|WO/2011/126636||LUBRICATING OIL COMPOSITIONS CONTAINING EPOXIDE ANTIWEAR AGENTS|
|WO/2015/139209||CORROSION RESISTANT LUBRICANT|
C. V. SMALHEER; R. KENNEDY SMITH: 'Lubricant Additives', 1967 pages 1 - 11
See also references of EP 1392804A2
|1.||A lubricant composition comprising: a major portion of a base oil; an effective amount of a sulfur and phosphorus antiwear additive; and an effective amount of an antioxidant or mixture of antioxidants.|
|2.||The composition of claim 1 wherein the antioxidant additives is an effective amount of an aromatic amine antioxidant or mixture of aromatic amine antioxidants.|
|3.||The composition of claim 1 wherein the antiwear additive is an alkylated ester derivative of a sulfurized phosphite or phosphate.|
|4.||The composition of claim 1 wherein the antiwear additives has the formula I : where Rl, R2, R3 and R4 may be the same or different hydrocarbyl groups of from about 1 to about 18 carbon atoms.|
|5.||The composition of claim 4 wherein the antioxidant or mixture thereof are selected from amines having formula II and III: where RI and R2 are independently hydrogen or Ci to C 18 alkyl.|
|6.||The composition of claim 5 wherein, in the antiwear additive of formula I, RI and R2 are the same and are branched alkyl groups of from about 6 to about 10 carbon atoms, R3 is an alkyl group of from about 1 to about 4 carbon atoms, and R4 is an alkyl group of from about 6 to about 10 carbon atoms.|
|7.||The composition of claim 6 wherein the antioxidant is a mixture of amines having formulae II and III, and in which Ri and R2 are hydrogen in formula II, and Ri and R2 are C4 to C8 alkyl in formula III.|
|8.||The composition of claim 6 wherein the base oil is a mineral oil of API Groups II or III, or a mixture of oils of API Groups I and II or III and/or IV.|
|9.||A method for improving the wear performance of an industrial lubricant which substantially retains the oxidation stability of the lubricant, by providing the lubricant with an effective amount of a sulfur and phosphorous antiwear additive; and an effective amount of an aromatic amine antioxidant or mixture of aromatic amine antioxidants.|
|10.||The method of claim 9 wherein the antiwear addition has the formula I : where RI, R2, R3 and R4 may be the same or different hydrocarbyl groups of from about 1 to about 18 carbon atoms.|
|11.||The method of claim 10 wherein the antioxidant or mixture thereof are selected from amines having formula II and III: where Ru and R2 are independently hydrogen or Cl to C18 alkyl.|
|12.||The method of claim 11 wherein in the antiwear addition of formula I Ri and R2 are the same and are branched alkyl groups of from about 6 to about 10 carbon atoms, R3 is an alkyl group of from about 1 to about 4 carbon atoms, and R4 is an alkyl group of from about 6 to about 10 carbon atoms, and wherein the antioxidant is a mixture of amines having formulae II and III, and in which Rl and R2 are hydrogen.|
BACKGROUND OF INVENTION  The art of lubricating oil formulation has become increasingly complex with ever more stringent industry standards dictated by developing industrial equipment technology. One requirement for industrial lubricants is to provide wear control. At the same time the lubricant formulation should provide resistance to oxidation and sludge formation in order to achieve operation life of adequate length. Experience has shown that the incorporation of one type of additive in a lubricant composition can have a negative impact on the function of another type of additive in that composition. Indeed, the presence of antiwear additives in lubricants often reduces the oxidation stability and increases sludge formation compared to a similar oil where the antiwear additive is absent. Thus, there is a need for industrial lubricants that provide improved antiwear performance without sacrificing oxidation resistance and deposit control.
SUMMARY OF INVENTION  According to the invention, a lubricant composition especially suitable for use in industrial equipment requiring antiwear properties and oxidation resistance is provided, comprising a major portion of a base oil, an effective
amount of both a sulfur and phosphorous containing antiwear additive, and an antioxidant or a mixture of antioxidants.
