Hybrid lubricating grease prepared from anhydrous metal soap and high-alkalinity metal detergent and preparation method of hybrid lubricating grease

Abstract

Greases suitable for high temperature applications and are more cost-effective substitutes for lithium greases. Lubricating grease is prepared from: an oil of lubricating viscosity; 1.0 wt% to 22.5 wt% of an overbased metal detergent; 5.0 wt% to 18.5 wt% of a metal carboxylate soap component, the metal carboxylate soap component being a reaction product of a metal hydroxide and / or a metal carbonate and a fatty acid; 0.2% to 8.0% by weight of an oxygenate accelerator (e.g., an alcohol and / or an organic acid); and 1% to 15% by weight of water. The grease has a drop point of at least 220 DEG C as measured using ASTM D2265.

Description

Technical Field

[0001] The disclosed technology generally relates to greases prepared from a mixture of metal carboxylate soaps and highly alkaline metal detergents, and methods for preparing the same. Background Technology

[0002] To ensure lubrication performance at high temperatures, it is important to consider the heat resistance of greases. One method to obtain an indication of the heat resistance of a grease is to measure its dropping point. As defined in ASTM D2265, the dropping point is a numerical value assigned to a grease composition, representing the corrected temperature at which the first drop of material falls from the test cup and reaches the bottom of the test tube. At temperatures above 200°C, the dropping point test is used as a quality control tool to ensure that the thickener system has been properly prepared. Hydrated calcium soaps or cup greases are the lowest cost of any grease thickener. However, due to their low dropping points, they are generally limited to applications with a maximum temperature of around 80°C. Anhydrous calcium soaps, made from slaked lime and 12-hydroxystearic acid, typically have dropping points ranging from 150°C to 160°C and are also relatively low-cost and easy to use as a grease thickener.

[0003] However, most specifications for multi-purpose commercial greases require a dropping point higher than 175°C. Conventional (anhydrous) lithium 12-hydroxystearate soap is commonly used in multi-purpose applications because its dropping point is approximately 200°C. The dropping point of both lithium 12-hydroxystearate soap and calcium 12-hydroxystearate soap, or anhydrous grease types, can be increased by adding borate / ester-containing additives such as borate esters. Conventional lithium 12-hydroxystearate grease treated with complexing agents such as boron-containing additives will have a dropping point of approximately 260°C, while anhydrous calcium grease will typically have a dropping point of only approximately 180°C.

[0004] In recent years, highly alkaline metal detergent greases, typically based on highly alkaline calcium sulfonate, have become more prevalent in industrial applications. These greases can function up to approximately 160°C and have dropping points above 300°C. These greases typically come with a significant cost premium, costing 50% more than commercial lithium greases and 30% more than thermally stabilized lithium greases with boron-containing additives.

[0005] However, due to increased demand for lithium batteries in the electronics and electric vehicle markets, the price of lithium hydroxide has risen significantly, pushing the cost of lithium greases to levels unacceptable to the global grease market. Therefore, a more cost-effective alternative to commercially available lithium greases is needed. Summary of the Invention

[0006] Therefore, the disclosed technology provides a more cost-effective alternative to lithium greases with improved temperature stability in high-temperature applications. These greases are prepared using a combination of metal carboxylate soaps and highly alkaline metal detergents, and have a higher dropping point than greases made with anhydrous calcium soap and performance comparable to greases thickened with 12-hydroxystearate lithium soap.

[0007] Therefore, a grease prepared from the following is disclosed: an oil having a lubricating viscosity; 1.0 wt% to 22.5 wt% of a highly alkaline metal detergent dissolved in a liquid diluent; 5 wt% to 18.5 wt% (or 9.0 wt% to 18.5 wt%) of a metal carboxylate soap component, which is a reaction product of metal hydroxide and / or metal carbonate with fatty acid; 0.2 wt% to 8.0 wt% (or 0.2 wt% to 5 wt%) of an oxygen-containing compound promoter (e.g., alcohol and / or organic acid); and 1 wt% to 15 wt% of water.

[0008] In some embodiments, the high-alkalinity metal detergent may be present in the range of 5% to 15% by weight, or 10% to 15% by weight, based on the total yield of the grease. The high-alkalinity metal detergent may have a total base number (TBN) of 150 mg KOH / g equivalent to 500 mg KOH / g equivalent (or 200 mg KOH / g equivalent to 500 mg KOH / g equivalent, 300 mg KOH / g equivalent to 400 mg KOH / g equivalent, or 400 mg KOH / g equivalent). In some embodiments, the dissolved high-alkalinity metal detergent contains no more than 75% by weight (or no more than 70% by weight, 60% by weight, or 55% by weight) of a liquid diluent. Suitable high-alkalinity metal detergents include high-alkalinity metal sulfonates, salicylates, naphthenates, phenolates, or oleates, or mixtures thereof. These highly alkaline metal detergents can be prepared from at least one highly alkaline alkali metal or alkaline earth metal salt (e.g., sodium, calcium, magnesium, barium, lithium, potassium, or mixtures thereof). In some embodiments, the highly alkaline metal detergent is a highly alkaline calcium sulfonate detergent, which optionally has 400 mg KOH / g equivalent TBN.

[0009] The metal carboxylate soap can be a reaction product of 0.5% to 2.1% (or 1.5% by weight) of a metal hydroxide and 5% to 16% (or 11.3% by weight) of a fatty acid, wherein the metal hydroxide includes at least one alkali metal or alkaline earth metal hydroxide (e.g., sodium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, lithium hydroxide, potassium hydroxide, or mixtures thereof). In some embodiments, the metal hydroxide is calcium hydroxide. The fatty acid may include at least one of oleic acid, stearic acid (e.g., 12-hydroxystearic acid), ricinoleic acid, or combinations thereof.

[0010] Oxygen-containing compound promoters used in the preparation of lubricating greases can be organic acids and / or alcohols. Suitable organic acids include, but are not limited to, acetic acid, succinic acid, phosphoric acid, aminosulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, alkylbenzenesulfonic acid, or combinations thereof. Suitable alcohols include, but are not limited to, methanol, isopropanol, 2-methoxyethanol, propylene glycol (which may be a mixture of 1,2-propanediol and 1,3-propanediol), dipropylene glycol, butanol, pentanol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 2-methoxyethanol, diethylene glycol monobutyl ether, 1,2-hexanediol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 2,5-dimethyl-2,5-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, triethylene glycol methyl ether, 3-methyl-1,3-butanediol, 1,2-pentanediol, 2-butoxyethanol, or combinations thereof.

[0011] Oils with lubricating viscosity include at least one paraffin oil, naphthenic oil, polyalphaolefin, liquid ethylene oxide / propylene oxide copolymer, polyalkylene glycol, seed oil, vegetable oil, ester, or mixture thereof. In some embodiments, the oil with lubricating viscosity may include at least one API Group I, II, III, IV, or V oil, or ATIEL Group VI oil, or mixture thereof. In other embodiments, the oil with lubricating viscosity may be an API Group II oil.

