EP0854905A1 - Fluides hydro-solubles ameliores de transformation des metaux - Google Patents

Fluides hydro-solubles ameliores de transformation des metaux

Info

Publication number
EP0854905A1
EP0854905A1 EP96928010A EP96928010A EP0854905A1 EP 0854905 A1 EP0854905 A1 EP 0854905A1 EP 96928010 A EP96928010 A EP 96928010A EP 96928010 A EP96928010 A EP 96928010A EP 0854905 A1 EP0854905 A1 EP 0854905A1
Authority
EP
European Patent Office
Prior art keywords
composition
corrosion inhibitor
weight
metal
benzotriazole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96928010A
Other languages
German (de)
English (en)
Other versions
EP0854905A4 (fr
Inventor
Dennis J. Kalota
David A. Martin
David C. Silverman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solutia Inc
Original Assignee
Monsanto Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Monsanto Co filed Critical Monsanto Co
Publication of EP0854905A1 publication Critical patent/EP0854905A1/fr
Publication of EP0854905A4 publication Critical patent/EP0854905A4/fr
Withdrawn legal-status Critical Current

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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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    • C10M2223/042—Metal salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2010/00—Metal present as such or in compounds
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • C—CHEMISTRY; METALLURGY
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • C—CHEMISTRY; METALLURGY
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/241—Manufacturing joint-less pipes
    • C—CHEMISTRY; METALLURGY
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C10N2040/242—Hot working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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    • C10N2040/20—Metal working
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    • C10N2040/245—Soft metals, e.g. aluminum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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    • C10N2040/246—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
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    • C10N2040/247—Stainless steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • This invention relates to novel water soluble metal working fluids which are biodegradable and do not require reclaiming. More particularly, this invention relates to an improved formulation containing polyamino acid, salts and amides useful in cutting, grinding, shaping and other metal working operations which require a metal working fluid.
  • the disclosed polyamino acid compounds have improved anticorrosive properties and are environmentally more acceptable than current oil containing fluids. BACKGROUND OF THE INVENTION Because of the concern for environmental factors, previously known oil-containing metal working fluids require reclaiming or disposal by means other than by discharging them to common sewage treatment systems.
  • Metal working fluids fulfill numerous functions in various metal working applications. Typically, such functions include removal of heat from the work piece and tool (cooling), reduction of friction among chips, tool and work piece (lubrication), removal of metal debris produced by the work, reduction or inhibition of corrosion and prevention or reduction of build-up on edges as between the work piece and the tool. This combination of functions usually requires a formulation or combination of ingredients in the fluid to accomplish the best attributes required for a particular metal working operation.
  • compositions When diluted in water, such compositions provide a highly desirable water-based metal-working fluid useful in such operations as cutting, threading, bending, grinding, broaching, tapping, planing, gear shaping, reaming, deep hole drilling/gundrilling, drilling, boring, hobbing, milling, turning, sawing and shaping of various ferrous and non-ferrous metals.
  • water-based metal-working fluid useful in such operations as cutting, threading, bending, grinding, broaching, tapping, planing, gear shaping, reaming, deep hole drilling/gundrilling, drilling, boring, hobbing, milling, turning, sawing and shaping of various ferrous and non-ferrous metals.
  • Figure 1 is a graphical representation of data obtained in an experiment showing the effect on pH of carbon dioxide on an aqueous solution of sodium polyaspartate containing a small amount of sodium phosphate and benzotriazole.
  • the metal-working fluids of this invention comprise an effective amount of polyaspartic acid or a salt or an amide thereof or any compound which provides an effective amount of the same in solution, preferably in concentrations in the range of from about 0.5% to about 70%, by weight in water.
  • This very broad range covers both the composition as used in metal working applications (working fluid) and as typically packaged commercially as a concentrate adapted for dilution prior to actual use as a working fluid. It has been found convenient to provide a working fluid by dilution of the commercial composition in a ratio of about 10: 1 although other ratios may be employed. Other concentrations and dilution ratios will be apparent to those skilled in the art.
  • compositions of this invention comprise from about 3% to about 25% polyaspartic acid, and preferably from about 5% to about 20% salt or amide in water as the concentrate.
