Emulsifiers for metalworking fluids

Abstract

An emulsifier system is selected for use with emulsified oil systems such as metal working lubricants. The emulsifier includes an acylated polyolefin emulsifier, wherein each molecule of the acylated polyolefin emulsifier includes an oil-soluble polyolefin portion and, on average across all molecules of the acylated polyolefin emulsifier, wherein at least 25 wt% of the polyolefin portion is derived from a biomass resource, at least one acyl group attached to the oil-soluble polyolefin portion, wherein at least 25 wt% of the polyolefin portion is formed from a bio-derived feedstock.

Description

4848-01EMULSIFIERS FOR METALWORKING FLUIDSBACKGROUND OF THE INVENTION

[0001] The disclosed technology relates to emulsifiers and compositions including the emulsifiers, which may be used for metalworking applications.

[0002] A large portion of cutting and machining lubricant is based on an oil in water emulsion. This presence of water in the fluid has many advantages including cost and cooling efficiency. For the fluid to perform efficiently, the emulsion needs to be strong and the tendency for the oil phase to separate from the water phase is overcome with a variety of emulsification agents (known as emulsifiers). At the end of the fluid's useful life, it is desirable to then separate the oil phase from the water phase, in order to minimize the disposal costs, and to minimize the negative impact of fluid disposal on the environment. Often, this separation is achieved by adding strong acids to the fluid, followed perhaps by neutralization. This acidification and neutralization step results in cost to the user in the form of handling hazardous materials, storing these materials and other costs.SUMMARY OF THE INVENTION

[0003] The disclosed technology provides emulsifiers which can be used as primary and / or secondary emulsifiers in metalworking fluid compositions and, at least in certain embodiments, may provide more efficient emulsifiers and / or eliminate the need to use separate emulsifier compositions to achieve the objectives previously achieved by using separate primary and secondary emulsifiers.

[0004] The subject matter disclosed herein provides an emulsifier for use in an emulsified oil system, the emulsifier comprising an acylated polyolefin emulsifier. In certain embodiments, each molecule of the acylated polyolefin emulsifier consists of an oil-soluble polyolefin portion and, on average across all molecules of the acylated polyolefin emulsifier, at least one acyl group attached to the oil-soluble polyolefin portion. In certain embodiments, the oil-soluble polyolefin portion has a number-average molecular weight of 450 to 3000 Daltons. In certain embodiments, at least 25 wt.%, or at least 50 wt.%, or at least 75 wt.%, or at least 80 wt.% of the polyolefin portion is derived from a biomass-based hydrocarbon stream. In certain embodiments, the biomass-based hydrocarbon stream comprises 1 -butene, 2-butene, isobutane, and4848-01isobutene. In certain embodiments, the biomass-based hydrocarbon stream is derived from bio-naphtha. In certain embodiments, at least 25 mol% of all the at least one acyl groups present in the acylated polyolefin emulsifier contain at least one of an ester group, a carboxylic acid group, or a carboxylate salt. The composition may be used as a metalworking fluid or as a drilling fluid in drilling applications, such as in wellbore drilling operations.DETAILED DESCRIPTION

[0005] Various features and embodiments of the present subject matter will be described below by way of non-limiting illustration.

[0006] As used herein, the term “condensation product” is intended to encompass esters, amides, imides and other such materials that may be prepared by a condensation reaction of an acid or a reactive equivalent of an acid (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, irrespective of whether a condensation reaction is actually performed to lead directly to the product. Thus, for example, a particular ester may be prepared by a transesterification reaction rather than directly by a condensation reaction. The resulting product is still considered a condensation product.

[0007] The amount of each chemical component described herein is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated. Unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, byproducts, derivatives, and other such materials which are normally understood to be present in the commercial grade.

