EP3344734B1 - Lubricating mixture having glycerides - Google Patents

Lubricating mixture having glycerides Download PDF

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Publication number
EP3344734B1
EP3344734B1 EP16754476.6A EP16754476A EP3344734B1 EP 3344734 B1 EP3344734 B1 EP 3344734B1 EP 16754476 A EP16754476 A EP 16754476A EP 3344734 B1 EP3344734 B1 EP 3344734B1
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EP
European Patent Office
Prior art keywords
lubricating
mixture
glycerides
mixture according
mass fraction
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EP16754476.6A
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German (de)
French (fr)
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EP3344734A1 (en
Inventor
Peter Eisner
Thomas HERFELLNER
Andreas STÄBLER
Andreas Malberg
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32Esters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/281Esters of (cyclo)aliphatic monocarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/281Esters of (cyclo)aliphatic monocarboxylic acids
    • C10M2207/2815Esters of (cyclo)aliphatic monocarboxylic acids used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/287Partial esters
    • C10M2207/289Partial esters containing free hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/287Partial esters
    • C10M2207/289Partial esters containing free hydroxy groups
    • C10M2207/2895Partial esters containing free hydroxy groups used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40Fatty vegetable or animal oils
    • C10M2207/401Fatty vegetable or animal oils used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines

Definitions

  • the invention relates to a lubricating mixture which contains at least a proportion by mass of ⁇ 50% of glycerides of natural origin and a proportion of fatty acid alkyl esters and is particularly suitable for use in gears, electric motors or internal combustion engines.
  • lubricating liquids made from mineral oils, synthetic oils, vegetable oils or water, to which additives are usually added to improve the lubricating properties.
  • the task of the liquids is to generate a liquid film on the surface of components, thereby reducing friction losses between components that move against one another and minimizing wear.
  • natural raw materials are increasingly being used, which are often modified before being used as a lubricant (e.g. cellulose in the DE202009018507U1 ) and/or additives can be added.
  • Very high demands are placed on gear or engine oils in the lubricant sector in particular, since they should be chemically stable over a long period of time and are often exposed to high temperature fluctuations, which can affect the lubricating properties. Those high In many cases, requirements cannot be met by either synthetic or natural fats and oils.
  • viscosity index describes the temperature dependency of the kinematic viscosity of a lubricating oil. Oils with a low viscosity index show a greater change in viscosity with temperature than those with a high viscosity index. The latter are particularly desirable in lubricating applications.
  • Vegetable oils are an environmentally friendly alternative to products based on Petroleum based and based on renewable natural resources.
  • the use of vegetable oils as lubricants is limited by the property of some oils to solidify at low temperatures, due to a low viscosity index and because of the often lacking oxidative stability.
  • EP2350240A1 describes the use of vegetable oil with a high proportion of unsaturated fatty acids as gear oil or hydraulic fluid to improve the viscosity properties, the oil having a natural viscosity index (VI) of greater than or equal to 200 and a proportion of monounsaturated fatty acids of greater than 80%, a proportion twice unsaturated fatty acids of a maximum of 1-10% and a proportion of triunsaturated fatty acids of less than 1%.
  • a part of the vegetable oil can be used in the form of an unsaturated ester of the vegetable oil.
  • gear oils or hydraulic oils should be thin at low temperatures ( ⁇ 40°C) in order to be easier to pump, which is achieved by using vegetable oil such as rapeseed or sunflower oil with a high proportion of unsaturated fatty acids.
  • vegetable oil such as rapeseed or sunflower oil with a high proportion of unsaturated fatty acids.
  • the occurrence of a solid phase in the lubricating medium should be avoided according to the description.
  • Industrial oils should also exhibit high oxidative stability, which is generally related to the unsaturated fatty acids present in vegetable fatty acid alkyl chains.
  • the reaction of a vegetable oil with oxygen can lead to polymerization and crosslinking of the fatty acid alkyl chains and reduced oxidative stability.
  • Oils based on saturated hydrocarbons contain little or no unsaturated fatty acids and therefore have high oxidative stability.
  • DE60031505T2 describes a method for increasing the oxidative stability and improving the lubricating properties of a vegetable oil.
  • the vegetable oil is transesterified with a short-chain fatty acid ester and volatile components are separated after transesterification.
  • the vegetable oil can have a monounsaturated fatty acid content of at least 50% and can be selected, for example, from the group consisting of corn oil, rapeseed oil, soybean oil and sunflower oil.
  • the short chain fatty acid ester can be saturated and is four to 10 carbon atoms in length. This type of transesterification with different synthetic components is an expensive process and therefore has economic disadvantages.
  • Hydraulic oils based on mineral oil are known. These usually have a viscosity index of around 100. Additives are added to the mineral oil to ensure protection against corrosion and increase its resistance to aging.
  • viscosity index improvers are added. These are long-chain synthetic hydrocarbon compounds that are homogeneously distributed in cold oils and only slightly increase viscosity, but unfold at higher operating temperatures and increase in volume when dissolved in the oil. This thickens the oil and increases the viscosity index.
  • Such viscosity index improvers have the disadvantage, however, that the long-chain hydrocarbon compounds are broken down into smaller fragments under stress, as a result of which their original thickening effect is sometimes significantly altered. This effect is also known as permanent shear loss.
  • a lubricant based on fatty acid esters is described.
  • vegetable or animal fats are transesterified with monohydric alcohols, which have a chain length of between three and six carbon atoms.
  • glycerol is a by-product and is separated because it is insoluble in the fatty acid alkyl esters.
  • the Indian DE20305164U1 The lubricant described therefore contains no glycerides.
  • the lubricant consists of natural or synthetic triglycerides, one organic solvent and an antioxidant. Lactic acid ethyl ester (ethyl lactate), mineral oils and mixtures of both are suggested as solvents.
  • fatty acid methyl esters from soybean oil can optionally be added.
  • partial glycerides is not described. Since this lubricant is explicitly a penetrating oil, i.e. a medium with low viscosity and good penetration properties, a solids content is undesirable.
  • a lubricant consisting of palm oil and palm oil by-products.
  • Base fluid for this lubricating medium is palm olein, a liquid fraction of palm oil.
  • the iodine value of the palm olein used must be at least 56 in order to avoid the formation of fat crystals.
  • Other lubricant components are tocopherols from palm oil and fatty acid alkyl esters. The latter are synthesized from free fatty acids and hindered polyhydric alcohols. Neopentyl glycol, trimethylolpropane, pentaerythritol and dipentylerythritol are used as hindered alcohols. Thus, the resulting esters are not mono- and diglycerides. Due to the use of palm olein, the lubricant has no solid fraction.
  • WO 2010/118891 A1 describes a lubricating fluid and a method for its production. This is a mixture of mono-, di- and triacylglycerides, free fatty acids and fatty acid alkyl esters. This lubricant is explicitly a liquid. A solid content is not described.
  • the object of the present invention is to provide a lubricating medium with a high viscosity index, which can be used advantageously in gears, engines or other units to be lubricated, which can be produced inexpensively and can also consist entirely of renewable raw materials and thus does not present a high hazard potential if released into the environment.
  • the proposed mixture contains at least a mass fraction of ⁇ 50% natural glycerides Origin and a proportion of fatty acid alkyl esters with 1 to 4 carbon atoms in the alkyl group.
  • the glycerides are at least partly mono- and/or diglycerides, which form a mass fraction of ⁇ 10% in the mixture, and the mixture has a temperature range of > 10°C to at least 15°C, preferably to at least 20°C, a liquid phase with a solids content of ⁇ 1% by volume, which is formed from a proportion of the glycerides and/or the fatty acid alkyl esters.