[0012] In some embodiments, the grease may contain at least one additive to improve one or more of the grease's performance characteristics. The additive may include, but is not limited to, anti-wear agents, friction modifiers, extreme pressure agents, corrosion inhibitors, antioxidants, viscosity modifiers, thickeners, or mixtures thereof.

[0013] The resulting grease may be a hybrid grease comprising both anhydrous metal soap and a highly alkaline metal detergent. A method for preparing the hybrid grease is also disclosed. The method may include preparing the hybrid grease in two steps (steps (I) and (II)). Step (I) may include the following steps: mixing (i) an oil having a lubricating viscosity; (ii) 0.5% to 2.1% (or 1.5% by weight) of a metal hydroxide and / or a metal carbonate; and (iii) 5% to 16% (or 11.3% by weight) of a fatty acid and (iv) 1% to 15% by weight of water to form an anhydrous grease. The mixture of step (I) may be mixed at 70°C to 90°C and heated for 1 to 2 hours until it is saponified and forms an anhydrous grease.

[0014] For step (II), the resulting anhydrous grease can then be mixed with (i) 1% to 22.5% (or 12% by weight) of a highly alkaline metal detergent dissolved in a liquid diluent, (ii) 0.2% to 5.0% by weight of an oxygen-containing compound accelerator (e.g., alcohols and / or organic acids), and (iii) 1% to 15% by weight of water to form a hybrid grease. The mixture of step (II) can be mixed at 70°C to 95°C for 1 to 2 hours. The resulting hybrid grease of step (II) can have a thickness ranging from 850 cm⁻¹. -1 Up to 900cm -1 Or 870cm -1 Up to 890cm -1 The FTIR peak. The dropping point of hybrid greases can be greater than 220°C, 250°C or 300°C, as measured using dropping point tests (e.g. ASTM D2265, ISO 2176 or IP 396). Detailed Implementation

[0015] This article discloses novel greases prepared using a combination of metal carboxylate soaps and highly alkaline metal detergents. These greases have higher dropping points than greases prepared using anhydrous metal soaps. Various preferred features and embodiments are described below by way of non-limiting description.

[0016] The grease can be prepared from the following: an oil having a lubricating viscosity; 1.0 wt% to 22.5 wt% of a highly alkaline metal detergent; 5.0 wt% to 18.5 wt% (or 9.0 wt% to 18.5 wt%) of a metal carboxylate soap component, which is a reaction product of metal hydroxides and / or metal carbonates with fatty acids; 0.2 wt% to 8.0 wt% (or 0.2 wt% to 5 wt%, or 0.5 wt% to 5.0 wt%) of an oxygen-containing compound accelerator (e.g., alcohols and / or organic acids); and 1 wt% to 15 wt% of water.

[0017] Highly alkaline metal detergents

[0018] Greases can be prepared using any highly basic metal detergent known in the art. Highly basic metal detergents are also referred to as highly basic detergents, metal-containing highly basic detergents, or superbasic salts, characterized by a metal content exceeding the amount necessary for a neutralization reaction according to the stoichiometry of the metal, and a specific acidic organic compound (i.e., the substrate) reacting with the metal. Highly basic detergents may include one or more of the following: sulfur-free phenolates, sulfur-containing phenolates, sulfonates, salicylates, and mixtures thereof. Alternatively, highly basic metal detergents may include at least one highly basic metal sulfonate, salicylate, naphthenate, or oleate detergent, or mixtures thereof.

[0019] The amount of excess metal is usually expressed as a substrate-to-metal ratio. The term "metal ratio" is used in the prior art and herein to define the ratio of the total stoichiometric amount of a metal in a highly basic salt to the stoichiometric amount of a metal in the salt, which is expected to be obtained from the reaction between a hydrocarbon-substituted organic acid, a hydrocarbon-substituted phenol, or a mixture thereof to be over-alkaliened, and an alkali metal compound, based on the known chemical reactivity and stoichiometry of the two reactants. Thus, in ordinary or neutral salts (i.e., soaps), the metal ratio is one, and in highly basic salts, the metal ratio is greater than one, particularly greater than 1.3. The metal ratio of highly basic detergents can be from 5 to 30, or from 7 to 22, or at least 11.

[0020] Metal-containing detergents may also comprise "hybrid" detergents formed from a mixed surfactant system containing phenolate and / or sulfonate components, such as phenolate-salicylate, sulfonate-phenolate, sulfonate-salicylate, and sulfonate-phenolate-salicylate. In the case of, for example, the use of a hybrid sulfonate / phenolate detergent, the hybrid detergent will be considered equivalent to the amounts of different phenolate and sulfonate detergents respectively introduced in similar amounts of phenolate and sulfonate soaps.

[0021] Highly alkaline detergents are characterized by their Total Base Number (TBN), the amount of strong acid required to neutralize the alkalinity of all substances, expressed in mg KOH / g sample. TBN is a well-known parameter described in ASTM D4739. Since the highly alkaline detergents used herein are typically supplied in forms containing liquid diluents, for the purposes of this document, the TBN will be recalculated on an oil-free basis. Various detergents may have TBNs of 100 to 1000, or 150 to 800, or 400 to 700. Detergents may have TBNs of at least 640, for example 650 to 1000, or even 680 to 800. In each case, the unit is mg KOH / g equivalent. Highly alkaline phenolates and salicylates typically have a Total Base Number of 180 to 450. Highly alkaline sulfonates typically have a Total Base Number of 250 to 600, or 300 to 500.

[0022] Alkylphenols are commonly used as components in and / or as structural units in highly alkaline detergents. Alkylphenols can be used to prepare phenolates, salicylates, salicyl alcohols, or salicin detergents, or mixtures thereof. Suitable alkylphenols may include para-substituted hydrocarbon phenols. The hydrocarbon group can be a straight-chain or branched aliphatic group having 1 to 60 carbon atoms, 8 to 40 carbon atoms, 10 to 24 carbon atoms, 12 to 20 carbon atoms, or 16 to 24 carbon atoms.

[0023] Highly alkaline metal-containing detergents can be alkali metal salts or alkaline earth metal salts. In one embodiment, the highly alkaline detergent can be a sodium, calcium, magnesium, barium, lithium salt, or mixture thereof of phenolates, sulfur-containing phenolates, sulfonates, salicylates, salicylates, naphthalene, naphthalate, or oleate, or mixtures thereof. In one embodiment, the highly alkaline detergent is a calcium detergent, a magnesium detergent, or a mixture thereof. In one embodiment, the highly alkaline detergent is sodium-free or substantially sodium-free.