[0008] As used herein, the term “emulsion” is intended to cover oil-in-water emulsions of sufficient fluidity to be useful as functional fluids. As used herein, the term “hydrocarbyl” refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group includes at least carbon and hydrogen atoms. If the hydrocarbyl group comprises more than one carbon atom, then those carbons need not necessarily be linked to each other. For example, at least two of the carbons may be linked via a suitable element or group. In various embodiments, the term “hydrocarbyl” refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group consists of carbon, hydrogen, optionally one or more heteroatoms provided the4848-01heteroatoms do not alter the predominantly hydrocarbon nature of the substituent. The heteroatom may link to at least two of the carbons in the hydrocarbyl group, and optionally no more than two non-hydrocarbon substituents. Suitable heteroatoms will be apparent to those skilled in the art and include, for instance, sulphur, nitrogen, oxygen, phosphorus and silicon. Where the hydrocarbyl contains heteroatoms, optionally, no more than two heteroatoms will be present for every ten carbon atoms in the hydrocarbyl group. Suitable non-hydrocarbon substituents will also be apparent to those skilled in the art and include, for instance, halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy.

[0009] Examples of hydrocarbyls within the context of the present technology therefore include: (i) hydrocarbon groups selected from aliphatic (e.g. alkyl or alkenyl), alicyclic (e.g. cycloalkyl, cycloalkenyl, cycloalkadienyl), and aromatic groups; (ii) substituted hydrocarbon groups, selected from hydrocarbon groups defined in (i) substituted with no more than two non-hydrocarbon substituents and / or one or more hydrocarbon substituents, the non-hydrocarbon substituents being selected from the group consisting of halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy; and / or (iii) hetero-containing hydrocarbon groups, selected from hydrocarbon groups defined in (i) containing one or more heteroatom in the ring or chain, provided that the group has no more than two heteroatoms present for every ten carbon atoms in the group, the heteroatoms being selected from sulphur, nitrogen, oxygen, phosphorus and silicon. The hetero-containing hydrocarbon groups may be substituted with no more than two non-hydrocarbon substituents and / or one or more hydrocarbon substituents. In certain embodiments, the term “hydrocarbyl” refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group consists of carbon and hydrogen atoms.

[0010] It is known that some of the materials described herein may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. For instance, metal ions (of, e.g., a detergent) may migrate to other acidic or anionic sites of other molecules. The products formed thereby, including the products formed upon employing the composition of the present subject matter in its intended use, may not be susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present subject4848-01matter; the present subject matter encompasses the composition prepared by admixing the components described herein.

[0011] As used herein, the indefinite article “a” / “an” is intended to mean one or more than one. As used herein, the phrase “at least one” means one or more than one of the following terms. Thus, “a” / “an” and “at least one” may be used interchangeably. For example, “at least one of A, B or C” means that just one of A, B or C may be included, and any mixture of two or more of A, B and C may be included, in alternative embodiments.

[0012] As used herein, the term “substantially” means that a value of a given quantity is within ±10% of the stated value. In other embodiments, the value is within ±5% of the stated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments, the value is within ±1% of the stated value.

[0013] As used herein, the term “substantially free of’ means that a component does not include any intentional addition of the material which the component is “substantially free of’. For example, the component may include a material which the component is “substantially free of’ at no more than impurity levels, which may be the result of incomplete chemical reactions and / or unintended / undesired (but perhaps unavoidable) reaction products.

[0014] As used herein, the transitional term “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps. However, in each recitation of “comprising” herein, it is intended that the term also encompass, as alternative embodiments, the phrases “consisting essentially of’ and “consisting of,” where “consisting of’ excludes any element or step not specified and “consisting essentially of’ permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.

