MXPA97003453A - Copolymers containing sulphonate as fog suppressors in fluids from working soluble oil-based metals (based on ag - Google Patents

Abstract

Aqueous fluids are described for working metals containing a mist suppressor copolymer. The copolymer includes hydrophobic and hydrophilic monomers. Eventually, the metalworking fluid may be an oil-in-oil emulsion

Description

COPOLYMERS CONTAINING SULPHONATE AS FOG SUPPRESSORS IN FLUIDS FROM WORKING SOLUBLE OIL-BASED METALS (BASED ON WATER) BACKGROUND OF THE INVENTION This invention relates to aqueous fluids for working metals consisting of water and a mist suppressor copolymer. Eventually, the fluid may be an oil-in-water emulsion. Said emulsions include oil and an emulsifier. In addition to the mist suppressant copolymer, metal cutting operations frequently include a workpiece rotating at a relatively high speed and a cutting instrument, both lubricated by a metalworking fluid. Under these conditions, the metalworking fluid is frequently thrown from the surface of the metal in the form of droplets. Frequently, these droplets are small enough to be classified as fog. The fog, or the formation of a fog, is considered undesirable, since it represents a loss of the cutting fluid and the mist of the cutting fluid is considered as a pollutant in the air surrounding the cutting machine. It is known that polymers containing acrylamides thicken aqueous materials. U.S. Pat. No. 4,432,881 discloses an aqueous composition containing a water soluble polymer having pendant hydrophobic groups, for example a copolymer of acrylamide / dodecyl acrylate, and a water dispersible surfactant, for example sodium oleate or dodecyl polyethylene glycol mono ether. As an example, water-soluble monomers include ethylenically unsaturated amides such as acrylamide and 2-acrylamido-2-methylpropanesulfonic acid. The molar ratio of the water-soluble monomer to the hydrophobic monomer is in the range of 98: 2 to about 99.995: 0.005. The uses described for this composition include higher oil recovery processes, as agents for the control of fluid mobility, fracturing fluids and drilling muds, as well as hydraulic fluids and lubricants. The use of the composition in metal working fluids is not a described application. U.S. Pat. No. 4,520,182 describes water-soluble acrylamide / alkyl acrylamide copolymers which are efficient water or brine viscosifiers. It also describes a process for the copolymerization of water insoluble acrylamides with water soluble acrylamide. The molar percentage of the water-soluble acrylamide in the composition ranges from about 90.1 to about 99.9 mole percent. U.S. Pat. No. 5,089,578 discloses novel hydrophobically associated terpolymers which contain sulfonate functionality and which are useful as modifiers of aqueous fluid rheology or flow control. The water-soluble monomers are acrylamide and a salt of an ethylenically unsaturated sulfonic acid and the water-insoluble monomer is a higher alkyl acrylamide. The ethylenically unsaturated sulfonic acids include materials such as sodium 2-acrylamido-2-methylpropanesulfonate. The molar percentage of acrylamide is preferably from about 5 to about 98, more preferably from 10 to 90 mole percent; the molar percentage of the salt of the sulfonate-containing monomer is preferably about 2 about 95, and the mole percent of the hydrophobic monomer is preferably about 0.1 to about 10.0, more preferably 0.2 to 5 per one hundred molar. Metalworking applications are not described. Acrylic polymers are used to control fog in metal working applications. U.S. Pat. No. 3,833,502 describes water-based metalworking fluids that incorporate small amounts of water-soluble polymers. The polymers described fall into three (3) classes. Anionic polymers, cationic polymers and nonionic polymers containing a sufficient number of hydrophilic groups to be dispersible in water. U.S. Pat. No. 4,493,777 discloses substantially oil-free aqueous industrial fluids possessing superior lubrication and wear prevention characteristics which are useful as hydraulic fluids and metalworking compositions. The fluids of the invention consisted of (1) an aqueous liquid and (2) a water-soluble synthetic addition copolymer of (a) an ethylenically unsaturated crosslinking monomer, (b) an ethylenically