  • the occurrence of the solid phase is characterized by the fact that the light transmission of the mixture is 10% to 90% lower than that of a completely liquid reference of the same composition at a correspondingly higher temperature.
  • the proportion of solids is preferably selected in such a way that the light transmission is 10% to 50%, ideally 10% to 20%, lower than that of the reference.
  • Methods for determining the light transmission are, for example, photometers or measuring devices that work according to the TURBISCAN ® principle.
  • the lubricating mixture according to the invention also referred to below as lubricant, thus fulfills the lubricating effect of two systems at once by combining the properties of lubricating oils (liquid phase) and lubricating greases (solid phase).
  • the mixture has a predominantly liquid consistency, so the volume fraction of liquid in the mixture is >40%, advantageously >80%, especially advantageously >90%.
  • the mixture can also be formed or produced entirely from renewable raw materials, in particular vegetable oils and fats.
  • the proportion of solids does not impair the properties of the lubricant, or only insignificantly, but leads to better chemical resistance of the lubricant than when using pure vegetable oils.
  • the lubricant can therefore be used in technical lubrication applications without any problems.
  • the size of the solid particles that form the solids content of the proposed mixture have an edge length in the range between 4 ⁇ m and 5 mm. They show a good lubricating effect, since they get into the space between the gear wheels in transmissions, for example, and can develop an advantageous lubricating effect there. This significantly reduces the wear between the metal surfaces compared to other non-lubricating solid particles in the lubricant and prevents abrasive components from penetrating between the gears or into gaps and developing their abrasive effect there.
  • the lubricant according to the invention consists predominantly of triglycerides and partial glycerides natural oils and fats and fatty acid alkyl esters with 1 to 4 carbon atoms in the alkyl group.
  • Particularly advantageous properties result when the mass fraction of the triglycerides in the lubricant is >30%, preferably >40%, ideally >50%.
  • the mass fraction of fatty acid alkyl esters is >10%, ideally >15%.
  • Particularly advantageous properties result when the proportion of diglycerides is >10%, ideally >15%, and that of monoglycerides is >5%.
  • the lubricant contains a proportion of unbound monohydric or polyhydric alcohol. This proportion is preferably between 0.1 and 4%, ideally between 0.1 and 2%.
  • the solids content will advantageously consist of components that are contained in the natural raw material (fat, oil) from which the glycerides for the mixture are obtained or that are obtained from this raw material.
  • the lubricant contains, in addition to the above-mentioned solids based on fats and oils and/or fatty acid alkyl esters, other organic or inorganic components which do not come from the natural raw material and which remain active even at high temperatures of at least 90°C are always fixed.
  • These particles preferably have a diameter of 0.1 to 1.5 ⁇ m, ideally 0.2 to 1 ⁇ m, and surprisingly improve the running-in properties of gears.
  • the proportion of this solid fraction in the lubricant is preferably between 0.1 and 3%, ideally between 0.15 and 2%.
  • foreign particles are non-oxidative metals and metal compounds such as iron or aluminum oxides, inert silicon-based compounds such as silicon oxide, and synthetic and natural polymers such as polystyrene, polyethylene, polyethylene terephthalate, polypropylene, polycarbonate, polyhydroxyalkanoates, polylactic acid, proteins, starches, Celluloses and their derivatives.
  • the composition of the solid particles from the glycerides differs from the composition of the liquid phase.
  • the monoglyceride content in the solid phase is ideally higher by a factor of >1.5, advantageously by a factor of >2, particularly advantageously by a factor of >5, than in the liquid phase.
  • fats containing a high proportion of saturated fatty acids being used at least in part as the raw material.
  • These can be vegetable fats such as palm oil, palm kernel oil or coconut fat or other fats that contain a high proportion of saturated fatty acids >30% by mass, particularly advantageously >80% by mass and are still solid at a temperature of 20°C.
  • a very oxidation-stable lubricant is obtained, which is largely liquid at a temperature of 20°C, so that pumping is possible and a surprisingly high lubricating effect is achieved . This is not the case with untreated vegetable fat.
  • the use of unrefined or only partially refined vegetable oils and fats as raw material is particularly advantageous.
  • the lubricant obtained from this has particularly good oxidation stability.
  • the lubricant has particularly advantageous properties if only the hydratable phospholipids are removed in the refining process or if fat components, which are usually separated off in vegetable oil refining, are not removed or added back.
  • examples of such compounds are carotenoids, non-hydratable lecithins, phenols and phenolic acids, tocopherols, phorbol esters, etc.
  • the mixture of triglycerides and partial glycerides and fatty acid esters according to the invention has a higher viscosity index of >200 compared to the untreated oils and fats.
  • oils that are liquid at this temperature and contain long-chain unsaturated fatty acids in addition to the fat components that are still solid at a temperature of 20°.
  • This can be achieved by adding oils that a contain a high content of unsaturated fatty acids, such as rapeseed or sunflower oil, with the proportion of these oils being selected to be less than 50% by mass, advantageously less than 10% by mass, in order to maintain oxidation stability. It is possible to add the low-viscosity oil before the conversion of the triglycerides or after the conversion.
  • Such mixtures can also be fractions of vegetable oils in the form of pumpable residues which are separated off as minor components during the winterization of oils. At a temperature of 20°C, these contain both liquid and solid components, which have a surprisingly good lubricating effect. Further configurations can be mixtures of these winterization residues with fats or oils, which are optionally also subjected to a partial transesterification.
  • antioxidant substances to further increase the oxidation stability.
  • plant ingredients are used to advantage, which are also contained in natural fats and are also soluble there. These can be carotenes, tocopherols, tocotrienols and other oil-soluble substances with an antioxidant effect.
  • antioxidant plant substances between 0.1 and 10% by mass of antioxidant plant substances should be used for technical applications.
  • the lubricant has particularly advantageous properties if it has a low proportion of inorganic particles ( ⁇ 1.5 ⁇ m). These serve as nuclei for fat crystallization and accelerate the formation of the solid phase.
  • composition and application of the proposed lubricant are shown below using an example.

