Polymeric surfactants for improved emulsion and flow properties at low temperatures

Abstract

Described herein is a polymeric surfactant for improving the emulsion properties of engine oils of lubricating compositions mixed with water and / or fuel contamination, particularly at extremely cold temperatures. In the method, the selected polymeric and functionalized compounds can impart robust emulsion properties to lubricating compositions that may contain residual amounts of water and / or fuel contamination, while providing good low temperature fluidity. Lubricating compositions including such surfactants exhibit robust properties at temperatures as low as about ‑30°C.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 064,777, filed on August 12, 2020, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure relates to polymeric surfactants and lubricants including such surfactants that provide improved emulsion and flow properties at low temperatures, such as temperatures as low as about -30°C. Background Art

[0004] Under certain operating conditions, water and fuel may accumulate in lubricating compositions, such as lubricants in engine oil sumps. In cold ambient conditions, this residual contamination may pose a challenge to efficient engine operation. For example, a frozen water phase or an emulsion of oil, water and fuel with high viscosity may reduce the proper lubricity of the engine and, in some extreme cases, cause engine damage. Problems may arise because frozen or high viscosity lubricating fluids may prevent the engine oil pump from drawing oil through the oil pick-up line.

[0005] Residual fuel and / or water may accumulate in the engine oil of many modern passenger vehicles, typically during normal engine operation. One exemplary mechanism by which water may accumulate in the crankcase is if the driving pattern is such that the crankcase does not heat to 100°C during engine operation, so that any water present may not boil and evaporate. This undesirable contamination, while rare, may be further exacerbated in cold or extremely cold operating conditions, and / or when frequent start / stop cycles accumulate without bringing the engine to normal operating temperatures at which any residual water and / or fuel would leave the sump by evaporation.

[0006] Another exemplary mechanism of water pollution can be when the fuel contains alcohol, such as ethanol. Common fuel blended with ethanol is E85, which is a blend of 85 volume % ethanol and 15 volume % gasoline. Although ethanol can easily dissolve water, when the solubility limit in ethanol is reached, water will separate from the blend of gasoline and ethanol. The amount of water required for this phase separation varies with temperature. This water-ethanol phase may compete with the blended oil for combining with metal engine parts. As a result, the engine will not be able to obtain enough lubrication, which may cause engine damage. Therefore, maintaining the emulsion stability of alcohol-gasoline mixed fuel and lubricating oil composition is a primary issue.

[0007] This problem may also be particularly challenging in the operation of hybrid vehicles or vehicles that have an automatic engine stop feature when the vehicle is stationary. As these types of vehicles become more important, it can be expected that the incidence of water and / or fuel contamination of the fuel sump may also become more prevalent.

[0008] When engine oil, water and fuel are mixed, they can generate an emulsion phase. If the emulsion is homogeneous and stable, it can still provide lubrication for engine operation. However, if the emulsion is not stable, it will separate from the water at the bottom of the sump into an aqueous phase and an oil phase. When only water is pumped into the engine, the water cannot provide sufficient lubrication for engine operation and may cause engine problems. In addition, if the car is stored in an environment with extremely low temperatures, the aqueous phase or emulsion may freeze or become viscous, and starting the car in such a situation may cause the risk of engine damage due to insufficient oil. Summary of the invention

[0009] In one method or embodiment, described herein is a polymeric surfactant for improving the properties of engine oil emulsions in oil:water:fuel systems, particularly at very low temperatures.

[0010] In the method, the polymeric and functionalized compounds are selected to impart both robust emulsion properties and good low temperature fluidity to lubricating compositions that may contain residual amounts of water and / or fuel contamination. Lubricating compositions including such surfactants exhibit robust properties at temperatures as low as about -30°C.

[0011] In other methods or embodiments, low temperature stable lubricating compositions are described herein. The compositions include a base oil of lubricating viscosity; a polymeric surfactant having a non-polar portion and a polar functional group that is effective in maintaining a fluid emulsion, as evidenced by a flow point of about 75% or less measured at a lubricant temperature as low as about -30°C; and water and / or fuel contamination. The flow point is further discussed in the examples below and is the shear strain where G' (storage modulus) is equal to G" (loss modulus).

[0012] In other embodiments, the polymer surfactant or lubricating composition described in any of the first three paragraphs may also include one or more optional features in any combination. These optional features may include: wherein the polymer surfactant is a copolymer obtained from a reactant having ethylenic unsaturation, the reactant being functionalized by grafting polar groups or by incorporating polar co-reactants in the polymerization; and / or wherein the polymer surfactant is a copolymer obtained from a reactant including an alkyl (meth)acrylate and a heterocyclic reactant having a polymerizable ethylenically unsaturated substituent; and / or wherein the heterocyclic reactant having a polymerizable ethylenically unsaturated substituent includes vinyl lactone, vinyl lactam, combinations thereof, and derivatives thereof; and / or wherein the heterocyclic reactant having a polymerizable ethylenically unsaturated substituent includes vinyl pyrrolidone, vinyl pyridine, combinations thereof, and derivatives thereof; and / or wherein the alkyl (meth)acrylate reactant includes a reactant selected from C1 to C20 linear or branched alkyl (meth)acrylate reactants; and / or wherein the weight average molecular weight of the polymer surfactant is about 40,000 or greater; and / or wherein the polymer surface and / or wherein the lubricating composition comprises from about 0.01 to about 3 weight percent of the polymeric surfactant, preferably less than about 1 weight percent, and more preferably less than about 0.5 weight percent of the polymeric surfactant; and / or wherein the fuel is gasoline; and / or wherein the polar functional groups are pendant to the non-polar polymer backbone; and / or wherein the polar functional groups of the polymeric surfactant comprise one or more of oxygen, nitrogen, sulfur or phosphorus atoms; and / or wherein the lubricating composition is emulsified with water and the fuel to form a fluid emulsion at a temperature as low as about -30°C; and / or wherein the lubricating composition is an engine oil; and / or wherein the lubricating composition is a passenger car motor oil; and / or wherein the fuel is selected from the group consisting of gasoline, alcohol-based fuels and fuels blended with alcohol; and / or wherein the fuel is gasoline blended with ethanol; and / or wherein the fuel is selected from the group consisting of E10, E50, E85 and E100 fuels.

[0013] In another method or embodiment, provided herein is the use of any embodiment of the above polymeric surfactant (having any of the optional features noted above) to provide a flowable lubricating composition emulsified with water and / or fuel at a temperature of up to about -30°C.

[0014] In another method or embodiment, a method of lubricating an engine at low temperatures is described herein. In the method, the method includes providing the lubricating composition of any of the preceding embodiments of the preceding paragraphs of the present disclosure, and lubricating the engine with the lubricating composition at a temperature of up to about -30°C.

[0015] In an embodiment, the method may include adding to the lubricating composition an additive including a polymeric surfactant having a non-polar portion and a polar functional group effective to maintain a fluid emulsion when the lubricating composition is mixed with water and / or fuel contamination, as evidenced by a flow point of about 75% or less measured at a lubricant temperature as low as about -30°C; and / or wherein the polymeric surfactant is described in any of the preceding paragraphs of the present disclosure.

[0016] The following definitions of terms are provided to clarify the meaning of certain terms as used herein.

[0017] The terms "oil composition", "lubricating composition", "lubricating oil composition", "lubricating oil", "lubricant composition", "lubricating composition", "fully formulated lubricant composition", "lubricant", "crankcase oil", "crankcase lubricant", "engine oil", "engine lubricant", "motor oil" and "motor lubricant" are considered to be fully interchangeable synonymous terms referring to a finished lubricating product comprising a major base oil and a minor additive composition.

[0018] As used herein, the terms "additive package," "additive concentrate," "additive composition," "engine oil additive package," "engine oil additive concentrate," "crankcase additive package," "crankcase additive concentrate," "motor oil additive package," "motor oil concentrate" are considered to be fully interchangeable synonymous terms, all referring to the portion of the lubricating oil composition that does not include the bulk base oil stock blend. The additive package may or may not include a viscosity index improver or a pour point depressant.

[0019] As used herein, the term "fuel" may include diesel, biodiesel, gasoline (also referred to as petrol), alcohol-based fuels, fuels blended with alcohol, and mixtures thereof. Specifically, fuels blended with alcohol may include fuels blended with ethanol, such as gasoline. Common fuels blended with ethanol are E85, which is a blend of 85% by volume ethanol and 15% by volume gasoline. Other ethanol fuels may include, for example, 10% by volume ethanol (E10), 50% by volume ethanol (E50), and 100% by volume ethanol (E100). E85, gasoline, and diesel may be seasonally adjusted to ensure proper startup and performance in different geographic locations. For example, E85 sold in colder months typically contains only 70% by volume ethanol, and then 30% by volume petroleum additives to produce the required vapor pressure for startup at low temperatures. In warmer months, the petroleum additive content of E85 may typically be, for example, 17% by volume to about 20% by volume.

[0020] As used herein, "ethanol" means ethyl alcohol, i.e., compound C 2 H 5OH. This compound can occur or be provided in many qualities or grades, such as commercial fuel grade, as well as pure ethanol or reagent grade ethanol, and can be obtained from any source, such as, but not limited to, petroleum refinery streams, fractions, and bioderived (e.g., such as bioethanol from corn).

[0021] The term "overbased" relates to metal salts, such as metal salts of sulfonic acids, carboxylic acids, salicylates and / or phenols, in which the amount of metal present exceeds the stoichiometric amount. These salts may have a conversion level exceeding 100% (i.e., these salts may contain more than 100% of the theoretical amount of metal required to convert the acid into its "normal", "neutral" salt). The expression "metal ratio", usually abbreviated as MR, is used to specify the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is unity, while in overbased salts, MR is greater than unity. They are often referred to as overbased, superbased or ultrabasic salts, and may be salts of organic sulfuric acids, carboxylic acids, salicylates and / or phenols.

[0022] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl" is used in its ordinary sense, which is well known to those skilled in the art. Specifically, the term refers to a group having carbon atoms directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Each hydrocarbyl group is independently selected from a hydrocarbon substituent and a substituted hydrocarbon substituent containing one or more of the following: halo, hydroxy, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furanyl, imidazolyl, oxygen, and nitrogen, and wherein no more than two non-hydrocarbon substituents are present for every ten carbon atoms in the hydrocarbyl group.

[0023] As used herein, the term "alkylene substituent" or "alkylene group" is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group that is directly attached to the remainder of the molecule at two positions in the molecule through carbon atoms and has a predominantly hydrocarbon character. Each alkylene group is independently selected from divalent hydrocarbon substituents, and substituted divalent hydrocarbon substituents containing the following: halo, alkyl, aryl, alkaryl, aralkyl, hydroxy, alkoxy, mercapto, nitro, nitroso, amino, pyridyl, furyl, imidazolyl, oxygen and nitrogen, and wherein no more than two non-hydrocarbon substituents are present for every ten carbon atoms in the alkylene group.

[0024] Unless expressly stated otherwise, as used herein, the term "weight percent" means the percentage of the component by weight of the entire composition.

[0025] As used herein, the terms "soluble," "oil-soluble," or "dispersible" may, but do not necessarily, indicate that a compound or additive is soluble, dissolvable, miscible, or capable of being suspended in oil in all proportions. However, the foregoing terms do mean that it is, for example, soluble, suspendable, dissolvable, or stably dispersible in oil to an extent sufficient to exert its intended effect in the environment in which the oil is employed. Furthermore, the additional incorporation of other additives may also allow for the incorporation of higher levels of a particular additive, if desired.

[0026] As employed herein, the term "TBN" is used to denote the Total Base Number in mg KOH / g as measured by the method of ASTM D2896 or ASTM D4739 or DIN 51639-1.

[0027] As used herein, the term "alkyl" refers to a straight chain, branched chain, cyclic and / or substituted saturated chain moiety having from about 1 to about 100 carbon atoms.

[0028] As used herein, the term "alkenyl" refers to a straight chain, branched chain, cyclic and / or substituted unsaturated chain moiety having about 3 to about 10 carbon atoms.

[0029] As used herein, the term "aryl" refers to monocyclic and polycyclic aromatic compounds which may include alkyl, alkenyl, alkaryl, amino, hydroxy, alkoxy, halide substituents and / or heteroatoms including, but not limited to, nitrogen, oxygen, and sulfur.

