Patent Application
20200299608
The present invention relates generally to a stable non-flammable multiuse lubricants and more specifically to aerosol non-flammable multiuse lubricants.
A lubricant is a substance introduced to reduce friction between surfaces in mutual contact, which can reduce the heat generated when the surfaces move. The typical characteristics required for a good lubricant include low viscosity, corrosion prevention, non-flammability, thermal stability, and a high resistance to oxidation.
Take WD-40® multiuse product as an example, for over 50 years, consumers have used WD-40® Multi-Use Product (hereinafter “WD-40®”) to protect metal from rust and corrosion and for penetrating lubrication. WD-40® protects and lubricates effectively, in part, because it so effectively displaces water. Typical lubricant composition contains hydrocarbons and can be flammable.
There has long been a need for a stable non-flammable multiuse lubricant. However, there is an inherent tension between performance and non-flammability in multiuse aerosol lubricants. While hydrocarbons impart much of the performance in multiuse lubricants like WD-40®, hydrocarbons are inherently flammable. Additionally, applying a lubricant in the form of aerosol can be a unique way of facilitating surface wetting, displacing water on the surface, and penetrating through rust in a machine. However, for aerosol products the aerosols add to the danger of creating a flammable product. Conversely, while water decreases the flammability profile of the product, water causes rust and corrosion, which is exactly what multiuse aerosol lubricants are designed to prevent.
Accordingly, what is needed is an aerosol lubricant composition, as well as a method and an apparatus to make the same, which can provide a good lubricating property without posing the problem of flammability.
In one embodiment, the present invention is directed to methods of making an invert emulsion lubricating composition. In some aspects, the method can include (A) adding a ester base oil and a water-in-oil emulsifier into a reaction vessel; (B) homogenizing the ester base oil and the water-in-oil emulsifier; (C) adding water into the reaction vessel; and (D) homogenizing the mixture in the reaction vessel until all the water is emulsified and no residual water is left at the bottom of the reaction vessel, wherein the invert emulsion lubricating composition can include the ester base oil at about 25% to 55% by weight, the water-in-oil emulsifier at about 2% to 14% by weight, and water at about 35% to 65% by weight. The invert emulsion lubricating composition can be non-flammable. In some aspects, the water-in-oil emulsifier can have a hydrophilic-lipophilic balance (HLB) value of about 1 to 10 or about 3 to 6. In various aspects, the water-in-oil emulsifier can be an oligomeric ester emulsifier with a viscosity of about 1000 to 3500 mPa·s or about 1200 to 1500 mPa·s when measured at 25° C. In an additional aspect, the ester base oil is an unsaturated mono ester with a viscosity index of higher than about 100 or higher than about 200. In a further aspect, the ester base oil can have a viscosity of about 5 to 7 mPa·s at 40 Celsius. The loading of the ester base oil can be at about 30% to 50% or about 35% to 45% by weight. The loading of the water-in-oil emulsifier can be at about 3% to 12% or about 5% to 10% by weight. The loading of water can be at about 40% to 60% or about 45% to 55% by weight. In various aspects, wherein the invert emulsion lubricating composition can further include a preservative at about 0.01 to 1% by weight of the lubricating composition. The preservative can include bronopol (2-bromo-2-nitro-1,3-propanediol).
In an additional embodiment, the present invention is directed to methods of making an aerosol lubricant, the method can include delivering a liquid through a stem with a radius of about 0.015 to 0.030 inch (about 0.038 to 0.076 cm), and actuating the liquid into the aerosol lubricant. In some aspects, the liquid can comprise a lubricating composition produced by the method of (A) adding a ester base oil and a water-in-oil emulsifier into a reaction vessel; (B) homogenizing the ester base oil and the water-in-oil emulsifier; (C) adding water into the reaction vessel; and (D) homogenizing the mixture in the reaction vessel until all the water is emulsified and no residual water is left at the bottom of the reaction vessel, wherein the invert emulsion lubricating composition can include the ester base oil at about 25% to 55% by weight, the water-in-oil emulsifier at about 2% to 14% by weight, and water at about 35% to 65% by weight. In various aspects, the stem can have a radius of about 0.020 inch (about 0.051 cm). The aerosol lubricating composition can have no flame extension and no flashback. In an additional aspect, the liquid for making the aerosol lubricating composition can further include a propellant. The liquid can include the propellant at about 10% to 20% by weight and the lubricating composition at about 80% to 90% by weight. In a further aspect, the liquid can include the propellant at about 13% by weight and the lubricating composition at about 87% by weight. The propellant can include 1,3,3,3-tetrafluoropropene.
In a further embodiment, the present invention is directed to methods of using an invert emulsion lubrication, the invert emulsion lubrication can include an ester base oil at about 25% to 55% by weight, a water-in-oil emulsifier at about 2% to 14% by weight, water at about 35% to 65% by weight, and a preservative. The use can include, but is not limited to, preventing corrosion; providing protection by lubrication; loosening rust and/or corrosion; removing grease, dirt, and oil; and driving out moisture via water displacement.
In one embodiment, the present invention is directed to an aerosol lubrication composition including an invert emulsion, the invert emulsion can include an ester base oil at about 25% to 55% by weight, the ester base oil is an unsaturated mono ester with a viscosity index of higher than about 200; a water-in-oil emulsifier at about 2% to 14% by weight, the water-in-oil emulsifier is an oligomeric ester emulsifier with a viscosity of about 1200 to 1500 mPa·s measured at 25° C. with an HLB value of about 3 to 6; water at about 35% to 65% by weight; and a preservative. The aerosol lubrication composition can be generated by delivering the invert emulsion through a stem with a radius of about 0.015 to 0.030 inch (about 0.038 to 0.076 cm). In some aspects, the stem can have a radius of about 0.020 inch (about 0.051 cm).
