EP0011730A1 - Brake fluids having a conserving activity and an amount of oleic acid - Google Patents

Brake fluids having a conserving activity and an amount of oleic acid Download PDF

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Publication number
EP0011730A1
EP0011730A1 EP79104326A EP79104326A EP0011730A1 EP 0011730 A1 EP0011730 A1 EP 0011730A1 EP 79104326 A EP79104326 A EP 79104326A EP 79104326 A EP79104326 A EP 79104326A EP 0011730 A1 EP0011730 A1 EP 0011730A1
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EP
European Patent Office
Prior art keywords
brake
weight
molecular weight
brake fluids
formula
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.)
Granted
Application number
EP79104326A
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German (de)
French (fr)
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EP0011730B1 (en
EP0011730B2 (en
Inventor
Gert Dr. Dipl.-Chem. Liebold
Klaus Dr. Dipl.-Chem. Barthold
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BASF SE
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BASF SE
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Publication of EP0011730B2 publication Critical patent/EP0011730B2/en
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/78—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing boron
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
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    • 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
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    • C10M2207/128—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 containing hydroxy groups; Ethers thereof
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • 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
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the invention relates to brake fluids containing fatty acids.
  • brake fluids which correspond to the US standards of the Federal Motor Vehicle Safety Standard FMVSS 116, DOT 3 and the Handbook of the Society of Automotive Engineers SAE J 1703, essentially consist of: Glycol ethers as basic components, polyglycols as lubricant components and contain Anti-corrosion inhibitors and antioxidants.
  • DOT-3 brake fluids generally have good corrosion protection against tinplate, steel, cast iron, brass, copper and aluminum. Corrosion protection is only guaranteed if the metals are completely immersed in the liquid or otherwise well wetted by it.
  • a major disadvantage of these brake pastes is that when the brake system is refilled with brake fluid, Increase the viscosity considerably, so that the viscosity of the filled brake fluid may exceed the maximum viscosities of 1500 cSt at -40 ° C. Such mixtures then no longer meet the requirements of FMVSS 116, DOT 3.
  • the task was therefore to propose brake fluids that can be used simultaneously for impregnation and that allow the components to be stored for longer periods without corrosion.
  • the high molecular weight polyalkylene glycols are carrier substances that have low water solubility and are characterized by high lipophilicity. As a result, they can dissolve the fatty acids more, so that the concentration of the fatty acids can be up to 3% in the brake fluid.
  • the polyalkylene glycols of the formula I contained in the brake fluids according to the invention can consist solely of polypropylene glycols, by mixing predominantly polypropylene glycols with polyethylene glycols or by reacting mixtures of ethylene oxide and (in excess) propylene oxide, statistical mixtures of compounds being formed on average Contain more propylene oxide than ethylene oxide residues and have molecular weights in the range specified.
  • polyethylene glycols with propylene oxide or polypropylene glycols with ethylene oxide the starting polyglycols, the amount of alkylene oxides and the polymerization conditions being chosen so that polyalkylene glycols according to formula I with the molecular weights specified there of 300 to 3000, preferably 1800 to 2200, are formed.
  • the procedure for the preparation of the polyalkylene glycols of the formula I is such that an epoxy mixture consisting of the desired molar ratios of ethylene oxide and propylene oxide is polymerized by methods known per se.
  • Fatty acids to be added as corrosion inhibitors are in particular C 12 to C 24 monocarboxylic acids or their derivatives.
  • fatty acids with and without olefinic double bonds come into consideration, in particular C 13 fatty acids.
  • Suitable fatty acids are, for example, oleic acid, ricinoleic acid, stearic acid, linoleic acid or linolenic acid.
  • the basic components are the polyglycol ethers of formula II that are common in brake fluids into consideration, in which R 1 is a low molecular weight alkyl radical, preferably methyl, R 2 is hydrogen or methyl and n is the numbers 2 to 4.
  • R 1 is a low molecular weight alkyl radical, preferably methyl
  • R 2 is hydrogen or methyl
  • n is the numbers 2 to 4.
  • the brake fluids according to the invention can also contain boric acid esters of glycol ethers of the formula II, e.g. in amounts of 20 to 50% by weight.
  • Suitable boric acid esters are e.g. Methyl tri glycol ortho borate, ethyl tri glycol ortho borate, methyl / ethyl di / tri ortho borate.
  • wheel brake cylinders made of gray cast iron are halved on the long side, cleaned with isopropanol and well dried.
  • the halved brake cylinder is then immersed in the commercially available brake fluid or in the brake fluids with improved corrosion protection for 5 seconds each, drained for 5 seconds and stored in a closed vessel over a water vapor-saturated atmosphere.
  • the build-up of rust is avoided, even after storage for 30 days above the water vapor-saturated atmosphere at room temperature.