[0030] The lubricant of this specification, the combination of components or individual components can be applied to various types of internal combustion engines. Suitable engine types may include but are not limited to heavy-duty diesel engines, passenger cars, light diesel engines, medium-speed diesel engines or marine engines. The internal combustion engine can be a diesel fuel engine, a gasoline fuel engine, a natural gas fuel engine, a biofuel engine, a mixed diesel / biofuel fuel engine, a mixed gasoline / biofuel fuel engine, an alcohol fuel engine, a mixed gasoline / alcohol fuel engine, a compressed natural gas (CNG) fuel engine or a mixture thereof. The diesel engine can be a compression ignition engine. The gasoline engine can be a spark ignition engine. The internal combustion engine can also be used in combination with an electric power source or a battery power source. The engine configured in this way is generally referred to as a hybrid engine. The internal combustion engine can be a 2-stroke, 4-stroke or rotary engine. Suitable internal combustion engines include marine diesel engines (such as inland ships), aviation piston engines, low-load diesel engines and motorcycles, automobiles, railway locomotives and truck engines.

[0031] The internal combustion engine may contain components of one or more of aluminum alloys, lead, tin, copper, cast iron, magnesium, ceramics, stainless steel, composite materials, and / or mixtures thereof. The components may be coated with, for example, diamond-like carbon coatings, lubricating coatings, phosphorus-containing coatings, molybdenum-containing coatings, graphite coatings, nanoparticle-containing coatings, and / or mixtures thereof. The aluminum alloy may include aluminum silicate, aluminum oxide, or other ceramic materials. In one embodiment, the aluminum alloy is an aluminum silicate surface. As used herein, the term "aluminum alloy" is intended to be synonymous with "aluminum composite material" and describes a component or surface comprising aluminum and another component that is intermixed or reacted at a microscopic or near-microscopic level, regardless of its specific structure. This would include any conventional alloy having a metal other than aluminum and a composite or alloy-like structure (such as having a ceramic-like material) having a non-metallic element or compound.

[0032] The lubricating oil composition for internal combustion engines can be applicable to any engine lubricant, regardless of the sulfur, phosphorus or sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricant can be about 1wt% or less, or about 0.8wt% or less, or about 0.5wt% or less, or about 0.3wt% or less, or about 0.2wt% or less. In one embodiment, the sulfur content can be in the range of about 0.001wt% to about 0.5wt%, or about 0.01wt% to about 0.3wt%. The phosphorus content can be about 0.2wt% or less, or about 0.1wt% or less, or about 0.085wt% or less, or about 0.08wt% or less, or even about 0.06wt% or less, about 0.055wt% or less, or about 0.05wt% or less. In one embodiment, the phosphorus content can be about 50ppm to about 1000ppm, or about 325ppm to about 850ppm. The total sulfated ash content may be about 2 wt% or less, or about 1.5 wt% or less, or about 1.1 wt% or less, or about 1 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less. In one embodiment, the sulfated ash content may be about 0.05 wt% to about 0.9 wt%, or about 0.1 wt% or about 0.2 wt% to about 0.45 wt%. In another embodiment, the sulfur content may be about 0.4 wt% or less, the phosphorus content may be about 0.08 wt% or less, and the sulfated ash may be about 1 wt% or less. In yet another embodiment, the sulfur content may be about 0.3 wt% or less, the phosphorus content may be about 0.05 wt% or less, and the sulfated ash may be about 0.8 wt% or less.

[0033] In one embodiment, the lubricating oil composition is an engine oil, wherein the lubricating oil composition may have (i) a sulfur content of about 0.5 wt % or less, (ii) a phosphorus content of about 0.1 wt % or less, and (iii) a sulfated ash content of about 1.5 wt % or less.

[0034] In one embodiment, the lubricating oil composition is suitable for use in a 2-stroke or 4-stroke marine diesel internal combustion engine. In one embodiment, the marine diesel internal combustion engine is a 2-stroke engine. In some embodiments, the lubricating oil composition is not suitable for use in a 2-stroke or 4-stroke marine diesel internal combustion engine for one or more reasons, including but not limited to the high sulfur content of the fuel used to power the marine engine and the high TBN required for a marine-suitable engine oil (e.g., greater than about 40 TBN in a marine-suitable engine oil).

[0035] In some embodiments, the lubricating oil composition is suitable for use in engines powered by low sulfur fuels (eg, fuels containing from about 1 to about 5% sulfur). Highway vehicle fuel contains about 15 ppm sulfur (or about 0.0015% sulfur).

[0036] Low speed diesel engines typically refer to marine engines, medium speed diesel engines typically refer to railway locomotives, and high speed diesel engines typically refer to highway vehicles. The lubricating oil composition may be suitable for use in only one or all of these types.

[0037] In addition, the lubricants of the present description may be adapted to meet one or more industry specification requirements, such as ILSAC GF-3, GF-4, GF-5, GF-6, PC-11, CF, CF-4, CH-4, CK-4, FA-4, CJ-4, CI-4Plus, CI-4, API SG, SJ, SL, SM, SN, ACEA A1 / B1, A2 / B2, A3 / B3, A3 / B4, A5 / B5, C1, C2, C3, C4, C5, E4 / E6 / E7 / E9, Euro 5 / 6, JASO DL-1, Low SAPS, Mid SAPS, or original equipment manufacturer specifications, such as DexosTM 1, DexosTM 2. 2. MB-Approval229.1, 229.3, 229.5, 229.51 / 229.31, 229.52, 229.6, 229. 71, 226.5, 226.51, 228.0 / .1, 228.2 / .3, 228.31, 228.5, 228.51, 228.61, VW 501.01, 502.00, 503.00 / 503.01, 504.00, 505.00, 505.01, 506.00 / 506.01, 507.00, 508.00, 509.00, 508.88, 509. 99. BMW Longlife-01, Longlife-01FE, Longlife-04, Longlife-12FE, Longlife-14FE+, Longlife-17FE+, Porsche A40, C30, Peugeot Automobiles B71 2290, B71 2294, B71 2295, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, RenaultRN0700, RN0710, RN0720, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, WSS-M2C913-D, WSS-M2C948-B, WSS-M2C948-A, GM 6094-M, Chrysler MS-6395, Fiat 9.55535G1, G2, M2, N1, N2, Z2, S1, S2, S3, S4, T2, DS1, DSX, GH2, GS1, GSX, CR1, Jaguar Land Rover STJLR.03.5003, STJLR.03.5004, STJLR.03.5005, STJLR.03.5006, STJLR.03.5007, STJLR.51.5122, or any past or future PCMO or HDD specification not mentioned herein. In some embodiments, for passenger car motor oil (PCMO) applications, the amount of phosphorus in the finished fluid is 1000 ppm or less, or 900 ppm or less, or 800 ppm or less.

[0038] Other hardware may not be suitable for use with the disclosed lubricants. "Functional fluid" is a term that encompasses a variety of fluids, including but not limited to tractor hydraulic fluids, power transmission fluids including automatic transmission fluids, continuously variable transmission fluids, and manual transmission fluids, hydraulic fluids including tractor hydraulic fluids, some gear oils, power steering fluids, fluids used in wind turbines, compressors, some industrial fluids, and fluids associated with powertrain components. It should be noted that within each of these fluids, such as within automatic transmission fluids, there are a variety of different types of fluids because various transmissions have different designs, which results in the need for fluids with significantly different functional characteristics. This is in contrast to the term "lubricating fluid," which is not used to generate or transmit power.

[0039] With regard to tractor hydraulic fluids, for example, these fluids are general-purpose products used for all lubricant applications in tractors other than lubricating the engine. These lubrication applications may include lubrication of gearboxes, power take-offs and clutches, rear axles, reduction gears, wet brakes, and hydraulic accessories.

[0040] When the functional fluid is an automatic transmission fluid, the automatic transmission fluid must have sufficient friction for the clutch plates to transmit power. However, when the fluid heats up during operation, the fluid's coefficient of friction tends to decrease due to temperature. It is important that the tractor hydraulic fluid or automatic transmission fluid maintains its high coefficient of friction at high temperatures, otherwise the brake system or automatic transmission may fail. This is not a function of the engine oil.

[0041] Tractor fluids, and such as Super Tractor Universal Oil (STUO) or Universal Tractor Transmission Oil (UTTO), combine the performance of engine oil with the performance of transmission, differential, final drive planetary gears, wet brakes and hydraulics. Although many of the additives used to formulate UTTO or STUO fluids are similar in function, these additives may have detrimental effects if not properly incorporated. For example, some anti-wear and extreme pressure additives used in engine oils can be extremely corrosive to copper components in hydraulic pumps. Detergents and dispersants used for gasoline or diesel engine performance can be detrimental to wet brake performance. Friction modifiers specifically designed to eliminate wet brake noise may lack the thermal stability required for engine oil performance. Each of these fluids, whether functional, tractor or lubricating, is designed to meet specific and stringent manufacturer requirements.

[0042] The present disclosure provides novel lubricating oil blends formulated for use as automotive crankcase lubricants. The present disclosure provides novel lubricating oil blends formulated for use as 2T and / or 4T motorcycle crankcase lubricants. Embodiments of the present disclosure can provide lubricating oils suitable for crankcase applications and having improvements in the following features: aspiration, alcohol fuel compatibility, oxidation resistance, anti-wear performance, biofuel compatibility, defoaming properties, friction reduction, fuel economy, pre-ignition prevention, rust prevention, sludge and / or smoke dispersibility, piston cleanliness, deposit formation, and water tolerance.

[0043] The engine oils of the present disclosure can be formulated by adding one or more additives (as described in detail below) to a suitable base oil formulation. The additives can be combined with the base oil in the form of an additive package (or concentrate) or, alternatively, can be combined with the base oil (or a mixture of the two) alone. Based on the additives added and their respective proportions, the fully formulated engine oil can exhibit improved performance characteristics.

[0044] Other details and advantages of the present disclosure will be partially described in the following description and / or can be learned by practicing the present disclosure. The details and advantages of the present disclosure can be realized and obtained by means of the elements and combinations specifically pointed out in the attached claims. It should be understood that the foregoing general description and the following detailed description are only exemplary and explanatory and do not limit the disclosure as claimed. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 is a graph of the viscosity of an emulsion at -30°C, wherein the emulsion is produced by mixing the lubricating composition with a fuel and water (the emulsion has been stored at room temperature for 3 hours prior to measurement); and

[0046] Figures 2 to 8 is a strain sweep graph showing the storage modulus (G') and loss modulus (G") at -30°C of an emulsion produced by mixing the lubricating composition with water and fuel (the emulsion had been stored at room temperature for 3 hours prior to measurement). DETAILED DESCRIPTION

[0047] Engine or crankcase lubricant compositions are commonly used in vehicles containing spark ignition and compression ignition engines to provide reduced friction and other benefits. Such engines may be used in automobile, truck and / or train applications to name just a few applications, and may run on fuels including, but not limited to, gasoline, diesel, alcohol, biofuels, compressed natural gas, etc. These engines may include hybrid electric engines that include an internal combustion engine and an electric or battery power source; and / or advanced hybrid or internal combustion engines that include an automatic engine stop function when the vehicle is stationary.

[0048] The present disclosure describes polymeric surfactants and lubricating compositions including such surfactants, which are suitable for use as engine lubricants, such as automotive crankcase lubricants, and in some cases may meet or exceed ILSAC GF-6 and / or API CK lubricant standards, providing robust functionality at temperatures as low as about -30° C. (e.g., from about 0° C. to about -30° C.). Other lubricating compositions that may be expected to operate at extremely low temperatures, such as, but not limited to, automotive transmissions or gearboxes, industrial or personal machines, metalworking, turbines, gear oils, etc., may also benefit from the polymeric surfactants of the present disclosure.

[0049] In one aspect, the present disclosure provides a polymeric surfactant that can be blended into a finished lubricating composition at a low treat rate (e.g., a treat rate of about 3 wt. % or less) and provides not only improved emulsion stability of lubricating compositions with residual water and / or fuel contamination, but also significantly improves the low temperature properties of the emulsion phase. Specifically, the polymers herein and fluids including such polymers can reduce the freezing point of the emulsion phase, maintain fluid viscosity, and / or slow / prevent the formation of a solid phase at low temperatures as low as about -30°C. Therefore, even in winter in very cold regions, when starting a cold engine, the fluids of the present disclosure, even with residual amounts of water and / or fuel contamination, can still be pumped through the engine to reduce and prevent potential engine failures.

