EP2446003A1 - Acides étherpyrrolidone carboxyliques à base de polyalkylène glycol et concentrés destinés à la préparation de réfrigérants lubrifiants synthétiques les contenant - Google Patents

Acides étherpyrrolidone carboxyliques à base de polyalkylène glycol et concentrés destinés à la préparation de réfrigérants lubrifiants synthétiques les contenant

Info

Publication number
EP2446003A1
EP2446003A1 EP10724279A EP10724279A EP2446003A1 EP 2446003 A1 EP2446003 A1 EP 2446003A1 EP 10724279 A EP10724279 A EP 10724279A EP 10724279 A EP10724279 A EP 10724279A EP 2446003 A1 EP2446003 A1 EP 2446003A1
Authority
EP
European Patent Office
Prior art keywords
group
acid
acids
water
etherpyrrolidoncarbonsäuren
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Withdrawn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
EP10724279A
Other languages
German (de)
English (en)
Inventor
Rainer Kupfer
Carsten Cohrs
Alexander Rösch
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.)
Clariant International Ltd
Original Assignee
Clariant Finance BVI Ltd
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=42611688&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2446003(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Clariant Finance BVI Ltd filed Critical Clariant Finance BVI Ltd
Publication of EP2446003A1 publication Critical patent/EP2446003A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/273—2-Pyrrolidones with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
    • C07D207/277—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • 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
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • 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
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/44—Five-membered ring containing nitrogen and carbon only
    • 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
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • 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
    • C10M2215/222—Triazines
    • 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
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/011—Cloud point
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • 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

