Industrial gear lubricant

Abstract

The present technology includes a combination of a sulfurized olefin extreme pressure agent and a zinc dialkyldithiophosphate to provide an industrial gear lubricating composition having a reduced sulfur content, providing good extreme pressure properties to industrial gears. The present invention includes a lubricating composition comprising an oil of lubricating viscosity, an extreme pressure agent comprising a sulfurized olefin, the extreme pressure agent being present in an amount to deliver up to 3000 ppm sulfur to the lubricating composition, and a zinc dialkyldithiophosphate agent being present in an amount to deliver from 100 ppm to 600 ppm phosphorus to the lubricating composition, wherein the lubricating composition has a total sulfur content of less than about 6000 ppm sulfur.

Description

Background Art

[0001] Industrial gearboxes are subject to extreme operating conditions that can cause damage, such as wear and tear of internal gearbox components. This damage can shorten the life of the industrial gearbox and can lead to expensive and long-term maintenance, repair costs, unplanned downtime of equipment containing the industrial gearbox, and similar problems.

[0002] There is a continuing need for improved industrial gearbox lubricants for protecting industrial gearboxes to help extend the useful life of the industrial gearboxes and equipment containing the industrial gearboxes.

[0003] One approach to protecting industrial gearboxes is to lubricate them with lubricants containing sulfur compounds. The sulfur in these compounds reacts with the metal surfaces of the gears, creating a thin, extreme-pressure protective layer. However, the use of large amounts of sulfur can lead to environmental concerns.

[0004] Due to the importance of sulfur in providing extreme pressure protection, there is no viable solution to reduce or eliminate such sulfur compounds while maintaining extreme pressure performance. Therefore, there is a need to develop industrial gear lubricant compositions with reduced sulfur content while maintaining adequate protection for industrial gears. Summary of the Invention

[0005] The present invention provides a lubricating composition for industrial gears, which comprises oil of lubricating viscosity, a sulfurized olefin extreme pressure agent, and zinc dialkyldithiophosphate ("ZDDP").

[0006] In one embodiment, this sulphurized olefin extreme pressure agent is present in this lubricating composition with the amount of sending 3000ppm sulphur at the most to this lubricating composition.In one embodiment, this sulphurized olefin extreme pressure agent comprises the sulphurized olefin containing 2 to 40 carbon atoms or is made up of this sulphurized olefin.In another embodiment, this sulphurized olefin extreme pressure agent comprises sulphurized isobutylene or is made up of sulphurized isobutylene.In another embodiment, this sulphurized olefin can comprise the sulphurized olefin derived from natural source, such as sulphurized vegetable oil or sulphurized lard.

[0007] In one embodiment, the ZDDP is present in the lubricating composition in an amount sufficient to deliver 100 ppm to 600 ppm of phosphorus to the lubricating composition. In one embodiment, the ZDDP is derived from a C3 to C12 secondary alcohol. In one embodiment, the ZDDP contains at least 30 mole % secondary alkyl groups, or at least 50 mole % secondary alkyl groups, or at least 90 mole % secondary alkyl groups. In another embodiment, the ZDDP contains alkyl groups that comprise or consist essentially of secondary alkyl groups containing 3 to 12 carbon atoms. In another embodiment, the ZDDP contains at least 25 mole %, or at least 40 mole % or even at least 60 mole % alkyl groups having 3 or 4 carbon atoms.

[0008] It has been observed that the present invention provides suitable gearbox protection as measured by Timken (ASTM D2782) by employing the components described herein.

[0009] Also provided is a method of operating an industrial gear, the method comprising applying an industrial gear oil as described herein to the industrial gear and operating the industrial gear. DETAILED DESCRIPTION

[0010] Various preferred features and embodiments will now be described by way of non-limiting illustration.

[0011] The present technology relates in part to lubricating compositions comprising (a) an oil of lubricating viscosity, (b) a sulfurized olefin, and (c) a zinc dialkyldithiophosphate.

[0012] Oil of lubricating viscosity

[0013] In the present invention, the oil of lubricating viscosity can be present in a major amount for lubricating compositions or in a concentrate-forming amount for concentrates and / or additive compositions. The oil of lubricating viscosity can be biodegradable or non-biodegradable. The additives described herein can be blended with the oil of lubricating viscosity to prepare industrial gear lubricants that unexpectedly provide comparable or improved industrial gear lubricant performance at lower sulfur concentrations.

[0014] Suitable oils include natural and synthetic lubricating oils and mixtures thereof. In fully formulated lubricants, the oil of lubricating viscosity is typically present in a major amount (i.e., an amount greater than 50% by weight). Typically, the oil of lubricating viscosity is present in an amount of 75% to 98% by weight of the entire composition, and often greater than 80% by weight.

[0015] Oil with lubricating viscosity can comprise natural and synthetic oils, oil derived from hydrocracking, hydrogenation and hydrofining, unrefined oil, refined oil and re-refined oil or their mixture.Unrefined oil is the oil directly obtained from natural or synthetic source usually without (or through a small amount of) further purification treatment.Refined oil is similar to unrefined oil, except that refined oil has been further processed in one or more purification steps to improve one or more characteristics.Purification techniques are known in the art and include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and similar processes.Re-refined oil is also referred to as regenerated oil or reprocessed oil, and is obtained by processes similar to those processes for obtaining refined oil.Re-refined oil is often processed by the technology that is intended to remove spent additives and oil decomposition products.

[0016] Natural oils useful as the oil of lubricating viscosity include animal and vegetable oils (e.g., castor oil, lard oil), mineral lubricating oils (such as liquid petroleum oil), and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, cycloparaffinic, or mixed paraffinic-cycloparaffinic type, and oils derived from coal or shale, or mixtures thereof.

[0017] Industrial gear lubricants may contain synthetic oils of lubricating viscosity. Synthetic oils may be saturated or unsaturated. Synthetic oils of lubricating viscosity include hydrocarbon oils such as polymerized olefins and interpolymerized olefins (e.g., polybutene, polypropylene, propylene isobutylene copolymer); poly(1-hexene), poly(1-octene), poly(1-decene), and mixtures thereof; alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-(2-ethylhexyl)-benzene); polyphenylenes (e.g., biphenyl, terphenyl, alkylated polyphenylenes); esters and complex esters of acids from plant sources (e.g., diesters, monoesters, saturated polyol esters, trimethylolpropane carboxylates, neopolyol carboxylates, neopentyl glycol esters, pentaerythritol esters, etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides, and their derivatives, analogs, and homologs, or mixtures thereof. In some embodiments, the oil of lubricating viscosity used herein is a synthetic oil comprising polymerized polyisobutylene, and in some embodiments, the oil of lubricating viscosity used herein is a synthetic oil comprising polymerized polyisobutylene and a polyalphaolefin.

[0018] Other synthetic oils of lubricating viscosity include polyol esters, dicarboxylic acid esters, liquid esters of phosphoric acid (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl decylphosphoric acid), or polytetrahydrofuran. Conventional synthetic oils of lubricating viscosity also include those produced by the Fischer-Tropsch reaction and are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, oils of lubricating viscosity can be produced by a Fischer-Tropsch gas-to-liquid synthesis process, as well as other gas-to-liquid oils.

