Metal working fluid composition and method of making same

Abstract

The present disclosure relates to bio-based metal working fluid (MWF) compositions and methods of making the same, and more particularly to metal working fluids containing bio-based lubricants with improved emulsion stability. At least 50 wt. % of the base oil component in the MWF concentrate is a plant-derived liquid decarboxylated rosin acid oil (“DCR”). The DCR comprises 50 to 100 wt. % of tricyclic compounds having 18-20 carbon atoms, one or more C=C groups and m / z (mass / charge) values of 220-280; an oxygen content of <5%; and an acid value of <10 mg KOH / g. The resulting MWF is characterized by comparable performance, even better performance, compared to MWFs containing only mineral oil (e.g., Group I or Group II).

Description

TECHNICAL FIELD

[0001] The present disclosure relates to bio-based metal working fluid (MWF) compositions and methods of making the same, and more particularly to metal working fluids containing decarboxylated rosin acid as a lubricant with improved emulsion stability. BACKGROUND

[0002] In metal machining processes such as cutting and grinding, metal working fluids are used to improve machining efficiency, prevent wear between the workpiece and the tool machining the workpiece, prolong tool life (cooling), and remove metal chips. Such metal working fluids include an oil-based agent (base oil) such as mineral oil, animal and vegetable oils or synthetic oils, water, and a surface-active compound. Metal working fluids containing mineral oil have challenges in the industry with respect to derivation from petroleum (fossil) and the ability to emulsify to form stable emulsions.

[0003] There is a need for environmentally friendly and effective metal working fluids that reduce friction and dissipate heat generated by frictional contact between the tool and the workpiece due to removal of material from the surface of the workpiece. SUMMARY

[0004] In an aspect, a bio-based metal working fluid concentrate is provided. The metal working fluid concentrate comprises: a base oil component in an amount of 5-90 wt.%, based on the total weight of the concentrate; an emulsifier in an amount of 0.1 to 15 wt.%, selected from any of conventional anionic, cationic, non-ionic or amphoteric surfactants; at least one optional additive in an amount of 0.1 to 15 wt.%, selected from saponifiers, pH buffers, preservatives, extreme pressure (EP) additives, corrosion inhibitors, anti-wear agents, metal deactivators, anti-foaming agents, anti-rust agents, deodorants, dyes, fungicides, bactericides, antioxidants, emulsion stabilizers, dispersion stabilizers; wherein the base oil component contains at least 50 wt.% of decarboxylated rosin acid (DCR) oil, based on the total weight of the base oil component. The DCR oil comprises 50 to 100 wt.% of tricyclic compounds having 18-20 carbon atoms, one or more C=C groups, and m / z (mass / charge) value of 220-280, as measured by GC-FID-MS; oxygen content <5%; and acid value <50 mg KOH / g, as measured using ASTM E28-18.

[0005] In another aspect, a method of preparing a metal surface for subsequent processing of the metal to manufacture an article is provided. The method includes: diluting a MWF concentrate in water to form a metal working fluid (MWF) in the form of an oil-in-water emulsion, the water concentration being 80-99% by weight based on the total weight of the MWF, and applying the oil-in-water emulsion as a substantially continuous layer onto the metal surface to deposit an ultra-thin film of the metal working fluid on the metal surface. The DCR oil comprises 50 to 100 wt% of tricyclic compounds having 18-20 carbon atoms, one or more C=C groups and a m / z (mass / charge) value of 220-280. The DCR comprises >50 wt% of tricyclic and polycyclic compounds having 18-20 carbon atoms, the amount of tricyclic compounds in the DCR as reactive double bonds DCR (C=C groups) is <45 wt% based on the total weight of the DCR, and the sum of the amount of tricyclic compounds in the DCR as aromatic DCR and alicyclic DCR is >55 wt% based on the total weight of the DCR.

[0006] DESCRIPTIO

[0007] Unless otherwise indicated, the following terms are used throughout the specification with the following meanings.

[0008] "at least one of [for example, a group of A, B and C]" or "any of [for example, a group of A, B and C]" or "selected from a group consisting of [A, B and C], and combinations thereof means a single member from the group, more than one member from the group, or a combination of members from the group. For example, at least one of A, B and C includes, for example, only A, only B, or only C, as well as A and B, A and C, B and C, or A, B and C, or any other all combinations of A, B and C. In another example, at least one of A and B means only A, only B, and A and B.