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  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Lubricants (AREA)

Description

Technisches AnwendungsgebietTechnical field of application

Die Erfindung betrifft eine schmierend wirkende Mischung, die wenigstens einen Massenanteil von ≥ 50% an Glyceriden natürlichen Ursprungs und einen Anteil an Fettsäurealkylester enthält und sich besonders für die Anwendung in Getrieben, Elektromotoren oder Verbrennungsmotoren eignet.The invention relates to a lubricating mixture which contains at least a proportion by mass of ≧50% of glycerides of natural origin and a proportion of fatty acid alkyl esters and is particularly suitable for use in gears, electric motors or internal combustion engines.

Stand der TechnikState of the art

Aus der industriellen Anwendung bekannt sind schmierend wirkende Flüssigkeiten aus Mineralölen, synthetischen Ölen, Pflanzenölen oder Wasser, denen meist Additive zur Verbesserung der Schmiereigenschaften zugesetzt sind. Die Aufgabe der Flüssigkeiten besteht darin, auf der Oberfläche von Bauteilen einen Flüssigkeitsfilm zu erzeugen, dadurch Reibungsverluste zwischen gegeneinander bewegten Bauteilen zu reduzieren und den Verschleiß zu minimieren. Neben etablierten Rohstoffen wie z.B. Erdöl kommen zunehmend natürliche Rohstoffe zur Anwendung, die vielfach vor einem Einsatz als Schmierstoff modifiziert werden (z.B. Cellulose bei der DE202009018507U1 ) und/oder additiviert werden können. Besonders an Getriebe- oder Motorenöle werden im Schmierstoffbereich sehr hohe Anforderungen gestellt, da sie über lange Zeit chemisch stabil sein sollen und in vielen Fällen hohen Temperaturschwankungen ausgesetzt sind, die sich auf die Schmiereigenschaften auswirken können. Diese hohen Anforderungen können vielfach weder von synthetischen noch von natürlichen Fetten und Ölen erfüllt werden.Known from industrial use are lubricating liquids made from mineral oils, synthetic oils, vegetable oils or water, to which additives are usually added to improve the lubricating properties. The task of the liquids is to generate a liquid film on the surface of components, thereby reducing friction losses between components that move against one another and minimizing wear. In addition to established raw materials such as crude oil, natural raw materials are increasingly being used, which are often modified before being used as a lubricant (e.g. cellulose in the DE202009018507U1 ) and/or additives can be added. Very high demands are placed on gear or engine oils in the lubricant sector in particular, since they should be chemically stable over a long period of time and are often exposed to high temperature fluctuations, which can affect the lubricating properties. Those high In many cases, requirements cannot be met by either synthetic or natural fats and oils.

Zur Bewertung der Temperaturabhängigkeit von Schmierstoffen wurde der sog. Viskositätsindex definiert, der die Temperaturabhängigkeit der kinematischen Viskosität eines Schmieröls beschreibt. Öle mit einem niedrigen Viskositätsindex zeigen eine stärkere temperaturabhängige Viskositätsänderung als solche mit einem hohen Viskositätsindex. Letztere sind in den Schmierstoffanwendungen besonders erwünscht.To evaluate the temperature dependency of lubricants, the so-called viscosity index was defined, which describes the temperature dependency of the kinematic viscosity of a lubricating oil. Oils with a low viscosity index show a greater change in viscosity with temperature than those with a high viscosity index. The latter are particularly desirable in lubricating applications.

