US 2003.0171222A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2003/0171222 A1 Sullivan et al. (43) Pub. Date: Sep. 11, 2003

(54) SULFIDE-AND POLYSULFIDE-CONTAINING Publication Classification LUBRICATING OIL ADDITIVE

COMPOSITIONS AND LUBRICATING (51) Int. Cl." ...... C10M 135/22 COMPOSITIONS CONTAINING THE SAME (52) U.S. Cl...... 508/192; 508/199; 508/378; 508/421; 508/569 (76) Inventors: William T. Sullivan, Brick, NJ (US); Percy Rohinton Kanga, Cherry Hill, (57) ABSTRACT NJ (US); Thomas Smith Coolbaugh, Yardley, PA (US) This invention relates to a lubricating composition compris ing a major amount of an oil of lubricating Viscosity, at least Correspondence Address: one organic polysulfide comprising less than about 88% EXXONMOBIL CHEMICAL COMPANY dihydrocarbyl trisulfide, from up to about 5% dihydrocarbyl PO BOX 2149 disulfide, and more than about 7 wt.% dihydrocarbyl higher BAYTOWN, TX 77522-2149 (US) polysulfides, and at least one phosphorus or boron com pound, or mixtures of two or more thereof. The invention (21) Appl. No.: 10/091,249 also relates to concentrates and greases containing the above combination. The invention also relates to methods of mak (22) Filed: Mar. 5, 2002 ing the organic poly Sulfide. US 2003/0171222 A1 Sep. 11, 2003

SULFDE- AND POLYSULFDE-CONTAINING such as PAOs do not favorably interact with the additives LUBRICATING OIL ADDITIVE COMPOSITIONS used for this purpose. It is therefore a continuing problem to AND LUBRICATING COMPOSITIONS produce a good combination of Surface-related properties CONTAINING THE SAME including anti-wear performance and anti-rust performance in Synthetic oils based on hydrocarbon base StockS Such as TECHNICAL FIELD OF THE INVENTION PAOS. 0001. The present invention relates to the preparation and 0005. A need exists for a polysulfide additive that pro use of an additive for lubrication oils in which the additive vides improved performance characteristics for a finished includes at least one dihydrocarbyl polysulfide compound. lubricant composition comprising the polysulfide additive. A The present invention also relates to finished lubrication oils need exists for a polysulfide additive that improves at least having the dihydrocarbyl polysulfide additive and a base one performance characteristic of a finished lubricant while Stock. In particular, the present invention relates to the use reducing at least one of the deleterious effects caused by the of a mixture of a dihydrocarbyl sulfide and dihydrocarbyl use of a polysulfide additive in a finished lubricant. polysulfides having a desired ratio to provide a finished lubrication oil having certain desired performance attributes. SUMMARY OF THE INVENTION This invention further relates to lubricating compositions, concentrates and greases containing the combination of a 0006 The present invention relates to lubricating oil dihydrocarbyl polysulfide and a phosphorus or boron com compositions, including dihydrocarbyl poly Sulfides, which pound. are especially adapted for use in mechanical Systems where gears are Subjected to great StreSS and extremely high preSSures Such as those found in automotive rear axles or off BACKGROUND OF THE INVENTION highway transmissions and gear boxes. The present inven 0002 Polysulfides have been used in lubrication compo tion relates to lubricants and functional fluids, having a Sitions to provide extreme pressure protection. The poly Sul dihydrocarbyl polysulfide, that are useful particularly in fides have certain disadvantages including copper corrosion, environments characterized by high pressure and rubbing oxidation Stability, thermal instability and Seal compatibility Surfaces. problems. Additionally, the use of a polysulfide compound 0007 One embodiment according to the present inven to improve one performance parameter, e.g., wear resis tion includes a lubricating composition comprising a major tance, may introduce a deleterious performance character amount of an oil of lubricating Viscosity, at least one istic, i.e., gear tooth breakage in Severe application or attack dihydrocarbyl polysulfide comprising less than about 88% of elastomeric Seals. It is desirable to find a polysulfide dihydrocarbyl trisulfide; and a phosphorous compound or a which, when used alone or in combination with other boron compound, or mixtures of phosphorous compounds additives, provides good extreme pressure properties to and boron compounds. The oil of lubricating Viscosity is lubricants without adverse effects. generally in a major amount when the oil is about 70 wt.% 0003. Different types of base stocks have different per or greater of the total lubrication composition, preferably formance characteristics. Ester base Stocks, for example, the when the oil is about 90 wt. % or greater of the total neopentyl polyol esterS Such as the pentaerythritol esters of lubrication composition. monobasic carboxylic acids, have excellent high perfor mance properties as indicated by their common use in gas 0008 Another embodiment according to the present turbine lubricants. They also provide excellent anti-wear invention further includes the polysulfide having at least characteristics when conventional anti-wear additives are about 7.5 wt.% dihydrocarbyl tetrasulfide or higher polysul present and they do not have any adverse effect on the fides. performance of rust inhibitors. On the other hand, esters 0009. One embodiment of the present invention includes have relatively poor hydrolytic Stability, undergoing a complex mixture of organic Sulfides forming an additive hydrolysis readily in the presence of water at even moderate that includes a monosulfide having the formula R-S-R, temperatures. They are, therefore, leSS well Suited for use in where R and R may independently be a hydrocarbyl group wet applications Such as papermaking machinery. as described below and a polysulfide having the formula 0004 Hydrolytic stability can be improved by the use of R-S-R, wherein R and R may independently be a hydrocarbon base StockS. The use of alkyl aromatics in hydrocarbyl group as described below and X is equal to or combination with the other hydrocarbon base StockS Such as greater than about 2. The ratio of R-S-R to polysulfides, hydrogenated polyalphaolefin (PAO) synthetic hydrocar wherein X is equal to or greater than about 4, ranges from bons and the improved hydrolytic stability of these combi about 0.087 to about 0.112. nations is described, for example, in U.S. Pat. No. 5,602, 0010 Another embodiment of the present invention is a 086, corresponding to EP 496 486. Traditional formulations lubricant oil composition containing the polysulfide additive containing PAOS, however, present other performance prob and an oil or base Stock of lubricating Viscosity in which the lems. Although the hydrolytic stability of hydrocarbon base base Stock may be a mineral oil or a Synthetic base Stock. Stocks, including PAOS is Superior to that of the esters, it is frequently difficult to obtain a good balance of the Surface 0011) Another embodiment according to the present related properties Such as anti-wear and anti-rust because, as invention includes a lubricating composition including a noted above, these Surface-related properties are dependent major amount of an oil of lubricating Viscosity, at least one upon the extent to which the additives present in the base dihydrocarbyl polysulfide having less than about 88% dihy Stock compete for Sites on the metal Surfaces which they are drocarbyl trisulfide, less than about 5.5 wt.% dihydrocarbyl intended to protect and high quality hydrocarbon base StockS disulfide; at least about 7.5 wt.% dihydrocarbyl tetrasulfide US 2003/0171222 A1 Sep. 11, 2003 or higher polysulfides, and a phosphorous compound or a 0018. As described above, the present invention relates to boron compound, or mixtures thereof. compositions containing at least one polysulfide having Specific proportions of monoSulfides and/or polysulfides in 0012 Another embodiment according to the present combination with at least one phosphorus or boron com invention includes a concentrate comprising from 0.1% to pound, or mixtures thereof In one embodiment, the organic 49.9% by weight of a substantially inert, organic diluent and polysulfide is present in a base Stock at concentrations, based at least one dihydrocarbyl polysulfide comprising less than on the weight of the fully formulated lubricant composition, about 88% dihydrocarbyl trisulfide, less than about 5.5 wt. in the range of about 0.1% to about 10% by weight, or from % dihydrocarbyl disulfide, at least about 7.5 wt.% dihy about 0.2% up to about 8%, or from about 0.3% up to about drocarbyl tetrasulfide or higher poly Sulfides and at least one 7%, or from about 0.5% to about 5% by weight. Here, as phosphorus or boron compound or mixtures thereof. well as elsewhere in the Specification and claims, the range 0013 Another embodiment according to the present and ratio limits may be combined. In one embodiment, the invention includes a grease composition comprising at least phosphorus or boron compound, or mixture thereof is one oil of lubricating Viscosity, at least one thickening agent, present in an amount from about 0.05% up to about 10%, or and at least one dihydrocarbyl polysulfide comprising leSS from about 0.08% up to about 8%, or from about 0.1% up than about 88% dihydrocarbyl trisulfide, less than about 5.5 to about 5% by weight. wt.% dihydrocarbyl disulfide, and at least about 7.5 wt.% dihydrocarbyl tetrasulfide or higher poly Sulfides, and at least 0019 Organic Polysulfide one phosphorus or boron compound, or mixtures thereof. 0020. The dihydrocarbyl polysulfide is a mixture includ ing less than about 88 wt.% dihydrocarbyl trisulfide, from 0.014) Another embodiment of the present invention about 4 wt.% to about 6 wt.% dihydrocarbyl disulfide, and includes the polysulfide additive, a mineral oil, alkyl phos from about 7 wt. % to about 10 wt.% dihydrocarbyl phate/phosphite ester, a detergent or dispersant, borated tetrasulfide or higher polysulfides. Preferably, the dihydro alkylsuccinimide, primary amine, heterocyclic copper pas carbyl polysulfide mixture includes less than about 85 wt.% Sivator, and a defoamant. dihydrocarbyl trisulfide. The term “polysulfide” as used DETAILED DESCRIPTION OF THE herein may also include minor amounts of dihydrocarbyl INVENTION monosulfides, also referred to monoSulfide or Sulfide. Gen erally, the monosulfide is present in relatively Small amounts 0.015 The invention described herein includes polysul of less than about 1 wt.% of the total sulfur-containing fide additives that provide improved performance charac compounds present. In one embodiment according to the teristics, Such as extreme pressure protection, When used in present invention, the amount of trisulfide is at least less than lubricating compositions, greases, and concentrates, and about 88 wt.