[0019] Oils of lubricating viscosity may also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five groups of base oils are as follows: Group I (sulfur content > 0.03 wt% and / or < 90 wt% saturates, viscosity index 80-120); Group II (sulfur content > 0.03 wt% and / or < 90 wt% saturates, viscosity index 80-120); < 0.03 wt%, and > 90% saturates by weight, viscosity index 80-120); Class III (sulfur content < 0.03 wt%, and > 90 wt% saturates, viscosity index > 120); Group IV (all polyalphaolefins (PAOs), such as PAO-2, PAO-4, PAO-5, PAO-6, PAO-7, or PAO-8); and Group V (covering "all others"). The oil of lubricating viscosity may also be an API Group II+ base oil, which term refers to a Group II base oil having a viscosity index greater than or equal to 110 and less than 120, as described in the following documents: SAE publication "Design Practice: Passenger Car Automatic Transmissions", Fourth Edition, AE-29, 2012, pages 12-9 and US 8,216,448, column 1, line 57.

[0020] The oil with lubricating viscosity comprises API I class, II class, II+ class, III class, IV class, V class oil or their mixture. In one embodiment, the oil with lubricating viscosity is API I class, II class, III class, IV class oil or their mixture. Preferably, the oil with lubricating viscosity can comprise at least 50 % by weight or at least 75 % by weight or at least 90 % by weight or at least 99 % by weight of the I class base oil. In some embodiments, the lubricating oil adopted in the present composition is only the I class base oil basically, wherein can have the base oil of a small amount of other types, but its amount can not significantly affect the characteristic or the performance of the whole composition.

[0021] In some embodiments of the present invention, the oil of lubricating viscosity comprises a Group II oil. In some embodiments, the lubricating oil employed in the compositions of the present invention is essentially solely a Group II base oil, with minor amounts of other types of base oils present in amounts that do not significantly affect the properties or performance of the overall composition.

[0022] In some embodiments, the oil of lubricating viscosity may comprise at least 50 wt%, or at least 75 wt%, or at least 90 wt%, or at least 99 wt% Group I base oil, with the balance being Group II base oil.

[0023] Viscosity grades typically suitable for industrial gear lubricating compositions are typically ISO 68 to 1000. The viscosity of each grade is the kinematic viscosity at 40°C + / - 10%, as measured by ASTM D445 or ISO 3104. Thus, an ISO 46 with a kinematic viscosity of 46 cSt at 40°C may have a kinematic viscosity of 41.4 cSt to 50.6 cSt at 40°C. The ISO viscosity classification system is defined in ISO 3448. Exemplary viscosity grades are listed in the following table:

[0024] Thus, in some embodiments, the lubricating composition of the present invention may have an ISO viscosity grade (VG) of 68 to 1000, or 100 to 480, or 150 to 320, or 100, 150, 220, 320, 460, 480, or 1000.

[0025] The various oils of lubricating viscosity described can be used alone or in combination. The oils of lubricating viscosity can be used in the described industrial gear lubricants in a range of from about 80% to about 98% by weight, or 80%, 85%, 90%, 95%, 97%, or even 97.5% or 98% oil, or up to 90%, 95%, 97%, 97.5%, or even 98% oil by weight.

[0026] Sulfurized olefins

[0027] Sulfurized olefins are well-known commercial materials that can be prepared by reacting a single reactant or a mixture of appropriate reactants with a sulfur source. The sulfurization reaction is typically carried out at an elevated temperature (e.g., 50°C to 350°C or 100°C to 200°C) with effective stirring and often in an inert atmosphere such as nitrogen, optionally in the presence of an inert solvent. Sulfurizing agents can include elemental sulfur (preferred), hydrogen sulfide, sulfur halides, sodium sulfide, and mixtures of hydrogen sulfide and sulfur or sulfur dioxide. Typically, the amount of sulfur or sulfurizing agent employed is calculated based on the total olefinic unsaturation in the mixture. Typically, 0.5 to 3 moles of sulfur are employed per mole of olefinic bonds. One type of sulfurized olefin can be prepared according to the detailed teachings of U.S. Patent No. 4,957,651.

[0028] In the case of sulfiding olefins, the reactant may be an olefinic compound. Olefinic compounds that may be sulfided are diverse in nature and are broadly defined as those containing at least one olefinic double bond, which is defined as a non-aromatic double bond; that is, a double bond connecting two aliphatic carbon atoms. In its broadest sense, an olefin may be represented by the formula R 1 R 2 C=CR 3R 4 Definition, where R 1 、R 2 、R 3 and R 4 Each of the R groups in the above formula which is not hydrogen can be represented by, for example, -C(R 5 )3. -COOR 5 、-COOM、-X、-YR 5 or -Ar groups satisfying the following conditions: 5 are independently hydrogen, alkyl, alkenyl, aryl, substituted alkyl, substituted alkenyl or substituted aryl, provided that any two R 5 The group can be an alkylene or substituted alkylene group, thereby forming a ring of up to 12 carbon atoms; M is one equivalent of a metal cation (preferably Class I or Class II, such as sodium, potassium, barium, calcium); X is a halogen (such as chloro, bromo or iodo); Y is oxygen or divalent sulfur; Ar is an aryl or substituted aryl group of up to 12 carbon atoms. R 1 、R 2 、R 3 and R 4 Any two of may also be taken together to form an alkylene or substituted alkylene group; ie, the olefinic compound may be cycloaliphatic.

[0029] Olefinic compounds are typically olefinic compounds in which each of the above R groups that is not hydrogen is independently an alkyl, alkenyl or aryl group. Monoolefinic and diolefinic compounds (particularly the former) are preferred, and especially terminal monoolefins; that is, in which R 3 and R 4 is hydrogen and R 1 and R 2 The olefinic compounds are alkyl or aryl groups, especially those having alkyl groups of 1 to 30, or 1 to 16, or 1 to 8, or 1 to 4 carbon atoms (i.e., the olefin is aliphatic). Olefinic compounds having 3 to 30 or 3 to 16 (usually less than 9) carbon atoms can be used.

[0030] Isobutylene, diisobutylene, butene, propylene and dimers, trimers and tetramers thereof and mixtures thereof can be used as olefinic compounds for sulfidation, terpene compounds (i.e., compounds having the empirical formula C 10 H 16 various isomeric terpene hydrocarbons) and their various synthetic and naturally occurring oxygenated derivatives.

[0031] Other sulphurized olefins include those sulphurized olefins derived from natural sources such as sulphurized vegetable oils and sulphurized lard (that is, generally sulphurized oils of animal origin). The example of the natural oil that can derive this type of sulphurized olefin can include but is not limited to coconut oil, corn oil, cottonseed oil, castor oil, sunflower oil, olive oil, palm oil, peanut oil, rapeseed oil, safflower oil, sesame oil, soybean oil, tallow, lard, fatty acid and their mixture. The preferred organic part of sulphurized vegetable oil is those derived from sunflower oil, olive oil and rapeseed oil.

[0032] In one embodiment, the sulfur component of the additive package of the present technology may comprise a biodegradable sulfurized olefin derived from a natural source such as sulfurized vegetable oil or sulfurized lard.

[0033] The total level of sulfur in the sulfided olefin can be measured according to ASTM D129Q. No matter whether it is capable of biodegradation or not, the sulfided olefin can have a "high," "nominal" or "minimum" level of total sulfur. "High" sulfur level means that the sulfided olefin contains approximately 30 % by weight or more sulfur. "Nominal" sulfur level means that the sulfided olefin contains approximately 10 % by weight to approximately 30 % by weight of sulfur, and "minimum" sulfur level means that the sulfided olefin contains less than approximately 10 % by weight of sulfur, or approximately 0.01 % by weight to approximately 10 % by weight of sulfur.

[0034] In the present invention, it has been discovered that the addition of small amounts of ZDDP, which is a known antiwear agent, can reduce the amount of sulphurised olefins in lubricating compositions while maintaining extreme pressure properties.