unsaturated water-soluble monomer and (c) an ethylenically unsaturated hydroinsoluble monomer. Water-soluble monomers include acrylamido-2-methylpropanesulfonic acid. The water-insoluble monomers include styrene compounds, vinyl esters and acrylate esters. The crosslinking monomers are polyvinyl compounds which are present in sufficient amounts to control the degree of swelling of said copolymerization product, while imparting a mechanical reinforcement to said copolymerization product. U.S. Pat. 4,770,814 and its Divisional Patent 4,880,565 disclose suitable, stable, anti-fog aqueous compositions for metalworking. The compositions contain a viscoelastic surfactant, that is, a surfactant having a hydrophobic moiety chemically bound to an ionic hydrophilic moiety and an electrolyte having a moiety that is capable of associating with the surfactant ion. The viscoelastic surfactant can also be a nonionic surfactant. The surfactants described are monomeric. International Patent / O93 / 2 601 describes transparent water-soluble polymeric compounds having an average molecular weight greater than 1 million and selected from polyalkylene oxides, polyacrylamides, polymethacrylamides and the copolymers of an acrylamide and / or methylacrylamide with unsaturated organic carboxylic acids having from three (3) to five (5) carbon atoms, which are used in water miscible coolants and mixed with water, to reduce the formation of fog. The polymeric anti-fog additives reduce the fog formation of the fluids for machinery at the source, stabilizing them against decomposition during the extreme cutting conditions that occur during metal working operations. High molecular weight poly (ethylene oxide) is commonly used in this application. A typical polymer is POLYOX (R), from Union Carbide. Typically, these polymers have a molecular weight of 1 to 2 million. However, these polymers are susceptible to cutting. The application of metalworking frequently involves a high cut and, as a result, metalworking fluids containing high molecular weight poly (ethylene oxide) suffer frequently in terms of their performance when subjected to cutting. This degradation occurs when high-cut conditions cause the breakdown of high molecular weight poly (ethylene oxide) and the loss of its ability to suppress fog formation. In such high cut applications, the polymer must be filled frequently. COMPENDIUM OF THE INVENTION A water-based metalworking fluid consisting of water and a fog-forming copolymer formed by copolymerization of (A) a hydrophobic monomer selected from the group consisting of A (I) a substituted acrylamide compound alkyl having the formula: R3 wherein Ri is a hydrogen or a methyl group and R2 and R3 are independently hydrogen or hydrocarbyl groups, provided that the total number of carbon atoms in R2 and R3 combined is between 2 and 36, and A (II) an ester of acrylate of the following formula: Ri OI "CH2 = C C-0-R9 where Ri is a hydrogen or a methyl group and R9 is a hydrocarbyl group containing between 1 and 20 carbon atoms, and (B) a monomeric hydrophilic compound selected from the group consisting of B (I) acrylamidosulfonic acids having the formula: wherein R 4 is a hydrogen or a methyl group and R is an aliphatic or aromatic hydrocarbon group containing 2 to 8 carbon atoms; B (II) acids acrylamido disulfonic having the formula: R4 0 S03"X + I" I CH2 = C C-NH-R-SO3 X where R4 is a hydrogen or a methyl group and R is an aliphatic or aromatic hydrocarbon group containing from 2 to 8 atoms of carbon and B (III) a styrenesulfonic acid that has the formula : Clí2 = CH and X + is a cation selected from the group consisting of alkali metal cations, alkaline earth cations, transition metal cations - Se, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and ammonium cations. the following formula: where R5, Re, R? and Re are independently hydrogen or hydrocarbyl groups, provided that the total number of carbon atoms in an ammonium cation does not exceed 21 carbon atoms and always also that, if A is A (I), then the ratio of moles of A a B is in the range of 95: 5 to 25:75 and, if A is A (II), then the ratio of moles from A to B is in the range of 90:10 to 25:75. DETAILED DESCRIPTION OF THE INVENTION The term "hydrocarbyl" includes hydrocarbon groups, as well as substantially hydrocarbons.

