Oil-based corrosion inhibitors

Abstract

To provide an oil-based corrosion inhibitor.SOLUTION: A composition comprises a) a metal detergent and b) an acid comprising at least one hydrocarbyl-substituted carboxylic acid. The metal detergent comprises at least one alkali metal, alkaline earth metal, or a combination thereof. A weight ratio of the metal detergent a) to the acid b) is in a range of 50:1 to 1:10, or 25:1 to 1:10, or 10:1 to 1:10, or 5:1 to 1:7, or 2:1 to 1:3. The composition may be added to an industrial coating or a lubricant composition and can reduce corrosion of metal components.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The field of the disclosed technology relates generally to oil-based corrosion inhibitors for use in lubricating compositions. [Background technology]

[0002] Oil-based corrosion inhibitors are essential components of countless industrial, automotive, and manufacturing fluids, from engine oils to hydraulic fluids to metal forming fluids. While these materials clearly need to exhibit excellent corrosion protection, they must also be low-cost and sustainable to manufacture. Commonly used corrosion inhibitors used in metal working lubricants rely on petroleum waxes as a key ingredient (e.g., Lubrizol's ALOX 2100). The decline in Group I oil refineries has resulted in a shortage of petroleum waxes for use as raw materials, making them more expensive. Therefore, there is a need for corrosion inhibitors that do not rely on petroleum waxes.

[0003] Overbased metal sulfonates having a high total base number ("TBN") of about 200-500 mg / KOH / g are known to be effective corrosion inhibitors because their basicity can neutralize corrosive acids that may be present in lubricants. Prior to the present invention, slightly overbased metal sulfonates (TBN about 40-50 mg KOH / g) tended to be poor corrosion inhibitors because they contained less base. Summary of the Invention

[0004] However, the inventors of this technology have discovered that the reaction of an overbased metal sulfonate with a mixture of an organic sulfonic acid and at least one carboxylic acid results in a low-TBN detergent that is a surprisingly effective corrosion inhibitor. These products do not use petroleum waxes, making them more sustainably sourced. Furthermore, these new materials are less expensive and easier to manufacture than many currently available corrosion inhibitors. The disclosed corrosion inhibitors also perform well as oil-based corrosion inhibitors or as thin-film rust inhibitors, making them versatile enough to be used in multiple technical applications. This versatility may be attractive to lubricant formulators who want to source a single material to serve multiple purposes.

[0005] Thus, a composition is disclosed that includes a metallic detergent and at least one hydrocarbyl-substituted carboxylic acid. The metallic detergent may include at least one alkali metal, alkaline earth metal, or combination thereof. The weight ratio of metallic detergent a) to acid b) may range from 50:1 to 1:10, or from 25:1 to 1:10, or from 10:1 to 1:10, or from 5:1 to 1:7, or from 2:1 to 1:3.

[0006] In some embodiments, the metal detergent comprises at least one phenate, salicylate, salixarate, sulfonate, or combinations thereof. The metal detergent may be a metal overbased detergent. Suitable metals include, but are not limited to, calcium, sodium, barium, magnesium, or combinations thereof.

[0007] In some embodiments, the acid further comprises at least one hydrocarbyl-substituted organic sulfonic acid. The weight ratio of the at least one organic sulfonic acid to the at least one carboxylic acid can range from 15:1 to 3:1. In other embodiments, the hydrocarbyl-substituted organic sulfonic acid can be a mono- or di-substituted alkyl sulfonic acid, such as naphthalene sulfonic acid, alkyl benzene sulfonic acid, or a combination thereof.

[0008] In some embodiments, the at least one carboxylic acid is at least one C-C 36 In other embodiments, the acid may comprise at least two carboxylic acids, at least one of which is a C to C hydrocarbyl-substituted polycarboxylic acid. 36 In yet another embodiment, at least one of the carboxylic acids is a monocarboxylic acid, and the weight ratio of polycarboxylic acid to monocarboxylic acid ranges from 10:1 to 1:1, or 3:1.

[0009] Monocarboxylic acids are linear or branched C8-C 36 In some embodiments, the monocarboxylic acid may be a saturated or unsaturated C-C 36 It may be a hydrocarbyl-substituted monocarboxylic acid. Thus, in some embodiments, the monocarboxylic acid is a linear unsaturated C, C 10 , C 12 , or C 14 ~C 36 , or C 10 ~C 18 It may be a hydrocarbyl-substituted monocarboxylic acid.

[0010] In some embodiments, the polycarboxylic acid can have at least 4 carbon atoms separating the acid functional groups, while in still other embodiments, the polycarboxylic acid can have 4 to 18 carbon atoms separating the acid functional groups.

[0011] In some embodiments, the at least one carboxylic acid may comprise a hydroxyalkyl carboxylic acid ester. In some embodiments, the at least one polycarboxylic acid is a dicarboxylic acid, a tricarboxylic acid, or a mixture thereof. Suitable dicarboxylic acids include C 36 Dicarboxylic acids, C 21 tricarboxylic acids, and combinations thereof. Thus, in some embodiments, the dicarboxylic acid is C 36The monocarboxylic acid may be a dicarboxylic acid, and the linear unsaturated C 14 ~C 18 It may also be a hydrocarbyl-substituted monocarboxylic acid. DETAILED DESCRIPTION OF THE INVENTION

[0012] Various preferred features and embodiments are described below by way of non-limiting example. The disclosed technology relates to compositions that surprisingly perform better as corrosion inhibitors than slightly overbased metal sulfonates. The novel compositions include a) a metal detergent and b) an acid comprising at least one hydrocarbyl-substituted carboxylic acid. The metal detergent can include at least one alkali metal, alkaline earth metal, or combination thereof. The weight ratio of metal detergent a) to acid b) can range from 50:1 to 1:10, or from 25:1 to 1:10, or from 10:1 to 1:10, or from 5:1 to 1:7, or from 2:1 to 1:3.

[0013] In some embodiments, the metal detergent comprises at least one phenate, salicylate, salixarate, sulfonate, or combinations thereof. In some embodiments, the metal detergent is a metal sulfonate detergent. The metal sulfonate may typically be a salt of an alkylaryl sulfonate having one or more hydrocarbyl or alkyl groups of sufficient length to provide solubility in hydrocarbon oils. "Sufficiently long" can be at least 12 carbon atoms and up to 200 carbon atoms, e.g., 18 to 100 or 24 to 48 carbon atoms in the combined alkyl or hydrocarbyl groups, or, if there are two or more such groups, in the longest group thereof. In one embodiment, each hydrocarbyl or alkyl group individually can contain at least 8 or at least 12 carbon atoms and up to 200, or 18 to 100, or 24 to 48 carbon atoms. Examples of metal sulfonates include relatively low molecular weight salts such as calcium mono-, di-, or trinonylnaphthalene sulfonate (or mixtures of mono-, di-, and tri-alkyl species), and relatively high molecular weight salts such as calcium oligo- or poly-propenebenzenesulfonate or calcium oligo- or poly-toluenesulfonate.

[0014] These may be neutral or overbased salts. Neutral salts contain approximately or exactly the stoichiometric amount of metal ions to neutralize the acid functionality of the alkaryl sulfonic acid. Overbased salts are prepared by reaction with a stoichiometric excess of a metal, such as calcium, barium, magnesium, potassium, zinc, or sodium, resulting in a basic compound, such as the oxide, hydroxide, or, ultimately, the carbonate salt as a result of treatment with carbon dioxide. Thus, in some embodiments, the metal detergent may be a metal overbased detergent. Overbased materials are well known in the lubricant industry as overbased detergents and may also function as surfactants or wetting agents. In certain embodiments, the salt may be a calcium, barium, or sodium salt. In yet other embodiments, the salt may be a calcium or magnesium salt. The TBN of the metal detergent may range from 15 to 500 mg KOH / g, or from 25 to 400 mg KOH / g. TBN is a term frequently used to describe the basicity of lubricant additives and / or lubricants. It is the amount of potassium hydroxide (mg KOH) required to neutralize 1 gram of the sample being tested using bromophenol blue as the titrant and indicator. Such TBN titration methods are well known in the art and are standardized in the industry, such as ASTM D2896.

[0015] In some embodiments, the metal sulfonate can be a salt of an alkaryl sulfonic acid containing an alkyl group of 9 to 200, or 12 to 200, or 18 to 100, or 25 to 50, or 30 to 40 carbon atoms. Such materials are typically provided in commercial form in the presence of an amount of diluent oil, typically a mineral oil such as an API Group I oil, in which they are often prepared. The amount of diluent oil that can be associated with and accompanied by the alkylaryl sulfonic acid metal salt can be in a ratio of salt to oil of 1:5 to 5:1. Overbased detergents are described in detail in U.S. Patent Nos. 2,501,731, 2,616,905, 2,616,911, 2,616,925, 2,777,874, 3,256,186, 3,384,585, 3,365,396, 3,320,162, 3,318,809, 3,488,284, and 3,629,109. Accordingly, in some embodiments, the metal detergent can be a calcium sulfonate detergent. The calcium sulfonate detergent can be neutral or overbased. In yet other embodiments, the metal detergent is an overbased calcium sulfonate detergent.