[0050] In some methods, polymer surfactants include copolymers of selected non-polar parts or chains and effective polar functional groups to achieve the benefits of emulsion stability and / or flowable viscosity at such low temperatures. As used herein, the terms 'non-polar' and 'polar' are used in the common sense and also refer to hydrophobic and hydrophilic groups or parts respectively. In the method, the polar functional group can be included in the polymer chain or from the polymer chain side joint and have a selected part of the group containing O, N, S or P, and in other methods and as further described below, the polar functional group can be obtained from amidoamine, succinimide and / or heterocyclic reactants with polymerizable ethylenically unsaturated substituents, such as but not limited to alkylaminopropyl methacrylamide, N-phenyl-phenylenediamine succinimide, N-vinyl pyrrolidone and other effective lactones and lactams of the desired functions pointed out herein. In other methods, the non-polar chain or main chain can mainly include the polymer chain of polyalkyl acrylate part, olefin part or other non-polar monomers. In other approaches, the weight percentage of the selected polar functional groups of the polymeric surfactants herein is low, such as about 30 weight percent or less of the total polymeric surfactant. Unexpectedly, even with such low polar functional groups, it has been found that the polymeric surfactants selected herein achieve surprising low temperature functionality at a minimum treat rate of about 3 weight percent or less in the finished lubricating composition.

[0051] As used herein, low temperature fluidity is measured by the so-called pour point, which is defined as the shear strain at the temperature of interest where G' (storage modulus) equals G" (loss modulus), including temperatures down to about -30°C for the compositions herein. A lower pour point measured using the method herein indicates that the lubricating composition has better fluidity at the test conditions or temperature. The pour point is measured using an Anton Paar oscillating MCR rheometer (or equivalent) by performing a strain sweep from 0.01 to 100% shear strain with a parallel plate spindle. This test is described in more detail in the Examples below. The polymeric surfactants herein can unexpectedly improve the emulsion low temperature fluidity of the lubricant and exhibit a pour point of about 75% or less at -30°C.

[0052] Polymeric surfactants:In one aspect, the polymeric surfactants herein include copolymers having a polymer chain or backbone containing (i) a non-polar portion and (ii) a polar functional group, which is effective in maintaining a fluid emulsion when the lubricating composition includes residual amounts of water and / or fuel contamination, as evidenced by a pour point of about 75% or less (about 45% or less, about 10% or less, or even about 5% or less or about 1% or more, about 5% or more, or about 10% or more) measured at a lubricant temperature as low as about -30°C (e.g., about 0 to about -30°C). In one approach, the polymeric surfactant is a polymer or copolymer obtained from reactants having, for example, ethylenic unsaturation and functionalized by grafting polar groups, incorporating polar reactants / monomers into the polymerization reaction, and / or reactants having polar substituents. In some methods, the polymeric surfactant is a copolymer obtained from at least the following reactants: (i) non-polar moieties derived from alkyl (meth)acrylates, olefins and similar non-polar reactants and (ii) polar functional groups and similar groups derived from reactants including one or more of oxygen, nitrogen, sulfur or phosphorus atoms. In another method, the polar functionality (polar functionality / polar functional group) is derived from a heterocyclic reactant having a polymerizable ethylenically unsaturated substituent. In other methods, the polar functionality can be derived from an amidoamine having a polymerizable ethylenically unsaturated substituent or a reactant having an imide or amide substituent, such as succinimide and similar moieties. The polar functionality of the resulting polymeric surfactant is a group within the polymer chain and / or a group attached to the polymer chain.

[0053] In one method, the polar functional groups are preferably provided by one or more heterocyclic reactants that also include polymerizable ethylenically unsaturated substituents. These reactants can be grafted onto the main polymer backbone or can be polymerized within the backbone and provide polar functionalized side chains or polar functionalized side groups. In the method, the polar functional groups can be provided by polymerizable reactants, which include vinyl lactones, vinyl lactams, combinations thereof, and derivatives thereof and preferably, can include polymerizable reactants selected from vinyl pyrrolidone, vinyl pyridine, N-vinyl pyrrolidone, N-vinyl imidazole, N-vinyl caprolactam, combinations thereof, or derivatives thereof.

[0054] In other approaches, the polar functionality may be provided by a polymerizable amidoamine, such as an acrylamide reactant represented by the formula:

[0055]

[0056] Where R 4 is hydrogen or an alkyl radical containing 1 to 4 carbon atoms, R 3 is hydrogen, an alkyl or alkenyl group containing from one to thirty carbon atoms, or an aryl group, R5 is an alkylene group, an aralkylene group, a cycloalkylene group, an arylene group or an alkarylene group, and R 6 and R 7 Independently selected from hydrogen, branched or straight chain alkyl or alkenyl, aryl, aralkyl, cycloalkyl or alkaryl.

[0057] In the above formula (2), when R 6 or R 7 When R is an alkyl group, each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, octyl, decyl, octadecyl, etc. 6 or R 7 When R is an aralkyl group, it may be a benzyl group, a β-phenylethyl group, or the like. 6 or R 7 When R is a cycloalkyl group, it may be a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 2-methylcycloheptyl group, a 3-butylcyclohexyl group, a 1,3-methylcyclohexyl group, or the like. 6 or R 7 When it is an alkylaryl group, it may be tolyl, xylyl, etc. 6 or R 7 It may be inertly substituted, that is, it may carry non-reactive substituents such as alkyl, aryl, cycloalkyl, ether, etc. Preferred R 6 or R 7 The group may be a lower alkyl group, ie, a C1-C10 alkyl group, including, for example, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, and the like.

[0058] As disclosed above, R 5 can be selected from alkylene, aralkylene, cycloalkylene, arylene and alkarylene. 5 When R is an alkylene group, it may be methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, sec-butylene, octylene, decylene, octadecylene, etc. 5 When R is an aralkylene group, it may be a benzylidene group, a β-phenylethylene group, or the like. 5 When it is a cycloalkylene group, it may be cyclohexylene, cycloheptylene, cyclooctylene, 2-methylcycloheptylene, 3-butylcyclohexylene, 3-methylcyclohexylene, or the like. 5 It may also be inertly substituted, i.e. it may carry non-reactive substituents, such as alkyl, aryl, cycloalkyl, ether, etc. Preferred R 5 The group may be a lower alkylene group, i.e., a C1-C10 alkylene group, and the group includes, for example, methylene, ethylene, n-propylene, isopropylene, butylene, pentylene, hexylene, octylene, decylene, etc. 5 Preferably it is propylene (-CH 2 CH 2 CH2 -). Representatives of the compound of formula (2) include N,N-dimethylaminopropylmethacrylamide, N,N-diethylaminopropylmethacrylamide and N,N-dimethylaminoethylacrylamide.

[0059] In another method, the polar functional group can be provided by succinimide. The formation of succinimide is well known in the art, and can be completed by converting succinic acid or anhydride, and then reacting it with a nitrogen source to form an olefin copolymer (i.e., olefin copolymer succinimide). Acylated copolymers can be made by reacting the double bonds on the end groups of the copolymer with an acylating agent (e.g., maleic acid or maleic anhydride) via thermal olefin reaction and / or halogenation-condensation, see, for example, U.S. Patent No. 7,897 696, which is incorporated herein by reference. In acylated copolymers such as alkenyl succinic acid or anhydride, the ratio of succinic acid moiety: copolymer backbone can be about 0.8:1 to about 2:1, or about 1:1 to about 1.8:1, or about 1.2:1 to about 1.5:1. In some methods, the acylating agent of the above-mentioned process is an unsaturated substituted or unsubstituted organic acid or anhydride, such as maleic acid or fumaric acid reactants of the following general formula:

[0060]

[0061] wherein X and X' are the same or different, provided that at least one of X and X' is a group capable of reacting to esterify an alcohol, to form an amide or amine salt with ammonia or an amine, to form a metal salt with an active metal, or to react substantially with a metal compound, or to otherwise function as an acylating agent. Typically, X and / or X' is -OH, -O-alkyl, -NH 2 , and X and X' together can be -O- to form an anhydride. In some embodiments, X and X' are such that both carboxyl functional groups can enter into an acylation reaction.

[0062] Maleic anhydride is a suitable acylating agent that can subsequently form a succinimide polar group. Other suitable acylating agents include electron-deficient olefins such as monophenyl maleic anhydride; monomethyl maleic anhydride, dimethyl maleic anhydride, N-phenyl maleimide and other substituted maleimides; isomaleimide; fumaric acid, maleic acid, maleic acid and alkyl hydrogen fumarate esters, fumaric acid and dialkyl maleate esters, fumaric acid and maleic acid; and maleonitrile and fumaronitrile.

[0063] As mentioned above, it is well known in the art that acylated copolymers such as alkenyl succinic acid or anhydride are converted into succinimide, and can be completed by reacting acylated copolymers with nitrogen sources, such as ammonia or amines, such as polyamines with at least one basic nitrogen. Alkenyl succinic acid or anhydride are converted into succinimide and are described in U.S. Patent No. 3,215,707 and U.S. Patent No. 4,234,435, which are all incorporated herein by reference. Suitable nitrogen sources include ammonia, monoamines, polyamines, benzyl, naphthyl, phenyl, polyalkylene polyamines and mixtures thereof. Polyalkylene polyamines may include polyethylene polyamines, triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and a mixture of combinations thereof having an average of 5 nitrogen atoms.

[0064] Amines used herein are well known in the art and generally have at least one reactive NH bond (nitrogen-hydrogen bond). Amines are optionally further substituted with other functional groups (such as hydroxyls). In one embodiment, amines contain one or more primary amine or secondary amine groups. In one embodiment, monoamines have 1 to 22 carbon atoms. Examples of monoamines include butylamine, methylamine, dimethylamine, alkanolamines (such as ethanolamine) containing one or more hydroxyls, or mixtures thereof.

[0065] In some cases, polyalkylene polyamines may have at least three nitrogen atoms and about 4 to 20 carbon atoms. One or more oxygen atoms may also be present in polyamines. Several polyamines can be used to prepare dispersants. Except for the nitrogen source mentioned above, non-limiting exemplary polyamines may include aminoguanidine bicarbonate (AGBC), ethylenediamine (EDA), N-methylpropylenediamine, diethylenetriamine (DETA), pentaethylenehexamine (PEHA) or other heavy polyamines. Some heavy polyamines may include a mixture of polyalkylene polyamines with a small amount of low-grade polyamine oligomers (such as TEPA and PEHA), but the main polyamine oligomers have seven or more nitrogen atoms, two or more primary amines and more extensive branching than conventional polyamine mixtures per molecule. Other non-limiting polyamines that can be used to prepare dispersants are disclosed in U.S. Patent No. 6,548,458, and its disclosure is incorporated herein by reference in its entirety.

[0066] Other examples of suitable polyalkylene polyamines include, but are not limited to, propylenediamine, isopropylenediamine, butylenediamine, pentylenediamine, hexylenediamine, dipropylenetriamine, dimethylaminopropylamine, diisopropylenetriamine, dibutyltriamine, di-sec-butyltriamine, tripropylenetetramine, triisobutyltetramine, pentaethylenehexamine, and mixtures thereof.

[0067] Particularly suitable groups of polyalkylene polyamines may contain from about 2 to about 12 nitrogen atoms and from about 2 to about 24 carbon atoms. The alkylene group of such polyalkylene polyamines may contain from about 2 to about 6 carbon atoms, more preferably from about 2 to about 4 carbon atoms. Many polyamines suitable for use in the present disclosure are commercially available, and others may be prepared by methods well known in the art. For example, methods for preparing amines and reactions thereof are described in Sidgewick's The Organic Chemistry of Nitrogen, Clarendon Press, Oxford, 1966; Noller's Chemistry of Organic Compounds, Saunders, Philadelphia, 2nd Edition, 1957; and Kirk-Othmer's Encyclopedia of Chemical Technology, 2nd Edition, especially Volume 2, pages 99-116, each of which is incorporated herein by reference.