Definitions

  • the present invention relates to polyalkylene glycol-based etherpyrrolidonecarboxylic acids and concentrates for the production of synthetic cooling lubricants containing these etherpyrrolidonecarboxylic acids as lubricants.
  • a water-based concentrate for producing synthetic coolants typically contains the following components (described, for example, BT Mang, W. Dressel: “Lubricants and Lubrication”, Wiley-VCH, Weinheim, 2001, Chapter 14, or JP Byer's “Metalworking Fluids”, Taylor & Francis, 2006, p. 127 ff.):
  • pH adjusting agent eg alkanolamine
  • the pH is typically in alkaline, usually pH> 8. Increasing the pH contributes to corrosion protection. decisive
  • lubricants are polyalkylene glycols (T. Mang, W. Dressel: “Lubricants and Lubrication”, Wiley-VCH, Weinheim, 2001, p 378), by sequential or random polymerization of alkylene oxides, preferably ethylene oxide and The mode of action of these lubricants is based on "hydrodynamic lubrication".
  • the polyalkylene glycols have a cloud point, d. H. at a certain temperature, the polymers become insoluble in water. When this temperature is reached by the heat released when grinding or cutting metal, the polymers exit the solution and form a thin film of lubricant between the metal and the tool. Due to this property, however, there is also a disadvantage: the polyglycols leave behind sticky residues, especially when older grinding and cutting fluids after long use have a high lime soap content and electrolyte content which lowers the cloud point.
  • WO-00/53701 describes carboxyl-terminated polyalkylene glycols as lubricants.
  • the carboxyl groups are introduced either by reaction of a polyalkylene glycol with anhydrides in a simple condensation reaction or by formation of an ether carboxylic acid by reaction of the polyalkylene glycols with monochloroacetic acid salt. After neutralization by the
  • esters produced by reaction with the anhydrides are very limited in their lifetime by the hydrolysis occurring under the alkaline conditions, so that very quickly only the polyalkylene glycols are present again.
  • a disadvantage of the ether carboxylic acids is the waste produced in the production of at least 4 moles of sodium chloride per mole of difunctional polyalkylene glycol and the low space-time yield in the production, which leads to high overall costs.
  • Another problem is the achievement of a complete implementation. If the polyalkylene glycol itself is not water-soluble, for. As a polypropylene glycol, residues of the free glycol lead to an undesirable turbidity or two-phase of the concentrate.
  • Etherpyrrolidonecarboxylic acids (hereinafter also “EPC") and their preparation are known in the art.
  • EPC Etherpyrrolidonecarboxylic acids
  • US Pat. Nos. 4,304,690, 4,298,708 and 4,235,811 describe the preparation of etherpyrrolidonecarboxylic acids based on fatty alcohol (poly) etheramines and their use in detergents and as catalyst for the preparation of polyurethane foams.
  • fatty alcohol (poly) etheramines and their use in detergents and as catalyst for the preparation of polyurethane foams.
  • These derived from fatty alcohols and their alkoxylates Pyrrolidoncarbonklaren are oil-soluble, water-dispersible and can be used after neutralization in emulsifiable cooling lubricant concentrates as an emulsifier and corrosion inhibitor.
  • GB-A-1 323 061 claims hydraulic fluids containing pyrrolidonecarboxylic acids, which may also be polyalkylene glycol based etherpyrrolidone mono- and dicarboxylic acids.
  • GB-A-1 323 061 describes only etherpyrrolidonecarboxylic acids derived from (poly) ethylene glycol amines, namely only the short-chain polyamine H 163 (9-hydroxy-4,7-dioxanonanamine) and its monoethanolamine derivative.
  • EPCs are used as corrosion inhibitors in hydraulic fluids. Another use described as the corrosion inhibitor in acidic cleaners. A lubricating effect is not taught.
  • etherpyrrolidonecarboxylic acids of the formula 1 which, in addition to ethylene glycol and also propylene glycol units or in particular only propylene glycol units, are particularly effective lubricants in alkaline cooling lubricants.
  • the effect is particularly pronounced when the etherpyrrolidonecarboxylic acids contain long polyalkylene glycol, in particular polypropyleneglycol, units, ie have a high molecular weight.
  • These etherpyrrolidonecarboxylic acids can replace polyalkylene glycols and other prior art lubricants in concentrates for the production of synthetic (water-soluble) coolants, with much lower levels
  • etherpyrrolidonecarboxylic acids can be carried out analogously to the fatty alcohol-etherpyrrolidonecarboxylic acids by reacting itaconic acids with the polyetheramines.
  • polyetheramines are under the trade names polyetheramines (BASF) or Jeffamine ® (Huntsman) partly commercially available or can be obtained with acrylonitrile and subsequent hydrogenation of the nitrile either by aminolysis of suitable polyalkylene glycols with ammonia or by reaction of polyalkylene glycols.
  • the invention thus provides etherpyrrolidonecarboxylic acids of the formula (1)
  • R 1 is a Ci-C 6 hydrocarbon group with 1-4 oxy groups
  • AO a (poly) alkylene glycol unit which has one or more C 2 -C 4 -