[0024] Salicylate detergents and highly basic salicylate detergents can be prepared in at least two different ways. In a first way, a highly basic salicylate detergent can be prepared by carbonylation (also known as carboxylation) of an alkylphenol followed by over-alkalization. Suitable alkylphenols include those with straight-chain and / or branched hydrocarbon groups having 1 to 60 carbon atoms. Salicylate detergents can also be prepared by alkylation of salicylic acid followed by over-alkalization. Salicylate detergents prepared in this way can be prepared from straight-chain and / or branched alkylating agents (typically 1-olefins) containing 6 to 50 carbon atoms, 10 to 30 carbon atoms, or 14 to 24 carbon atoms.

[0025] In one embodiment, the highly alkaline metal-containing detergent may primarily be a linear alkylbenzene sulfonate detergent with a metal ratio of at least 8. The linear alkyl group may be attached to the benzene ring at any position along the straight chain of the alkyl group (but typically at the 2, 3, or 4 position of the straight chain, and in some cases, primarily at the 2 position), resulting in a linear alkylbenzene sulfonate detergent.

[0026] Therefore, in some embodiments, the high-alkalinity metal detergent may have a total base number (TBN) of 150 mg KOH / g equivalent to 500 mg KOH / g equivalent (or 200 mg KOH / g equivalent to 500 mg KOH / g equivalent, 300 mg KOH / g equivalent to 400 mg KOH / g equivalent, or 400 mg KOH / g equivalent). Suitable high-alkalinity metal detergents include high-alkalinity metal sulfonates, salicylates, naphthenates, phenolates, or oleates, or mixtures thereof. These high-alkalinity metal detergents may be prepared from at least one high-alkalinity alkali metal or alkaline earth metal salt (e.g., sodium, calcium, magnesium, barium, lithium, potassium, or mixtures thereof). In some embodiments, the high-alkalinity metal detergent is a high-alkalinity calcium sulfonate detergent, which optionally has a TBN of 400 mg KOH / g equivalent. In some implementations, the high-alkaline metal detergent may be present in the range of 1% to 22.5% by weight, or 5% to 15% by weight or 12% by weight, based on the total amount of grease produced.

[0027] Dissolved high-alkalinity metal detergents can be dissolved in a liquid diluent. The liquid diluent is not excessively limited and includes those known in the art. The liquid diluent can be selected based on the substrate type, the over-alkalization process, or even the intended end use of the high-alkalinity detergent. Suitable liquid diluents include mineral oils (including food-grade white oil) and polyalphaolefins. For the greases disclosed herein, the dissolved high-alkalinity metal detergent contains no more than 75% by weight (or no more than 70% by weight, 60% by weight, or 55% by weight) of liquid diluent. In some embodiments, the dissolved high-alkalinity metal detergent contains 30% to 40% by weight of liquid diluent, which is mineral oil. The diluent oil can be of ISO viscosity grade (VG) 22 to 32. Oils with lubricating viscosity can also be used as diluent oils, having a kinematic viscosity in the range of ISO VG 46 to ISO VG 150.

[0028] Metal carboxylate soaps

[0029] Metal carboxylate soaps can be the product of the reaction of a metal hydroxide with a fatty acid, wherein the metal hydroxide includes at least one alkali metal or alkaline earth metal hydroxide (e.g., sodium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, lithium hydroxide, potassium hydroxide, or mixtures thereof). In some embodiments, the metal hydroxide is calcium hydroxide. The fatty acid may include at least one of oleic acid, stearic acid (e.g., 12-hydroxystearic acid), ricinoleic acid, or combinations thereof. Based on the total yield of the grease, the metal carboxylate soap may be present in amounts of 5.0% to 18.5% by weight, or 9% to 18.5% by weight, or 12% to 13% by weight.

[0030] Oxygen-containing compound accelerator

[0031] Oxygen-containing compound accelerators can be used to reduce conversion time and promote grease formation. Suitable oxygen-containing compound accelerators are not excessively limited and include any accelerators known in the art, such as water, alcohols, acids, or mixtures thereof. Therefore, in some embodiments, the oxygen-containing compound accelerator used to prepare the grease can be an organic acid and / or an alcohol. Suitable organic acids include, but are not limited to, acetic acid, succinic acid, phosphoric acid, aminosulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, alkylbenzenesulfonic acid, or combinations thereof. In one embodiment, the alkylbenzenesulfonic acid can be C9 to C9. 12 Or C 10 -C 13 Or C9-C 16Alkylbenzenesulfonic acid. Suitable alcohols include, but are not limited to, methanol, isopropanol, 2-methoxyethanol, propylene glycol (which may be a mixture of 1,2-propanediol and 1,3-propanediol), dipropylene glycol, butanol, pentanol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 2-methoxyethanol, diethylene glycol monobutyl ether, 1,2-hexanediol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 2,5-dimethyl-2,5-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, triethylene glycol methyl ether, 3-methyl-1,3-butanediol, 1,2-pentanediol, 2-butoxyethanol, or combinations thereof. Based on the total yield of the grease, the oxygen-containing compound accelerator may be present at 0.2% to 5% by weight, or 0.2% to 5% by weight, or 0.5% to 2.5% by weight.

[0032] Oil with lubricating viscosity

[0033] One component of a grease composition is an oil having a lubricating viscosity. These include natural and synthetic oils with lubricating viscosities, oils derived from hydrocracking, hydrogenation, and hydrorefining, as well as unrefined, refined, and refined oils and mixtures thereof.

[0034] Natural oils include animal oils, vegetable oils, mineral oils, and mixtures thereof. Synthetic oils include hydrocarbon oils, silicon-based oils, and phosphoric acid-containing liquid esters. Synthetic oils can be prepared via the Fischer-Tropsch gas-to-oil synthesis process and other gas-to-oil processes. In one embodiment, the compositions of the present invention are useful when used in gas-to-oil processes. Typically, Fischer-Tropsch hydrocarbons or waxes can be hydroisomerized. In one embodiment, the base oil comprises a polyalphaolefin, including PAO-2, PAO-4, PAO-5, PAO-6, PAO-7, or PAO-8. In one embodiment, the polyalphaolefin can be prepared from octene, decene, dodecene, or mixtures thereof. Other suitable polyalphaolefins are metallocene polyalphaolefins. In one embodiment, the oil having a lubricating viscosity comprises an ester, such as an adipate ester.

[0035] Oils with lubricating viscosity can also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.

[0036]

[0037] Group I, II, and III are mineral oil base feedstocks. Other generally recognized categories of base oils may be used, even if not formally classified by the American Petroleum Institute (API): Group II+ refers to Group II substances with a viscosity index of 110 to 119 and lower volatility than other Group II oils; and Group III+ refers to Group III substances with a viscosity index greater than or equal to 130. Oils with lubricating viscosity may include natural or synthetic oils and mixtures thereof. Mixtures of mineral and synthetic oils, such as polyalphaolefin oils and / or polyester oils, may be used.

