EP4504880B1 - Halbsynthetische metallbearbeitungsflüssigkeitszusammensetzung auf wasserbasis mit einem cyclischen polyfunktionellen amin - Google Patents

Halbsynthetische metallbearbeitungsflüssigkeitszusammensetzung auf wasserbasis mit einem cyclischen polyfunktionellen amin

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Publication number
EP4504880B1
EP4504880B1 EP22719780.3A EP22719780A EP4504880B1 EP 4504880 B1 EP4504880 B1 EP 4504880B1 EP 22719780 A EP22719780 A EP 22719780A EP 4504880 B1 EP4504880 B1 EP 4504880B1
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EP
European Patent Office
Prior art keywords
semi
working fluid
metal working
synthetic metal
synthetic
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EP22719780.3A
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English (en)
French (fr)
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EP4504880A1 (de
Inventor
Qi JIANG
Xue CHEN
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Classifications

    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/54—Amines
    • 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
    • C10M173/00—Lubricating compositions containing more than 10% water
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/16—Antiseptic; (micro) biocidal or bactericidal
    • 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
    • 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
    • C10N2050/011—Oil-in-water

Definitions

  • the current invention relates to a method of controlling microbial growth in metal working fluids, comprising adding a particular class of cyclic polyfunctional amines to the metal working fluid.
  • Other embodiments relate to semi-synthetic metal working fluid compositions which include the microbial growth control agent comprising this particular class of cyclic polyfunctional amines.
  • Metal working fluids are used for lubrication of metal cutting and tool forming. These fluids provide cooling for the metal work tooling, removal of cutting chips from the tool/work piece interface and help provide an acceptable post-machining finished surface.
  • Amines are a popular MWF component widely used in a variety of applications due to their properties of anti-corrosion, neutralization, and pH adjustment.
  • Organic amines are usually used as corrosion inhibitors because MWFs are degraded over time due to microbial growth which is negatively impact fluid performance and the microbes feed on the active ingredients in the fluid.
  • Such microbial growth in the MWFs may cause serious problems in metalworking processing in many forms including: MWFs general souring, MWFs viscosity changing, MWFs shelf life shortening, and the corroding of tools and materials. Additionally, the functioning of equipment and processes such as feeding nozzles, storage tanks, pipelines and recycling system facilities may also be impacted by microbe growth in MWFs. This souring increases the cost of MWFs, accelerates corrosion rates and decreases efficiency of metal processing. Thus, there is an unfulfilled need in the MWF industry for components which do not support microbial growth and maintain performance over a long time.
  • biocides and amine alcohols either continuously or as a batch treatment to a given MWF.
  • biocides and some secondary amine alcohols are limited by regulatory restrictions and most of the biocide chemicals will release formaldehyde over time which is hazardous to human health.
  • MWFs are typically classified as neat oil, soluble oil, semi-synthetic fluid, or synthetic fluid, with each category exhibiting different functions of cooling. lubricating, anti-rust and cleaning.
  • Soluble oil MWFs comprise 50-70 wt.% neat oil with the remainder of the MWF being anti-wear/extreme pressure additives and emulsifiers.
  • Neat oils and soluble oils typically do not provide the same level of cooling compared with water-based metalworking fluids.
  • Synthetic fluids typically cannot provide the good lubricity performance because their lubricity function is affected by polyalkylene glycol reverse dissolution when the temperature is higher than cloud point.
  • Semi-synthetic materials offer the possibility of simultaneously providing good lubricity and cooling for use in demanding applications.
  • a typical semi-synthetic fluid consists of oils, organic acid, emulsifiers, lubricants, amines, water and other ingredients.
  • the amount of water in such semi-synthetic MWFs is typically up to 50-60 wt.%, with around 10-40 wt.% base oil, around 10-20wt.% emulsifiers, around 10-20 wt.% amine, and other functional additives such as acid, lubricant, solubilizer, biocide etc.