[0016] The amount of metal detergent (e.g., metal sulfonate) in the disclosed compositions can range from 2 to 30 weight percent, or 3 to 30, or 3 to 25, or 4 to 20, or 5 to 15 weight percent on an oil-free basis. The above quoted amounts exclude the amount of any volatile diluent that may be present.

[0017] In some embodiments, the acid used to make the novel composition may further comprise at least one hydrocarbyl-substituted organic sulfonic acid. The weight ratio of the at least one organic sulfonic acid to the at least one carboxylic acid may range from 15:1 to 3:1. In other embodiments, the hydrocarbyl-substituted organic sulfonic acid may be a mono- or di-substituted alkyl sulfonic acid, such as naphthalene sulfonic acid, alkyl benzene sulfonic acid, or a combination thereof.

[0018] 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 remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include:

[0019] hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, as well as aromatic, aliphatic, and alicyclic-substituted aromatic substituents, and cyclic substituents in which the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);

[0020] substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon character of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);

[0021] Hetero substituents, i.e., in the context of this invention, are included which have predominantly hydrocarbon character but contain other than carbon atoms in the ring or chain composed of carbon atoms, including substituents such as piedyl, furyl, thienyl, and imidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. Generally, no more than two, or no more than one non-hydrocarbon substituent will be present for every 10 carbon atoms in the hydrocarbyl group; alternatively, the hydrocarbyl group may have no non-hydrocarbon substituents.

[0022] The disclosed technology also includes hydrocarbyl-substituted carboxylic acids. The acids can be mono- or poly-acids. "Poly-acid" refers to materials with two or more carboxylic acid groups. In some embodiments, the acids can be polycarboxylic acids having at least 8 carbon atoms.

[0023] Suitable polyacids include diacids. One type of diacid is known as dimer acid or dimerized acid. Dimer acids are typically products prepared by the dimerization of long-chain, e.g., C18, unsaturated fatty acids. They are often prepared by the self-condensation of oleic or tall oil fatty acids. Dimer acids are mixtures of relatively high molecular weight materials (approximately 560), but are liquids at room temperature. They are commercially available materials that can be prepared by either the Diels-Alder reaction or free radical route, or by catalysis on substrates such as clays. Dimer acids and their preparation are described in detail in Kirk-Othmer Discussed extensively in Encyclopedia of Chemical Technology, 3rd ed., Vol. 7, pp. 768-782, John Wiley & Sons, New York (1979).

[0024] In another embodiment, the diacid may comprise a hydrocarbyl-substituted succinic acid having at least 14 carbon atoms, including the 4 carbon atoms of the succinic acid moiety, such as a succinic acid substituted with a 10-carbon alkyl. In other embodiments, there are at least 12, 14, 16, or 18 carbon atoms in such alkyl substituents (for a total of 16, 18, 20, or 22 carbon atoms). The number of atoms in the alkyl substituent may be up to 36, 30, 24, or 22 carbon atoms.

[0025] In another embodiment, the diacid can be an α,ω-alkylenedioic acid of at least 10 or 12 carbon atoms, and up to, for example, 36 or 24 or 18 carbon atoms. Examples include 1,10-decanedioic acid, 1,12-dodecanedioic acid, and 1,18-octadecanedioic acid. In one embodiment, the hydrocarbyl-substituted carboxylic acid is C 36 It may contain carboxylic dimer acid.

[0026] In some embodiments, the at least one carboxylic acid is at least one C-C 36In other embodiments, the acid may comprise at least two carboxylic acids, at least one of which is a C to C hydrocarbyl-substituted polycarboxylic acid. 36 These are hydrocarbyl-substituted polycarboxylic acids. In some embodiments, the polycarboxylic acid may have at least four carbon atoms separating the acid functional groups. In yet other embodiments, the polycarboxylic acid may have 4 to 18 carbon atoms separating the acid functional groups. The separating carbon atoms in such embodiments are typically non-aromatic, and in one embodiment, they comprise a carbon chain, i.e., uninterrupted by inserted oxygen or nitrogen atoms. In certain embodiments, the carboxyl groups may be separated by 8 to 24 carbon atoms, or 10 to 20 carbon atoms, or 12 to 20 carbon atoms, or 14 to 18 carbon atoms.

[0027] In some embodiments, at least one of the carboxylic acids is a monocarboxylic acid, and the weight ratio of polycarboxylic acid to monocarboxylic acid ranges from 10:1 to 1:1, or 3:1. The monocarboxylic acid may have at least 10 carbon atoms. In some embodiments, it may have a carbon chain length of 8 to 24 carbon atoms. Such acids are often obtained by hydrolysis of natural fats and oils. They may be saturated or unsaturated and may contain additional substituents such as hydroxy groups. These acids, sometimes referred to as fatty acids, are well known and typically include stearic acid, hydroxystearic acid, or oleic acid. Thus, in one embodiment, the hydrocarbyl-substituted carboxylic acid may include oleic acid.

[0028] In some embodiments, the monocarboxylic acid is a linear or branched C-C 36 In some embodiments, the monocarboxylic acid may be a saturated or unsaturated C-C 36 It may be a hydrocarbyl-substituted monocarboxylic acid. Thus, in some embodiments, the monocarboxylic acid is a linear unsaturated C, C 10 , C 12 , or C 14~C 36 , or C 10 ~C 18 It may be a hydrocarbyl-substituted monocarboxylic acid.

[0029] In some embodiments, the at least one carboxylic acid may comprise a hydroxyalkyl carboxylic acid ester, such as dodecenyl succinic acid, hydroxypropyl monoester, etc. In some embodiments, the at least one polycarboxylic acid is a dicarboxylic acid, a tricarboxylic acid, or a mixture thereof. Suitable dicarboxylic acids include C 36 Dicarboxylic acids are included. 21 Tricarboxylic acids include triazine-triyltriiminotris-hexanoic acid. Thus, in some embodiments, the dicarboxylic acid is C 36 The monocarboxylic acid may be a dicarboxylic acid, and the linear unsaturated C 14 ~C 18 It may also be a hydrocarbyl-substituted monocarboxylic acid.

[0030] In some embodiments, the at least one carboxylic acid is at least one C-C 36 In other embodiments, the acid mixture comprises at least two carboxylic acids, at least one of which is a C to C hydrocarbyl-substituted polycarboxylic acid. 36 In yet another embodiment, the hydrocarbyl-substituted carboxylic acid is a C 36 Carboxylic dimer acid and C 21 It may contain tricarboxylic acids.

[0031] Accordingly, specific carboxylic acids suitable for use in the disclosed technology include C36 dimer carboxylic acids, C 21 Tricarboxylic acids, adipic acid (C6 diacid), oleic acid (C 18 Linear unsaturated carboxylic acid), neodaconic acid (C 10 Branched saturated carboxylic acids), cocoa fatty acids (C 12Examples of suitable carboxylic acids include, but are not limited to, C36 dimer carboxylic acid and oleic acid.

[0032] The amount of the carboxylic acid, whether mono-, di-, or poly-acid in the disclosed compositions, can be 4 to 25 weight percent, or 6 to 10 weight percent, calculated excluding the presence of any volatile diluent or diluent oil.

[0033] The composition also contains an amount of oil sufficient to dissolve the metal salt of alkylarylsulfonic acid. The oil may be natural or synthetic, derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, rerefined, or a mixture thereof. A more detailed description of unrefined, refined, and rerefined oils is provided in paragraphs

[0054] to

[0056] of International Publication WO 2008 / 147704 and the corresponding paragraphs of US-2010-0197536. A more detailed description of natural and synthetic lubricating oils is provided in paragraphs

[0058] to

[0059] of WO 2008 / 147704, respectively. Synthetic oils may also be produced by the Fischer-Tropsch reaction and are typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by a Fischer-Tropsch gas-to-liquids synthesis procedure, as well as other gas-to-liquids oils. In another embodiment, the oil may be selected from any of Groups I to V of the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are as follows: Group I: >0.03% sulfur and / or <90% saturates and a viscosity index (VI) of 80-120; Group II: ≤0.03% sulfur and ≥90% saturates and a VI of 80-120; Group III: ≤0.03% sulfur and ≥90% saturates and a VI >120; Group IV: all polyalphaolefins; and Group V: all others. Groups I, II, and III are mineral oil base stocks. Natural oils also include vegetable oils such as coconut oil, castor oil, olive oil, peanut oil, rapeseed (canola) oil, corn oil, sesame oil, cottonseed oil, soybean oil, palm oil, sunflower oil, safflower oil, linseed oil, and tung oil. In one embodiment, the oil is a hydrocarbon oil. In other embodiments, the oil may be a mineral oil or a non-mineral oil, such as a poly-α-olefin oil, trimethylolpropane trioleate (TMP-TO), a polyalkylene glycol, or a vegetable oil.

[0034] The amount of oil, such as a hydrocarbon oil, in the disclosed compositions can be 2 to 80 weight percent, 5 to 70, or 10 to 45, or 15 to 35 weight percent, or 2 to 30 weight percent. In another embodiment, the oil, such as a hydrocarbon oil, can be 70 to 98 weight percent of the composition. In one embodiment, the amount of metal detergent is 2 to 30 weight percent, the amount of at least one carboxylic acid is 4 to 25 weight percent, and the amount of hydrocarbon oil is 45 to 94 weight percent.