Auf die Nachteile der erhöhten Viskosität bei niedrigen Temperaturen wird beispielsweise in der DE 102010009030A1 genauer eingegangen. Danach weisen Getriebeöle bei niedriger Umgebungstemperatur im Vergleich zur Betriebstemperatur vielfach eine deutlich erhöhte Viskosität auf, die nach Inbetriebnahme des Kraftfahrzeugs allein durch die im Getriebe erzeugte Reibungswärme nur langsam abnimmt, was Leistungsverluste zur Folge hat. Zur Vermeidung dieses Nachteils beschreibt DE 102010009030A1 ein Verfahren, in dem das Getriebe eines Kraftfahrzeugs vorgewärmt wird, um die Viskosität des Schmierstoffs während der Anwendung weitgehend konstant zu halten. Dieser Lösungsansatz ist jedoch mit hohen Kosten verbunden.The disadvantages of increased viscosity at low temperatures are discussed, for example, in DE 102010009030A1 received in more detail. According to this, transmission oils often have a significantly higher viscosity at low ambient temperatures compared to the operating temperature, which only slowly decreases after the vehicle has been put into operation solely due to the frictional heat generated in the transmission, which results in power losses. To avoid this disadvantage describes DE 102010009030A1 a process in which the transmission of a motor vehicle is preheated in order to keep the viscosity of the lubricant largely constant during use. However, this approach is associated with high costs.

Bei technischen Anwendungen in Getrieben oder Motoren werden als Basismedium in der Regel auf Erdöl basierende Kohlenwasserstoffe eingesetzt, die die Umwelt schädigen können und deren Verwendung Gesundheitsrisiken mit sich bringt. Pflanzenöle sind eine umweltfreundliche Alternative zu Produkten auf Erdölbasis und basieren auf erneuerbaren natürlichen Ressourcen. Der Verwendung von Pflanzenölen als Schmierstoff sind jedoch durch die Eigenschaft einiger Öle, sich bei niedrigen Temperaturen zu verfestigen, aufgrund eines niedrigen Viskositätsindex und wegen der oft fehlenden oxidativen Stabilität Grenzen gesetzt.In technical applications in gears or engines, petroleum-based hydrocarbons are usually used as the base medium, which can damage the environment and the use of which entails health risks. Vegetable oils are an environmentally friendly alternative to products based on Petroleum based and based on renewable natural resources. However, the use of vegetable oils as lubricants is limited by the property of some oils to solidify at low temperatures, due to a low viscosity index and because of the often lacking oxidative stability.

In der EP2350240A1 wird zur Verbesserung der Viskositätseigenschaften die Verwendung von Pflanzenöl mit einem hohen Anteil ungesättigter Fettsäuren als Getriebeöl oder Hydraulikflüssigkeit beschrieben, wobei das Öl einen natürlichen Viskositätsindex (VI) von grösser oder gleich 200 aufweist und einen Anteil einfach ungesättigter Fettsäuren von größer 80%, einen Anteil zweifach ungesättigter Fettsäuren von maximal 1-10% und einen Anteil an dreifach ungesättigter Fettsäure von kleiner 1% enthält. Dabei kann ein Teil des Pflanzenöls in Form eines ungesättigten Esters des Pflanzenöls eingesetzt werden. In der Beschreibung wird darauf verwiesen, dass Getriebeöle oder Hydrauliköle bei niedrigen Temperaturen (<40°C) dünnflüssig sein sollten um besser pumpbar zu sein, was durch den Einsatz von Pflanzenöl wie Raps- oder Sonnenblumenöl mit einem hohen Anteil an ungesättigten Fettsäuren erreicht wird. Das Auftreten einer festen Phase im schmierenden Medium sollte entsprechend der Beschreibung unbedingt vermieden werden.In the EP2350240A1 describes the use of vegetable oil with a high proportion of unsaturated fatty acids as gear oil or hydraulic fluid to improve the viscosity properties, the oil having a natural viscosity index (VI) of greater than or equal to 200 and a proportion of monounsaturated fatty acids of greater than 80%, a proportion twice unsaturated fatty acids of a maximum of 1-10% and a proportion of triunsaturated fatty acids of less than 1%. A part of the vegetable oil can be used in the form of an unsaturated ester of the vegetable oil. The description refers to the fact that gear oils or hydraulic oils should be thin at low temperatures (<40°C) in order to be easier to pump, which is achieved by using vegetable oil such as rapeseed or sunflower oil with a high proportion of unsaturated fatty acids. The occurrence of a solid phase in the lubricating medium should be avoided according to the description.