Substantially hydrocarbon describes groups containing non-hydrocarbon substituents that do not alter the predominantly hydrocarbon nature of the group. Examples of hydrocarbyl groups include the following: (1) hydrocarbon substituents, ie, aliphatic (eg, alkyl or alkenyl) substituents, alicyclic (eg, cycloalkyl, cycloalkenyl), aromatic-aromatic substituents, aliphatic - and acyl-substituted and the like, as well as cyclic substituents where the ring is completed through another portion of the molecule (i.e., for example, any two indicated substituents can together form an alicyclic radical); (2) substituted hydrocarbon substituents, that is, those substituents containing non-hydrocarbon groups, which, in the context of this invention, do not alter the predominantly hydrocarbon substituent; those skilled in the art will have knowledge of such groups (for example, halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, sulphoxy, etc.), and (3) heterosubstitute, i.e. , substituents which will contain, while having a predominantly hydrocarbon character within the context of this invention, other non-carbon atoms present in a ring or chain otherwise composed of carbon atoms. Suitable heteroatoms will be apparent to those of ordinary skill in the art and include, for example, sulfur, oxygen, nitrogen and substituents such as, for example, pyridyl, furyl, thienyl, imidazole, etc. In general, no more than about 2, preferably no more than one non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group. Typically, there will be no such non-hydrocarbon substituents in the hydrocarbyl group. In that case, the hydrocarbyl group is purely hydrocarbon. COPOLYMER Aqueous anti-fog compositions contain a copolymer which is formed by copolymerization of a water-soluble monomer, often referred to as a hydrophilic monomer, and a water-insoluble monomer, often referred to as a hydrophobic monomer. The hydrophobic monomers are alkyl-substituted acrylamides, alkyl-substituted methacrylamides, acrylate esters and methacrylate esters; the hydrophilic monomers are sulfonate molecules that contain a single ethylenic linkage. When the polymer contains alkyl-substituted acrylamides and alkyl-substituted methacrylamides as the hydrophobic monomer, then the mole percentage of the hydrophobic monomer is in the range of 25 to 95 percent. In this case, the molar percentage of the hydrophilic monomer is in the ratio of 5 to 75 mole percent. When the polymer contains alkyl-substituted acrylates and alkyl-substituted methacrylates as the hydrophobic monomer, then the mole percentage of hydrophobic monomer is from 25 to 90 percent and the molar percentage of the hydrophilic monomer is from 10 to 75 percent. In the polymerization reaction, the ethylenic linkages polymerize and the polymer The resultant consists of a polyethylene skeleton with hydrophobic and hydrophobic side chains. Polyvinyl crosslinking monomers are not included among the monomers that can be used in the practice of the present invention. Crosslinking monomers are not desirable in the polymers of the present invention. VISCOSITY The viscosity measurements of the solution were made comparing the evacuation time t required for a specified volume of polymer solution to flow through a capillary tube (Ostwald-Fenske capillary viscometer) with the corresponding evacuation time t0 of the solvent. From t, tQ and polymer concentration c, the inherent viscosity is derived based on the following equation hin? = [In (t / t0)] / c where the concentration c is expressed in grams per deciliter. Methanol was used as solvent. All inherent viscosities were measured at 30 ° C and c = 1.0 g / dl. HYDROPHILIC MONKMERS The hydrophilic monomers usable in the present invention are ethylenic monomers containing a sulfonate group. Three types of sulfonate monomers have proved useful in the present invention. The first type of hydrophilic monomers are substituted acrylamides containing a sulfonate group: R4 OI "CH2 = C C-NH-R-SO3" X + where R4 is a hydrogen or a methyl group and R is an aliphatic or aromatic hydrocarbon group it contains from two / (2) to eight (8) carbon atoms and acts as a bridge between the nitrogenous portion of the acrylamido group and the sulfonate group. The group R can be branched, as in the molecule of 2-acrylamido-2-methylpropanesulfonic acid, which has the following structure: O CH3 CH2 = CC-NH-C-CH2-S03"X + CH3 The group R can also include phenyl groups, phenyl groups substituted with alkyl and cycloaliphatic groups The second type of sulfonate monomer are substituted acrylamides containing two sulfonate group structures : R4 O S03"X + I" I CH2 = C C-NH-R-S03"X + where R4 is a hydrogen or a methyl group and R is as defined above for the acrylamides with a single sulfonate group. The sulfonate groups can be attached to the same or different carbon atoms. The third type is styrene sulfonate illustrated by the following formula: X + X + is a cation selected from the group consisting of alkali metal cations, alkaline earth cations, cations of the transition metals - cations of Se, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and ammonium of the following formula: where R, R6, R? and Re are independently hydrogen or hydrocarbyl groups, provided that the total number of carbon atoms in the ammonium cation does not exceed 21 carbon atoms. HYDROPHOBIC MONOMERS The hydrophobic monomer can be an acrylamide or methacrylamide corresponding to the following formula: Ra In this formula, Ri can be a hydrogen or a methyl group corresponding to an acrylamide or methacrylamide, respectively. R2 and R3 are independently a hydrogen or a hydrocarbyl group, provided that the total number of carbons in R2 and R3 is in the range of 2 to 36 carbon atoms. Accordingly, when R2 is a methyl group, then R3 must be an alkyl group rather than a hydrogen. It is preferred that the total number of carbon atoms in R2 and R3 be in the range of 4 to 36 carbon atoms, or 4 to 24 carbon atoms, or 4 to 12 carbon atoms. Other preferred ranges for the total number of carbon atoms in R2 and R3 are 8 to 36 carbon atoms, or 8 to 24 carbon atoms, or 8 to 12 carbon atoms. The most preferred range for the total number of carbon atoms in R2 and R3 is 4 to 8 carbon atoms.

The hydrophobic monomer can also be an acrylate or methacrylate ester of the formula: where Ri is a hydrogen or a methyl group and R9 is a hydrocarbyl group containing between 1 and 20 carbon atoms. It is preferred that R9 contains between 2 and 18 carbon atoms, 4 and 18 carbon atoms, 4 and 12, 4 and 8 carbon atoms, 8 and 20 carbon atoms, 8 and 16 carbon atoms or 8 and 12 carbon atoms. carbon. FORMATION OF THE COPOLYMER The copolymer is produced by polymerization of free radicals. The polymerization is carried out by well-known free radical methods. The general properties of acrylamide polymers, as well as their methods of preparation are discussed in The Encyclopedia of Polymer Science and Engineering, Volume 1, John Wiley & Sons, 1985 (pp. 169-211). The "Encyclopedia" discusses techniques useful in the formation of acrylic ester polymers (pp. 265-273). The polymerization can be carried out in solution and by various suspension or emulsion methods. In the solution polymerization, a solvent is selected that allows both the hydrophilic and the hydrophobic monomers to remain in solution. Mixtures of water, acetic acid, alcohols of various molecular weights such as methanol, ethanol and butyl alcohol, as well as polar solvents such as acetone, acetic acid, tetrahydrofuran, dimethyl sulfoxide, dioxane, dimethylformamide and N-methylpyrrolidinone. A wide variety of free radical sources can be used as initiators, including persulfates, redox couples, azo compounds and the like. Specifically, emulsion polymerization methods can be used to form polymers useful in the present invention. The preferred polymerization method is solution polymerization and is illustrated in the following examples.

PREPARATION OF THE POLYMER EXAMPLE 1 A 200 ml resin flask was charged with 40 grams (0.101 mole) of sodium salt of 2-acrylamido-2-methylpropanesulfonic acid (58% monomer), 42% H20), 4.3 g (0.033 mole) of t-butylacrylamide (t-BAA), 0.014 g (0.00016 mole) of sodium bicarbonate (NaHCO3) and 20 g of MeOH. A nitrogen purge at 0.1 SCFH was started and the mixture was heated to 70 ° C with stirring. In a separate beaker, 0.014 g (0.00006 mol) of sodium persulfate (Na2S208) was dissolved in 3 g of H20. This solution was collected in a 20 ml syringe. The syringe was placed in a syringe pump that was adjusted to deliver 0.07 ml / minute. The Na2S208 solution was added via the syringe pump to the resin flask over a period of 45 minutes. The two combined monomers constituted 42.7% of the total mixture. At thirty minutes. After the addition was complete, 20 ml of H20 and 45 ml of MeOH were added and the mixture was stirred at 70 ° C for three hours. The contents of the flask were poured into a crystallizer and dried at 80 ° C for 20 hours to obtain 27.5 g (100%) of product, which contained 11.3% sulfur and 6.4% nitrogen and had an inherent viscosity of 2.28 dl / g at 30 ° C in MeOH. Additional examples were prepared using the same method and different proportions of the monomers. The results appear in Table I.