%. In another embodiment according to the methods for the use thereof. present invention, the amount of dihydrocarbyl disulfide is 0016. The term “hydrocarbyl” includes hydrocarbon, as more than about 4 wt.%, preferably more than about 5 wt. well as substantially hydrocarbon groups. “Substantially %. Typically, monoSulfides may be present in amounts hydrocarbon describes groups which contain heteroatom ranging from about 0.3 wt.% to about 0.4 wt.%. The Substituents that do not Substantially alter the predominantly monosulfides are preferably less than about 0.4 wt.% and hydrocarbon nature of the substituent. Non-limiting more preferably less than about 0.3 wt.%. examples of hydrocarbyl groups include the following: (1) 0021. The compositions of two non-limiting, exemplary hydrocarbon Substituents, i.e., aliphatic (e.g., alkyl or alk polysulfide mixtures, as determined by gas chromatography enyl) and alicyclic (e.g., cycloalkyl, cycloalkenyl, etc.) and reported as weight % of the total Sulfur-containing Substituents, aromatic-, aliphatic-, and alicyclic-Substituted compounds, are shown below in Table 1: aromatic Substituents and also includes cyclic Substituents wherein the ring is completed through another portion of the molecule (that is, for example, any two indicated Substitu TABLE 1. ents may together form an alicyclic radical); (2) Substituted Polysulfide Compositions hydrocarbon Substituents, i.e., those Substituents containing non-hydrocarbon groups which do not Substantially alter the S1 S4 predominantly hydrocarbon nature of the Substituent and Light (mono- S2 S3 (tetrasulfide or which includes groups Such as, e.g., halo (especially chloro Example Ends sulfide) (disulfide) (trisulfide) higher polysulfides) and fluoro), hydroxy, mercapto, nitro, nitroso, and Sulfoxy; A. O.O3 O.36 5.35 84.82 9.46 (3) heteroatom substituents, i.e., substituents which will B O.O2 O.28 4.37 87.70 7.62 contain an atom other than carbon in a ring or chain otherwise composed of carbon atoms (e.g., alkoxy or alky 0022. The sulfide analysis is performed on a Varian 6000 lthio). Suitable heteroatoms include, for example, Sulfur, Gas Chromatograph and FID detector SP-4100 computing oxygen, nitrogen and Such Substituents containing one or integrator. The column is a 25 m. Megabore SGE BP-1. The more heteroatoms exemplified by, pyridyl, furyl, thienyl, temperature profile is 75 C., hold time of 2 min., then heat and imidazolyl. to 250° C. at a rate of 6 C.Amin. The helium flow is 6.0 0.017. In general, no more than about 2, preferably no ml/min plus make-up. The injection temperature is 40 C. more than one heteroatom substituent will be present for and the detector temperature is 260C. The injection size is every ten carbon atoms in the hydrocarbyl group. Typically, 0.6 ul. References are the monosulfide, disulfide and trisul there will be no heteroatom substituents in the hydrocarbyl fide analogues to the Sulfur composition for analysis. The group in which case the hydrocarbyl group is a hydrocarbon. references may be obtained by fractionating the product to A preferred hydrocarbyl group is tertiary butyl. form sulfide fractions (S1, S2 and S3) to be used for US 2003/0171222 A1 Sep. 11, 2003

analysis. The procedure for analysis is as follows: (1) An group. R generally contains from about 2 to about 30 carbon area % determination is conducted on each reference Sample atoms, or from about 2 to about 24 carbon atoms, or from to determine its purity. (2) An area % determination is about 3 to about 18 carbon atoms. Examples include, but are conducted on the Sample to be tested to get an approximate not limited to, butyl mercaptan, amyl mercaptan, hexyl value of its composition. (3) A calibration blend is accurately mercaptan, octyl mercaptan, 6-hydroxymethyloctanethiol, weighed based on the area % results of the sample to be nonyl mercaptan, decyl mercaptan, 10-aminododecanethiol, tested; then the internal Standard toluene is added to the dodecyl mercaptan, 10-hydroxymethyl-tetradecanethiol, blend in an amount equal to approximately one-half of the and tetradecyl mercaptan. weight of the largest component. This provides an area 0028. The dihydrocarbyl polysulfide may be prepared by approximately the same as that of the largest component. (4) reacting, optionally under Superatmospheric pressure, one or The weights of each component (i.e., S1, S2 and S3) are more of the above olefins with a mixture of Sulfur and corrected by the 7% purity from step 1. (5) The calibration hydrogen Sulfide in the presence, or absence, of a catalyst, blend is analyzed in triplicate using the corrected weights Such as an alkyl amine catalyst, followed by removal of low and then calculated, using the following formula, to reflect boiling materials. The olefins which may be sulfurized, the the multiple peaks in S1 and S2: Sulfurized olefin, and methods of preparing the same are described in U.S. Pat. Nos. 4,119,549; 4,191,659; and 4,344, 854. The disclosure of these patents is hereby incorporated by reference for its description of the sulfurized olefins and (concentration of components) (area of internal standard) preparation of the Same. (total area of peaks) (concentration of internal standard) 0029. The following examples relate to polysulfide addi Adjusted for purity of the standard, i.e., component tives according to the present invention and methods of weight times percent purity equals concentration of component making the Same. 0030 The compositions of Examples A and B, shown in Table 1, may be prepared from olefins using the methods 0023 (6) These response factors, plus the response factor described above or, alternatively, may be prepared by blend for the Single S3 peak, are used for determining weight ing polysulfide containing materials. percent results for the samples to be tested. (7) Results for S1 and S2 are adjusted to include all the peaks attributed to 0031 Example A may be obtained by blending a trisul them. (8) Higher polysulfides are determined by difference fide such as TBPS 344, commercially available from Chev using the following formula: ronPhillips, and a polysulfide mixture such as MOBILADTM C170, commercially available from ExxonMobil, in a 75:25 ratio by weight. Example B may be obtained by blending TBPS 344 and MOBILADTM C170 in an 80:20 ratio by 0024 Light ends are defined as any peaks eluted weight. Blending of TBPS 344 and MOBILADTM C70 may prior to the internal Standard. be accomplished by any conventional method. 0.025 The organic polysulfide generally has hydrocarbyl groups each independently having from about 2 to about 30 0032. As described above, the lubricating compositions, carbon atoms, preferably from about 2 to about 20, or from concentrates and greases additionally contain at least one about 2 to about 12 carbon atoms. The hydrocarbyl groups phosphorus or boron compound, or mixtures of two or more may be aromatic or aliphatic, preferably aliphatic. In one thereof. The phosphorus and boron compounds are embodiment according to the present, the hydrocarbyl described in more detail below. groups are alkyl groups. In a specific embodiment according 0033 Phosphorus Compounds to the present invention, the hydrocarbyl groups are t-butyl. 0034. The lubricating compositions, concentrates, and 0026. The organic polysulfides may be derived from an greases may include a phosphorus compound. The phospho olefin or a mercaptan. The olefins, which may be Sulfurized, rus compound is Selected from a metal dithiophosphate, a contain at least one olefinic, i.e., a non-aromatic, double phosphoric acid ester or Salt thereof, a reaction product of a bond. Olefins having from 2 to about 30 carbon atoms, or phosphite and Sulfur or a Source of Sulfur, a phosphite, a from about 3 to about 16 (most often less than about 9) reaction product of a phosphorus acid or anhydride and an carbon atoms are particularly useful. Olefins having from 2 unsaturated compound, and mixtures of two or more thereof. to about 5, or from 2 to about 4 carbon atoms are particularly Typically, the phosphorus containing anti-wear/extreme useful. Isobutylene, propylene and their dimers, trimers and preSSure agent is present in the lubricants and functional tetramers, and mixtures thereof are especially preferred fluids at a level from about 0.01% to about 10%, or from olefins. Of these compounds, isobutylene and diisobutylene about 0.05% or to about 4%, or from about 0.08% to about are preferred. 3%, or from 0.1% to about 2% by weight. 0027. The mercaptains used to make the polysulfide may 0035. The metal thiophosphates are prepared by reacting be hydrocarbyl mercaptans, Such as those represented by the a metal base with one or more thiophosphorus acids. The formula R-S-H, wherein R is a hydrocarbyl group as thiophosphorus acid may be prepared by reacting one or defined above. In one embodiment according to the present more phosphorus Sulfides, which include phosphorus pen invention, each R is independently an alkyl, an alkenyl, tasulfide, phosphorus Sesquisulfide, phosphorus heptasulfide cycloalkyl, or cycloalkenyl group. Each R independently and the like, with one or more alcohols. The thiophosphorus may be a haloalkyl, hydroxyalkyl, or hydroxyalkyl Substi acid may be mono- or dithiophosphorus acid. The alcohols tuted (e.g., hydroxymethyl, hydroxyethyl, etc.) aliphatic generally contain from 1 to about 30 carbon atoms, or from US 2003/0171222 A1 Sep. 11, 2003