[0035] The composition may also optionally contain a volatile diluent. By "volatile diluent" is meant a typically liquid component with a volatility greater than that of an oil, such as mineral oil. Volatile diluents can include water or one or more organic solvents. Thus, diluents can include volatile organic solvents such as naphtha (also known as petroleum ether), mineral spirits, kerosene, or ethyl lactate. Among these materials can be hydrocarbon solvents. Such materials can have boiling points in the range of 30-60°C or higher, up to 175-280°C. Such volatile diluents can have boiling points in the range of 130-210°C, and others in the range of 196-205°C. Overall, a diluent can be considered volatile if its boiling point is below 280°C.

[0036] While the volatile diluent may be present as a concentrate of the aforementioned components if desired, most commonly the diluent, or a majority of the diluent, is added when preparing a fully formulated diluted composition. The amount of diluent is typically an amount that provides adequate viscosity and rheological performance so that the composition can be applied to a substrate, such as a metal article or surface. Thus, if a concentrate is diluted to 20 percent in the final composition, the total amount of diluent will typically be 80 percent of the additional solvent or diluent used to make the diluent (in addition to the oil used to dissolve the metal salt, which does not count toward the amount of volatile diluent). The overall total amount of diluent (if present) will, of course, depend on the amount of diluent used to prepare the final composition and may therefore be 40-98 weight percent, or 60-98, or 40-95, or 60-88, or 80-86, or 82-84 weight percent. The amount of other components is typically 100 weight percent minus the amount of optional volatile diluent, e.g., 2-60 weight percent, and other amounts that can be easily determined by one of ordinary skill in the art.

[0037] Compositions comprising a metal detergent and an acid comprising at least one hydrocarbyl-substituted carboxylic acid may have a total base number ("TBN") in the range of at least 10 to 65 mg KOH / g. In other embodiments, the TBN may range from 20 to 60 mg KOH / g, or from 40 to 60 mg KOH / g, or from 25 to 55 mg KOH / g. The TBN may include the optional oil or solvent, if present. The TBN of compositions diluted with solvent and / or oil may range from 0.1 to 50 mg KOH / g, or from 0.1 to 40 mg KOH / g.

[0038] The compositions disclosed herein may have the compositions defined in Table 1 below. [Table 1-1]

[0039] Also disclosed is a method for reducing corrosion of a metal part. The method may include coating the metal part with the above-described composition. The disclosed compositions may be used in fluids, such as coatings, industrial gear oils, or hydraulic fluids, to reduce corrosion of metals in contact with such fluids. In some embodiments, the composition is a coating composition comprising a metal detergent and the above-described acid, along with a solvent (e.g., mineral spirits or naphtha), an oil (e.g., Group I or Group II paraffinic oil), or a mixture thereof. In some embodiments, the composition is an industrial gear oil composition comprising a Group I base stock, along with the above-described metal detergent and acid. In yet other embodiments, the composition is a hydraulic fluid composition comprising a Group II base stock, along with the above-described metal detergent and acid.

[0040] Industrial Applications The disclosed compositions can be used as corrosion inhibitors. Some of the disclosed compositions can be soluble in oil or solvents, and some can even be soluble in both oil and solvents. The disclosed compositions can be further diluted and used in coating compositions or other metal working fluids and applied to metal parts to reduce corrosion of the metal parts. The disclosed compositions can be present at about 1 to 60 wt. % in a diluent oil or solvent for use as a coating composition or metal working fluid.

[0041] The disclosed compositions can also be used in hydraulic fluid and industrial gear oil applications. Further details on how the disclosed compositions can be used are described below.

[0042] Metal Working Fluid In one embodiment, the lubricant composition is a metal working fluid. Typical metal working fluid applications can include metal removal, metal forming, metal treating, and metal protection, for example, in coating compositions.

[0043] The coating composition may also include Group I, Group II, or Group III, or naphthenic base stocks as defined by the American Petroleum Institute. In some embodiments, the coating composition may be blended with Group IV or Group V base stocks.

[0044] In some embodiments, the coating composition may include an oil. The oil may include most liquid hydrocarbons, such as paraffinic, olefinic, naphthenic, aromatic, saturated, or unsaturated hydrocarbons. Generally, the oil is a water-immiscible, emulsifiable hydrocarbon, and in some embodiments, the oil is liquid at room temperature. Oils from a variety of sources may be used, including natural and synthetic oils and mixtures thereof.

[0045] Natural oils include animal and vegetable oils (e.g., soybean oil, lard oil), as well as solvent- or acid-refined mineral oils of the paraffinic, naphthenic, or mixed paraffinic-naphthenic types. Oils derived from coal or shale are also useful. Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and copolymerized olefins, e.g., polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene; alkyl benzenes, e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, or di-(2-ethylhexyl)benzene.

[0046] Another suitable class of synthetic oils that can be used comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, pentaerythritol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, or the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.

[0047] Esters useful as synthetic oils include C5-C 12 Also included are those made from monocarboxylic acids and polyols, and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and the like.

[0048] Unrefined, refined, and rerefined oils (and mixtures thereof with each other) of the types disclosed above can be used. Unrefined oils are obtained directly from natural or synthetic sources without further purification treatment. For example, shale oil obtained directly from a retorting operation, petroleum oil obtained directly from distillation, or ester oil obtained directly from an esterification process and used without further treatment can be unrefined oils. Refined oils are similar to unrefined oils, except that they have been further processed in one or more purification steps to improve one or more properties. Many such purification techniques, such as solvent extraction, distillation, acid or base extraction, filtration, percolation, etc., are known to those skilled in the art. Rerefined oils are obtained by processes similar to those used to obtain refined oils that are already in practical use. Such rerefined oils are also known as reclaimed or reprocessed oils and are often further processed by techniques aimed at removing spent additives and oil breakdown products.

[0049] Optional additional materials may be incorporated into the coating compositions disclosed herein. Typical finished coating compositions may include lubricants such as fatty acids and waxes, antiwear agents, dispersants, corrosion inhibitors (in addition to the novel compositions disclosed herein), conventional and overbased detergents, demulsifiers, biocides, metal deactivators, antifoam agents, or mixtures thereof.

[0050] Examples of waxes include petroleum, synthetic and natural waxes, oxidized waxes, microcrystalline waxes, wool fat (lanolin) and other waxy esters, and mixtures thereof. Petroleum waxes are paraffinic compounds isolated from crude oil through several refining processes, such as slack wax and paraffin wax. Synthetic waxes are waxes derived from petrochemicals such as ethylene or propylene. Synthetic waxes include polyethylene, polypropylene, and ethylene-propylene copolymers. Natural waxes are waxes produced by plants and / or animals or insects. These waxes include beeswax, soy wax, and carnauba wax. Insect and animal waxes include beeswax or spermaceti. Petroleum and oxidized petroleum can also be used in these compositions. Petroleum and oxidized petroleum can be defined as refined mixtures of semi-solid hydrocarbons derived from petroleum and its oxidation products, respectively. Microcrystalline waxes can be defined as higher-melting waxes refined from petroleum. The wax may be present in the metal-working composition in an amount of from 0.1% to 75% by weight, such as from 0.1% to 50% by weight.

[0051] Examples of suitable friction modifiers include long-chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty phosphonates; fatty phosphites; boronated phospholipids, boronated fatty epoxides; glycerol esters; boronated glycerol esters; fatty amines; alkoxylated fatty amines; boronated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines, including tertiary hydroxy fatty amines; hydroxyalkylamides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols; condensation products of carboxylic acids and polyalkylene-polyamines; or reaction products of fatty carboxylic acids with guanidine, aminoguanidine, urea, or thiourea, and their salts. As used herein, the terms "fatty alkyl" or "fatty" in reference to friction modifiers refer to a carbon chain having 10 to 22 carbon atoms, typically a linear carbon chain. Alternatively, the fatty alkyl may be a mono-branched alkyl group, typically branched at the β-position. Examples of mono-branched alkyl groups include 2-ethylhexyl, 2-propylheptyl, or 2-octyldodecyl.

[0052] Friction modifiers can also include materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, or other oil-soluble molybdenum complexes, such as Molyvan® 855 (commercially available from R.T. Vanderbilt, Inc.) or Sakuralube® S-700 or Sakuralube® S-710 (commercially available from Adeka, Inc.) Oil-soluble molybdenum complexes help reduce friction but can compromise seal compatibility.

[0053] In one embodiment, the friction modifier may be an oil-soluble molybdenum complex. The oil-soluble molybdenum complex may include molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum blue oxide complex, or other oil-soluble molybdenum complexes or mixtures thereof. The oil-soluble molybdenum complex may be a mixture of molybdenum oxide and hydroxide, the so-called "blue" oxide. Molybdenum blue oxide has molybdenum in an average oxidation state of 5-6, and is composed of MoO2(OH) and MoO 2.5 (OH) 0.5 An oil-soluble example is the molybdenum blue oxide complex known under the tradename Luvodor® MB or Luvador® MBO (commercially available from Lehmann and Voss GmbH), and the oil-soluble molybdenum complex may be present at 0% to 5% or 0.1% to 5% or 1 to 3% by weight of the metal-working composition.