[0015] In certain embodiments, the oil-soluble polyolefin portion has a numberaverage molecular weight of 450 to 3000 (such as from 500 to 3000, from 550 to 3000, from 600 to 3000, from 700 to 3000, from 800 to 3000, from 900 to 3000, from 1000 to 3000, from 1200 to 3000, from 1500 to 3000, from 450 to 2500, from 500 to 2500, from 550 to 2500, from 600 to 2500, from 700 to 2500, from 800 to 2500, from 900 to 2500,4848-01from 1000 to 2500, from 1200 to 2500, from 1500 to 2500, from 450 to 2000, from 500 to 2000, from 550 to 2000, from 600 to 2000, from 700 to 2000, from 800 to 2000, from 900 to 2000, from 1000 to 2000, from 1200 to 2000, from 1500 to 2000, from 450 to 1500, from 500 to 1500, from 550 to 1500, from 600 to 1500, from 700 to 1500, from 800 to 1500, from 900 to 1500, from 1000 to 1500, or from 1200 to 1500) Daltons.

[0016] In certain embodiments, at least 25 wt.% (such as at least 50 wt.%, or at least 75 wt.%, or at least 80 wt.%) of the oil soluble polyolefin portion is derived from a bioderived feedstock. The bio-derived feedstock includes a bio-derived C4 stream, which contains different hydrocarbons containing 4 carbon atoms per molecule, such as, for example, 1 -butene, 2-butene, isobutane, and isobutene. The bio-derived C4 stream may also contain certain C3-C6 hydrocarbons. In certain embodiments, the bio-derived feedstock is derived from bio-naphtha. In certain embodiments, the bio derived feedstock is derived from plant matter, for example, vegetable oil, corn oil, soybean oil, crude palm oil, camelina oil, jatropha oil, rapeseed oil. The bio derived feedstock may also be derived from waste animal fat from food processing. In certain embodiments, the bio derived feedstock may include used cooking oil.

[0017] In certain embodiments, at least 25 (such as at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, at least 70, or at least 75) mol% of all the at least one acyl groups present in the acylated polyolefin emulsifier contain at least one of an ester group, a carboxylic acid group, or a carboxylate salt.

[0018] In certain embodiments, the acylated polyolefin emulsifier comprises at least one polymer of branched or linear 1 -olefin monomers having from 4 to 8 (such as from 4 to 7, from 4 to 6, from 4 to 5, from 5 to 8, from 5 to 7, from 5 to 6, from 6 to 8, from 6 to 7, from 7 to 8, or 4, 5, 6, 7, or 8) carbon atoms. In the context of the previous sentence, “comprises” means that that the acylated polyolefin emulsifier includes the described material, and may also include any other material which falls within the above description of what the acylated polyolefin emulsifier consists of.

[0019] In certain embodiments, the acylated polyolefin emulsifier comprises at least one polymer of branched or linear monomers having from 4 to 6 (such as from 4 to 5, from 5 to 6, or 4, 5, or 6) carbon atoms, and wherein at least 90 (such as at least 91, at least 92, at least 93, at least 94, at least 95, at least 96, at least 97, at least 98, or at least 99) mol percent of the monomers are 1 -butene and / or isobutylene. In the context of the previous4848-01sentence, “comprises” means that that the acylated polyolefin emulsifier includes the described material, and may also include any other material which falls within the above description of what the acylated polyolefin emulsifier consists of.

[0020] In certain embodiments, ester groups are present in the acylated polyolefin, and the ester groups comprise at least one hydrocarbyl group having from 2 to 18 (such as from 4 to 18, from 6 to 18, from 8 to 18, from 10 to 18, from 12 to 18, from 14 to 18, from 16 to 18, from 2 to 16, from 4 to 16, from 6 to 16, from 8 to 16, from 10 to 16, from 12 to 16, from 14 to 16, from 2 to 14, from 4 to 14, from 6 to 14, from 8 to 14, from 10 to 14, from 12 to 14, from 2 to 12, from 4 to 12, from 6 to 12, from 8 to 12, from 10 to 12, from 2 to 10, from 4 to 10, from 6 to 10, from 8 to 10, from 2 to 8, from 4 to 8, from 6 to 8, from 2 to 6, from 4 to 6, from 2 to 4, or 2, 4, 6, 8, 10, 12, 14, 16, or 18) carbon atoms.