[0035] In the present invention, sulphurized olefins can be included in the complete formulation lubricant with a level of approximately 0.1 % by weight to approximately 0.9 % by weight, or approximately 0.2 % by weight to approximately 0.8 % by weight, or even approximately 0.4 % by weight to approximately 0.6 % by weight. In some embodiments, sulphurized olefins can be used as measured at 150 ℃ according to ASTM D1662, with the amount being enough to deliver 75ppm to 450ppm, or 100ppm to 400ppm, or even 150ppm to 300ppm of the total active sulphur level in the complete formulation lubricant." activity" means the amount of sulphur that can be used for reaction at a certain temperature. The molar percentage of active sulphur in the sulphur-containing compound is determined empirically according to ASTM D1662. In some embodiments, sulphurized olefins are present in the lubricating composition with the amount being enough to deliver the total sulphur of 40 % by weight to 60 % by weight.

[0036] Zinc dialkyl dithiophosphate ( ZDDP )

[0037] The lubricating composition of the present invention also includes zinc dialkyldithiophosphate (ZDDP). ZDDP is known in the art and is commonly used as an antiwear agent.

[0038] Zinc dialkyldithiophosphates (ZDDPs), or simply zinc dithiophosphates (ZDPs), are well known and readily available to those skilled in the art of lubricant formulation. Additionally, zinc dialkyldithiophosphates can be described as primary or secondary, depending on the structure of the alcohol used in their preparation. In some embodiments, the present compositions may include primary zinc dialkyldithiophosphates. In some embodiments, the compositions include secondary zinc dialkyldithiophosphates. In some embodiments, the compositions include a mixture of primary and secondary zinc dialkyldithiophosphates. In some embodiments, the ZDDP is a mixture of primary and secondary zinc dialkyldithiophosphates, wherein the ratio (on a weight basis) of primary to secondary zinc dialkyldithiophosphates is at least 1:1, or even at least 1:1.2, or even at least 1:1.5, or 1:2, or 1:10.

[0039] Examples of suitable dialkyldithiometallate phosphates include metal salts of the formula:

[0040] where R 1 and R 2 is independently a hydrocarbyl group containing 3 to 24 carbon atoms, or 3 to 12 carbon atoms, or 3 to 8 carbon atoms; M is a metal having a valence of n, and typically includes zinc, copper, iron, cobalt, antimony, manganese, and combinations thereof. In one embodiment, R 1 and R 2 is a secondary aliphatic hydrocarbyl group containing from 3 to 8 carbon atoms, and M is zinc.

[0041] In one embodiment, the ZDDP comprises at least 30 mole % secondary alkyl groups, or at least 50 mole % secondary alkyl groups, or at least 90 mole % secondary alkyl groups. In one embodiment, the ZDDP consists essentially of secondary alkyl groups containing 3 to 12 carbon atoms.

[0042] In one embodiment, the ZDDP comprises at least 25 mole % of alkyl groups having 3 or 4 carbon atoms, or at least 40 mole % of alkyl groups having 3 or 4 carbon atoms, or at least 50 mole % of alkyl groups having 3 or 4 carbon atoms. In one embodiment, the ZDDP comprises at least 40 mole % of secondary alkyl groups having 3 or 4 carbon atoms. Examples of suitable alkyl groups include isopropyl, sec-butyl, n-butyl, pentyl, n-pentyl, methylpentyl, n-hexyl, n-octyl, n-nonyl, isooctyl, 2-ethylhexyl, n-decyl, isodecyl, n-dodecyl, isododecyl, and any combination thereof.

[0043] ZDDP can be prepared with zinc in an amount exceeding the stoichiometric amount shown in the above structure. ZDDP prepared in this manner may be referred to as "overbased." Overbased ZDDP compositions may be in the form of an inert organic liquid solution characterized by a zinc content exceeding the amount present according to the stoichiometric ratio of the metal (e.g., zinc) and the particular acidic organic compound (e.g., a low molecular weight dialkyl dithiophosphoric acid) reacting with the metal. Overbased (or high-base-content) ZDDP will contain zinc in excess of the stoichiometric amount. For example, a low molecular weight dialkyl dithiophosphoric acid and / or its zinc salt may be reacted with a zinc base, and the resulting overbased low molecular weight ZDDP may contain zinc in excess of the amount necessary to neutralize the acid, e.g., approximately 1.15 times the zinc present in the neutralizing salt. Stoichiometric ZDDP has a zinc to phosphorus weight ratio of 1.05:1. Overbased ZDDP may be characterized by a zinc to phosphorus weight ratio of at least 1.25:1.0, at least 1.28:1.0, at least 1.30:1.0, or at least 1.32:1.0. Thus, in some embodiments, the ZDDP can be an overbased (or high-based) ZDDP, wherein the ratio of zinc to phosphorus can be between 1.1:1.0 and 1.3:1.0. In other embodiments, the ratio of zinc to phosphorus can be at least 1.25:1.0. In one embodiment, the ZDDP of the present invention comprises less than 50 wt%, or less than 25 wt%, or less than 5 wt% of overbased ZDDP. In one embodiment, the lubricating composition of the present invention is free of, or substantially free of, overbased (or high-based) ZDDP.

[0044] The ZDDP may be present in the lubricating composition of the present invention in an amount of at least 0.1% to 0.5%, or 0.2% to 0.4%, or 0.2% or 0.4% by weight of the lubricating composition. In another embodiment, the ZDDP is present in an amount such that the total phosphorus contributed to the lubricant composition is at least 100 ppm to 600 ppm, or 150 ppm to 500 ppm, or 175 ppm to 450 ppm. It should be understood that the zinc dialkyl dithiophosphate also contributes some sulfur to the lubricating composition. Thus, it can also be considered that the zinc dialkyl dithiophosphate is present in an amount that contributes about 200 ppm to about 1000 ppm, or about 300 ppm to about 900 ppm of sulfur to the lubricating composition.

[0045] Without being bound by any particular theory, the effect of adding ZDDP in the present invention is unexpected, at least because ZDDP is generally understood to act as an antiwear agent, not an extreme pressure agent. Furthermore, while ZDDP does provide some sulfur to lubricating compositions, ZDDP is generally understood not to provide active sulfur to lubricating compositions. Therefore, it is expected that the additional elemental sulfur added by including ZDDP in the lubricating composition would not have an effect on extreme pressure performance similar to an additive that delivers active sulfur to the lubricating composition.

[0046] Other additives

[0047] The industrial gear lubricant may contain other additive components suitable for industrial gear lubricants.Any combination of conventional additive components suitable for industrial gear applications may be used.

[0048] In addition to the aforementioned sulfurized olefins and ZDDP, other additive components that may be present in the industrial gear additive package include, but are not limited to, foam suppressants, demulsifiers, pour point depressants, antioxidants, dispersants, metal passivators (such as copper passivators), phosphorus-containing antiwear agents, viscosity modifiers, detergents, or some mixture thereof. Each of the other additive components may be present in an amount ranging from 50 ppm, 75 ppm, 100 ppm, or even 150 ppm to 5 wt%, 4 wt%, 3 wt%, 2 wt%, or even 1.5 wt%, or from 75 ppm to 0.5 wt%, from 100 ppm to 0.4 wt%, or from 150 ppm to 0.3 wt%, where the wt% values ​​are with respect to the individual components of the fully formulated industrial gear lubricant. However, it should be noted that some additives (including viscosity modifier polymers, which may alternatively be considered part of the oil of lubricating viscosity) may be present in higher amounts, including up to 30 wt%, 40 wt%, or even 50 wt%, when considered separately from the oil of lubricating viscosity. The additives may be used individually or as mixtures thereof.