2 to about 24 carbon atoms, or from about 3 to about 12 phate, copper di(isobutyl) dithiophosphate, calcium did carbon atoms, or from about 3 to about 8 carbon atoms. (hexyl) dithiophosphate, Zinc isobutyl isoamyl dithiophos Alcohols used to prepare the thiophosphoric acids include phate, and Zinc isopropyl Secondary-butyl dithiophosphate. propyl, butyl, amyl, 2-ethylhexyl, hexyl, octyl, oleyl, and creSol alcohols. 0040. In one embodiment according to the present inven tion, the phosphorus compound is a phosphorus acid ester. 0036). In one embodiment, the phosphorus acid is a thio The ester is prepared by reacting one or more phosphorus phosphoric acid, preferably a monothiophosphoric acid. acids or anhydrides with an alcohol containing from one to Thiophosphoric acids may be prepared by the reaction of a about 30 carbon atoms, or from two to about 24, or from sulfur source with a dihydrocarbyl phosphite. The sulfur about 3 to about 12 carbon atoms. The alcohols used to Source may be, for instance, elemental Sulfur, or a Sulfide, prepare the phosphorus acid esters include those described Such as a Sulfur coupled olefin or a Sulfur coupled dithio above for metal thiophosphates. The phosphorus acid or phosphate. Elemental Sulfur is a preferred Sulfur Source. The anhydride is generally an inorganic phosphorus reagent, preparation of monothiophosphoric acids is disclosed in Such as phosphorus pentoxide, phosphorus trioxide, phos U.S. Pat. No. 4,755,311 and PCT Publication WO 87/07638, phorus tetroxide, phosphorous acid, phosphoric acid, phos which are incorporated herein by reference for their disclo phorus halide, C-7 phosphorus esters, or one of the above Sure of monothiophosphoric acids, Sulfur Sources, and the described phosphorus Sulfides. In one embodiment, the proceSS for making monothiophosphoric acids. Monothio phosphorus acid is a thiophosphorus acid or Salt thereof. The phosphoric acids may also be formed in the lubricant blend thiophosphoric acids and their Salts are described above. by adding a dihydrocarbyl phosphite to a lubricating com Non-limiting examples of phosphorus acid esters include position containing a Sulfur Source, Such as a Sulfurized phosphoric acid di- and tri-esters prepared by reacting a olefin. The phosphite may react with the sulfur source under phosphoric acid or anhydride with creSol alcohols, e.g., blending conditions (i.e., temperatures from about 30° C. to tricreSylphosphate. about 100° C., or higher) to form the monothiophosphoric acid. 0041. In another embodiment according to the present invention, the phosphorus compound is a phosphorus ester 0037. In another embodiment, the phosphorus acid is a prepared by reacting one or more dithiophosphoric acids dithiophosphoric acid or phosphorodithioic acid. The dithio with an epoxide or a glycol. This reaction product may be phosphoric acid may be represented by the formula used alone, or further reacted with a phosphorus acid, (RO)2PSSH, wherein each R is independently a hydrocar anhydride, or lower ester. The epoxide is generally an byl group, containing from about 3 to about 30 carbon aliphatic epoxide or a Styrene oxide. Examples of useful atoms, or from about 3 to about 18, or from about 4 to about epoxides include, but are not limited to, ethylene oxide, 12, or to about 8 carbon atoms. Non-limiting examples of R propylene oxide, butene oxide, octene oxide, dodecene include isopropyl, isobutyl, n-butyl, Sec-butyl, amyl, oxide, Styrene oxide, etc. Propylene oxide is preferred. The n-hexyl, methylisobutyl carbinyl, heptyl, 2-ethylhexyl, glycols may be aliphatic glycols, having from 1 to about 12 isooctyl, nonyl, behenyl, decyl, dodecyl, tridecyl, alkylphe carbon atoms, or from about 2 to about 6, or from about 2 nyl groups, or mixtures thereof. Illustrative lower alkylphe to about 3 carbon atoms, or aromatic glycols. Glycols nyl R. groups include butylphenyl, amylphenyl, and hep include, but are not limited to, ethylene glycol, propylene tylphenyl and mixtures thereof. Examples of mixtures of R glycol, catechol, resorcinol, and the like. The dithiophos groups include, but are not limited to: 1-butyl and 1-octyl, phoric acids, glycols, epoxides, inorganic phosphorus 1-pentyl and 2-ethyl-1-hexyl, isobutyl and n-hexyl, isobutyl reagents and methods of reacting the same are described in and isoamyl; 2-propyl and 2-methyl-4-pentyl; isopropyl and U.S. Pat. Nos. 3,197,405 and 3,544.465 which are incorpo Sec-butyl, and isopropyl and isooctyl. rated herein by reference for their disclosure to these. 0.038. The metal thiophosphates are prepared by the reac 0042 Acidic phosphoric acid esters may be reacted with tion of a metal base with the thiophosphorus acid. The metal ammonia, an amine, or metallic base to form an ammonium base may be any metal compound capable of forming a or metal Salt. The Salts may be formed Separately and then metal Salt. Non-limiting examples of metal bases include the Salt of the phosphorus acid ester may be added to the metal oxides, hydroxides, carbonates, Sulfates, borates, or lubricating composition. Alternatively, the Salts may also be the like. The metals of the metal base include Group IA, IIA, formed in Situ when the acidic phosphorus acid ester is IB through VIIB, and VIII metals (CAS version of the blended with other components to form a fully formulated Periodic Table of the Elements). These metals include the lubricating composition. When the phosphorus acid esters alkali metals, alkaline earth metals, and transition metals. In are acidic, they may be reacted with ammonia, an amine, or one embodiment, the metal is a Group IIA metal, Such as metallic base to form the corresponding ammonium or metal calcium or magnesium, a Group IB metal, Such as copper, a Salt. The Salts may be formed Separately and then the Salt of Group IIB metal, such as zinc, or a Group VIIB metal, such the phosphorus acid ester added to the lubricating or func as manganese. Preferably the metal is magnesium, calcium, tional fluid composition. Alternatively, the Salts may also be copper or zinc. Examples of metal compounds that may be formed when the phosphorus acid ester is blended with other reacted with the phosphorus acid include, but are not limited components to form the lubricating or functional fluid to, Zinc hydroxide, Zinc oxide, copper hydroxide, copper composition. The phosphorus acid ester may then form Salts Oxide, etc. with basic materials that are in the lubricating composition or functional fluid composition Such as basic nitrogen con 0.039 Examples of metal dithiophosphates include, but taining compounds (e.g., acylated amines). are not limited to, Zinc isopropyl, methylamyl dithiophos phate, Zinc isopropyl iscoctyl dithiophosphate, barium 0043. The ammonium salts of the phosphorus acid esters di(nonyl) dithiophosphate, Zinc di(cyclohexyl) dithiophos may be formed from ammonia, or an amine, or mixtures US 2003/0171222 A1 Sep. 11, 2003

thereof. These amines can be monoamines or polyamines. -Oxazolidines, -thiazolidines and the like. Typically, how Useful amines include those disclosed in U.S. Pat. No. ever, each R" is independently a methyl, ethyl, propyl, butyl, 4,234,435 at col. 21, line 4 to col. 27, line 50, this section of pentyl, or hexyl group. Examples of these alkanolamines this reference being incorporated herein by reference. include mono-, di-, and triethanolamine, diethylethanola mine, ethylethanolamine, butyldiethanolamine, etc. 0044) The monoamines generally have at least one hydro carbyl group containing from 1 to about 30 carbon atoms, 0048. The hydroxyamines may also be an ether N-(hy with from 1 to about 20 carbon atoms being preferred, with droxyhydrocarbyl)amine. These are hydroxypoly(hydrocar from 1 to about 16 being more preferred. Non-limiting byloxy) analogs of the above-described hydroxyamines examples of monoamines include methylamine, ethylamine, (these analogs also include hydroxyl-Substituted oxyalky propylamine, butylamine, 2-ethylhexylamine, octylamine, lene analogs). Such N-(hydroxyhydrocarbyl)amines can be and dodecylamine. Non-limiting examples of Secondary conveniently prepared by reaction of one or more of the amines include dimethylamine, diethylamine, dipropy above epoxides with aforedescribed amines and may be lamine, dibutylamine, methylbutylamine, ethylhexylamine, represented by the formulae: HN-(R'O)-H (VIII), etc. Tertiary amines include, but are not limited to, trim H(R')-N-R'O)-H (IX), and (R')-N-(R'O)-H ethylamine, tributylamine, methyldiethylamine, ethyldibu (X), wherein X is a number from about 2 to about 15 and R; tylamine, etc. and R' are as described above. R' may also be a hydroxy poly(hydrocarbyloxy) group. 0.045. In one embodiment according to the present inven tion, the amine is a tertiary-aliphatic primary amine. Gen 0049. In another embodiment, the amine is a erally, the aliphatic group, preferably an alkyl group, con hydroxyamine which may be represented by the formula tains from about 4 to about 30 carbon atoms, or from about wherein R is a hydrocarbyl group containing from about 6 6 to about 24, or from about 8 to about 22 carbon atoms. to about 30 carbon atoms; R is an alkylene group having Usually the tertiary alkyl primary amines are monoamines from about 2 to about 12 carbon atoms, preferably an represented by the formula Re-C(R)-NH, wherein Rs ethylene or propylene group; R is an alkylene group con is a hydrocarbyl group containing from 1 to about 27 carbon taining from 1 to about 8, or from 1 to about 5 carbon atoms; atoms and R is a hydrocarbyl group containing from 1 to y is Zero or one; and each Z is independently a number from about 12 carbon atoms. Such amines are illustrated by Zero to about 10, with the proviso that at least one Z is Zero. t-butylamine, t-hexylamine, 1-methyl-1-amino-cyclohex Useful hydroxyhydrocarbyl amines where y in the above ane, t-octylamine, t-decylamine, t-dodecylamine, t-tetrade formula is Zero include 2-hydroxyethylhexylamine, 2-hy cylamine, t-hexadecylamine, t-octadecylamine, t-tetracosa droxyethyloctylamine; 2-hydroxyethylpentadecylamine; nylamine, and t-Octacosanylamine. 2-hydroxyethyloleylamine; 2-hydroxyethylsoyamine; bis(2- hydroxyethyl)hexylamine; bis(2-hydroxyethyl)oleylamine; 0046) Mixtures of tertiary aliphatic amines may also be and mixtures thereof. Also included are the comparable used. Illustrative of amine mixtures of this type are members wherein in the above formula at least one Z is at “Primene TM 81R which is a mixture of C-C tertiary least 2, as for example, 2-hydroxyethoxyethylhexylamine. alkyl primary amines and “Primene JMT' which is a similar mixture of C-C tertiary alkyl primary amines (both are 0050. The amine may also be a polyamine. The available from Rohm and Haas Company). The tertiary polyamines include alkoxylated diamines, fatty diamines, aliphatic primary amines and methods for their preparation described above, alkylenepolyamines (described above), are known to those of ordinary skill in the art. The tertiary hydroxy containing polyamines, condensed polyamines, aliphatic primary amines are described in U.S. Pat. No. described above, and heterocyclic polyamines, described 2.945,749, which is hereby incorporated by reference for its above. Commercially available examples of alkoxylated teaching in this regard. diamines include those amines where y in the above formula S Oc. 0047. In another embodiment according to the present 0051. In another embodiment, the polyamine is a fatty invention, the amine may be a hydroxyamine. Typically, the diamine. The fatty diamines include mono- or dialkyl, hydroxyamines are primary, Secondary or tertiary alkanol Symmetrical or asymmetrical ethylenediamines, propanedi amines or mixtures thereof. Such amines can be represented by the formulae: H-N-R'-OH, H(R')N-R'-OH, and amines (1.2 or 1,3), and polyamine analogs of the above. (R)-N-R-OH, wherein each R" is independently a 0052. In another embodiment, the amine is an alkylene hydrocarbyl group having from 1 to about 8 carbon atoms or polyamine. Alkylenepolyamines are represented by the for a hydroxyhydrocarbyl group having from 1 to about 8 mula HRN-(Alkylene-N), (R), wherein each R is indepen carbon atoms, or from 1 to about 4 carbon atoms, and R is dently hydrogen; or an aliphatic or hydroxy-Substituted a divalent hydrocarbyl group of about 2 to about 18 carbon aliphatic group of up to about 30 carbon atoms; n is a atoms, or from 2 to about 4. The group -R'-OH in Such number from 1 to about 10, or from about 2 to about 7, or formulae represents the hydroxyhydrocarbyl group. R' can from about 2 to about 5; and the “Alkylene' group has from be an acyclic, alicyclic or aromatic group. Typically, R is an 1 to about 10 carbon atoms, or from about 2 to about 6, or acyclic Straight or branched alkylene group Such as an from about 2 to about 4. In another embodiment, R2s is ethylene, propylene, 1,2-butylene, 1,2-octadecylene, etc., defined the same as R', above. Such alkylenepolyamines group. Where two R' groups are present in the same include methylenepolyamines, ethylenepolyamines, butyle molecule they can be joined by a direct carbon-to-carbon nepolyamines, propylenepolyamines, pentylenepolyamines, bond or through a heteroatom (e.g., oxygen, nitrogen or etc. The higher homologs and related heterocyclic amines, sulfur) to form a 5-, 6-, 7- or 8-membered ring structure. Such as piperazines and N-amino alkyl-Substituted pipera Examples of Such heterocyclic amines include N-(hydroxyl Zines, are also included. Specific examples of Such lower alkyl)-morpholines, -thiomorpholines, -piperidines, polyamines are ethylenediamine, triethylenetetramine, tris US 2003/0171222 A1 Sep. 11, 2003