[0068] The reaction of a nitrogen source such as ammonia or a polyamine with alkenyl succinic acid or anhydride gives monosuccinimide, bis-succinimide, trisuccinimide or other succinimides, depending on the charge ratio of the nitrogen source and the alkenyl succinic acid or anhydride. The charge ratio between the alkenyl succinic acid or anhydride and the nitrogen source is from about 1:1 to about 3.2:1, or from about 2.5:1 to about 3:1, or from about 2.9:1 to about 3:1, or from about 1.6:1 to about 2.5:1, or from about 1.6:1 to about 2:1, or from about 1.6:1 to about 1.8:1, from about 1.3:1 to about 1.8:1, from about 1.4:1 to about 1.8:1, or from about 1:6 to about 1.8:1.

[0069] The copolymer surfactants herein may include up to about 30% by weight of such polar functional groups, in other approaches, up to about 25% by weight, up to about 20% by weight, or up to about 15% by weight. The polymer may include about 5% by weight or more of polar groups, 10% by weight or more, or about 15% by weight or more of polar groups.

[0070] In another approach, the non-polar portion of the polymerizable surfactant can be provided by a polymerizable reactant that forms the main chain or backbone, and can include, for example, an alkyl (meth)acrylate reactant to form a polyalkyl (meth)acrylate (PMA) copolymer. In this approach, the copolymer can be derived from a linear or branched alkyl ester of (meth)acrylic acid. Suitable alkyl (meth)acrylate reactants can have an alkyl chain length of 1 to 20 carbons. As used herein, "(meth)acrylate" refers to a methacrylate and / or acrylate monomer or monomer unit (or mixture) required for a particular polymeric surfactant.

[0071] As also used herein, polymerizable reactants are monomers that form polymers or copolymers. Reactants or monomers generally refer to compounds in reaction mixtures before polymerization, and monomeric units or (alternatively) repeating units refer to reactants or monomers polymerized in polymer chains. Various monomers herein are randomly polymerized into monomeric units or repeating units in the main chain. If the discussion mentions reactants or monomers, the monomeric units or repeating units obtained in the polymer are also implied. Similarly, if the discussion mentions monomeric units or repeating units, the reactant mixture or monomer mixture used to form a polymer and the related monomers or repeating units therein are also implied.

[0072] The poly(meth)acrylate polymers suitable for use as surfactants herein can be prepared by any suitable conventional or controlled radical polymerization technique. Examples include conventional free radical polymerization (FRP), reversible addition-fragmentation chain transfer (RAFT), atom transfer radical polymerization (ATRP), and other controlled types of polymerization known in the art. Polymerization procedures are known to those skilled in the art and include the use of, for example, common polymerization initiators such as Vazo TM 67 (2.2'-azobis(2-methylbutyronitrile)), if conventional FRP is used, a chain transfer agent (such as dodecyl mercaptan) is used, or if RAFT polymerization is used, a RAFT agent (such as 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, etc.) is used. Other initiators, chain transfer agents, RAFT agents, ATRP catalysts and initiator systems may be used, as known in the art, depending on the polymerization method selected as required for a specific application.

[0073] In yet another approach, the non-polar groups or moieties may be provided by an olefin copolymer, which may be a copolymer backbone of ethylene and an alkylene group having 3 to 18 carbon atoms, such as 3 to 5, 3 to 10, 3 to 15, 5 to 10, 8 to 12, 10 to 15, or 10 to 18 carbon atoms. In some approaches, the alkylene group may be propylene, isopropylene, butylene, isobutylene, n-pentene, isopentene, and / or neopentene, and mixtures thereof. In other approaches, the polymer is ethylene and one or more C 3To C 18 Copolymers of alpha-olefins. Copolymers of ethylene and propylene are most preferred. Other alpha-olefins suitable for use in place of propylene to form copolymers or in combination with ethylene and propylene to form terpolymers include 1-butene, 1-pentene, 1-hexene, 1-octene and styrene; alpha-omega dienes such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene; branched alpha-olefins such as 4-methylbutene-1,5-methylpentene-1 and 6-methylheptene-1; and mixtures thereof.

[0074] More complex polymer matrices (generally represented as interpolymers) can be prepared using a third component and are also suitable for use in the polymer surfactants herein. The third component generally used to prepare the interpolymer matrix is ​​a polyene monomer selected from non-conjugated dienes and trienes. The non-conjugated diene component is a component having 5 to 14 carbon atoms in the chain. Preferably, the diene monomer is characterized by the presence of vinyl in its structure and may include cyclic and bicyclic compounds. Representative dienes include 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 1,5-heptadiene and 1,6-octadiene. A mixture of more than one diene can be used to prepare the interpolymer. The preferred non-conjugated diene for preparing the terpolymer or interpolymer matrix is ​​1,4-hexadiene.

[0075] The triene component has at least two non-conjugated double bonds in the chain and up to about 30 carbon atoms. Typical trienes useful in preparing the disclosed interpolymers are 1-isopropylidene-3a,4,7,7a-tetrahydroindene, 1-isopropylidene dicyclopentadiene, dihydro-isodicyclopentadiene, and 2-(2-methylene-4-methyl-3-pentenyl)[2.2.1]bicyclo-5-heptene.

[0076] The ethylene-propylene or higher α-olefin copolymer may be composed of about 15 to 80 mole % of ethylene and about 85 to 20 mole % of C 3 To C 18 α-olefins, wherein the preferred molar ratio is about 35 to 75 mole % ethylene and about 65 to 25 mole % C 3 To C 18 α-olefins, wherein the preferred molar ratio is about 50 to 70 mole % ethylene and about 50 to 30 mole % C 3 To C 18 α-olefins, and most preferably in a ratio of 55 to 65 mol % ethylene and 45 to 35 mol % C 3 To C 18 Alpha-olefins. Terpolymer variations of the foregoing polymers may contain from about 0.1 to 10 mole percent of a non-conjugated diene or triene.

[0077] The terms polymer and copolymer are generally used to encompass ethylene copolymers, terpolymers or interpolymers. These materials may contain minor amounts of other olefin monomers as long as the basic characteristics of the ethylene copolymer are not substantially altered.

[0078] In some methods, the polymerization reaction for forming the ethylene-olefin copolymer matrix can generally be carried out in the presence of a conventional Ziegler-Natta or metallocene catalyst system. As known to those skilled in the art, the polymerization medium is not special and can include solution, slurry or gas phase processes. When solution polymerization is used, the solvent can be any suitable inert hydrocarbon solvent that is liquid under the reaction conditions of α-olefin polymerization; examples of satisfactory hydrocarbon solvents include straight-chain alkanes having 5 to 8 carbon atoms, with hexane being preferred. Aromatic hydrocarbons, preferably aromatic hydrocarbons having a single benzene nucleus, such as benzene, toluene, etc.; and saturated cyclic hydrocarbons with a boiling point range close to the above-mentioned straight-chain alkanes and aromatic hydrocarbons are particularly suitable. The selected solvent can be a mixture of one or more of the aforementioned hydrocarbons. When slurry polymerization is used, the liquid phase for polymerization is preferably liquid propylene. It is desirable that the polymerization medium does not contain substances that will interfere with the catalyst components.

[0079] In some methods or embodiments, the weight average molecular weight of the polymer surfactant suitable for providing stable low temperature performance is about 40,000 or more, about 100,000 or more, about 150,000 or more, about 200,000 or more, about 300,000 or more, or about 400,000 or more. In other methods or embodiments, the weight average molecular weight of the polymer surfactant is about 800,000 or less, about 500,000 or less, about 480,000 or less, about 450,000 or less, about 300,000 or less, about 250,000 or less, about 220,000 or less, about 200,000 or less, about 150,000 or less, or about 100,000 or less. As shown in the following examples, the preferred molecular weight range may also be related to the selected polar functional group.

[0080] The molecular weight of any of the embodiments herein may be measured using an instrument such as a gel permeation chromatography (GPC) instrument obtained from Waters, and the data may be processed using software such as Waters Empower software. The GPC instrument may be equipped with a Waters separation module and a Waters refractive index detector (or similar optional equipment). GPC operating conditions may include a guard column, 4 Agilent PLgel columns (length 300×7.5 mm; particle size 5 μ, and pore size range ), wherein the column temperature is about 40° C. Unstable HPLC grade tetrahydrofuran (THF) can be used as a solvent with a flow rate of 1.0 ml / min. The GPC instrument can be calibrated with commercially available polystyrene (PS) standards having a narrow molecular weight distribution in the range of 500-380,000 g / mol. For samples with a mass of less than 500 g / mol, the calibration curve can be extrapolated. Samples and PS standards can be dissolved in THF and prepared at a concentration of 0.1 to 0.5 wt.%, and used without filtering. GPC measurements are also described in US 5,266,223, which is incorporated herein by reference. The GPC method additionally provides molecular weight distribution information; see, for example, WW Yau, JJ Kirkland and DD Bly, Modern Size Exclusion Liquid Chromatography, John Wiley and Sons, New York, 1979, also incorporated herein by reference.

[0081] Lubricating oil composition The polymeric surfactants described herein can be blended with a large amount of base oil or base oil of lubricating viscosity (as described below) and one or more other optional additives to produce a lubricating oil composition having good emulsion stability and fluidity and a robust low temperature viscosity profile when contaminated with residual amounts of water and / or gasoline and / or ethanol. The lubricating oil composition herein may include an amount of active polymeric surfactant ranging from about 0.01 wt % or more, about 0.02 wt % or more, about 0.03 wt % or more, about 0.04 wt % or more, about 0.05 wt % or more, or even 0.1 wt % or more to about 3 wt % or less, about 2 wt % or less, about 1 wt % or less, about 0.5 wt % or less, or about 0.4 wt % or less, or about 0.3 wt % or less, based on the total weight of the lubricant composition.

[0082] As noted above, during normal operation, the lubricating oil composition may be contaminated by residual amounts of fuel and / or water. In some cases, any lubricating composition embodiment herein may include water and / or fuel contamination in an amount of up to about 40% by weight of water contamination and / or up to about 40% by weight of fuel contamination (and other ranges therein). In other methods, the lubricating oil composition may include up to about 30% by weight, up to about 25% by weight, up to about 20% by weight, up to about 15% by weight, up to about 10% by weight, or up to about 5% by weight of water contamination and / or the lubricating oil composition may include up to about 30% by weight, up to about 25% by weight, up to about 20% by weight, up to about 15% by weight, up to about 10% by weight, or up to about 5% by weight of fuel contamination. Even under such contamination conditions, the lubricating composition herein can maintain a stable performance by a stable emulsion that does not affect the function, and can also maintain a flowable viscosity at a temperature as low as about -30°C. In some methods, the fuel may be gasoline. As used herein, contamination refers to water and / or fuel (or other additives) that are not intentionally added to a lubricating composition. Contamination may occur through use of a lubricating composition as a lubricant in an engine.

[0083] Base Oil: The base oil used in the lubricating oil composition herein can be selected from any one of the base oils in Group IV as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil categories are as follows:

[0084] Table 1

[0085]

[0086] I, II and III classes are mineral oil processing raw materials.Class IV base oil contains true synthetic molecular material (truesynthetic molecular specie), which is produced by the polymerization of olefinic unsaturated hydrocarbons.Many Class V base oils are also real synthetic products, and can include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphates, polyvinyl ethers and / or polyphenyl ethers etc., but can also be naturally occurring oils, such as vegetable oils.It should be noted that although Class III base oils are derived from mineral oils, the strict processing experienced by these fluids makes its physical properties very similar to some pure synthetics, such as PAO.Therefore, in the industry, the oil derived from Class III base oil can be called synthetic fluid.Class II+ can include high viscosity index Class II.

[0087] The base oil used in the disclosed lubricating oil composition can be a mineral oil, an animal oil, a vegetable oil, a synthetic oil, a synthetic oil blend or a mixture thereof. Suitable oils can be derived from hydrocracked, hydrogenated, hydrorefined, unrefined, refined and re-refined oils and mixtures thereof.

[0088] Unrefined oils are those derived from natural, mineral or synthetic sources with little or no further purification treatment. Refined oils are similar to unrefined oils except that the refined oils have been treated in one or more purification steps, which may result in improvements in one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, etc. Oils refined to edible quality may or may not be applicable. Edible oils may also be referred to as white oils. In certain embodiments, the lubricating oil composition does not contain edible oils or white oils.