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Abstract

1. Brake fluids based on polyglycol ethers and polyglycols and containing fatty acids, characterized in that they contain A) 10 to 40% by weight, based on the brake fluid, of polyalkylene glycols, in the form of uniform compounds or mixtures of compounds, of the formula I HO [R-O]n H where R is a 1,2-ethylene and/or 1,2 propylene radical, the number of propylene radicals, based on the individual compound of the mixture, predominating, and n being a number of 10 or more, and the average molecular weight being 500 to 3000, B) 0.1 to 3% by weight of a fatty acid known to be a corrosion inhibitor, and, to make up 100%, the following constituents C) polyglycol ethers of the formula see diagramm : EP0011730,P6,F1 where R**1 is methyl or ethyl, R**2 is hydrogen or methyl, and n is a number from 2 to 4, D) if desired, polyglycols of ethylene oxide and/or propylene oxide having a molecular weight in the molecular weight range of lubricants usually used in brake fluids, and/or E) if desired, 20 to 50% by weight of boric acid esters of glycol ethers of the formula II, and F) small amounts of conventional antioxidants and inhibitors.

Description

Die Erfindung betrifft Bremsflüssigkeiten mit einem Gehalt an Fettsäuren.The invention relates to brake fluids containing fatty acids.

Handelsüblichen Bremsflüssigkeiten, die den US-Mormen des Federal Motor Vehicle Safety Standard FMVSS 116, DOT 3 bzw. des Handbook of the Society of Automotive Engineers SAE J 1703 entsprechen, bestehen im wesentlichen aus: Glkyol- äthern als Basiskomponenten, Polyglykolen als Schmiermittelkomponenten und enthalten Inhibitoren zwecks Korrosionsschutz und Antioxidationsmittel.Commercially available brake fluids, which correspond to the US standards of the Federal Motor Vehicle Safety Standard FMVSS 116, DOT 3 and the Handbook of the Society of Automotive Engineers SAE J 1703, essentially consist of: Glycol ethers as basic components, polyglycols as lubricant components and contain Anti-corrosion inhibitors and antioxidants.

Diese DOT-3-Bremsflüssigkeiten weisen im allgemeinen guten Korrosionsschutz gegenüber Weißblech, Stahl, Grauguß, Messing, Kupfer und Aluminium auf. Der Korrosionsschutz ist jedoch nur dann gewährleistet, wenn die Metalle vollständig in die Flüssigkeit eingetaucht werden oder sonst von ihr gut benetzt werden.These DOT-3 brake fluids generally have good corrosion protection against tinplate, steel, cast iron, brass, copper and aluminum. Corrosion protection is only guaranteed if the metals are completely immersed in the liquid or otherwise well wetted by it.

Um Bremsteile, insbesondere Radbremszylinder aus Grauguß, nach der Herstellung und Funktionsprüfung rostfrei lagern zu können, ist die Imprägnierung mit speziellen Bremspasten üblich.In order to be able to store brake parts, in particular cast iron wheel brake cylinders, after manufacture and functional test, they are impregnated with special brake pastes.