[0038] Oils with lubricating viscosity can also be defined as specified in the Technical Association of the European Lubricants Industry (ATIEL) Base Oil Interchangeability Guidelines. The ATIEL guidelines include polyolefin base oil categories, namely ATIEL Category VI.

[0039] Therefore, in some embodiments, the oil having lubricating viscosity may include at least one paraffin oil, naphthenic oil, liquid ethylene oxide / propylene oxide copolymer, polyalphaolefin, polyalkylene glycol, seed oil, vegetable oil, ester, or mixture thereof. In some embodiments, the oil having lubricating viscosity may include at least one API Group I, II, III, IV, or V oil, or ATIEL Group VI oil, or mixture thereof. In another embodiment, the oil having lubricating viscosity is a Group II base oil, which may include polybutene and / or polyisobutylene to increase viscosity and improve adhesion and water treatment performance.

[0040] The amount of oil with lubricating viscosity present is typically the balance remaining after subtracting the sum of the amounts of other components disclosed herein for preparing the grease (including any of the performance additives described below) from 100% by weight. Generally, the oil with lubricating viscosity may be present at least 50% by weight based on the total weight of the grease composition. In some embodiments, the grease is present at 50% to 90% by weight, or 60% to 80% by weight, or 65% to 75% by weight based on the total weight of the grease composition.

[0041] Additional performance additives

[0042] In some embodiments, the grease may contain at least one additive to improve one or more of the grease's performance characteristics. Additives may include, but are not limited to, anti-wear agents, friction modifiers, extreme pressure agents, corrosion inhibitors, antioxidants, viscosity modifiers, thickeners, or mixtures thereof. These additives can help improve the wear or friction properties of the grease. Some additives, such as antioxidants, can help improve the stability of the grease and / or reduce its reactivity to other materials in the environment. The grease may also contain corrosion inhibitors to help inhibit corrosion of the metals it contacts.

[0043] Typically, anti-wear agents can be phosphorus-based anti-wear agents. The anti-wear agent may be present in 0% to 5% by weight, 0.001% to 2% by weight, or 0.1% to 2.0% by weight of the grease. Phosphorus-based anti-wear agents may comprise phosphamine salts, calcium salts, or mixtures thereof. Phosphamine salts include amine salts of phosphites or mixtures thereof. Amino salts of phosphate esters include phosphate esters and their amine salts; dialkyl dithiophosphate esters and their amine salts; phosphites; and amine salts containing phosphocarboxylic esters, ethers, and amides; hydroxyl-substituted diesters or triesters of phosphoric acid or thiophosphate and their amine salts; phosphorylated hydroxyl-substituted diesters or triesters of phosphoric acid or thiophosphate and their amine salts; and mixtures thereof. In one embodiment, the oil-soluble phosphamine salt comprises a partially amine salt-partially metal salt compound or a mixture thereof. In one embodiment, the phosphorus compound further comprises a sulfur atom in the molecule. In another embodiment, the phosphorus compound is a calcium derivative.

[0044] Other examples of anti-wear agents may include nonionic phosphorus compounds (typically compounds having phosphorus atoms in an oxidation state of +3 or +5). In one embodiment, the amine salt of the phosphorus compound may be ashless, i.e., metal-free (before being mixed with other components).

[0045] In one embodiment, the anti-wear additive may include zinc dialkyl dithiophosphate. In other embodiments, the grease is substantially free of zinc dialkyl dithiophosphate or even completely free of zinc dialkyl dithiophosphate. In yet another embodiment, the grease includes a dithiocarbamate anti-wear agent as defined in column 2, lines 35 through 6, lines 11 of U.S. Patent 4,758,362. When present, the dithiocarbamate anti-wear agent may be present in an amount from 0.25 wt%, 0.3 wt%, 0.4 wt%, or even 0.5 wt% to a maximum of 3.0 wt%, 2.5 wt%, 2.0 wt%, or even 0.55 wt% throughout the composition.

[0046] In some embodiments, the grease may contain one or more extreme pressure agents. Suitable extreme pressure agents include organic sulfides. In one embodiment, the organic sulfide includes at least one of a polysulfide, a thiadiazole compound, or a mixture thereof. The extreme pressure agent may be present in the range of 0% to 10% by weight, 0.01% to 10% by weight, 0.1% to 8% by weight, 0.25% to 6% by weight, 2% to 5% by weight, or 3% to 5% by weight of the grease.

[0047] Examples of thiadiazoles include 2,5-dimercapto-1,3,4-thiadiazole or oligomers thereof, alkyl-substituted 2,5-dimercapto-1,3,4-thiadiazoles, alkyl-sulfur-substituted 2,5-dimercapto-1,3,4-thiadiazoles or oligomers thereof. Oligomers of alkyl-substituted 2,5-dimercapto-1,3,4-thiadiazoles typically form oligomers of two or more of the thiadiazole units by forming sulfur-sulfur bonds between the 2,5-dimercapto-1,3,4-thiadiazole units. Other examples of thiadiazole compounds can be found in WO 2008 / 094759, paragraphs 0088 to 0090.

[0048] The organosulfur compound may alternatively be a polysulfide. In one embodiment, at least about 50% by weight of the polysulfide molecules is a mixture of trisulfides or tetrasulfides. In other embodiments, at least about 55% by weight, or at least about 60% by weight, of the polysulfide molecules is a mixture of trisulfides or tetrasulfides. The polysulfide includes vulcanized organosulfur polysulfides derived from oils, fatty acids or esters, olefins, or polyolefins.

[0049] Oils that can be vulcanized include natural or synthetic oils, such as mineral oils, lard, carboxylic acid esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (e.g., myristate oleate and oleyl oleate), and synthetic unsaturated esters or glycerides.

[0050] 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. Sulfated fatty acid esters are prepared from a mixture of unsaturated fatty acid esters, such as those obtained from animal fats and vegetable oils (including tall oil, flaxseed oil, soybean oil, rapeseed oil, and fish oil).

[0051] Polysulfides can also be derived from olefins, which are derived from a wide range of alkenes (typically having one or more double bonds). In one embodiment, the olefin contains 3 to 30 carbon atoms. In other embodiments, the olefin contains 3 to 16 or 3 to 9 carbon atoms. In one embodiment, the sulfurized olefin includes olefins derived from propylene, isobutylene, pentene, or mixtures thereof. In one embodiment, the polysulfide includes polyolefins derived from polyolefins polymerized using known techniques. In one embodiment, the polysulfide includes dibutyltetrasulfide, methyl sulfide of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized dicyclopentadiene, sulfurized terpenes, and sulfurized Diels-Alder adducts; phosphorus sulfurized hydrocarbons.