[0089] Re-refined oils are also called reclaimed oils or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Typically these oils are additionally processed by techniques directed to the removal of spent additives and oil breakdown products.

[0090] Mineral oil can include oil or any mixture thereof obtained by drilling or from plants and animals. For example, such oil can include but is not limited to castor oil, lard, olive oil, peanut oil, corn oil, soybean oil and linseed oil, and mineral lubricating oil, such as liquid petroleum and paraffin, cycloparaffin or mixed paraffin-cycloparaffin type solvent-treated or acid-treated mineral lubricating oil. If desired, such oil can be partially or completely hydrogenated. Oil derived from coal or shale can also be applicable.

[0091] Suitable synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomeric or interpolymerized olefins (e.g., polybutene, polypropylene, propylene isobutylene copolymers); poly(1-hexene), poly(1-octene); trimers or oligomers of 1-decene, such as poly(1-decene), such materials are generally referred to as alpha-olefins; and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)-benzene); polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides, and derivatives, analogs and homologs thereof or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

[0092] Other synthetic lubricating oils include polyol esters, diesters, phosphoric acid-containing liquid esters (for example, diethyl esters of tricresyl phosphate, trioctyl phosphate and decanephosphonic acid) or polymerized tetrahydrofuran. Synthetic oils can be produced by Fischer-Tropsch reaction and can typically be Fischer-Tropsch hydrocarbons or waxes of hydroisomerization. In one embodiment, oil can be prepared by Fischer-Tropsch gas-to-liquid synthesis procedure and other gas-to-liquid preparations.

[0093] The major amount of base oil included in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and a combination of two or more of the foregoing, and wherein the major amount of the base oil is not a base oil resulting from providing an additive component or a viscosity index improver in the composition. In another embodiment, the major amount of base oil included in the lubricating composition may be selected from the group consisting of Group II, Group III, Group IV, Group V, and a combination of two or more of the foregoing, and wherein the major amount of the base oil is not a base oil resulting from providing an additive component or a viscosity index improver in the composition.

[0094] The amount of oil of lubricating viscosity present can be the balance remaining after subtracting the sum of the amounts of performance additives from 100 wt%, including viscosity index improvers and / or pour point depressants and / or other pre-treatment additives. For example, the amount of oil of lubricating viscosity that can be present in the finished fluid can be a large amount, such as greater than about 50 wt%, greater than about 60 wt%, greater than about 70 wt%, greater than about 80 wt%, greater than about 85 wt%, or greater than about 90 wt%.

[0095] Antioxidants The lubricating oil composition herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenolates, phenol sulfides, sulfided olefins, sulfided terpenes, sulfided esters, aromatic amines, alkylated diphenylamines (e.g., nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

[0096] Hindered phenol antioxidants may contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenol group may be further substituted with a hydrocarbon group and / or a bridging group connected to a second aromatic group. Examples of suitable hindered phenol 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 phenol antioxidant may be an ester and may include, for example, Irganox®, available from BASF. TM L-135 or the addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester and may include Ethanox acrylate available from Albemarle Corporation. TM 4716.

[0097] Useful antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols such that each antioxidant may be present in an amount sufficient to provide up to about 5 weight percent based on the final weight of the lubricating oil composition. In one embodiment, the antioxidant may be a mixture of about 0.3 to about 1.5 weight percent diarylamine and about 0.4 to about 2.5 weight percent high molecular weight phenol based on the final weight of the lubricating oil composition.

[0098] Examples of suitable olefins that can be sulfurized to form sulfurized olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecaene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecaene, or mixtures thereof, and dimers, trimers, and tetramers thereof are particularly useful olefins. Alternatively, the olefin can be a Diels-Alder adduct of a diene (such as 1,3-butadiene) and an unsaturated ester (such as butyl acrylate).

[0099] Another class of sulphurized olefins includes sulphurized fatty acids and esters thereof. Fatty acids are usually obtained from vegetable oils or animal oils and typically contain about 4 to about 22 carbon atoms. Examples of suitable fatty acids and esters thereof include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof. Usually, fatty acids are obtained from lard, pine oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof. Fatty acids and / or esters can be mixed with olefins (such as alpha-olefins).

[0100] In another alternative embodiment, in addition to the phenolic and / or aminic antioxidants discussed above, the antioxidant composition also contains a platinum-containing antioxidant. When a combination of these three antioxidants is used, preferably, the ratio of phenolic antioxidant to aminic antioxidant to platinum-containing antioxidant is (0 to 2):(0 to 2):(0 to 1).

[0101] One or more antioxidants may be present in the lubricating oil composition in a range from about 0 wt % to about 20 wt %, or from about 0.1 wt % to about 10 wt %, or from about 1 wt % to about 5 wt %.

[0102] Anti-wear agent :The lubricating oil composition herein may also optionally contain one or more anti-wear agents. Examples of suitable anti-wear agents include, but are not limited to, metal thiophosphates; metal dialkyl dithiophosphates; phosphoric acid esters or their salts; phosphoric acid esters; phosphites; phosphorus-containing carboxylates, ethers or amides; sulfurized olefins; compounds containing thiocarbamates, including thiocarbamates, alkylene coupled thiocarbamates and bis(S-alkyldithiocarbamoyl) disulfides; and mixtures thereof. A suitable anti-wear agent may be molybdenum dithiocarbamates. Phosphorus-containing anti-wear agents are more fully described in European Patent 612 839. The metal in the dialkyl dithiophosphate may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium or zinc. A suitable anti-wear agent may be zinc dialkyl dithiophosphate.

[0103] Yet another example of a suitable anti-wear agent includes titanium compounds, tartrates, tartrimides, oil-soluble amine salts of phosphorus compounds, sulphurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds (such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene coupled thiocarbamates and bis(S-alkyldithiocarbamoyl) disulfides). The tartrate or tartrimide may contain an alkyl ester group, wherein the total number of carbon atoms in the alkyl group may be at least 8. In one embodiment, the anti-wear agent may include a citrate ester.

[0104] The antiwear agent may be present in a range comprising about 0 wt % to about 15 wt %, or about 0.01 wt % to about 10 wt %, or about 0.05 wt % to about 5 wt %, or about 0.1 wt % to about 3 wt % of the lubricating oil composition.

[0105] Boron compounds:The lubricating oil composition herein may optionally contain one or more boron-containing compounds. Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Pat. No. 5,883,057. The boron-containing compound, if present, may be used in an amount sufficient to provide up to about 8 wt%, about 0.01 wt% to about 7 wt%, about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt% of the lubricating oil composition.

[0106] Cleaning Agents The lubricating oil composition may optionally further comprise one or more neutral, low-alkaline or high-alkaline detergents and mixtures thereof. Suitable detergent bases include: phenates, sulfur-containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphoric acids, monothiophosphoric acids and / or dithiophosphoric acids, alkylphenols, sulfur-coupled alkylphenol compounds or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in more detail in a number of patent publications, including US Pat. No. 7,732,390 and references cited therein.

[0107] The detergent matrix can be salified with an alkali metal or alkaline earth metal such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent does not contain barium. In some embodiments, the detergent may contain trace amounts of other metals such as magnesium or calcium, such as 50 ppm or less, 40 ppm or less, 30 ppm or less, 20 ppm or less, or 10 ppm or less. Suitable detergents may include alkali metal or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or dialkyl aryl sulfonic acids, wherein the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable cleaning agents include, but are not limited to, calcium phenates, sulfur-containing calcium phenates, calcium sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylates, calcium phosphates, calcium monothiophosphates and / or dithiophosphates, calcium alkyl phenates, sulfur-coupled alkyl phenate calcium compounds, methylene-bridged calcium phenates, magnesium phenates, sulfur-containing magnesium phenates, magnesium sulfonates, magnesium calixarates, magnesium salixarates, magnesium salicylates, magnesium carboxylates, magnesium phosphates, magnesium monothiophosphates and / or dithiophosphates, magnesium alkyl phenates, sulfur-coupled alkyl phenate magnesium compounds, methylene-bridged magnesium phenates, sodium phenates, sulfur-containing sodium phenates, sodium sulfonates, sodium calixarates, sodium salixarates, salixarates), sodium salicylates, sodium carboxylates, sodium phosphates, sodium monothiophosphates and / or sodium dithiophosphates, sodium alkylphenols, sodium sulfur-coupled alkylphenol compounds, or sodium methylene-bridged phenols.

[0108] Overbased detergent additives are well known in the art and may be alkali metal or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

[0109] The term "overbased" relates to metal salts, such as metal salts with sulfonic acids, carboxylic acids and phenols, in which the amount of metal present exceeds the stoichiometric amount. These salts may have a conversion level exceeding 100% (i.e., these salts may contain more than 100% of the theoretical amount of metal required to convert the acid into its "normal", "neutral" salt). The expression "metal ratio", usually abbreviated as MR, is used to specify the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the neutral salt, based on known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is unity, while in overbased salts, MR is greater than unity. They are often referred to as overbased, superbased or ultrabasic salts, and may be salts of organic sulfuric acid, carboxylic acid, or phenol.

[0110] The overbased detergent of the lubricating oil composition may have a total base number (TBN) of about 200 mg KOH / gram or greater, or as other examples, about 250 mg KOH / gram or greater, or about 350 mg KOH / gram or greater, or about 375 mg KOH / gram or greater, or about 400 mg KOH / gram or greater.

[0111] Examples of suitable overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salicylates, overbased calcium carboxylates, overbased calcium phosphates, overbased calcium monothiophosphates and / or dithiophosphates, overbased calcium alkylphenates, overbased sulfur-coupled alkylphenate calcium compounds, overbased methylene-bridged calcium phenates, overbased magnesium phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salicylates, overbased magnesium carboxylates, overbased magnesium phosphates, overbased magnesium monothiophosphates and / or dithiophosphates, overbased magnesium alkylphenates, overbased sulfur-coupled alkylphenate magnesium compounds, or overbased methylene-bridged magnesium phenates.

[0112] The total base number of the overbased calcium phenate detergent is at least about 150 mg KOH / g, at least about 225 mg KOH / g, at least about 225 mg KOH / g to about 400 mg KOH / g, at least about 225 mg KOH / g to about 350 mg KOH / g, or about 230 mg KOH / g to about 350 mg KOH / g, all as measured by the method of ASTM D-2896. When such detergent compositions are formed in an inert diluent (e.g., process oil, typically mineral oil), the total base number reflects the alkalinity of the entire composition, including the diluent and any other materials that may be contained in the detergent composition (e.g., accelerators, etc.).

[0113] The metal to substrate ratio of the overbased detergent may be 1.1:1, or 2:1, or 4:1, or 5:1, or 7:1, or 10:1. In some embodiments, the detergent is effective in reducing or preventing rust in an engine. The detergent may be present in an amount of from about 0 wt% to about 10 wt%, or from about 0.1 wt% to about 8 wt%, or from about 1 wt% to about 4 wt%, or greater than about 4 wt% to about 8 wt%.

[0114] Dispersants: The lubricating oil composition may optionally further comprise one or more dispersants or mixtures thereof. Dispersants are generally referred to as ashless dispersants because, prior to being mixed into the lubricating oil composition, the dispersant does not contain ash-forming metals and, when added to the lubricant, it generally does not provide any ash. Ashless dispersants are characterized in that polar groups are attached to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides, wherein the number average molecular weight of the polyisobutylene substituent is in the range of about 350 to about 50,000 or to about 5,000 or to about 3,000 as measured by GPC. Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The polyolefins may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly(ethylene amine).

[0115] Preferred amines are selected from polyamines and hydroxylamines. Examples of polyamines that can be used include, but are not limited to, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and higher homologues, such as pentaethylaminehexamine (PEHA) and the like.

[0116] Suitable heavy polyamines are mixtures of polyalkylene-polyamines containing small amounts of lower polyamine oligomers such as TEPA and PEHA (pentaethylenehexamine) but predominantly oligomers having 6 or more nitrogen atoms per molecule, 2 or more primary amines and more extensive branching than conventional polyamine mixtures. Heavy polyamines preferably include polyamine oligomers containing 7 or more nitrogen atoms per molecule and 2 or more primary amines per molecule. Heavy polyamines contain greater than 28 wt.% (e.g. >32 wt.%) total nitrogen and an equivalent weight of primary amine groups of 120-160 g / equivalent.