  • Semi-synthetic MWFs are usually diluted with additional water at an end user's site to a base oil concentration of 1-20 wt.%, more typically 5-7 wt.% concentration by weight of the diluted formulation.
  • emulsifiers are often added to form stable dispersion of oil in water. Emulsifier particles are located around the oil droplets to give them a negative charge that will bind them to the water molecules. The size of such emulsified oil drops is very important to fluid performance, as it is generally easier for the smaller emulsion sizes to penetrate the interface of the cutting zone. The emulsifiers also contribute to the stability of semi-synthetic fluids.
  • MWFs Semi-synthetic fluids will degrade over time in part due to microbial growth which negatively impacts fluid performance because microbes feed on the active ingredients in the fluid.
  • Such microbial growth in the MWFs may cause serious problems in metal working processing in many forms including: MWFs general souring, MWFs viscosity changing. MWFs shelf life shortening, and the corroding of tools and materials.
  • MWFs general souring
  • MWFs shelf life shortening and the corroding of tools and materials.
  • the functioning of equipment and processes such as feeding nozzles, storage tanks, pipelines and recycling system facilities may also be impacted by microbe growth in MWFs. This souring increases the cost of MWFs, accelerates corrosion rates and decreases efficiency of metal processing.
  • biocidal compositions comprising primary amino alcohols and their use as metal working fluids in aqueous media.
  • This invention addresses at least some of the above-described needs.
  • the present invention relates to a method of controlling microbial growth in metal working fluids, wherein the method includes the addition of at least one of a particular class of cyclic polyfunctional amines to the metal working fluid.
  • the present invention also describes a water based semi-synthetic metal working fluid comprising a base oil, an organic acid, emulsifiers, a concentrate additive, water and a microbial growth control agent which comprises the novel cyclic polyfunctional amine.
  • metal working fluids are classified as neat oil.
  • soluble oil semi-synthetic fluid, or synthetic fluid.
  • Soluble oil MWFs comprise 50-70 wt.% oil with the rest being anti-wear/extreme pressure additives and emulsifiers.
  • Semi-synthetic MWFs contain a significant amount of water, typically up to 50-60 wt.%. Semi-synthetic fluids have balanced lubricity and cooling performance and are thus attractive for use as MWFs.
  • the present invention relates to semi-synthetic metal working fluids, and new materials which can be used as antimicrobials for use in such fluids.
  • the materials of the present invention are cyclic polyfunctional amines corresponding to the following formula (I): wherein each R, T, U. V, W. X, Y, and Z group, in Formula (I) above, is independently selected from hydrogen, or a hydrocarbyl group: and the value of x is 0 to 10.
  • Hydrocarbyl groups that may be used in the practice of the invention may be substituted (typically with N. O, or S atoms) or unsubstituted.
  • R, T, U, V, W, X, Y, and Z are H or straight, branched, or cyclic hydrocarbyl such as alkyl of 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms such as methyl or ethyl groups.
  • T, U, V, W, X, Y, and Z are H.
  • the values of x in the practice of the invention are typically in the range of from 1 to 10, preferably in the range of from 2 to 5. and more preferably in the range of from 2 to 3 and most preferably in the range of 0-1.
  • Such cyclic polyamines can be commercially obtained, or produced by transamination of cyclic amines as is generally known in the art.
  • Examples of the high molecular weight, cyclic polyamines consistent with above Formula (I) that are useful in the present invention include bis(2-(piperazin-1-yl)ethyl)amine (BPEA).
  • One preferred embodiment of the cyclic polyamine compound useful in preparing the composition of the present invention includes for example bis(2-(piperazin-1-yl)ethyl)amine (BPEA); high molecular weight BPEA oligomers; and mixtures thereof.
  • BPEA bis(2-(piperazin-1-yl)ethyl)amine
  • the MWFs of the present invention comprise water, one or more base oils, one or more organic acids, one or more emulsifiers, one or more lubricants, one or more amines, where amines function as pH adjusters and/or microbial growth control agents, where the at least one amine comprises at least a cyclic polyamine of formula (I).