  • Another object of the invention are concentrates for the production of synthetic coolants containing Etherpyrrolidoncarbonklaren of formula (1) and the use of these concentrates for the production of synthetic coolants.
  • the polyalkylene glycol unit (AO) in formula (1) is one or a series of a plurality of C 2 -C 4 alkylene oxide units which may be different from each other. The different units may be arranged in random order or arranged sequentially (in blocks).
  • (AO) represents a single alkoxy group
  • (AO) represents a propoxy or butoxy group. If (AO) is more than one alkoxy group, (AO) contains at least one propoxy group or at least one butoxy group.
  • These polyalkylene glycol units are formed in the first step of preparing the etherpyrrolidonecarboxylic acids by alkoxylating a hydroxyl group of a starting alcohol with one or more C 2 -C 4 -alkylene oxides to give a
  • Polyalkylene glycol wherein the alkoxylation with several alkylene oxides either with a mixture of alkylene oxides or can be carried out sequentially. According to the invention, however, one of the alkylene oxides must be different from ethylene oxide.
  • the polyalkylene glycol units (A-O) contain sequentially arranged alkoxy groups.
  • the proportion of propoxy and / or butoxy groups is more than 20 mol%, in particular more than 50 mol%. In a particularly preferred embodiment, these are pure polypropylene glycol units.
  • the group - (AO) - represents in a preferred embodiment a poly (oxyalkylene) group of the formula (2)
  • I is a number 0 to 200
  • m is a number from 0 to 200
  • n is a number from 0 to 200
  • l + n is at least equal to 1.
  • I preferably represents a number from 1 to 10.
  • m preferably represents a number from 20 to 50.
  • n preferably represents a number from 1 to 10.
  • I is zero
  • m is a number from 1 to 50, in particular 5 to 25
  • n is 1 to 200, in particular 2 to 25.
  • I and m are zero, and n is 1 to 50, in particular 2 to 30.
  • the number of alkoxy groups contained in the (AO) units of the etherpyrrolidonecarboxylic acids of the present invention is best defined by the molecular weight of the polyalkylene glycol groups.
  • the number average molecular weight of the polyalkylene glycol group is generally at least 75 g / mol, preferably greater than 200 g / mol, particularly preferably 1,000-10,000 g / mol.
  • the number-average molecular weight of the polyalkylene glycol group can be determined, for example, by gel permeation chromatography (GPC) on the unit R 1 - [(AO) -H] X.
  • the effectiveness of the etherpyrrolidonecarboxylic acids according to the invention increases with the molecular weight of the polyalkylene glycols used as intermediates.
  • the molecular weight is However, limited by the onset of insolubility in particular of a high proportion of propoxy- or butoxy-containing, high molecular weight etherpyrrolidonecarboxylic acids at pH> 7.
  • R 1 is a radical obtained by the formal abstraction of the hydroxyl hydrogen atom from a mono-, di-, tri-or tetravalent alcohol comprising 1 to 7 carbon atoms. Preferably, this alcohol comprises 2 to 6 carbon atoms. Furthermore, R 1 is preferably an aliphatic group. By formal abstraction is meant herein that the hydroxyl hydrogen atom is omitted. Starting from methanol CH 3 OH, R 1 is thus CH 3 O, starting from ethylene glycol HO-CH 2 -CH 2 -OH R 1 is either 0-CH 2 -CH 2 -OH or 0-CH 2 -CH 2 -O. The single oxygen atom -O is referred to herein as the oxy group. The number of oxy groups equals x.
  • the number of oxy groups may be equal to or less than the number of OH groups of dihydric, trihydric or tetrahydric alcohols.
  • the group R 1 CH 3 O-, in a further preferred embodiment is a difunctional group, especially ethylene glycol and 1, 2-propylene glycol.
  • the starting alcohol may already contain one or more alkoxy groups, which are then further alkoxylated.
  • Suitable starting alcohols are thus therefore methyl glycol, methyl diglycol, methyltriglycol, butylglycol, butyldiglycol, butyltriglycol, diethylene glycol, triethylene glycol, tetraethylene glycol, low molecular weight polyalkylene glycols, dipropylene glycol, tripropylene glycol, butylpropylene glycol, butyldipropylene glycol and low molecular weight polypropylene glycols.
  • Polyalkylene glycol etheramines a high degree of conversion is preferred, it is at least 95%, preferably 97%, more preferably> 99%.
  • ether amines with different alkoxy groups, molecular weights and functionalities are commercially available for example under the name Jeffamine ® or polyether amines.
  • the resulting Etherpyrrolidoncarbonchuren can be used for the production of cooling lubricant concentrates, which are diluted before use with water to the finished cooling lubricants.
  • Typical dilution ratios are 1: 1-1: 100, preferably between 1:25 and 1:10 parts of concentrate to water.
  • smaller amounts are needed to comparable lubricating effects, measured z. B. on a Reichert Reibver gleichwaage to achieve. Since the etherpyrrolidonecarboxylic acids according to the invention have no cloud point at the typical pH values of a synthetic metalworking fluid, no disturbing residues remain on the workpieces or tools and the liquids have lime soaps and so on because of their high stability