(2-aminoethyl)amine, propylenediamine, trimethylenedi weights ranging from about 200 to about 4,000, or from amine, tripropylenetetramine, triethylenetetramine, tetraeth about 400 to about 2,000. The preferred polyoxyalkylene ylenepentamine, hexaethyleneheptamine, polyamines include the polyoxyethylene and polyoxypro pentaethylenehexamine, etc. Higher homologs obtained by pylene diamines and the polyoxypropylene triamines. condensing two or more of the above-noted alkyleneamines 0058. In another embodiment, the polyamines are are similarly useful as are mixtures of two or more of the hydroxy-containing polyamines. Hydroxy-containing aforedescribed polyamines. polyamine analogs of hydroxy monoamines, particularly 0053. In one embodiment, the polyamine is an ethylene alkoxylated alkylenepolyamines, e.g., N,N-(diethanol)ethyl polyamine. Such polyamines are described in detail under ene diamines can also be used. Such polyamines can be the heading Ethylene Amines in Kirk Othmer’s “Encyclo made by reacting the above-described alkylene amines with pedia of Chemical Technology', 2d Edition, Vol. 7, pages one or more of the above-described alkylene oxides. Similar 22-37, Interscience Publishers, New York (1965). Ethylene alkylene oxide-alkanol amine reaction products may also be polyamines are often a complex mixture of polyalkylenep used Such as the products made by reacting the above olyamines including cyclic condensation products. Other described primary, Secondary, or tertiary alkanol amines useful types of polyamine mixtures are those resulting from with ethylene, propylene or higher epoxides in a 1:1 to 1:2 Stripping of the above-described polyamine mixtures to molar ratio. Reactant ratioS and temperatures for carrying leave, as residue, what is often termed “polyamine bottoms'. out Such reactions are known to those skilled in the art. In general, alkylenepolyamine bottoms can be characterized Specific examples of hydroxy-containing polyamines as having less than 2%, usually less than 1% (by weight) include N-(2-hydroxyethyl)ethylenediamine, N,N'-bis(2-hy material boiling below about 200 C. These alkylenep droxyethyl)ethylenediamine, 1-(2-hydroxyethyl)piperazine, olyamine bottoms include cyclic condensation products mono(hydroxypropyl)-substituted tetraethylenepentamine, Such as piperazine and higher analogs of diethylenetriamine, N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher triethylenetetramine and the like. These alkylenepolyamine homologs obtained by condensation of the above-illustrated bottoms may be reacted Solely with the acylating agent or hydroxy-containing polyamines through amino groups or they may be used with other amines, polyamines, or mix through hydroxy groups are likewise useful. Condensation tures thereof. through amino groups results in a higher amine accompa 0.054 Another useful polyamine is a condensation reac nied by removal of ammonia while condensation through the tion between at least one hydroxy compound with at least hydroxy groups results in products containing ether linkages one polyamine reactant containing at least one primary or accompanied by removal of water. Mixtures of two or more Secondary amino group. The hydroxy compounds are pref of any of the above-described polyamines are also useful. erably polyhydric alcohols and amines. The polyhydric 0059. In another embodiment, the amine is a heterocyclic alcohols are described below. In one embodiment, the amine. The heterocyclic polyamines include aziridines, aze hydroxy compounds are polyhydric amines. Polyhydric tidines, azolidines, tetra- and dihydropyridines, pyrroles, amines include any of the above-described monoamines indoles, piperidines, imidazoles, di- and tetrahydroimida reacted with an alkylene oxide (e.g., ethylene oxide, propy Zoles, piperazines, isoindoles, purines, morpholines, thio lene oxide, butylene oxide, etc.) having from 2 to about 20 morpholines, N-aminoalkylmorpholines, N-aminoalkylthi carbon atoms, or from 2 to about 4 carbon atoms. Examples omorpholines, N-aminoalkylpiperazines, N,N'- of polyhydric amines include tri-(hydroxypropyl)amine, diaminoalkylpiperazines, azepines, azocines, azonines, tris-(hydroxymethyl)amino methane, 2-amino-2-methyl-1, aZecines and tetra-, di- and perhydro derivatives of each of 3-propanediol, N.N.N',N'-tetrakis (2-hydroxypropyl) ethyl the above and mixtures of two or more of these heterocyclic enediamine, and N.N.N',N'-tetrakis (2-hydroxyethyl) ethyl amines. Preferred heterocyclic amines are the Saturated 5 enediamine, preferably tris(hydroxymethyl) aminomethane and 6-membered heterocyclic amines containing only nitro gen, oxygen and/or Sulfur in the hetero ring, especially the piperidines, piperazines, thiomorpholines, morpholines, pyr 0.055 Polyamines that may react with the polyhydric rolidines, and the like. Piperidine, aminoalkyl-Substituted alcohol or amine to form the condensation products or piperidines, piperazine, aminoalkyl-Substituted piperazines, condensed amines are described above. Preferred morpholine, aminoalkyl-Substituted morpholines, pyrroli polyamines include triethylenetetramine (TETA), tetraeth dine, and aminoalkyl-Substituted pyrrolidines, are especially ylenepentamine (TEPA), pentaethylenehexamine (PEHA), preferred. Usually the aminoalkyl Substituents are Substi and mixtures of polyamines Such as the above-described tuted on a nitrogen atom forming part of the hetero ring. “amine bottoms'. The condensation reaction of the Specific examples of Such heterocyclic amines include polyamine reactant with the hydroxy compound is con N-aminopropylmorpholine, N-aminoethylpiperazine, and ducted at an elevated temperature, usually from about 60° C. N,N'-diaminoethylpiperazine. Hydroxy heterocyclic amines to about 265 C., or from about 220 C. to about 250° C. in are also useful. Examples include N-(2-hydroxyethyl)cyclo the presence of an acid catalyst. hexylamine, 3-hydroxycyclopentylamine, parahydroxya 0056. The amine condensates and methods of making the niline, N-hydroxyethylpiperazine, and the like. same are described in PCT publication WO86/05501 and 0060 Hydrazine and hydrocarbyl-substituted hydrazine U.S. Pat. No. 5,230,714 (Steckel), which are incorporated by may also be used to form the acylated nitrogen dispersants. reference for its disclosure to the condensates and methods At least one of the nitrogen atoms in the hydrazine must of making contain a hydrogen directly bonded thereto. Preferably there 0057. In another embodiment, the polyamines are poly are at least two hydrogens bonded directly to hydrazine oxyalkylene polyamines, e.g., polyoxyalkylene diamines nitrogen and, more preferably, both hydrogens are on the and polyoxyalkylene triamines, having average molecular Same nitrogen. Specific examples of Substituted hydrazines US 2003/0171222 A1 Sep. 11, 2003

are methylhydrazine, N,N-dimethyl hydrazine, N,N'-dim with the unsaturated amide may be further reacted with ethyl hydrazine, phenylhydrazine, N-phenyl-N'-ethylhydra linking or coupling compounds, Such as formaldehyde or zine, N-(para-tolyl)-N'-(n-butyl)-hydrazine, N-(para-nitro paraformaldehyde, to form coupled compounds. The phos phenyl)-hydrazine, N-(para-nitrophenyl)-N- phorus-containing amides are known in the art and are methylhydrazine, N,N'-di(para-chlorophenol)-hydrazine, disclosed in U.S. Pat. Nos. 4,876,374; 4,770,807; and 4,670, N-phenyl-N'-cyclohexylhydrazine, and the like. 169 that are incorporated by reference for their disclosures of phosphorus amides and their preparation. 0061 The metal salts of the phosphorus acid esters are prepared by the reaction of a metal base with the phosphorus 0065. In one embodiment, the unsaturated compound, an acid ester. The metal base may be any metal compound unsaturated carboxylic acid or ester, Such as a vinyl or allyl capable of forming a metal Salt. Examples of metal bases acid or ester. If the carboxylic acid is used, the ester may include metal oxides, hydroxides, carbonates, borates, or the then be formed by Subsequent reaction with an alcohol. In like. The metals of the metal base include Group IA, IIA, IB one embodiment, the unsaturated carboxylic acids include through VIIB, and VIII metals (CAS version of the Periodic the unsaturated fatty acids and esters described above. The Table of the Elements). These metals include the alkali Vinyl ester of a carboxylic acid may be represented by the metals, alkaline earth metals, and transition metals. In one formula RCH=CH-O(O)CR', wherein R is a hydrogen or embodiment, the metal is a Group IIA metal, Such as calcium hydrocarbyl group having from 1 to about 30 carbon atoms, or magnesium, a Group IB metal, Such as copper, a Group preferably hydrogen or a hydrocarbyl group having 1 to IIB metal, such as zinc, or a Group VIIB metal, such as about 12, more preferably hydrogen, and R' is a hydrocarbyl manganese. Preferably the metal is magnesium, calcium, group having 1 to about 30 carbon atoms, preferably 1 to copper, or zinc. Examples of metal compounds that may be about 12 carbon atoms, more preferably 1 to about 8 carbon reacted with the phosphorus acid include Zinc hydroxide, atoms. Examples of vinyl esters include, but are not limited Zinc oxide, copper hydroxide, copper oxide, etc. to, Vinyl acetate, vinyl 2-ethylhexanoate, Vinyl butanoate, and Vinyl crotonate. 