[0009] A list of embodiments indicated with "A, B, or C" should be interpreted to include the embodiment of only A, only B, only C, "A or B," "A or C," "B or C," or "A, B, or C."

[0010] "Deionized water" (DI water, DIW, or deionized water) or demineralized water (DM water) is water that has had almost all of its mineral ions, such as cations like sodium, calcium, iron and copper, and anions like chloride and sulfate, removed.

[0011] "Metal working fluid" can be used interchangeably with MWF, or "metal working composition," "metal removal fluid," "cutting fluid," "machining fluid," and refers to a composition that can be used in industrial metal cutting, metal grinding operations, or in the semiconductor industry, where the shape of the final object (e.g., a silicon wafer or a machine part) is obtained with or without gradual removal of metal or silicon. The metal working fluid serves, among other functions, to cool and lubricate.

[0012] “Soluble oil” refers to MWFs that contain appreciable amounts of water and are provided to the end user in the form of an oil-in-water emulsion containing special additives. Soluble oil MWF concentrates have an oil content ranging from 40-90%, with the oil content in the final MWF ranging from about 5-10 wt% in the application, and are typically diluted with water at the user’s site.

[0013] “Semi-synthetic fluid” refers to MWF concentrates that contain 5-40 wt% oil and are diluted in water at the user’s site.

[0014] wt% refers to weight concentration.

[0015] Density is measured according to ASTM D792-13.

[0016] The present disclosure relates to bio-based metal working fluid (“MWF”) compositions and methods of making the same, and more particularly to MWFs with bio-based base oils having improved emulsion stability. The bio-based base oil is a plant-derived decarboxylated rosin acid (“DCR”) liquid product.

[0017] Water component : The metal working fluid contains an aqueous phase, which can be deionized water (DI water) or hard water, or any combination thereof.

[0018] In embodiments and depending on the application, the amount of water in the final MWF (at the application site) ranges from 80-99%, or 85-92%, or >90%, or up to 95%, or up to 99% of the total weight of the final MWF.

[0019] Main component - decarboxylated abietic acid (DCR) as base oil : In embodiments, the MWF contains DCR as the sole base oil component (100%), or >50 wt%, or >60 wt%, or >70 wt% of the base oil component. The DCR can be crude DCR, distilled or purified DCR (>90% purity), or mixtures thereof. Crude DCR is almost similar in composition to distilled DCR, with the removal of heavy fractions (10-15%) to improve color, reduce sulfur, etc.

[0020] DCR is produced by the decomposition of rosin acids at high temperatures. Rosin acids are typically solids with a softening point of, for example, 65-85°C. Rosin acids are non-petroleum and are plant-derived, derived from gum (from pine trees), wood (from tree stumps), and tall oil (a byproduct from the papermaking industry). Rosin acids can be fully or partially decarboxylated, forming decarboxylated rosin acids (DCR or DCR oil).

[0021] DCR is a mixture of molecules, some of which contain a hydrocarbon group with the general formula of, for example, C 20 H 30monocarboxylic acids of O2. In embodiments, the DCR is characterized by containing 40-100 wt% of tricyclic and polycyclic compounds having 18-20 carbon atoms, one or more C=C groups, and m / z (mass / charge) values of 220-280, or 230-270, or 234-262, or 235-265, or >230, or <265, as measured by GC-FID-MS. m / z is defined as the molecular weight (MW) of the compound divided by the charge, which is ~1 for DCRs.

[0022] In embodiments, the sum of tricyclic compounds that are aromatic and alicyclic in the DCR is >50 wt%, or >55 wt%, or >60 wt%, or >74 wt%, or >90 wt% of the total weight of the DCR. Aromatic DCR is defined as DCR species with MW of 252 or 256, and alicyclic DCR is defined as DCR species with MW of 260 or 262.

[0023] In embodiments, the amount of alicyclic DCR is >30 wt%, or >40 wt%, or >50 wt%, or >80 wt%, based on the total weight of the DCR.

[0024] In embodiments, the total amount of tricyclic compounds that are reactive double bonds (C=C groups) is <45 wt%, or <40 wt%, or <30 wt%, or <10 wt% of the total weight of the DCR. Reactive C=C groups are defined as DCR species with MW of 254 and 258.

[0025] In embodiments, the DCR is characterized by having an oxygen content of <5%, or <3%, or <2%, or 0-1%. The oxygen content in the DCR (in %) is calculated as the ratio of oxygen to carbon, or the sum of oxygen atoms present divided by the sum of carbon atoms present, where the number of oxygen and carbon atoms are obtained from elemental analysis.

