EP0349534B1 - Hydraulische flüssigkeiten - Google Patents

Hydraulische flüssigkeiten Download PDF

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Publication number
EP0349534B1
EP0349534B1 EP88901051A EP88901051A EP0349534B1 EP 0349534 B1 EP0349534 B1 EP 0349534B1 EP 88901051 A EP88901051 A EP 88901051A EP 88901051 A EP88901051 A EP 88901051A EP 0349534 B1 EP0349534 B1 EP 0349534B1
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EP
European Patent Office
Prior art keywords
oxidant
hydraulic fluids
composition
hydraulic
base composition
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.)
Expired - Lifetime
Application number
EP88901051A
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English (en)
French (fr)
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EP0349534A1 (de
Inventor
Gert Stenmark
Kari Jokinen
Heikki Kerkkonen
Eero LEPPÄMÄKI
Eino PIIRILÄ
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.)
Raisio Oyj
Original Assignee
Raision Tehtaat Oy AB
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Priority claimed from US07/007,627 external-priority patent/US4783274A/en
Application filed by Raision Tehtaat Oy AB filed Critical Raision Tehtaat Oy AB
Priority to AT88901051T priority Critical patent/ATE83003T1/de
Publication of EP0349534A1 publication Critical patent/EP0349534A1/de
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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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    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
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    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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    • C10M2223/045—Metal containing thio derivatives
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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    • C10M2223/049—Phosphite
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/10—Phosphatides, e.g. lecithin, cephalin
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the present invention is concerned with hydraulic fluids based on oily triglycerides of fatty acids.
  • the hydraulic fluids commonly used are petroleum-based, chemically saturated or unsaturated, straight-chained, branched or ring-type hydrocarbons.
  • Hydrocarbons may constitute a cancer risk when in prolonged contact with the skin, as well as a risk of damage to the lungs when inhaled with the air.
  • oil allowed to escape into the environment causes spoiling of the soil and the ground water, even in small quantities. They are also toxic to the aquatic life in rivers, lakes, etc.
  • hydrocarbon oils as such have in fact a rather limited applicability for hydraulic purposes, wherefor the hydraulic fluids based on such oils contain a variety of additives in considerable amounts. Petroleum is also a non-renewable, and consequently limited, natural resource.
  • the triglycerides described in the said specification GB 2 134 923 are glycerol esters of fatty acids, and the chemical structure of the said esters can be defined by means of the following formula: wherein R1, R2 and R3 can be the same or different and are selected from the group consisting of saturated and unsaturated straight-chained alkyl, alkenyl, and alkadienyl chains of ordinarily 9 to 22 carbon atoms.
  • the triglyceride may also, according to the teaching of the specification GB 2 134 923, contain a small quantity of an alkatrienylic acid residue, but a larger quantity is detrimental, because it promotes oxidation of the triglyceride oil.
  • Certain triglyceride oils, so-called drying oils contain considerable quantities of alkatrienyl and alkadienyl groups, and they form solid films, under the effect of the oxygen in the air.
  • Such oils the iodine number of which is usually higher than 130 and which are used i.a. as components of special coatings, cannot be considered for use in the hydraulic fluids.
  • any other oily triglyceride with an iodine number of at least 50 and no more than 128 is suitable for the purpose.
  • Particularly suitable are the triglycerides of the oleic acid-linoleic acid type which contain no more than 20 per cent by weight of esterified saturated fatty acids calculated on the quantity of esterified fatty acids.
  • These oils are liquids at 15 to 20°C, and their most important fatty acid residues are derived from the following unsaturated acids: oleic acid, 9-octadecenoic acid, linoleic acid, 9,12-octa-decadienoic acid.
  • the fume point of triglycerides is above 200°C and the flash point above 300°C (both determinations as per AOCS Ce 9a-48 or ASTM D 1310).
  • the flash points of hydrocarbon basic oils are, as a rule, clearly lower.
  • the triglyceride oils differ from the non-polar hydrocarbons completely in the respect that they are of a polar nature. This accounts for the superb ability of triglycerides to be adsorbed on metal faces as very thin adhering films.
  • Rape seed oil has been considered as an example of the monomeric triglyceride oils used in the hydraulic fluids in accordance with the specification GB 2 134 923, which rape seed oil is also obtained from the sub-species Brassica campestris and which oil, in its present-day commercial form, contains little or no erucic acid, 13-docosenoic acid.
  • applicable triglyceride oils differ from rape seed oil only in respect of the composition of the fatty acids esterified with glycerol, which difference comes out as different pour points and viscosities of the oils.
  • oils obtained from different sub-species of rape and from their related sub-species display differences in pour points and viscosities, owing to differences in the compositions of fatty acids, as appears from Table 3.
  • the first one (eruca) has been obtained from a sub-species that has a high content of erucic acid (C 22:1).
  • the characterizing data of rape seed oil are compared in Table 4 with certain commercial basic mineral oils.