Technische Öle sollten auch eine hohe oxidative Stabilität aufweisen, die im Allgemeinen mit dem in den in pflanzlichen Fettsäurealkylketten vorliegenden ungesättigten Fettsäuren zusammenhängt. Die Reaktion eines Pflanzenöls mit Sauerstoff kann zur Polymerisation und Vernetzung der Fettsäurealkylketten und verringerter oxidativer Stabilität führen. Auf gesättigten Kohlenwasserstoffen basierende Öle weisen keine oder nur geringe Anteile an ungesättigten Fettsäuren auf und haben daher eine hohe oxidative Stabilität. In der DE60031505T2 ist ein Verfahren zur Steigerung der oxidativen Stabilität und zur Verbesserung der Schmiereigenschaften eines Pflanzenöls beschrieben. Dabei wird das Pflanzenöl mit einem kurzkettigen Fettsäureester umgeestert und flüchtige Komponenten nach der Umesterung abgetrennt. Das Pflanzenöl kann einen Gehalt an einfach ungesättigten Fettsäuren von mindestens 50% aufweisen und beispielsweise aus der Gruppe ausgewählt sein, welche aus Maisöl, Rapsöl, Sojaöl und Sonnenblumenöl besteht. Der kurzkettige Fettsäureester kann gesättigt sein und ist vier bis 10 Kohlenstoffatome lang. Diese Art der Umesterung mit unterschiedlichen synthetischen Bestandteilen ist ein teurer Prozess und bringt damit wirtschaftliche Nachteile mit sich.Industrial oils should also exhibit high oxidative stability, which is generally related to the unsaturated fatty acids present in vegetable fatty acid alkyl chains. The reaction of a vegetable oil with oxygen can lead to polymerization and crosslinking of the fatty acid alkyl chains and reduced oxidative stability. Oils based on saturated hydrocarbons contain little or no unsaturated fatty acids and therefore have high oxidative stability. In the DE60031505T2 describes a method for increasing the oxidative stability and improving the lubricating properties of a vegetable oil. The vegetable oil is transesterified with a short-chain fatty acid ester and volatile components are separated after transesterification. The vegetable oil can have a monounsaturated fatty acid content of at least 50% and can be selected, for example, from the group consisting of corn oil, rapeseed oil, soybean oil and sunflower oil. The short chain fatty acid ester can be saturated and is four to 10 carbon atoms in length. This type of transesterification with different synthetic components is an expensive process and therefore has economic disadvantages.

Bekannt sind Hydrauliköle auf Mineralölbasis. Diese weisen in der Regel einen Viskositätsindex von ca. 100 auf. Additive werden dem Mineralöl zugesetzt, um einen Korrosionsschutz zu gewährleisten und seine Alterungsbeständigkeit zu erhöhen. Zusätzlich werden Viskositätsindex-Verbesserer zugesetzt. Darunter sind langkettige synthetische Kohlenwasserstoffverbindungen zu verstehen, die in kalten Ölen homogen verteilt vorliegen und nur wenig viskositätserhöhend wirken, sich aber bei höheren Betriebstemperaturen auffalten und gelöst im Öl ihr Volumen vergrößern. Das Öl dickt dadurch ein und der Viskositätsindex erhöht sich. Solche Viskositätsindex-Verbesserer haben allerdings den Nachteil, dass die langkettigen Kohlenwasserstoffverbindungen unter Belastung in kleinere Bruchstücke gespalten werden, wodurch sich ihre ursprüngliche verdickende Wirkung teilweise deutlich ändert. Dieser Effekt ist auch als permanenter Scherverlust bekannt.Hydraulic oils based on mineral oil are known. These usually have a viscosity index of around 100. Additives are added to the mineral oil to ensure protection against corrosion and increase its resistance to aging. In addition, viscosity index improvers are added. These are long-chain synthetic hydrocarbon compounds that are homogeneously distributed in cold oils and only slightly increase viscosity, but unfold at higher operating temperatures and increase in volume when dissolved in the oil. This thickens the oil and increases the viscosity index. Such viscosity index improvers have the disadvantage, however, that the long-chain hydrocarbon compounds are broken down into smaller fragments under stress, as a result of which their original thickening effect is sometimes significantly altered. This effect is also known as permanent shear loss.