0.062. In another embodiment, the phosphorus compound 0066. In one embodiment, the unsaturated carboxylic is a metal thiophosphate, preferably a metal dithiophosphate. ester is an ester of an unsaturated carboxylic acid, Such as The metal thiophosphates are described above. In another maleic, fumaric, acrylic, methacrylic, itaconic, citraconic embodiment, the metal dithiophosphates are further reacted acids and the like. The ester can be represented by the with one or more of the above described epoxides, prefer formula RO-(O)C-HC=CH-C(O)OR, wherein each R ably propylene oxide. These reaction products are described is independently a hydrocarbyl group having 1 to about 18 in U.S. Pat. Nos. 3,213,020; 3,213,021; and 3,213,022, carbon atoms, preferably 1 to about 12, more preferably 1 to issued to Hopkins et al. These patents are incorporated by about 8 carbon atoms. Non-limiting examples of unsaturated reference for Such description of the reaction products. carboxylic esters, useful in the present invention, include 0.063. In another embodiment, the phosphorus compound methylacrylate, ethylacrylate, 2-ethylhexylacrylate, 2-hy may be a phosphite. In one embodiment, the phosphite is a droxyethylacrylate, ethylmethacrylate, 2-hydroxyethyl di- or trihydrocarbyl phosphite. Preferably each hydrocarbyl methacrylate, 2-hydroxypropylmethacrylate, 2-hydroxypro group has from 1 to about 24 carbon atoms, more preferably pylacrylate, ethylmaleate, butylmaleate and from 1 to about 18 carbon atoms, and more preferably from 2-ethylhexylmaleate. The above list includes mono- as well about 2 to about 8 carbon atoms. Each hydrocarbyl group as diesters of maleic, fumaric and citraconic acids. may be independently alkyl, alkenyl, aryl, and mixtures 0067. In one embodiment, the phosphorus compound is thereof. When the hydrocarbyl group is an aryl group, then the reaction product of a phosphorus acid and a vinyl ether. it contains at least about 6 carbon atoms, preferably about 6 The vinyl ether is represented by the formula to about 18 carbon atoms. Non-limiting examples of the R-CH=CH-OR", wherein R is hydrogen or a hydro alkyl or alkenyl groups include propyl, butyl, hexyl, heptyl, carbyl group having 1 to about 30 carbon atoms, preferably octyl, oleyl, linoleyl, Stearyl, etc. Examples of aryl groups 1 to about 24, more preferably 1 to about 12 carbon atoms, include, but are not limited to, phenyl, naphthyl, heptylphe and R is a hydrocarbyl group having 1 to about 30 carbon nol, etc. Preferably each hydrocarbyl group is independently atoms, preferably 1 to about 24, more preferably 1 to about propyl, butyl, pentyl, hexyl, heptyl, oleyl or phenyl, more 12 carbon atoms. Examples of vinyl ethers include, but are preferably butyl, oleyl or phenyl and more preferably butyl, not limited to, vinyl methylether, vinyl propylether, vinyl oleyl, or phenyl. Phosphites and their preparation are known 2-ethylhexylether and the like. and many phosphites are available commercially. Particu 0068 Boron-Containing Anti-Wear/Extreme Pressure larly useful phosphites are dibutyl hydrogen phosphite, Agents dioleyl hydrogen phosphite, di(Cs) hydrogen phosphite, 0069. The lubricants and/or functional fluids may addi and triphenyl phosphite. tionally contain a boron compound. Typically, the boron 0064. In one embodiment, the phosphorus compound containing anti-wear/extreme pressure agent is present in the may be a reaction product of a phosphorus acid and an lubricants and functional fluids at a level from about 0.01% unsaturated compound. The unsaturated compounds include up to about 10%, or from about 0.05% or up to about 4%, unsaturated amides, esters, acids, anhydrides, and ethers. or from about 0.08% up to about 3%, or from 0.1% to about The phosphorus acids are described above; preferably the 2% by weight. Non-limiting examples of boron-containing phosphorus acid is a dithiophosphoric acid. In one embodi anti-wear/extreme pressure agents include aborated dispers ment, the unsaturated compound is an unsaturated amide. ant; an alkali metal or a mixed alkali metal, alkaline earth Examples of unsaturated amides include acrylamide, N,N'- metal borate; a borated epoxide; and a borate ester. methylene bis-acrylamide, methacrylamide, crotonamide, 0070. In one embodiment, the boron compound is a and the like. The reaction product of the phosphorus acid borated dispersant. Borated dispersants are prepared by US 2003/0171222 A1 Sep. 11, 2003

reaction of one or more dispersants with one or more boron one or more of the above-described polyamines, Such as the compounds. The dispersants include, but are not limited to, polyalkylenepolyamines. Mannich dispersants are described acylated amines, carboxylic esters, Mannich reaction prod in the following patents: U.S. Pat. Nos. 3,980,569; 3,877, ucts, hydrocarbyl-Substituted amines, and mixtures thereof. 899; and 4,454,059 (herein incorporated by reference for The acylated amines include reaction products of one or their disclosure to Mannich dispersants). more of the above carboxylic acylating agents and one or more amines. The amines may be any of those described 0076. In another embodiment, the dispersant is aborated above, preferably a polyamine, Such as an alkylenep dispersant. The borated dispersants are prepared by reacting olyamine or a condensed polyamine. one or more of the above dispersants with one or more of the above-described boron compounds. 0071 Acylated amines and methods for preparing the same are described in U.S. Pat. Nos. 3,219,666; 4,234,435; 0077. Typically, the borated dispersant contains from 4,952,328; 4.938,881; 4,957,649; and 4,904,401. The dis about 0.1% to about 5%, or from about 0.5%- to about 4%, closures of acylated nitrogen dispersants and other disperS or from 0.7% to about 3% by weight boron. In one embodi ants contained in those patents are hereby incorporated by ment, the borated dispersant is a borated acylated amine, reference. Such as a borated Succinimide dispersant. Borated disperS ants are described in U.S. Pat. Nos. 3,000,916; 3,087,936; 0.072 In another embodiment, the dispersant may also be 3.254,025; 3,282,955; 3,313,727; 3,491,025; 3,533,945; a hydrocarbyl-substituted amine. These hydrocarbyl-substi 3,666,662; and 4,925,983. These references are incorporated tuted amines are well known to those skilled in the art. These by reference for their disclosure of borated dispersants. amines are disclosed in U.S. Pat. Nos. 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,755,433; and 3,822,289. These pat 0078. In one embodiment, the boron compound is an ents are hereby incorporated by reference for their disclosure alkali or an alkali metal and alkaline earth metal borate. of hydrocarbyl amines and methods of making the same. These metal borates are generally hydrated particulate metal Typically, hydrocarbyl-Substituted amines are prepared by borates that are known in the art. Alkali metal borates reacting olefins and olefin polymers, including the above include mixed alkali and alkaline metal borates. These metal polyalkenes and halogenated derivatives thereof, with borates are available commercially. Representative patents amines (mono- or polyamines). The amines may be any of disclosing Suitable alkali and alkali metal and alkaline earth the amines described above, preferably an alkylenep metal borates and their methods of manufacture include U.S. olyamine. Non-limiting examples of hydrocarbyl-Substi Pat. Nos. 3,997,454; 3,819,521; 3,853,772; 3,907,601; tuted amines include poly(propylene)amine; N,N-dimethyl 3,997,454; and 4,089,790. These patents are incorporated by N-poly(ethylene/propylene)amine, (50:50 mole ratio of reference for their disclosures of the metal borates and monomers); polybutene amine; N,N-di(hydroxyethyl)-N- methods of their manufacture. polybutene amine; N-(2-hydroxypropyl)-N-polybutene 0079. In another embodiment, the boron compound is a amine, N-polybutene-aniline, N-polybutenemorpholine; borated fatty amine. The borated amines are prepared by N-poly(butene)ethylenediamine; N-poly(propylene)trimeth reacting one or more of the above boron compounds with ylenediamine; N-poly(butene)diethylenetriamine; N',N'-po one or more of the above fatty amines, e.g., an amine having ly(butene) tetraethylenepentamine; N,N-dimethyl-N'- from about 4 up to about 18 carbon atoms. The borated fatty poly(propylene)-1,3-propylenediamine and the like. amines are prepared by reacting the amine with the boron 0073. In another embodiment, the dispersant may also be compound from about 50 C. to about 300 C., preferably a Mannich dispersant. Mannich dispersants are generally from about 100° C. to about 250 C., and at a ratio from formed by the reaction of at least one aldehyde, Such as about 3:1 to about 1:3 equivalents of amine to equivalents of formaldehyde and paraformaldehyde, at least one of the boron compound. above-described amines and at least one alkyl-Substituted 0080. In another embodiment, the boron compound is a hydroxyaromatic compound. The reaction may occur from borated epoxide. The borated fatty epoxides are generally room temperature to about 225 C., or from about 50° C. to the reaction product of one or more of the above boron about 200 C., or from about 75° C. to about 150° C. The compounds with at least one epoxide. The epoxide is gen amounts of the reagents are Such that the molar ratio of erally an aliphatic epoxide having from 8 up to about 30 hydroxyaromatic compound to formaldehyde to amine is in carbon atoms, preferably from about 10 up to about 24 the range from about (1:1:1) to about (1:3:3). carbon atoms, more preferably from about 12 up to about 20 0.074 The first reagent is an alkyl-substituted carbon atoms. Examples of useful aliphatic epoxides include hydroxyaromatic compound. This term includes the above heptyl epoxide, octyl epoxide, oleyl epoxide and the like. described phenols. The hydroxyaromatic compounds are Mixtures of epoxides may also be used, for instance, com those Substituted with at least one, and preferably not more mercial mixtures of epoxides having from about 14 to about than two, aliphatic or alicyclic groups having from about 6 16 carbon atoms and from about 14 to about 18 carbon to about 400 carbon atoms, or from about 30 to about 300, atoms. The borated fatty epoxides are generally known and or from about 50 to about 200 carbon atoms. These groups are disclosed in U.S. Pat. No. 4,584,115. This patent is may be derived from one or more of the above described incorporated by reference for its disclosure of borated fatty olefins or polyalkenes. In one embodiment, the hydroxyaro epoxides ad methods for preparing the Same. matic compound is a phenol Substituted with an aliphatic or alicyclic hydrocarbon-based group having a number average 0081. In one embodiment, the boron compound is a borate ester. The borate esterS may be prepared by reacting molecular weight, Mn, of about 420 to about 10,000. one or more of the above boron compounds with one or 0075. The third reagent is any amine described above more of the above alcohols. Typically, the alcohols contain containing at least one NH group. Preferably the amine is from about 6 up to about 30 carbon atoms, or from about 8 US 2003/0171222 A1 Sep. 11, 2003