[0052] Friction modifiers include fatty amines, boronized glyceryl esters, fatty acid amides, boron-free fatty epoxides, boronized fatty epoxides, alkoxylated fatty amines, boronized alkoxylated fatty amines, metal salts of fatty acids, fatty imidazolines, metal alkyl salicylates (which may also be referred to as detergents), metal sulfonates (which may also be referred to as detergents), condensation products of carboxylic acids or polyalkylene polyamines, or amides of hydroxyalkyl compounds. In one embodiment, the friction modifier includes a fatty acid ester of glycerol. The fatty acid may contain 6 to 24 or 8 to 18 carbon atoms. In one embodiment, the friction modifier may include a product of isostearic acid and tetraethylenepentamine. A more detailed list of possible friction modifiers is given in WO 2008 / 094759, paragraphs 0100 to 0113. Friction modifiers may be present in amounts of 0% to 7% by weight, 0.1% to 6% by weight, 0.25% to 5% by weight, or 0.5% to 5% by weight of the grease.

[0053] In some embodiments, the grease may contain at least one metal deactivator (commonly referred to as a corrosion inhibitor). The metal deactivator may include one or more of the following: 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, 2-alkyldithio-5-mercaptothiadiazole, or mixtures thereof.

[0054] The benzotriazole compound may contain a hydrocarbon group substituted at one or more of the following ring positions: 1-, 2-, 4-, 5-, 6-, or 7-benzotriazole. The hydrocarbon group may contain 1 to 30 carbons, and in one embodiment, 1 to 15 carbons, and in another embodiment, 1 to 7 carbons. The metal deactivator may include 5-methylbenzotriazole. The metal deactivator may be present in the grease composition at a concentration of up to 5% by weight, or from 0.0002% by weight to 2% by weight, or from 0.001% by weight to 1% by weight.

[0055] In some embodiments, the grease may contain at least one rust inhibitor (commonly referred to as a corrosion inhibitor). The rust inhibitor may include one or more metal sulfonates (such as calcium sulfonate, magnesium sulfonate, or barium sulfonate), amine salts of carboxylic acids (such as octylamine octanoate), dodecylenyl succinic acid or anhydride and a condensation product of fatty acids (such as oleic acid) and polyamines (such as polyalkylene polyamines, such as triethylenetetramine), or a half-ester of alkenyl succinic acid (wherein the alkenyl group contains 8 to 24 carbon atoms) and an alcohol (such as polyethylene glycol).

[0056] The rust inhibitor may be present in the grease composition at a concentration of up to 4% by weight, and in one embodiment the concentration ranges from 0.02% by weight to 2% by weight, and in another embodiment the concentration ranges from 0.05% by weight to 1% by weight.

[0057] In one embodiment, the grease composition comprises an antioxidant or a mixture thereof. The antioxidant may be present in 0% to 15% by weight, or 0.1% to 10% by weight, or 0.5% to 5% by weight, or 0.5% to 3% by weight, or 0.3% to 1.5% by weight of the grease composition. The antioxidant includes diarylamines alkylated with diarylamines, hindered phenols, dithiocarbamates, 1,2-dihydro-2,2,4-trimethylquinoline, hydroxy sulfides, or mixtures thereof.

[0058] Alkylated diarylamines can be phenyl-α-naphthylamine (PANA), alkylated diphenylamine, or alkylated phenylnaphthylamine, or mixtures thereof. Alkylated diphenylamines can include dinonylated diphenylamine, nonyldiphenylamine (such as Lubrizol), etc. ™ GR9510), octyl diphenylamine, dioctylated diphenylamine, or dedecylated diphenylamine. Alkylated diarylamines may include octyl, dioctyl, nonyl, dinonyl, decyl, or dedecylphenylnaphthylamine. In one embodiment, the alkylated diphenylamine may include at least one of octylated diphenylamine, butylated diphenylamine, or mixtures thereof, such as Irganox from BASF. ™ L57.

[0059] Hindered phenolic antioxidants often contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenolic group can typically be further replaced by a hydrocarbon group (usually a straight-chain or branched alkyl group) and / or a bridging group connected to a second aromatic group. The bridging atom can be carbon or sulfur. Examples of suitable hindered phenolic antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenolic antioxidant can be an ester and may include, for example, Irganox from BASF. ™ L135. A more detailed description of suitable ester-containing hindered phenolic antioxidant chemistry is found in U.S. Patent 6,559,105.

[0060] Dithiocarbamate antioxidants can be metal-containing, such as molybdenum dithiocarbamate or zinc dithiocarbamate, or they can be "ashless." Ashless means that the dithiocarbamate does not contain metal, and the linking group is usually methylene. 1,2-Dihydro-2,2,4-trimethylquinoline can exist in a unique molecular form or as an oligomer of up to five repeating units, and it is commercially known as "Resin D" or simply "RD," and is available from many suppliers.

[0061] Suitable viscosity modifiers may include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutylene, hydrogenated styrene-isoprene polymers, styrene / maleate copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, α-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrene, hydrogenated alkenylaryl conjugated diene copolymers, and mixtures thereof. Viscosity modifiers may include star polymers, for example, as described in U.S. Publication No. 2012 / 0101017 A1.

[0062] The grease composition may additionally or alternatively contain one or more dispersant viscosity modifiers. Suitable dispersant viscosity modifiers include functionalized polyolefins, such as ethylene-propylene copolymers functionalized with the reaction product of an acylation agent (such as maleic anhydride) and an amine; amine-functionalized polymethacrylates; esterified maleic anhydride-styrene copolymers reacted with amines; and mixtures thereof.

[0063] When present, one or more viscosity modifiers total at least 0.01% by weight, or at least 0.1% by weight, or at least 0.5% by weight, or at most 10% by weight, or at most 5% by weight, or at most 3% by weight of the grease composition.

[0064] The tackifier can be polybutene and / or polyisobutylene with a number average molecular weight of 2000 to 4000. Examples of commercially available tackifiers and their chemical types may include the following: polyisobutylene (such as Indopol from Ineos). ™ Or Parapol from ExxonMobil ™ ); olefin copolymers (such as Lubrizol from Lubrizol) ™ 7065c and 7067c, as well as Lucant from Mitsui. ™ HC-2000L, HC-1000, and HC-600); hydrogenated styrene-isoprene copolymers (such as Shellvis from Infineum). ™ 40 and 50, as well as Lubrizol from Lubrizol. ™ 7306 and 7308); styrene / butadiene copolymers, such as Lubrizol from Lubrizol. ™ (7408A); concentrations of 0.2% to 3% by weight based on the total weight of the grease composition may also be used.

[0065] A method for preparing a grease is also disclosed. The grease preparation method can be carried out in an open or closed vessel typically used for grease manufacturing, or in a pressurized reactor. The method can be performed at standard atmospheric pressure, although it can be carried out under pressure in a closed pressurized reactor or autoclave. In one embodiment, the method is carried out in an open vessel. Post-treatment of the grease may include one or more steps of grinding, filtering, adding performance additives, and packaging the grease, and is carried out in a manner known to a person skilled in the art of grease manufacturing.