In der US4783274A wird ein Hydraulikmedium beschrieben, welches auf Triglyceriden aus Fettsäuren basiert. Die in dem diesem Schmiermedium verwendeten Triglyceride müssen eine Jodzahl zwischen 50 und 100 aufweisen. Dies umfasst nichttrocknende und halbtrocknende Triglyceride wie Erdnuss-, Oliven-, Sonnenblumen-, Mais- und Rapsöl. Derartige Öle weisen einen Cloudpunkt von ca. 5°C im Fall von Olivenöl sogar von -5°C auf. Das in der US4783274A beschriebene Pflanzenöl-basierte Schmiermedium weist somit bei Temperaturen größer 10°C keinen Feststoffanteil auf.In the US4783274A describes a hydraulic medium which is based on triglycerides from fatty acids. The triglycerides used in this lubricating medium must have an iodine number between 50 and 100. This includes non-drying and semi-drying triglycerides such as peanut, olive, sunflower, corn, and canola oils. Such oils have a cloud point of around 5°C, in the case of olive oil even -5°C. That in the US4783274A The vegetable oil-based lubricating medium described thus has no solid content at temperatures above 10°C.

In der DE20305164U1 wird ein Schmierstoff auf Basis von Fettsäureestern beschrieben. Hierfür werden pflanzliche oder tierische Fette mit einwertigen Alkoholen, die eine Kettenlänge zwischen drei und sechs C-Atomen aufweisen, umgeestert. Bei diesem Umesterungsprozess entsteht Glycerin als Nebenprodukt und wird abgetrennt, da es in den Fettsäurealkylestern unlöslich ist. Der in der DE20305164U1 beschriebene Schmierstoff enthält somit keine Glyceride.In the DE20305164U1 a lubricant based on fatty acid esters is described. For this purpose, vegetable or animal fats are transesterified with monohydric alcohols, which have a chain length of between three and six carbon atoms. In this transesterification process, glycerol is a by-product and is separated because it is insoluble in the fatty acid alkyl esters. The Indian DE20305164U1 The lubricant described therefore contains no glycerides.

In der US2003040444A1 wird ein bioabbaubares Kriechöl mit antikorrosiven Eigenschaften beschrieben. Der Schmierstoff besteht aus natürlichen oder synthetischen Triglyceriden, einem organischen Lösungsmittel sowie einem Antioxidans. Als Lösemittel werden Milchsäureethylester (Ethyllactat), Mineralöle sowie Mischungen aus beidem vorgeschlagen. Um das Eindringverhalten des Schmierstoffes zu verbessern, können optional Fettsäuremethylester aus Sojaöl zugesetzt werden. Der Einsatz von Partialglyceriden wird nicht beschrieben. Da es sich bei diesem Schmierstoff explizit um ein Kriechöl, also um ein Medium mit niedriger Viskosität und gutem Eindringverhalten handelt, ist ein Feststoffanteil unerwünscht.In the US2003040444A1 a biodegradable penetrating oil with anti-corrosive properties is described. The lubricant consists of natural or synthetic triglycerides, one organic solvent and an antioxidant. Lactic acid ethyl ester (ethyl lactate), mineral oils and mixtures of both are suggested as solvents. In order to improve the penetration behavior of the lubricant, fatty acid methyl esters from soybean oil can optionally be added. The use of partial glycerides is not described. Since this lubricant is explicitly a penetrating oil, i.e. a medium with low viscosity and good penetration properties, a solids content is undesirable.

In der US2005112267A1 wird ein Schmierstoff bestehend aus Palmöl und Palmölnebenprodukten beschrieben. Grundfluid für dieses Schmiermedium ist Palmolein, eine flüssige Teilfraktion von Palmöl. Die Jodzahl des verwendeten Palmoleins muss laut dieser Schrift mindestens 56 betragen, um die Bildung von Fettkristallen zu vermeiden. Weitere Schmierstoffbestandteile sind Tocopherole aus Palmöl und Fettsäurealkylester. Letztere werden aus freien Fettsäuren und gehinderten mehrwertigen Alkoholen synthetisiert. Als gehinderte Alkohole werden Neopentylglykol, Trimethylolpropan, Pentaerythrit und Dipentylerythritol eingesetzt. Somit handelt es sich bei den entstehenden Estern nicht um Mono- und Diglyceride. Aufgrund der Verwendung von Palmolein weist der Schmierstoff keine Feststofffraktion auf.In the US2005112267A1 describes a lubricant consisting of palm oil and palm oil by-products. Base fluid for this lubricating medium is palm olein, a liquid fraction of palm oil. According to this document, the iodine value of the palm olein used must be at least 56 in order to avoid the formation of fat crystals. Other lubricant components are tocopherols from palm oil and fatty acid alkyl esters. The latter are synthesized from free fatty acids and hindered polyhydric alcohols. Neopentyl glycol, trimethylolpropane, pentaerythritol and dipentylerythritol are used as hindered alcohols. Thus, the resulting esters are not mono- and diglycerides. Due to the use of palm olein, the lubricant has no solid fraction.