to about 24 carbon atoms. The methods of making Such the methods disclosed by U.S. Pat. No. 3,382.291 may be borate esters are known to those in the art. conveniently used herein. Other descriptions of PAO syn thesis are found in the following U.S. Pat. No. 3,742,082 0082) Lubricants (Brennan); U.S. Pat. No. 3,769,363 (Brennan); U.S. Pat. No. 0.083 AS previously indicated, the combination of a 3,876,720 (Heilman); U.S. Pat. No. 4,239,930 (Allphin); dihydrocarbyl polysulfide and a phosphorus or boron com U.S. Pat. No. 4,367,352 (Watts); U.S. Pat. No. 4413,156 pound, or mixture thereof are useful as additives for lubri (Watts); U.S. Pat. No. 4,910,355 (Shubkin); U.S. Pat. No. cants in which they can function primarily as anti-Wear, 4.956,122 (Watts); and, U.S. Pat. No. 5,068,487 (Theriot). A anti-Weld, and/or extreme preSSure agents. Lubricants con particularly favorable class of PAO type base stocks are the taining this combination have improved properties Such as High Viscosity Index PAOs (HVI-PAOs) prepared by the those relating to odor, copper Strip, thermal Stability wear, action of a reduced chromium catalyst with the alpha-olefin; Scuffing, oxidation, Surface fatigue, Seal compatibility, cor the HVI-PAOs are described in U.S. Pat. No. 4,827,073 rosion resistance, and thermal durability. They may be (Wu); U.S. Pat. No. 4,827,064 (Wu); U.S. Pat. No. 4,967, employed in a variety of lubricants based on diverse oils of 032 (Ho et al.); U.S. Pat. No. 4,926,004 (Pelrine et al.); and, lubricating Viscosity, including natural and Synthetic lubri U.S. Pat. No. 4,914,254 (Pelrine). The dimers of the C to cating oils and mixtures thereof. These lubricants include Cs olefins are described in U.S. Pat. No. 4,218,330. crankcase lubricating oils for Spark-ignited and compres 0087. The average molecular weight of the PAO typically Sion-ignited internal combustion engines, including automo varies from about 250 to about 10,000 with a preferred range bile and truck engines, two-cycle engines, aviation piston of from about 300 to about 3,000 with a viscosity varying engines, marine and railroad diesel engines, and the like. from about 3 cSt to about 200 cSt at 100° C. The PAO, being They can also be used in gas engines, Stationary power the majority component of the formulation will have the engines and turbines and the like. Automatic or manual greatest effect on the Viscosity and other Viscometric prop transmission fluids, transaxle lubricants, gear lubricants, erties of the finished product. Since the finished lubricant including open and enclosed gear lubricants, tractor lubri products are Sold by Viscosity grade, blends of different cants, metal-working lubricants, hydraulic fluids and other PAOS may be used to achieve the desired viscosity grade. lubricating oil and grease compositions can also benefit from Typically, the PAO component will comprise one or more the incorporation therein of the compositions of the present PAOs of varying viscosities, usually with the lightest com invention. They may also be used as wirerope, walking cam, ponent being nominally a 2 cSt (100° C.) component with way, rock drill, chain and conveyor belt, worm gear, bearing, other, more Viscous PAOS also being present in order to give and rail and flange lubricants. the final desired viscosity to the finished formulation. Typi 0084. As described above, the lubricating composition cally, PAOS may be made in viscosities up to about 1,000 cSt contains an oil of lubricating Viscosity. The oils of lubricat (100 C.) although in most cases, Viscosities greater than ing Viscosity include natural or Synthetic lubricating oils and 100 cSt will not be required except in minor amounts as mixtures thereof. Natural oils include animal oils, mineral Viscosity indeX improvers. lubricating oils, and Solvent or acid treated mineral oils. Synthetic lubricating oils include hydrocarbon oils (polyal 0088 Additionally, alkylated aromatic compounds may phaolefins), halo-Substituted hydrocarbon oils, alkylene be used as a base Stock. The alkylated aromatic compounds oxide polymers, esters of dicarboxylic acids and polyols, include, but are not limited to, alkylated naphthalenes in esters of phosphorus-containing acids, polymeric tetrahy which the alkyl group may be a hydrocarbyl group as drofurans and silicon-based oils. Preferably, the oil of lubri described above. The base stock may also be from the class cating Viscosity is a hydrotreated mineral oil or a Synthetic of hydrocarbon-Substituted aromatic compounds, Such as the lubricating oil, Such as a polyolefin. A description of oils of long chain alkyl-Substituted aromatics. The preferred hydro lubricating viscosity occurs in U.S. Pat. No. 4,582,618 (col. carbon Substituents for all these materials are, of course, the 2, line 37 through col. 3, line 63, inclusive), herein incor long chain alkyl groups with at least 8 and usually at least porated by reference for its disclosure to oils of lubricating 10 carbon atoms, to confer good Solubility in the primary Viscosity. hydrocarbon blend component. Alkyl substituents of 12 to 18 carbon atoms are Suitable and can readily be incorporated 0085 Synthetic hydrocarbon base stocks include the by conventional alkylation methods using olefins or other polyalphaolefins (PAOs). The PAOs are known materials alkylating agents. The aromatic portion of the molecule may and typically comprise relatively low molecular weight be hydrocarbon or non-hydrocarbon as in the examples hydrogenated polymers or oligomers of alphaolefins which given below. include but are not limited to C to about C alphaolefins with the Cs to about C alphaolefins, Such as 1-octene, 0089. Included in this class of base stock are, for 1-decene, 1-dodecene and the like being preferred. The example, long chain alkylbenzenes and long chain alkyl preferred polyalphaolefins are poly-1-decene and poly-1- naphthalenes which are particularly preferred materials since they are hydrolytically stable and may therefore be dodecene although the dimers of higher olefins in the range used alone or in combination with the PAO component of of C to Cs provide low Viscosity base StockS. the base Stock in wet applications. The alkylnaphthalenes are 0086) The PAO fluids may be conveniently made by the known materials and are described, for example, in U.S. Pat. polymerization of an alpha-olefin in the presence of a No. 4,714,794 (Yoshida et al.). The use of a mixture of polymerization catalyst Such as the Friedel-Crafts catalysts monoalkylated and polyalkylated naphthalene as a base for including, for example, aluminum trichloride, boron trifluo synthetic functional fluids is also described in U.S. Pat. No. ride or complexes of boron trifluoride with water, alcohols 4,604,491 (Dressler). The preferred alkylnaphthalenes are Such as ethanol, propanol or butanol, carboxylic acids or those having a relatively long chain alkyl group typically esterS Such as ethyl acetate or ethyl propionate. For example from 10 to 40 carbon atoms although longer chains may be US 2003/0171222 A1 Sep. 11, 2003 used if desired. Alkylnaphthalenes produced by alkylating not limited to, mineral oil (Group I base stocks), hydropro naphthalene with an olefin of 14 to 20 carbon atoms have cessed mineral oil (Group II and III base Stocks), conven particularly good especially when Zeolites Such as the large tional PAO (Group IV base stocks), and esters (Group V pore size Zeolites are used as the alkylating catalyst, as base Stocks). described in U.S. Pat. No. 5,602,086, corresponding to EP 496 486 to which reference is made for a description of the 0093 Methods of preparing high VI base stocks are Synthesis of these materials. These alkylnaphthalenes are disclosed in U.S. Pat. Nos. 4,827,064, 4,827,073; 5,012,020; predominantly monoSubstituted naphthalenes with attach and 5,146,021,which are fully incorporated by reference. ment of the alkyl group taking place predominantly at the 1 0094. In one embodiment, the oil of lubricating viscosity or 2-position of the alkyl chain. The presence of the long is Selected to provide lubricating compositions with a kine chain alkyl groups conferS good Viscometric properties on matic viscosity of at least about 3.5 cSt, or at least about 4.0 the alkylnaphthalenes, especially when used in combination cSt at 100° C. The viscosity grades for the final product may with the PAO components which are themselves materials of typically be in the range of ISO 20 to ISO 1,000 or even high Viscosity index, low pour point, and good fluidity. higher for gear lubricant applications, for example, up to about ISO 46,000. While the finished lubricant viscosity will 0090 An alternative blending stock, used alone or in be determined by the Viscosity Grades, one embodiment combination with other base Stocks, is an alkylbenzene or according to the present invention has finished fluids with mixture of alkylbenzenes. The alkyl substituents in these viscosities in the range of from about 9 to about 41 cSt at fluids are typically alkyl groups of about 8 to 25 carbon 100° C. The viscosity grade of the final product is adjusted atoms, usually from 10 to 18 carbon atoms and up to three by Suitable blending of base Stock components of differing Such Substituents may be present as described in ACS Viscosities, together with the use of thickeners, if desired. Petroleum Chemistry Preprint 1053-1058, “Poly n-Alkyl Differing amounts of the various base Stock components benzene Compounds: A Class of Thermally Stable and Wide (primary hydrocarbon base Stocks, Secondary base Stock and Liquid Range Fluids”, Eapen et al., Phila. 