pour point depressants, friction modifies, fluidity modifiers, seal swell agents, color stabilizers, dyes, anti foam agents, etc.
The inventive lubricating compositions and fiutctional fluids can contain one or more detergents or dispersants of the ash producing or ashless type. The ash producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, or organic phosphorus acids. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium. These ash-producing detergents are described in greater detail above as beang among the oveabased materials used in Preparing the borated overbased materials (A) of the invention.
Ashless detergents and dispersants are so called despite the fact that, depending on its constitution, the dispersarit may upon combustion yield a non volatile matezial such as boric oxide or phosphorus p~toxide; however, it does not ordinarily contain metal and therefore does not yield a metal-containing ash on combustion. Many types are known in the art, and any of them are suitable for use in the lubricant compositions and functional fluids of this invention. The following are illustrative:
(1) Reaction products of carboxylic acids (or derivatives thereof) containing at least about 34 and preferably at least about 54 carbon atoms with nitrogen containing compounds such as amine, organic hydroxy compounds such as ph~ols and aloohols, and/or basic inorganic materials. Examples of these "carboxylic dispersants"
are described in many U.S. Patents including 3,219,666; 4,234,435; and 4,938,881.
These include the products formed by the reaction of a polyisobutenyl succinic anhydride of the type: described above under the subtitle "Carboxylic Acids (a)" with an amine such as a polyethylene amine, as weu as such polyisobutenyl sua~nic anhydride amine re3cxion products which have been post-treated with a boron compound such as boric acid.
(2) Reaction products of relatively high molecular weight aliphatic or alicyclic halides with amines, preferably oxyalkylene polyamines. These may be W ara~~ized as "ami;ne dispersants" and examples thereof are described for example, in the following U.S. Patents: 3,275,554; 3,438,757; 3,454,555; and 3;565,804.
(3) Re~tion products of alkyl phenols in which the alkyl group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines), which may be chararctrerized as "Mannish dispersants". The materials described in the following U.S. Patents are illustrative:
3,649,229; 3,697,574; 3,725,277; 3,725,480; 3,726,882; and 3,980,569.
(4) Produ~~s obtained by post treating the amine or Mannish dispe~nts with such reagents a:c urea, thiounn., carbon disulfide, aldehydes, laetones, carboxylic acids, hydrocarbon substituted suocinic anhydrides, nitriles, epoxides, boron compounds, phosphorus oompoiuids or the like. Exemplary materials of this kind are described in the following U.S. Patents: 3,639,242; 3,649,229; 3,649,659;
3,658,836; 3,697,574; 3,702,757; 3,703,536; 3,704,308; and 3,708,422.
(~ Interpolymers of oil solubilizing monomers such as decyl methacrylate, vinyl decyl ether andl high molfxx~lar weight olefins with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and.
poly-(oxyethylene)-substituted acrylates. These may be characterized as "polymeric dispersants" and ex~nples thereof are disclosed in the following U.S. Patents:
3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; and 3,702,300.
The inventive lubricating compositions and functional fluids can contain one or more extreme pressure, corrosion inhl-bitors and/or oxidation inhibitors.
Extreme pressure agents and a~rrosion- and oxidafion-inhibiting agents which may be included in the lubricants and functional fluids of the invention are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and polysulfides such as benzyl disulfide; bis(chlorot~zyl)disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, s~uifurized altrylphenol, sulfurized dipentene, and sulfurized terpene;
phosphosulfuriz~ed hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl. oleate; metal thiocarbamates, such as zinc dioctyldithiocarbamae, and barium heptylphenyl dithiocarbamate;
dithiocarbamate esters from the reitction product of dithiocarbamic acid and acrylic, methacrylic, malefic, fumaric or itaconic esters; dithiorarbamate containing amides prepared from dithiocarbamic acid and an acrylamide; alkylene-coupled dithiocarbamates;
sulfur-coupled dithiocartxunates. ~iroup II metal phosphorodithioates such as zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptylphen-yl)-phosphomdifhio~~te, cadmium dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic a~~d produced by the reason of phosphorus pentasulfide with an equimolar mixriue of isopropyl alcohol and n-hexyl alcohol.
Zinc salts am added to lubricating compositions to provide antiwear protection.
The zinc salts are normally added as zinc salts of phosphorodithioic acids.
Among the prefen~ed compounds are zinc diisooctyl dithiophosphate and zinc dibenzyl dithiophosphate. Also included in lubricating compositions in the same weight percent range as the zmc salts to give antiwear/extreme pressure performance is dibutyl hydrogen phosphite (DBPI~ and triphenyl monothiophosphate, and the thiocarbamate ester formed by reading dibutyl amine-carbon disulfide- and the methyl ester of acrylic acid. The thiocarbamate is des~~n'bed in U.S. Pat. No. 4,758,362 and the phosphorus-containing metal salts are described in U.S. Pat. No. 4,466,894.
Sp~ific oxidation-inhibitors that are useful include the mono- and di-paraalkylated (e.g., ~:9) diphenylamines, hydroxythioether of t-dodecyl mercaptan and propylene oxide, and hydroxyelhyl dodecyl sulfide. Specific corrosion-inhibitors that are useful include tolyltriazole and the dialkylated (e.g., Cg) sulfur-coupled dimercaptothiadiazoles.