[0049] Phosphorus-containing antiwear agents and / or extreme pressure agents commonly used in industrial gear lubricants are mostly partially or fully esterified phosphoric acid. All of these are suitable for the industrial gear lubricant additive package herein. Such antiwear agents include, but are not limited to, acid phosphonates, hydrogen phosphinates, phosphinates, phosphonates, phosphonates, phosphinates and phosphonic acid amides. The antiwear agents may further include mono-hydrocarbon phosphinates, di-hydrocarbon phosphinates and tri-hydrocarbon phosphinates; mono-hydrocarbon phosphinates, di-hydrocarbon phosphinates and tri-hydrocarbon phosphinates; mono-hydrocarbon monothiophosphinates, di-hydrocarbon monothiophosphinates, tri-hydrocarbon monothiophosphinates, di-hydrocarbon dithiophosphinates, tri-hydrocarbon dithiophosphinates, mono-hydrocarbon trithiophosphinates, di-hydrocarbon dithiophosphinates, tri-hydrocarbon trithiophosphinates, tetra-hydrocarbon monothiophosphinates, di-hydrocarbon tetrathiophosphinates and tri-hydrocarbon tetrathiophosphinates; mono-hydrocarbon monothiophosphinates, di-hydrocarbon monothiophosphinates, tri-hydrocarbon monothiophosphinates, di-hydrocarbon di ... trithiophosphinates, tri-hydrocarbon trithiophosphinates, tetra-hydrocarbon monothiophosphinates, di-hydrocarbon tetrathiophosphinates Hydrocarbon esters, dihydrocarbon monothiophosphinates, trihydrocarbon monothiophosphinates, monohydrocarbon dithiophosphinates, dihydrocarbon dithiophosphinates, trihydrocarbon dithiophosphinates, monohydrocarbon trithiophosphinates, dihydrocarbon trithiophosphinates, trihydrocarbon trithiophosphinates, monohydrocarbon tetrathiophosphinates, dihydrocarbon tetrathiophosphinates, trihydrocarbon tetrathiophosphinates; various hydrocarbyl phosphonates and thiophosphonates; dialkyl dithiophosphates and their derivatives, as well as various hydrocarbyl phosphonates and thiophosphinates, etc.

[0050] Examples of phosphonites include mono-hydrocarbyl-substituted phosphonites, di-hydrocarbyl-substituted phosphonites, or tri-hydrocarbyl-substituted phosphonites, as well as those having at least one hydrocarbyl group containing 4 or more carbon atoms, as shown in the following formula: or

[0051] where R 8 、R 6 and R 7 At least one of may be a hydrocarbyl group containing at least 4 carbon atoms, and the remainder may be hydrogen atoms or hydrocarbyl groups. 8 、R 6 and R 7 The hydrocarbon group may be an alkyl group, a cycloalkyl group, an aryl group, an acyclic group or a mixture thereof. 8 、R 6 and R 7 In the formula, the compound may be a trialkyl-substituted phosphinate, i.e., R 8 、R 6 and R 7 are all hydrocarbon groups. Alkyl groups can be straight chain or branched, usually straight chain, and saturated or unsaturated, usually saturated. 8 、R 6 and R 7 Examples of alkyl groups include octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl, or mixtures thereof.

[0052] These include all amine salts that can be formed with the above-mentioned phosphorus-containing antiwear agents. The amines can be primary, secondary, tertiary, acyclic or cyclic amines, monoamines or polyamines. They can also be heterocyclic. Amines with aliphatic properties are generally preferred. Some specific examples of amines used to produce amine salts in phosphorus-containing antiwear agents include octylamine, decylamine, C10, C12, C14, and C16 tertiary alkyl primary amines (or combinations thereof), laurylamine, hexadecylamine, heptadecanylamine, octadecylamine, decenylamine, dodecenylamine, palmitamide, oleylamine, linoleylamine, diisopentylamine, dioctylamine, di-(2-ethylhexyl)amine, dilaurylamine, cyclohexylamine, 1,2-propyleneamine, 1,3-propylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, triethanolamine, trioctylamine, pyridine, morpholine, 2-methylpiperazine, 1,2-bis(N-piperazinyl-ethane), 1,2-diamine, tetraiminooctadecene, triaminooctadecene, N-hexylaniline, etc. These amines may also be triazoles or triazole derivatives.

[0053] In one embodiment, the amine salt of the phosphorus-containing antiwear agent is of the formula:

[0054] where R 9 and R 10 is independently an aliphatic group containing from about 4 up to about 24 carbon atoms, R 22 and R 23 are independently hydrogen atoms or aliphatic groups containing from about 1 to about 18 aliphatic carbon atoms, the sum of m and n is 3 and X is an oxygen atom or a sulfur atom. In preferred embodiments, R 9 Containing from about 8 to a maximum of 18 carbon atoms, R 10 for:

[0055] where R 11 is an aliphatic group containing from about 6 to about 12 carbon atoms, R 22 and R 23 is a hydrogen atom, m is 2, n is 1 and X is an oxygen atom.

[0056] Specific examples of phosphorus-containing antiwear agents may include tricresyl phosphate, tributyl phosphite, triphenyl phosphite, 2-ethylhexyl phosphate, diisobutyl hydrogen phosphite, diisopropyl dithiophosphate, diphenyl phosphate, fatty phosphites, and the like. Some embodiments of phosphorus-containing antiwear agents may include dialkyl phosphates and diaryl phosphates and their amine salts. Aryl phosphonates are also contemplated, such as the commercially available Irgalube® from Ciba. ™ 349 and alkyl acid phosphonates, including di- and / or mono-2-ethylhexylphosphonic acid.

[0057] Phosphorus-containing antiwear agents (other than ZDDP used in the present invention) may be employed in amounts sufficient to deliver 50 ppm to 400 ppm, or 100 ppm to 300 ppm, or even 150 ppm to 250 ppm phosphorus to the lubricant composition.

[0058] Defoamers (also known as foam suppressors) are known in the art and include, but are not limited to, organosilicones and non-silicone foam suppressors. Examples of organosilicones include dimethyl silicone and polysiloxanes. Examples of non-silicone foam suppressors include, but are not limited to, polyethers, polyacrylates, and mixtures thereof, as well as copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate. In some embodiments, the defoamer is a polyacrylate. The defoamer may be present in the composition at 0.001% to 0.012% by weight, or 0.004% by weight, or even 0.001% to 0.003% by weight.

[0059] Demulsifier is known in the art and includes but is not limited to the derivatives of propylene oxide, ethylene oxide, polyoxyalkylene alcohol, alkylamine, amino alcohol, diamine or polyamines reacted continuously with ethylene oxide or substituted ethylene oxide or their mixture. The example of demulsifier includes polyethylene glycol, polyethylene oxide, polypropylene oxide, (ethylene oxide-propylene oxide) polymer and their mixture. In some embodiments, the demulsifier is a polyether. Demulsifier can be present in the composition at 0.002 weight % to 0.2 weight %.

[0060] Pour point depressants are known in the art and include, but are not limited to, esters of maleic anhydride-styrene copolymers, polymethacrylates; polyacrylates; polyacrylamides; condensation products of halogenated paraffins and aromatic compounds; vinyl carboxylate polymers; and terpolymers of dialkyl fumarates, vinyl esters of fatty acids, ethylene-vinyl acetate copolymers, alkylphenol formaldehyde condensation resins, alkyl vinyl ethers, and mixtures thereof.