  • the working fluid would contain from about 0.15% to about 20% of the polymer upon dilution to form a working fluid although greater or lesser amounts may be employed.
  • Any number of basic compounds can be used as additives to produce polyaspartic compositions having improved stability in accordance with this invention. It is preferred that the basic additive be at least somewhat soluble in water. Because of the small amount in solution actually required to impart stability, the basic compounds need only be soluble to a relatively small extent to be effective.
  • the basic additive should have sufficiently high basicity and buffering power to effectively maintain the pH of the polymer solution (measured as at 10% or below aqueous solution at normal room temperature) above about 8.5 to about 11 and more preferably from about 9 to about 10.5. However, at effective levels, it should preferably not result in a pH of the polymer solution greater than about 11 because it might render the fluid more hazardous for use, particularly with respect to machine operators.
  • suitable basic additives include alkali metal carbonates, alkali metal orthophosphate, alkali metal polyphosphates, alkali metal silicates, alkali metal borates and the like, including mixtures thereof.
  • Alkali metal carbonates are preferred in view of their low cost, appropriate basicity, solubility characteristics and availability.
  • alkali metal as employed herein means lithium, sodium, potassium, rubidium and cesium and mixtures thereof.
  • the alkali metal employed in this invention is potassium. It has been found that potassium salts, as employed in this invention, result in metal working fluids having greater solubility in water and, more importantly, depress the freezing point of the composition below that of other commonly available and inexpensive alkali metals such as sodium.
  • the potassium ion in all of the steps employed to prepare compositions of this invention That is, hydrolysis of the polysuccinimide intermediate, such hydrolysis being known in the art, is preferably performed with potassium hydroxide rather than the usual sodium hydroxide.
  • the alkali metal basic additive is preferably potassium salt, particularly, potassium carbonate.
  • the basic additive may be a potassium salt such as potassium carbonate.
  • the amount of basic additive employed to form a stabilized polyaspartic metal working fluid can vary widely with good results and the minimum effective level can be determined for any selected additive by routine experimentation in view of the present description, keeping in mind the above noted preferred pH ranges.
  • the preferred range is, by weight, from about 0.02% and up in a working fluid and up to about 7% by weight of the sodium carbonate in a concentrate while a range of from 0.02% to about 4% and preferably from about 1% to about 3% by weight of the sodium carbonate is especially preferred in a concentrate.
  • the basic additive of this invention is mixed with the polyaspartic solution by any typical and suitable mixing or blending means.
  • polysuccinimide is usually first produced which is a solid material. This material is hydrolyzed by any typical known means, usually with an aqueous solution of a base, which renders the material in a liquid form.
  • the basic additive is typically added to the liquid during the formulation step. Since only small amounts are employed the blending of the basic additive may be performed during the final stages of preparation and packaging of the fluid. No special means of procedures are required so long as adequate mixing to obtain a uniformly constituted formulation is achieved. With respect to the basic additive, sodium carbonate, any amount up to the solubility limit, may be employed.
  • solubility of the potassium salt is higher in such aqueous solutions, slightly higher amounts than sodium salts can be employed as for example 9% by weight in a concentrated solution of the polyamide.
  • the polyaspartic metal working fluid of this invention is typically prepared as a concentrate containing in the range from about 2% to about 70% by weight or up to the solubility limit of polyaspartic acid, salt or amide.
  • the amount of sodium carbonate present may be in the range of from about 0.2% to about 7% by weight of the total mixture.
  • a concentrate of this invention is typically diluted to about 0.7% with respect to the polyaspartate polymer and from about 0.02% to about the solubility limit of sodium carbonate perhaps about 7% whichever is higher, or from about 0.03% to about 10% and preferably from about 0.08% to about 0.8% of potassium carbonate.
  • additives may be employed in compositions of this invention to enhance or contribute properties which enable broader functions with respect to the use of the compositions in metal working applications.
  • the types of additives include boundary lubricants, corrosion inhibitors, oxidation inhibitors, detergents and dispersant, viscosity index improves, emulsion modifiers, antiwear and antifriction agents and foam depressors.