In order to facilitate a full understanding of the present disclosure, reference is now made to the accompanying drawings, in which like elements are referenced with like numerals. These drawings should not be construed as limiting the present disclosure, but are intended to be illustrative only. The drawings are not necessarily to scale, or inclusive of all elements of a system, emphasis instead generally being placed upon illustrating the concepts, structures, and techniques sought to be protected herein.
The present invention is based on the seminal discovery that a stable non-flammable composition in the form of a substantially stable water-in-oil emulsion for use in protecting metal from rust and corrosion, penetrating stuck parts, displacing moisture and lubricating almost anything. More particularly, such non-flammable composition consists of water, an oil base, an invert emulsifier, and a preservative. Further, the invention provides an aerosol formulation for the non-flammable lubricant composition. The aerosol delivery system can include a standard aerosol mechanism with increased stem orifice radius sufficient to create larger than standard droplets in the aerosol to reduce the flammability profile of the aerosol mist.
Before the present compositions and methods are described, it is to be understood that this invention is not limited to particular compositions, methods, and experimental conditions described, as such compositions, methods, and conditions may vary. It is also to be understood that the terminology used herein is for purposes of describing particular embodiments only, and is not intended to be limiting, since the scope of the present invention will be limited only in the appended claims.
As used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise. Thus, for example, references to “the method” includes one or more methods, and/or steps of the type described herein which will become apparent to those persons skilled in the art upon reading this disclosure and so forth.
All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the invention, it will be understood that modifications and variations are encompassed within the spirit and scope of the instant disclosure. The preferred methods and materials are now described.
The use of water-in-oil emulsions has been used in other fields to create non-flammable lubricants. For example, in the hydraulic field, invert emulsions are routinely used to create non-flammable hydraulic fluids that have lubricating properties. However, because of the higher demands for lubrication and non-flammability, inverse emulsions have not been used for multiuse aerosol lubricants. In addition, in order to prevent the water component in the lubricant composition coming in contact with the applied surface, it is important to ensure the stability of the invert emulsion. Otherwise, water may cause rust formation when applied to machinery, counter-effective to the purpose of preventing corrosion and loosening rust.
The present disclosure has found surprisingly that when an invert emulsion made with a synthetic ester base oil and a compatible invert emulsifier is delivered through an aerosol apparatus that creates certain larger than standard droplets it creates a non-flammable multiuse lubricant aerosol. It is also surprisingly found the aerosol invert emulsion lubricant of the present disclosure imparts a highly stable water-in-oil emulsion during the application. A preservative can be included in the composition to prevent the growth of bacteria, yeast, and molds that would interfere with the creation and stability of the emulsion.
The improved water-in-oil aerosol non-flammable multiuse lubricating composition appears to be an improvement over the prior art lubricating compositions because of its improved combination of lubrication, corrosion and rust prevention, water displacement, and fire resistance.
For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities of ingredients, percentages or proportions of materials, reaction conditions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about.” Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment that is +/-10% of the recited value. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Ranges may be expressed herein as from “about” or “approximately” one particular value and/or to “about” or “approximately” another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value.
The term “aerosol”, as used herein, refers to a material which is dispensed from its container as a mist, spray, or foam by a propellant under pressure, or an “aerosol product” means a product characterized by a pressurized spray system that dispenses product ingredients in aerosol form by means of a propellant (i.e., a liquefied or compressed gas that is used in whole or in part, such as a co-solvent, to expel a liquid or any other material from the same self-pressurized container or from a separate container) or mechanically induced force. In referencing the propellant, aerosol means any non-refillable receptacle containing a gas compressed, liquefied or dissolved under pressure, the sole purpose of which is to expel a nonpoisonous liquid, paste, or powder and fitted with a self-closing release device allowing the contents to be ejected by the gas.
The term “non-aerosol”, as used herein, refers to pump sprays. Non-aerosol sprays are normally in a bottle with an atomizer attachment (such as a pump-sprayer). The pump sprayer uses springs, valves and tubes to mix the liquid with a small amount of air and emits the liquid as small droplets propelled in short bursts.
In one embodiment, the present invention is directed to methods of making an invert emulsion lubricating composition. In some aspects, the method can include (A) adding a ester base oil and a water-in-oil emulsifier into a reaction vessel; (B) homogenizing the ester base oil and the water-in-oil emulsifier; (C) adding water into the reaction vessel; and (D) homogenizing the mixture in the reaction vessel until all the water is emulsified and no residual water is left at the bottom of the reaction vessel, wherein the invert emulsion lubricating composition can include the ester base oil at about 25% to 55% by weight, the water-in-oil emulsifier at about 2% to 14% by weight, and water at about 35% to 65% by weight. The invert emulsion lubricating composition can be non-flammable.
In some aspects, the water-in-oil emulsifier can have a hydrophilic-lipophilic balance (HLB) value of about 1 to 10 or about 3 to 6. In certain aspects, the water-in-oil emulsifier can be an oligomeric ester emulsifier with a viscosity of about 1000 to 3500 mPa·s or about 1200 to 1500 mPa·s when measured at 25° C. In various aspects, the ester base oil is an unsaturated mono ester with a viscosity index of higher than about 100 or higher than about 200. In an additional aspect, the ester base oil can have a viscosity of about 5 to 7 mPa·s at 40 Celsius. The loading of the ester base oil can be at about 30% to 50% or about 35% to 45% by weight. The loading of the water-in-oil emulsifier can be at about 3% to 12% or about 5% to 10% by weight. The loading of water can be at about 40% to 60% or about 45% to 55% by weight. In a further aspect, the invert emulsion lubricating composition can further include a preservative at about 0.01 to 1% by weight of the lubricating composition. The preservative can include bronopol (2-bromo-2-nitro-1,3-propanediol).