  • the microbial growth control agent may further comprise one or more additional antimicrobial materials such as glycol ether amines which may be used in combination with the above disclosed materials to achieve a certain microbial growth control targets.
  • the concentration of the microbial growth control agent/pH adjuster in the MWF may range from 1, 4, 6, 8. or 10 percent by weight of the formulation up to 30, 25, 15, or 12 percent of the formulation.
  • the cyclic polyamines (s) of formula (I) comprise from 2, preferably 3, or even 5 percent up to 25, preferably 20 or even 15 percent by weight of the MWF.
  • the semi-synthetic MWFs of the present invention also include a base oil.
  • the base oil can be any base oil generally known in the art for use in MWFs.
  • the base oil is a base oil selected from tall oils, naphthenic oils, paraffinic oils or ester oils, or combinations thereof.
  • the concentration of the base oil(s) in the MWF may range from 5, 7, 10, or 15 percent by weight of the formulation up to 50, 45. 40, or 35 percent of the formulation.
  • the water used in the present formulations is preferably deionized water, and may comprise from at least 20, preferably 25. 30, or even 35 percent by weight of the formulation up to a maximum of 70, 65, 60, 55 or even 50 percent by weight of the formulation. It is contemplated that these formulations may be further diluted with additional water prior to use, altering these ranges accordingly. For example, prior to use, the formulations may be diluted such that the base oil concentration is from 1 to 20 percent by weight of the diluted formulation, more typically 5 to 7 percent by weight.
  • the semi-synthetic MWFs of the present invention also include one or more organic acids as solubilizers and/or corrosion inhibitors.
  • Preferred organic acids include 2-ethylhexoic acid, azelaic acid, toll oil fatty acid, 12-hydoxyl-(cis)-9-octadecenoic acid, dicarboxylic acid, and 9-octadecenoic acid.
  • concentration of the organic acid in the MWF may range from 2, 3, 4, or 5 percent by weight of the formulation up to 12, 10. 8. or 7 percent of the formulation.
  • the semi-synthetic MWFs of the present invention also include one or more emulsifiers.
  • the emulsifier may be anionic, cationic or nonionic.
  • suitable anionic surfactants or emulsifiers are alkali metal, ammonium and amine soaps: the fatty acid part of such soaps contains preferably at least 10 carbon atoms.
  • the soaps can also be formed "in situ;” in other words, a fatty acid can be added to the oil phase and an alkaline material to the aqueous phase.
  • Suitable anionic surfactants or emulsifiers are alkali metal salts of alkyl-aryl sulfonic acids, sodium dialkyl sulfosuccinate, sulfated or sulfonated oils, e.g., sulfated castor oil; sulfonated tallow, and alkali salts of short chain petroleum sulfonic acids.
  • Suitable cationic surfactants or emulsifiers are salts of long chain primary, secondary or tertiary amines, such as oleylamide acetate, acetylamine acetate, di-dodecylamine lactate, the acetate of aminoethyl-aminoethyl stearamide, dilauroyl triethylene tetramine diacetate, 1-aminoethyl-2-heptadecenyl imidazoline acetate: and quaternary salts, such as cetylpyridinium bromide, hexadecyl ethyl morpholinium chloride, and diethyl di-dodecyl ammonium chloride.
  • quaternary salts such as cetylpyridinium bromide, hexadecyl ethyl morpholinium chloride, and diethyl di-dodecyl ammonium chloride.
  • Suitable nonionic surfactants or emulsifiers are condensation products of higher fatty alcohols with ethylene oxide, such as the reaction product of oleyl alcohol with 10 ethylene oxide units; condensation products of alkylphenols with ethylene oxide, such as the reaction product of isoctylphenol with 12 ethylene oxide units; condensation products of higher fatty acid amides with 5.