[0026] In embodiments, the DCR has a density of 0.9-1.0 g / cm3at 20 °C 3 , 0.91-0.99 g / cm3 3 , or 0.92-0.98 g / cm3 3 , or 0.93-0.97 g / cm3 3 , or 0.94-0.96 g / cm3 3 , >0.9 g / cm3 3 , or <1.1 g / cm3 3 .

[0027] DCR has a lower acid value (carboxylic acid content) than rosin acids. In embodiments, the DCR has an acid value of <50 mg KOH / g, or <45 mg KOH / g, or <40 mg KOH / g, or <35 mg KOH / g, or <30 mg KOH / g, or <25 mg KOH / g, or <20 mg KOH / g, or <15 mg KOH / g, or <5 mg KOH / g, or 2-30 mg KOH / g, or 4-25 mg KOH / g, or 5-20 mg KOH / g, as measured using ASTM E28-18.

[0028] In embodiments, the DCR has an aromatic content of 30-60 wt%, or 32-56 wt%, or 35-54 wt%, or 38-52 wt%, or 40-50 wt%, or >30 wt%, or <45 wt%, based on the total weight of the DCR, according to ASTM D2140.

[0029] In embodiments, the DCR has a naphthene content of 40-60 wt%, or 42-58 wt%, or 45-55 wt%, or 42-52 wt%, or >45 wt%, or <55 wt%, based on the total weight of the DCR, according to ASTM D2140.

[0030] In embodiments, the DCR has a paraffin content of 20-35 wt%, or 22-34 wt%, or 24-32 wt%, or 26-30 wt%, or >22 wt%, or <32 wt%, based on the total weight of the DCR, according to ASTM D2140.

[0031] In embodiments, the DCR is characterized by having a viscosity comparable to that of a petrochemical base oil, which is due in part to its relatively high molecular weight, for example, a viscosity of 20-50 cSt, or 22-48 cSt, or 25-45 cSt, or 28-42 cSt, or 30-40 cSt, or >28 cSt, or <45 cSt, measured according to ASTM D-445 at 40 °C.

[0032] In embodiments, the DCR has an aniline point of 5-40 °C, or 10-25 °C, or 13-29 °C, or <25 °C, or >8 °C, according to ASTM D611.

[0033] In embodiments, the DCR has a pour point of -30 to +10 °C, -28 to +8 °C, or -25 to +5 °C, or >-25 °C, or <+5 °C, according to ASTM D97.

[0034] In embodiments, the DCR has a flash point of 140-160°C, or 142-158°C, or 144-156°C, or 146-154°C, or > 146°C, or < 154°C, or < 160°C, according to ASTM D92.

[0035] In embodiments, the DCR has a boiling point of 235-390°C, or > 230°C, or < 400°C, measured according to ASTM D2887.

[0036] In embodiments, the DCR has a Gardner color of 1.0-3.0, or 1.1-2.9, or 1.2-2.8, or 1.3-2.7, or 1.4-2.6, or 1.5-2.5, > 1.2, or < 2.4, or < 3.0, according to ASTM D6166.

[0037] In embodiments, the DCR has a sulfur content of < 0.05 wt.%, or < 0.04 wt.%, or < 0.03 wt.%, or < 0.02 wt.%, or < 0.01 wt.%, or < 0.001 wt.%, or 40-200 ppm, or < 500 ppm, or < 100 ppm, based on the total weight of the DCR, measured according to ASTM D5453.

[0038] In embodiments, the DCR has a VOC of < 5 wt.%, or < 4.75 wt.%, or < 4.5 wt.%, or < 4.25 wt.%, or < 4.0 wt.%, or < 3.75 wt.%, < 3.5 wt.%, < 3.25 wt.%, < 3.0 wt.%, < 2.75 wt.%, or < 2.5 wt.%, < 2.25 wt.%, < 2.0 wt.%, or < 1.5 wt.%, < 1.0 wt.%, or < 0.5 wt.%, based on the total weight of the DCR. The VOC of the DCR is measured according to EPA (Environmental Protection Agency) Method 24 or its equivalent by summing the wt.% contribution of all VOCs present in the product at 0.01% or more.

[0039] In embodiments of semi-synthetic liquid MWFs, the DCR oil amount ranges from 5-40 wt.%, or > 5 wt.%, or > 30 wt.%, or > 35 wt.%, or < 45 wt.%, of the total weight of the MWF concentrate.