1984. Tri-alkyl any additional base stock components) of different viscosi benzenes may also be produced by the cyclodimerization of ties, may be Suitably blended together to obtain a base Stock 1-alkynes of 8 to 12 carbon atoms as described in U.S. Pat. blend with a viscosity appropriate for blending with the No. 5,055,626. Other alkylbenzenes are described in EP 168 other components of the finished lubricant. In one embodi 534 and U.S. Pat. No. 4,658,072. Alkylbenzenes have been ment, the lubricating compositions have an SAE gear vis used as lubricant base Stocks, especially for low temperature cosity grade of at least about SAE 70W. The lubricating applications (Arctic vehicle Service and refrigeration oils) composition may include a winter grade as low as 70W and and in papermaking oils. The linear alkylbenzenes typically a Summer grade as high as 140W. The lubricating compo have good low pour points and low temperature Viscosities Sition may include, but is not limited to, So-called multi and VI values greater than 100 together with good solvency grade rating such as SAE 70W-80, 70W-85, 70W-90, 75W for additives. Other alkylated aromatics which may be used 140, 80W-90, 80W-140, 85W-90, or 85W-140. Multi-grade when desirable are described, for example, in “Synthetic lubricants may include a Viscosity improver that is formu Lubricants and High Performance Functional Fluids', lated with the oil of lubricating viscosity to provide the Dressler, H., chap 5, R. L. Shubkin (Ed.)), Marcel Dekker, above lubricant grades. Useful Viscosity improvers include, N.Y. 1993. but are not limited to, polyolefins, Such as ethylene-propy 0.091 Also included in this class and with very desirable lene copolymers, or polybutylene rubbers, including hydro lubricating characteristics are the alkylated aromatic com genated rubbers, Such as Styrene-butadiene or Styrene-iso pounds including the alkylated diphenyl compounds Such as prene rubbers; O polyacrylates, including the alkylated diphenyl oxides, alkylated diphenyl Sulfides polymethacrylates. and alkylated diphenyl methanes and the alkylated phenox 0095. In one embodiment, the oil of lubricating viscosity athins as well as the alkylthiophenes, alkylbenzofurans and includes at least one ester of a Such as Styrene-butadiene or the ethers of Sulfur-containing aromatics. Lubricant blend Styrene-isoprene rubbers, or polyacrylates, including dicar components of this type are described, for example, in U.S. boxylic acid. Typically the esters containing from about 4 to Pat. Nos. 5,552,071; 5,171,195; 5,395,538; 5,344,578; about 30 carbon atoms, preferably from about 6 to about 24, 5,371,248; and EP 815187. or from about 7 to about 18 carbon atoms in each ester 0092. In one embodiment, the oil of lubricating viscosity group. Here, as well as elsewhere, in the Specification and is a polyalphaolefin (PAO). Typically, the polyalphaolefins claims, the range and ratio limits may be combined. N are derived from monomers having from about 3 to about 30 on-limiting examples of dicarboxylic acids include glutaric, carbon atoms, or from about 4 to about 20, or from about 6 adipic, pimelic, Suberic, azelaic and Sebacic. Examples of to about 16 carbon atoms. Examples of useful PAOs include ester groups include, but are not limited to, hexyl, octyl, those derived from decene. These PAOS may have a viscos decyl, and dodecyl ester groups. The ester groups include ity from about 3 to about 150, or from about 4 to about 100, linear, as well as branched ester groupS. Such as iso arrange or from about 4 to about 8 cSt at 100° C. Examples of PAOs ments of the ester group. A particularly useful ester of a include 4 cSt polyolefins, 6 cSt polyolefins, 40 cSt polyole dicarboxylic acid is diisodecyl azelate. Other useful esters fins and 100 cSt polyalphaolefins. Other suitable PAOs include polyolesters. include ExxonMobil High Viscosity Index (HVI) PAOs, 0096. The polyols include, but are not limited to, trim sold under the name SuperSynTM PAO, having a viscosity ethylol propane and pentaerythritol. ranging from about 150 to about 3,000 cSt at 100° C. Additionally, HVI SuperSynTM PAO having viscosities rang 0097. The esters which may be used for this purpose ing from about 300 to about 800 KVoo are also suitable include the esters of dibasic acids with monoalkanols and PAOs. Other suitable base stock components include, but are the polyol esters of monocarboxylic acids. Esters of the US 2003/0171222 A1 Sep. 11, 2003

former type include, for example, the esters of dicarboxylic wt.% to about 2 wt.%. The weight % of the defoamant is acids Such as phthalic acid, Succinic acid, alkyl Succinic preferably from about 0.5 wt.% to about 3 wt.%, more acid, alkenyl Succinic acid, maleic acid, azelaic acid, Suberic preferably from about 0.5 wt.% to about 2 wt.%. The acid, Sebacic acid, fumaric acid, adipic acid, linoleic acid diluent oil is added to make the total percentages of all dimer, malonic acid, alkyl malonic acid, alkenyl malonic components of the additive package to total to 100%. acid, etc., with a variety of alcohols Such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc. 0102) Additional Additives Specific examples of these types of esters include dibutyl 0103) In one embodiment, the lubricating compositions adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dio and functional fluids contain one or more auxiliary extreme ctyl Sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl preSSure and/or anti-wear agents, corrosion inhibitors and/or phthalate, didecyl phthalate, dieicosyl Sebacate, etc. oxidation inhibitors. Auxiliary extreme pressure agents and 0.098 Particularly useful synthetic esters are those which corrosion and oxidation inhibiting agents, which may be are obtained by reacting one or more polyhydric alcohols, included in the lubricants and functional fluids of the inven preferably the hindered polyols Such as the neopentyl poly tion, are exemplified by halogenated, e.g., chlorinated, ali ols, e.g., neopentyl glycol, trimethylol ethane, 2-methyl-2- phatic hydrocarbons Such as chlorinated olefins or waxes, propyl-1,3-propanediol, trimethylol propane, pentaerythritol metal thiocarbamates, Such as Zinc dioctyldithiocarbamate, and dipentaerythritol with alkanoic acids containing at least and barium heptylphenyl dithiocarbamate; dithiocarbamate 4 carbon atoms exemplified by Cs to Co acids Such as esters from the reaction product of dithiocarbamic acid and Saturated Straight chain fatty acids including caprylic acid, acrylic, methacrylic, maleic, fumaric or itaconic esters (e.g., the reaction product of dibutylamine, carbon disulfide, and capric acid, lauric acid, myristic acid, palmitic acid, Stearic methyl acrylate); dithiocarbamate-containing amides, pre acid, arachic acid, and behenic acid, or the corresponding pared from dithiocarbamic acid and an acrylamide (e.g., the branched chain fatty acids or unsaturated fatty acids Such as reaction product of dibutylamine, carbon disulfide, and oleic acid. acrylamide); alkylene-coupled dithiocarbamates (e.g., meth 0099. The most suitable synthetic ester oils are the esters ylene or phenylene bis(dibutyldithiocarbamate); and sulfur of trimethylol propane, trimethylol butane, trimethylol coupled dithiocarbamates e.g., bis(S-alkyldithiocarbamoyl) ethane, pentaerythritol and/or dipentaerythritol with one or disulfides). Many of the above-mentioned auxiliary extreme more monocarboxylic acids containing from about 5 to preSSure agents and corrosion-oxidation inhibitors also serve about 10 carbon atoms are widely available commercially, as anti-Wear agents. for example, the EsterexTM NP341 and NP344 esters (avail 0104. The lubricating compositions and functional fluids able from ExxonMobil Chemical Company). may contain one or more pour point depressants, color 0100. A lubricating oil composition was prepared by Stabilizers, metal deactivators and/or anti-foam agents. Pour mixing the materials listed in Table 1 with a base stock or point depressants are a particularly useful type of additive blend of base stocks. The materials may be mixed by any often included in the lubricating oils described herein. The conventional method. use of Such pour point depressants in oil-based compositions to improve low temperature properties of oil-based compo TABLE 2 Sitions is well known in the art. See, for example, page 8 of “Lubricant Additives” by C. V. Smalheer and R. Kennedy Weight % of Typical Components of Additive Package Smith (Lezius-Hiles Co. publishers, Cleveland, Ohio, 1967). Polysulfide Mixture A (Table 1) about 20 wt.% to about 60 wt.% Examples of useful pour point depressants are poly Alkyl phosphate, Alkyl phosphite about 3 wt.% to about 15 wt.% methacrylates, polyacrylates, polyacrylamides, condensa Dispersant about 5 wt.% to about 30 wt.% tion products of haloparaffin waxes and aromatic com Borated Dispersant about 0 wt.% to about 10 wt.% Amine about 1 wt.% to about 20 wt.% pounds, Vinyl carboxylate polymers, and terpolymers of Metal Passivator about 0.1 wt.% to about 5 wt.% dialkylfumarates, Vinyl esters of fatty acids and alkyl vinyl Diluent oil about 0 wt.% to about 25 wt.% ethers. Defoamant about 0 wt.% to about 5 wt.% 0105 Pour point depressants useful for the purposes of this invention, techniques for their preparation and their uses 0101 The weight 9% of the polysulfide mixture in the are described in U.S. Pat. Nos. 2,387,501; 2,015,748; 2,655, additive package is preferably from about 30 wt.% to about 479; 1815,022; 2,191,498; 2,666,746; 2,721877; 2,721, 50 wt.%, more preferably from about 43 wt.% to about 49 878; and 3,250,715 which are herein incorporated by refer wt. 76, based on the total additive package as are the ence for their relevant disclosures. following components. The weight % of the alkyl phosphate 0106 Anti-foam agents are used to reduce or prevent the is preferably from about 3 wt.% to about 10 wt.%, more formation of Stable foam. Typical anti-foam agents include preferably from about 6 wt.% to about 9 wt.%. The weight Silicones or organic polymers. Additional anti-foam compo % of the dispersant is preferably from about 5 wt.% to about sitions are described in “Foam Control Agents”, by Henry T. 20 wt.%, more preferably from about 5 wt.% to about 12 wt.%. The weight % of the borated dispersant is preferably Kemer (Noyes Data Corporation, 1976), pages 125-162. from about 0.5 wt.% to about 8 wt.%, more preferably from 0107 These additional additives, when used, are present about 2 wt.% to about 5 wt.%. The weight 9% of the amine in the inventive lubricating and functional fluid composi is preferably from about 8 wt.% to about 20 wt.%, more tions at Sufficient concentrations to provide the compositions preferably from about 12 wt.% to about 16 wt.%. The with enhanced properties depending upon their intended use. weight % of the metal passivator is preferably from about For example, the detergents are added at Sufficient concen 0.5 wt.% to about 5 wt.%, more preferably from about 0.5 trations to provide the inventive compositions with US 2003/0171222 A1 Sep. 11, 2003