  • polyethylene glycol esters of long chain fatty acids such as tetraethylene glycol monopalmitate, hexaethyleneglycol monolaurate, nonaethyleneglycol monostearate, nonaethyleneglycol dioleate, tridecaethyleneglycol monoarachidate, tricosaethyleneglycol monobehenate, tricosaethyleneglycol dibehenate, polyhydric alcohol partial higher fatty acid esters such as sorbitan tristearate, ethylene oxide condensation products of polyhydric alcohol partial higher fatty acid esters, and their inner anhydrides (mannitol-anhydride, called Mannitan, and sorbitol-anhydride, called Sorbitan), such as glycerol monopalmitate reacted with 10 molecules of ethylene oxide, pentaerythritol monooleate reacted with 12 molecules of ethylene oxide, sorbitan monostearate reacted with 10-15 molecules of ethylene oxide, mannitan
  • Particularly suitable emulsifiers include C16-18 alcohols which have been ethoxylated or propoxylated; ethoxylated C12-C15 alcohols; sodium alkane sulfonate and alky ether carboxylates.
  • the concentration of the emulsifier(s) in the MWF may range from 4, 5, 6, 8, or 10 percent by weight of the formulation up to 25, 20, 15, or 12 percent of the formulation.
  • the semi-synthetic MWFs of the present invention may also include one or more concentrate additives.
  • preferred concentrate additives include diethylene glycol butyl ether, ethylene glycol monobutyl ether, and propylene glycol butyl ether.
  • concentration of the concentrate additive(s) in the MWF may range from 0.3, 0.5. 1.0, or 1.5 percent by weight of the formulation up to 2.5, 2.0, or 1.8 percent of the formulation.
  • the semi-synthetic MWFs of the present invention may also include other additives to provide additional functionality as generally known in the art.
  • the microbial growth controlled by the presently disclosed biocide typically consists of contaminations which are a bacterial and fungal mixture.
  • Some typical fungi and bacterial 5 containments include but are not limited to Aeromonas hydrophila (ATCC 13444), Candida albicans (ATCC 752), Desulfovibrio desulfuricans (ATCC 7757), Escherichia coli (ATCC 8739), Flavobacterium ferrugineum (ATCC 13524), Fusarium oxysporum (ATCC 7601), Klebsiella pneumoniae (ATCC 13883), Proteus mirabilis (ATCC 4675), Pseudomonas aeruginosa (ATCC 8689).
  • Aeromonas hydrophila ATCC 13444
  • Candida albicans ATCC 752
  • Desulfovibrio desulfuricans ATCC 7757
  • Escherichia coli ATCC 8739
  • Table 1 contains a description of the materials used in these examples.
  • Table 1 - Diluted Metalworking Fluid Ingredients Material Type Source Mineral oil Oily agent SCRC EcoSurf SA-7 Emulsifer Dow Dowfax 20A42 Emulsifer Dow Secondary alkane sulphonate Anionic surfactant SCRC Tall oil acid Corrosion agent SCRC Sebacic acid Corrosion agent SCRC Bis(piperazine ethyl) amine pH adjustor Dow Monoisopropanolamine pH adjustor Dow AMP-95 (2-amino-2-methyl-1-propanol) pH adjustor Angus Chem Processing Water Water containing common bacterial agents found in metal working processes N/A Tap Water Water containing 50 ppm metal N/A Aluminum strip (#ADC12) Metal TCI A series of formulations is prepared according to Table 2.
  • the concentrated formulations are prepared as follows. The indicated amount of deionized water is poured into a container. Add mineral oil. EcoSurf SA-7, Dowfax 20A42, secondary alkane sulfonate, tall oil acid and diacid (sebacic acid) into the water. Stir the formulation by magnetic stirrer at 200 rpm at 60°C for 1 hour. Add the indicated amine as pH adjustor.
  • the concentrated formulations are then diluted by processing water or tap water or deionized water (as indicated in Table 3) by a factor of 20 times. based on the quantity of the whole concentrated formulation. Test pH value by pH titrator (Mettler Toledo: #SevenMulti). If pH value of the diluted formulation is below 9.5, introduce additional monoethanolamine (1-2 droplets) to increase pH value to at least 9.5.