[0066] The method may include preparing a hybrid grease in two steps (steps (I) and (II)). Step (I) may include the following steps: mixing (i) an oil having a lubricating viscosity; (ii) 0.5 wt% (or 1 wt% to 2.1 wt%, or 1.5 wt%) of a metal hydroxide and / or metal carbonate; (iii) 5 wt% to 16 wt% (or 8 wt% to 16 wt%, or 11.3 wt%) of a fatty acid and (iv) 1 wt% to 15 wt% (or 2 wt% to 5 wt%) of water to form an anhydrous grease. The mixture of step (I) may be mixed at 70°C to 90°C and heated for 1 to 2 hours until it is saponified and forms an anhydrous grease. Fourier transform infrared spectroscopy (“FTIR”) may be used to determine the conversion of the mixture to an anhydrous grease. When the conversion occurs, the grease should have at least one 1540 cm⁻¹ value. -1 Up to 1600cm -1 The FTIR spectral peaks between.

[0067] For step (II), the resulting anhydrous calcium grease can then be mixed with (i) 1% to 22.5% (or 12% by weight) of a highly alkaline metal detergent, (ii) 0.2% to 8.0% (or 0.5% to 5% by weight) of an oxygen-containing compound accelerator (e.g., alcohols and / or organic acids), and (iii) 1% to 15% (or 2% to 5% by weight) of water to form a hybrid grease. The mixture of step (II) can be mixed at 70°C to 95°C for 1 to 2 hours. The resulting hybrid grease of step (II) can have a thickness ranging from 850 cm⁻¹. -1 Up to 900cm -1 Or 870cm -1 Up to 890cm -1 The FTIR peak. The dropping point of hybrid greases can be greater than 220°C, 250°C or 300°C, as measured using dropping point tests (e.g. ASTM D2265, ISO 2176 or IP 396).

[0068] The water used in both steps (I) and (II) helps to promote the reaction of the various components. If excess water is used, it can be evaporated in step (II) or as part of the finishing process. In some embodiments, the water used in both steps (I) and (II) ranges from 2% to 5% by weight, and any excess water is evaporated in step (II) or as part of the finishing process.

[0069] In one embodiment, the grease may be prepared from 54% to 90% by weight of base oil (e.g., Group II base oil), 1% to 2.1% by weight of metal hydroxide (e.g., calcium hydroxide), 8% to 16% by weight of fatty acid (e.g., 12-hydroxystearic acid), 1% to 15% by weight of water, 1% to 22.5% by weight of highly basic metal detergent (e.g., highly basic calcium sulfonate detergent), 0.2% to 2.5% by weight of an oxygenated compound accelerator of an alcohol (e.g., 2-ethyl-1,3-hexanediol), and 0.5% to 2.5% by weight of an oxygenated compound accelerator of an acid (e.g., alkylbenzenesulfonic acid). In another embodiment, the grease may be prepared from 72.8 wt% base oil (e.g., Group II base oil), 1.5 wt% metal hydroxide (e.g., calcium hydroxide), 11.3 wt% fatty acid (e.g., 12-hydroxystearic acid), 8 wt% water, 12 wt% highly basic metal detergent (e.g., highly basic calcium sulfonate detergent), 1.1 wt% an oxygenated compound accelerator of an alcohol (e.g., 2-ethyl-1,3-hexanediol), and 1.3 wt% an oxygenated compound accelerator of an acid (e.g., alkylbenzenesulfonic acid). Further details regarding the preparation of the grease can be found in the NLGI Lubricating Grease Guide.

[0070] As used herein, the term "hydrocarbon group" refers to a group having carbon atoms directly attached to the remainder of the molecule, wherein the group comprises at least carbon and hydrogen atoms. If the hydrocarbon group contains more than one carbon atom, these carbons do not necessarily have to be connected to each other. For example, at least two carbons may be connected via suitable elements or groups. In various embodiments, the term "hydrocarbon group" refers to a group having carbon atoms directly attached to the remainder of the molecule, wherein the group consists of carbon, hydrogen, and optionally one or more heteroatoms, provided that the heteroatom does not alter the predominantly hydrocarbon nature of the substituent. The heteroatom may connect at least two carbons and optionally no more than two non-hydrocarbon substituents in the hydrocarbon group. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen, oxygen, phosphorus, and silicon.

[0071] When the hydrocarbon group contains heteroatoms, optionally, no more than two heteroatoms will be present for every ten carbon atoms in the hydrocarbon group. Suitable non-hydrocarbon substituents will also be apparent to those skilled in the art, and include, for example, halogens, hydroxyl groups, alkoxy groups, mercapto groups, alkyl mercapto groups, nitro groups, nitroso groups, and thiooxy groups.

[0072] Therefore, examples of hydrocarbon groups in the context of this technology include: Hydrocarbon groups, selected from aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl, cyclodienyl) and aromatic groups; The substituted hydrocarbon group is selected from the hydrocarbon group defined in (i) that is substituted by no more than two non-hydrocarbon substituents and / or one or more hydrocarbon substituents, wherein the non-hydrocarbon substituents are selected from the group consisting of: halogen, hydroxyl, alkoxy, mercapto, alkyl mercapto, nitro, nitroso and thiooxy. A hydrocarbon group containing heteroatoms is selected from hydrocarbon groups defined in (i) that contain one or more heteroatoms in a ring or chain, provided that no more than two heteroatoms are present for every ten carbon atoms in the group, and the heteroatoms are selected from sulfur, nitrogen, oxygen, phosphorus, and silicon. A hydrocarbon group containing heteroatoms may be substituted by no more than two non-hydrocarbon substituents and / or one or more hydrocarbon substituents.

[0073] In some implementations, the term "hydrocarbon group" refers to a group having carbon atoms directly attached to the rest of the molecule, wherein the group consists of carbon and hydrogen atoms.

[0074] Unless otherwise stated, the amounts of each chemical component described do not include any solvents or diluents that are commonly found in commercial substances, i.e., based on active chemicals. However, unless otherwise stated, each chemical or composition mentioned herein should be interpreted as a commercial-grade substance that may contain isomers, byproducts, derivatives, and other such substances generally understood to be present in commercial-grade forms.

[0075] It is known that some of the substances described above can interact in the final formulation, such that the composition of the final formulation may differ from those initially added. For example, metal ions (e.g., metal ions in detergents) can migrate to other acidic or anionic sites of other molecules. The resulting products, including those formed when the compositions of the present invention are used for their intended purpose, may not be easily described. However, all such modifications and reaction products are included within the scope of the present invention; the present invention includes compositions prepared by mixing the aforementioned components.

[0076] The grease preparation method disclosed herein produces grease compositions having a dropping point of at least 220°C, or at least 250°C, and in some cases at least 300°C, which makes these greases particularly suitable for higher temperature applications, and can be better understood with reference to the following examples.