[0040] In embodiments of soluble oil MWFs, the amount of DCR ranges from 40-90 wt.%, or > 55 wt.%, or > 60 wt.%, or > 65 wt.%, or < 85 wt.%, of the total weight of the MWF concentrate.

[0041] Optional base oil component In some embodiments, a small amount of (different) oil can be used as a base oil component in addition to the DCR.

[0042] In embodiments, the additional base oil is selected from Group I and / or Group II base oils, such as paraffinic base crude oils, intermediate crude oils, or naphthenic base crude oils; vegetable oils (e.g., soybean oil, etc.), short chain or branched chain esters derived from fats and oils (e.g., methyl esters of soybean oil, isopropyl oleate, trimethylolpropane trioleate, etc.), and refined oils obtained by refining these distillates.

[0043] If used, the amount of additional base oil (non-DCR) is less than 50% of the total amount of base oil. In embodiments of semi-synthetic fluids, the amount of additional base oil used ranges from 2-25%, or <20%, or <10% of the total weight of the MWF. In embodiments of soluble oils, if used, the amount of additional base oil ranges from 20-45% by weight, or <40%, or <30%, or <20% of the total weight of the MWF concentrate.

[0044] In embodiments, the additional base oil component is a Group I base oil, and the weight ratio of DCR: Group I base oil ranges from 50:50 to 90:10 (based on the total weight of base oil).

[0045] Emulsifier component The MWF further comprises at least one emulsifier, and preferably two or more emulsifiers (e.g., an emulsifier and a co-emulsifier), which can be the same or different types. The selection of the emulsifier depends on the amount of water, the amount and type of oil component used. The emulsifier is selected from any of the conventional anionic, cationic, nonionic, or amphoteric surfactants.

[0046] In embodiments, the emulsifier component is selected from amphoteric compounds. Examples include 3-iminodipropionic acid alkyl esters; 3-amino-propionic acid alkyl esters; fatty imidazolines and betaines, more specifically 1-coco-5-hydroxyethyl-5- carboxymethylimidazoline; dodecyl-3-propionic acid; N-dodecyl-N,N-dimethylaminoacetic acid; 2-trimethylammonium lauric acid inner salt, etc.

[0047] In embodiments, the emulsifier component is selected from nonionic surfactants, such as ethylene oxide adducts of alcohols, polyols, phenols, carboxylic acids, and carboxylic acid esters, such as ethylene oxide adducts of oleyl alcohol, nonylphenol, glycerol, sorbitol, mannitol, pentaerythritol, sorbitan monolaurate, glycerol monooleate, pentaerythritol monostearate, oleic acid, stearic acid, etc.

[0048] In embodiments, the emulsifier component is selected from cationic compounds, including cetylpyridinium bromide cetyl morpholinium chloride Di-dodecyl triethylenetetramine diacetate, didodecylamine lactate, 1-amino-2- heptadecenylimidazoline acetate, hexadecylamine acetate, oleylamine acetate, ethoxylated tallow amine, cocamine, stearamine, oleylamine, or soyaamine, and the like. Useful anionic compounds include alkali metal salts of petroleum sulfonic acids, alkali metal salts of fatty acids, amine and ammonium soaps of fatty acids, alkali metal salts of dialkyl sulfosuccinic acids, sulfated oils, sulfonated oils, alkali metal salts of alkyl sulfates, and the like.

[0049] In embodiments, the emulsifier is an oil-soluble emulsifier, such as an organic sulfonate, a fatty acid ester, a polyoxyethylene acid, an alcohol and a alkanolamide, and an alkanolamine, the latter being generally preferred. Examples include monoethanolamine, diethanolamine, triethanolamine, or isopropanolamine.

[0050] In embodiments, 50-100% of the emulsifier is soluble in water, such as a rosin acid ester. In embodiments, distilled tall oil (DTO) or tall oil fatty acid (TOFA) is used, with a primary emulsifier, or a co-emulsifier and another emulsifier, such as a sulfonate.

[0051] The amount of emulsifier ranges from 0.1-15%, or 0.3%-12%, or at least 10%, of the total weight of the MWF concentrate.

[0052] Optional components: The metalworking fluid optionally comprises one or more components selected from a saponifier or (pH) buffer, a corrosion inhibitor, an extreme pressure (EP) or anti-wear additive, a corrosion inhibitor, an anti-wear agent, a metal deactivator, an antifoam agent, a rust inhibitor, a deodorant, a dye, a fungicide, a bactericide, an antioxidant, an emulsion or dispersion stabilizer, and the like, a deodorant, a dye, a fungicide, a bactericide.