The inventive lubricating compositions and functional fluids can contain one or more pour point depmssants, vi5oosity-indea~ improvers, color stabilizers, dyes and/or anti-foam agents. Pour point depressants are a particularly useful type of additive often included in the lubrio~ting oils and functional fluids described hen.an. The use of such pour point dt~ in oil-basil compositions to improve low tempeiahire properties of oil-based compositions is well lmown in the art. See, for example, page 8 of "Lubricant Additives" by C.V. Smalheer and R. Kennedy Smith (Ixzius-l~Ies Co.
publishers, Cleveland, Ohio, 19~.
Examples o:P useful pour point depressants are polymethacrylates;
polyacrylates; polyacxylamides; condensation products of haloparaffin waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers of diallrylfum-arates, vinyl esters of fatty acids and allryl vinyl ethea~s. A specific pour point depressant that can be used i.4 the product made by alkylating naphthalene with polychlorinated paraffin and Cl~-Cl$ alpha-olefin. Pour point depressants useful for the purposes of this invention, techniques for their preparation and their uses are deseiibed in U.S. Patents 2,38'1,501; 2,015,748; 2,655,479; 1,815,022;
2,191,498;
2,666,746; 2,721,8T7; 2,721,878; and 3,250,715.
Examples of commercially available pour point depressants and their chemical types are:
pour Point P~epressant Tradename ource I. Polymethacrylates Acryloid~ 154-70, Rohm &
3004, 3007 Haas LZ~ 7749B, 7742 Lubrizol TC 5301, 10314 Texaco Viscoplex~ 1-31, Rohm 1-330, 5-557 GmbH

(Cont'd.) Pour Point Depressant Tradename Source 2. Vinyl acetate/fumate ECA 11039, Exxon or maleate copolymers 9153 (Paramins) 3. Styrene, maleate LZ~ 6662 Lubrizol copolymers Viscosity modifiers (VM) and dispersant viscosity modifiers (DVM) are well known. Examples of VMs and DVMs are polymethacrylates, polyacrylates, polyolefins, styrene-malefic ester copolymers, and similar polymeric substances including homopolymers, copolymers and graft copolymers.
In general, dispersant viscosity modifiers are polymers in which polar groups have been added or included. The polar groups, which are often basic in nature add dispersing properties to the viscosity modifiers.
Examples of commercially available VMs, DVMs and their chemical types are listed below. The DVMs are designated by a (D) after their number.
Tradename and Viscositx Modifiers Commercial Source 1. Polyisobutylenes Indopol~ Amoco Parapol Exxon (Paramins) Polybutene Chevron Hyvis~ British Petroleum 2. Olefin copolymers Lubrizol~ 7060, 7065, 7067 Lubrizol Paratone 8900, 8940, 8452 Exxon 8512 (Paramins) (Cont'd.) Tradename and Viscosity Modifiers Commercial Source ECA-6911 Exxon (Paramins) TLA 347E, 555(D), 6723(D) Texaco Trilene CP-40, CP-60 Uniroyal 3. Hydrogenated styrene-dieneShellvis 50, 40 Shell copolymers LZ 7341, 7351, 7441 Lubrizol 4. Styrene, maleate copolymersLZ 3702(D), 3715(D), Lubrizol 3703(D) 5. Polymethacrylatea Acryloid~ 702, 954(D), Rohm &