  • pH aging test test pH value by pH titrator (Mettler Toledo: #SevenMulti) of prepared diluted formulations for 0-day and 14-day. Samples are placed in ambient temperature. Table 4: pH aging test: Sample # Initial pH value 1-week aging pH value 2-week aging pH value pH loss (%) IE1 9.54 9.43 9.43 - 1.2% CE1 9.55 8.72 8.52 - 10.8% CE2 9.54 9.29 9.29 - 2.6% CE3 9.63 9.33 9.30 - 3.4%
  • the pH decrement after 2-week aging should be as small as possible.
  • CE2 & 3 with AMP-95 and dicyclohexylamine are in similar level which pH loss is controlled within 5%.
  • CE1 with monoisopropanolamine is not good that pH loss exceeds 10%.
  • Aluminum corrosion test Clean the Al strips (# ADC12) with alcohol and weigh strips. Immerse the Al strips into the test solution at 40°C for 48 hours with capped vials (a half volume of Al strip in solution and a half volume of Al strip exposed to air). Observe the corrosion of Al strip surface, measure weight loss of Al strips and use ICP-OES: inductively coupled plasma-optical emission spectrometer (Perkin Elmer: # Optima 5300DV) to detect Al content in formulations.
  • Table 5 Aluminum corrosion test: Sample # Corrosion Aluminum content by ICP-OES IE2 ⁇ 1 ppm CE4 ⁇ 1 ppm CE5 ⁇ 1 ppm CE6 2.60 ppm
  • the ICP-OES data shows alignment with qualitative observation of aluminum strip corrosion. Larger area with yellow color demonstrates serious corrosion and higher aluminum content in test fluid. The qualitative description “pass”, “marginal” or “fail” are added to comparatively describe the results observed.
  • the ICP-OES data shows CE6 with dicyclohexylamine corroding over 1 ppm aluminum leaching from the strip. The outlook of sample CE6 is the worst with largest rust area. For other samples including IE1, CE4 & 5, there is ⁇ 1 ppm aluminum leaching from the strip.
  • pH value with antimicrobial test Samples are operated under ASTM E 2275 method. This method can be summarized as follows: The inoculum is a mixture of ATCC strains of bacteria and fungi as set forth in Table 6. The Emulsion Products Mixed Inoculum is prepared by adding 0.1 mL of each bacterial overnight broth culture and 1.0 mL of each yeast broth culture to the 10 mL of mold suspension and blending.
  • IE3 with Bis(piperazine ethyl) amine shows only a 0.12 pH value decrement in antimicrobial evaluation.
  • CE7 with monoisopropanolamine shows 0.30 pH value decrement in antimicrobial evaluation.
  • Microbial stability of IE3 is therefore expected to be better than monoisopropanolamine when used in metal working fluid formulations.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (13)

  1. Halbsynthetische Metallbearbeitungsflüssigkeit, umfassend:
    a. mindestens ein Basisöl;
    b. mindestens ein Mittel zur Kontrolle mikrobiellen Wachstums, das ein Alkylamin mit der Struktur umfasst: wobei jedes R, T, U, V, W, X, Y und Z in der obigen Formel (I) unabhängig aus Wasserstoff oder einer Hydrocarbylgruppe ausgewählt ist; und der Wert von x unabhängig 0 bis 10 ist;
    c. eine oder mehrere organische Säuren als Lösungsvermittler und/oder Korrosionsinhibitoren,
    d. einen oder mehrere Emulgatoren,
    e. ein oder mehrere Konzentratzusätze und
    f. Wasser.
  2. Halbsynthetische Metallbearbeitungsflüssigkeit nach Anspruch 1, wobei jedes R, T, U, V, W, X, Y und Z in dem Mittel zur Kontrolle mikrobiellen Wachstums jeweils H ist.
  3. Halbsynthetische Metallbearbeitungsflüssigkeit nach Anspruch 1, wobei das Mittel zur Kontrolle mikrobiellen Wachstums Bis(2-(piperazin-1-yl)ethyl)amin (BPEA) ist.