In an additional embodiment, the present invention is directed to methods of making an aerosol lubricant, the method can include delivering a liquid through a stem with a radius of about 0.015 to 0.030 inch (about 0.038 to 0.076 cm), and actuating the liquid into the aerosol lubricant.
In one aspect, the liquid can comprise a lubricating composition produced by the method of (A) adding a ester base oil and a water-in-oil emulsifier into a reaction vessel; (B) homogenizing the ester base oil and the water-in-oil emulsifier; (C) adding water into the reaction vessel; and (D) homogenizing the mixture in the reaction vessel until all the water is emulsified and no residual water is left at the bottom of the reaction vessel, wherein the invert emulsion lubricating composition can include the ester base oil at about 25% to 55% by weight, the water-in-oil emulsifier at about 2% to 14% by weight, and water at about 35% to 65% by weight.
In an additional aspect, the stem can have a radius of about 0.020 inch (about 0.051 cm). The aerosol lubricating composition can have no flame extension and no flashback. In certain aspects, the liquid for making the aerosol lubricating composition can further include a propellant. The liquid can include the propellant at about 10% to 20% by weight and the lubricating composition at about 80% to 90% by weight. In various aspects, the liquid can include the propellant at about 13% by weight and the lubricating composition at about 87% by weight. The propellant can include 1,3,3,3-tetrafluoropropene
In a further embodiment, the present invention is directed to methods of using an invert emulsion lubrication, the invert emulsion lubrication can include an ester base oil at about 25% to 55% by weight, a water-in-oil emulsifier at about 2% to 14% by weight, water at about 35% to 65% by weight, and a preservative. The use can include, but is not limited to, preventing corrosion; providing protection by lubrication; loosening rust and/or corrosion; removing grease, dirt, and oil; and driving out moisture via water displacement.
In a further embodiment, the present invention is directed to an aerosol lubrication composition including an invert emulsion, the invert emulsion can include an ester base oil at about 25% to 55% by weight, the ester base oil is an unsaturated mono ester with a viscosity index of higher than about 200; a water-in-oil emulsifier at about 2% to 14% by weight, the water-in-oil emulsifier is an oligomeric ester emulsifier with a viscosity of about 1200 to 1500 mPa·s measured at 25° C. with an HLB value of about 3 to 6; water at about 35% to 65% by weight; and a preservative. The aerosol lubrication composition can be generated by delivering the invert emulsion through a stem with a radius of about 0.015 to 0.030 inch (about 0.038 to 0.076 cm). In some aspects, the stem can have a radius of about 0.020 inch (about 0.051 cm).
In some aspects, the aerosol lubrication composition according to the present disclosure can include a base oil. The base oil can be a water insoluble organic compound. The base oil can be an ester base oil, an ether base oil, or a hydrocarbon base oil. In some embodiments, the base oil can be a water insoluble organic compound including one, two, three, or more oxygen atoms. In some embodiments, the aerosol lubrication composition includes an ester base oil. The ester base oil can be natural or synthetic. In some aspects, the base oil can be an ester of a long chain carboxylic acid such as fatty acid with a short china alcohol. The short chain alcohol can have about five or fewer carbon atoms. The base oil can be an ester including a mono-, di-, tri, or poly-hydric alcohol, with one or more of the hydroxyl groups each being coupled to a carboxylic acid as an ester group. In some embodiments, the base oil can be a mono ester.
The base oil can include esters of mono-carboxylic fatty acids and di- and poly-carboxylic acid compounds. Non-limiting examples of fatty acid components of the ester can include octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, palmitic acid, stearic acid, oleic acid, or mixture thereof. Non-limiting examples of di- and poly carboxylic acid components of the ester can include adipic acid, succinic acid, glutaric acid, sebacic acid, phthalic acid, trimellitic acid, and mixtures thereof.
The base oil can include esters including any of a variety of alcohol moieties, such as monohydric fatty alcohols and di- and polyhydric compounds. Non-limiting examples of monohydric alcohol components of the ester can include primary aliphatic alcohols, such as aliphatic hydrocarbon alcohols, for example, methanol, ethanol, and linear and branched primary alcohols with 3 to 25 carbon atoms. Non-limiting examples of di- and poly-hydric alcohol components of the ester can include those containing from 2 to about 8 hydroxy groups, such as alkylene glycols, e.g., ethylene glycol, diethylene glycol, neopentyl glycol, tetraethylene glycol, or mixture thereof. Additional suitable alcohol components of the ester can include, but are not limited to, glycerine, erythritol, mannitol, sorbitol, glucose, trimethylolpropane (TMP), pentaerythritol, dipentaerythritol, sorbitan, or mixture thereof.
In some embodiments, the base oil according to the present disclosure can include ester of a variety of carboxylic acid and alcohol residues that provide a water insoluble (not capable to be dissolved in water to give clear solutions at concentrations greater than about 0.1% by weight at room temperature) ester that is a liquid, semi-solid, or a low melting solid. Room temperature in the present disclosure can be about 20 to 30 Celsius.