[0117] Suitable polyamines are generally referred to as PAMs and contain a mixture of ethyleneamines with TEPA and pentaethylenehexamine (PEHA) comprising the major portion of the polyamine, typically less than about 80%.

[0118] Typically, PAM has 8.7-8.9 milliequivalents of primary amine per gram (equivalent weight per primary amine equivalent is 115 to 112 grams) and a total nitrogen content of about 33-34 wt.%. A heavy fraction of PAM oligomers that is almost free of TEPA and contains only very little PEHA but contains mainly oligomers with more than 6 nitrogens and more extensive branching can produce a dispersant with improved dispersibility.

[0119] In one embodiment, the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000 or to about 5000 or to about 3000 as determined by GPC. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

[0120] In some embodiments, the polyisobutylene (when included) may have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIBs are also referred to as highly reactive PIBs ("HR-PIBs"). HR-PIBs having a number average molecular weight in the range of about 800 to about 5000 as determined by GPC are suitable for embodiments of the present disclosure. Conventional PIBs typically have a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

[0121] HR-PIBs with number average molecular weights ranging from about 900 to about 3000 as determined by GPC may be suitable. Such HR-PIBs are commercially available or may be synthesized by polymerizing isobutylene in the presence of a non-chlorinated catalyst such as boron trifluoride, as described in U.S. Pat. No. 4,152,499 to Boerzel et al. and U.S. Pat. No. 5,739,355 to Gateau et al. When used in the aforementioned thermal olefin reaction, HR-PIBs may result in higher conversions of the reaction and less precipitation formation due to increased reactivity. Suitable methods are described in U.S. Pat. No. 7,897,696.

[0122] In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA").PIBSA may have an average of between about 1.0 and about 2.0 succinic acid moieties per polymer.

[0123] The % activity of the alkenyl or alkyl succinic anhydride may be determined using chromatographic techniques. This method is described in columns 5 and 6 of US Patent No. 5,334,321.

[0124] The percent conversion of the polyolefin was calculated from the % activity using the equations in columns 5 and 6 of US Patent No. 5,334,321.

[0125] Unless otherwise indicated, all percentages are by weight and all molecular weights are number average molecular weights as determined by gel permeation chromatography (GPC) using commercially available polystyrene standards with number average molecular weights ranging from 180 to about 18,000 as calibration reference.

[0126] In one embodiment, the dispersant may be derived from polyalphaolefin (PAO) succinic anhydride. In one embodiment, the dispersant may be derived from olefin maleic anhydride copolymer. As an example, the dispersant may be described as polyPIBSA. In one embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

[0127] Suitable classes of nitrogen-containing dispersants can be derived from olefin copolymers (OCPs), more specifically ethylene-propylene dispersants, which can be grafted with maleic anhydride. A more complete list of nitrogen-containing compounds that can be reacted with functionalized OCPs is described in U.S. Pat. Nos. 7,485,603; 7,786,057; 7,253,231; 6,107,257; and 5,075,383; and / or the nitrogen-containing compounds are commercially available.

[0128] The hydrocarbyl part of the hydrocarbyl-dicarboxylic acid or anhydride of component A) may alternatively be derived from ethylene-alpha-olefin copolymers. These copolymers contain a plurality of ethylene units and a plurality of one or more C 3 -C 10 α-olefin unit. C 3 -C 10 The α-olefin unit may include a propylene unit.

[0129] The number average molecular weight of the ethylene-alpha olefin copolymer is typically less than 5,000 g / mol, as measured by GPC using polystyrene as a calibration reference; or the number average molecular weight of the copolymer may be less than 4,000 g / mol, or less than 3,500 g / mol, or less than 3,000 g / mol, or less than 2,500 g / mol, or less than 2,000 g / mol, or less than 1,500 g / mol, or less than 1,000 g / mol. In some embodiments, the number average molecular weight of the copolymer may be between 800 and 3,000 g / mol.

[0130] The ethylene content of ethylene-alpha olefin copolymer can be less than 80mol%; less than 70mol%, or less than 65mol%, or less than 60mol%, or less than 55mol%, or less than 50mol%, or less than 45mol%, or less than 40mol%. The ethylene content of the copolymer can be at least 10mol% and less than 80mol%, or at least 20mol% and less than 70mol%, or at least 30mol% and less than 65mol%, or at least 40mol% and less than 60mol%.

[0131] C of ethylene-α-olefin copolymer 3 -C 10The alpha-olefin content may be at least 20 mol%, or at least 30 mol%, or at least 35 mol%, or at least 40 mol%, or at least 45 mol%, or at least 50 mol%, or at least 55 mol%, or at least 60 mol%.

[0132] In some embodiments, at least 70 mol% of the molecules of the ethylene-alpha olefin copolymer may have unsaturated groups, and at least 70 mol% of the unsaturated groups may be located in terminal vinylidene or trisubstituted isomers of terminal vinylidene, or at least 75 mol% of the copolymer terminates in terminal vinylidene or trisubstituted isomers of terminal vinylidene, or at least 80 mol% of the copolymer terminates in terminal vinylidene or trisubstituted isomers of terminal vinylidene, or at least 80 mol% of the copolymer terminates in terminal vinylidene or trisubstituted isomers of terminal vinylidene, or at least 85 mol% of the copolymer terminates in terminal vinylidene or trisubstituted isomers of terminal vinylidene, or at least 90 mol% of the copolymer terminates in terminal vinylidene or trisubstituted isomers of terminal vinylidene, or at least 95 mol% of the copolymer terminates in terminal vinylidene or trisubstituted isomers of terminal vinylidene. The terminal vinylidene and trisubstituted isomers of the terminal vinylidene of the copolymer have one or more of the following structural formulas (A)-(C):

[0133] and / or

[0134] Where R represents C 1 -C 8 Alkyl, and The indicated bond is attached to the remainder of the copolymer.

[0135] If through 13 The ethylene-alpha olefin copolymer may have an average ethylene unit continuous chain length (n) of less than 2.8 as determined by C NMR spectroscopy. C2 ), and also satisfy the relationship shown in the following expression:

[0136]

[0137] in

[0138] EEE=(x C2 ) 3 ,

[0139] EEA=2(x C2 ) 2 (1-x C2 ),

[0140] AEA=x C2(1-x C2 ) 2 ,

[0141] x C2 Is through 1 The mole fraction of ethylene incorporated into the polymer as measured by H-NMR spectroscopy, E represents ethylene units, and A represents α-olefin units. The average ethylene unit continuous segment length of the copolymer may be less than 2.6, or less than 2.4, or less than 2.2, or less than 2. The average ethylene continuous segment length n c2 The relationship shown in the following expression can also be satisfied:

[0142] Where n C2,实际值 <n C2,统计值 .

[0143] The crossover temperature of the ethylene-alpha olefin copolymer may be -20°C or less, or -25°C or less, or -30°C or less, or -35°C or less, or -40°C or less. The polydispersity index of the copolymer may be less than or equal to 4, or less than or equal to 3, or less than or equal to 2. Less than 20% of the unit triads in the copolymer may be ethylene-ethylene-ethylene triads, or less than 10% of the unit triads in the copolymer may be ethylene-ethylene-ethylene triads, or less than 5% of the unit triads in the copolymer may be ethylene-ethylene-ethylene triads. Additional details of ethylene-alpha olefin copolymers and dispersants made therefrom may be found in PCT / US18 / 37116 filed with the U.S. Office of Acceptance, the disclosure of which is incorporated herein by reference in its entirety.

[0144] One class of suitable dispersants may be Mannich bases. Mannich bases are materials formed by the condensation of higher molecular weight, alkyl-substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in more detail in U.S. Pat. No. 3,634,515.

[0145] A class of suitable dispersants may be high molecular weight esters or half ester amides. Suitable dispersants may also be post-treated by conventional methods by reacting with any of a variety of reagents. Among these are boron, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitrile, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. US 7,645,726, US 7,214,649, and US 8,048,831 are incorporated herein by reference in their entirety.

[0146] In addition to carbonate and boric acid post-treatments, both compounds may be post-treated or further post-treated with a variety of post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of U.S. Patent No. 5,241,003, incorporated herein by reference. Such treatments include treatment with inorganic phosphoric acid or anhydrides (e.g., U.S. Patent Nos. 3,403,102 and 4,648,980); organic phosphorus compounds (e.g., U.S. Patent No. 3,502,677); phosphorus pentasulfide; boron compounds as noted above (e.g., U.S. Patent Nos. 3,178,663 and 4,652,387); carboxylic acids, polycarboxylic acids, anhydrides and / or acid halides (e.g., U.S. Patent Nos. 3,708,522 and 4,648,980); 948,386); epoxy polyepoxy esters or thioepoxy esters (e.g., U.S. Pat. Nos. 3,859,318 and 5,026,495); aldehydes or ketones (e.g., U.S. Pat. No. 3,458,530); carbon disulfide (e.g., U.S. Pat. No. 3,256,185); glycidol (e.g., U.S. Pat. No. 4,617,137); urea, thiourea or guanidine (e.g., U.S. Pat. Nos. 3,312,619, 3,865,813 and GB 1,065,595); organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and GB 2,140,811); alkenyl cyanides (e.g., U.S. Pat. Nos. 3,278,550 and 3,366,569); diketenes (e.g., U.S. Pat. No. 3,546,243); diisocyanates (e.g., U.S. Pat. No. 3,573,205); alkane sultones (e.g., U.S. Pat. No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675); sulfates of alkoxylated alcohols or phenols (e.g., U.S. Pat. No. 3,954,639); Cyclic lactones (e.g., U.S. Pat. Nos. 4,617,138, 4,645,515, 4,668,246, 4,963,275, and 4,971,711); cyclic carbonates or thiocarbonic acid linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,648,886, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. No. 4,971,598 and British Patent No. GB ​​2,140,811); hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460);Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132, 4,647,390, 4,646,860, and 4,670,170); nitrogen-containing carboxylic acids (e.g., U.S. Pat. Nos. 4,971,598 and GB 2,440,811); hydroxy protected chlorodicarbonyloxy compounds (e.g., U.S. Pat. No. 4,614,522); lactams, thiolactams, thiolactones or dithiolactones (e.g., U.S. Pat. Nos. 4,614,603 and 4,666,460); cyclic carbamates, cyclic thiocarbamates or cyclic dithiocarbamates (e.g., U.S. Pat. Nos. 4,663,062 and 4,666,459); hydroxy aliphatic carboxylic acids (e.g., U.S. Pat. Nos. 4,482,464, 4,521,318, 4,713,189); oxygen catalyzer (e.g., U.S. Pat. No. 4,379,064); combination of phosphorus pentasulfide and polyalkylene polyamine (e.g., U.S. Pat. No. 3,185,647); combination of carboxylic acid or aldehyde or ketone with sulfur or sulfur chloride (e.g., U.S. Pat. Nos. 3,390,086 and 3,470,098); combination of hydrazine and carbon disulfide (e.g., U.S. Pat. No. 3,519,564); combination of aldehyde and phenol (e.g., U.S. Pat. Nos. 3,649,229, 5,030,249 and 5,039,307); combination of aldehyde and dithiophosphate O-diester (e.g., U.S. Pat. No. 3,649,229 ... ,865,740); a combination of a hydroxyaliphatic carboxylic acid and boric acid (e.g., U.S. Pat. No. 4,554,086); a combination of a hydroxyaliphatic carboxylic acid followed by formaldehyde and phenol (e.g., U.S. Pat. No. 4,636,322); a combination of a hydroxyaliphatic carboxylic acid followed by an aliphatic dicarboxylic acid (e.g., U.S. Pat. No. 4,663,064); a combination of formaldehyde and phenol followed by glycolic acid (e.g., U.S. Pat. No. 4,699,724); a combination of a hydroxyaliphatic carboxylic acid or oxalic acid followed by a diisocyanate (e.g., U.S. Pat. No. 4,713,191); an anhydride or a portion thereof of an inorganic acid or phosphorus. Combinations of part or all of a sulfur analog and a boron compound (e.g., U.S. Pat. No. 4,857,214); combinations of an organic diacid, followed by an unsaturated fatty acid, and followed by a nitrosoaromatic amine, optionally followed by a boron compound and followed by a glycolizing agent (e.g., U.S. Pat. No. 4,973,412); combinations of aldehydes and triazoles (e.g., U.S. Pat. No. 4,963,278); combinations of aldehydes and triazoles, followed by a boron compound (e.g., U.S. Pat. No. 4,981,492); combinations of cyclic lactones and boron compounds (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). The above-mentioned patents are incorporated herein in their entirety. ;

[0147] The TBN of a suitable dispersant may be from about 10 to about 65 mg KOH / g of dispersant on an oil-free basis, which is equivalent to about 5 to about 30 TBN if measured on a sample of the dispersant containing about 50% diluent oil. TBN is measured by the method of ASTM D2896.