  • Electrolytes have a long life.
  • the concentration in the concentrate can be from 0.1 to 60% by weight, preferably from 1 to 25% by weight, more preferably from 5 to 15% by weight, and is chosen such that a sufficient lubricating effect is achieved in the application z.
  • B. can be determined on the Reichert-ReibverInstitutwaage.
  • the etherpyrrolidonecarboxylic acids themselves need not be soluble in distilled water, it is sufficient or even preferred if they become soluble at pH> 7 by the use of neutralizing agent.
  • these concentrates contain the etherpyrrolidonecarboxylic acids according to the invention as lubricants and a neutralizing agent for adjusting the pH which, after dilution to the final working concentration, is between 7 and 11, preferably between 8 and 10 and more preferably between 8.5 and 9.5 ,
  • Neutralizers suitable for this purpose are amines of the formula (3)
  • R 5 , R 6 and R 7 are independently hydrogen or a
  • Hydrocarbon radical having 1 to 100 carbon atoms.
  • R 5 and / or R 6 and / or R 7 independently of one another represent an aliphatic radical.
  • This preferably has 1 to 24, more preferably 2 to 18 and especially 3 to 6 C atoms.
  • the aliphatic radical may be linear, branched or cyclic. It can still be saturated or unsaturated. Preferably, the aliphatic radical is saturated.
  • the aliphatic group may have substituents such as hydroxyl, Ci -C 5 alkoxy- -alkyl, cyano, nitrile, nitro and / or C 5 -C 2 o-wear aryl groups such as phenyl.
  • the C 5 -C 2 o-aryl radicals may in turn optionally substituted with halogen atoms, halogenated alkyl groups, -C 2 o alkyl, C 2 -C 2 o-alkenyl, hydroxyl, -C 5 alkoxy such as methoxy, amide , Cyano, nitrile, and / or nitro groups.
  • R 5 and / or R 6 and / or R 7 independently of one another are hydrogen, a C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl or C 3 -C 6 -cycloalkyl radical and especially an alkyl radical with 1, 2, or 3 C atoms.
  • radicals can carry up to three substituents.
  • Particularly preferred aliphatic radicals R 5 and / or R 6 and / or R 7 are hydrogen, methyl, ethyl, hydroxyethyl, n-propyl, isopropyl, hydroxypropyl, n-butyl, isobutyl and tert-butyl, hydroxybutyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, n-dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl and methylphenyl.
  • R 5 and R 6 together with the nitrogen atom to which they are attached form a ring.
  • This ring preferably has 4 or more, such as 4, 5, 6 or more ring members.
  • Preferred further ring members are carbon, nitrogen, oxygen and sulfur atoms.
  • the rings in turn may carry substituents such as alkyl radicals.
  • Suitable ring structures are, for example, morpholinyl, pyrrolidinyl, piperidinyl, imidazolyl and azepanyl radicals.
  • R 7 is H or an alkyl radical having 1 to 12 carbon atoms.
  • R 5, R 6 and / or R 7 are independently an optionally substituted C 6 -C 2 aryl group or an optionally substituted heteroaromatic group having 5 to 12 ring members.
  • R 5 , R 6 and / or R 7 independently of one another represent an alkyl radical interrupted by heteroatoms.
  • Particularly preferred heteroatoms are oxygen and nitrogen.
  • R 5 , R 6 and / or R 7 independently of one another preferably represent radicals of the formula (4)
  • R 8 is an alkylene group having 2 to 6 carbon atoms and preferably 2 to
  • R 9 is hydrogen, a hydrocarbon radical having 1 to 24 C atoms or a group of the formula -R 8 -NR 10 R 11 , a is a number between 2 and 50, preferably between 3 and 25 and in particular between 4 and 10 and
  • R 10 , R 11 independently of one another represent hydrogen, an aliphatic radical having 1 to 24 C atoms and preferably 2 to 18 C atoms, an aryl group or heteroaryl group having 5 to 12 ring members, a poly (oxyalkylene) group having 1 to 50 Poly (oxyalkylene) units, wherein the polyoxyalkylene units of alkylene oxide units with 2 to 6 C atoms, or R 10 and R 11 together with the nitrogen atom to which they are attached form a ring with 4, 5, 6 or more ring members stand.
  • R 5 ; R 6 and / or R 7 independently of one another represent radicals of the formula (5)
  • R 12 is an alkylene group having 2 to 6 carbon atoms and preferably 2 to
  • each R 13 is independently hydrogen, an alkyl or hydroxyalkyl having up to 24 carbon atoms such as 2 bis
  • R 8 , R 9 , R 12 and R 13 are as defined above and q and p are independently from 1 to 50 and b is a number from 1 to 20 and preferably from 2 to 10 such as three, four, five or six.
  • the radicals of the formula (5) preferably contain 1 to 50, in particular 2 to 20, nitrogen atoms.
  • Particularly preferred neutralizing agents are water-soluble alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine and longer-chain mono-, di- and trialkylamines, provided that they are at least 1 wt .-%, preferably 1-5 wt .-% water-soluble ,
  • the alkyl chains can be branched here.
  • oligoamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, their higher homologs and mixtures of these.
  • alkylated, especially methylated, representatives of these oligoamines such as N, N-dimethyldiethyleneamine, N, N-dimethylpropylamine and longer-chain and / or higher alkylated amines of the same construction principle.
  • alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, diglycolamine, triglycolamine and higher homologs, methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine and longer-chain alkyldiethanolamines, where the alkyl radical may be cyclic and / or branched.
  • alkanolamines are dialkylethanolamines such as dimethylethanolamine, diethylethanolamine, dipropylethanolamine, dibutylethanolamine and longer-chain dialkylethanolamines, where the alkyl radical may also be branched or cyclic.
  • dialkylethanolamines such as dimethylethanolamine, diethylethanolamine, dipropylethanolamine, dibutylethanolamine and longer-chain dialkylethanolamines, where the alkyl radical may also be branched or cyclic.
  • aminopropanol, aminobutanol, aminopentanol and higher homologs, as well as the corresponding mono- and dimethylpropanolamines and longer-chain mono- and dialkylamino alcohols can be used.
  • amines such as 2-amino-2-methylpropanol (AMP), 2-aminopropanediol, 2-amino-2-ethylpropanediol, 2-aminobutanediol and other 2-aminoalkanols, aminoalkylamine alcohols, tris (hydroxylmethyl) aminomethane are suitable, as well as end-capped Representatives such as methylglycolamine, methyldiglycolamine and higher homologs, di (methylglycol) amine, di (methyldiglycol) amine and their higher homologs and the corresponding triamines and polyalkylene glycol amines (eg Jeffamine ® ).
  • AMP 2-amino-2-methylpropanol
  • 2-aminopropanediol 2-amino-2-ethylpropanediol
  • 2-aminobutanediol and other 2-aminoalkanols aminoalkylamine alcohols
  • mixtures of the abovementioned amines are used to adjust desired pH values.
  • concentration of these amines in the concentrate can be 1 to 60% by weight, preferably 10 to 30% by weight, more preferably 15 to 25% by weight, and is chosen so that the desired pH is obtained after dilution.
  • Nitrogen-containing neutralizing agents cause M to be an ammonium group.
  • ammonium group means with respect to M that this group may also be substituted.
  • the nature of the substituents arises from the nature of the nitrogenous neutralizing agents as described above.
  • Suitable neutralizing agents are the oxides and hydroxides of the alkali and / or alkaline earth metals, such as. For example, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and calcium oxide.
  • a polyalkylene glycol can be added, but this is used in significantly smaller amounts than when used as a lubricant.
  • the concentrate may contain at most 10% by weight, preferably 0.1-5% by weight, particularly preferably 0.5-1.5% by weight, of polyalkylene glycol.
  • Suitable polyalkylene glycols have the same basic structure as the polyalkylene glycols suitable as raw materials for the preparation of the etherpyrrolidonecarboxylic acids, but the quantitative ratio of the various alkoxy groups is chosen such that the desired cloud point is reached.
  • these are EO-PO-EO block polymers, which themselves have a cloud point (1% in water) 25-90 0 C, preferably 30 - 80 0 C, in particular 30 - 60 0 C.
  • the cooling lubricant concentrates furthermore contain water-soluble corrosion inhibitors in amounts of from 0.1 to 60% by weight, preferably from 5 to 25% by weight, particularly preferably from 10 to 20% by weight.
  • Suitable corrosion inhibitors are benzenesulfonic acid amidocaproic acid, toluenesulfonic acid amidocaproic acid, benzenesulfonic acid (N-methyl) amidocaproic acid, toluenesulfonic acid (N-methyl) amidocaproic acid (all formula (6)), alkanoylamidocarboxylic acids, especially isononanoylamidocaproic acid (formula (7)) and triazine-2,4,6-tris (aminohexanoic acid) (formula (8)), or the alkali, alkaline earth and amine salts of the compounds of formulas (6) - (8).
  • R 14 , R 15 H or CH 3
  • Suitable corrosion inhibitors are linear or branched Ce- to C ⁇ -carboxylic acids such.
  • octanoic acid, 2-ethylhexanoic acid, n-nonanoic acid, n-decanoic acid, n-lsodekanklare dicarboxylic acids such as succinic acid, adipic acid, maleic acid, citric acid, and long-chain dicarboxylic acids such as decanedioic, undecanedioic or dodecanedioic acid, the chains may be branched or cyclic, and polycarboxylic acids.
  • suitable corrosion inhibitors are alkanesulfonic acid amides, alkanesulfonamidocarboxylic acids and Phtalklareraumamide.
  • the salts of the compounds listed above can also be used.
  • a widely used inorganic corrosion inhibitor is boric acid and its salts, amides and esters.
  • the salts of one of the abovementioned corrosion inhibitors are used, these are preferably salts which are formed by reaction of the free acids with a neutralizing agent which is contained in the hydraulic fluid.
  • a neutralizing agent which is contained in the hydraulic fluid.
  • the use of EP / AW additives to reduce abrasion is required.
  • the concentrates can be used as EP / AW additives, for example water-soluble phosphoric acid esters, their salts, but also water-insoluble phosphoric esters, which are converted by the neutralizing agents into their salts and become soluble.
  • Suitable phosphoric acid esters are the mono- and diesters of ethanol, butanol, propanol, methanol, hexanol, octanol, iso-octanol, phenol and other higher alcohols, ethylene glycol, propylene glycol, butyl glycol, butyl diglycol and mixtures thereof, as well as the mono- and diesters of ethoxylated alcohols and their mixtures.