In some embodiments, the base oil can have a low viscosity to enhance wetting, penetration, and lubrication. The viscosity of the base oil used in the disclosed aerosol lubrication composition, when measured at about at 40 Celsius, can be about 1 to 500 mPa·s, about 2 to 400 mPa·s, about 3 to 300 mPa·s, about 4 to 200 mPa·s, about 5 to 100 mPa·s, about 6 to 50 mPa·s, about 7 to 30 mPa·s, about 1 to 30 mPa·s, about 7 to 500 mPa·s, or about 5 to 7 mPa·s. In some embodiments, the base oil can have a viscosity of about 5 to 7 mPa·s at 40 Celsius.
The above-mentioned viscosity values can be measured using a Brookfield viscometer. The viscometer motor rotates the spindle at a defined speed (measured in rpm) or shear rate and the viscometer measures the resistance to rotation and reports a viscosity value. In some aspects, the viscosity can be measured according to the standard ASTM D2983.
In some aspects, the viscosity of the base oil can be characterized via viscosity index (VI), measured according to the international standard ASTM D2270. A higher VI points to a lower viscosity. In some aspects, the base oil can have a VI of greater than or equal to about 130, greater than or equal to about 150, greater than or equal to about 160, or greater or equal to about 200.
In some aspects, the base oil used for the aerosol lubrication composition can include Priolube™ LL-564. Priolube LL564™ is a low viscosity, non-volatile mono ester that enhances wetting, penetration and lubrication. It is biodegradable, with an acid value of about 1.0 mgKOH/g and a density of about 0.87 g/mL at 20 Celsius. It has a hydroxyl value of about 6 mgKOH/g and an iodine value of about 30 g/100 g. Priolube LL564™ has a viscosity of about 5 to 7 mPa·s at 40 Celsius, and a viscosity index of about 228. In some aspects, Synative® DPHA comprising di-(2-propylheptyl) adipate can be used as base oil for the present disclosure.
In some aspects, some non-limiting concentrations of the base oil by weight of the invert emulsion liquid can include about 10% to 70%, about 20% to 60%, about 25% to 55%, about 30% to 50%, about 35% to 45%, about 10% to 45%, or about 35% to 70%. In some aspects, the concentration of the base oil can be about 25% to 55% by weight of the invert emulsion liquid. In some aspects, the concentration of base oil can be about 30% to 50% by weight of the invert emulsion liquid. In some aspects, the concentration of base oil can be about 45% to 55% by weight of the invert emulsion liquid. In some aspects, the concentration of the base oil is at least about 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, or 60% by weight of the invert emulsion liquid.
Surfactants are typically amphiphilic molecules that contain both hydrophilic and lipophilic groups. The hydrophile-lipophile balance (HLB) number is used as a measure of the ratio of these groups. It is a value between 0-60 defining the affinity of a surfactant for water or oil. HLB numbers are calculated for nonionic surfactants, and these surfactants have numbers ranging from 0-20. HLB numbers >10 have an affinity for water (hydrophilic) and number <10 have an affinity of oil (lipophilic). Ionic surfactants have recently been assigned relative HLB values, allowing the range of numbers to extend to 60.
In some aspects, the emulsifier used in the present disclosure can have an HLB value of about 1 to 100. Some other non-limiting HLB values of the emulsifier used in the non-flammable aerosol lubricants disclosed herein can include, but not limited to, about 1 to 50, about 2 to 30, about 3 to 10, about 4 to 8, about 1 to 8, or about 4 to 50. In some aspects, the HLB value of the emulsifier can be about 1 to 10. In some aspects, the HLB value of the emulsifier can be about 4 to 6.
A major issue encountered in water-in-oil (W/O) emulsions is their instability. The advantage brought about by polymeric/oligomeric emulsifiers over conventional species is a consequence of the multiple and extensive interactions with both the continuous and dispersed phases. In the classical chemistry of surface active agents, ionic or non-ionic polar groups and hydrophobes of C12-C18 chain length are combined to produce molecules that have one single weak point of interaction with each of the immiscible phases. Polymeric/oligomeric emulsifiers, on the other hand, can be adsorbed onto the particle surface, their polymeric chains penetrate into the medium and provide a barrier which prevents strong interactions between particles.
In some aspects, the water-in-oil emulsifier can have a high viscosity. The viscosity of the water-in-oil emulsifier used in the present disclosure, when measured at about at 25 Celsius, can be about 500 to 5000 mPa·s, about 700 to 4000 mPa·s, about 1000 to 3500 mPa·s, about 1100 to 3000 mPa·s, about 1150 to 2500 mPa·s, about 1200 to 2000 mPa·s, about 1300 to 1500 mPa·s, about 500 to 1500 mPa·s, or about 1300 to 5000 mPa·s. In some aspects, the water-in-oil emulsifier can have a viscosity of about 1200 to 1500 mPa·s at 25 Celsius. In some aspects, the viscosity can be measured according to the standard ASTM D2983.
In some aspects, a water-in-oil emulsifier can be used to enable an invert emulsion lubricant composition. Some non-limiting concentrations of water-in-oil emulsifier by weight of the invert emulsion liquid can include about 0.1% to 30%, about 0.5% to 25%, about 1% to 20%, about 1.5% to 18%, about 2% to 16%, about 3% to 15%, about 5% to 10%, about 0.1% to 10%, about 5% to 30%, about 2% to 14%, or about 3% to 12%. In some aspects, the concentration of the water-in-oil emulsifier can be about 2% to 14%. In some aspects, the concentration of the water-in-oil emulsifier can be about 3% to 12%. In some aspects, the concentration of the water-in-oil emulsifier can be about 5% to 10%. In some aspects, the concentration of the water-in-oil emulsifier is at least about 4%, 5%, 6%, 7%, 8%, 9%, 10%, or 11% by weight of the invert emulsion liquid.