985(D), 1019, 1265(D) Haas TLA 388, 407, 5010(D), Texaco 5012(D) Viscoplex~ 4-950(D), Rohm 6-500(D), 5151(D) GmbH

6. Olefin-graft-polymethacrylateViscopleX 2-500, 2-600 Rohm polymers GmbH

7. Hydrogenated polyisopreneShellvis 200, 260 Shell star polymers Recent summaries of viscosity modifiers can be found in U.S. patents 5,157,088, 5,256,752 and 5,395,539.

A specific preferred viscosity-index improver that can be used is Viscoplex 5151 which is a product of Rohm GMBH identified as a polymethacrylate. In the preferred mode of this invention, a dispersant viscosity modifier is selected which provides the compositions of the invention with superior shear stability. For instance, when Visoplex 5151 is used in the formulations presented herein the kinematic 100°C viscosity dropped from 7.52 cSt to only 7.41 cSt after 40 passes in the FISST apparatus used in ASTM D5275.
The shear stable dispersara viscosity mod~ers of this invention are selected so that their inclusion in a formulated automatic transmission fluid gives a formulation wherein kinematic viscosity at 100°C does not drop more than 10% when viscosity is determined after 40 passes in the FISST apparatus used in ASTM 5275.
Anti-foam agents are used to reduce or prevent the formation of stable foam.
Typical anti-foam agents include silicones or organic polymers. Additional anti-foam compositions are described in "Foam Control Agents", by Henry T. Kerner (Noyes Data Corporation, 1976), pages 125-162.
An example of a fluidity modifier is Hydrocal-38 which is a product Calumet identified as a refined naphthenic oil. An example of a seal swell agent is polyisobutyl-o-aminophenol. Emery 2971, which is a product of Emery identified as a mixture of di- and tri-decyladipate, can function as both a fluidity modifier and a seal swell agent.
Ethomeen T/12, which is a product of Armak identified as bis(2-hydroxyethyl) tallowamine, is useful as a friction modifier.
Each of the foregoing additives, when used, is used at a functionally effective amount to impart the desired properties to the lubricant or functional fluid. Thus, for example, if an additive is a dispersant, a functionally effective amount of this dispersant would be an amount sufficient to impart the desired dispersancy characteristics to the lubricant or functional fluid.
Similarly, if the additive is an extreme-pressure agent, a functionally effective amount of the extreme-pressure agent would be a sufficient amount to improve the extreme-pressure characteristics of the lubricant or functional fluid. Generally, the concentration of each of these additives, when used, ranges from about 0.001 % to about 20% by weight, and in one embodiment about 0.01 % to about 10% by weight based on the total weight of the lubricant or functional fluid.
The lubricant compositions of the present invention may be in the form of a grease in which any of the above-described oils of lubricating viscosity can be 21892u~~
employed as a vehicle. Where the lubricant is to be used in the form of a grease, the lubricating oil generally is employed in an amount sufficient to balance the total grease composition and generally, the grease compositions will contain various quantities of thickening agents and other additive components to provide desirable properties.
A wide variety of thick~ing ag~ts can be used in the preparation of the greases of this invention. Included among the thickening ag~ts are alkali and alkaline earth metal soaps of fatty acids and fatty materials having from about 12 to about 30 carbon atoms. The metals are typified by sodium, lithium, calcium and barium.
Examples of fatty materials include stearic acid, hydroxy stearic acid, stearin, oleic acid, palmitic acid, my~sbic acid, ooh oil acids, and hydrogenated fish oils.