  • EP / AW additives are water-soluble sulfur compounds such.
  • dimercaptothiodiazole and its salts dithiodicarboxylic acids, especially dithio (diarylcarboxylic acids) such.
  • the concentration of EP / AW additives is generally between 0.1 and 20% by weight, preferably between 1 and 10% by weight.
  • the concentrates according to the invention also biocides, defoamers, water softeners or solubilizers, z. B. butyl glycol or butyl diglycol.
  • the preparation of the cooling lubricant concentrates can be done by simply mixing the additives in any order. To avoid highly viscous phases, however, it is advisable first to introduce the water and then to add the immediately water-soluble additives in any order. Subsequently, the neutralizing agents can be added and subsequently the additives which first become water-soluble by neutralization.
  • the etherpyrrolidonecarboxylic acids can be added at any point. In a preferred embodiment, the etherpyrrolidonecarboxylic acids are not soluble in pure water, but only at pH values> 7. In these cases Preferably, the neutralizing agents are first dissolved in water and then added the Etherpyrrolidoncarbonklaren.
  • the concentrates prepared in this way are diluted to water with distilled water or else other process water or tap water in a ratio of 1: 1 to 1: 100, generally between 1:25 and 1:10 parts of concentrate and used.
  • the product obtained is characterized by acid number (SZ) and base nitrogen (bas-N).
  • Example 5 From 442 g (1 mole) of polyetheramine D-400 ® (Polypropylenglykoldiamin having an average molecular weight of 400 g / mol) and 260 g (2 mol) itaconic acid was 665 g of product with bas-N ⁇ 0.1% and SZ of 164 mg KOH / g as a light yellow liquid.
  • polyetheramine D-400 ® Polypropylenglykoldiamin having an average molecular weight of 400 g / mol
  • itaconic acid was 665 g of product with bas-N ⁇ 0.1% and SZ of 164 mg KOH / g as a light yellow liquid.
  • the etherpyrrolidonecarboxylic acids from Examples 1 to 11 were reacted with a double excess of triethanolamine to form the actual water-soluble lubricant, and in aqueous solution the behavior against hard water, the cloud point and the lubricity on the Reichert friction weighing scale (loading: 1.5 kg / travel 100 m / Steel rolls / results of the ground joint in mm 2 ).
  • the polyalkylene glycols Genapol ® and Genapol PN30 ® B from the prior art were measured.
  • Examples 1-3 correspond to the prior art of GB-A-1 323 061, ie ether pyrrolidone carboxylic acids derived from (poly) ethylene glycol amines.
  • etherpyrrolidonecarboxylic acid has been abbreviated to EPC in the table. In cases where the cut mark was> 30 mm 2 , no lower concentration was measured. Table 1: Properties and lubricating values of etherpyrrolidonecarboxylic acids
  • the polyalkylene Genapol ® B and PN30 have very good lubricating properties, but also the detrimental cloud point described on.
  • Examples 1 - 3 show that low-molecular-weight etherpyrrolidonecarboxylic acids containing only PEG chains derived from ethylene oxide do not meet the requirements of a good lubricant, since the grinding marks are at least less than 10% in these Reichert measurements at a use concentration of 10% 20 mm 2 should be.
  • Etherpyrrolidoncarbonklaren In particular high molecular weight (Examples 6,7,9,11) representatives have improved lubricating effects.
  • high molecular weight (Examples 6,7,9,11) representatives have improved lubricating effects.
  • etherpyrrolidonecarboxylic acids with pure polypropylene chains Examples 4 - 6, 10, 11
  • Example 6.11 etherpyrrolidonecarboxylic acids with pure polypropylene chains
  • Example 13 Coolant concentrate containing
  • Etherpyrrolidonecarboxylic acid from example 6 45 g of water are placed in a 250 ml beaker. With constant stirring, first 17 g of triethanolamine, then 20 g of isononanoyl-caproic acid and then 8 g of the ECS from Example 6 are added.
  • Example 14 Cooling lubricant concentrate containing Etherpyrrolidoncarbonklare from Example 6
  • Example 15 Coolant concentrate containing
  • Etherpyrrolidonecarboxylic acid from Example 11 A 250 ml beaker is charged with 45 g of water. With constant stirring, first 17 g of triethanolamine, then 20 g of isononanoyl-caproic acid and then 8 g of the ECS from Example 11 are added.
  • Table 2 lists the performance data of synthetic coolants prepared from the concentrates of the present invention containing the most effective etherpyrrolidone carboxylic acids of Examples 6 and 11 and the prior art. The pHs were adjusted to 8.5 with traces of monoethanolamine.
  • Table 2 shows the effectiveness of the cooling lubricants produced from the ether carboxylic acids containing (Example 13 - 15) cooling lubricant concentrates compared to the prior art (Example 12).
  • the ether carboxylic acids are used together with the neutralizing agent, corrosion inhibitors and optionally EP / AW additive (Example 14) in smaller amounts than the polyalkylene glycols (Genapol PN 30, Genapol B). Corrosion protection and stability against hard water are not affected.