DETAILED DESCRIPTION OF INVENTION  The lubricant composition described herein comprises a major amount of a base oil of lubricating viscosity, a sulfur and phosphorus containing anti- wear additive, and a mixture of one or more antioxidant additives. Compressor, hydraulic, turbine or other industrial lubricating compositions can be formulated using this combination of components.
[00051 The lubricating oil base stock is any natural or synthetic lubricating base oil stock fraction typically having a kinematic viscosity at 40°C of about 14 to 220 cSt, more preferably about 20 to 150 cSt, most preferably about 32 to 68 cSt.
 The lubricating oil basestock can be derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof. Suitable lubricating oil basestocks include basestocks obtained by isomerization of synthetic wax and slack wax, as well as hydrocrackate basestocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude.
Suitable basestocks include those in API categories I, II and III, where saturates level and Viscosity Index are: Group I-less than 90% and 80-120, respectively; Group II-greater than 90% and 80-120, respectively; and Group III-greater than 90% and greater than 120, respectively.
 Natural lubricating oils include petroleum oils, mineral oils, and oils derived from coal or shale.
 Synthetic oils include hydrocarbon oils and halo-substituted hydro- carbon oils such as polymerized and inter-polymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs and homologs thereof, and the like. Synthetic lubricat- ing oils also include alkylen oxide polymers, interpolymers, copolymers and derivatives thereof wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc. Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids with variety of alcohols. Esters useful as synthetic oils also include those made from Cs to C12 monocarboxylic acids and polyols and polyol ethers.
 The lubricating oil may be derived from unrefined, refined, rerefined oils, or mixtures thereof. Unrefined oils are obtained directly from a natural source or synthetic source (e. g., coal, shale, or tar sand bitumen) without further purification or treatment. Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment. Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties. Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art. Rerefined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
 Lubricating oil base stocks derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks. Such wax isomerate oil is produced by the hydro- isomerization of natural or synthetic waxes or mixtures thereof over a hydro- isomerization catalyst.
 Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typically the wax produced by the Fischer-Tropsch process.
 The resulting isomerate product is typically subjected to solvent dewaxing and fractionation to recover various fractions of specific viscosity range. Wax isomerate is also characterized by possessing very high viscosity indices, generally having a VI of at least 130, preferably at least 135 and higher and following dewaxing, a pour point of about-20°C and lower.
 The production of wax isomerate oil meeting the requirements of the present invention is disclosed and claimed in U. S. Patent Nos. 5,049,299 and 5,158,671 which are incorporated herein by reference.
 The compositions of the invention include an effective amount of a sulfur and phosphorus containing antiwear compound or additive. A preferred additive is an alkylated ester derivative of a sulfurized phosphite or phosphate.
A more preferred additive compound has the formula I :
where R1, R2, R3 and R4 may be the same or different hydrocarbyl groups of from about 1 to about 18 carbon atoms. Preferably RI and R2 are the same and are branched alkyl groups of from about 6 to about 10 carbon atoms, R3 is an alkyl group of from about 1 to about 4 carbon atoms, and R4 is an alkyl group of from about 6 to about 10 carbon atoms. Typically the antiwear additive will comprise from about 0.05 to about 2.5 wt%, based on the total weight of the composition.
 The lubricant composition of the invention also includes an effective amount of an antioxidant or mixtures of antioxidants, such as aryl amines, phenylene diamines, hindered phenolics and thiocarbamates, or derivatives thereof, which may or may not be sulfurized. A preferred embodiment of the invention incorporates an effective amount of aromatic amine anti-oxidant or mixture of aromatic amine antioxidants. Aromatic amine antioxidants useful in the present invention are selected from the aromatic amines and mixtures thereof represented by formulae II and III.
where RI and R2 are independently hydrogen or Ci to Cl8 alkyl. Typically the amine or mixture of amines will constitute from about 0.05 to about 2.5 wt%, based on the weight of the composition. An especially preferred composition includes amines of formula II and III in the weight ratio of about 0.2 to about 4.0. Indeed, a most preferred composition includes amine II in which Rl and R2 are hydrogen, and amine III in which RI and R2 are C4 to Cg alkyl.