Other thickening agents include salt and salt soap complexes as calcium stearate-acetate (U.S. Patent 2,197,263), barium stearate a:~te (U.S. Pat~t 2,564,561), calcium stearate.-caprylate-mate complexes (U.S. Pat~t 2,999,06, calcium caprylat~ao~ate t;U.S. Patrat 2,999,Ofi6), and calcium salts and soaps of low-, intermediate- and high_molecular weight acids and of nut oil acids.
In one embodiment, thick~ing agents employed in the grease compositions are essentially hydrophilic in character, but which have been converted into a hydrophobic condition by the introduction of long gain hydrocarbon radicals onto the surface of the clay particles prior to their use as , a component of a grease composition, as, for example, by being subjected to a preliminary >xeahnent with an organic cationic surface-active agent, such as an opium compound. Typical opium compounds are te>saalkylammonium chlorides, such as dimethyl dioc~decyl ammonium chloride, dimethyl dibenzyl ammonium chloride and mixtures thereof. This method of conversion, being well known to those skilled in the art, and is believed to require no further discussion. More specifically, the clays which are useful as starting materials in forming the thickening agents to be employed in the grease compositions, can comprise the naturally occurring chemically unmodified clays. These clays are crystalline complex silicates, the exact composition of which is not subject to precise description, since they vary widely from one natural source to another. These clays can be described as complex inorganic silicates such as aluminum silicates, magnesium 21892~~
-~7-silicates, barium silicates, and the like, containing, in addition to the silicate lattice, varying amounts of ration-exchangeable groups such as sodium. Hydrophilic clays which are particularly useful for conversion to desired thickening agents include montmorillonite clays, such as bentonite, attapulgite, hectorite, illite, saponite, sepiolite, biotite, vermiculite, zeolite clays, and the like. The thickening agent is employed in an amount from about 0.5 % to about 30%, and in one embodiment from about 3% to about 15% by weight of the total grease composition.
Components (A), (B), (C) and (D) of the inventive compositions of this invention can be added directly to the lubricant or functional fluid. In one embodiment, however, they are diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benz,ne, toluene or xylene, to form an additive concentrate. These concentrates usually contain from about 10% to about 90% by weight of the inventive compositions (that is, (A), (B), (C) and (D)) and may contain, in addition, one or more other additives known in the art or described hereinabove. The remainder of the concentrate is the substantially inert normally liquid diluent.
Examples The following Examples are provided in Table I below for the purpose of illustrating specific embodiments of the invention. Each of these examples consists of automatic transmission fluid formulations that are characterized by enhanced antiwear properties. Test results involving the following antiwear tests are also disclosed for representative compositions ..
of each of these formulations in Table II: (1) Vane Pump Wear Test (ASTM D-2882); (2) Four-Ball Wear Test (ASTM D-4172); Falex EP Test (ASTM D-3233); Timken Wear Test (ASTM D-2782); and FZG Gear Wear Test. The disclosed test results demonstrate the enhanced antiwear properties of the inventive compositions. Column 4 of Table II represents a commercially-available ATF which is inferior in test results to those of this invention. The weight percent of each component added to a base oil is on an oil-free basis and is based on the weight of the lubricant/functional fluid.
The ATFs of this invention are blended to have Brool~eld viscosity values at -40°C of less than 20,Oi00 cP. Preferably the -40°C viscosity ranges from about 8,000 cP to about 13,000.
The ATFs of this invention are blended so that the 100°C kinematic viscosity ranges for the fluid range between about 6 and 8.5 cSt. The preferred 100°C
kinematic viscosity range is roughly between 7 and 8.