[0061] The composition of the present technology may also include a rust inhibitor. Suitable rust inhibitors include hydrocarbylamine salts of dialkyldithiophosphoric acids, hydrocarbylamine salts of hydrocarbylaromatic sulfonic acids, and fatty carboxylic acids or esters thereof, esters of nitrogen-containing carboxylic acids, ammonium sulfonates, imidazolines, monothiophosphates or esters, or any combination thereof, or mixtures thereof.

[0062] Examples of hydrocarbylamine salts of dialkyl dithiophosphoric acid of the present technology include, but are not limited to, diheptyl, dioctyl or dinonyl dithiophosphoric acid with ethylenediamine, morpholine, Primene ™ 81R or a mixture thereof.

[0063] Suitable hydrocarbylamine salts of hydrocarbyl arene sulfonic acids for use in the rust inhibitor packages of the present technology are represented by the formula:

[0064] Wherein Cy is a benzene ring or a naphthalene ring. 12 is a hydrocarbyl group having from about 4 to about 30 carbon atoms, preferably from about 6 to about 25 carbon atoms, more preferably from about 8 to about 20 carbon atoms. z is independently 1, 2, 3 or 4 and most preferably z is 1 or 2. R 13 、R 14 and R 15 are independently hydrogen, a branched alkyl chain, or a straight alkyl chain, and in some embodiments, R 13 、R 14 and R 15 At least one or even both of are hydrogen, and further, wherein R 13 、R 14 and R 15 At least one of them is a hydrocarbon group containing at least 8 carbon atoms.13 、R 14 and R 15 Examples of alkyl groups include, but are not limited to, butyl, sec-butyl, isobutyl, tert-butyl, amyl, n-hexyl, sec-hexyl, n-octyl, 2-ethyl, hexyl, ethyl-hexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl, or mixtures thereof. Examples of alkylamine salts of alkylaromatic sulfonic acids of the present technology include, but are not limited to, ethylenediamine salts of dinonylnaphthalenesulfonic acid. Examples of suitable fatty carboxylic acids or esters thereof include glycerol monooleate and oleic acid.

[0065] Examples of suitable esters of nitrogen-containing carboxylic acids include oleoylsarcosine. The rust inhibitor may be present in an amount ranging from 0.02% to 0.2%, 0.03% to 0.15%, 0.04% to 0.12%, or 0.05% to 0.1% by weight of the industrial gear lubricant. The rust inhibitors of the present technology may be used alone or as mixtures thereof.

[0066] The composition of the present technology may also include a metal deactivator. The metal deactivator is used to neutralize the catalytic effect of metals in industrial gear lubricants to promote oxidation. Suitable metal deactivators include, but are not limited to, triazoles, tolyltriazoles, thiadiazoles, or combinations thereof, and their derivatives. Examples include benzotriazole, benzimidazole, 2-alkyldithiobenzimidazole, 2-alkyldithiobenzothiazole, 2-(N,N'-dialkyldithiocarbamoyl)benzothiazole, 2,5-bis(alkyldithio)-1,3,4-thiadiazole, 2,5-bis(N,N'-dialkyldithiocarbamoyl)-1,3,4-thiadiazole, derivatives of 2-alkyldithio-5-mercaptothiadiazole, or mixtures thereof. The amount of these additives in the total composition can be 0.01 wt % to 0.25 wt %. In some embodiments, the metal deactivator is a hydrocarbon-substituted benzotriazole compound. The hydrocarbyl-substituted benzotriazole compound includes at least one of the following ring positions: 1-, 2-, 4-, 5-, 6-, or 7-benzotriazole. The hydrocarbyl group contains from about 1 to about 30 carbon atoms, preferably from about 1 to about 15 carbon atoms, more preferably from about 1 to about 7 carbon atoms, and most preferably, the metal deactivator is 5-methylbenzotriazole, used alone or as a mixture thereof. The metal deactivator may be present in an amount ranging from 0.001% to 0.5%, 0.01% to 0.04%, or 0.015% to 0.03% by weight of the industrial gear lubricant. The metal deactivator may also be present in the composition at 0.002% or 0.004% to 0.02% by weight. The metal deactivator may be used alone or as a mixture thereof.

[0067] Antioxidants may also be present, including (i) alkylated diphenylamines, and (ii) substituted hydrocarbyl monosulfides. In some embodiments, the alkylated diphenylamines of the present technology are bis-nonylated diphenylamine and bis-octylated diphenylamine. In some embodiments, the substituted hydrocarbyl monosulfide includes n-dodecyl-2-hydroxyethyl sulfide, 1-(tert-dodecylthio)-2-propanol, or a combination thereof. In some embodiments, the substituted hydrocarbyl monosulfide is 1-(tert-dodecylthio)-2-propanol. The antioxidant package may also include hindered phenols. Examples of suitable hydrocarbyl groups of the hindered phenol include, but are not limited to, 2-ethylhexyl or n-butyl esters, dodecyl, or mixtures thereof. Examples of methylene-bridged hindered phenols include, but are not limited to, 4,4 -Methylene-bis(6-tert-butyl-o-cresol), 4,4 -Methylene-bis(2-tert-amyl-o-cresol), 2,2 -Methylene-bis(4-methyl-6-tert-butylphenol), 4,4 -methylene-bis(2,6-di-tert-butylphenol) or a mixture thereof. The antioxidant may be present in the composition at 0.01 wt % to 6.0 wt % or 0.02 wt % to 1 wt %. The additive may be present in the composition at 1 wt %, 0.5 wt % or less.

[0068] In some embodiments, the industrial gear lubricant additive package of the present technology includes a nitrogen-containing dispersant, such as a hydrocarbyl-substituted nitrogen-containing additive. Suitable hydrocarbyl-substituted nitrogen-containing additives include ashless dispersants and polymeric dispersants. Ashless dispersants are so named because, when employed, they do not contain metals and therefore do not typically contribute sulfated ash when added to a lubricant. However, once they are added to a lubricant that includes metal-containing species, they can of course interact with the surrounding metal. Likewise, some derivatives of ashless dispersants can be derivatized and contain molecules that form ash, such as borated derivatives. Ashless dispersants are characterized by polar groups attached to relatively high molecular weight hydrocarbon chains. Examples of such substances include succinimide dispersants, Mannich dispersants, and their borated derivatives.

[0069] In one embodiment, the lubricating composition of the present invention may contain a detergent. In some embodiments, the detergent may be a metal-containing detergent. In some embodiments, the metal-containing detergent may be a calcium or magnesium detergent. In one embodiment, the metal-containing detergent may also be an overbased detergent having a total base number in the range of 30 to 500 mg KOH / g equivalent. In another embodiment, the metal-containing detergent may be a neutral detergent having a total base number in the range of 0 to 30, or even 0 to 10, or even 30 or less, or even 10 or less mg KOH / g equivalent. The detergent may be selected from sulfur-free phenates, sulfur-containing phenates, sulfonates, salicylates, salicylates, mixtures thereof, or their borated equivalents. The detergent may be borated with a borated agent such as boric acid, such as a borated overbased calcium or magnesium sulfonate detergent, or mixtures thereof. Detergents may be present at 0% to 5%, or 0.001% to 1.5%, or 0.005% to 1%, or 0.01% to 0.5% by weight of the hydraulic composition.In some embodiments, the lubricating compositions of the present invention are substantially free or free of metal-containing detergents.

[0070] In some embodiments, the industrial gear additive package or the resulting industrial gear lubricant composition includes a demulsifier, a corrosion inhibitor, a friction modifier, or a combination of two or more thereof. In some embodiments, the corrosion inhibitor includes tolyltriazole. In other embodiments, the industrial gear additive package or the resulting industrial gear lubricant composition includes one or more polysulfides; one or more phosphamidonium salts; one or more thiophosphates, one or more thiadiazoles, tolyltriazoles, polyethers, and / or alkenylamines; one or more ester copolymers; one or more carboxylic acid esters; one or more succinimide dispersants, or any combination thereof.