  • additives may be employed to enhance boundary lubrication such as wear inhibitors, lubricity agents, extreme pressure agents, friction modifiers and the like.
  • Typical examples of such additives are metal dialkyl dithiophosphates, metal diaryl dithiophosphates, alkyl phosphates, alkali metal phosphates, tricresyl phosphate, 2-alkyl-4-mercapto-l,3,4-thiadiazole, metal dialkyldithiocarbonates, metal dialkyl phosphorodithioates wherein the metal is typically zinc, molybdenum, tungsten or other metals, phosphorized fats and olefins, sulfurized or chlorinated fats and olefins and paraffins, fatty acids, carboxylic acids and their salts, esters of fatty acids, organic molybdenum compounds, molybdenum disulfide, graphite and borate dispersions.
  • Such boundary lubrication additives are well known in the
  • polyaspartic acid compounds of this invention function as corrosion inhibitors in a certain range of pH
  • corrosion inhibitors may be employed in compositions of this invention which will function in a pH range in which the polyaspartic acid, salt or amide may not function as a corrosion inhibitor.
  • Typical but not limiting examples of corrosion inhibitors known in the art and useful herein include zinc chromate, dithiophosphates such as zinc dithiophosphate, metal sulfonates wherein the metal is an alkali metal, alkanolamines such as ethanolamine and substituted alkanolamines wherein the backbone of the alkyl group is substituted to provide various properties, alkyl amines such as hexylamine and triethanol amine, borate compounds such as sodium borate and mixtures of borates with amines, carboxylic acids including polyaspartic acid at high pH (10 and above)and alkyl amino carboxylic acids particularly useful in hard water, sodium molybdate, boric acid ester such as monobenzyl borate and boric acid with various ethanol amines (also acting as a biostat), benzoic acid, nitro derivatives of benzoic acid, ammonium benzoate, hydroxybenzoic acid, sodium benzoate, triethanolamine salts of carboxylic acids with
  • compositions of this invention comprise, in a preferred embodiment a corrosion inhibitor and a complementary corrosion inhibitor comprising an alkali metal orthophosphate.
  • the complementary alkali metal orthophosphate is employed in amounts depending on the metal working operation in the range of from about 0.1% to about 10% by weight in the working fluid. Other concentrations will be apparent to those of ordinary skill in the art as the amount of polyamino polymer is adjusted in concentrate as well as working fluid embodiments.
  • corrosion inhibitor as employed herein include those chemicals which when employed with other components of compositions of this invention exhibit corrosion inhibition.
  • Table I The compositions in Table I are shown in parts by weight.
  • Atypical concentrate composition of this invention is an aqueous solution containing from about 3% to about 30%, by weight, of the salt or amide of polyaspartic acid together with about 1% to about 10% by weight corrosion inhibitor and from about 200 ppm to about 5% by weight of the solution of a basic additive.
  • composition of this invention may also contain minor amounts of catalyst employed in the thermal condensation reaction of L- aspartic acid whereby the polymer was made.
  • catalyst is an acid such as phosphoric acid which is converted to the corresponding salt and salts of the pyrophosphate by-product during hydrolysis of the succinimide polymer.
  • Typical oxidation inhibitors may also be incorporated into the compositions of this invention and include for example zinc and other metal dithiophosphates, hindered phenols, metal phenol sulfides, metal-free phenol sulfides, aromatic amines as well as mixtures thereof. Because many operations in which compositions of this invention are employed create particulates that must be carried away from metal surface, there are employed in compositions of this invention detergents and dispersant.
  • Typical dispersant(s) include polyamine succinimides, alkaline oxides, hydroxy benzyl polyamines, polyhydroxy succinic esters and polyamine amide imidazolines and mixtures thereof.
  • Typical detergents include metal sulfonates, overbased metal sulfonates, metal phenate sulfides, overbased metal phenate sulfides, metal salicylates and metal thiophosphonates and mixtures thereof.
  • compositions of this invention may also include surfactants, extreme pressure agents, buffers, thickeners, antimicrobial agents and other adjuvants commonly employed in such compositions and mixtures thereof.