[0054] In one embodiment, the friction modifier may be a long-chain fatty acid ester. In another embodiment, the long-chain fatty acid ester may be a monoester, and in another embodiment, the long-chain fatty acid ester may be a triglyceride, such as sunflower oil or soybean oil, or a monoester of a polyol and an aliphatic carboxylic acid. The friction modifier may be present at 0% to 6%, or 0.01% to 4%, or 0.05% to 2%, or 0.1% to 2% by weight of the metal-working / coating composition.

[0055] Fatty acids useful herein include monocarboxylic acids having 8 to 35 carbon atoms, and in one embodiment, 16 to 24 carbon atoms. Examples of such monocarboxylic acids include unsaturated fatty acids such as myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid; α-linolenic acid; arachidonic acid; eicosapentaenoic acid; erucic acid, docosahexaenoic acid; and saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, isostearic acid, gadoleic acid, tall oil fatty acid, or combinations thereof. These acids can be saturated, unsaturated, or have other functional groups, such as hydroxy groups, from the hydrocarbyl backbone, as in 12-hydroxystearic acid. Other examples of carboxylic acids are described in U.S. Patent No. 7,435,707. The fatty acid may be present in the metal-working composition at 0.1% to 50% by weight, or 0.1% to 25% by weight, or 0.1% to 10% by weight.

[0056] Suitable metal detergents include those mentioned above. The metal detergents may be used alone or in combination. The metal detergent may be present in an amount ranging from 0.1% to 20% by weight of the composition, for example, at least 1% by weight or up to 10% by weight.

[0057] Exemplary surfactants include nonionic polyoxyethylene surfactants such as ethoxylated alkylphenols and ethoxylated fatty alcohols, polyethylene glycol esters of fats, resins, and tall oil acids, and polyoxyethylene esters of fatty acids, or anionic surfactants such as linear alkylbenzene sulfonates, alkyl sulfonates, alkyl ether phosphonates, ether sulfates, sulfosuccinates, and ether carboxylates. The surfactants may be present in the metal-working composition at 0.0001% to 10% by weight, or 0.0001% to 2.5% by weight.

[0058] The antifoaming agent can include organic silicones and non-silicon foam suppressors. Examples of organic silicones include dimethyl silicones and polysiloxanes. Examples of non-silicon foam suppressors include polyethers, polyacrylates, and mixtures thereof, as well as copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate. In some embodiments, the antifoaming agent can be a polyacrylate. The antifoaming agent can be present in the composition at 0.001% by weight or even 0.0025% to 0.10% by weight.

[0059] Demulsifiers useful herein include polyethylene glycol, polyethylene oxide, polypropylene alcohol oxide (ethylene oxide-propylene oxide) polymers, polyoxyalkylene alcohols, alkylamines, amino alcohols, diamines or polyamines reacted in turn with ethylene oxide or substituted ethylene oxide mixtures, trialkyl phosphates, and combinations thereof. The demulsifier may be present in the corrosion-inhibiting composition at 0.0001% to 10% by weight, e.g., 0.0001% to 2.5% by weight.

[0060] In addition to the exemplary compounds, other corrosion inhibitors can also be used in the compositions provided herein. Corrosion inhibitors that can be used include thiazoles, triazoles, and thiadiazoles. Examples include benzotriazole, tolyltriazole, octyltriazole, decyltriazole, dodecyltriazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazole, 2,5-bis(hydrocarbylthio)-1,3,4-thiadiazole, and 2,5-bis(hydrocarbyldithio)-1,3,4-thiadiazole. Other suitable corrosion inhibitors include ether amines; polyethoxylated compounds, such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; and imidazolines. Other suitable corrosion inhibitors include alkenyl succinic acids in which the alkenyl group contains 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, hexadecenyl succinic acid; long chain alpha, omega-dicarboxylic acids in the molecular weight range of 600 to 3000; and other similar materials.Other non-limiting examples of such inhibitors are described in U.S. Pat. Nos. 3,873,465, 3,932,303, 4,066,398, 4,402,907, 4,971,724, 5,055,230, 5,275,744, 5,531,934, 5,611,991, 5,616,544, 5,744,069, 5,750,070, 5,779,938, and 5,785,896; Corrosion Inhibitors, CC Nathan, ed., NACE, 1973; I.L. Rozenfeld, Corrosion Inhibitors, McGraw-Hill, 1981; Metals Handbook, 9th Ed., Vol. 13 - Corrosion, pp. 478-497; Corrosion Inhibitors for Corrosion Control, BG Clubley, ed., The Royal Society of Chemistry, 1990; Corrosion Inhibitors, European Federation of Corrosion Publications Number 11, The Institute of Materials, 1994; Corrosion, Vol. 2 - Corrosion Control, L.L. Sheir, R.A. Jarman, and G.T. Burstein, eds., Butterworth-Heinemann, 1994, pp. 17:10-17:39; Y.I. Kuznetsov, Organic Inhibitors of Corrosion of Metals, Plenum, 1996; and V.S. Sastri, Corrosion Inhibitors: Principles and Applications, Wiley, 1998. Other corrosion inhibitors may be present in the metal-working composition at 0.0001% to 5% by weight, such as 0.0001% to 3% by weight.

[0061] Dispersants that can be included in the composition include those having an oil-soluble polymeric hydrocarbon backbone and functional groups capable of associating with the particles to be dispersed. The polymeric hydrocarbon backbone may have a weight average molecular weight ranging from 750 to 1500 daltons. Exemplary functional groups include amine, alcohol, amide, and ester polar moieties, often attached to the polymer backbone via a bridging group. Exemplary dispersants include Mannich dispersants described in U.S. Pat. Nos. 3,697,574 and 3,736,357, ashless succinimide dispersants described in U.S. Pat. Nos. 4,234,435 and 4,636,322, amine dispersants described in U.S. Pat. Nos. 3,219,666, 3,565,804, and 5,633,326, Koch dispersants described in U.S. Pat. Nos. 5,936,041, 5,643,859, and 5,627,259, and polyalkylene succinimide dispersants described in U.S. Pat. Nos. 5,851,965, 5,853,434, and 5,792,729. The dispersant may be present in the metal working composition at 0.0001% to 10% by weight, for example, 0.0005% to 2.5% by weight.

[0062] The extreme pressure agent may be a compound containing sulfur and / or phosphorus and / or chlorine. Examples of extreme pressure agents include polysulfides, sulfurized olefins, thiadiazoles, chlorinated paraffins, overbased sulfonates, or mixtures thereof.

[0063] Examples of thiadiazoles include 2,5-dimercapto-1,3,4-thiadiazole or oligomers thereof, hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazoles, hydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazoles or oligomers thereof. Oligomers of hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazoles are typically formed by forming a sulfur-sulfur bond between 2,5-dimercapto-1,3,4-thiadiazole units to form two or more oligomers of the thiadiazole unit. Examples of suitable thiadiazole compounds include at least one of dimercaptothiadiazole, 2,5-dimercapto-[1,3,4]-thiadiazole, 3,5-dimercapto-[1,2,4]-thiadiazole, 3,4-dimercapto-[1,2,5]-thiadiazole, or 4-5-dimercapto-[1,2,3]-thiadiazole. Typically, readily available materials, such as 2,5-dimercapto-1,3,4-thiadiazole or hydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole or hydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazole, are commonly utilized. In various embodiments, the number of carbon atoms on the hydrocarbyl substituent may be 1 to 30, 2 to 25, 4 to 20, 6 to 16, or 8 to 10. The 2,5-dimercapto-1,3,4-thiadiazole may be 2,5-dioctyldithio-1,3,4-thiadiazole or 2,5-dinonyldithio-1,3,4-thiadiazole.

[0064] In one embodiment, at least 50% by weight of the polysulfide molecules are a mixture of tri- or tetra-sulfides, hi other embodiments, at least 55% by weight, or at least 60% by weight, of the polysulfide molecules are a mixture of tri- or tetra-sulfides.

[0065] Polysulfides include sulfurized organic polysulfides from oils, fatty acids or esters, olefins or polyolefins.

[0066] Oils that can be sulfurized include natural or synthetic oils, such as mineral oil, lard oil, carboxylic acid esters derived from fatty alcohols and fatty acids or aliphatic carboxylic acids (e.g., myristyl oleate and oleyl oleate), and synthetic unsaturated esters or glycerides.

[0067] Fatty acids include those containing 8 to 30 or 12 to 24 carbon atoms. Examples of fatty acids include oleic acid, linoleic acid, linolenic acid, and tall oil. Sulfurized fatty acid esters prepared from mixed unsaturated fatty acid esters are derived from animal fats and vegetable oils, including tall oil, linseed oil, soybean oil, rapeseed oil, and fish oil.

[0068] Polysulfides include olefins derived from a wide range of alkenes. Alkenes typically have one or more double bonds. In one embodiment, the olefins contain 3 to 30 carbon atoms. In other embodiments, the olefins contain 3 to 16 or 3 to 9 carbon atoms. In one embodiment, the sulfurized olefins include olefins derived from propylene, isobutylene, pentene, or mixtures thereof.