[0148] Dispersants, if present, may be used in an amount sufficient to provide up to about 20 wt % based on the final weight of the lubricating oil composition. Another amount in which the dispersant may be used may be about 0.1 wt % to about 15 wt %, or about 0.1 wt % to about 10 wt %, or about 3 wt % to about 10 wt %, or about 1 wt % to about 6 wt %, or about 7 wt % to about 12 wt %, based on the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition employs a mixed dispersant system. A single type of dispersant or a mixture of two or more types of dispersants may be used in any desired ratio.

[0149] Extreme Pressure Agents The lubricating oil composition herein may also optionally contain one or more extreme pressure agents. Extreme pressure (EP) agents soluble in oil include sulfur-containing and chlorine-containing sulfur-containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents. Examples of such EP agents include: chlorinated waxes; organic sulfides and polysulfides, such as benzhydryl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, methyl sulfide of oleic acid, sulfide of alkylphenols, sulfide of dipentenes, sulfide of terpenes, and sulfide of Diels-Alder adducts; phosphosulfurized hydrocarbons, such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphorus esters, such as dialkyl and trialkyl phosphites, for example, dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, amylphenyl phosphite; diamylphenyl phosphite, tridecyl phosphite, distearyl phosphite, and polypropylene-substituted phenyl phosphites; metal thiocarbamates, such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkyl phosphoric acids, including, for example, amine salts of the reaction product of dialkyldithiophosphoric acids with propylene oxide; and mixtures thereof.

[0150] Friction modifiers The lubricating oil composition herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerides, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring plant or animal oils, dicarboxylic acid esters, esters or partial esters of polyols, and one or more aliphatic or aromatic carboxylic acids, and the like.

[0151] Suitable friction modifiers may contain a hydrocarbon group selected from linear, branched or aromatic hydrocarbon groups or mixtures thereof, and may be saturated or unsaturated. The hydrocarbon group may be composed of carbon and hydrogen or heteroatoms, such as sulfur or oxygen. The hydrocarbon group may be in the range of about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long-chain fatty acid ester. In another embodiment, the long-chain fatty acid ester may be a monoester or a diester or a (tri)glyceride. The friction modifier may be a long-chain fatty amide, a long-chain fatty ester, a long-chain fatty epoxide derivative or a long-chain imidazoline.

[0152] Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and generally include polar end groups (e.g., carboxyl or hydroxyl groups) covalently bonded to oleophilic hydrocarbon chains. An example of an organic ashless, nitrogen-free friction modifier is generally known as glyceryl monooleate (GMO), which may contain monoesters, diesters, and triesters of oleic acid. Other suitable friction modifiers are described in U.S. Pat. No. 6,723,685, which is incorporated herein by reference in its entirety.

[0153] Amine friction modifiers may include amines or polyamines. Such compounds may have straight chain, saturated or unsaturated hydrocarbon groups, or mixtures thereof, and may contain from about 12 to about 25 carbon atoms. Other examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have straight chain, saturated or unsaturated hydrocarbon groups, or mixtures thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

[0154] The amines and amides can be used as such or in the form of adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acid or mono-, di- or tri-alkyl borate esters. Other suitable friction modifiers are described in U.S. Pat. No. 6,300,291, which is incorporated herein by reference in its entirety.

[0155] Friction modifiers may optionally be present in a range of, for example, about 0 wt % to about 10 wt %, or about 0.01 wt % to about 8 wt %, or about 0.1 wt % to about 4 wt %.

[0156] Molybdenum-containing components:The lubricating oil composition herein may also optionally contain one or more molybdenum-containing compounds. The oil-soluble molybdenum compound may have the functional properties of an anti-wear agent, an antioxidant, a friction modifier, or a mixture thereof. The oil-soluble molybdenum compound may include molybdenum dithiocarbamate, molybdenum dialkyl dithiophosphate, molybdenum dithiophosphinate, amine salts of molybdenum compounds, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organic molybdenum compound, and / or a mixture thereof. Molybdenum sulfide includes molybdenum disulfide. Molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil-soluble molybdenum-containing compound may be selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyl dithiophosphate, amine salts of molybdenum-containing compounds, and mixtures thereof. In one embodiment, the oil-soluble molybdenum compound may be molybdenum dithiocarbamate.

[0157] Suitable examples of molybdenum compounds that may be used include commercial materials sold under the following trade names: Molyvan 822 from RT Vanderbilt Co., Ltd. TM 、Molyvan TM A. Molyvan 2000 TM and Molyvan 855 TM and Sakura-Lube available from Adeka Corporation TM S-165, S-200, S-300, S-310G, S-525, S-600, S-700 and S-710, and mixtures thereof. Suitable molybdenum components are described in US 5,650,381; US ​​RE 37,363 E1; US ​​RE 38,929 E1 and US RE 40,595 E1, which are incorporated herein by reference in their entirety.

[0158] In addition, the molybdenum compound may be an acidic molybdenum compound. Including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, molybdenum can be provided to the composition by a molybdenum / sulfur complex of a basic nitrogen compound, as described, for example, in U.S. Pat. Nos. 4,263,152; 4,285,822; 4,283,295; 4,272,387; 4,265,773; 4,261,843; 4,259,195 and 4,259,194; and WO 94 / 06897, which are incorporated herein by reference in their entirety.

[0159] Another class of suitable organomolybdenum compounds are trinuclear molybdenum compounds, such as those having the formula Mo3SkLnQz and mixtures thereof, wherein S represents sulfur, L represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to render the compound soluble or dispersible in oil, n is 1 to 4, k varies in the range of 4 to 7, Q is selected from the group of neutral electron donating compounds, such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. There may be a total of at least 21 carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms, in the organic groups of all ligands. Other suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685, which is incorporated herein by reference in its entirety.

[0160] The oil-soluble molybdenum compound may be present in an amount sufficient to provide about 0.5 ppm to about 2000 ppm, about 1 ppm to about 700 ppm, about 1 ppm to about 550 ppm, about 5 ppm to about 300 ppm, or about 20 ppm to about 250 ppm of molybdenum.

[0161] Compounds containing transition metals In another embodiment, the oil-soluble compound may be a compound containing a transition metal or a metalloid. The transition metal may include, but is not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, etc. Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, etc.

[0162] In one embodiment, the oil-soluble transition metal-containing compound may function as an anti-wear agent, a friction modifier, an antioxidant, a deposit control additive, or more than one of these functions. In one embodiment, the oil-soluble transition metal-containing compound may be an oil-soluble titanium compound, such as a titanium (IV) alkoxide. Titanium-containing compounds that can be used in the disclosed technology or can be used to prepare the oil-soluble materials of the disclosed technology are various Ti (IV) compounds, such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, 2-ethylhexyl titanium; and other titanium compounds or complexes, including but not limited to titanium phenolates; titanium carboxylates, such as 2-ethyl-1-3-hexanodioate titanium or titanium citrate or titanium oleate; and (triethanolate) isopropoxide titanium (IV). Other forms of titanium encompassed within the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., titanium dialkyl dithiophosphates), and titanium sulfonates (e.g., titanium alkylbenzene sulfonates), or generally, reaction products of titanium compounds reacting with various acidic materials to form salts (e.g., oil-soluble salts). Titanium compounds can therefore be derived, in particular, from organic acids, alcohols, and glycols. Ti compounds can also exist in dimerized or oligomeric forms, containing Ti--O--Ti structures. Such titanium materials are commercially available or can be easily prepared by appropriate synthesis techniques readily known to those skilled in the art. It exists in solid or liquid form at room temperature, depending on the specific compound. It can also be provided in the form of a solution in a suitable inert solvent.

[0163] In one embodiment, titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl-(or alkyl) succinic anhydride. The resulting titanate-succinate intermediate can be used directly, or can be reacted with any of a variety of substances, such as (a) a polyamine-type succinimide / amide dispersant having a free, condensable-NH functional group; (b) components of a polyamine-type succinimide / amide dispersant, i.e., alkenyl-(or alkyl-) succinic anhydride and a polyamine, (c) a hydroxyl-containing polyester dispersant prepared by reacting a substituted succinic anhydride with a polyol, an amino alcohol, a polyamine, or a mixture thereof. Alternatively, the titanate-succinate intermediate can be reacted with other reagents, such as alcohols, amino alcohols, ether alcohols, polyether alcohols, or polyols or fatty acids, and the product thereof can be used directly to impart Ti to the lubricant, or further reacted with a succinic acid dispersant as described above. As an example, 1 part (by mole) of tetraisopropyl titanate can be reacted with about 2 parts (by mole) of polyisobutylene-substituted succinic anhydride at 140-150° C. for 5 to 6 hours to provide a titanium-modified dispersant or intermediate. The resulting material (30 g) can be further reacted with a succinimide dispersant from polyisobutylene-substituted succinic anhydride and a polyethylene polyamine mixture (127 g + diluent oil) at 150° C. for 1.5 hours to produce a titanium-modified succinimide dispersant.

[0164] Another titanium-containing compound can be a titanium alkoxide and a C 6 To C 25 The reaction product of carboxylic acid. The reaction product can be represented by the following formula:

[0165]

[0166] wherein n is an integer selected from 2, 3 and 4, and R is a hydrocarbon group containing from about 5 to about 24 carbon atoms, or is represented by the formula:

[0167]

[0168] Where m+n=4 and n is in the range of 1 to 3, R 4 is an alkyl moiety having 1 to 8 carbon atoms, R 1 is selected from hydrocarbon groups containing from about 6 to 25 carbon atoms, and R 2 and R 3 The same or different and selected from hydrocarbon groups containing about 1 to 6 carbon atoms, or the titanium compound can be represented by the following formula:

[0169]

[0170] Where x is in the range of 0 to 3, R 1 is selected from hydrocarbon groups containing from about 6 to 25 carbon atoms, R2 and R 3 are the same or different and are selected from hydrocarbon groups containing about 1 to 6 carbon atoms, and R 4 Choose from H, or C 6 To C 25 The group consisting of carboxylic acid moieties.

[0171] Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

[0172] In one embodiment, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount providing 0 to 3000 ppm by weight titanium, or 25 to about 1500 ppm by weight titanium, or about 35 to 500 ppm by weight titanium, or about 50 ppm to about 300 ppm by weight.

[0173] Viscosity Index Improver :The lubricating oil composition herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers 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, polyalkylstyrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, and suitable examples are described in U.S. Publication No. 20120101017A1.

[0174] The lubricating oil compositions herein may optionally contain one or more dispersant viscosity index improvers in addition to or in place of the viscosity index improvers. Suitable viscosity index improvers may include functionalized polyolefins, for example, ethylene-propylene copolymers functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine; polymethacrylates functionalized with amines, or esterified maleic anhydride-styrene copolymers reacted with amines.

[0175] Viscosity Index Improvers and / or Dispersants The total amount of viscosity index improver may be from about 0 wt % to about 20 wt %, from about 0.1 wt % to about 15 wt %, from about 0.1 wt % to about 12 wt %, or from about 0.5 wt % to about 10 wt % of the lubricating oil composition.

[0176] Other optional additives Other additives may be selected to perform one or more functions required of a lubricating fluid. In addition, one or more of the additives mentioned may be multifunctional and provide functions other than or different from those specified herein.