  • Concentrate compositions of this invention most conveniently employed commercially and adapted for dilution prior to use will preferably contain potassium salts of the various components in varying ranges of concentration but typically comprising by weight from about 0.5% potassium polyaspartate, or up to its solubility limit, from about 0.1% to about 10% potassium orthophosphate dibasic as a complementary corrosion inhibitor, from about 0.02% to about its solubility limit perhaps about 9.5%, of potassium carbonate, and from about 200 ppm to about 3% by weight of a corrosion inhibitor.
  • the preferred corrosion inhibitor is tolyltriazole which comprises by weight about 40 to about 0% 4-methyl-lH-benzotriazole and about 60% to about 100% 5-methyl-lH-benzotriazole.
  • alkylbenzotriazoles such as C,-C 4 alkylbenzotriazoles and butylbenzotriazole.
  • the polyaspartic acid of this invention is preferably provided by the thermal condensation of aspartic acid.
  • Polyaspartic acid can also be prepared by the polymerization of other monomers such as mono -or diammonium maleate, mono -or diammonium fumarate, and maleamic acid.
  • Many different processes are known for such purpose. For example, there has recently been discovered a continuous process employing a tray dryer wherein the aspartic acid is introduced into the top level of trays which cyclically travel in the horizontal plane to deliver the reacting material to the next adjacent lower level of trays. The residence time in the dryer is controlled by the number of tray levels, the tray rotation rate, circulation of heated gas, such as air, through the dryer, and temperature.
  • the temperature in such a device is usually in the range of from about 180°C to about 350°C with a residence time in the range of from about 0.5 to about 6 hours.
  • a typical tray dryer is commercially available from the Wyssmont Company, Incorporated, Fort Lee, New Jersey.
  • tray dryer which may be employed in such process is a tray dryer commercially produced by Krauss Maffei of Florence, Kentucky.
  • a tray dryer commercially produced by Krauss Maffei of Florence, Kentucky.
  • heated trays are stationary and the reactant is moved across each plate by axially rotating plows or shovels.
  • the reactant alternatively falls from one tray level to the next at the internal or external edge of the tray.
  • the reactant is directly heated by the trays.
  • L-aspartic acid While there are several isomers of aspartic acid which may be employed to prepare polyaspartic acid, such as D-, L- or DL-aspartic acid, it is preferred herein to employ L-aspartic acid. If a catalyst is employed the reaction, residence time in the dryer may be less, in the range of from about 30 minutes to about 2 hours, depending upon other factors noted above. It has recently been discovered that carbon dioxide in the circulating gas catalyzes the thermal condensation when present in amounts of at least about 5%, by volume. Amounts of carbon dioxide in the circulated gas is usually about 10%, by volume.
  • Typical reactors include the List reactor commercially available from Aerni, A.G.
  • the Littleford mixer provides sufficient agitation to produce a fluid bed condition and may be equipped with a chopper to break up any lumps or clumps of particles that develop and to provide additional shear forces to the fluid bed.
  • the agitation provided by the mixer is sufficient to maintain the particles in a substantially free-flowing state throughout the time period of the reaction.
  • the Littleford mixer is operated at a temperature of at least about 180°C and is capable of maintaining the heated bed at a temperature in the range of about 180°C to about 250 °C or higher for a time sufficient to polymerize the aspartic acid.
  • the mixer is desirably equipped to provide a purge gas stream through the reactor.
  • the gas stream is provided with sufficient amounts of carbon dioxide so as to catalyze the condensation reaction, thus greatly reducing the amount of time to reach complete polymerization of the aspartic acid.
  • the usual thermal condensation reaction of aspartic acid produces the polysuccinimide intermediate.
  • the intermediate is easily hydrolyzed by alkaline solution to polyaspartic acid salt.
  • alkaline solutions are alkali metal hydroxides, triethanolamine (TEA) and the like, ammonium hydroxide, and the like.
  • Any water-soluble salts of polyaspartic acid including those which can be produced by the thermal condensation of L-aspartic acid may be employed in the metal-working composition of this invention.
  • Typical water soluble salts include alkali metal salts, ammonium, organic ammonium and mixtures thereof.
  • alkali metal encompasses lithium, sodium, potassium, cesium and rubidium and mixtures thereof.