Ein wesentlicher Nachteil dieser Bremspasten besteht darin, daß sie bei Wiederbefüllung des Bremssystems mit Bremsflüss- igkeit die Viskosität erheblich erhöhen, so daß die Viskosität der eingefüllten Bremsflüssigkeit unter Unständen die maximalen Viskositäten von 1500 cSt bei -40°C wesentlich übersteigt. Derartige Mischungen erfüllen dann nicht mehr die Anforderungen der FMVSS 116, DOT 3.A major disadvantage of these brake pastes is that when the brake system is refilled with brake fluid, Increase the viscosity considerably, so that the viscosity of the filled brake fluid may exceed the maximum viscosities of 1500 cSt at -40 ° C. Such mixtures then no longer meet the requirements of FMVSS 116, DOT 3.

Es bestand daher die Aufgabe, Bremsflüssigkeiten vorzuschlagen, die gleichzeitig zur Imprägnierung verwendet werden können und die die Lagerung der Bauteile über längere Perioden ohne Korrosion ermöglichen.The task was therefore to propose brake fluids that can be used simultaneously for impregnation and that allow the components to be stored for longer periods without corrosion.

Allein die Erhöhung der Inhibitorkonzentration bzw. die Verwendung anderer Inhibitoren, z.B. von Fettsäuren kann zwar die korrosionsschützende Wirkung auf den benetzten Teil erhöhen. Man erhält aber nicht Flüssigkeiten die den Anforderungen, die an Bremsenschutzflüssigkeiten, gestellt werden, entsprechen. Außerdem kann man die Konzentration der Fettsäuren oder Fettsäurederivate nur geringfügig steigern, weil diese Komponenten bei tiefer Temperatur zur Ausfällung neigen bzw. erhöhte Gummiquellung der SBR-Manschetten verursachen.Simply increasing the inhibitor concentration or using other inhibitors, e.g. of fatty acids can increase the anti-corrosion effect on the wetted part. However, fluids are not obtained that meet the requirements placed on brake protection fluids. In addition, the concentration of fatty acids or fatty acid derivatives can only be increased slightly because these components tend to precipitate at low temperatures or cause increased rubber swelling of the SBR cuffs.

Es wurde nun überraschenderweise gefunden, daß Bremsflüssigkeiten auf der Grundlage von Polyglykoläthern als Basiskomponenten, Polyglykolen als Schmiermittelkomponenten, Inhibitoren und Antioxydationsmittel der genannten Forderung genügen, wenn sie einen Gehalt von

  • A) 10 bis 40 Gew.%, bezogen auf die Bremsflüssigkeit von Polyalkylenglykolen in Form von einheitlichen Verbindungen oder Gemischen von Verbindungen der Formel I
    Figure imgb0001
    in der R einen 1,2-Äthylen- und/oder 1,2-Propylenrest, wobei, bezogen auf die einzelne Verbindung oder das Gemisch, die Zahl der Propylenreste überwiegt und n eine Zahl von 10 oder mehr bedeutet, und wobei das durchschnittliche Molekulargewicht 500 bis 3 000 beträgt, und
  • B) 0,1 bis 3 Gew.% einer an sich als Korrosionsinhibitor bekannten Fettsäure

aufweisen.It has now surprisingly been found that brake fluids based on polyglycol ethers as base components, polyglycols as lubricant components, inhibitors and antioxidants meet the stated requirement if they have a content of
  • A) 10 to 40% by weight, based on the brake fluid of polyalkylene glycols in the form of uniform compounds or mixtures of compounds of the formula I.
    Figure imgb0001
     in which R is a 1,2-ethylene and / or 1,2-propylene radical, where, based on the individual compound or the mixture, the number of propylene radicals predominates and n represents a number of 10 or more, and wherein the average molecular weight 500 to 3,000, and
  • B) 0.1 to 3% by weight of a fatty acid known per se as a corrosion inhibitor

exhibit.

Die hochmolekularen Polyalkylenglykole sind dabei Trägersubstanzen, die geringe Wasserlöslichkeit aufweisen und durch hohe Lipophilität gekennzeichnet sind. Dadurch können sie die Fettsäuren vermehrt lösen, so daß die Konzentration der Fettsäuren bis zu 3 % in der Bremsflüssigkeit betragen kann.The high molecular weight polyalkylene glycols are carrier substances that have low water solubility and are characterized by high lipophilicity. As a result, they can dissolve the fatty acids more, so that the concentration of the fatty acids can be up to 3% in the brake fluid.