[0069] In one embodiment, the polysulfide comprises a polyolefin derived from polymerization by known techniques, such as those olefins described above.

[0070] In one embodiment, the polysulfides include dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenols, sulfurized dipentene, sulfurized dicyclopentadiene, sulfurized terpenes, and sulfurized Diels-Alder adducts.

[0071] Chlorinated paraffins are long chain chlorinate paraffins (C 20+ and medium-chain chlorinated paraffins (C 14 ~C 17)) may contain both. Examples include Choroflo, Paroil, and Chlorowax products from Dover Chemical.

[0072] Overbased sulfonates are discussed above. Examples of overbased sulfonates include Lubrizol® 5283C, Lubrizol® 5318A, Lubrizol® 5347LC, and Lubrizol® 5358.

[0073] The extreme pressure agent may be present at 0% to 25% by weight, or 1.0% to 15.0% by weight, or 2.0% to 10.0% by weight of the metal working composition.

[0074] Coating compositions can be prepared by further diluting the compositions of Table 1 above with solvents and / or diluent oils, such as the API base oils described above. Coating compositions can be prepared by diluting the disclosed compositions with 5%, 6%, 10%, 20%, or even 70-90% by weight of a solvent or diluent oil, based on the total weight of the coating composition. Suitable diluents include naphthenic oil, mineral spirits, Group I paraffinic base oil, Group II paraffinic base oil, and Group II+ paraffinic base oil, or combinations thereof.

[0075] Coating compositions having the disclosed corrosion inhibiting compositions comprising a metal detergent and at least one hydrocarbyl-substituted carboxylic acid can be evaluated using a salt spray test, as described in ASTM B117.

[0076] Lubricant Compositions - Industrial Gear and Hydraulic Oils The disclosed compositions include industrial additive packages, which may also be referred to as industrial lubricant additive packages. These industrial additive packages are designed for use in industrial gear and / or hydraulic oil lubricants. The lubricant compositions may include an oil of lubricating viscosity. Such oils include natural and synthetic fluids, oils derived from hydrocracking, hydrogenation, and hydrofinishing processes, unrefined oils, refined oils, rerefined oils, or mixtures thereof. In some embodiments, the oil of lubricating viscosity includes a Group I, Group II, or Group II+ base oil, or a combination thereof.

[0077] In addition to the corrosion inhibitors disclosed herein, additives that may be present in the industrial additive package include foam suppressors, demulsifiers, pour point depressants, antioxidants, dispersants, metal deactivators (such as copper deactivators), antiwear agents, extreme pressure agents, viscosity modifiers, or some mixture thereof. The additives may be present in a range of 50 ppm, 75 ppm, 100 ppm, or even 150 ppm up to 5 wt%, 4 wt%, 3 wt%, 2 wt%, or even 1.5 wt%, or 75 ppm to 0.5 wt%, 100 ppm to 0.4 wt%, or 150 ppm to 0.3 wt%, respectively, where the weight percentages are based on the total lubricant composition. In other embodiments, the total industrial additive package may be present at 1 to 20, or 1 to 10 wt% of the total lubricant composition. However, it should be noted that some additives, including viscosity modifying polymers, which may alternatively be considered part of the base fluid, can be present in greater amounts, including up to 30%, 40% or even 50% by weight when considered separately from the base fluid. The additives can be used alone or as mixtures thereof.

[0078] The lubricant can also include an antifoaming agent. The antifoaming agent can include organic silicones and non-silicon foam suppressors. Examples of organic silicones include dimethyl silicones and polysiloxanes. Examples of non-silicon foam suppressors include polyethers, polyacrylates, and mixtures thereof, as well as copolymers of ethyl acrylate, 2-ethylhexyl acrylate, and optionally vinyl acetate. In some embodiments, the antifoaming agent can be a polyacrylate. The antifoaming agent can be present in the composition in an amount of 0.001% to 0.012% by weight, or 0.004% by weight, or even 0.001% to 0.003% by weight.

[0079] The lubricant may also contain a demulsifier. The demulsifier may include derivatives of propylene oxide, ethylene oxide, polyoxyalkylene alcohol, alkylamine, amino alcohol, diamine, or polyamine sequentially reacted with ethylene oxide or substituted ethylene oxide, or mixtures thereof. Examples of demulsifiers include polyethylene glycol, polyethylene oxide, polypropylene oxide, (ethylene oxide-propylene oxide) polymers, and mixtures thereof. The demulsifier may be a polyether. The demulsifier may be present in the composition at 0.002% to 0.2% by weight.

[0080] The lubricant may contain pour point depressants, such as esters of maleic anhydride-styrene copolymers, polymethacrylates, polyacrylates, polyacrylamides, condensation products of haloparaffin waxes with 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.

[0081] The lubricant may also contain a corrosion inhibitor or rust inhibitor other than those disclosed above. Suitable rust inhibitors include hydrocarbyl amine salts of alkylphosphoric acids, hydrocarbyl amine salts of dialkyldithiophosphoric acids, hydrocarbyl aryl sulfonic acids, hydrocarbyl amine salts of fatty carboxylic acids or esters thereof, esters of nitrogen-containing carboxylic acids, ammonium sulfonates, imidazolines, or any combination thereof; or mixtures thereof.

[0082] Suitable hydrocarbyl amine salts of alkyl phosphates are represented by the formula [ka] (In the formula, R 26 and R 27 are independently hydrogen, an alkyl chain, or a hydrocarbyl, and are typically R 26 and R 27 at least one of R is hydrocarbyl; 26 and R 27 contains 4 to 30, or 8 to 25, or 10 to 20, or 13 to 19 carbon atoms; R 28 , R 29 , and R 30 are independently hydrogen, alkyl branched or linear alkyl chains having 1 to 30, or 4 to 24, or 6 to 20, or 10 to 16 carbon atoms; R 28 , R 29 , and R 30 are independently hydrogen, alkyl branched or linear alkyl chains, or R 28 , R 29 , and R 30 wherein at least one or two of the groups are hydrogen.

[0083] R 28 , R 29 , and R 30Examples of suitable alkyl groups include butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sec-hexyl, n-octyl, 2-ethyl, hexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl, or mixtures thereof.

[0084] In one embodiment, the hydrocarbyl amine salt of an alkyl phosphate is 11 ~C 14 Primene 81R (produced and sold by Rohm & Haas) which may be a mixture of tertiary alkyl primary amines and C 14 ~C 18 It may be the reaction product of an alkylated phosphoric acid.

[0085] The hydrocarbyl amine salts of dialkyl dithiophosphoric acids can include rust inhibitors such as hydrocarbyl amine salts of dialkyl dithiophosphoric acids, which can be the reaction products of heptyl, octyl, or nonyl dithiophosphoric acid with ethylenediamine, morpholine, or Primene 81R, or mixtures thereof.

[0086] The hydrocarbyl amine salt of a hydrocarbyl aryl sulfonic acid may include the ethylenediamine salt of dinonylnaphthalene sulfonic acid.

[0087] Examples of suitable fatty carboxylic acids or esters thereof include glycerol monooleate and oleic acid. An example of a suitable ester of a nitrogen-containing carboxylic acid includes oleyl sarcosine.

[0088] The lubricant may contain a metal deactivator or mixtures thereof. The metal deactivator may be selected from derivatives of benzotriazole (typically tolyltriazole), 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole, 1-amino-2-propanol, derivatives of dimercaptothiadiazole, octylamine octanoate, dodecenyl succinic acid or anhydride and / or condensation products of fatty acids, such as oleic acid, with polyamines. The metal deactivator may also be described as a corrosion inhibitor. The metal deactivator may be present in the range of 0.001% to 0.5%, 0.01% to 0.04%, or 0.015% to 0.03% by weight of the lubricating oil composition. The metal deactivator may also be present in the composition at 0.002% or 0.004% to 0.02% by weight. The metal deactivators may be used alone or in mixtures thereof.

[0089] The lubricant can also contain an antioxidant or mixture thereof. The antioxidant includes (i) alkylated diphenylamines and (ii) substituted hydrocarbyl monosulfides. In some embodiments, the alkylated diphenylamines include 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 may be 1-(tert-dodecylthio)-2-propanol. The antioxidant package can also include a sterically hindered phenol. Examples of suitable hydrocarbyl groups for the sterically hindered phenol include 2-ethylhexyl or n-butyl esters, dodecyl, or mixtures thereof. Examples of methylene-bridged sterically hindered phenols include 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 mixtures thereof.

[0090] The antioxidant may be present in the composition at 0.01% to 6.0% by weight, or 0.02% to 1% by weight. The additive may be present in the composition at 1% by weight, 0.5% by weight, or less.

[0091] The lubricant can also contain nitrogen-containing dispersants, such as hydrocarbyl-substituted nitrogen-containing additives. Suitable hydrocarbyl-substituted nitrogen-containing additives include ashless dispersants and polymeric dispersants. Ashless dispersants are so named because, as supplied, they are metal-free and therefore do not typically contribute to sulfated ash when added to a lubricant. However, when metal-containing species are added to a lubricant, they can of course interact with surrounding metals. Ashless dispersants are characterized by polar groups attached to relatively high molecular weight hydrocarbon chains. Examples of such materials include succinimide dispersants, Mannich dispersants, and their boronated derivatives.