[00161 Fully formulated industrial oils typically may also contain additional additives, known to those skilled in the industry, used on an as-received basis.
The lubricating oils of the present invention may contain, in addition to the aforesaid antioxidant and antiwear additives, other additives typically used in lubricating oils, such as pour depressants, rust inhibitors, thickeners, metal passivators, demulsifiers and antifoamants.
 Pour depressant additives for lubricating oils are typically polymers or co-polymers, with polymethacrylates and poly-vinlyacetate alkylfumarate as commonly used examples. Rust inhibitor additives can be of a variety of chemical types, with ester and amide derivatives of alkylated succinic acid being among the most commonly used in lubricating oils. Thickeners may be any oligomer, polymer or co-polymer which can be employed to increase the viscosity of the oil in a controlled manner. Such materials include hydrocarbons, such as polybutenes, olefm copolymers and high viscosity poly-alpha olefins, and polyalkyacrylates, such as polymethacrylates and olefin-acrylate co- polymers.
 Metal passivators can be of a wide variety of chemical types which interact with metals typically present in lube systems to prevent such metals from exercising a deleterious effect on the functionality of the lubricant.
Commonly used metal passivators include thiazines, triazoles, benzotriazoles and dimercaptothiadiazoles, including alkyl and other derivatives, and mixtures thereof. Demulsifiers are employed to enhance the rapid separation of oil and water in lube systems, and most often consist of poly-oxyalkylated derivatives of multi-hydroxyl substrates such as sugars. Poly-acrylates and poly- alkylsiloxanes, and their derivatives, are widely employed in lubricants as antifoamants.
 Materials such as these are well known in the art. Lubricating oil additives are described generally in"Lubricants and Related Products"by Dieter Klamann, Verlag Chemie, Deerfield, Florida, 1984, and also in"Lubricant Additives"by C. V. Smalheer and R. Kennedy Smith, 1967, pages 1-11.
 The following non-limiting Examples and Comparative Examples illustrate the invention.
EXAMPLES  Lubricant compositions were prepared based on the ingredients shown in Table 1 below.
TABLE 1 Component Component Example Comparative Comparative Example Example Example Function Tyep 1 Example 1 Example 2 2 3 4 ISo Viscosity Grade 32 32 32 46 68 68 Components (wt%) Basestock SN 90 API Group II 34.755 34.601 37.448 -- -- -- Basestock SN 250 API Group II 63.96 64.563 62.00 95.965 47.00 69.365 Basestock SN 600 API Group I -- -- -- 2.750 51.715 25.85 Thickener Poly-isobutylene -- -- -- -- -- 3.5 Phenyl naphthyl 0.5 -- Anti-oxidant 0.4 0.4 0.4 0.4 amine Anti-oxidant Octyl-phenyl -- -- 0.3 -- -- -- naphthyl amine Antioxidant N-butyl-N-octyl 0.22 -- -- 0.22 0.22 0.22 Diphenylamine Alkylated ester Antiwear derivative of 0.33 -- -- 0.33 0.33 0.33 tri-thiophosphite Balance of Additive Additive blend 0.335 0.336 0.252 0.335 0.335 0.335 System (1) A compound of Formula I with R1, R2 and R4 having 8 carbon atoms and R2 having 2 carbon atoms.
 These compositions were then subjected to industry standard tests for air compressors (DIN 51506, DIN 51532/2 (Pneurop oxidation) and DIN 51356), and some were also subjected to proposed heavy duty vane and screw compressor test performance standards within ISO L-DAJ (ISO/DIS 6521).
Other laboratory and performance tests were also conducted. These tests and their results are shown in Table 2. Industry standards are also included in Table 2.