-4g-The antiwear ,properties of the fully formulated ATFs which meet the low viscosity parameters outlined above are accomplished by use of components listed herein arid shown in examples 1 ~-3 arid S-7. Polysu~de compositions as disclosed in Schwind U.S. Pateru' 5,403,501 are spec~cally excluded from this invention.
Polysu~des as disclosed in 501 are too corrosive for use in ATFs, and would be detrimental to an ATF's passing a copper corrosion test.
Table I reveals that both (B), a phosphorus acid, ester or derivative thereof and (D) a thiocarbamate are included in the three listed compositions. Preferred embodiments for component (B) are listed below together with their weight percent ~g~ on ~ oil-free basis in lubricating fluids.
(B)-1 Dibutyl hydrogen phosphite 0.05-2%
(B)-2 Triphenyl monothiaphosphate 0.01-2 (B)-3 85 % phosphoric acid 0.01-1.5 In another preferred embodiment, compounds (B)-1 and (B)-2 may be used 1 S ~,~,i~ ~) a ~~~.ate. Thus, compositions may embody (D) with (B) as shown in Table I where (B) may encompass (B)-1 through (B)-3 shown above, (D) may also be used in combination with only (13)-1 and (B)-2.
In still another preferred embodiment (B) may be used without (D) and in this instance (B) may encompass (B)-1 through (B)-3.
Table III lists compositions 5-7. Composition 5 corresponds to a lubricating composition with (D;1 and (B)-~I through (B)-3. Composition 6 corresponds to a lubricating composition without (D) but with (B)-1 through (B)-3. Composition corresponds to a composition having (D) with (B)-1 and (B)-2.
Further, the 5'01 patent discloses only SAE 90 as the base oil in its examples which are used in determining antiwear properties of the compositions. SAE 90 oil cannot meet the 100°C kinematic viscosity range or -40°C
Brookfield viscosity range of the formulated ATFs c f this invention.

21892~~

TABLE I

Base oil (75 % 6 cSt. poly-oc-olefinicabout +

25 % 4 cSt. poly-a-olefin), 78-82 - --v~rt. %

Base oil (85 % 4 cst. poly-a-olefin about +

% 40 cSt. poly-a-olefin) - 78-82 -Base oil (50% 90 N mineral about oil + 50%

4 cSt. poly~c-olefin) - - 78-82 (A) Boratecl overbased magnesium sulfonate 15 of Example A-1, v~rt. % 0.05-.200.05-.2 0.05-0.2 (B) Phophorus acid, ester or 0.2-0.6 0.2-0.6 0.2-0.5 derivative thereof vvt. %

(C~ Borated C 16 -olefin epoxide0.15-0.30.15-0.3 0.15-0.3 vvt. %

(D) A thiocarbamate wt. % 0.05 0.05 0.05 Reaction productsof polyisobutenyl succinic anhydride and polyamines, v~rt.1.75-3.01.75-3.0 1.75-3.0 %

Borated reaction product of polyisobutenyl succinic anhydride and polyethylene amines, ~ % 0.35-0.60.35-0.6 0.35-0.6 Friction modifiers wt. % 0.15-0.250.05-.15 0.05-0.15 Oxidation Inhibitors 0.75-1.250.75-1 0.75-1 3 Viscosity improver wt. % 0-4 2-4 3-7.5 Tolytriazole wt. % 0-0.03 0-0.03 0.01-0.03 Di-alkylated (Cg) sulfur coupled0-0,5 0-0.5 0.01-0.5 dimerc~ptothiadiawle wt.

TABLE lI
1 2 ~ 4_ Vane Pump Wear Test, wt.
loss (ASTM D-2882 at 80C, 6.9 0.2 1.6 14.0 8.0 MPa), mg.