TABLE I Hydrophobic monomer "= t-butylacrylaroid Hydrophilic monomer = Na salt of 2-acrylamido-2-methylpropanesulphonic acid Molar ratio of hydrophobic / hydrophobic monomers Polymeric product trógeno Vis. - monomers NaHCO, Ha2s2 ° n Me0H '"' "'/. sulfur% ni Hydrohhihydro- (mi) inhefóbico ffüüiiccoo (% mol) (% mol) cial rente * dl / g, 28 1 25 75 42.7 0.12 0.04 20 11.3 6.4 2 2.5 9.9 1.89 2 90 10 28.8 0.060 0.02 75 5.0 8.7 2.46 3 75 25 41 0.096 0.03 40 3.2 9.5 1.69 4 85 15 28 0.063 0.02 100 4.4 9.2 9.28 80 20 45 0.05 0.02 40 50 8.9 6.7 2.1 * 6 50 50 36 0.075 0.025 7 95 5 42 0.25 0.1 32 1.1 9.8 2.08 * Viscosity inherent at 30 ° C in methanol EXAMPLE 8 A 200 ml resin flask was charged with 59 g (0.15 mole) of Na salt of 2-acrylamido-2-methylpropanosulfonic acid (58% monomer, 42% H20), 19.2 g (0.15 mole) of t-butyl acrylate and g of MeOH. The mixture was stirred until homogeneous and then heated to 70 ° C with a N2 purge at 0.3 SCFM. In a separate beaker, 0.021 g (0.00009 mole) of Na2S208 was dissolved in 2 g of H20 and 1 g of MeOH and the solution was collected in a 20 ml syringe. The syringe was placed in a syringe pump, which was adjusted to release 0.07 ml / min. The initiator was added to the resin flask for about 45 minutes. After the addition was complete, the solution was stirred for another 4 hours at 70 ° C. The contents of the flask were then poured into a crystallizer and dried at 90 ° C overnight to obtain a product with 3.0% nitrogen, 6.5% sulfur and with an inherent viscosity of 2, 1 dl / g at 30 ° C in MeOH. Additional examples were prepared using the same method and different proportions of the monomers. The results appear in Table II.

TABLE 2 Examples 8 - 10 Hydrophobic monomer = t-butyl acrylate Hydrophilic monomer = Na salt of 2-acrylamido-2-methylpropanesulphonic acid |) - hydrotoxic / ru.aroi .111CUÍ polymeric product mrdar monome monomers MeOH ini % Sulfur% Nitrogen, Vis, Example, Hydro-Hydro-% N32S2 ° 8 (mol%) cial (mi) her < phylic object philic dl / g 8 50 50 26 0.06 100 6.3 3.7 1.1 9 50 50 43.13 45 45 6.5 3.0 2.1 1.8 65 35 39.7 0.03 50 4.8 2.9 * Viscosity inherent at 30 ° C in methanol ASSAY In order to evaluate the performance of the polymers of the invention, a method was developed for the ability of a polymer to reduce the formation of fog. This method involved pumping the liquid containing a dye and 0.5 percent by weight of the mist suppressor to be studied through the central tube of a coaxial air jet atomizer. The air, at high pressure, flows from the outer tube of the atomizer. The test liquid is atomized and the resulting spray hits a screen located 38 centimeters from the end of the atomizer. The atomization procedure continues for a standard period of time, after which the screen dries. The spray coming out of the atomizer hits the screen with a circular pattern. The size of the pattern depends on the distance of the screen from the atomizer, the flow velocity of the liquid and the air pressure. These parameters were standardized and maintained constant through the measurements described below. It was found that the known mist suppressor polymers had a strong influence on the diameter of the pattern produced on the screen. Water, which can be atomized with relative ease in a fine mist, produced the largest diameter pattern. When a known mist suppressor, POLYOX (R), was added to the water, a large reduction in the diameter of the pattern was observed. Similarly, the samples of the polymers described herein were dissolved in water and resulted in substantially reducing the diameter of the spray patterns produced on the screen. Samples of approximately 350 grams of the test solutions containing each suppressor were cut for two minutes in a commercial Waring Model 700 mixer with a rotation speed of 20,000 rpm. The samples were then re-studied for the effectiveness of the mist suppressor polymer. The efficiency of the fog suppression was calculated using the following equation: '-'water ~ ^ test sample D = uagua where D is the diameter of the spray pattern. Table 3. Changes in the efficiency of fog suppression with cutting MATERIAL DI%? D%? D% Loss of fog suppression with [Cut = 0 [Cut = 2 cut = 2 min min in mixer mixer] Water 0, 00 0.00 0.00 POLYOX of 20.33 6.50 68.00 1 million of PM POLYOX of 39.84 2.68 93.27 2 million MW (Ex 5) 18.13 20.73 14.35 (Ex 3) 16.67 14.23 (14.63) gain (Ex 6) ) 10,16 8,37 17,60 (Ex 9) 17,32 8,94 48,36 (Ex 10) 19,11 12,20 36,17 COMPOSITIONS The fluids for working metals of the present invention include