In some aspects, Hypermer™ emulsifiers. can be used for the present disclosure. As shown in Table 1, Hypermer™ emulsifiers are a series of polymeric or oligomeric emulsifiers with high viscosity. In some aspects, Hypermer™ 2524 can be used as a water-in-oil emulsifier for the present disclosure. Hypermer™ 2524 is an oligomeric ester emulsifier for use in the manufacture of inverse polymer emulsions. It is compatible with synthetic esters such as Priolube™ LL-564 as an inverse emulsifier. Hypermer™ 2524 has a viscosity of about 1200 to 1500 mPa·s when measure at 25 Celsius, a density of about 0.96 g/cm3 at about 25 Celsius, and HLB of about 4.9. In some aspects, Lubrizol® 5629 can be used as a water-in-oil emulsifier for the present disclosure.
In some aspects, the invert emulsion lubricant of the present disclosure can include water, in the so called water-in-oil emulsion. Some non-limiting concentrations of water by weight of the invert emulsion liquid can include, but not limited to, about 10% to 90%, about 20% to 80%, about 30% to 70%, about 35% to 65%, about 40% to 60%, about 45% to 55%, about 10% to 55%, or about 45% to 90%. In some aspects, the concentration of water can be about 35% to 65% by weight of the invert emulsion liquid. In some aspects, the concentration of water can be about 40% to 60% by weight of the invert emulsion liquid. In some aspects, the concentration of water can be about 45% to 55% by weight of the invert emulsion liquid. In some aspects, the concentration of water is at least about 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59% or 60% by weight of the invert emulsion liquid.
In some aspects, the process of making the invert emulsion in the present disclosure can include adding water or mixture thereof into a mixture of a base oil and a water-in-oil emulsifier. In some aspects, the addition of water should proceed slowly in order to enable formation of a complete and stable invert emulsion. In some aspects, the actual addition rate of water can depend on the amount of the reaction materials and the scale of the reaction. In some aspects, water can be added with a rate of about 0.1 vol % to 5 vol %, about 0.3 vol % to 4.8 vol %, about 0.5 vol % to 4.5 vol %, about 0.8 vol % to 4.2 vol %, about 1.0 vol % to 4.0 vol %, about 1.2 vol % to 3.5 vol %, about 1.5 vol % to 3.0 vol %, about 1.8 vol % to 2.8 vol %, about 2.0 vol % to 2.5 vol %, about 0.1 vol % to 2.5 vol %, or about 2.0 vol % to 5 vol % of the entire amount of water per minute. In some aspects, water can be added at a rate of about 3 vol % of the entire amount of water per minute.
In some aspects, the disclosed invert emulsion lubricant can include a preservative. In some aspects, the preservative can be loaded at about 0.001 to 10%, about 0.002 to 9%, about 0.003 to 8%, about 0.004 to 7%, about 0.005 to 6%, about 0.006 to 5%, about 0.007 to 4%, about 0.008 to 3%, about 0.009 to 2%, about 0.01 to 1%, about 0.01 to 10%, or about 0.001 to 1%, by weight of the invert emulsion lubricating composition. In some aspects, the preservative can be loaded at about 0.01 to 1% by weight of the invert emulsion lubricating composition. In some aspects, the concentration of the preservative is at least about 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9or 1% by weight of the invert emulsion lubricating composition. In one aspect, the preservative is an anti-microbial preservative. In some aspects, the preservative can perform the function of preventing the growth of bacteria, mold, yeast, and algae.
In some aspects, Reputain™ B30 antimicrobial can be used as preservative. Reputain™ B30 is a liquid antimicrobial for use in controlling the growth of bacteria and algae, and as a preservative to inhibit bacterial spoilage. Reputain™ B30 is a solution of about 30%nbronopol (2-bromo-2-nitro-1,3-propanediol) in about 57.5-62.5% in propylene glycol and about 7-10% water. It has a pH of less than 4.5 and a boiling point of about 54 Celsius. Reputain™ B30 can be soluble in water.
In some aspects, a propellant can be used to convert the disclosed invert emulsion to an aerosol. The propellant used herein can be liquefied gas or compressed gas. Exemplary propellant based on liquefied gas can include, but not limited to, chlorofluorocarbon, hydrocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, and any combinations thereof. Exemplary propellant based on compressed gas can include, but not limited to nitrogen, nitrous oxide, carbon dioxide, and any combinations thereof. In some aspects, Solstice® (HFO-1234ze) can be used as propellant. Solstice® includes 1,3,3,3-tetrafluoropropene as active component. Some non-limiting concentrations of propellant by weight of the sum of invert emulsion liquid and propellant can include, but not limited to, about 1% to 50%, about 5% to 45%, about 10% to 40%, about 11% to 35%, about 12% to 30%, about 13% to 20%, about 1% to 20%, about 13% to 50%, or about 10% to 20%. In some aspects, the concentration of the propellant can be about 10% to 20%. In some aspects, the concentration of the propellant can be about 13%. In some aspects, the concentration of the propellant can be about 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, or 25% by weight of the sum of invert emulsion liquid and propellant.
In some aspects, disclosed herein is a multiuse composition in the form of a substantially stable water-in-oil emulsion consists of 13% Solstice (HFO-1234ze) propellent by weight and 87% to a base including by weight: (a) 51.95% of deionized water; (b) 8% Hypermer 2524; (c) 40% of Priolube LL-564; and (d) 0.05% of Reputain B-30. The aerosol apparatus for delivering the formulation in a stable non-flammable form consists of standard aerosol components with a stem with increased orifice of 0.020 inch (0.051 cm) and two entry ways for uptake of the base liquid. The above composition has shown surprisingly good lubricating and anticorrosion properties while maintaining non-flammability in both the liquid and aerosol form.