[0092] The lubricant can also contain a sulfur-containing compound. Suitable sulfur-containing compounds include sulfurized olefins and polysulfides. The sulfurized olefin or polysulfide can be derived from isobutylene, butylene, propylene, ethylene, or some combination thereof. In some examples, the sulfur-containing compound is a sulfurized olefin derived from any of the natural or synthetic oils described above, or even some combination thereof. For example, the sulfurized olefin can be derived from a vegetable oil. The sulfurized olefin can be present in the lubricant composition at 0 wt. % to 5.0 wt. %, 0.01 wt. % to 4.0 wt. %, or 0.1 wt. % to 3.0 wt. %.

[0093] The lubricant can also include a phosphorus-containing compound, such as a fatty phosphite. The phosphorus-containing compound can include a hydrocarbyl phosphite, a phosphoric acid ester, an amine salt of a phosphoric acid ester, or any combination thereof. In some embodiments, the phosphorus-containing compound includes a hydrocarbyl phosphite, an ester thereof, or a combination thereof. In some embodiments, the phosphorus-containing compound includes a hydrocarbyl phosphite. In some embodiments, the hydrocarbyl phosphite can be an alkyl phosphite. Alkyl refers to an alkyl group containing only carbon and hydrogen atoms, although saturated or unsaturated alkyl groups, or mixtures thereof, are contemplated. In some embodiments, the phosphorus-containing compound includes an alkyl phosphite having a fully saturated alkyl group. In some embodiments, the phosphorus-containing compound includes an alkyl phosphite having some unsaturation, for example, one double bond between carbon atoms. Such unsaturated alkyl groups may also be referred to as alkenyl groups, but are included in the term "alkyl group" as used herein unless otherwise specified. In some embodiments, the phosphorus-containing compound includes an alkyl phosphite, a phosphoric acid ester, an amine salt of a phosphoric acid ester, or any combination thereof. In some embodiments, the phosphorus-containing compound comprises an alkyl phosphite, an ester thereof, or a combination thereof. In some embodiments, the phosphorus-containing compound comprises an alkyl phosphite. In some embodiments, the phosphorus-containing compound comprises an alkenyl phosphite, a phosphate ester, an amine salt of a phosphate ester, or any combination thereof. In some embodiments, the phosphorus-containing compound comprises an alkenyl phosphite, an ester thereof, or a combination thereof. In some embodiments, the phosphorus-containing compound comprises an alkenyl phosphite. In some embodiments, the phosphorus-containing compound comprises a dialkyl hydrogen phosphite. In some embodiments, the phosphorus-containing compound is essentially free of, or even completely free of, a phosphate ester and / or an amine salt thereof.In some embodiments, the phosphorus-containing compound may be described as a fatty phosphite. Suitable phosphites include those having at least one hydrocarbyl group with 4 or more, or 8 or more, or 12 or more carbon atoms. Typical ranges for the number of carbon atoms in the hydrocarbyl group include 8 to 30, or 10 to 24, or 12 to 22, or 14 to 20, or 16 to 18. The phosphite may be a monohydrocarbyl-substituted phosphite, a dihydrocarbyl-substituted phosphite, or a trihydrocarbyl-substituted phosphite. In one embodiment, the phosphite may be sulfur-free, i.e., the phosphite is not a thiophosphite. Phosphites having at least one hydrocarbyl group with 4 or more carbon atoms may be represented by the formula: [ka] (In the formula, R 6 , R 7 , and R 8 may be represented by (at least one of which may be a hydrocarbyl group containing at least 4 carbon atoms, and the others may be hydrogen or hydrocarbyl groups). 6 , R 7 , and R 8 are all hydrocarbyl groups. The hydrocarbyl groups may be alkyl, cycloalkyl, aryl, acyclic, or mixtures thereof. 6 , R 7 , and R 8 In formulas having all three groups, the compound may be a trihydrocarbyl-substituted phosphite, i.e., R 6 , R 7 , and R 8 are all hydrocarbyl groups, which in some embodiments may be alkyl groups.

[0094] The alkyl group may be linear or branched, typically linear, and saturated or unsaturated, typically saturated. 6 , R 7 , and R8 Examples of alkyl groups for include octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl, or mixtures thereof. In some embodiments, the overall fatty phosphite component lubricant composition is essentially free, or even completely free, of phosphoric acid esters and / or amine salts thereof. In some embodiments, the fatty phosphite comprises an alkenyl phosphite or an ester thereof, such as an ester of dimethyl hydrogen phosphite. The dimethyl hydrogen phosphite may be esterified, and in some embodiments, transesterified, by reaction with an alcohol, such as oleyl alcohol.

[0095] The lubricant may also contain one or more phosphate amine salts, but in amounts such that the additive package, or in other embodiments, the resulting industrial lubricant composition, contains no more than 1.0 wt. %, or even no more than 0.75 wt. % or 0.6 wt. % of such materials. In other embodiments, the industrial lubricant additive package, or the resulting industrial lubricant composition, is essentially free of, or even completely free of, phosphate amine salts.

[0096] The lubricant may also include one or more anti-wear and / or extreme pressure agents, one or more rust and / or corrosion inhibitors, one or more anti-foam agents, one or more demulsifiers, or any combination thereof.

[0097] In some embodiments, the industrial lubricant additive package, or the resulting industrial lubricant composition, is essentially free of, or even completely free of, phosphorus amine salts, dispersants, or both.

[0098] In some embodiments, the industrial lubricant additive package, or the resulting industrial 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 still other embodiments, the industrial additive package, or the resulting industrial lubricant composition, includes one or more sulfurized olefins or polysulfides; one or more phosphorus amine salts; one or more thiophosphate esters, one or more thiadiazoles, tolyltriazole, polyethers, and / or alkenylamines; one or more ester copolymers; one or more carboxylic acid esters; one or more succinimide dispersants, or any combination thereof.

[0099] The industrial lubricant additive package may be present in the total industrial lubricant from 1 wt.% to 5 wt.%, or in other embodiments from 1 wt.%, 1.5 wt.%, or even 2 wt.% up to 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 7 wt.%, or even 10 wt.%. The amount of industrial gear additive package that may be present in the industrial gear lubricant concentrate is the amount corresponding to the weight percents above, and these values ​​are considered in the absence of oil (i.e., they may be treated as weight percent values ​​together with the actual amount of oil present).

[0100] The lubricant may also include derivatives of hydroxycarboxylic acids. Suitable acids may contain 1 to 5 or 2 carboxy groups or 1 to 5 or 2 hydroxy groups. In some embodiments, the friction modifier may be a compound of the formula [ka] wherein a and b may independently be integers from 1 to 5 or 1 to 2; X may be an aliphatic or alicyclic group, or an aliphatic or alicyclic group containing an oxygen atom in the carbon chain, or a substituent of the type described above, which group contains up to 6 carbon atoms and has a+b available points of attachment; and each Y may independently be —O—, >NH, or >NR 3or two Y's together form an imide structure R formed between two carbonyl groups. 4 -N< represents nitrogen, and each R 3 and R 4 may independently be hydrogen or a hydrocarbyl group, provided that at least one R 1 and R 3 The groups may be hydrocarbyl groups, and each R 2 may independently be hydrogen, a hydrocarbyl group, or an acyl group, provided that at least one -OR 2 The group is -C(O)-YR 1 is located on a carbon atom within X that is α or β to at least one of the groups, provided that, in addition, at least one R 2 wherein R is hydrogen. The hydroxy-carboxylic acid can be reacted with an alcohol and / or an amine via a condensation reaction to form a derivative of the hydroxy-carboxylic acid, which may also be referred to herein as a friction modifying additive. In one embodiment, the hydroxy-carboxylic acid used in the preparation of the derivative of the hydroxy-carboxylic acid has the formula [ka] (In the formula, each R 5 may independently be H or a hydrocarbyl group, or R 5 The R groups are represented by the formula: 5 In one embodiment where is H, the condensation product is optionally further functionalized by acylation or reaction with a boron compound. In another embodiment, the friction modifier is not boronated. In any of the above embodiments, the hydroxy-carboxylic acid may be tartaric acid, citric acid, or a combination thereof, or a reactive equivalent of such an acid, including an ester, acid halide, or anhydride.