[0053] Examples of saponifiers / buffers include alkanolamines such as primary, secondary, and tertiary aminomethyl propanol (AMP-95), diglycolamine (DGA), monoethanolamine (MEA), monoisopropanolamine (MIPA), butylethanolamine (NBEA), dicyclohexylamine (DCHA), diethanolamine (DEA), butyldiethanolamine (NBDEA), triethanolamine (TEA), alkali metal hydroxides, potassium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, metal carbonates and bicarbonates, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate, ethanolamine, and ethylenediaminetetraacetic acid.

[0054] Examples of corrosion inhibitors include, but are not limited to, organic amines, metal salts of organic sulfonates, petroleum oxides, organic diamines, organic amine condensates of fatty alcohols, and substituted imidazolines.

[0055] Examples of anti-wear additives (AW, lubricity improvers) include organic acids. Examples of such organic acids include octanoic acid, nonanoic acid, isononanoic acid, decanoic acid, lauric acid, stearic acid, oleic acid, benzoic acid, p-tert-butyl benzoic acid, adipic acid, suberic acid, sebacic acid, azelaic acid, and dodecanedioic acid.

[0056] In embodiments, the MWF includes at least an extreme pressure (EP) / coupling agent selected from zinc dithiophosphates (ZDP), zinc dialkyldithiophosphates (ZDDP), tricresyl phosphate (TCP), halogenated hydrocarbons (chlorinated paraffins), glycerol monooleate, stearic acid, nonionic surfactants including ethers such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl ethers; esters such as sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene fatty acid esters; and conventional coupling agents such as volatile alcohols such as sec-butyl alcohol, butyl oxitol, or cyclohexanol.

[0057] In embodiments, the amount ranges from 0.1-15 wt%, or <10 wt%, or >0.5 wt%, or <5 wt%, or <2 wt% of the total weight of the MWF concentrate, depending on the optional additives.

[0058] Method of preparation / application : Depending on the base oil employed (100% DCR, or a mixture of DCR and at least a different base oil), the components can be mixed simultaneously or in a certain order to form the concentrate. In embodiments, the additives such as corrosion inhibitors and emulsifiers are first absent, then additives such as saponifiers are added, followed by the buffering agents.

[0059] In use, the MWF is subsequently generated by dispersing the concentrate with water, for example using a high shear mixer, for use in metal machining processes such as cutting, grinding, stamping, polishing, deep drawing, drawing, and rolling, to provide excellent lubricity for machining so-called difficult-to-machine materials.

[0060] Properties : Metal working fluids prepared from concentrates having DCR (or a mixture of DCR and a different base oil) as the base oil component are characterized by providing the same or better performance relative to MWFs prepared from mineral oils such as Group I or Group II oils alone.

[0061] In embodiments using a base oil component containing at least 50% DCR (based on the amount of DCR in the total amount of base oil components), the MWFs prepared show excellent stability even after 28 days at 60°C. In high frequency reciprocating rig (HFRR) testing, the MWFs show comparable film thickness and coefficient of friction relative to the corresponding MWF water-in-oil emulsions containing naphthenic oil. The oil-in-water MWFs also show minimal foam formation, less than 50 mm / foam test (as explained below). DETAILED DESCRIPTION

[0062] Examples The following tests were performed on the samples in the examples:

[0063] Lubricity test HFRR (high frequency reciprocating rig): Average 63% film thickness and a 0.104 coefficient of friction were reported per ASTM D6079. This is done by measuring the electrical resistance between two mating objects. It is zero percent film when there is no resistance and 100% when there is high resistance.

[0064] Stability test Initial stability of both the concentrate and emulsion, centrifuge stability, and long term stability at 60°C were tested for each sample. Centrifuge stability was performed at 3000 rpm after 30 minutes and separation was observed.

[0065] Foaming tendency Foam testing included shaking 100 mL of emulsion in a 250 mL graduated cylinder for 1 minute, then measuring the initial foam height and the foam height after 1 minute of standing.

[0066] Particle size Particle size was measured using a Beckman Coulter Delsa Nano particle analyzer.

[0067] Rust corrosion Evaluation was performed per ASTM 4267.

[0068] DCR DCR from Kraton Corporation with properties as shown in Table 1 were used in the examples.

[0069] Table 1 .