oil-free water-based compositions. In its simplest form, these compositions include water and the anti-fog polymer. It is desirable to include the polymer at an effective level to suppress the fog. However, even with the recovery of fluids for working metals used, something is lost in use and the anti-fog polymer is an expense. Accordingly, it is also desirable to use the anti-fog polymers at the lower levels of their effective concentration range. Many factors affect the level of polymer required to achieve an anti-fog effect. The shape of the tool and the workpiece, the level of cut in the particular application and the speed of movement of the workpiece all influence the amount of mist suppression required. The anti-fog polymer is used in a concentration range of 0.02 weight percent to 10 weight percent, based on the total weight of the composition. A mixture of the antifog polymers can also be used to prepare the compositions. In addition to the anti-fog polymer, aqueous metalworking fluids may contain additives to improve the properties of the composition. These additives include antifoaming agents, metal deactivators and corrosion inhibitors, antimicrobial, anti-corrosion, extreme pressure, anti-wear, anti-friction and anti-oxidation agents. Such materials are well known to those skilled in the art. The metalworking fluids of the present invention may also be oil-pet emulsions. The emulsion compositions contain the same types and amounts of anti-fog polymers as the purely aqueous compositions discussed above. The compositions may also contain the additives to improve the property that have been used in the purely aqueous fluids indicated above. The oils used in the emulsion compositions may include petroleum oils, such as lubricating viscosity oils, crude oils, diesel oils, mineral sealing oils, kerosenes, fuel oils, white oils and aromatic oils. Liquid oils include natural lubricating oils, such as animal oils, vegetable oils, mineral lubricating oils, mineral oils treated with solvents or acids, coal or shale derived oils and synthetic oils. Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and interpolymerized olefins, for example polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly (1-hexenes), poly (1-octenes), poly (1) -decenos); alkylbenzenes, such as dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di (2-ethylhexyl) benzenes; polyphenyls, such as biphenyls, terphenyls and alkylated polyphenyls, and alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogs and homologs thereof. The alkylene oxide polymers and their derivatives, where the terminal hydroxy groups have been modified by esterification, etherification, etc., constitute another class of synthetic oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers such as methyl polyisopropylene glycol ethers, polyethylene glycol diphenyl and diethyl ethers, and mono and polycarboxylic esters of they are, for example, acetic esters, mixed esters of C3-C8 fatty acids and OxO Ci3 diester of tetraethylene glycol. Simple aliphatic ethers can be used as synthetic oils, such as dioctyl ether, didecyl ether, di (2-ethylhexyl) ether. Another suitable class of synthetic oils consists of the esters of fatty acids, such as ethyl oleate, lauryl hexanoate and decyl palmitate. Esters of dicarboxylic acids such as italic acid, succinic acid, maleic acid, azelaic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenylmalonic acids with a variety of alcohols, such as alcohol butyl, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoethyl ether, propylene glycol. Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, dioctyl phthalate, didecyl phthalate, diethyrosyl sebacate, 2-ethylhexyl diester of the linoleic acid dimer and the complex ester formed by the reaction of one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid. The oil to water ratio can vary from about 1: 5 to about 1: 200. Any oil-in-water emulsifier can be used to prepare the emulsions of the present invention. The emulsifiers can be simple materials or they can be mixtures of surfactants. Typical emulsifiers include alkali metal sulfonates and carboxylates, salts derived from the reaction product of carboxylic acylating agents with amines and hydroxylamines, polyols, polyether glycols, polyethers and polyesters and the like. The Kirk-Othmer Encyclopedia of Chemical Technology (3rd Edition V.8 pp. 900-930) provides a good discussion of emulsions and gives a list of emulsifiers useful in the preparation of oil-in-water emulsions.