[0101] The resulting friction modifier may comprise an imide, di-ester, di-amide, or ester-amide derivative of tartaric acid or citric acid, or a mixture thereof. In one embodiment, the derivative of a hydroxycarboxylic acid comprises an imide, di-ester, di-amide, imide-amide, imide-ester, or ester-amide derivative of tartaric acid or citric acid. In one embodiment, the derivative of a hydroxycarboxylic acid comprises an imide, di-ester, di-amide, imide-amide, imide-ester, or ester-amide derivative of tartaric acid. In one embodiment, the derivative of a hydroxycarboxylic acid comprises an ester derivative of tartaric acid. In one embodiment, the derivative of a hydroxycarboxylic acid comprises an imide and / or amide derivative of tartaric acid. The amine used in preparing the friction modifier may have the formula RR'NH, where R and R' each independently represent H, a hydrocarbon-based radical of 1, 8 to 30, or 150 carbon atoms, i.e., 1 to 150, 8 to 30, 1 to 30, or 8 to 150 atoms. Amines having a range of carbon atoms, with lower limits of 2, 3, 4, 6, 10, or 12 carbon atoms and upper limits of 120, 80, 48, 24, 20, 18, or 16 carbon atoms, can also be used. In one embodiment, each of the groups R and R' has 8, 6, to 30, or 12 carbon atoms. In one embodiment, the total number of carbon atoms in R and R' is at least 8. R and R' can be linear or branched. Alcohols useful for preparing friction modifiers will similarly contain 1, 8, to 30, or 150 carbon atoms. Alcohols having a range of carbon atoms, with lower limits of 2, 3, 4, 6, 10, or 12 carbon atoms and upper limits of 120, 80, 48, 24, 20, 18, or 16 carbon atoms, can also be used. In certain embodiments, the number of carbon atoms in the alcohol-derived group can be 8 to 24, 10 to 18, 12 to 16, or 13 carbon atoms. The alcohols and amines may be linear or branched, and if branched, the branch may occur at any point in the chain and the branch may be of any length.In some embodiments, the alcohols and / or amines used include branched compounds; in still other embodiments, the alcohols and amines used are at least 50%, 75%, or even 80% branched. In other embodiments, the alcohols are linear. In some embodiments, the alcohols and / or amines have at least 6 carbon atoms. Accordingly, certain embodiments include products prepared from branched alcohols and / or amines of at least 6 carbon atoms, such as branched C6-18 or C8-18 alcohols or branched C12-16 alcohols, either as single materials or mixtures. Specific examples include 2-ethylhexanol and isotridecyl alcohol, the latter of which can represent a commercial-grade mixture of various isomers. Also, certain embodiments include products prepared from linear alcohols of at least 6 carbon atoms, such as linear C6-18 or C8-18 alcohols or linear C12-16 alcohols, either as single materials or mixtures. The tartaric acid used to prepare the tartrates, tartolimides, or tartramides is a commercially available type (available from Sargent Welch) and often exists in one or more isomers, such as d-tartaric acid, l-tartaric acid, d,l-tartaric acid, or meso-tartaric acid, depending on the source (natural) or method of synthesis (e.g., from maleic acid). These derivatives can also be prepared from functional equivalents of the diacid, such as esters, acid chlorides, or anhydrides, readily apparent to those skilled in the art.

[0102] In some embodiments, the additive package includes one or more corrosion inhibitors, one or more dispersants, one or more antiwear and / or extreme pressure additives, one or more extreme pressure agents, one or more antifoam agents, one or more detergents, and optionally an amount of base oil or similar solvent as a diluent.

[0103] The additional additives may be present in the overall industrial gear lubricant composition from 0.1 wt.% to 30 wt.%, or from minimum levels of 0.1 wt.%, 1 wt.%, or 2 wt.% to maximum levels of 30 wt.%, 20 wt.%, 10 wt.%, 5 wt.%, or even 2 wt.%, or from 0.1 wt.% to 30 wt.%, 0.1 wt.% to 20 wt.%, 1 wt.% to 20 wt.%, 1 wt.% to 10 wt.%, 1 wt.% to 5 wt.%, or even about 2 wt.%. These ranges and limits may apply to each individual additional additive present in the composition, or to all of the additional additives present.

[0104] Industrial gear lubricants include 0.01% to 5% by weight of a phosamine salt; may include 0.0001 wt. % to 0.15 wt. % of the disclosed corrosion inhibitors, used alone or in combination with 2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole, tolyltriazole, or mixtures thereof; an oil of lubricating viscosity; 0.02% to 3% by weight of an antioxidant selected from an aminic or phenolic antioxidant, or a mixture thereof; 0.005% to 1.5% by weight of a boronated succinimide or a non-boronated succinimide; 0.001% to 1.5% by weight of a neutral or slightly overbased calcium naphthalene sulfonate (typically a neutral or slightly overbased calcium dinonyl naphthalene sulfonate); and 0.001% to 2%, or 0.01% to 1%, by weight of an antiwear agent selected from zinc dialkyldithiophosphate, zinc dialkylphosphate, amine salts of phosphoric acid or esters, or mixtures thereof.

[0105] The industrial gear lubricant may also include the formulation defined in the table below. [Table A]

[0106] The antiwear performance of each lubricant may be evaluated according to ASTM D2782-02(2008) Standard Test Method for Measuring Extreme Pressure Properties of Lubricating Fluids (Timken Method), ASTM D2783-03(2009) Standard Test Method for Measuring Extreme Pressure Properties of Lubricating Fluids (Four-Ball Method), ASTM D4172-94(2010) Standard Test Method for Antiwear Properties of Lubricating Fluids (Four-Ball Method), and ASTM D5182-97(2014) Standard Test Method for Evaluating the Scuffing Resistance of Oils (FZG Visual Method).

[0107] Hydraulic lubricants are 0.01% to 3% by weight of phosamine salt may include 0.0001 wt. % to 0.15 wt. % of the disclosed corrosion inhibitors, used alone or in combination with 2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole, tolyltriazole, or mixtures thereof; an oil of lubricating viscosity; 0.02% to 3% by weight of an antioxidant selected from an aminic or phenolic antioxidant, or a mixture thereof; 0.005% to 1.5% by weight of a boronated succinimide or a non-boronated succinimide; 0.001% to 1.5% by weight of a neutral, slightly overbased calcium naphthalene sulfonate (typically, a neutral or slightly overbased calcium dinonyl naphthalene sulfonate); and 0.001% to 2%, or 0.01% to 1%, by weight of an antiwear agent (other than the proton salt of the present invention) selected from zinc dialkyldithiophosphate, zinc dialkylphosphate, amine salts of phosphoric acid or esters, or mixtures thereof.

[0108] The hydraulic lubricant may also include the formulation defined in the table below. [Table B]

[0109] The anti-wear performance of each lubricant was evaluated according to ASTM D6973-08e1, Standard Test Method for Depicting the Wear Characteristics of Petroleum Hydraulic Fluids in High-Pressure, Constant-Displacement Vane Pumps. Anti-wear performance was also evaluated using a standard Falex Block-on-Ring Wear and Friction Tester. In this test, a standard test block was modified to accommodate a portion of an actual 35VQ pump vane. The vane was in contact with a standard Falex ring, and a load was applied to the stationary vane, causing the ring to rotate. The screen test was performed under the same load, slide speed, and oil temperature conditions as the standard 35VQ pump test. The mass of the test vane and ring was measured before and after the test. Performance was determined by the total mass loss measured.

[0110] grease In one embodiment, the lubricant may be used in a grease. The grease may have a composition including an oil of lubricating viscosity, a grease thickener, and the corrosion inhibitor composition disclosed herein.

[0111] In one embodiment, the grease can also be a sulfonate grease. Such greases are known in the art. In another embodiment, the sulfonate grease can be a calcium sulfonate grease prepared by overbasing a neutral calcium sulfonate to form amorphous calcium carbonate, which is subsequently converted to calcite or vaterite or a mixture thereof.

[0112] The grease thickener may be any grease thickener known in the art. Suitable grease thickeners include, but are not limited to, metal salts of carboxylic acids, metal soap grease thickeners, mixed alkali soaps, complex soaps, non-soap grease thickeners, metal salts of such acid-functionalized oils, polyurea and diurea grease thickeners, or calcium sulfonate grease thickeners. Other suitable grease thickeners include polymeric thickeners such as polytetrafluoroethylene, polystyrene, and olefin polymers. Inorganic grease thickeners may also be used. Exemplary inorganic thickeners include clay, organoclay, silica, calcium carbonate, carbon black, pigments, or copper phthalocyanine. Additional thickeners include urea derivatives such as polyurea or diurea. Specific examples of greases include those summarized in the following table: [Table C]

[0113] To demonstrate improved performance in grease compositions, the compositions may be evaluated against controls in accordance with ASTM D1743 Standard Test Method for Determining the Corrosion Inhibitory Properties of Lubricating Greases, ASTM D5969-11e: Standard Test Method for the Corrosion Inhibitory Properties of Lubricating Greases in the Presence of a Dilute Synthetic Seawater Environment, and ASTM D6138-13: Standard Test Method for the Determination of the Corrosion Inhibitory Properties of Lubricating Greases under Wet Dynamic Conditions (Emcor Test).

[0114] The amounts disclosed in the table above are calculated based on the active ingredient and exclude any oils or volatile diluents that may be present with the metal detergent and / or carboxylic acid. That is, one way in which the present technology can be used is by preparing an initial mixture of the components described herein without the optional volatile diluent present, or with only a small amount present, such as up to 10 weight percent, 5 weight percent, 2 weight percent, 1 weight percent, or 0.1 weight percent of the composition. Thus, the amounts of other components can be expressed as a percentage of the composition excluding the amount of optional volatile diluent. It is in this form (without volatile diluent or solvent) that the materials of the disclosed technology are often commercially prepared and distributed. However, because diluent-free materials may have a viscosity that is inappropriate for easy handling, it may be desirable to add a volatile diluent before applying the composition to a substrate as a coating. If a diluent is present during coating application, the actual amounts of the other components can be calculated to take into account the presence of the diluent.