[0021] In certain embodiments, the at least one hydrocarbyl group further comprises at least one additional heteroatom comprising at least one of nitrogen or oxygen.

[0022] In certain embodiments, the ester group comprises a hydrocarbyl group substituted with at least one secondary or tertiary nitrogen group.

[0023] In certain embodiments, the acylated polyolefin emulsifier has a total base number of at least 20 mg KOH / g. In certain embodiments, the acylated polyolefin emulsifier has a total acid number of at least 10 mg KOH / g. In certain embodiments, the acylated polyolefin emulsifier has a total base number and a total acid number, wherein the total acid number is at least 50% (such as at least 100%) of the value of the total base number.

[0024] In certain embodiments, each molecule of the acylated polyolefin emulsifier consists of an oil-soluble polyolefin portion and, on average across all molecules of the acylated polyolefin emulsifier, at least two acyl groups attached to the oil-soluble polyolefin portion, wherein, on average across all molecules of the acylated polyolefin emulsifier, at least one of the at least two acyl groups present in the acylated polyolefin emulsifier is an ester group, and wherein the ester group is an ester of an alkanolamine and the alkanolamine comprises a tertiary or secondary amine. In certain embodiments, the alkanolamine comprises at least one of diethanolamine, diethyl ethanolamine, triethanolamine, monomethyl ethanolamine, methyl diethanolamine, or aminoethyl ethanolamine.4848-01

[0025] In certain embodiments, the acylated polyolefin emulsifier is present in an amount of from 0.1 to 15 (such as from 0.5 to 15, from 1 to 15, from 2 to 15, from 3 to 15, from 4 to 15, from 5 to 15, from 0.1 to 12, from 0.5 to 12, from 1 to 12, from 2 to 12, from 3 to 12, from 4 to 12, from 5 to 12, from 0.1 to 10, from 0.5 to 10, from 1 to 10, from 2 to 10, from 3 to 10, from 4 to 10, or from 5 to 10) weight percent, based on the total weight of the composition. As described above, the acylated polyolefin emulsifier may be used as either or both of a primary emulsifier or a secondary emulsifier. When used as a primary emulsifier or a secondary emulsifier, the acylated polyolefin emulsifier may be used in an amount which is generally understood as acceptable by those of ordinary skill in the art in such situations. However, it is also possible that the acylated polyolefin emulsifier may be used as the only emulsifier in the composition, such that an additional primary or secondary emulsifier is not required; in these instances, use of the acylated polyolefin emulsifier in amounts similar to those generally used for primary emulsifiers may be sufficient, but in any event a person of ordinary skill in the art would be able to determine the appropriate amount for a particular composition by routine experimentation.

[0026] In certain embodiments, compositions of the present invention include an emulsified oil in water composition containing an oil phase and an aqueous phase. In some embodiments, the oil phase comprises at least one of natural oils, synthetic oils, diesel oil, or mineral oil. In certain embodiments, the synthetic oils may comprise at least one of esters, olefins, or paraffins. In this context, esters are synthetic oils which may be derived from the reaction of an alcohol and an organic acid and may include methyl ester and / or phthalate ester. In this context, olefins are synthetic oils, such as polyalphaolefins, which may be derived from the polymerization of alpha-olefins. In this context, paraffins are synthetic oils which may be synthesized by isomerizing liner alpha-olefins.

[0027] In certain embodiments, the aqueous phase comprises at least one of water, sea water, or brine, optionally further comprising at least one water-soluble organic compound. In this context, the water may be fresh water and / or produced water. In certain embodiments, the non-oleaginous discontinuous phase comprises a brine, wherein the brine comprises water and at least one salt, wherein the at least one salt comprises sodium, calcium, aluminum, magnesium, potassium, strontium, and / or lithium salts of chlorides, bromides, carbonates, iodides, chlorates, bromates, formates, nitrates, oxides, sulfates, silicates, phosphates, and / or fluorides.4848-01

[0028] In certain embodiments, the ratio of the oil phase to the aqueous phase is from 40:60 to 95:5.