  4. Halbsynthetische Metallbearbeitungsflüssigkeit nach Anspruch 1, wobei das Mittel zur Kontrolle mikrobiellen Wachstums ferner ein weiteres Amin umfasst.
  5. Halbsynthetische Metallbearbeitungsflüssigkeit nach Anspruch 1, wobei das Basisöl aus naphtenhaltigen Ölen, paraffinischen Ölen, Esterölen und Mischungen davon ausgewählt ist.
  6. Halbsynthetische Metallbearbeitungsflüssigkeit nach Anspruch 1, wobei der Emulgator aus ethoxylierten oder propoxylierten C16-18-Alkoholen, ethoxylierten C12-C15-Alkoholen, Natriumalkansulfonat und Alkylethercarboxylaten sowie Mischungen davon ausgewählt ist.
  7. Halbsynthetische Metallbearbeitungsflüssigkeit nach Anspruch 1, wobei der Lösungsvermittler/Korrosionsinhibitor aus Ethylhexylsäure, Azelainsäure, Tallölfettsäure, 12-Hydroxy-(cis)-9-octadecensäure, Dicarbonsäure, 9-Octadecensäure, Sebacinsäure und Mischungen davon ausgewählt ist.
  8. Halbsynthetische Metallbearbeitungsflüssigkeit nach Anspruch 1, wobei der Konzentratzusatz aus Diethylenglykolbutylether, Ethylenglykolmonobutylether, Propylenglykolbutylether und Mischungen davon ausgewählt ist.
  9. Halbsynthetische Metallbearbeitungsflüssigkeit nach Anspruch 1, wobei das Mittel zur Kontrolle mikrobiellen Wachstums in einer Menge von 6 bis 15 Gewichtsprozent der halbsynthetischen Metallbearbeitungsflüssigkeit vorhanden ist.
  10. Halbsynthetische Metallbearbeitungsflüssigkeit nach Anspruch 1, wobei das Basisöl in einer Menge von 10 bis 45 Gewichtsprozent der halbsynthetischen Metallbearbeitungsflüssigkeit vorhanden ist.
  11. Halbsynthetische Metallbearbeitungsflüssigkeit nach Anspruch 1, wobei der Emulgator in einer Menge von 5 bis 20 Gewichtsprozent der halbsynthetischen Metallbearbeitungsflüssigkeit vorhanden ist.
  12. Halbsynthetische Metallbearbeitungsflüssigkeit nach Anspruch 1, wobei der Lösungsvermittler/Korrosionsinhibitor in einer Menge von 3 bis 10 Gewichtsprozent der halbsynthetischen Metallbearbeitungsflüssigkeit vorhanden ist.
  13. Halbsynthetische Metallbearbeitungsflüssigkeit nach Anspruch 1, wobei das Wasser in einer Menge von 20 bis 60 Gewichtsprozent der halbsynthetischen Metallbearbeitungsflüssigkeit vorhanden ist.
EP22719780.3A 2022-04-01 2022-04-01 Halbsynthetische metallbearbeitungsflüssigkeitszusammensetzung auf wasserbasis mit einem cyclischen polyfunktionellen amin Active EP4504880B1 (de)

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JP4836341B2 (ja) * 2001-03-23 2011-12-14 協同油脂株式会社 水溶性金属加工油剤組成物
JP5841445B2 (ja) * 2012-02-06 2016-01-13 ユシロ化学工業株式会社 水溶性金属加工油剤組成物、クーラント、アミン化合物の気相防カビ剤としての使用、気相防カビ方法、及び金属加工方法
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JP6051026B2 (ja) * 2012-11-20 2016-12-21 出光興産株式会社 水溶性金属加工油剤、金属加工液、及び金属加工方法
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JP7030713B2 (ja) * 2015-12-21 2022-03-07 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 金属加工液
US10988703B2 (en) * 2019-07-16 2021-04-27 Italmatch Chemicals SC LLC Metal working fluid

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