[0077] Example

[0078] Example A: Preparation of anhydrous calcium grease

[0079] For Example A, 75% by weight of Group II base oil, 1.25% by weight of calcium hydroxide, 3% by weight of water, and 8.4% by weight of 12-hydroxystearic acid were added to a reaction vessel and mixed at room temperature for 30 minutes. The temperature was slowly raised to 70°C and maintained at this temperature for 1 hour with stirring. The temperature was then slowly raised again to approximately 120°C (not exceeding 125°C) and maintained at this temperature for 1 hour with stirring. The heating of the vessel was then turned off, and the remaining oil (14.35% by weight) was slowly added to the grease in the vessel. Post-treatment was performed while the grease was still hot.

[0080] Example B: Preparation of conventional (anhydrous) lithium grease

[0081] For Example B, 43 wt% of Group II base oil and 12.2 wt% of 12-hydroxystearic acid were added to the reaction vessel and mixed while heating to 90°C. An additional 43 wt% of Group II base oil was reserved. In a separate vessel, 1.8 wt% of lithium hydroxide monohydrate and five times the amount of water were heated to near boiling. Once the contents of the first reactor reached 90°C, the lithium hydroxide solution was slowly added to the first reactor. The temperature of the reaction vessel was then slowly increased to 205°C, and some of the reserved base oil was added as needed. Once the contents of the reaction vessel reached 205°C, the heating of the vessel was turned off, but mixing continued. Once the grease was below 190°C, any remaining reserved Group II base oil was slowly added. Post-treatment was performed while the grease was hot.

[0082] Example C, Preparation of anhydrous 50 / 50 calcium / lithium mixed grease

[0083] For Example C, the anhydrous mixed grease was prepared from 50 wt% calcium soap and 50 wt% lithium soap. Approximately 44 wt% of Group II base oil and 10.15 wt% of 12-hydroxystearic acid were added to a reaction vessel and mixed while heating to 80°C. An additional 44 wt% of Group II base oil was stored. Once the acid dissolved, 0.74 wt% of lithium hydroxide monohydrate, 0.64 wt% of calcium hydroxide, and 2.6 wt% of water were added to the reaction vessel. The reactor temperature was then slowly raised to 150°C and maintained at this temperature for 1 hour while mixing. The stored Group II base oil was slowly added and the mixture was cooled to 80°C. Post-treatment was performed while the grease was hot.

[0084] Example D: Preparation of anhydrous 75 / 25 calcium / lithium mixed grease

[0085] For Example D, the same process as in Example C was used, except that the anhydrous mixed grease was prepared using 75% by weight calcium soap and 25% by weight lithium soap.

[0086] Example E: Preparation of anhydrous 25 / 75 calcium / lithium mixed grease

[0087] For Example E, the same process as in Example C was used, except that the anhydrous mixed grease was prepared using 25% by weight calcium soap and 75% by weight lithium soap.

[0088] Example F (of the present invention): Preparation of anhydrous / complex hybrid grease

[0089] For Example F, 60 wt% (600 g) of Group II base oil, 1.25 wt% (12.5 g) of calcium hydroxide, 9.4 wt% (94 g) of 12-hydroxystearic acid, and 2 wt% (20 g) of water were added to the reactor and mixed while heating to 70°C and maintained for 1.5 hours. The conversion was checked using FTIR. At 1540 cm⁻¹... -1 and 1580cm -1 A peak should be present nearby. Then, add 0.99 wt% (9.9 g) 2-ethyl-1,3-hexanediol, 12.0 wt% (120 g) highly basic calcium sulfonate (400 TBN), and 3 wt% (30 g) water. Then slowly add 1.3 wt% (13 g) dodecylbenzenesulfonic acid and raise the temperature to 90°C. Maintain at 90°C and check the grease conversion using FTIR. At 875 cm⁻¹ -1 A peak should be present nearby. Once the conversion is complete, slowly raise the temperature of the reaction vessel to 125°C and slowly add an additional 15.06% by weight (150.6 g) of Group II base oil. Then allow the grease to cool to 80°C. Perform post-treatment while the grease is still hot.

[0090] Example G (of the present invention): Preparation of anhydrous / complex hybrid grease

[0091] For Example G, an anhydrous mixed grease was prepared using the same process as in Example F above, except that 2.5% by weight of a high-performance multipurpose (“HPM”) additive package was added to the grease during post-treatment. The additive package contained a combination of an antioxidant as an alkylaryl amine, a zinc dialkyl dithiophosphate anti-wear additive, a zinc neodecanoate rust inhibitor, and a sulfurized olefin extreme pressure additive.

[0092] Example H (of the present invention): Preparation of anhydrous / complex hybrid grease

[0093] For Example H, 58.24 wt% of Group II base oil, 1.5 wt% of calcium hydroxide, 11.3 wt% of 12-hydroxystearic acid, and 2.96 wt% of water were added to a reaction vessel and mixed at room temperature for 30 minutes. The contents were continuously mixed and heated to 70°C and maintained at this temperature for 1 hour. The conversion was checked using FTIR. (The last sentence appears to be incomplete and possibly refers to a measurement at 1540 cm⁻¹.) -1 and 1580cm -1A peak should be present nearby. Once conversion is complete, add 1.1 wt% 2-ethyl-1,3-hexanediol, 12.0 wt% highly basic calcium sulfonate (400 TBN), and 5.84 wt% water and mix at 70°C for 30 minutes. Then slowly raise the temperature to 90°C and mix for 1.5 hours. Check the conversion again using FTIR. At 875 cm⁻¹ -1 A peak should be present nearby. Then, slowly raise the reactor temperature to 120°C and maintain it for 1 hour. Then, turn off the heating of the container and slowly add 14.56% by weight of Group II base oil, allowing the grease to cool to 80°C. Perform post-treatment while the grease is still hot.

[0094] The dropping point of the grease was measured using ASTM D2265. The results are shown in Table 1 below.

[0095] Table 1

[0096] As shown in Table 1, hybrid greases have a higher dropping point than anhydrous lithium greases, thus providing a more cost-effective alternative to lithium greases, suitable for both ambient and higher temperature applications.

[0097] application

[0098] The greases described herein have been found to be usable as high-performance multipurpose (HPM) greases and high-load-bearing (HPM + HL) greases, as defined by the NLGI. They have also been found to be suitable for applications requiring high temperatures and good load-bearing capacity, such as in ironmaking applications, heavy industrial machinery, mining, and food manufacturing.

[0099] Each of the foregoing references is incorporated herein by reference, including any prior application claiming priority thereto, whether or not specifically listed above. Any reference to any reference is not an admission that the reference conforms to the prior art or constitutes general knowledge of a person skilled in the art in any jurisdiction. Unless expressly stated in the examples or otherwise, all numerical quantities of matter, reaction conditions, molecular weight, number of carbon atoms, 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 quantities, ranges, and proportions described herein can be combined independently. Similarly, the ranges and quantities of each element of the invention can be used in conjunction with the ranges or quantities of any other element.