[0029] Optional additional materials may be incorporated in the composition of the present invention. Typical finished compositions may include lubricity agents; anti-wear agents; dispersants; corrosion inhibitors; surfactants; biocides, such as o-phenylphenol; bactericides, fungicides and algaecides; colorants; fragrances; surfactants; chelating agents; pH buffering agents; solubilizers, anti-oxidants; anti-foaming agents; extreme pressure agents; and mixtures thereof. In an embodiment of the invention, the emulsions invention are shelf stable, which means they exhibit shelf stability of at least six months and typically one year or more.

[0030] A method for making the emulsions of the invention comprises the steps of (1) mixing the emulsifier with the oil phase, (2) mixing the additives with the oil phase, (3) stirring the oil phase with the water phase to form a oil-in-water emulsion. Mixing of the oil with the appropriate additives may be conducted in any suitable mixing apparatus. Any type of apparatus capable of either low or high shear mixing may be used to mix the oil and water phases to prepare these oil-in-water emulsions.

[0031] The emulsified oil in water system may be formed as a concentrate which may be used “as-is” or may be diluted with water or other aqueous solution prior to addition to the aqueous medium. Thus, in another embodiment, water is added to the emusified oil in water system concentrate to dilute the oil concentrate of the present disclosure and the oil concentrate is then added to the aqueous medium to form a stable, aqueous emulsion

[0032] As noted above, the emulsion of the present disclosure, upon addition to an aqueous medium, forms a stable, aqueous emulsion which may be used in many applications, such as metalworking fluids for metalworking processes. In addition, the emulsion exhibits surprisingly good wetting properties and metal protection and may also be used in cleaning fluids.

[0033] In another embodiment, there is provided a metalworking or cleaning fluid comprising an emulsion comprising an emulsifier, wherein the emulsifier comprises or consists of an acylated polyolefin, wherein each molecule of the acylated polyolefin emulsifier consists of an oil-soluble polyolefin portion and, on average across all molecules of the acylated polyolefin emulsifier, at least one acyl group attached to the oilsoluble polyolefin portion, wherein at least 25 wt.%, or at least 50 wt.%, or at least 754848-01wt.%, or at least 80 wt.% of the polyolefin portion is formed from a bio-derived feedstock. In certain embodiments, the oil-soluble polyolefin portion has a number-average molecular weight of 450 to 3000 Daltons. In certain embodiments, at least 25 wt.%, or at least 50 wt.%, or at least 75 wt.%, or at least 80 wt.% of the polyolefin portion is derived from a biomass-based hydrocarbon stream. In certain embodiments, the biomass-based hydrocarbon stream comprises 1 -butene, 2-butene, isobutane, and isobutene, wherein the aqueous emulsion includes an oil phase dispersed in a continuous aqueous medium, the oil phase containing the lubricating oil concentrate and the aqueous medium containing water.

[0034] Metalworking processes where the metalworking fluid may be used include, but are not limited to, elastic deformation, plastic deformation and cold working of metals, with or without metal removal. In some of these operations the metal piece is deformed only; like in rolling, drawing, stamping, forging and blanking of steel and aluminum, while in others metal is removed rather than deformed, like in cutting, grinding, turning, milling, tapping, broaching, machining and drilling of metals. The metallic material from which the metalworking apparatus and articles to be fabricated are made, include steel, cast iron, and ferrous alloys, as well as aluminum alloys and other non-ferrous alloys, including such components as titanium, magnesium, copper, tin and brass.

[0035] In another embodiment, the emulsion of the present invention may be used in a cutting process or an aluminum cutting or grinding process.

[0036] The subject matter disclosed herein may be better understood with reference to the following examples, which are set forth merely to further illustrate the subject matter disclosed herein. The illustrative examples should not be construed as limiting the subject matter in any manner.