Die erfindungsgemäß in den Bremsflüssigkeiten enthaltenen Polyalkylenglykole der Formel I können durch allein aus Polypropylenglykolen bestehen, durch Mischen von vorwiegend Polypropylenglykolen mit Polyäthylenglykolen oder durch Umsetzen von Gemischen von Äthylenoxid und (in Überschuß) Propylenoxid hergestellt werden, wobei statistische Gemische von Verbindungen entstehen, die im Mittel mehr Propylenoxid als Äthylenoxidreste enthalten und Molekulargewichte in dem angegebenen Bereich aufweisen.The polyalkylene glycols of the formula I contained in the brake fluids according to the invention can consist solely of polypropylene glycols, by mixing predominantly polypropylene glycols with polyethylene glycols or by reacting mixtures of ethylene oxide and (in excess) propylene oxide, statistical mixtures of compounds being formed on average Contain more propylene oxide than ethylene oxide residues and have molecular weights in the range specified.

Man kann aber auch Polyäthylenglykole mit Propylenoxid oder Polypropylenglykole mit Äthylenoxid umsetzen, wobei die Ausgangspolyglykole die Menge der Alkylenoxide und die Polymerisationsbedingungen so gewählt werden, daß Polyalkylenglykole gemäß Formel I mit den dort spezifizierten Molgewichten von 300 bis 3000, vorzugsweise 1800 bis 2200 entstehen.But you can also implement polyethylene glycols with propylene oxide or polypropylene glycols with ethylene oxide, the starting polyglycols, the amount of alkylene oxides and the polymerization conditions being chosen so that polyalkylene glycols according to formula I with the molecular weights specified there of 300 to 3000, preferably 1800 to 2200, are formed.

Zweckmäßig geht man zur Herstellung der Polyalkylenglykole der Formel I im einzelnen so vor, daß ein Epoxid-Gemisch, bestehend aus den jeweils gewünschten Molverhältnissen Äthylenoxid und Propylenoxid nach an sich bekannten Methoden polynerisiert wird.Appropriately, the procedure for the preparation of the polyalkylene glycols of the formula I is such that an epoxy mixture consisting of the desired molar ratios of ethylene oxide and propylene oxide is polymerized by methods known per se.

Als Korrosionsinhibitoren zuzusetzende Fettsäuren kommen vor allem C12- bis C24-Monocarbornsäuren oder deren Derivate in Betracht.Fatty acids to be added as corrosion inhibitors are in particular C 12 to C 24 monocarboxylic acids or their derivatives.

Im einzelnen kommen Fettsäuren mit und ohne olefinische Doppelbindungen insbesondere C13-Fettsäuren in betracht. Geeignete Fettsäuren sind z.B. Ölsäure, Ricinolsäure, Stearinsäure, Linolsäure oder Linolensäure.In particular, fatty acids with and without olefinic double bonds come into consideration, in particular C 13 fatty acids. Suitable fatty acids are, for example, oleic acid, ricinoleic acid, stearic acid, linoleic acid or linolenic acid.

Als Basiskomponenten kommen die in Bremsflüssigkeiten üblichen Polyglykoläther der Formel II

Figure imgb0002
in Betracht, in der R1 einen niedermolekularen Alkylrest, vorzugsweise Methyl, R2 Wasserstoff oder Methyl und n die Zahlen 2 bis 4 bedeutet. Im einzelnen seien genannt:
Figure imgb0003
 The basic components are the polyglycol ethers of formula II that are common in brake fluids
Figure imgb0002
 into consideration, in which R 1 is a low molecular weight alkyl radical, preferably methyl, R 2 is hydrogen or methyl and n is the numbers 2 to 4. The following may be mentioned in detail:
Figure imgb0003

Als weitere Inhibitoren und als Antioxydationsmittel kommen ebenfalls an sich bekannte Verbindungen in Betracht, wie sie z.B. in der US-Patentschrift 3 711 410, Spalten 9 bis 11 im einzelnen aufgeführt sind. Insbesondere sind zu nennen:

  • Benzotriazol, Imidazol, Imidazolin, prim., sek. Amine, Äthanolamine, Bisphenol A, Triphenylphosphit oder 2,4-Di-tert.--butyl-kresol.
Also known as further inhibitors and as antioxidants are compounds which are known per se, as detailed, for example, in US Pat. No. 3,711,410, columns 9 to 11. The following should be mentioned in particular:
  • Benzotriazole, imidazole, imidazoline, prim., Sec. Amines, ethanolamines, bisphenol A, triphenyl phosphite or 2,4-di-tert-butyl-cresol.

Die erfindungsgemäßen Bremsflüssigkeiten können auch Borsäureester von Glykoläthern der Formel II enthalten, z.B. in Mengen von 20 bis 50 Gew.%. Geeignete Borsäureester sind z.B. Methyl-tri-glykol-ortho-borat, Äthyl-tri-glykol-ortho--borat, Methyl-/Äthyl-di/tri-ortho-borat.The brake fluids according to the invention can also contain boric acid esters of glycol ethers of the formula II, e.g. in amounts of 20 to 50% by weight. Suitable boric acid esters are e.g. Methyl tri glycol ortho borate, ethyl tri glycol ortho borate, methyl / ethyl di / tri ortho borate.

Weitere Boresterverbindungen sind in der US-Patentschrift 3 711 410 im einzelnen beschrieben.Further borester compounds are described in detail in US Pat. No. 3,711,410.

Zur Untersuchung der imprägnierenden Wirkung der erfindungsgemäßen Bremsflüssigkeiten werden Radbremszylinder aus Grauguß längsseitig halbiert, mit Isopropanol gereinigt und gut getrocknet. Man taucht dann den halbierten Bremszylinder jeweils 5 Sekunden in die handelsübliche Bremsflüssigkeit bzw. in die Bremsflüssigkeiten mit verbessertem Korrosionsschutz ein, läßt 5 Sekunden abtropfen und lagert sie in einem geschlossenen Gefäß über einer wasserdampfgesättigten Atmosphäre. Hierbei zeigt sich, daß bei Verwendung handelsüblicher Bremsflüssigkeiten bereits nach wenigen Stunden ein starkes Rosten der Graugußteile beobachtet werden kann. Bei den erfindungsgemäßen Flüssigkeiten wird hingegen der Ansatz von Rost, selbst nach einer Lagerung von 30 Tagen über der wasserdampfgesättigten Atmosphäre bei Raumtemperatur vermieden.

Figure imgb0004
To investigate the impregnating effect of the brake fluids according to the invention, wheel brake cylinders made of gray cast iron are halved on the long side, cleaned with isopropanol and well dried. The halved brake cylinder is then immersed in the commercially available brake fluid or in the brake fluids with improved corrosion protection for 5 seconds each, drained for 5 seconds and stored in a closed vessel over a water vapor-saturated atmosphere. This shows that when using commercially available brake fluids, severe rusting of the cast iron parts can be observed after only a few hours. In the case of the liquids according to the invention, on the other hand, the build-up of rust is avoided, even after storage for 30 days above the water vapor-saturated atmosphere at room temperature.
Figure imgb0004

Zum Vergleich mit üblichen Bremsflüssigkeiten wurden folgende Versuche durchgeführt:

  • 1. Feuchtigkeitskorrosionstest mit der SAE RM 1 Reference--Fluid: Bereits nach wenigen Tagen war starke Korrosion der Graugußbremszylinder festzustellen.
  • 2. Verwendung einer handelsüblichen Bremsflüssigkeit gemäß DOT 3 der folgenden Zusammensetzung: 20 % Polyglykol, Mol.-Verh. EO/PO 2:4, Mol.-Gew. 300 20 % Triäthylenglykol, 5 % Butyltriglykol, 25 % Äthyltriglykol, 29,4 % Äthyldiglykol, 0,25 % Dibutylamin, 0,30 % Bisphenol A, 0,05 % Benzotriazol. Nach wenigen Stunden bis zwei Tagen war starker Rostansatz auf den Graugußteilen zu beobachten.
  • 3. Verwendung von einer Bremsflüssigkeit bestehend aus ca. 70 Gewichtsteilen Glykoläther, 25 % eines handelsüblichen Schmiermittels auf EO/PO-Basis, (Molverhältnis 2:1, Molgewicht 1100) 3 % einer Mischung von Korrosionsinhibitoren aus Benzotriazol, Dodecylamin, Triäthanolamin und 2 % ölsäure. (Die Ölsäure scheidet sich beim Abkühlen teilweise aus; es tritt eine Trübung ein.) Nach ca. 8 Stunden konnte Rostansatz beobachtet werden.
  • 4. Es wurde die gleiche Mischung wie unter 3. angegeben verwendet, nur wurden anstelle der 25 % Schmiermittel nur 15 % Schmiermittel verwendet und 10 % eines PO-Adduktes in Kombination mit einem PO/EO-Addukt. (Zusammensetzung 90 % PO/10 % EO, mittlerer MG 2000) Im Korrosionsversuch zeigte sich nach 30 Tagen keinerlei Rostansatz.
  • 5. 25 % Polypropylenglykol mit Molgewicht 900, 20 % Äthyltriglykol, 30 % Äthyldiglykol, 2 % Ölsäure, 1,5 % Dibutylamin, 4 % eines Glycerin-Borsäureadduktes, 0,05 % Benzotriazol und 17,45 % Methyltriglykol. Die Viskosität bei -40°C betrug 1276 cSt, der Kochpunkt 215°C, pH-Wert 9,3. Die Flüssigkeit entspricht SAE J 1703. Im Feuchtigkeitskorrosionstest nach 30 Tagen kein Rostansatz.
  • 6. Im Feuchtigkeitskorrosionstest ergab eine Bremsflüssigkeit bestehend aus: 10 % eines Polypropylenglykols vom Molgewicht ca. 1000, 7,5 % eines Polypropylenglykols, ca. Molgewicht 2000; 7,5 % eines Schmiermittels bestehend aus ca. 3 Molen Äthylenoxid und 3 Molen Propylenoxid, 20 % Äthyltriglykol, 30 % Äthyldiglykol, 0,5 % Rizinolsäure, 0,05 % Benzotriazol, 4,3 % Korrosionsinhibitor (Umsetzungsprodukt aus Glycerin mit Borsäureester) 1 % Dibutylamin, ca. 20 % Methyltrilglykol. Das Produkt weist eine Viskosität von 1175 cSt bei -40°C auf, einen Kochpunkt von 213°C, pH-Wert 9,7; nach 30 Tagen keinen Rostansatz. Wird anstelle des Polypropylenglykols mit Molgewicht ca. 1000 + Polypropylenglykol mit Molgewicht ca. 2000 und dem EO/PO-Addukt ein handelsübliches Schmiermittel eingesetzt, so tritt bereits nach wenigen Tagen starker Korrosionsansatz ein.
The following tests were carried out for comparison with conventional brake fluids:
  • 1. Moisture corrosion test with the SAE RM 1 Reference - Fluid: After just a few days, the cast iron brake cylinder showed severe corrosion.
  • 2. Use of a commercially available brake fluid according to DOT 3 of the following composition: 20% polyglycol, mol. EO / PO 2: 4, mol. 300 20% triethylene glycol, 5% butyl triglycol, 25% ethyl triglycol, 29.4% ethyl diglycol, 0.25% dibutylamine, 0.30% bisphenol A, 0.05% benzotriazole. After a few hours to two days, heavy rust formation was observed on the gray cast iron parts.
  • 3. Use of a brake fluid consisting of approx. 70 parts by weight of glycol ether, 25% of a commercially available lubricant based on EO / PO, (molar ratio 2: 1, molecular weight 1100) 3% of a mixture of corrosion inhibitors made of benzotriazole, dodecylamine, triethanolamine and 2% oleic acid. (The oleic acid is partially eliminated on cooling; it becomes cloudy.) After about 8 hours, rust formation could be observed.
  • 4. The same mixture was used as indicated under 3., only instead of the 25% lubricant only 15% lubricant was used and 10% of a PO adduct in combination with a PO / EO adduct. (Composition 90% PO / 10% EO, medium MG 2000) The corrosion test showed no rust formation after 30 days.
  • 5. 25% polypropylene glycol with a molecular weight of 900, 20% ethyl triglycol, 30% ethyl diglycol, 2% oleic acid, 1.5% dibutylamine, 4% of a glycerol-boric acid adduct, 0.05% benzotriazole and 17.45% methyl triglycol. The viscosity at -40 ° C was 1276 cSt, the boiling point 215 ° C, pH 9.3. The liquid corresponds to SAE J 1703. No rust formation in the moisture corrosion test after 30 days.
  • 6. In the moisture corrosion test, a brake fluid consisting of: 10% of a polypropylene glycol with a molecular weight of about 1000, 7.5% of a polypropylene glycol, about a molecular weight of 2000; 7.5% of a lubricant consisting of approx. 3 moles of ethylene oxide and 3 moles of propylene oxide, 20% ethyl triglycol, 30% ethyl diglycol, 0.5% ricinoleic acid, 0.05% benzotriazole, 4.3% corrosion inhibitor (reaction product of glycerol with boric acid ester) 1% dibutylamine, approx. 20% methyltrilglycol. The product has a viscosity of 1175 cSt at -40 ° C, a boiling point of 213 ° C, pH 9.7; no rust formation after 30 days. If, instead of the polypropylene glycol with a molecular weight of approx. 1000 + polypropylene glycol with a molecular weight of approx. 2000 and the EO / PO adduct, a commercially available lubricant is used, severe corrosion starts to appear after only a few days.