The composition according to the present invention can further comprise at least one additive or several additives as described below. The additive or additives that are added are selected depending on the use of the lubricant composition. These additives can be introduced separately and/or included in additive packages used in the formulations of lubricant compositions. Thus, the lubricant compositions according to the present disclosure can in particular and non-limitatively contain anti-wear and extreme pressure additives, antioxidants, detergents that are overbased or not, viscosity modifiers, pour point improvers, dispersants, anti-foaming agents, thickeners, antimicrobial agents, colorants, cracking inhibitors (e.g., PET stress cracking inhibitors), film forming materials, surfactants, antistatic agents, corrosion inhibitors and mixtures thereof.
The anti-wear and extreme pressure additives protect friction surfaces by the formation of a protective film adsorbed on these surfaces. There is a great variety of anti-wear additives, but the category most used in lubricant compositions in particular for engines is that of the phosphorus- and sulphur-containing additives such as the metal alkylthiophosphates, in particular the zinc alkylthiophosphates, and more specifically the zinc dialkyldithiophosphates or ZnDTP. The preferred compounds are of formula Zn((SP(S)(OR1)(OR2))2, where R1 and R2 are alkyl groups, preferably comprising from 1 to 18 carbon atoms. The amine phosphates are also commonly used anti-wear additives. However, the phosphorus supplied by these additives acts as a poison of automotive catalytic systems, and they also supply ash. These effects can be minimized by partially substituting with additives that do not supply phosphorus, such as for example the polysulphides, in particular the sulphur-containing olefins.
Anti-wear and extreme pressure additives of the nitrogen-containing and sulphur-containing type, for example the metal dithiocarbamates, in particular molybdenum dithiocarbamate, which also generate ash, are also usually found in the lubricant compositions. The anti-wear and extreme-pressure additives are present in the lubricant compositions according to the disclosure in contents about 0.01 and 6% by mass, about 0.05 and 4%, or about 0.1 and 2%, by weight of the invert emulsion liquid.
Friction modifiers can optionally be added to the lubricant compositions comprising at least two glycerol esters E1 and E2. There can also be solid compounds such as molybdenum disulphide, graphite or polytetrafluoroethylene (PTFE).
The metal compounds are for example complexes of transition metals such as Mo, Sb, Sn, Fe, Cu, Zn, the ligands of which can be hydrocarbon compounds containing oxygen, nitrogen, sulphur or phosphorus atoms. In particular, the compounds containing molybdenum can be particularly effective, such as for example the molybdenum dithiocarbamates or dithiophosphates.
The ash-free friction modifiers can be for example fatty alcohols, fatty acids, esters, fatty amines. These friction modifying additives, optionally added, are present in contents between about 0.01 and 5% by mass relative to the total mass of the lubricant composition, preferably about 0.1 and 2%. By combining two glycerol esters E1 and E2, it is possible to formulate lubricant compositions which have, advantageously during the phase of engine starting, improved friction properties relative to the lubricant compositions comprising Mo-DTC. These friction modifiers E1 and E2 have the advantage of being additives that do not supply sulphated ash, phosphorus and Sulphur.
The antioxidants slow down the degradation of the oils in service; degradation which can result in the formation of deposits, the presence of sludge, or an increase in the viscosity of the oil. They act as radical inhibitors or hydroperoxide destroyers. The antioxidants commonly used include the antioxidants of the phenolic or amino type. Some of these additives, for example the phosphorus- and sulphur-containing antioxidants, may generate ash.
The phenolic antioxidants may be ash-free, or be in the form of neutral or basic metal salts. Typically, they are compounds containing a sterically hindered hydroxyl group, for example when two hydroxyl groups are in the ortho or para position relative to one another, or when the phenol is substituted with an alkyl group comprising at least 6 carbon atoms. The amino compounds are another class of antioxidants that can be used, optionally in combination with the phenolic antioxidants. Another class of antioxidants is that of the oil-soluble copper compounds, for example the copper thio- or dithiophosphates, the salts of copper and carboxylic acids, the copper dithiocarbamates, sulphonates, phenates, and acetylacetonates. The copper I and II salts of succinic acid or anhydride are used. The antioxidants, alone or in a mixture, are typically present in the lubricant compositions according to the disclosure in quantities comprised between about 0.1 and 5% by weight, relative to the total mass of the lubricant compositions.
The detergents reduce the formation of deposits on the surface of metal parts by dissolving the by-products of oxidation and combustion. The detergents commonly used in the formulation of lubricant compositions are typically anionic compounds comprising a long lipophilic hydrocarbon chain and a hydrophilic head. The associated cation is typically a metal cation of an alkali or alkaline-earth metal.
The detergents are preferably selected from the alkali- or alkaline-earth metal salts of carboxylic acids, sulphonates, salicylates, naphthenates, as well as the salts of phenate. The alkali and alkaline-earth metals are preferably calcium, magnesium, sodium or barium. These metal salts can contain the metal in an approximately stoichiometric quantity or in excess (in a quantity greater than the stoichiometric quantity). In the latter case, these detergents are referred to as overbased detergents. The excess metal providing the detergent with its overbased character is present in the form of metal salts which are insoluble in oil, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.