TABLE 2 Test Test Example Comparative Comparative Example Example Example Industry Description Reference Units 1 Example 1 Example 2 2 3 4 Standard Kin. viscosity @6 cSt 31.63 32 32.12 44.85 65.26 66.71 40°C Viscosity Index ASTM D 17 117 117 116 106 125 Copper Corrosion ASTM D130 -- -- 1a 1b -- -- 1b max. Anti-rust no -- no no no no no ASTM D 665B Performance corrosion corrosion corrosion corrosion corrosion Oxidation Life ASTM D 2272 minutes 1708 1778 1745 Oxidation Life ASTM D 943 hours >10,000 7102 >8500 -- -- >3000 Oxidation Sludge ASTM D 4310 mg -- -- 19 136 -- -- <200 penurop Oxidation DIN 51352 part 2 -% weight loss wt% 11.3 5.075.97 5.17 #20 -% CCR wt% 1.10 0.95 1.43 0.23 #2.5 ROCOT Oxidation ISO/DIS 6521 -Evaporation loss 3.95 2.10 1.89 2.21 -Acid value 0.18 0.32 0.34 0.31 -Heptane insolubles 0.13 0.8 0.21 0.15 -kin. visc. increase 6.5 4.8 7.0 6.3 Distillation 20% DIN 51356 residue - kin. viscosity cSt 77.14 96.01 143.8 300.5 <5 x new @ 40°C -% CCR wt% 0.04 0.02 0.05 0.11 #0.3 4-Ball wear ASTM D 2266 mm 0.411 -- 0.78 0.421
 As can be seen the compositions of the invention meet or significantly exceed the industry standards. In non-industry oil stability tests, such as ASTM D2272 and ASTM D943, and metal corrosion tests, such as ASTM D665B and ASTM D130, results were excellent, and comparable to the non-antiwear oil comparative examples. However, the examples of the invention show superior performance to the comparative examples in the ASTM D2266 four-ball wear test.
TABLE 3 Compressor run time 0 22 565 1030 1610 2365 2846 3278 3649 (hours) Kin. viscosity @ 40°C 45.61 45.42 46.30 47.00 47.37 47.55 47.96 48.17 48.57 ASTM Color 0.5 2.0 5.5 7.0 7.0 7.0 7.5 < 8.0 <8.0 Total Acid Number 0.35 0.39 0.23 0.19 0.20 0.20 0.13 0.21 0.21 0.29 Element in oil (ppm) Iron 0 0 0 0 0 0 0 0 0 Copper 0 13 2 5 4 2 2 4 6
 Industrial oils formulated according to the preferred embodiments of this invention have been tested in compressor equipment, and the condition of the oils sampled during service are shown in accompanying tables.
 In one test an ISO VG 46 grade oil was run in an Atlas-Copco 200 HP GA rotary screw compressor in routine industrial service over a period of 5 months. Results from testing of oils sampled from the compressor lube system at regular intervals are shown in Table 3, with Total Acid Number and kinematic viscosity being principal indicators of oil degradation. It can be seen that both of these properties changed very little during this period of operation, indicating that the oil was not significantly oxidatively degraded. The oil previously used in this compressor has historically been changed out every 1500 hours operation due to the level of oxidative degradation. At the same time, levels of iron and copper in the in the oil samples were very low, demonstrating that essentially no wear or corrosion of metal parts occurred.
 In another test an ISO VG 32 grade oil was run in a Gardner-Denver 50 HP rotary screw compressor in routine industrial air compression service.
Results from testing of oils sampled from the compressor lube system at regular intervals are shown in Table 4. Again, very little change was seen in the kinematic viscosity and Total Acid Number properties of the oil, indicating insignificant oxidative degradation. No iron or copper were detected, demonstrating no wear or corrosion of metal parts.
TABLE 4 Compressor run time (hours) 0 5 #500 1098 1812 2628 3614 Kinematic viscosity @40°C 31.69 31.87 33.22 33.68 34.54 34.77 34.97 ASTM Color 0.5 <1.0 5.5 6.5 <7.5 7.5 .5 Total Acid Number 0.27 0.31 0.11 0.10 0.11 0.13 0.11 Elements in oil (ppm) Iron 0 0 0 0 0 0 0 Copper 0 0 0 0 0 0 0