(ASTM D-2882 at 150C, 6.9 2.9 9.7 14.8 > 1,000 MPa), mg.

Four-Ball Wear Test, 40 Kg.
load, 2 hrs.

(ASTM D-4172) Average Wear Scar Diameter, mm.

1200 RPM, 100C 0.38 0.41 0.43 0.57 , 1200 RPM, 150C 0.42 0.47 0.49 0.63 Average Wear Scar Diameter, mm.

600 RPM, 100C 0.35 0.36 0.34 0.48 600 RPM, 150C 0.37 0.39 0.41 0.54 Falex EP Test (ASTM D-3233) No seizure load at 100C, 1750 1750 750, 1 min., lbs. 1000, 1000 No seizure load at 150C, 1000 1000 1250 500, 1 min., lbs. 750 Timken Wear Test, burnish width, mm.

(ASTM D-2782) 9 lb. load, 100C, 10 min. 0.58 0.43 0.75, 0.36 1.44 No Scoring No ScoringNo Scoring(Scoring 0.62 0.49 0.7, -0.46 No Scoring No Scoring FZG Gear Wear Test, Load Stage Pass 1450 RPM, 15 min. at 100C > 12 > 12 11 10 start temp.

1450 RPM, 15 min. at 150C 11, 11 10 8 start temp. > 12 21~92J

TABLE III

Base oil (75 % 6 cSt. poly-alpha olefin +

25% 4 cSt. poly-alpha olefin), 79.83 -wt. %

Base oil (50% 100 N mineral oil + 50%

4 cSt. poly alpha olefin) - -Base oil (50 % 90 N mineral oil + 50 %

4 cSt. poly-alpha olefin) - 79.60 78.93 (A) Borated overbased magnesium sulfonate of Example A-1, wt. % 0.25 0.25 0.25 (B~1 Dibutyl hydrogen phosphite,0.25 0.25 0.25 wt. %

(B~2 Triphenyl monothiophosphate,0.10 0.10 0.10 wt. %

(B)-3 Phosphoric acid (85 % ), 0.04 0.04 -vvt. %

(~ ~Cis ~p~ olefin epoxide, wt. 0.25 0.20 0.25 %

(D) S-carbomethoxyethyl-N,N-dibutyl-~~~~~ ~ % 0.20 - 0.20 Reaction product of polyisobutenyl succinic anhydride and polyethylene amines,4.00 4.00 4.0 wt. %

Borated reaaron product of polyisobutenyl succinic anhydride and polyethylene amines, ~- % 0.50 0.50 0.5 C9 mono- and di paraalkylateti diphenylamine diluted with oil (16% oil), wt. 0.50 0.50 0.5 %

HY~xY ~oether of t-dodecyl mercaptan and propylene oxide, wt. % 0.50 0.35 0 .

Tolyltriawle, wt. % 0.03 - 0.02 Di-alkylated (Cg) sulfur coupled dimercapto thiadiazole, wt. % - - 0.03 ' ~- ~ 218920 TABLE III (Cont' d) 5 Ethomeen T/12 (product of Arn~ak identified as bis(2-hydroxyethyl) tallowamine),0.12 0.12 0. I2 wt. %

Hydroxyethyl dodecyl sulfide, - 0.15 -wt. %

Polyisobutyl-o-aminophenol, 1.80 0.60 0.60 v~rt. %

Emery 2971 (product of Emery id~ti~fied as di-, iri-decyladipate), wt. 5.00 - --% .