[0037] Acylated polyolefin emulsifiers may be prepared from biomass derived polyisobutylene (PIB) acylated with maleic anhydride to form succinated polyisobutylene (PIBSA). The resulting PIB SA is reacted with alcohols and / or amines to form esters, amides, imides, and combinations thereof. Incomplete conversion of the succinate results in formation of ester / acids which then react with pendant amines to form ester / acid salts. The resulting emulsifiers can be characterized by total base number (TBN, total acid number (TAN), and nitrogen content (wt.% N).4848-01EXAMPLES

[0038] Metalworking fluids in accordance with the present invention may be prepared by combining components as set forth in Table 1. In some examples, at least 25 wt.%, or at least 50 wt.%, or at least 75 wt.%, or at least 80 wt.% of the polyolefin used to prepare the PIBSA dispersants may be derived from a bio-derived feedstock.Table 1EX 1 EX 2 EX 3 EX 4 EX 5 EX 6 mineral oil (paraffinic or naphthenic) Balance to 100%water 0.5 0.5 30.0 40.6 1000 MW conventional PIBSA 2.4 3.3 5.3 3.3 4.0 1000 MW direct alkylation PIBSA 4.0450 MW natural sodium sulfonate430 MW synthetic sodium sulfonate 3.6fatty acid 3.0 7.0 7.0 3.6 10.6 4.0 fatty acid sorbitan ester 6.0fatty alcohol alkoxylate 0.3 4.5 4.0 aqueous KOH 1.4 1.7 1.1 1.8 0.1 primary alkanolamine 1.5 1.8 0.9 1.8 2.4 tertiary alkanolamine 2.0 0.8 3.2 0.1 fatty acid alkanolamide 5.0 6.0 phosphate ester 0.9 4.2amine borate 4.1aqueous amine dicarboxylate 9.0 fatty alcohol coupler 2.0 2.7 2.0 glycol coupler 2.0 1.5 0.9carboxylic acid coupler 1.5 1.3glycol ether coupler 1.3 polymeric ester 0.4 1.5siloxane defoamer 0.1biocide 3.0

[0039] Oil-in-water emulsion type metalworking fluids can be evaluated for performance by a range of bench test methods. Test methods evaluate performance aspects of a metalworking fluids including concentrate and emulsion stability, lubricity, ferrous and nonferrous corrosion inhibition, foaming behavior, control of pH and concentration, tramp-oil rejection, resistance to bacteria and fungal growth, and operator acceptance. Below is a description of various test methods which may be used to evaluate metalworking fluids as described herein.4848-01

[0040] Concentrate and emulsion stability are assessed using a range of methods (including DIN 51367 and IP 580) to determine the stability of the concentrate across a range of temperatures including the stability of upper and lower cloud points and freezethaw stability. Emulsion stability evaluates the stability of oil-in-water emulsions. This test ensures that the emulsion does not separate over time, which is crucial for consistent performance. Furthermore, hard water stability assesses the fluid's performance in the presence of hard water. The fluid is mixed with water containing known concentrations of calcium and magnesium ions. The stability is determined by observing any precipitation or changes in the emulsion over time. Finally, sedimentation testing assesses the fluid's ability to keep solid particles suspended. The fluid is allowed to stand, and the rate and amount of particle settling are observed.

[0041] Lubricity testing measures the fluid's ability to reduce friction between metal surfaces, which is an essential function of a metalworking coolant. This can be done using a range of test methods including, but not limited to, Four-Ball Wear Test (ASTM D4172), Pin-on-Disk Test (ASTM G99), Tapping Torque Test (ASTM D8288), Timken OK Load Test (ASTM D2782), High-Frequency Reciprocating Rig (HFRR) (ASTM D6079), Falex Pin and Vee Block Test (ASTM D3233), SRV Test (DIN 51834), Brugger Test (DIN 51347), and Four-Ball Weld Test (ASTM D2783).

[0042] Corrosion Testing assesses the fluid's ability to protect metal surfaces from corrosion. Common methods include various Cast Iron Chip Tests (ASTM D4627, IP 287, DIN 51360), Humidity Cabinet Test (ASTM D1748), various metal coupon immersion tests (ASTM DI 30), and electrochemical corrosion tests.