[0177] Lubricating oil compositions according to the present disclosure may optionally include other performance additives. The other performance additives may be additives other than the specified additives of the present disclosure and / or may include one or more of the following: metal passivators, viscosity index improvers, detergents, ashless TBN promoters, friction modifiers, anti-wear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

[0178] Suitable metal deactivators may include benzotriazole derivatives (typically tolyltriazole), dithiothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.

[0179] Suitable suds suppressors include silicon based compounds such as siloxanes.

[0180] Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide about 0 wt.% to about 1 wt.%, about 0.01 wt.% to about 0.5 wt.%, or about 0.02 wt.% to about 0.04 wt.% based on the final weight of the lubricating oil composition.

[0181] Suitable rust inhibitors can be single compounds or compound mixtures having the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of useful rust inhibitors herein include: oil-soluble high molecular weight organic acids, such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid; and oil-soluble polycarboxylic acids including dimer acids and trimer acids, such as those produced by pine oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long-chain α, ω-dicarboxylic acids with a molecular weight ranging from about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropylene succinic acid, tetradecene succinic acid, and hexadecene succinic acid. Another type of acidic corrosion inhibitor available is a half ester of alkenyl succinic acid and an alcohol (such as polyethylene glycol) having about 8 to about 24 carbon atoms in the alkenyl group. The corresponding half amides of such alkenyl succinic acids are also available. Useful rust inhibitors are high molecular weight organic acids. In some embodiments, the engine oil does not contain a rust inhibitor.

[0182] Rust inhibitors, if present, may be used in amounts sufficient to provide from about 0 wt % to about 5 wt %, from about 0.01 wt % to about 3 wt %, from about 0.1 wt % to about 2 wt % based on the final weight of the lubricating oil composition.

[0183] Generally speaking, suitable crankcase lubricants may include an additive component within the ranges listed in the table below.

[0184] Table 2

[0185]

[0186] The percentages of each component above represent the weight percentage of each component by weight of the final lubricating oil composition. The remainder of the lubricating oil composition consists of one or more base oils. The additives used to formulate the compositions described herein can be blended into the base oils individually or in various sub-combinations. However, it may be appropriate to blend all components simultaneously using an additive concentrate (i.e., additives plus a diluent, such as a hydrocarbon solvent).

[0187] Examples

[0188] The following examples illustrate exemplary embodiments of the present disclosure. In these examples and elsewhere in this application, unless otherwise indicated, all ratios, parts and percentages are by weight. It is intended to present these examples only for illustrative purposes and is not intended to limit the scope of the invention disclosed herein.

[0189] Example 1

[0190] The following examples demonstrate the beneficial properties of the copolymer surfactants and lubricating compositions of the present disclosure. The test formulations are listed in Table 3 below and the polymer surfactants evaluated in the fluids are shown in Table 4. The additive package and viscosity modifiers for all test formulations were the same. The base oil (Group III) treatment rate was adjusted according to the amount of copolymer added.

[0191] For testing, each lubricating composition of Table 3, distilled water and EEE gasoline were mixed at a weight ratio of 60:20:20 (total weight 100 g) for 1 minute using a Waring mixer at 17,000 rpm to prepare an emulsion. EEE fuel is an unleaded fuel manufactured by Haltermann, as described in the E85 emulsion test (ASTM D7563). Then, the emulsion was transferred to a 100 mL graduated cylinder. The graduated cylinder was kept at room temperature for 3 hours. Then, a sample for viscosity and flow point measurement was obtained from the 15 mL mark at the bottom of the graduated cylinder, and an oscillating rheometer was used to measure.

[0192] The flow point was measured using an Anton Paar oscillating MCR rheometer by strain sweeping from 0.01 to 100% shear strain with a parallel plate spindle. The angular frequency in the test was 10 rad / s and the gap was set to 0.5 mm. After the sample was loaded onto the plates on the rheometer, the system was cooled to -30°C and maintained at this temperature for 5 hours before the strain sweep began. The sample was not further mixed before the flow test. The flow point is defined as the shear strain where G' (storage modulus) equals G" (loss modulus). A lower flow point indicates that the sample has better fluidity under the test conditions and temperature.

[0193] Table 3 lists the flow points of all tested samples, and Table 4 indicates the details about the polymeric surfactant. For example, the comparative sample 1 without any polymeric surfactant exhibits an extremely high flow point outside the tested shear strain range (>100%), indicating that the sample is still a viscoelastic solid within the measured strain range. The inventive sample 2 containing 0.3wt% of a poly(meth)acrylate copolymer surfactant (copolymer A) having a pyrrolidone polar portion exhibits a low flow point of about 1.4%. The inventive sample 3 containing 0.3wt% of a poly(meth)acrylate copolymer surfactant (copolymer B) that also includes pyrrolidone but has a lower molecular weight has a higher flow point than the inventive sample 2, but is still acceptable and detectable within the tested range. These results show that the inventive PMA copolymer surfactant having a pyrrolidone polar functional group in samples 2 and 3 can provide good low temperature fluidity of emulsions of lubricants, water and fuels at temperatures as low as -30°C.

[0194] Examples 4, 5, and 7 contain other types of polymeric surfactants with different polar and non-polar functionalities at 0.3% test rate. The flow points of samples 4 and 7 are lower than that of sample 5, indicating that higher molecular weight surfactants provide emulsions better at low temperatures (although the flow points of samples 4 and 7 are comparable). Sample 6, which has an olefin copolymer non-polar portion and N-phenyl-phenylenediamine succinimide polar functional groups, can also achieve a good flow point at low temperatures. The results show that the copolymers of the present disclosure unexpectedly improve the low temperature fluidity of the emulsion.

[0195] Table 3: Samples and measured flow points for each formulation

[0196]

[0197]

[0198] Table 4: Surfactants used in the examples

[0199]

[0200] Figure 1 It also provides the viscosity of the sample, while Figure 2-8 Displays flow point determination.

[0201] It should be noted that, unless expressly and affirmatively limited to one referent, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents. Thus, for example, reference to "an antioxidant" includes two or more different antioxidants. The term "comprising" and its grammatical variations as used herein are intended to be non-limiting, such that recitation of items in a list does not exclude other similar items that can be substituted or added to the listed items.

[0202] For the purposes of this specification and the appended claims, unless otherwise indicated, all numerical and other numerical values ​​indicating amounts, percentages or ratios used in this specification and the claims should be understood to be modified in all cases by the term "about". Therefore, unless otherwise indicated, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that may vary in view of the desired properties obtained by the present disclosure. At a minimum, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in light of the number of reported significant figures and by applying ordinary rounding techniques.

[0203] It should be understood that each component, compound, substituent or parameter disclosed herein should be interpreted as disclosed for use alone or in combination with one or more of each of the other components, compounds, substituents or parameters disclosed herein.

[0204] It should be further understood that each range disclosed herein should be interpreted as a disclosure of each specific value within the disclosed range with the same number of significant figures. Thus, for example, a range of 1 to 4 should be interpreted as an explicit disclosure of the values ​​1, 2, 3, and 4, as well as any range of such values.

[0205] It should be further understood that each lower limit of each scope disclosed herein should be interpreted as being disclosed in combination with each upper limit of each scope disclosed herein for the same component, compound, substituent or parameter and each specific value in each scope. Therefore, the disclosure should be interpreted as being disclosed by combining each lower limit of each scope with each upper limit of each scope or with each specific value in each scope, or by combining each upper limit of each scope with each specific value in each scope. That is, it should also be further understood that any scope between the endpoint values ​​in a wide range is also discussed herein. Therefore, the scope of 1 to 4 also means the scope of 1 to 3, 1 to 2, 2 to 4, 2 to 3, etc.

[0206] In addition, specific amounts / values ​​of components, compounds, substituents or parameters disclosed in this specification or examples should be interpreted as disclosure of the lower or upper limit of a range, and therefore can be combined with any other lower or upper limit or specific amount / value of a range for the same component, compound, substituent or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent or parameter.

[0207] Although specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not currently foreseen or may not currently be foreseen may occur to applicants or other persons skilled in the art. Therefore, the appended claims as filed and as they may be amended are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A low temperature stable lubricating composition comprising: a base oil of lubricating viscosity; 0.01% wt% to 3% wt% of a polymeric surfactant having a non-polar portion and 15% to 30% polar functionality effective to maintain a fluid emulsion as evidenced by a flow point of 45% or less measured at a lubricant temperature as low as about -30°C; and water and / or fuel contamination; and The weight average molecular weight of the polymer surfactant is 40,000 to 450,000.

2. The low temperature stable lubricating composition of claim 1, wherein the polymeric surfactant is a copolymer obtained from reactants having ethylenic unsaturation, the reactants being functionalized by grafting polar groups or by incorporating polar co-reactants in the polymerization reaction; and / or wherein the polymeric surfactant is a copolymer obtained from reactants comprising alkyl (meth)acrylates and heterocyclic reactants having polymerizable ethylenically unsaturated substituents.

3. The low temperature stable lubricating composition of claim 2, wherein the heterocyclic reactant having a polymerizable ethylenically unsaturated substituent comprises a vinyl lactone, a vinyl lactam, a combination thereof, and a derivative thereof.

4. The low temperature stable lubricating composition according to claim 2 or 3, wherein the alkyl (meth)acrylate reactant comprises a reactant selected from C1 to C20 linear or branched alkyl (meth)acrylate reactants.

5. The low temperature stable lubricating composition according to any one of claims 1 to 3, wherein the polar functional groups are pendant to the non-polar polymer backbone.

6. The low temperature stable lubricating composition according to any one of claims 1 to 3, wherein the polar functional groups of the polymer surfactant include one or more of oxygen, nitrogen, sulfur or phosphorus atoms.

7. The low temperature stable lubricating composition of any one of claims 1 to 3, wherein the lubricating composition is emulsified with water and fuel to form a fluid emulsion at a temperature as low as about -30°C.

8. The low temperature stable lubricating composition according to any one of claims 1 to 3, wherein the lubricating composition is an engine oil.

9. The low temperature stable lubricating composition according to any one of claims 1 to 3, wherein the lubricating composition is a passenger car motor oil.

10. The low temperature stable lubricating composition according to any one of claims 1 to 3, wherein the fuel is selected from the group consisting of gasoline and alcohol-based fuels.

11. The low temperature stable lubricating composition according to any one of claims 1 to 3, wherein the fuel is an alcohol blended fuel.

12. The low temperature stable lubricating composition according to any one of claims 1 to 3, wherein the fuel is gasoline blended with ethanol.

13. The low temperature stable lubricating composition of claim 12, wherein the fuel is a gasoline blended with ethanol selected from the group consisting of E10, E50, E85 and E100.

14. The low temperature stable lubricating composition of claim 2, wherein the heterocyclic reactant having a polymerizable ethylenically unsaturated substituent comprises vinyl pyrrolidone, vinyl pyridine, combinations thereof, and derivatives thereof.

15. A method of lubricating an engine at low temperatures, the method comprising providing a lubricating composition according to any one of claims 1 to 14, and lubricating the engine with the lubricating composition at a temperature of up to about -30°C.

16. A method for maintaining fluid viscosity of a lubricating composition, water and / or fuel, the method comprising adding an additive to the lubricating composition, the additive comprising 0.01% wt% to 3% wt% of a polymeric surfactant having a non-polar portion and 15% to 30% polar functional groups, effective to maintain a fluid emulsion when the lubricating composition is mixed with water and / or fuel contamination, as evidenced by a flow point of 45% or less measured at a lubricant temperature as low as about -30°C; and wherein the polymeric surfactant has a weight average molecular weight of 40,000 to 450,000.

17. The method of claim 16, wherein the polymeric surfactant is as described in any one of claims 2 to 6; and / or the lubricating composition is as described in any one of claims 7-9; and / or the fuel is as described in claim 10.

18. The method of claim 16, wherein the polymeric surfactant is as described in any one of claims 2 to 6; and / or the lubricating composition is as described in any one of claims 7-9; and / or the fuel is as described in claim 11.

19. The method of claim 16, wherein the polymeric surfactant is as described in any one of claims 2 to 6; and / or the lubricating composition is as described in any one of claims 7-9; and / or the fuel is as described in claim 12.

20. The method of claim 16, wherein the polymeric surfactant is as described in any one of claims 2 to 6; and / or the lubricating composition is as described in any one of claims 7-9; and / or the fuel is as described in claim 13.

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