[0115] *****The amount of each chemical component listed is exclusive of any solvent or diluent oil that may normally be present in commercially available materials, i.e., on an active chemical basis, unless otherwise indicated. However, unless otherwise indicated, each chemical or composition referred to herein should be construed as a commercial material, which may contain isomers, by-products, derivatives, and other materials normally understood to be present in articles of commerce.

[0116] *****It is known that some of the above materials may interact in the final formulation, and thus the components of the final formulation may differ from those originally added. For example, metal ions (e.g., of detergents) may migrate to other acidic or anionic sites on other molecules. The products formed thereby, including those formed by using the compositions of the present invention in their intended use, may not be easily described. Nevertheless, all such modifications and reaction products are within the scope of the present invention, and the present invention includes compositions prepared by mixing the above components.

[0117] The invention herein is useful for preventing corrosion of metal objects, which can be better understood with reference to the following examples. [Example]

[0118] The disclosed compositions can be prepared by mixing a metal detergent with at least one carboxylic acid, and the weight ratio of metal detergent a) to acid b) can range from 50:1 to 1:10, or 25:1 to 1:10, or 10:1 to 1:10, or 5:1 to 1:7, or 2:1 to 1:3. In some embodiments, the disclosed compositions can include a) a calcium sulfonate detergent and b) an acid mixture including alkylbenzene sulfonic acid, C36 dimer carboxylic acid, and oleic acid. The weight ratio of alkylbenzene sulfonic acid to carboxylic acid can range from 7:1 to 10:1. Polycarboxylic acids (e.g., C 36 The ratio of polycarboxylic acid to monocarboxylic acid (e.g., dimeric carboxylic acid) can range from 1:3 to 1:0 to 3:1. In yet other embodiments, the ratio of polycarboxylic acid to monocarboxylic acid can range from 2.5:1 to 3:1.

[0119] Various compositions were prepared and tested for performance. The general preparation of the examples is as follows: Diluent oil and overbased calcium sulfonate are charged to a reactor and heated to 50±5°C with stirring. To this heated mixture, alkylbenzene sulfonic acid is added in portions over 30-60 minutes to control foaming. The carboxylic acid is then charged and the temperature is increased to 130±5°C. The mixture is stirred at elevated temperature under a slow gas purge until no more water is collected (typically 3-4 hours). The material is then cooled to below 100°C and filtered through a suitable filter medium.

[0120] To prepare and coat compositions and test for salt spray performance, dilute the examples to the desired concentration (5-20%) with the desired diluent (e.g., mineral spirits or naphthenic oil) and stir to homogenize the fluid. Gentle heating (40-50°C) may be necessary to fully dilute viscous materials. Place the test diluent in a shallow dish. Immerse a steel panel in the test diluent for 60 seconds, then hang it in ambient air for 24 hours to dry. Typical thicknesses for dip coatings are 1-4 microns.

[0121] The immersed panels are then subjected to a salt spray test as described in ASTM B117. Time to failure is the time at which rust is visible on at least 5% of the treated surface as described in ASTM D610. Two numbers are given per sample, the first being the last time to pass and the second being the first time to failure. Multiple entries represent multiple runs. [Table 1-2] [Table 2a] [Table 2b] [Table 2c]

[0122] The above examples demonstrate that the disclosed compositions have good salt spray performance, although that performance may vary depending on the solvent / diluent oil used. The preforms of Examples 3 and 4 are readily soluble and have good salt spray performance in both mineral spirits and naphthenic oil diluents. Examples 3 and 4 are also readily soluble in Group I and Group II base oils. Each of the documents referenced above is incorporated herein by reference, including any prior application to which priority is claimed, whether specifically listed above or not. The mention of any document is not an admission that such document qualifies as prior art in any jurisdiction or constitutes general knowledge of those skilled in the art. Except in the examples, or where otherwise expressly indicated, all quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, etc., are to be understood as modified by the word "about." It is to be understood that the upper and lower limits of amounts, ranges, and ratios set forth herein may be independently combined. Similarly, the ranges and amounts of each element of the present invention may be used in conjunction with ranges or amounts of any other element.

[0123] Example 3 above was also used to prepare hydraulic and industrial gear oil lubricants. [Table 3a] [Table 3b-1] [Table 4a] [Table 3b-2]

[0124] As used herein, the transitional phrase "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. However, within each recitation of "comprising" herein, the term may, as an alternative embodiment, be used to refer to "consisting essentially of." The phrases "of" and "consisting of" are also intended to encompass the phrases "of" and "consisting of," where "consisting of" excludes any unspecified element or step, and "consisting essentially of" allows for the inclusion of additional unrecited elements or steps that do not materially affect the basic and novel characteristics of the composition or method under consideration.

[0125] While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, 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 invention. In this regard, the scope of the present invention is intended to be limited only by the claims that follow. The present invention provides, for example, the following items. (Item 1) 1. A composition comprising: a) a metal detergent, wherein the metal comprises at least one alkali metal, alkaline earth metal, or combination thereof; b) an acid comprising at least one hydrocarbyl-substituted carboxylic acid; A composition wherein the weight ratio of a) the metal detergent to b) the acid is in the range of 50:1 to 1:10, or 25:1 to 1:10, or 10:1 to 1:10, or 5:1 to 1:7, or 2:1 to 1:3. (Item 2) 2. The composition of claim 1, wherein the metal detergent comprises at least one phenate, salicylate, salixarate, sulfonate, or combination thereof. (Item 3) 3. The composition of claim 1 or 2, wherein the metal detergent is a metal overbased detergent. (Item 4) Item 10. The composition of any one of the preceding items, wherein the metal comprises calcium, sodium, barium, magnesium, or a combination thereof. (Item 5) Item 10. The composition of any one of the preceding items, wherein the acid further comprises at least one hydrocarbyl-substituted organic sulfonic acid. (Item 6) 6. The composition according to item 5, wherein the weight ratio of the at least one organic sulfonic acid to the at least one carboxylic acid is in the range of 15:1 to 3:1. (Item 7) 7. The composition of claim 5 or 6, wherein the hydrocarbyl-substituted organic sulfonic acid is a mono- or di-substituted alkyl sulfonic acid, such as a naphthalene sulfonic acid, an alkyl benzene sulfonic acid, or a combination thereof. (Item 8) The at least one carboxylic acid is at least one C8 to C 36 Item 10. The composition of any one of the preceding items, comprising a hydrocarbyl-substituted polycarboxylic acid. (Item 9) The acid comprises at least two carboxylic acids, at least one of which is a C to C 36 The composition of any one of the preceding items, which is a hydrocarbyl-substituted polycarboxylic acid. (Item 10) 10. The composition according to item 9, wherein at least one of the carboxylic acids is a monocarboxylic acid, and the weight ratio of the polycarboxylic acid to the monocarboxylic acid is in the range of 10:1 to 1:1, or 3:1. (Item 11) The monocarboxylic acid is a linear or branched C8 to C6 3611. The composition of claim 10, which is a hydrocarbyl-substituted monocarboxylic acid. (Item 12) The monocarboxylic acid is a saturated or unsaturated C8-C 36 12. The composition of claim 11, which is a hydrocarbyl-substituted monocarboxylic acid. (Item 13) The monocarboxylic acid is a linear unsaturated C8, C 10 , C 12 , or C 14 ~C 36 , or C 10 ~C 18 Item 13. The composition of item 12, which is a hydrocarbyl-substituted monocarboxylic acid. (Item 14) 14. The composition according to any one of items 8 to 13, wherein the polycarboxylic acid has at least 4 (and up to 18) carbon atoms separating the acid functional groups. (Item 15) Item 10. The composition of any one of the preceding items, wherein the at least one carboxylic acid comprises a hydroxyalkyl carboxylic acid ester. (Item 16) 16. The composition according to any one of items 8 to 15, wherein the at least one polycarboxylic acid is a dicarboxylic acid, a tricarboxylic acid, or a mixture thereof. (Item 17) The dicarboxylic acid is C 36 Item 17. The composition according to item 16, which is a dicarboxylic acid. (Item 18) The tricarboxylic acid is C 21 18. The composition according to item 16 or 17, which is a tricarboxylic acid. (Item 19) The dicarboxylic acid is C 36 dicarboxylic acid, and the monocarboxylic acid is a linear unsaturated C 14 ~C 18 19. The composition according to any one of items 16 to 18, which is a hydrocarbyl-substituted monocarboxylic acid. (Item 20) 20. A coating composition comprising the composition of any one of items 1 to 19, a solvent (e.g., mineral spirits or naphtha), an oil (e.g., Group I or Group II paraffinic oil), or a mixture thereof. (Item 21) 20. A lubricant composition comprising the composition of any one of items 1 to 19 and an oil of lubricating viscosity. (Item 22) 22. The lubricant composition of claim 21, wherein the lubricant composition is an industrial gear oil, hydraulic fluid, or grease. (Item 23) 23. A method for reducing corrosion of a metal part, comprising contacting the metal part with the composition according to any one of items 1 to 22. (Item 24) 26. Use of a composition according to any one of compositions 1 to 22 for reducing corrosion of metal parts.

Claims

[Claim 1] The invention described in the present specification.

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