[0070]

[0071]

[0072] Rosin oil Rosin oils were prepared by experimental procedures known in the art, as shown below for the comparative examples. The nomenclature xx as in "AN-26", "AN-80", etc. refers to the acid value of the (crude) rosin oil sample. PTSA refers to p-toluenesulfonic acid, and PTSA / S refers to experiments using PTSA in the presence of sulfur.

[0073] Rosin oil AN-10 (PTSA / S): Rosin acid was heated to 180°C in a round bottom flask and then 3.75 wt% sulfur was added. The temperature was increased after the sulfur was added and held at 230°C. After 4 hours, 2 wt% PTSA was added to the reaction mixture and the temperature was increased to 290°C. The reaction mixture was held at 290°C for 51 hours until an acid value of 10 mg KOH / g was obtained.

[0074] Rosin oil AN-80 (PTSA / S) : AN 80 was obtained in the same manner as AN-10 except the reaction mixture was held at 290°C for 1 hour to obtain an acid value of 80 mg KOH / g.

[0075] Rosin oil AN-80 (hot) : The experiment was performed without any catalyst such as PTSA / S. Rosin acid was heated to 320°C at 40°C / hr and the reaction was held at 320°C for 75 hours until 80 mg KOH / g was achieved.

[0076] Other rosin oils : The above experiments were repeated but with different reaction time periods for rosin oil samples with different acid values such as AN-23 (PTSA / S), AN-26 (PTSA / S), AN-37 (heat) and with a different catalyst (hydrophosphorous) for AN-6. These comparative rosin oils were used in Examples 5A-5E.

[0077] Distillate examples : Some prior art rosin oil samples and DCR samples were refined to obtain distillate samples. The properties of the crude DCR are shown in Table 2A below and the properties of the distilled DCR are shown in Table 2B below.

[0078] Table 2A - Properties of crude products (rosin oils and DCR)

[0079]

[0080]

[0081] Table 2B - Properties of distilled products prepared from rosin oils and DCR

[0082]

[0083] Examples 1A-1F DI water-in-oil soluble oil MWFMWF formulations were produced from concentrates having components according to Table 3, with different base oils replacing the naphthenic base oil in Table 3. For each example, an MWF formulation was prepared by dispersing 56 grams of each concentrate into 644 grams of DI (deionized) water. The differences in the examples were the base oil components (one or more) and proportions as indicated in Table 4, with some examples having DCR (acid number ~7 mg KOH / g) and mineral oil base components. Table 4 also shows test results for stability, particle size, foaming tendency, lubricity, and corrosion.

[0084] Table 3 - Soluble oil concentrate

[0085] Concentrate components Amount (g) wt% Naphthenic base oil 100 SUS 50.65 77.93 Synthetic sodium sulfonate MW 470 1.21 1.86 Distilled tall oil 6.91 10.64 Triethanolamine 1.73 2.66 Polyoxyl castor oil surfactant 4.49 6.91 Total 65.00 100.00

[0086] Table 4 - Soluble oil formulation - DI water

[0087]

[0088] Examples 2A-2F - DI water-in-oil semi-synthetic MWF MWF formulations were produced from concentrates having components according to Table 5, with different base oils as replacements. For each example, an MWF formulation was prepared by dispersing 30 grams of concentrate into 345 grams of DI (deionized) water. As with the above examples, the differences in the examples were the base oil components (one or more) and proportions as indicated in Table 6, with some examples having DCR (acid number ~7 mg KOH / g) and mineral oil base components. Table 6 also shows test results for stability, particle size, foaming tendency, lubricity, and corrosion.

[0089] Table 5 - Semi-synthetic concentrate

[0090] Concentrate components Amount wt% Base oil 25.33 63.85 Synthetic sodium sulfonate MW 470 1.21 3.05 Distilled tall oil 6.91 17.42 Triethanolamine 1.73 4.36 Polyoxyl castor oil surfactant 4.49 11.32 Total 39.67 100.00

[0091] Table 6 - Synthetic oil formulation - DI water

[0092]

[0093] Examples 3A-3F hard water-in-oil soluble oil MWF Examples 1A-1F with soluble oil concentrate formulations were repeated, but the concentrates were dispersed in hard water (500 ppm calcium chloride in DI water) instead of DI. Table 7 shows test results for stability, particle size, foaming tendency, lubricity, and corrosion.