  • the organic ammonium salts useful herein include those prepared from the low molecular weight organic amines, i.e. having a molecular weight below about 270.
  • Organic amines useful herein include the alkyl amines, alkylene amines, alkanol amines.
  • Typical organic amines include propylamine, isopropylamine, ethylamine, isobutylamine, n-amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undeclyamine, dodecylamine,hexadecylamine, heptadecylamine, ocatdecylamine, and basic amino acids such as lysine.
  • the polyaspartic acid or salt thereof produced by the thermal condensation of L-aspartic acid is useful in this invention. It has been discovered that this polymer provides sufficient lubrication to permit metal working operations on ferrous and non-ferrous metals. Any molecular weight of polyaspartic acid may be usefully employed herein.
  • polyaspartic acid derived from other sources are also useful in the compositions and method of this invention.
  • polyaspartic acid can be derived from the polycondensation processes employing maleic acid or derivatives thereof such as are known from U.S. Patents 3,846,380 to Fujimoto et al., U.S. 4,839,461 to Boehmke, U.S. 4,696,981 to Harada et al, all of which are incorporated herein by reference.
  • copolymers of amino acids can also be employed in the process of this invention such as copolymers prepared according to U.S. Patent 4,590,260 to Harada et al.
  • the water based metal-working fluids of this invention are particularly advantageous in that there is essentially no odor associated with water solutions of polyaspartic acid or salts or amines thereof. Further, it has been observed that the fluid dramatically reduces any mist around the tool working area as is common with water-based oil containing fluids. Because of the virtual lack of mist formation the work area is maintained virtually free of deflected fluid leaving the machinery and worker substantially free of contamination by the metal working fluid impracticing this invention.
  • the water-based metal-working fluids of this invention are most advantageous in that the active ingredient, polyaspartic acid or salts have been found to have a rapid rate of biodegradation.
  • the biodegradability of the metal working fluids of this invention allows their disposal through normal means such as by discharge into a sewage treatment system. The cost advantages of such a fluid of this invention are obvious in view of the environmental concerns resulting in alternative means of disposal.
  • the formulation employed with the polyaspartic acid or derivative of this invention results in an aqueous solution having a pH of about 10 or below it is recommended that additional anti-corrosion inhibitors be incorporated into the formulation of the metal-working fluid of this invention.
  • additional corrosion inhibitor(s) can vary widely depending upon the particular inhibitor and the environment in which the fluid is employed. For example, if zinc chromate is the corrosion inhibitor effective amounts range upwards from as little as 50 ppm in the working fluid.
  • the metal-working fluids of this invention are useful in the various metal-working applications such as were noted above with any number of types of metals.
  • they are useful in working ferrous metals and alloys such as iron, steel (carbon steel and low alloy carbon steel), cast iron, stainless steels, nickel-based alloys, and cobalt-containing alloys and the like.
  • Non-ferrous metals and alloys which can be worked with fluids of this invention are copper, brass, titanium, aluminum, bronze, and magnesium and the like. Such metals are safely worked with lubricity supplied by the water based fluids of this invention.
  • a particularly important function of a metal working fluid of this invention in cutting operations is the function of cooling so as to maintain lower temperature of the tool as well as the work temperature. Such control aids in minimizing tool wear and distortion of the workpiece.
  • Another function of the metal working fluid of this invention is lubrication which reduces friction as between the tool and chips produced during the cutting operation as well as reduction of the friction between the tool and the workpiece. In cutting operations of various types there are typically produced chips of small pieces of metal which are advantageously carried away from the workpiece as soon as possible so that they do not jam the cutting tool. DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • EXAMPLE 1 In the following example, a laboratory model of a tray dryer was employed having two trays which passed the reactant material from one to the other thereby simulating the conditions of a commercially available tray dryer referred to above. The reactant material was passed from one tray to the other so as to equal the desired number of tray levels of the commercial model.
  • the tray dryer, simulating the Wyssmont Turbo Dryer, available from the Wyssmont Company, Fort Lee, NJ was operated with the addition of 1 kg of L-aspartic acid per tray level at a depth of 2.5 cm on the trays. A total of 28 tray levels was employed. Circulated air temperature through the dryer of
  • EXAMPLE 2 An experiment was conducted to show the effect of carbon dioxide on the pH of the polyaspartic metal working fluids of this invention.