[0071] In the industrial gear lubricating composition of the present invention, the oil of lubricating viscosity may be present in an amount ranging from 80%, 85%, 90%, 95%, 97%, or even 97.5% or 98% oil to 90%, 95%, 97%, 97.5%, or even 98% oil by weight; the amount of sulfurized olefin is from about 0.1% to about 0.9%, or from about 0.2% to about 0.8%, or from about 0.4% to about 0.6%, and the amount of zinc dialkyldithiophosphate is from about 0.05% to about 0.8%, or from about 0.1% to about 0.6%, or from about 0.15% to about 0.5%, or even from about 0.2% to about 0.4%. Preferably, the industrial gear lubricating composition contains up to about 6000 ppm of sulfur, of which no more than about 3000 ppm is delivered by the sulfurized olefin.

[0072] The industrial gear lubricant of this technology can meet the performance requirements required of industrial gear lubricants as well as the standards set for environmental friendliness.

[0073] Industrial gear oils (IGOs) must maintain specific performance levels in typical bench tests that are part of well-known industrial gear certifications, such as USS 224, AGMA 9005-D94 (recently replaced by AGMA 9005-E02), DIN 51517-3:2009-06, Fives Cincinnati, etc. For extreme pressure performance, bench tests include, for example, Four-Ball EP (ASTM D2783) and Timken (ASTM D2782). Other tests include four-ball wear (ASTM D4172), FZG abrasion (DIN ISO 14635-1), copper corrosion protection (ASTM D130, ISO 2160), oxidation control (ASTM D2893, DIN EN ISO 4263-4, S-200), rust prevention (ASTM D665, ISO 7120), static seal compatibility (DIN EN ISO1817), demulsibility (ASTM D2711, ASTM D1401, ISO 6614), foam control (ASTM D892, ISO 6247), etc.

[0074] The present invention includes methods for preparing the aforementioned industrial gear lubricants and / or industrial gear additive concentrates. Such methods comprise combining the components. No particular order or manner of addition is believed to significantly affect the results.

[0075] The present invention also includes a method of adding one of the industrial gear lubricants described herein to an industrial gearbox and then operating the industrial gearbox.

[0076] As used herein, the term "condensation product" is intended to encompass esters, amides, imides, and other such materials that can be prepared by the condensation reaction of an acid or a reactive equivalent of an acid (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, regardless of whether the condensation reaction is actually carried out to produce the product directly. Thus, for example, a particular ester can be prepared by an ester exchange reaction rather than directly by a condensation reaction. The resulting product is still considered a condensation product.

[0077] Unless otherwise indicated, the amount of each chemical component described does not include any solvent or diluent oil, which may be customarily present in the commercial material, i.e., on an active chemical basis. However, unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.

[0078] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the rest of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbyl groups which, in the context of the present technology, do not alter the predominantly hydrocarbon nature of the substituent; and heterosubstituents, i.e., substituents that similarly have predominantly hydrocarbon character but contain non-carbon in a ring or chain. A more detailed definition of the term "hydrocarbyl substituent" or "hydrocarbyl group" is found in paragraphs

[0137] to

[0141] of published application US 2010-0197536.

[0079] It is known that some of the above-mentioned substances may interact in the final formulation, resulting in compositions that differ from those initially added. For example, metal ions (e.g., of a detergent) may migrate to other acidic or anionic sites on other molecules. The resulting products, including those formed when the compositions of the present technology are used for their intended uses, may not be easily described. However, all such modifications and reaction products are included within the scope of the present invention; the present technology encompasses compositions prepared by mixing the above-mentioned components.

[0080] Example

[0081] A series of lubricants were prepared as shown in Table 1. The extreme pressure properties of each lubricating composition were tested according to ASTM D2782.

[0082] Table 1 - Lubricant Formulations 1

[0083] 1. Unless otherwise stated, all amounts shown above are in weight percent and are oil-free.

[0084] 2. Sulfurized isobutylene (43 wt% sulfur; 10 wt% active sulfur, according to ASTM D1662)

[0085] 3. Sulfurized isobutylene (45 wt% sulfur; 35-40 wt% active sulfur according to ASTM D1662)

[0086] 4. Zinc dialkyl dithiophosphates having secondary C6 alkyl groups and a zinc to phosphorus ratio of about 1.1:1

[0087] 5. Zinc dialkyl dithiophosphates having a mixture of secondary C3 and C6 alkyl groups (60:40 molar ratio, respectively) and a zinc to phosphorus ratio of about 1.1:1

[0088] 6. Zinc dialkyl dithiophosphates having primary C8 alkyl groups and a zinc to phosphorus ratio of about 1.3:1.

[0089] 7. Cyclic phosphonate of 2-butyl-2-ethylpropane-1,3-diol (70 wt% cyclic material; 26 wt% oligomeric material)

[0090] 8. Octyl phosphate mixture salted with 2-ethylhexylamine

[0091] 9. Reaction products of PIBSA (Mn 1000; TAN 108) and polyethylene polyamine mixture

[0092] 10. Other additives include corrosion inhibitors, metal passivators, emulsifiers, pour point depressants, defoamers and lubricating additives

[0093] 11. Calculated Value

[0094] 12. Load at failure, repeated runs, measured in pounds (lb). According to ASTM D2782, when the load is below 30 lb, increase the load in 3 lb increments until failure. Once the load exceeds the 30 lb threshold, increase the load in 5 lb increments until failure. Record the test results until failure according to ASTM D2782.

[0095] As can be seen in Table 1, the lubricating compositions of the present invention exhibit at least two stages of improvement in Timken load extreme pressure performance even at low treat rates.

[0096] The advantages of the lubricating compositions of the present invention can also be demonstrated by evaluating the lubricating compositions according to various tests, including but not limited to 4-ball wear (ASTM D4172), 4-ball EP (ASTM D2783), oxidation (ASTM D2893 at 121°C), oxidation (ASTM D2893 at 95°C), steel corrosion (ASTM D665B), copper corrosion (ASTM D130, 3h, 100°C), demulsibility (ASTM D2711B), foam (ASTM D892), FZG scuff A / 8.3 / 90 (ASTM D5182), FE-8 (DIN 51819-3).

[0097] Certain aspects of the invention are more fully described in the following clauses.

[0098] Item 1: A lubricating composition comprising: an oil of lubricating viscosity; an extreme pressure agent comprising a sulfurized olefin, the extreme pressure agent present in an amount to deliver up to 3000 ppm sulfur to the lubricating composition; and a zinc dialkyl dithiophosphate (ZDDP), the zinc dialkyl dithiophosphate agent present in an amount to deliver 100 ppm to 600 ppm phosphorus to the lubricating composition, wherein the lubricating composition has a total sulfur content of less than about 6000 ppm sulfur, or even less than 5900 ppm sulfur.

[0099] Clause 2: The lubricating composition of clause 1, wherein the extreme pressure agent comprising a sulfurized olefin is present in an amount to deliver up to 1000 ppm to 3000 ppm of sulfur to the lubricating composition.

[0100] Clause 3: The lubricating composition of clause 1 or 2, wherein the extreme pressure agent comprising a sulfurized olefin is present in an amount to deliver up to 2000 ppm to 2500 ppm of sulfur to the lubricating composition.

[0101] Clause 4: The lubricating composition of any preceding clause, wherein the ZDDP is present in an amount to deliver 150 ppm to 500 ppm phosphorus to the lubricating composition.