OTHER COMPONENTS A typical fluid for working metals would include other components such as antifoam agents, metal deactivators, corrosion inhibitors, antimicrobial agents, extreme pressure, anti-wear, anti-friction and anti-oxidation. Typical anti-friction agents include overbased sulfonates, sulfur-containing olefins, chlorinated paraffins and olefins, sulfur-containing olefins, amine-terminated polyglycols, and sodium dioctyl phosphate salts. Useful antifoaming agents include: alkyl polymethacrylates and polymethylsiloxanes. Metal deactivators include materials such as tolyltriazoles. Corrosion inhibitors include carboxylic / boric acid diamine salts, carboxylic acid amine salts, alkanol amines, alkanolamin borates, and the like.

Claims (34)

CLAIMS 1. An aqueous fluid for metalworking consisting of water and a mist suppressor copolymer formed by copolymerization of (A) a hydrophobic monomer selected from the group consisting of (I) an alkyl-substituted acrylamide compound having the formula: Ri 0 R2 I "/ CH2 = C CN \ R3 where Ri is a hydrogen or a methyl group and R2 and R3 are independently hydrogen or hydrocarbyl groups, provided that the total number of carbon atoms in R2 and R3 combined is between 2 and 36, and A (II) an acrylate ester of the following formula: where Ri is a hydrogen or a methyl group and R9 is a hydrocarbyl group containing between 1 and 20 carbon atoms, and (B) a hydrophilic monomeric compound selected from the group consisting of B (I) acrylamidosulfonic acids of the formula: R O
1. CH2 = C i C "-NH-R-S03-X ++ where R is a hydrogen or a methyl group and R is an aliphatic or aromatic hydrocarbon group containing from 2 to 8 carbon atoms; B (II) acrylamido disulfonic acids of formula: R4 O S03"X +
2. X wherein R 4 is a hydrogen or a methyl group and R is an aliphatic or aromatic hydrocarbon group containing from 2 to 8 carboride atoms, and B (III) a styrenesulfonic acid of the formula:
3. CH2 = CH and X + is a cation selected from the group consisting of alkali metal cations, alkaline earth cations, transition metal cations - Se, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and ammonium cations. the following formula: where R5, R6, R7 and Re are independently hydrogen or hydrocarbyl groups, provided that the total number of carbon atoms in an ammonium cation does not exceed 21 carbon atoms and always also that, if A is A ( I), then the ratio of moles from A to B is in the range of 95: 5 to 25:75 and, if A is A (II), then the ratio of moles from A to B is in the range of 90: 10 a.:25:75. 2. An aqueous fluid for working metals according to claim 1, wherein the hydrophobic monomer is
4. A (I). 3. An aqueous fluid for working metals according to claim 2, wherein the total number of carbon atoms in R2 and R3 combined is from 4 to 24 carbons. 4. An aqueous fluid for working metals according to claim 2, wherein the total number of carbon atoms in R2 and R3 combined is from 4 to 12 carbons.
5. 5. An aqueous metalworking fluid according to claim 2, wherein the total number of carbon atoms in R2 and R3 combined is from 4 to 8 carbons.
6. 6. An aqueous fluid for working metals according to claim 2, wherein the total number of carbon atoms in R2 and R3 combined is from 8 to 24 carbons.