The viscosity modifiers make it possible to guarantee good low-temperature stability and minimum viscosity at high temperature, in particular for formulating multigrade oils. Addition of these compounds to the lubricant compositions allows them to reach viscosity index (VI) values giving them good wetting properties. Thus, preferably, the viscosity index (VI) of the lubricant compositions according to the disclosure, measured according to the international standard ASTM D2270, is greater than or equal to about 130, greater than or equal to about 150, or greater than or equal to about 160. In some aspects, the VI of the lubricant compositions according to the present disclosure has a VI of higher than about 200.
Among the compounds that can be used as viscosity modifiers, the polymer esters, the copolymer olefins (CPO), the homopolymers or copolymers of styrene, butadiene or isoprene, hydrogenated or not, and the polymethacrylates (PMA) may for example be mentioned. The lubricant compositions according to the present disclosure can contain of the order of about 0.1 to 10% by weight of viscosity index improving polymers, relative to the total weight of the lubricant compositions, or from about 0.5 to 5%, or from about 1 to 2%.
The pour point depressants improve the low-temperature behaviour of the oils, by slowing the formation of paraffin crystals. Non-limiting examples can include alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes, and alkylated polystyrenes. The dispersants, such as for example succinimides, PIB (polyisobutene) succinimides, Mannich bases, ensure maintenance in suspension and the removal of insoluble solid impurities constituted by the oxidation by-products that form when a lubricant composition is in service.
The presently-disclosed lubricating composition can have different applications. In some aspects, it can provide protection by lubrication. In some aspects, it can prevent corrosion. In some aspects, it can loosen rust and/or corrosion. In some aspects, it can remove and/or dissolve grease, dirt, and oil. In some aspects, it can drive out moisture via water displacement.
Presented below are examples discussing the making of the aerosol invert emulsion lubricant contemplated for the discussed applications, as well as the characterization of the properties thereof. The following examples are provided to further illustrate the aspects of the present invention, but are not intended to limit the scope of the invention. While they are typical of those that might be used, other procedures, methodologies, or techniques known to those skilled in the art may alternatively be used.
Priolube LL-564 was weighed and added to a magnetically driven microtool (MMT). A small volume of Priolube LL-564 was retained to rinse the other raw material weighing vessels into the MMT. When there was sufficient and adequate amount of Priolube LL-564 in the MMT, agitation was initiated. As different raw materials were added, agitation was increased to maintain good mixing while avoiding vortexing. Hypermer 2524 was then weighed and added into the MMT. The contents of the MMT was blended at about 1,500 rpm for about 25 to 30 minutes.
In a separate mixing tank, DI water was weighed and added, then Reputain™ B-30 preservative was weighed and added into the separate mixing tank. The mixing tank containing DI water and preservative was agitated for about 10 to 15 minutes at low speed. The DI water/preservative mixture was slowly added to the MMT at about 16 gallon/minute (60.6 L/minute) to create the emulsion. Once all contents of DI water mixing tank was added to the MMT, the content in the MMT was allowed to blend for about 25 to 30 minutes at about 1,500 rpm. The contents in the MMT were transferred through in-line homogenizer running at about 60 Hz into a second mixing tank for approximately 30 minutes. The product was sampled for quality control (QC) check. A slow mixing of the contents in the second mixing tank was maintained during the QC check. With QC approval, the final product was transferred for aerosol generation.
The invert emulsion was the only formulation that had lubricating and anticorrosion properties similar to the market leader WD-40®, while remaining non-flammable in both liquid and aerosol form. Alternative formulas tested included oil-in-water emulsions, chlorinated hydrocarbons and perfluoropolyether (PFPE), and phosphate esters, phosphate ester and fluorinated hydrocarbons. Those formulas included:
The invert emulsion was generally comparable or better than most of the other potential non-flammable multiuse lubricators. Three tests were performed on the formulations to determine their relative abilities to lubricate under varying conditions. Those tests and results are described below.
ASTM D-4172: Wear Preventive Characteristics fo Lubricating Fluid. This test is commonly known as the Four Ball Wear and measures the wear protection of a test fluid. Three steel balls are clamped together and covered with the lubricant to be evaluated. A fourth steel ball is pressed with force into the top cavity formed by the three lower balls. The temperature of the test lubricant can be regulated and then the top ball is rotated at 1200 rpm for 60 minutes. Lubricants are compared by the average of the measure (in mm) of the scar worn into the three lower balls. Good results are less than 1.0 mm with excellent results being around 0.5 mm. Anti-wear fluids will reduce the amount of metal lose due to friction during a metalworking process or metal to metal contact.
ASTM D-3233: Measurement of Extreme Pressure Properties of Fluid Lubricants (Falex Pin and Vee Block Methods). This test measures the load-carrying properties of a lubricant by rotating a steel pin at 290 rpm against two stationary V-blocks immersed in the lubricant sample. Load, in 250 foot pound increments, is applied to the V-blocks by a ratchet mechanism. The load is increased every minute until failure occurs as indicated by breakage of the shear pin or test pin, or inability to increase or maintain the load on the ratchet wheel. Results are reported as pounds with 4,500 being the maximum that can be detected. An extreme pressure fluid will maintain its lubricating properties as pressure and temperature increases.
ASTM D-5620: Evaluating Thin Film Fluid Lubricants in a Drain and Dry Mode. This test measures the endurance or wear life of a lubricant. The test fluid is deposited on the pin and V-blocks and allowed to drain for 1 to 4 minutes. The steel pin is rotated at 290 rpm against two stationary V-blocks and a load of 300 foot pounds is applied. If after 60 minutes, there is no failure, the load is increased to 500 foot pounds. Failure is when the steady state torque is interrupted by a sharp increase or spike in the torque, breakage of the shear pin, or failure to maintain the load. Results are reported in minutes at load pounds.