[0102] Clause 5: The lubricating composition of any preceding clause, wherein the ZDDP is present in an amount to deliver 175 ppm to 450 ppm phosphorus to the lubricating composition.

[0103] Clause 6: The lubricating composition of any preceding clause, wherein the lubricating composition has a total sulfur content of about 4500 ppm to about 6000 ppm.

[0104] Clause 7: The lubricating composition of any preceding clause, wherein the lubricating composition has a total sulfur content of about 5000 ppm to about 5900 ppm.

[0105] Clause 8: The lubricating composition of any preceding clause, wherein the ZDDP is derived from a primary alcohol.

[0106] Clause 9: The lubricating composition of any preceding clause, wherein the ZDDP is derived from a secondary alcohol.

[0107] Clause 10: The lubricating composition of any preceding clause, wherein the ZDDP is derived from a mixture of primary and secondary alcohols.

[0108] Clause 11: The lubricating composition of any preceding clause, wherein the ZDDP is derived from a C3 to C12 secondary alcohol.

[0109] Clause 12: The lubricating composition of any preceding clause, wherein the ZDDP contains at least 30 mole % secondary alkyl groups.

[0110] Clause 13: The lubricating composition of any preceding clause, wherein the ZDDP contains at least 50 mole % secondary alkyl groups.

[0111] Clause 14: The lubricating composition of any preceding clause, wherein the ZDDP contains at least 90 mole % secondary alkyl groups.

[0112] Clause 15: The lubricating composition of any preceding clause, wherein the ZDDP contains an alkyl group comprising a secondary alkyl group containing 3 to 12 carbon atoms.

[0113] Clause 16: The lubricating composition of any preceding clause, wherein the ZDDP contains an alkyl group consisting essentially of secondary alkyl groups containing 3 to 12 carbon atoms.

[0114] Clause 17. The lubricating composition of any preceding clause, wherein the ZDDP contains at least 25 mol% or at least 40 mol% of alkyl groups having 3 or 4 carbon atoms.

[0115] Clause 18: The lubricating composition of any preceding clause, wherein the ZDDP contains at least 40 mole % of secondary alkyl groups having 3 or 4 carbon atoms.

[0116] Clause 19: The lubricating composition of any preceding clause, wherein the ZDDP comprises or consists of a ZDP having a 60:40 molar ratio of C3 and C6 secondary alkyl groups.

[0117] Clause 20: The lubricating composition of any preceding clause, wherein the ZDDP is an overbased (or overbased content) ZDDP and wherein the ratio of zinc to phosphorus may range from 1.1:1.0 to 1.3:1.0.

[0118] Clause 21: The lubricating composition of any preceding clause, wherein the ZDDP has a zinc to phosphorus ratio of at least 1.25:1.0.

[0119] Clause 22: The lubricating composition of any preceding clause, wherein the ZDDP comprises less than 50 wt%, or less than 25 wt%, or less than 5 wt% of an overbased ZDDP.

[0120] Clause 23: The lubricating composition of any preceding clause, wherein the lubricating composition of the present invention is free or substantially free of overbased (or overbased content) ZDDP.

[0121] Clause 24: The lubricating composition of any preceding clause, wherein the sulfurized olefin contains 2 to 40 carbon atoms or 2 to 8 carbon atoms.

[0122] Clause 25: The lubricating composition of any preceding clause, wherein the sulfurized olefin comprises sulfurized isobutylene.

[0123] Clause 26: The lubricating composition of any preceding clause, wherein the sulphurised olefin consists of sulphurised isobutylene.

[0124] Clause 27: The lubricating composition of any preceding clause, wherein the sulfurized olefin comprises a sulfurized olefin derived from a natural source.

[0125] Clause 28: The lubricating composition of any preceding clause, wherein the sulfurized olefin comprises sulfurized vegetable oil or sulfurized lard.

[0126] Clause 29: The lubricating composition of any preceding clause, wherein the sulfurized olefin comprises a mixture of sulfurized isobutylene and sulfurized vegetable oil and / or sulfurized lard.

[0127] Clause 30: The lubricating composition of any preceding clause, wherein the oil of lubricating viscosity comprises a mineral base oil.

[0128] Clause 31: The lubricating composition of any one of clauses 1 to 29, wherein the oil of lubricating viscosity comprises a synthetic base oil.

[0129] Clause 32: The lubricating composition of any one of clauses 1 to 29, wherein the oil of lubricating viscosity comprises a Group I base oil.

[0130] Clause 33: The lubricating composition of any one of clauses 1 to 29, wherein the oil of lubricating viscosity consists of a Group I base oil.

[0131] Clause 34: The lubricating composition of clause 33, wherein the oil of lubricating viscosity is at least 50 wt.% Group I base oil.

[0132] Clause 35: The lubricating composition of clause 33, wherein the oil of lubricating viscosity is at least 75 wt.% Group I base oil.

[0133] Clause 36: The lubricating composition of clause 33, wherein the oil of lubricating viscosity is at least 90% by weight of a Group I base oil.

[0134] Clause 37: The lubricating composition of clause 33, wherein the oil of lubricating viscosity is at least 99% by weight of a Group I base oil.

[0135] Clause 38: The lubricating composition of any preceding clause, wherein the lubricating composition has an ISO viscosity grade of 68 to 1000.

[0136] Clause 39: The lubricating composition of any preceding clause, wherein the lubricating composition has an ISO viscosity grade of 100 to 480.

[0137] Clause 40: The lubricating composition of any preceding clause, wherein the lubricating composition has an ISO viscosity grade of 150 to 320.

[0138] Clause 41: The lubricating composition of any preceding clause, wherein the lubricating composition contains 0.15 wt% to 0.9 wt% of the sulfurized olefin.

[0139] Clause 42: The lubricating composition of any preceding clause, wherein the lubricating composition contains 0.2 wt% to 0.8 wt% of the sulphurised olefin.

[0140] Clause 43: The lubricating composition of any preceding clause, wherein the lubricating composition contains 0.4 wt% to 0.6 wt% of the sulphurised olefin.

[0141] Clause 44: The lubricating composition of any preceding clause, wherein the lubricating sulfurized olefin is present in an amount sufficient to deliver 40% to 60% by weight of the total sulfur content.

[0142] Clause 45: A lubricating composition according to any preceding clause, wherein the lubricating composition contains from 50 ppm, 75 ppm, 100 ppm or even 150 ppm to 5 wt%, 4 wt%, 3 wt%, 2 wt% or even 1.5 wt%, or from 75 ppm to 0.5 wt%, from 100 ppm to 0.4 wt%, or from 150 ppm to 0.3 wt%, up to 5 wt%, or up to 3 wt%, or up to 2 wt%, or from 0.1% to 5% of an additional additive selected from a foam inhibitor, a demulsifier, a pour point depressant, an antioxidant, a dispersant, a metal deactivator, a detergent, a viscosity modifier or some mixture thereof.

[0143] Clause 46: The lubricating composition of any preceding clause, wherein the lubricating composition further comprises 50 ppm to 400 ppm of a dispersant.

[0144] Clause 47: The lubricating composition of Clause 46, wherein the dispersant comprises or consists of a polyolefinamide enamine.

[0145] Clause 48: The lubricating composition of any preceding clause, wherein the lubricating composition is substantially free of metal-containing detergents.

[0146] Clause 49: The lubricating composition of any preceding clause, wherein the lubricating composition is substantially free of detergents selected from non-sulfur phenates, sulfur-containing phenates, sulfonates, salicylate alkoxides, salicylates, and mixtures thereof, or borated equivalents thereof.

[0147] Clause 50: The lubricating composition of any preceding clause, wherein the lubricating composition further comprises an alkenylamine friction modifier.