7. 7. An aqueous metalworking fluid according to claim 2, wherein the total number of carbon atoms in R2 and R3 combined is from 8 to 12.
8. 8. An aqueous metalworking fluid according to claim 1, wherein the hydrophobic monomer is A (II).
9. 9. An aqueous fluid for working metals according to claim 8, wherein R9 contains from 2 to 18 carbon atoms.
10. 10. An aqueous fluid for working metals according to claim 8, wherein R9 contains from 4 to 18 carbon atoms.
11. 11. An aqueous fluid for working metals according to claim 8, wherein R9 contains from 4 to 12 carbon atoms.
12. 12. An aqueous fluid for working metals according to claim 8, wherein R9 contains from 4 to 8 carbon atoms.
13. 13. An aqueous fluid for working metals according to claim 8, wherein R9 contains from 8 to 18 carbon atoms.
14. 14. An aqueous fluid for working metals according to claim 8, wherein R9 contains from 8 to 12 carbon atoms.
15. 15. An aqueous metalworking composition according to claim 1, wherein the hydrophilic monomer is B (I).
16. 16. An aqueous fluid for working metals according to claim 15, wherein R contains from 4 to 8 carbon atoms.
17. 17. An aqueous fluid for working metals according to claim 15, wherein the hydrophilic monomer is sodium salt of 2-acrylamido-2-methylpropanesulfonic acid.
18. 18. An aqueous metalworking fluid according to claim 1, wherein the hydrophilic monomer is the sodium salt of 2-acrylamido-2-methylpropanesulfonic acid and the hydrophobic monomer is t-butylacrylamide.
19. 19. An aqueous fluid for working metals according to claim 1, further comprising an oil and an emulsifier, wherein the fluid is an oil-in-water emulsion.
20. 20. A fluid for working metals in oil-in-water emulsion according to claim 19, wherein the hydrophobic monomer is A (I).
21. 21. A fluid for working metals in oil-in-water emulsion according to claim 20, wherein the total number of carbon atoms in R2 and R3 combined is from 4 to 24 carbons.
22. 22. A fluid for working metals in oil-in-water emulsion according to claim 20, wherein the total number of carbon atoms in R2 and R3 combined is from 4 to 12 carbons.
23. 23. A fluid for working metals in oil-in-water emulsion according to claim 20, wherein the total number of carbon atoms in R2 and R3 combined is from 4 to 8 carbons.
24. 24. A fluid for working metals in oil-in-water emulsion according to claim 20, wherein the total number of carbon atoms in R2 and R3 combined is from 8 to 24 carbons.
25. 25. A fluid for working metals in oil-in-water emulsion according to claim 20, wherein the total number of carbon atoms in R2 and R3 combined is 8 to 12 carbons.
26. 26. A fluid for working metals in oil-in-water emulsion according to claim 19, wherein the hydrophobic monomer is A (II).
27. 27. A fluid for working metals in oil-in-water emulsion according to claim 26, wherein R9 contains from 2 to 18 carbon atoms.
28. 28. A fluid for working metals in oil-in-water emulsion according to claim 26, wherein R9 contains from 4 to 18 carbon atoms.
29. 29. A fluid for working metals in oil-in-water emulsion according to claim 26, wherein R9 contains from 4 to 12 carbon atoms.
30. 30. A fluid for working metals in oil-in-water emulsion according to claim 26, wherein R9 contains from 4 to 8 carbon atoms.
31. 31. A fluid for working metals in oil-in-water emulsion according to claim 19, wherein the hydrophilic monomer is B (I).
32. 32. A fluid for working metals in oil-in-water emulsion according to claim 31, wherein R contains from 4 to 8 carbon atoms.
33. 33. A fluid for working metals in oil-in-water emulsion according to claim 31, wherein the hydrophilic monomer is sodium salt of 2-acrylamido-2-methylpropanesulfonic acid.
34. 34. A fluid for working metals in oil-in-water emulsion according to claim 19, wherein the hydrophilic monomer is the sodium salt of 2-acrylamido-2-methylpropanesulfonic acid and the hydrophobic monomer is t-butylacrylamide.