  • Table 4 Characteristic data of rape seed oil and certain basic mineral oils Rape seed oil Gulf 300 paramid Gulf 300 Texas oil Nynäs S 100 Nynäs H 22 Density g/cm3 1) 15°C 0.9205 0.878 0.914 0.910 0.926 Viscosity mm2/s -20°C 660 40°C 34.2 60.7 57.9 99 26 100°C 8 8.1 6.6 8.6 3.9
  • Method ASTM D 1298 Method ASTM D 93 3) Method ASTM D 974
  • the viscosity index (VI) of triglycerides is superior.
  • the viscosity index of the triclyceride oils is apparently also more stable against mechanical and heat stresses existing in the hydraulic systems than the viscosity index of the hydraulic fluids based on formulated mineral oils and containing polymeric viscosity index improves.
  • the ability of the polar triglyceride molecule to adhere onto metallic surfaces improves the lubricating properties of these triglycerides.
  • the oxidation has many negative effects to the properties of a natural triglyceride based hydraulic fluid, wherefore the fluid has to be replaced by fresh fluid more frequently than fluids based on hydrocarbon oils.
  • the viscosity of the natural triglyceride hydraulic fluid is increased due to the oxidation.
  • the oxidation causes also foaming of the fluid, the filtration properties of the fluid are decreased, and the higher water solubility causes problems in the hydraulic system.
  • the oxidation products are also corrosive. In order to avoid these problems caused by oxidation the working temperature of the hydraulic system is to be kept lower than when hydrocarbon based oils are used.
  • the stability of the hydraulic fluids against oxidative degradation was tested.
  • the fluids were tested with an apparatus according to the test method ASTM D 525 by introducing into a pressure vessel 100 ml of the fluid to be tested. The vessel was closed and placed into boiling water. During the test the oxygen pressure in the vessel was determined.
  • the additives used were: Irgalube 349 , amino phosphate derivative, Ciba-Geigy; Irganox L 130 , mixture of tertiary-butyl phenol derivatives, Ciba-Geigy; Reomet 39 , triazole derivative, Ciba-Geigy; Anglamol 75 , zinc dialkyldithio-phosphate, Lubrizol; EN 1235 , kortacid T derivative, Akzo Chemie; Hitec 4735 , mixture of tertiary-butyl phenol derivatives, Ethyl Pertoleum Additives Ltd; Irganox PS 800 , dilauryl thio di propionate, Ciba-Geigy; Irganox L 180 , triaryl phosphite, Ciba-Geigy; Irganox L 57 , mixed alkyl diphenyl amine, Ciba-Geigy
  • compositions 3, 4, 5, 6, 8, 10, 11, 12, 13 and 14 are clearly comparable with the common mineral-oil based hydraulic oils 15 and 16 used for comparison in this example.
  • the compositions 2 and 9 contain the anti-oxidant additives selected according to the invention, but the amounts used have not been sufficient. From the data in Table 5 it can be derived that a triglyceride complying with the definitions presented at the beginning of this description and containing a certain amount of carefully selected anti-oxidant additives can form a base for a fluid composition usable for hydraulic purposes.
  • the anti-oxidant fraction in the composition forms 2.0 to 4.5 percent by weight of the composition
  • the anti-oxidants are selected so that at least one compound is from the group (1) of hindered phenolics and aromatic amines, and the remaining compound(s) forming the balance in the composition, is from the group (2) of metal salts of dithioacids, phosphites and sulphides, or from the group (3) of amides, non-aromatic amines, hydrazides and triazols.
  • a Cameron Plint tester High Frequency Friction Machine TE. 77
  • the friction between a moving and a stationary element is determined at increasing temperatures.
  • the moving element a steel ball having a diameter of 6 mm
  • the stationary element consists of a steel plate.
  • the lubricant to be tested is spread on the plate, and it is exposed to the ambient air oxygen during the tests.
  • the ball was pressed towards the plate by a force of 40 N during its reciprocating movement having an amplitude of 5 mm and a frequency of 20 Hz.
  • the temperature at the beginning of each test was adjusted to 40 °C, whereafter it was increased by 2 °C per minute.
  • the temperature in which the friction began to increase sharply was registered, and it was used as an indication of the failure of the lubricative film between the ball and the plate.
  • the film failure temperature is a measure of the oxidation resistance of the oil.
  • a vegetable oil based hydraulic fluid was tested using as a reference a commercial mineral oil based hydraulic fluid.
  • two new identical hydraulic driven mining loaders were used.
  • the pressures in the hydraulic circuits varied from 0 to 165 bar and the hydraulic fluid temperature from 60 to 80°C. Hydraulic pressure was generated by gear pumps and the power was taken out by means of cylinder-piston devices.
  • the hydraulic fluids tested were: The following Table 7 gives the viscosity of the oils after a prolonged time in operation. Table 7 Time, hours Viscosity, mm2/s / 40 °C Fluid 1 2 3 0 34 33.2 44.6 300 36.8 33.2 38.1 600 39.5 33.5 35.2 900 44.3 33.9 34.3 1200 51.8 34.1 34.2 1500 55.6 34.3 34.2
  • the efficiency tests were conducted using a fluid pressure of 165 bar, and a temperature of 65°C.
  • test results of Table 8 indicate that the efficiency of the system containing the vegetable oil based fluid decreased slower than that of the mineral oil based fluid.
  • hydraulic fluid according to the invention may also comprise other constituents such as:
  • From the base composition according to the invention can be made hydraulic fluids for different purposes by adjusting its viscosity.
  • Table 12 gives one example of adjusting possibilities.
  • Table 12 From a base composition according to the invention was made hydraulic fluids for different viscosity classes (ASTM D 2422) Oil comp. % by weight visc. mm2/s class 1.