[0043] Foaming Tests evaluate the tendency of the fluid to generate foam. Excessive foam can lead to operational problems, and these tests help in formulating fluids that minimize foam generation. Common foam tests for metalworking fluids include ASTM E3265, IP 312, IP 580, and DIN 53903.

[0044] To remain stable and effective, a metalworking fluid must maintain a certain concentration and pH range. Processes that may affect pH and concentration include evaporative loss of water, filtration, drag-out, bacterial and fungal contamination, and thermal and hydrolytic degradation, among others.

[0045] Concentration is assessed over time using a refractometer which measures the fluid’s index of refraction, which correlates with fluid concentration (ASTM D2881). The4848-01pH of the fluid is measured using a variety of methods including pH paper or one of several potentiometric methods including ASTM E70 or ASTM D1416. IP 580 is a standard test method that evaluates the thermal stability, emulsion stability, and foaming characteristics of water-mix metalworking fluids, providing insights into the fluid's concentration and suitability for specific applications; this method includes procedures to assess the fluid's behavior at different dilutions, allowing for concentration determination.

[0046] Contamination of a metalworking fluid by various slideway, hydraulic, and / or other oils, collectively referred to as “tramp-oil” can degrade fluid performance and shorten fluid lifetime. The ability of a metalworking to avoid contamination by “splitting” the contaminating oil out, which may then be removed via skimming ort centrifugation is referred to as “tramp oil rejection.” Methods to evaluate tramp-oil rejection include various contamination and splitting tests and acid splitting tests such as IP 137 and DIN 51368. More specific tests for compatibility of coolant with way-lube (one of the most common tramp oils) in evaluated using ASTM D6553.

[0047] Microbial Contamination Testing determines the presence of bacteria and fungi in the fluid. Microbial growth can degrade fluid performance and pose health risks. Methods include dip slides and agar plates. Some specific biological contamination tests for metalworking fluids include ASTM E2275 or IP 385 for bacteria and ASTM E2694 for fungi.

[0048] Finally, operator acceptance of metalworking fluids is essential, as these workers deal with the fluids every day. In addition to the performance attributes described above, other quality and health and safety aspects are considered including odor of the fluid, residue left on machined parts upon drying, and production of aerosols and mists during use (ASTM D7049).

[0049] Except in the Examples, or where otherwise explicitly indicated or required by context, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word “about”. As used herein, the term “about” means that a value of a given quantity is within ±20% of the stated value. In other embodiments, the value is within ±15% of the stated value. In other embodiments, the value is within ±10% of the stated value. In other embodiments, the value is within ±5% of the stated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments,4848-01the value is within ±1% of the stated value. In other embodiments, the value is within a range of the explicitly-described value which would be understood by those of ordinary skill, based on the disclosures provided herein, to perform substantially similarly to compositions including the literal amounts described herein.

[0050] It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined, and that any amount within a disclosed range is contemplated to provide a minimum or maximum of a narrower range in alternative embodiments (with the proviso, of course, that the minimum amount of a range must be lower than the maximum amount of the same range). Similarly, the ranges and amounts for each element of the subj ect matter disclosed herein may be used together with ranges or amounts for any of the other elements.

[0051] While certain representative embodiments and details have been shown for the purpose of illustrating the subject matter disclosed herein, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the scope of the subject matter. In this regard, the scope of the invention is to be limited only by the following claims.

Claims

4848-01What is claimed is:

1. An emulsifier for use in an emulsified oil system, the emulsifier comprising a acylated polyolefin, wherein each molecule of the acylated polyolefin emulsifier consists of an oil-soluble polyolefin portion and, on average across all molecules of the acylated polyolefin emulsifier, at least one acyl group attached to the oil-soluble polyolefin portion, wherein at least 25 wt.%, or at least 50 wt.%, or at least 75 wt.%, or at least 80 wt.% of the polyolefin portion is formed from a bio-derived feedstock.