[0094] Table 7 - Soluble oil formulation, hard water

[0095]

[0096]

[0097] Examples 4A-4B MWF formulations were produced from different concentrates having the components according to Table 3, with different rosin oils replacing the naphthenic base oil in Table 3. For each example, an MWF formulation was prepared by dispersing 56 grams of each concentrate into 644 grams of hard water. Table 8 shows the test results for stability, particle size, foaming tendency, lubricity, and corrosion.

[0098] Table 8 Soluble oil formulations - comparison rosin oil, in hard water

[0099] Performance parameters Example 4A Example 4B Base oil AN-7 AN-71 Concentrate stability Not separated Separated Emulsion stability, centrifuge Unstable Unstable Emulsion stability, 60C / % separation Not measured Not measured Cumulative particle size, nm Not measured Not measured HFRR, % film / friction Not measured Not measured Foam, mm, initial / 1 minute Not measured Not measured Corrosion, rust on paper % Not measured Not measured

[0100] Examples 5A-5E MWF formulations were produced from different concentrates having the components according to Table 3, with different rosin oils and distillates replacing the naphthenic base oil in Table 3. For each example, an MWF formulation was prepared by dispersing 56 grams of each concentrate into 644 grams of hard water. Table 9 shows the test results for stability, particle size, foaming tendency, lubricity, and corrosion.

[0101] Table 9 Soluble oil formulations - comparison rosin oil - distillates

[0102]

[0103]

[0104] Examples 6A-6E MWF formulations were produced from different concentrates having the components according to Table 3, with olive oil, methyl oleate, and isopropyl oleate replacing the naphthenic base oil in Table 3, with 56 grams of each concentrate added to 644 grams of hard water. Table 10 shows the test results for stability, particle size, foaming tendency, lubricity, and corrosion.

[0105] Table 10 Soluble oil formulations, hard water

[0106]

[0107] Examples 7A-7F hard water-in-oil semi-synthetic MWF Examples 2A-2F were repeated with the semi-synthetic concentrate formulations, but the concentrates were dispersed in hard water (500 ppm calcium chloride in DI water) instead of just DI. Table 11 shows the test results for stability, particle size, foaming tendency, lubricity, and corrosion.

[0108] Table 11 Semi-synthetic formulations, hard water

[0109]

[0110] As illustrated, DCR can replace mineral oil, such as Group I or Group II, in whole or in part. Group II oils that do not produce a stable product when used in the same formulation can be supplemented with 50% DCR to produce a stable product. Replacing paraffinic oil with 50% naphthenic oil does not provide the same remedy. There is little difference between traditional oils and DCR, mainly with respect to long term stability at 60°C, although there are some differences when formulated with hard water as compared to DI water.

[0111] While the terms "comprising" and "including" have been used herein in describing various aspects, the terms "consisting essentially of and "consisting of can be substituted for "comprising" and "including" to provide more particular aspects of the present disclosure and are also disclosed.

Claims

1. A metalworking fluid concentrate used as an oil-in-water emulsion, comprising: The amount of base oil components is 5-90% by weight, based on the total weight of the concentrate; The amount is 0.1 to 15% by weight of any emulsifier selected from conventional anionic, cationic, nonionic or amphoteric surfactants; At least optional additives, selected from saponifying agents, pH buffers, preservatives, extreme pressure EP additives, corrosion inhibitors, anti-wear agents, metal passivators, defoamers, rust inhibitors, deodorizers, dyes, antioxidants, emulsion stabilizers, and dispersion stabilizers, in an amount of 0.1 to 15% by weight. The base oil component contains at least 50% by weight of decarboxylated rosin acid (DCR), based on the total weight of the base oil component, and the remainder is oil selected from naphthenic oils, alkanes, bio-based oils, and mixtures thereof. The DCR described therein has: The m / z (mass / charge) value is 220-280, measured by GC-FID-MS. The oxygen content is <5%. The oxygen content is the ratio of the sum of the present oxygen atoms to the sum of the present carbon atoms, obtained through elemental analysis. The acid value is <10 mg KOH / g, as measured according to ASTM E28-18; and The DCR mentioned above includes: >50% by weight of tricyclic compounds having 18-20 carbon atoms, >55% by weight as aromatic and cyclic aliphatic tricyclic compounds, <45% by weight of tricyclic compounds as reactive double bonds (C=C groups), as measured by GC-FID-MS.

2. The metalworking fluid concentrate according to claim 1, wherein the DCR has >25% by weight aromatic content, >40% by weight cycloalkane content, and >15% by weight alkanes content, all based on the total weight of the DCR.