[0148] Clause 51: The lubricating composition of any preceding clause, wherein the lubricating composition further comprises a polyether-based demulsifier.

[0149] Clause 52: The lubricating composition of any preceding clause, wherein the lubricating composition further comprises a corrosion inhibitor selected from substituted thiadiazoles, triazole derivatives, or combinations thereof.

[0150] Clause 53: The lubricating composition of any preceding clause, wherein the lubricating composition further comprises an ester copolymer defoamer.

[0151] Clause 54: A method of lubricating an industrial gear, the method comprising: supplying the lubricating composition according to any preceding clause to the industrial gear.

[0152] Clause 55: Use of the lubricating composition according to any one of clauses 1 to 53 for improving the extreme pressure properties of industrial gears.

[0153] Clause 56: Use of the lubricating composition according to any one of clauses 1 to 53 for improving the Timken OK load performance of industrial gears.

[0154] Each document mentioned above is incorporated herein by reference, including any prior application claiming priority thereto, whether or not specifically listed above. The mention of any document is not an admission that the document conforms to the prior art or constitutes the general knowledge of technicians in any jurisdiction. Except where otherwise explicitly stated in the examples or elsewhere, all numerical values ​​for amounts of materials, reaction conditions, molecular weights, carbon atom numbers, etc., specified in this specification should be understood to be modified by the word "about". It should be understood that the upper and lower limits of the amounts, ranges, and ratios described herein can be independently combined. Similarly, the ranges and amounts of each element of the present technology can be used together with the ranges or amounts of any other elements.

[0155] As used herein, "substantially free" means that the amount of the substance in question is below an amount that would affect the relevant properties of the fluid in a measurable manner. "Substantially free" may also mean that the substance in question is not intentionally added to the composition, but does not exclude the presence of such materials as contaminants. "Substantially free" may also mean that the substance in question may be present in an amount below the detection limit of standard test methods now known or later developed by those skilled in the art. In some embodiments, "substantially free" may mean less than 10 ppm by weight or even less than 5 ppm by weight.

[0156] As used herein, the transitional term "comprising," which is synonymous with "comprising," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. However, in each use of "comprising" herein, it is intended that the term also encompass the phrases "consisting essentially of" and "consisting of" as alternative embodiments, wherein "consisting of" excludes any element or step not recited, and "consisting essentially of" permits the inclusion of additional, unrecited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.

[0157] Although certain representative embodiments and details have been shown for the purpose of illustrating the subject technology, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the subject technology. In this regard, the scope of the present technology is limited only by the following claims.

Claims

1. A lubricating composition comprising: oil of lubricating viscosity; an extreme pressure agent comprising a sulfurized olefin, said extreme pressure agent being present in an amount to deliver up to 3000 ppm sulfur to said lubricating composition; and a zinc dialkyl dithiophosphate agent, said zinc dialkyl dithiophosphate agent being present in an amount to deliver 100 ppm to 600 ppm phosphorus to said lubricating composition, wherein the lubricating composition has a total sulfur content of less than about 6000 ppm sulfur.

2. The lubricating composition of claim 1, wherein the zinc dialkyldithiophosphate is derived from a primary alcohol, a secondary alcohol, or a mixture thereof.

3. The lubricating composition of claim 1 or 2, wherein the zinc dialkyldithiophosphate comprises at least 30 mole % secondary alkyl groups, or at least 50 mole % secondary alkyl groups, or at least 90 mole % secondary alkyl groups.

4. The lubricating composition of any preceding claim, wherein the zinc dialkyldithiophosphate contains alkyl groups comprising or consisting essentially of secondary alkyl groups containing from 3 to 12 carbon atoms.

5. A lubricating composition according to any preceding claim, wherein the zinc dialkyldithiophosphate contains at least 25 mol% or at least 40 mol% of alkyl groups having 3 or 4 carbon atoms.

6. A lubricating composition according to any preceding claim, wherein the zinc dialkyldithiophosphate contains C3 and C6 secondary alkyl groups in a 60:40 molar ratio.

7. The lubricating composition of claim 4, wherein the zinc dialkyldithiophosphate contains a secondary C6 alkyl group.

8. A lubricating composition according to any preceding claim, wherein the sulphurised olefin contains from 2 to 40 carbon atoms.

9. A lubricating composition according to any preceding claim, wherein the sulphurised olefin comprises or consists of sulphurised isobutylene.

10. The lubricating composition of any preceding claim, wherein the sulphurised olefin comprises a sulphurised olefin derived from a sulphurised vegetable oil or sulphurised lard.

11. The lubricating composition of any preceding claim, wherein the sulphurised olefin comprises a mixture of sulphurised isobutylene and a sulphurised olefin derived from a natural source.

12. A lubricating composition according to any preceding claim, wherein the oil of lubricating viscosity comprises a mineral base oil.

13. The lubricating composition of any one of claims 1 to 11, wherein the oil of lubricating viscosity comprises a synthetic base oil.

14. The lubricating composition of any one of claims 1 to 11, wherein the oil of lubricating viscosity comprises or consists of a Group I base oil.

15. The lubricating composition of claim 14, wherein the oil of lubricating viscosity is at least 50 wt% or at least 75 wt% or at least 90 wt% or at least 99 wt% Group I base oil.

16. A lubricating composition according to any preceding claim, wherein the lubricating composition has an ISO viscosity grade of 68 to 1000 or 100 to 480.

17. A lubricating composition according to any preceding claim, wherein the lubricating composition contains from 0.15 wt% to 0.9 wt% sulphurised olefin.

18. A lubricating composition according to any preceding claim, wherein the lubricating sulphurised olefin is present in an amount sufficient to deliver from 40% to 60% by weight of the total sulphur content.

19. The lubricating composition of any preceding claim, wherein the lubricating composition contains from 50 ppm, 75 ppm, 100 ppm, or even 150 ppm to 5 wt%, 4 wt%, 3 wt%, 2 wt%, or even 1.5 wt%, or from 75 ppm to 0.5 wt%, from 100 ppm to 0.4 wt%, or from 150 ppm to 0.3 wt%, up to 5 wt%, or up to 3 wt%, or up to 2 wt%, or from 0.1% to 5% of an additional additive selected from a foam suppressor, a demulsifier, a pour point depressant, an antioxidant, a dispersant, a metal deactivator, a detergent, a viscosity modifier, or some mixture thereof.

20. The lubricating composition of any preceding claim, wherein the lubricating composition further comprises 50 ppm to 400 ppm of a dispersant.

21. The lubricating composition of claim 16, wherein the dispersant comprises or consists of a polyolefinamide enamine.

22. The lubricating composition according to any preceding claim, wherein the lubricating composition is substantially free of metal-containing detergents.

23. The lubricating composition of any preceding claim, wherein the lubricating composition further comprises an alkenylamine friction modifier.

24. The lubricating composition according to any preceding claim, wherein the lubricating composition further comprises a polyether based demulsifier.

25. The lubricating composition of any preceding claim, wherein the lubricating composition further comprises a corrosion inhibitor selected from substituted thiadiazoles, triazole derivatives, or combinations thereof.

26. The lubricating composition of any preceding claim, wherein the lubricating composition further comprises an ester copolymer defoamer.

27. A method of lubricating an industrial gear, the method comprising: The industrial gear is supplied with a lubricating composition according to any preceding claim.

28. Use of the lubricating composition according to any one of claims 1 to 26 for improving the extreme pressure properties of industrial gears.

29. Use of the lubricating composition according to any one of claims 1 to 26 for improving the Timken OK load performance of industrial gears.

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