Landscapes

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

Abstract

Acides étherpyrrolidone carboxyliques à base de polyalkylène glycol et concentrés destinés à la préparation de réfrigérants lubrifiants synthétiques les contenant. La présente invention concerne des acides étherpyrrolidone carboxyliques de formule (1) dans laquelle R1 représente un groupe hydrocarbure C1-C6 ayant 1 à 4 groupes oxy, R2 représente H, CH3, CH2CH3, (A-O) représente une unité (poly)alkylène glykol qui contient un ou plusieurs groupes alcoxy C2-C4 ou un mélange de plusieurs groupes alcoxy C2-C4, au moins un groupe alcoxy étant un groupe butoxy ou propoxy, M représente hydrogène, métal alcalin, métal alcalino-terreux ou un groupe ammonium, y vaut 1 ou 2, et x vaut 1, 2, 3 ou 4
EP10724279A 2009-06-25 2010-05-19 Acides étherpyrrolidone carboxyliques à base de polyalkylène glycol et concentrés destinés à la préparation de réfrigérants lubrifiants synthétiques les contenant Withdrawn EP2446003A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009030412A DE102009030412A1 (de) 2009-06-25 2009-06-25 Polyalkylenglykol basierende Etherpyrrolidoncarbonsäuren und Konzentrate zur Herstellung synthetischer Kühlschmierstoffe, die diese enthalten
PCT/EP2010/003063 WO2010149252A1 (fr) 2009-06-25 2010-05-19 Acides étherpyrrolidone carboxyliques à base de polyalkylène glycol et concentrés destinés à la préparation de réfrigérants lubrifiants synthétiques les contenant

Publications (1)

Publication Number Publication Date
EP2446003A1 true EP2446003A1 (fr) 2012-05-02

Family

ID=42611688

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10724279A Withdrawn EP2446003A1 (fr) 2009-06-25 2010-05-19 Acides étherpyrrolidone carboxyliques à base de polyalkylène glycol et concentrés destinés à la préparation de réfrigérants lubrifiants synthétiques les contenant

Country Status (7)

Country Link
US (1) US20120088705A1 (fr)
EP (1) EP2446003A1 (fr)
JP (1) JP5706405B2 (fr)
CN (1) CN102395660B (fr)
BR (1) BRPI1011781A2 (fr)
DE (1) DE102009030412A1 (fr)
WO (1) WO2010149252A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008003828B3 (de) * 2008-01-10 2009-09-03 Clariant International Limited Verwendung von Salzen als Korrosionsinhibitoren mit erhöhter biologischer Abbaubarkeit und verminderter Toxizität und diese Salze
DE102009030409A1 (de) 2009-06-25 2011-01-05 Clariant International Limited Wassergemischte Metallbearbeitungsflüssigkeiten, enthaltend Etherpyrrolidoncarbonsäuren
FR2961208B1 (fr) * 2010-06-09 2012-11-23 Oreal Poly 2-pyrrolidones fonctionnalisees par un radical ester, acide ou amide, composition cosmetique les comprenant et leur utilisation comme agent dispersant
AU2012284000A1 (en) 2011-07-21 2014-02-06 The Lubrizol Corporation Overbased friction modifiers and methods of use thereof

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3218264A (en) * 1961-10-24 1965-11-16 Katz Jacob Lubricants containing amine salts of n-substituted pyrrolidone carboxylic acids
US3224975A (en) * 1962-12-03 1965-12-21 Ethyl Corp Lubricating oil compositions
GB1323061A (en) 1969-06-16 1973-07-11 Castrol Ltd Functional fluids and additives therefor
GB1483457A (en) * 1973-09-18 1977-08-17 Cooper Ltd Ethyl Lubricant additives their preparation and compositions containing them
US4332720A (en) * 1976-05-24 1982-06-01 Texaco Development Corporation N,N'-Polyoxyalkylene bis(lactam carboxylic acids)
GB1578821A (en) * 1976-05-24 1980-11-12 Texaco Development Corp Polyoxyalkylenes
US4298708A (en) 1979-04-02 1981-11-03 Texaco Development Corp. Aminated alkoxylated aliphatic alcohol salts as polyisocyanurate catalysts
US4304690A (en) 1979-04-02 1981-12-08 Texaco Development Corp. Compounds from aminated alkoxylated aliphatic alcohol
US4235811A (en) 1979-04-02 1980-11-25 Texaco Development Corp. Compounds from aminated alkoxylated aliphatic alcohol
US4397750A (en) * 1979-12-17 1983-08-09 Mobil Oil Corporation N-Hydroxyalkyl pyrrolidinone esters as detergent compositions and lubricants and fuel containing same
DE19833894A1 (de) * 1998-07-28 2000-02-03 Fuchs Dea Schmierstoffe Gmbh & Wassermischbares Kühlschmierstoff-Konzentrat
GB9905055D0 (en) 1999-03-05 1999-04-28 Castrol Ltd A waste-treatable lubricant
WO2010069848A2 (fr) * 2008-12-19 2010-06-24 Basf Se Formulations agrochimiques contenant des oxydes de pyrrolidone alkylène
DE102009030411A1 (de) * 2009-06-25 2010-12-30 Clariant International Limited Wasser-in-Öl-Emulsion und Verfahren zu ihrer Herstellung
DE102009030409A1 (de) * 2009-06-25 2011-01-05 Clariant International Limited Wassergemischte Metallbearbeitungsflüssigkeiten, enthaltend Etherpyrrolidoncarbonsäuren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010149252A1 *