enhanced detergency characteristics, while the anti-foam agents are added at Sufficient concentrations to provide the TABLE 3-continued inventive compositions with enhanced anti-foaming charac teristics. Generally, each of these additional additives is Additive Package Without Base stock present in the lubricants and functional fluids at concentra Type of Additive Weight % Chemical Name tions from about 0.01%, or from about 0.05%, or from about 0.5%. These additional additives are generally present in an Rust Protection 12 alkyl amine Dispersant 8 alkenyl succinimide amount up to about 20% by weight, or up to about 10% by Dispersant 4 borated alkenyl succinimide weight, and or up to about 3% by weight. Corrosion Inhibitor 1. bis(dialkylthio)dimercapto thiadiazole 0108. In one embodiment, the lubricating compositions Defoamant 1. polybutyl acrylate contain less than 2%, or less than 1.5%, or less than 1% by Diluent Oil balance to 100%. Mineral Oil weight of a dispersant. In another embodiment, the lubri cating compositions are free of lead based additives, metal (Zinc) dithiophosphates, and alkali or alkaline earth metal 0115) borates. TABLE 4 0109. In another embodiment, the combination of the dihydrocarbyl polysulfide and the phosphorus or boron Finished 80W-90 Gear Lubricant Preparation compound, or mixtures thereof may be used in concentrates. Component Weight % Additive 0110. The concentrate may contain the above combina tion alone or with other components used in preparing fully Package Based on Polysulfide Formulation A 9.5% formulated lubricants. The concentrate also contains at least Mineral Base Stocks 89.5% one Substantially inert organic diluent, which includes kero Pour Point Depressant 1% Sene, mineral distillates, or one or more of the oils of lubricating Viscosity discussed above. In one embodiment, 0116. The lubricant composition was evaluated in a stan the concentrates contain from 0.01% up to about 49.9%, or dard gear lubricant test known as the FZG Shock Test from about 0.1% up to about 45% by weight of the organic S-A10/16, 6R/90 run by the FORSCHUNGSSTELLE FUR diluent. ZAHNRADER UND GETRIEBEBAU (FZG)), which 0111. The following Examples relates to lubricants of the examines the scuffing load capacity of API GLA and GL5 present invention using the polysulfide compositions A and lubricants, passing results were obtained. The results are B from Table 1. shown in Table 5. Although one embodiment of a finished 0112 A complete gear lubricant additive package 80W-90 gear oil lubricant is shown in Table 4, the formu includes at least one organic polysulfide comprising leSS lation may vary. For example, in another embodiment than about 88 wt.% trisulfide, at least one phosphorus or according to the present invention, the package based on boron compound or mixtures thereof, a primary amine, a polysulfide formulation A may range from about 9 to about metal passivator, a diluent oil and a defoamant. Preferably, 10 wt.%, the mineral base stock may range from about 80 the polysulfide in the additive package comprises at least to about 90 wt.%, the pour point depressant may range from about 7.5 wt.% dihydrocarbyl tetrasulfide or higher sulfides. about 1 to about 2 wt.%, and an optional defoamant may Preferably, the polysulfide in the additive package comprises range from about 0 to about 1 wt.%. less than about 5.5 wt.% dihydrocarbyl disulfide. More preferably, the polysulfide in the additive package comprises TABLE 5 less than about 88 wt.% dihydrocarbyl trisulfide and at least about 7.5 wt.% dihydrocarbyl tetrasulfide or higher polysul FZG Test Results fides. Load Stage Result Description EXAMPLE 1. 1O Pass No damage 11 Pass No damage 0113) Gear Oil Formulated with Low Trisulfide Compo 12 Pass Very light scuffing nent 0114. The additive package shown in Table 3 may be blended by any conventional method with at least one base EXAMPLE 2 stock to achieve a gear lubricant of 80W-90 viscosity grade. 0117 Comparative Example Using Gear Lubricant For The blend components are shown in Table 4. mulated with High Trisulfide Component TABLE 3 0118. A gear lubricant was prepared using an additive package analogous to that shown in Table 3. The only Additive Package Without Base stock difference in the two packages was the Substitution of an equivalent weight of pure alkyl-trisulfide (TBPS 344 from Type of Additive Weight % Chemical Name ChevronPhillips) extreme pressure agent for the polysulfide Extreme Pressure 46 di-alkyl polysulfide Agent component of the present invention. The resultant additive Extreme Pressure 9 alkyl phosphates/phosphites package was then blended by conventional means with Agent/Anti-wear appropriate base Stocks to achieve a gear lubricant of Agent 80W-90 viscosity grade. The blend components are shown in Table 6. US 2003/0171222 A1 Sep. 11, 2003 13

ammonium compound to render them hydrophobic. Typical TABLE 6 ammonium compounds are tetraalkyl ammonium chlorides. These clays are generally crystalline complex Silicates. Finished 80W-90 Gear Lubricant Preparation These clays include bentonite, attapulgite, hectorite, illite, Component Weight % Additive Saponite, Sepiolite, biotite, Vermiculite, Zeolite clays and the like. Package Based on Trisulfide 9.4% Mineral Base Stocks 88.8% 0.124 While the invention has been explained in relation Pour Point Depressant 1.6% to its preferred embodiments, it is to be understood that Defoamant O.2% various modifications thereof will become apparent to those skilled in the art upon reading the Specification. Therefore, it is to be understood that the invention disclosed herein is 0119 When evaluated in a standard gear lubricant test intended to cover Such modifications as fall within the Scope known as the FZG Shock Test S-A10/16, 6R/90 run by the FORSCHUNGSSTELLE FUR ZAHNRADER UND of the appended claims. GETRIEBEBAU (FZG)), which examines the scuffing load What is claimed: capacity of API GL4 and GL5 lubricants, failing results were 1. A lubricating composition comprising: obtained. The results are shown in Table 7. a major amount of an oil of a lubricating Viscosity, TABLE 7 at least one organic polysulfide comprising less than 88% FZG Test Results - dihydrocarbyl trisulfide; and a phosphorus compound or a boron compound, or mix Load Stage Result Description tures thereof. 1O Fail Light Scuffing 2. The lubricating composition according to claim 1, wherein the organic polysulfide further comprises at least about 7.5 wt.% dihydrocarbyl tetrasulfide or higher polysul 0120) A comparison of the results from the tests using fides. low trisulfide polysulfide versus the high trisulfide polysul 3. The lubricating composition according to claim 1, fide demonstrates Superior FZG test results for the low where the organic polysulfide further comprises less than 5.5 trisulfide polysulfide containing additive package and fully wt.% dihydrocarbyl disulfide. formulated lubricating oil containing the low trisulfide 4. The lubricating composition of claim 1, wherein the polysulfide containing additive package. organic polysulfide has hydrocarbyl groups that are each independently an alkyl group having from 1 to about 30 0121 Greases carbon atoms. 0122) Where the lubricant is to be used in the form of a 5. The lubricating composition of claim 1, wherein the grease, the lubricating oil generally is employed in an organic polysulfide comprises less than 88% dihydrocarbyl amount Sufficient to balance the total grease composition trisulfide and at least 7.5 wt.% dihydrocarbyl tetrasulfide or and, generally, the grease compositions will contain various higher polysulfides. quantities of thickenerS and other additive components to 6. The lubricating composition according to claim 1, provide desirable properties. The dihydrocarbyl polysulfide wherein the oil is a mineral oil or a Synthetic oil. is generally present in an amount from about 0.1% up to 7. A lubricating composition comprising: about 10%, or from about 0.5% up to about 5% by weight. The phosphorus or boron compound is generally present in a major amount of an oil of lubricating Viscosity; an amount from about 0.1% up to about 8%, or from about at least one dihydrocarbyl polysulfide comprising: 0.5% up to about 6% by weight. (i) less than 88% dihydrocarbyl trisulfide; 0123. A wide variety of thickeners can be used in the preparation of the greases of this invention. The thickener is (ii) less than 5.5 wt.% dihydrocarbyl disulfide; and employed in an amount from about 0.5 to about 30 percent, (iii) at least 7.5 wt.% dihydrocarbyl tetrasulfide or and preferably from 3 to about 15 percent by weight of the higher polysulfides, and total grease composition. Including among the thickeners are alkali and alkaline earth metal Soaps of fatty acids and a phosphorus compound or a boron compound, or mix fatty materials having from about 12 to about 30 carbon tures thereof. atoms. The metals are typified by Sodium, lithium, calcium 8. A concentrate comprising from 0.1% to 49.9% by and barium. Examples of fatty materials include Stearic acid, weight of a Substantially inert, organic diluent based on the hydroxyStearic acid, oleic acid, palmitic acid, myristic acid, total weight of the concentrate; cottonseed oil acids, and hydrogenated fish oil acids. Other at least one dihydrocarbyl polysulfide comprising leSS thickeners include Salt and Salt-Soap complexes, Such as than about 88% dihydrocarbyl trisulfide; calcium stearate-acetate (U.S. Pat. No. 2,197,263), barium stearate-acetate (U.S. Pat. No. 2,564,561), calcium stearate less than 5.5 wt.% dihydrocarbyl disulfide; caprylate-acetate complexes (U.S. Pat. No. 2,999,066), cal at least 7.5 wt.% dihydrocarbyl tetrasulfide or higher cium Salts and Soaps of low-, intermediate- and high polysulfides, and molecular weight acids and of nut oil acids, aluminum Stearate, and aluminum complex thickeners. Useful thick at least one phosphorus or boron compound or mixtures eners include hydrophilic clays that are treated with an thereof. US 2003/0171222 A1 Sep. 11, 2003

9. A grease composition comprising at least one oil of a 12. The method according to claim 10, wherein the lubricating Viscosity, contact Surface comprises at least a portion of an automatic at least one thickening agent, transmission, manual transmission, transaxle, gear, open gear, enclosed gear, tractor, metal-working tool, hydraulic at least one dihydrocarbyl polysulfide comprising leSS cylinder, wirerope, walking cam, rock drill, chain and con than 88% dihydrocarbyl trisulfide; veyor belt, worm gear, bearing, rail or flange. less than 5.5 wt.% dihydrocarbyl disulfide; 13. An additive package for a lubricant composition, the at least 7.5 wt.% dihydrocarbyl tetrasulfide or higher additive package comprising: polysulfides, and at least one organic polysulfide comprising less than 88% at least one phosphorus or boron compound, or mixtures dihydrocarbyl trisulfide; thereof. at least one phosphorus or boron compound, or mixtures 10. A method of lubricating at least one contact Surfaces to reduce friction, the method comprising the Steps of: thereof; introducing to at least one contact Surface a lubricating a primary amine; composition comprising: a metal passivator; a major amount of an oil of lubricating Viscosity; a diluent oil; and at least one organic polysulfide comprising less than 88% dihydrocarbyl trisulfide; a defoamant. 14. The additive package according to claim 13, wherein less than 5.5 wt.% dihydrocarbyl disulfide; the organic polysulfide further comprises at least 7.5 wt.% at least 7.5 wt.% dihydrocarbyl tetrasulfide or higher dihydrocarbyl tetrasulfide or higher polysulfides. polysulfides, and 15. The additive package according to claim 13, where the at least one phosphorus or boron compound, or mix organic polysulfide further comprises less than 5.5 wt.% tures thereof. dihydrocarbyl disulfide. 11. The method according to claim 10, wherein the 16. The additive package according to claim 13, wherein lubricating composition further comprises an automatic the organic polysulfide comprises less than 88% dihydro transmission fluid, manual transmission fluid, transaxle carbyl trisulfide and at least 7.5 wt.% dihydrocarbyl tetra lubricant, gear lubricant, open gear lubricant, enclosed gear Sulfide or higher polysulfides. lubricant, tractor lubricant, metal-working lubricant, hydraulic fluid or grease.