  • a 1% aqueous solution of sodium polyaspartate containing residual (1500 ppm as PO 4 ) sodium phosphate was subjected to aeration with a gaseous mixture of 2.5% carbon dioxide by volume in nitrogen as well as pure nitrogen.
  • the data is present in Figure 1 wherein Curve A is the data obtained with pure nitrogen and Curve B is the data obtained with the blend of carbon dioxide and nitrogen.
  • the rapid decline in pH as shown by Curve B indicates the influence of carbon dioxide on pH of the solution.
  • sample C A third sample, tap water, (Sample C) adjusted to a pH of 9.6 with sodium hydroxide was used as a control.
  • Ambient air typically containing 0.033% carbon dioxide, was entrained through the liquid samples at a constant rate of greater than 200cc/min at ambient room temperature and pressure.
  • the pH of each solution was measured once per day for six days. Amounts of sodium carbonate from 250 ppm to 1000 ppm were added to each sample at the beginning of the test. The results of the test is shown below in Table III. TABLE m
  • Polyaspartic acid, sodium salt was prepared by means of a Wyssmont Turbo Dryer in the presence of 7.5% phosphoric acid catalyst.
  • the acid polymer was hydrolysed with sodium hydroxide and diluted to a 1% by weight aqueous solution.
  • Two batches of the polyaspartic polymer were formulated with benzotriazole, which has a pKa of 8.3. Any effect on pH in this test is not affected by the benzotriazole since the pKa is below the pH of the test solutions. In one batch, containing 200 ppm benzotriazole, no sodium carbonate was added and in the other batch containing 950 ppm benzotriazole, sodium carbonate was added at a concentration of 1000 ppm.
  • Each batch of cutting fluid was employed as the cutting fluid in a Okuma LB 10 cutting machine.
  • the pH of each batch of cutting fluid was measured initially, after 1 day and after 5 days.
  • Each batch was used to cut 300 pieces of 1018 steel down from 2.54 cm to 0.934 cm using a Mitsubishi DMN G432MA insert.
  • the parting tool was a Manchester M50.
  • the results of periodic pH tests from the periodic pH measurement of the polyaspartic polymer cutting fluid are shown below in Table IV.
  • a preferred composition of this invention can be prepared by polymerizing L-aspartic acid as described in Example 4 and then hydroiyzing the resulting polysuccinimide by charging a suitable vessel with the following amounts in parts by weight shown in Table V below:
  • tolyltriazole is comprised of a mixture containing 40% 4-methyl-lH- benzotriazole and 60% 5-methyl-lH-benzotriazole. In the use of tolyltriazole, it is desirable to maintain the level above about 900 ppm in the working fluid for best results.
  • the potassium salt is highly advantageous in that it has a significantly reduced freezing temperature.
  • the reduced freezing temperature is the fact that no precipitate was observed, even at the freezing temperature indicating that no separation of the solution into different phases occurred. Therefore, the effect of freezing the potassium salt mixture is not as deleterious as either the sodium salt or mixed salt compositions which would require further mixing to redistribute the separated phases of the composition due to the occurrence of freezing temperatures.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne des fluides hydro-solubles améliorés de transformation des métaux comprenant de l'acide polyaspartique, ses amides et ses sels, un ou des inhibiteurs de corrosion et un additif basique ayant une basicité suffisante et un pouvor tampon suffisant pour maintenir le pH de la composition au-dessus d'environ 8,5 et, de préférence, au-dessus d'environ 9. Ces compositions sont d'utiles lubrifiants dans les opérations de coupe, de pliage, de meulage, et de formage des métaux à la fois ferreux et non ferreux et elles tendent à maintenir des valeurs de pH plus élevées grâce à l'adjonction d'un additif basique. L'acide polyaspartique et ses sels sont particulièrement avantageux en ce sens que les fluides peuvent facilement être jetés après utilisation sans traitement spécial, étant donné que l'acide polyaspartique et ses sels sont facilement biodégradables.