[0100] As used herein, the transitional term “comprising,” synonymous with “comprising,” “containing,” or “characterized in,” is inclusive or open-ended and does not exclude additional, unlisted elements or method steps. However, in every use of “comprising” herein, it is intended that the term also cover the phrases “consistently composed of” and “composed of” as alternative embodiments, wherein “composed of” excludes any elements or steps not specified, and “consistently composed of” allows for the inclusion of additional, undescribed elements or steps that do not materially affect the essential and novel characteristics of the composition or method under consideration.

[0101] While certain representative embodiments and details have been shown to illustrate the purpose of this 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 invention. In this regard, the scope of the invention is defined only by the following claims.

Claims

1. A lubricating grease, said lubricating grease being prepared from the following: I. Oils with lubricating viscosity; II. 1.0% to 22.5% by weight of highly alkaline metal detergent dissolved in a liquid diluent; III. 5.0% to 18.5% by weight (or 9% to 18.5% by weight) of a metal carboxylate soap component, wherein the metal carboxylate soap component is a reaction product of metal hydroxide and / or metal carbonate with fatty acid; IV. 0.2% to 8.0% by weight (or 0.2% to 5% by weight) of oxygen-containing compound accelerators (e.g., alcohols and / or organic acids); and V. 1% to 15% by weight of water.

2. The grease according to claim 1 or 2, wherein the dissolved highly alkaline metal detergent has a total base number (TBN) of 150 mg KOH / g equivalent to 500 mg KOH / g equivalent (or 200 mg KOH / g equivalent to 500 mg KOH / g equivalent, 300 mg KOH / g equivalent to 400 mg KOH / g equivalent or 400 mg KOH / g equivalent).

3. The grease according to claim 1 or 2, wherein the dissolved highly alkaline metal detergent contains no more than 75% by weight (or no more than 70% by weight, 60% by weight, or 55% by weight) of liquid diluent.

4. The grease according to any one of the preceding claims, wherein the dissolved highly alkaline metal detergent is present in the range of 5% to 15% by weight (or 10% to 15% by weight) based on the total production of the grease.

5. The grease according to any one of the preceding claims, wherein the high-alkalinity metal detergent is a high-alkalinity metal sulfonate, salicylate, naphthenate, phenolate, or oleate detergent or a mixture thereof.

6. The grease according to any one of the preceding claims, wherein the high-alkalinity metal detergent is prepared from at least one high-alkalinity alkali metal or alkaline earth metal salt, such as sodium salt, calcium salt, magnesium salt, barium salt, lithium salt, potassium salt, or mixtures thereof.

7. The grease according to any one of the preceding claims, wherein the highly alkaline metal detergent is a highly alkaline calcium sulfonate detergent, wherein the highly alkaline calcium sulfonate detergent optionally has 400 mg KOH / g equivalent TBN.

8. The grease according to any one of the preceding claims, wherein the metal carboxylate soap is a reaction product of 0.5% to 2.1% (or 1% to 2.1% (or 1.5% (or 1.5% (or 1.5% (or 1.5% (or 1.5% (or 1.5% ( or 1.5% ( or 1.5% ( or 1.5% ( or 1.5% ( or 1.5% ( or 1.5% ( or 1.5% ( ... 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5% 5 9. The grease according to any one of the preceding claims, wherein the metal hydroxide is calcium hydroxide.

10. The grease according to any one of the preceding claims, wherein the oxygen-containing compound accelerator comprises at least one organic acid, said organic acid being acetic acid, succinic acid, phosphoric acid, aminosulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, alkylbenzenesulfonic acid, or a combination thereof.

11. The grease according to any one of the preceding claims, wherein the oxygen-containing compound accelerator comprises at least one alcohol, said alcohol being methanol, isopropanol, 2-methoxyethanol, propylene glycol, dipropylene glycol, butanol, pentanol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 2-methoxyethanol, diethylene glycol monobutyl ether, 1,2-hexanediol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 2,5-dimethyl-2,5-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, triethylene glycol methyl ether, 3-methyl-1,3-butanediol, 1,2-pentanediol, 2-butoxyethanol, or combinations thereof.

12. The grease according to any one of the preceding claims, wherein the fatty acid comprises at least one of oleic acid, stearic acid (e.g., 12-hydroxystearic acid), ricinoleic acid, or combinations thereof.

13. The grease according to any one of the preceding claims, wherein the oil having a lubricating viscosity comprises at least one paraffin oil, naphthenic oil, polyalphaolefin, liquid ethylene oxide / propylene oxide copolymer, polyalkylene glycol, seed oil, vegetable oil, ester, or mixture thereof.

14. The grease according to any one of the preceding claims, wherein the oil having a lubricating viscosity comprises at least one API Group I, II, III, IV, V, or ATIEL Group VI oil or a mixture thereof.

15. The grease of claim 14, wherein the oil having a lubricating viscosity comprises API Group II oil.

16. The grease according to any one of the preceding claims, wherein the grease further comprises at least one additive, said additive being an anti-wear agent, a friction modifier, an extreme pressure agent, a corrosion inhibitor, an antioxidant, a viscosity modifier, a thickener, or a mixture thereof.

17. The grease according to any one of the preceding claims, wherein the grease is a hybrid grease.

18. A method for preparing a hybrid grease, the method comprising the following steps: I. Mix (i) an oil having a lubricating viscosity; (ii) 0.5% to 2.1% (or 1.5% by weight) of metal hydroxides and / or metal carbonates; and (iii) 5% to 16% (or 11.3% by weight) of fatty acids; and (iv) 1% to 15% (or 2% to 8% by weight) of water to form an anhydrous grease; II. To the anhydrous grease, (i) 1% to 22.5% (or 12%) of a highly alkaline metal detergent dissolved in a liquid diluent; (ii) 0.2% to 8.0% (or 0.5% to 5%) of an oxygen-containing compound accelerator (e.g., alcohols and / or organic acids); and (iii) 1% to 15% (or 2% to 8%) of water are mixed to form the hybrid grease.

19. The method according to claim 18, wherein the mixture of step (I) is mixed at 70°C to 90°C and heated for 1 hour to 2 hours.

20. The method according to claim 18 or 19, wherein the anhydrous grease in step (I) has a density between 1540 cm⁻¹. -1 Up to 1600cm -1 At least one FTIR spectral peak between.

21. The method according to any one of claims 18 to 20, wherein the mixture of step (II) is mixed at 70°C to 95°C and heated for 1 hour to 2 hours.

22. The method according to any one of claims 18 to 21, wherein the hybrid grease in step II has a range of 850 cm. -1 Up to 900cm -1 (or 870cm) -1 Up to 890cm -1 At least one FTIR spectral peak of ).

23. The hybrid grease according to any one of claims 17 to 22, wherein the hybrid grease has a dropping point greater than 220°C (or 250°C, or 300°C), as measured using a dropping point test (e.g., ASTM D2265, ISO 2176, or IP 396).

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