Claims (1)

Bremsflüssigkeiten auf der Grundlage von Polyglykoläthern als Basiskomponenten, Polyglykolen als Schmiermittelkomponenten, Inhibitoren und Antioxydationsmittel, gekennzeichnet durch einen Gehalt von A) 10 bis 40 Gew.%, bezogen auf die Bremsflüssigkeit von Polyalkylenglykolen in Form von einheitlichen Verbindungen oder Gemischen von Verbindungen der Formel I
Figure imgb0005
in der R einen 1,2-Äthylen- und/oder 1,2-Propylenrest, wobei, bezogen auf die einzelne Verbindung oder das Gemisch, die Zahl der Propylenreste überwiegt und n eine Zahl von 10 oder mehr bedeutet, und wobei das durchschnittliche Molekulargewicht 500 bis 3 000 beträgt, und B) 0,1 bis 3 Gew.% einer an sich als Korrosionsinhibitor bekannten Fettsäure. Brake fluids based on polyglycol ethers as basic components, polyglycols as lubricant components, inhibitors and antioxidants, characterized by a content of A) 10 to 40% by weight, based on the brake fluid of polyalkylene glycols in the form of uniform compounds or mixtures of compounds of the formula I.
Figure imgb0005
 in which R is a 1,2-ethylene and / or 1,2-propylene radical, where, based on the individual compound or the mixture, the number of propylene radicals predominates and n represents a number of 10 or more, and wherein the average molecular weight 500 to 3,000, and B) 0.1 to 3% by weight of a fatty acid known per se as a corrosion inhibitor.
EP79104326A 1978-11-25 1979-11-06 Brake fluids having a conserving activity and an amount of oleic acid Expired EP0011730B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19782851057 DE2851057A1 (en) 1978-11-25 1978-11-25 BRAKE FLUIDS WITH PRESERVATIVE EFFECT
DE2851057 1978-11-25

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EP0011730A1 true EP0011730A1 (en) 1980-06-11
EP0011730B1 EP0011730B1 (en) 1982-10-06
EP0011730B2 EP0011730B2 (en) 1986-06-04

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DE (2) DE2851057A1 (en)

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EP0011730B1 (en) 1982-10-06
DE2851057A1 (en) 1980-06-12
EP0011730B2 (en) 1986-06-04
DE2963824D1 (en) 1982-11-11

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