EP96928010A 1995-07-20 1996-07-19 Fluides hydro-solubles ameliores de transformation des metaux Withdrawn EP0854905A4 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US1810295P 1995-07-20 1995-07-20
US18102 1995-07-20
US217895P 1995-08-11 1995-08-11
US2178 1995-08-11
US501795P 1995-10-10 1995-10-10
PCT/US1996/011993 WO1997004052A1 (fr) 1995-07-20 1996-07-19 Fluides hydro-solubles ameliores de transformation des metaux
US5017 1998-01-09

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EP0854905A1 true EP0854905A1 (fr) 1998-07-29
EP0854905A4 EP0854905A4 (fr) 1999-12-15

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JP (1) JP2002503260A (fr)
KR (1) KR19990029090A (fr)
CN (1) CN1196079A (fr)
AU (1) AU6762596A (fr)
BR (1) BR9610062A (fr)
CA (1) CA2227330A1 (fr)
NO (1) NO980239L (fr)
PL (1) PL324550A1 (fr)
WO (1) WO1997004052A1 (fr)

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UY24689A1 (es) * 1996-08-30 1997-09-08 Solutia Inc Nuevos fluidos solubles en agua para maquinado de metales
US6238621B1 (en) 1998-05-27 2001-05-29 Solutia Inc. Corrosion inhibiting compositions
AT408103B (de) 1998-06-24 2001-09-25 Aware Chemicals Llc Verfahren zur vorbehandlung eines metallischen werkstückes für eine lackierung
WO2000005433A1 (fr) * 1998-07-23 2000-02-03 Solutia Inc. Procede d'inhibition de l'assombrissement, du noircissement ou du ternissement de l'aluminium et d'alliages d'aluminium et compositions pour ce faire
AU5005799A (en) * 1998-07-23 2000-02-14 Solutia Inc. Method of inhibiting darkening, blackening or tarnishing of magnesium and magnesium alloys and compositions therefor
DE10049175A1 (de) 2000-09-22 2002-04-25 Tea Gmbh Biologisch abbaubare Funktionsflüssigkeit für mechanische Antriebe
KR100443826B1 (ko) * 2002-08-22 2004-08-11 주식회사 이득 무급유 베어링에 사용되는 윤활유 조성물
KR100439663B1 (ko) * 2003-07-03 2004-07-12 주식회사 이득 유압작동유 및 습동면유 겸용 수용성 절삭유제 조성물
EP2132251B1 (fr) * 2006-12-21 2016-10-12 Croda Americas LLC Composition et procédé
CN101560430B (zh) * 2009-05-27 2011-12-07 中南大学 一种全合成切削液
JP6235997B2 (ja) * 2012-03-02 2017-11-22 出光興産株式会社 水系冷却剤
JP6227248B2 (ja) 2012-12-27 2017-11-08 出光興産株式会社 水系冷却剤
CN105238537B (zh) * 2015-10-29 2018-07-31 东莞华程金属科技有限公司 一种水基切削液及其制备方法
LU101645B1 (en) * 2020-02-17 2021-08-17 Metall Chemie Tech Gmbh Amino Acids as Green Neutralizing Agent for Acidic Corrosion Inhibitors
CN113549486A (zh) * 2021-07-26 2021-10-26 富兰克科技（深圳）股份有限公司 一种组合物的应用及其制备方法

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JPS5658977A (en) * 1979-10-15 1981-05-22 Kao Corp Rust preventive composite
DE4311237A1 (de) * 1993-04-06 1994-10-13 Basf Ag Verwendung von Polyasparaginsäure in Kettengleitmitteln für Transportbänder von Flaschenbefüllungs- und Reinigungsanlangen

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PL324550A1 (en) 1998-06-08
NO980239D0 (no) 1998-01-19
NO980239L (no) 1998-03-19
BR9610062A (pt) 1999-03-02
CA2227330A1 (fr) 1997-02-06
CN1196079A (zh) 1998-10-14
JP2002503260A (ja) 2002-01-29
AU6762596A (en) 1997-02-18
EP0854905A4 (fr) 1999-12-15
WO1997004052A1 (fr) 1997-02-06
KR19990029090A (ko) 1999-04-15

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