3. The metalworking fluid concentrate according to claim 1, wherein the DCR has at least one of the following: Brookfield viscosity at 40°C >20 cSt, as measured according to ASTM D445; The aniline point is at least 5°C, as measured according to ASTM D611; The pour point is less than 30°C, as measured according to ASTM D97. Sulfur content <0.05% by weight, as measured according to ASTM D5453; Gardner color <3, as measured according to ASTM D6166; and Flash point <160℃, measured according to ASTM D92.

4. The metalworking fluid concentrate according to claim 1, wherein the amount of the tricyclic alicyclic compound in the DCR is >30% by weight.

5. The metalworking fluid concentrate according to any one of claims 1-4, wherein the sum of the amounts of aromatic and alicyclic tricyclic compounds in the DCR is >60% by weight, based on the total weight of the DCR.

6. The metalworking fluid concentrate according to any one of claims 1-4, wherein the amount of the tricyclic compound as a reactive double bond is <30% by weight, based on the total weight of the DCR.

7. The metalworking fluid concentrate according to any one of claims 1-4, wherein the amount of the tricyclic compound as a reactive double bond DCR is <10% by weight, based on the total weight of the DCR.

8. The metalworking fluid concentrate according to any one of claims 1-4, wherein the concentrate is a soluble oil concentrate, and wherein the amount of the base oil component is 40-90% by weight, based on the total weight of the concentrate.

9. The metalworking fluid concentrate according to any one of claims 1-4, wherein the concentrate is a semi-synthetic fluid concentrate, and wherein the amount of the base oil component is 5-40% by weight, based on the total weight of the concentrate.

10. The metalworking fluid concentrate according to any one of claims 1-4, wherein the base oil component contains >50% by weight DCR based on the total weight of the base oil component, and the balance is Group I base oil.

11. A method for preparing a metal surface for subsequent processing of the metal to manufacture articles therefrom, the method comprising: The metalworking fluid concentrate of any one of claims 1-4 is diluted in water to form a water-in-oil emulsion (MWF) with a water concentration of 80-99% based on the total weight of the MWF. An ultrathin film of metalworking fluid is deposited on a metal surface by applying an oil-in-water emulsion as a substantially continuous layer.

12. A method for preparing a metal surface for subsequent processing of the metal to manufacture articles therefrom, the method comprising: Provides metalworking fluid MWF concentrate, containing: The amount of base oil components is 5-90% by weight, based on the total weight of the concentrate; The amount is 0.1 to 15% by weight of any emulsifier selected from conventional anionic, cationic, nonionic or amphoteric surfactants; At least optional additives, selected from saponifying agents, pH buffers, preservatives, extreme pressure EP additives, corrosion inhibitors, anti-wear agents, metal passivators, defoamers, rust inhibitors, deodorizers, dyes, antioxidants, emulsion stabilizers, and dispersion stabilizers, in an amount of 0.1 to 15% by weight. The base oil component contains at least 50% by weight of decarboxylated rosin acid (DCR), based on the total weight of the base oil component, and the remainder is oil selected from naphthenic oils, alkanes, bio-based oils, and mixtures thereof. The DCR described therein has: The m / z (mass / charge) value is 220-280, measured by GC-FID-MS. The oxygen content is <5%. The oxygen content is the ratio of the sum of the present oxygen atoms to the sum of the present carbon atoms, obtained through elemental analysis. The acid value is <10 mg KOH / g, as measured according to ASTM E28-18; and The DCR mentioned above includes: >50% by weight of tricyclic compounds having 18-20 carbon atoms, >55% by weight as aromatic and cyclic aliphatic tricyclic compounds, <45% by weight of tricyclic compounds as reactive double bonds (C=C groups), as measured by GC-FID-MS.

13. The method of claim 12, wherein the DCR has >25% by weight aromatic content, >40% by weight cycloalkane content, and >15% by weight alkanes content, all based on the total weight of the DCR.

14. The method according to any one of claims 12-13, wherein the amount of the tricyclic alicyclic compound in the DCR is >30% by weight.

15. The method according to any one of claims 12-13, wherein the DCR has at least one of the following: Brookfield viscosity at 40°C >20 cSt, as measured according to ASTM D445; The aniline point is at least 5°C, as measured according to ASTM D611; The pour point is less than 30°C, as measured according to ASTM D97. Sulfur content <0.05% by weight, as measured according to ASTM D5453; Gardner color <3, as measured according to ASTM D6166; and Flash point <160℃, measured according to ASTM D92.

Images