Hydrocal-38 (product of Calumet ideatified as refined naphthenic oil), - 3.00 3.00 wt. %

Naphthalene alkylated with polychlo~nabad parafOn and C16-Cl8 alpha olefin,- 0.30 0.30 wt. %

Viscoplex 5151 (product of Rohm GMBH

identified as a polymexhacrylate),6.50 10.00 10.30 wt. %

Diluent oil, wt. % 0.06 0.04 -Red dye, wt. % 0.025 0.025 -Silicone antifoam agent, wt. 0.042 0.042 -%

TEST RESULTS
Vane Pump Wear Test, wt. loss, (ASTM D-2882 at 80°C, 6.9 MPa), mg. 0.5 12.3, 4.9 14.0 (ASTM D-2882 at 150°C, 6.9 MPa), mg. 9.4 I0.6, 13.7 I4.8 Four-Ball Wear Test, 40 Kg. load, 2 hrs.
(ASTM D-4172) Average Wear Scar Diameter, mm.
1200 RPM, 100°C 0.42 0.54 0.43 1200 RPM, 150°C 0.44 0.56 0.49 ' ~ 218928 TABLE III - TEST ~ ~TTrJTS ~
fCont' Average Wear Scar Diameter, mm.

600 RPM, 100C 0.36 0.38 0.34 600 RPM, 150C 0.38 0.41 0.41 Falex EP Test (ASTM D-3233) No seizure load at 100C, 1 min.,1500, 1000 1000 lbs. 2000 No seizure Ioad at 150C, 1 min.,1000 1000 1250 lbs.

Timkenk Wear Test, burnish width, mm.

(ASTM D-2782) 9 lb. Ioad, 100C, 10 min. 0.52 0.74, 0.75, 0.8, 0.36 0.33 No ScoringNo ScoringNo Scoring 9 lb. load, 150C, 10 min. 0.58 0.82, 0.7, 0.68, 0.40 0.49 No ScoringNo ScoringNo Scoring FZG Gear Wear Test, Load Stage Pass 1450 RPM, 15 min. at 100C start10, > 10, > 10 temp. 12 12 1450 RPM, 15 min. at 150C start8, 9 11, 11 11 temp.

While the invention has been explained in -relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification.
lfierefore, it is to be understood that the inv~fion disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

1. A composition, comprising:
(A) a boron containing overbased material;
(B) a phosphorus acid, a phosphorus acid ester or derivatives thereof, or mixtures thereof;
(C) a borated friction modifier;
(D) a thiocarbamate; and (E) a dispersant viscosity modifier.

2. The composition according to claim 1, wherein (B) comprises a phosphite and a monothiophosphate.

3. The composition according to claim 2, wherein (B) further comprises phosphoric acid.

4. A composition comprising:
(A) a boron containing overbased material;
(B)-1 a phosphite;
(B)-2 a monothiophosphate;
(C) a borated friction modifier;
(D) a thiocarbamate; and (E) a dispersant viscosity modifier.

5. A composition according to claims 1 and 4, wherein (A) is a borated overbased magnesium sulfonate.

6. A composition according to claims 1 and 4, wherein said borated friction modifier is selected from the group consisting of (a) borated epoxides;
(b) borated fatty acid esters of glycerol;
(c) borated alkoxylated fatty amines or mixtures thereof.

7. A composition according to claims 1 and 4, wherein said borated friction modifier is a borated epoxide.

8. A composition according to claims 1 and 4, wherein (D) is a thiocarbamate of formula

9. A composition according to claims 1 and 4, wherein (D) is S-carbomethoxyethyl-N,N-dibutyl dithiocarbamate.

10. A composition according to claims 2 and 4, wherein said phosphite is a dialkylhydrogen phosphite and said monothiophosphate is a triaryl monothiophosphate.

11. A composition comprising:
(A) a borated overbased magnesium sulfonate;
(B)-1 dialkyl hydrogen phosphite;
(B)-2 triaryl monothiophosphate;
(B)-3 phosphoric acid;
(C) borated epoxide having about 10-20 carbon atoms; and (E) a dispersant viscosity modifier.

12. A composition according to claim 11, wherein (B)-1 is dibutyl hydrogen phosphite and (B)-2 is triaryl monothio phosphate.

13. The compositions as recited in claims 1-12 above added to an oil of lubricating viscosity wherein said oil comprises greater than 50% of the mixture.