Also Published As

Publication number Publication date
WO2010149252A1 (fr) 2010-12-29
JP2012530730A (ja) 2012-12-06
CN102395660B (zh) 2013-08-14
US20120088705A1 (en) 2012-04-12
BRPI1011781A2 (pt) 2016-03-22
CN102395660A (zh) 2012-03-28
JP5706405B2 (ja) 2015-04-22
DE102009030412A1 (de) 2010-12-30

Similar Documents

Publication Publication Date Title
DE102008064004B4 (de) Wasserbasierende Hydraulikflüssigkeiten enthaltend Dithiodi(arylcarbonsäuren) oder deren Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze
CN106459823B (zh) 水溶性金属加工油和金属加工用冷却剂
DE2558201B2 (de) Schmierölgemisch
DE2759233A1 (de) Hydraulikfluessigkeiten auf wasserbasis
DE3540246A1 (de) Verwendung von alkoxyhydroxyfettsaeuren als korrosionsinhibitoren in oelen und oelhaltigen emulsionen
DE2705877A1 (de) Schmiermittel
DE112015000678T5 (de) Wasserverdünnbarer Hochleistungsschmiersatz für Metallbearbeitungsanwendungen mit mehreren Metallen
DE3144013A1 (de) "arbeitsfluessigkeit"
EP2446006A1 (fr) Liquides de traitement de métaux mélangés à de l'eau, contenant des acides étherpyrrolidone carboxyliques
WO2010149252A1 (fr) Acides étherpyrrolidone carboxyliques à base de polyalkylène glycol et concentrés destinés à la préparation de réfrigérants lubrifiants synthétiques les contenant
DE10353603B4 (de) Verwendung von Ethercarbonsäuren auf Basis alkoxylierter Mono-, Di- und/oder Tri(1-phenylethyl)phenole in Kühlschmiermitteln
EP0090342A2 (fr) Lubrifiant à base d'eau pour des chaînes de scie
CH658075A5 (de) Korrosionsinhibierende waesserige fluessigkeit.
DE112021003394B4 (de) Viskositätsindex-Verbesserer-Zusammensetzung und Schmieröl-Zusammensetzung
EP2828419B1 (fr) Formulation aqueuse, agent de surface, anti-corrosive ainsi qu' une émulsion concentrée oléagineuse miscible avec l'eau
DE3808372A1 (de) Reaktionsprodukte aus borsaeure und alkanoletheraminen und deren verwendung als korrosionsschutzmittel
DE2447468C2 (de) Phosphonsäureesterzusammensetzung, Verfahren zu ihrer Herstellung und ihre Verwendung als reibungssenkende Zusätze in flüssigen Arbeitsmedien
DE10302626A1 (de) Phosphorsäureester von Polyisobuten-substituierten aromatischen Hydroxyverbindungen
MXPA02002510A (es) Superamidas polialcoxiladas, opcionamente funcionalizadas, y su empleo como emulsionantes.
EP2427536A1 (fr) Nouveaux additifs augmentant le pouvoir lubrifiant, procédé pour leur production, et leur utilisation
EP2796447B1 (fr) Nouveaux composés contenant des ponts de soufre, leur procédé de fabrication et leur utilisation
EP4286497A1 (fr) Fluides fonctionnelles de viscosite lows
JPH0680982A (ja) 含水系作動液
DE202013006324U1 (de) Verwendung von Polyestern als Schmierstoffe
JPH07166181A (ja) 水溶性金属加工用潤滑剤

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120125

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20141113

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CLARIANT INTERNATIONAL LTD

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CLARIANT INTERNATIONAL LTD

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20171212