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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)
  • Fluid-Pressure Circuits (AREA)

Claims (6)

  1. Basismischung für Hydraulikflüssigkeiten, bestehend aus:
    - einem oder mehreren Triglyceriden, die Ester von geradkettigen C₁₀ bis C₂₂ fettigen Säuren und Glycerol sind, wobei dieses Triglycerid eine Jodzahl von mindestens 50 und höchstens 128 hat sowie
    - einen oder mehrere Oxidationsschutzadditive,
    - dadurch gekennzeichnet,
    - daß der Anteil des Oxidationsschutzadditivs mindestens 1,5 Prozent Gewichtsanteil des Gemischs ausmacht,
    - daß der Anteil des Oxidationsschutzadditivs eine oder mehrere Verbindungen aus den folgenden Gruppen enthält:
    - (I) verhinderte Phenoplaste und aromatische Amine,
    - und dadurch, daß mindestens zu Oxidationsschutzanteilen von 1,5 bis 2,0 % der Oxidationsschutzanteil ein oder meherere weitere Oxidationschutzmittel enthält, die aus einer oder beiden der flgenden Gruppen stammen:
    - (II) Metallsalze von Dithiosäuren, Phosphiten und Sulfiden;
    - (III) Amiden, nicht-aromatischen Aminen, Hydraziden und Triazolen.
  2. Basismischung für Hydraulikflüssigkeiten nach Anspruch 1, dadurch gekennzeichnet, daß der Anteil des Oxidationsschutzadditivs 1,5 bis 4,5 Prozent Gewichtsanteil des Gemischs ausmacht.
  3. Basismischung für Hydraulikflüssigkeiten nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, daß die Oxidationsschutzmittel aus Gruppe I 1,0 bis 3,0 Prozent Gewichtsanteil des Gemischs ausmachen.
  4. Basismischung für Hydraulikflüssigkeiten nach Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß das Triglycerid von der Art der Ölsäure-Linolsäure ist und höchstens 20 % Gewichtsanteil gesättigte Fettsäuren enthält, berechnet nach der Menge mit Glycerol veresterter Fettsäuren.
  5. Basismischung für Hydraulikflüssigkeiten nach Anspruch 4, dadurch gekennzeichnet, daß das Triglycerid aus Rapssamenöl besteht.
  6. Hydraulikflüssigkeit hergestellt aus einer Basismischung nach einem der vorstehenden Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Flüssigkeit zusätzlich mindestens einen Bestandteil enthält, der aus einer der folgenden Gruppen stammt: Grenzschmieradditive, Korrosionsverhinderer, VI-Verbesserer, Stockpunkterniedriger, Schaumzerfallsmittel, Demulgatoren.
EP88901051A 1987-01-28 1988-01-27 Hydraulische flüssigkeiten Expired - Lifetime EP0349534B1 (de)

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AT88901051T ATE83003T1 (de) 1987-01-28 1988-01-27 Hydraulische fluessigkeiten.

Applications Claiming Priority (2)

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US7627 1987-01-28
US07/007,627 US4783274A (en) 1983-02-11 1987-01-28 Hydraulic fluids

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EP0349534B1 true EP0349534B1 (de) 1992-12-02

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WO (1) WO1988005808A1 (de)

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ATE210175T1 (de) * 1991-08-09 2001-12-15 Lubrizol Corp Die verwendung von funktionellen flüssigkeiten mit triglyceriden und verschiedenen additiven als traktorschmieröle
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DK536188D0 (da) 1988-09-27
DE3876432D1 (de) 1993-01-14
DE3876432T2 (de) 1993-04-08
ATE83003T1 (de) 1992-12-15
WO1988005808A1 (en) 1988-08-11
AU1227388A (en) 1988-08-24
NO884237L (no) 1988-09-23
NO174060B (no) 1993-11-29
EP0349534A1 (de) 1990-01-10
NO884237D0 (no) 1988-09-23
DK536188A (da) 1988-09-27

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