2. The emulsifier of claim 1, wherein the acylated polyolefin emulsifier comprises at least one polymer of branched or linear 1-olefin monomers having from 4 to 8 carbon atoms.

3. The emulsifier of either claim 1 or claim 2, wherein the acylated polyolefin emulsifier comprises at least one polymer of branched or linear monomers having from 4 to 6 carbon atoms, and wherein at least 90 mol percent of the monomers are 1 -butene and / or isobutylene.

4. The emulsifier of any one of claims 1 to 3, wherein ester, amide, or imide groups are present in the acylated polyolefin, and the ester, amide, or imide groups comprise at least one hydrocarbyl group having from 2 to 18 carbon atoms.

5. The emulsifier of claim 4, wherein the at least one hydrocarbyl group further comprises at least one additional heteroatom comprising at least one of nitrogen or oxygen.

6. The emulsifier of either claim 4 or claim 5, wherein the ester group comprises a hydrocarbyl group substituted with at least one secondary or tertiary nitrogen group.

7. The emulsifier of any preceding claim, wherein the acylated polyolefin emulsifier has a total base number of at least 20 mg KOH / g.

8. The emulsifier of any preceding claim, wherein the acylated polyolefin emulsifier has a total acid number of at least 10 mg KOH / g.4848-019. The emulsifier of any preceding claim, wherein the acylated polyolefin emulsifier has a total base number and a total acid number, wherein the total acid number is at least 50% of the value of the total base number.

10. The emulsifier of any preceding claim, wherein the oil-soluble polyolefin portion has a number-average molecular weight of 450 to 3000 Daltons.

11. The emulsifier of any preceding claim, wherein each molecule of the acylated polyolefin emulsifier consists of an oil-soluble polyolefin portion and, on average across all molecules of the acylated polyolefin emulsifier, at least two acyl groups attached to the oil-soluble polyolefin portion, wherein, on average across all molecules of the acylated polyolefin emulsifier, at least one of the at least two acyl groups present in the acylated polyolefin emulsifier is an ester group, and wherein the ester group is an ester of an alkanolamine and the alkanolamine comprises a tertiary or secondary amine.

12. The emulsifier of claim 11, wherein the alkanolamine comprises at least one of diethanolamine, diethyl ethanolamine, triethanolamine, monomethyl ethanolamine, methyl diethanolamine, or aminoethyl ethanolamine.

13. The emulsifier of any preceding claim, wherein the bio-derived feedstock comprises or consists of bio-naphtha.

14. The emulsifier of any of claims 1 to 12, wherein the bio-derived feedstock is derived from plant matter.

15. The emulsifier of any of claims 1 to 12, wherein the biomass resource is selected from vegetable oil, com oil, soybean oil, crude palm oil, camelina oil, jatropha oil, rapeseed oil, or mixtures thereof.

16. The emulsifier of any of claims 1 to 12, wherein the biomass resource is derived from waste animal fat from food processing.4848-0117. The emulsifier of any of claims 1 to 12, wherein the biomass resource comprises used cooking oil.

18. The emulsifier of any preceding claim, wherein the emulsified oil system is a metalworking lubricant.

19. An emulsified oil in water composition comprising the emulsifier of any of claims 1 to 17.

20. The emulsified oil in water composition of claim 19, wherein the wherein the acylated polyolefin emulsifier is present in an amount of from 0.1 to 15 weight percent, based on the total weight of the composition.

21. A method of lubricating a metalworking system comprising the steps of providing the emulsified oil in water composition of claim 19; andcontacting the emulsified oil in water composition with a surface of the metalworking system.

22. A metalworking equipment system comprising:the emulsified oil in water composition of claim 19, andat least one additional oil selected from the group consisting of cutting oil, hydraulic oil, gear oil and slideway oil.

23. The use of the emulsified oil in water composition of claim 19 to lubricate a metalworking system.

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