Table 2 illustrates the lubrication test results. For the wear preventive test based on ASTM D-4172, the disclosed invert emulsion formulation exhibited comparatively good result at about 0.60 mm compared to WD-40®, the Phosphate Ester formulation, and the Phosphate Ester and Fluorinated Hydrocarbons formulation. All the rest of the formulations exhibited much deeper scar worn into the three lower balls, which point to significant amount of metal lose due to friction, thus a poor wear preventive property.
With respect to the extreme pressure test based on ASTM D-3233, only the dislosed invert emulsion formulation, the Synthetic Emulsion formulation, and the Phosphate Ester and Fluorinated Hydrocarbons formulation exhibited carrying loads of about or higher than 4000 lbs. The rest of the formulations resulted in failure at a much lower load, suggesting inferior lubricating properties at extreme pressures.
The disclosed invert emulsion formulation clearly stood out in the endurance test according to ASTM D-5620, which was able to last for more than 20 minutes at about 300 lbs (about 136.1 kg), significantly longer than the rest of the tested formulations.
The disclosed invert emulsion was markedly better than most of the other potential non-flammable multiuse lubricators. Two tests were performed on the formulations to determine their relative abilities to prevent corrosion and rust. Those tests and results are described below.
ASTM B-117: Salt Spray (Fog) Apparatus. This test is used to measure the level of corrosion protection provided by a test fluid. Cold rolled steel panels, with surface prepared by sand blasting, are treated with the fluid by dipping or spray, allowed to drain for 2 hours, then placed in the salt spray cabinet that contains a fog of 5% salt (NaCl) water solution at 35° C. (95° F.). Panels are left in the closed cabinet for the entire test period; we typically use a 72 hour period.
FTM-3007: Water Displacement. This test is used to measure the ability of a fluid to displace water on a metal surface and then provide corrosion protection. Cold rolled steel panels, with surface prepared by sand blasting, are immersed in deionized water and then immersed in the test fluid just prior to being place in a static humidity chamber (25° C. and 50% humidity) for one hour. The procedure is repeated but using the test fluid after a 10% level of water has been added and mixed with it. Results are reported as % visible corrosion for both the as is and the contaminated fluid.
Table 3 illustrates the anticorrosion and water displacement testing results. For the anticorrosion test based on ASTM B-117, the disclosed invert emulsion formulation barely exhibited any rust formation, only WD-40® exhibited a comparatively good rust prevention result. All the rest of the formulations generated 90% or higher rust at 24 hours during the test.
For the water displacement test according to FTM-3007, there is minimum or no corrosion from the disclosed invert emulsion formulation, WD-40®, the Synthetic Emulsion formulation, the Semisynthetic Emulsion formulation, and the GPL and PFPE formulation. The other three formulations tested exhibited apparent corrosion during the test.
The invert emulsion was the only potential non-flammable multiuse lubricant with superior lubrication and anticorrosion properties that was also non-flammable in an aerosol form. The Invert Emulsion was tested for flammability using a straw connected the actuator and without. Three tests were performed on the formulations to determine their relative flammability profile. Using the larger stem orifice radius reduced the flammability profile of the invert emulsion. Those tests and results are described below.
Flame Extension and Flashback. This is characterized according to CFR Part 16 § 1500.45 entitled “method for determining extremely flammable and flammable contents of self-pressurized containers.” A spray can is placed in a holding device 15 cm from an open flame source set at a height of 5 cm. The spray can is discharged for 5 seconds and the flame extension is measured. The operator can then determine if a flashback exists by observing if a flame travels backwards toward the spray can.
GHS UN Ignition Distance performed per UNECE Part III 31.4. A spray can is discharged towards an open flame starting at a distance of 60 cm. The distance is shortened incrementally until a sustained ignition is observed.
Enclosed Space Ignition performed per UNECE Part III Section 31.5. A spray can is discharged into a test vessel (55 gallon/208 L drum) containing a burning candle. A timer is started at the time the can was discharged in order to determine the time elapsed before ignition, if any.
Table 4 illustrates the flammability test results. The initial testing focused on the disclosed invert emulsion formulation using different stem sizes for purposes of generating spray/aerosol. The typically used 0.013 inch (0.033 cm) stem produces aerosol with small size droplets and high surface area, which may proves counter-effective when it comes to non-flammable features. Indeed, the invert emulsion spray generated based on the 0.013 inch (0.033 cm) stem size resulted in inferior results at least for the Flame Extension and Flashback test and GHS UN Ignition Distance. When the stem size was increased to 0.02 inch (0.051 cm), a significant improvement of non-flammable property was demonstrated and no flame was generated under these tests.
Although the invention has been described with reference to the above examples, it will be understood that modifications and variations are encompassed within the spirit and scope of the invention. Accordingly, the invention is limited only by the following claims.
This application is a continuation-in-part application of U.S. patent application Ser. No. 16/668,020, filed on Oct. 30, 2019, currently pending, which is a continuation of U.S. patent application Ser. No. 15/946,611, filed on Apr. 5, 2018, now abandoned, which claims the benefit under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 62/623,610, filed on Jan. 30, 2018, and U.S. Provisional Application No. 62/482,305, filed on Apr. 6, 2017, expired. The entire content of these foregoing applications are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 62623610 | Jan 2018 | US | |
| 62482305 | Apr 2017 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15946611 | Apr 2018 | US |
| Child | 16668020 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16668020 | Oct 2019 | US |
| Child | 16893116 | US |