In der US2011039742A1 wird ein aus Pflanzenöl gewonnenes Schmierstoffadditiv beschrieben. Für die Herstellung werden ungesättigte Pflanzenöle durch Hitzeeinwirkung quervernetzt. Eine anschließende Umesterung der nichtpolymerisierten Öle erlaubt deren Abtrennung. Somit besteht das beschriebene Additiv aus über kovalente Bindungen verknüpften Poly-Triglyceriden.In the US2011039742A1 a lubricant additive obtained from vegetable oil is described. For the production, unsaturated vegetable oils are cross-linked by the action of heat. Subsequent transesterification of the unpolymerized oils allows them Separation. Thus, the additive described consists of poly-triglycerides linked via covalent bonds.

In der WO 2010/118891 A1 werden eine Schmierflüssigkeit sowie ein Verfahren zu deren Herstellung beschrieben. Dabei handelt es sich um eine Mischung aus Mono-, Di- und Triacylglyceriden, freien Fettsäuren sowie Fettsäurealkylestern. Bei dem diesem Schmierstoff handelt es sich explizit um eine Flüssigkeit. Ein Feststoffanteil wird nicht beschrieben.In the WO 2010/118891 A1 describes a lubricating fluid and a method for its production. This is a mixture of mono-, di- and triacylglycerides, free fatty acids and fatty acid alkyl esters. This lubricant is explicitly a liquid. A solid content is not described.

Die Aufgabe der vorliegenden Erfindung besteht darin, ein schmierend wirkendes Medium mit hohem Viskositätsindex bereit zu stellen, das vorteilhaft in Getrieben, Motoren oder anderen zu schmierenden Aggregaten zu Einsatz kommen kann, das sich kostengünstig herstellen lässt und auch vollständig aus nachwachsenden Rohstoffen bestehen kann und somit kein hohes Gefahrenpotenzial eröffnet, wenn es in die Umwelt gelangt.The object of the present invention is to provide a lubricating medium with a high viscosity index, which can be used advantageously in gears, engines or other units to be lubricated, which can be produced inexpensively and can also consist entirely of renewable raw materials and thus does not present a high hazard potential if released into the environment.

Darstellung der ErfindungPresentation of the invention

Gelöst wird die Aufgabe durch die schmierend wirkende Mischung nach Patentanspruch 1. Vorteilhafte Ausgestaltungen der Mischung sind Gegenstand der abhängigen Patentansprüche oder lassen sich der nachfolgenden Beschreibung sowie den Ausführungsbeispielen entnehmen.The object is achieved by the lubricating mixture according to patent claim 1. Advantageous configurations of the mixture are the subject matter of the dependent patent claims or can be found in the following description and the exemplary embodiments.

Die vorgeschlagene Mischung enthält wenigstens einen Massenanteil von ≥ 50% an Glyceriden natürlichen Ursprungs und einen Anteil an Fettsäurealkylester mit 1 bis 4 C-Atomen in der Alkylgruppe. Die Glyceride sind wenigstens zum Teil Mono- und/oder Diglyceride, die einen Massenanteil von ≥ 10% in der Mischung bilden, und die Mischung weist in einem Temperaturbereich von > 10°C bis wenigstens 15°C, vorzugsweise bis wenigstens 20°C, eine flüssige Phase mit einem Feststoffanteil von ≥ 1 Vol.% auf, der aus einem Anteil der Glyceride und/oder der Fettsäurealkylester gebildet ist.The proposed mixture contains at least a mass fraction of ≥ 50% natural glycerides Origin and a proportion of fatty acid alkyl esters with 1 to 4 carbon atoms in the alkyl group. The glycerides are at least partly mono- and/or diglycerides, which form a mass fraction of ≥ 10% in the mixture, and the mixture has a temperature range of > 10°C to at least 15°C, preferably to at least 20°C, a liquid phase with a solids content of ≥ 1% by volume, which is formed from a proportion of the glycerides and/or the fatty acid alkyl esters.

Das Auftreten der festen Phase (Feststoffanteil) ist dadurch gekennzeichnet, dass die Lichttransmission der Mischung um 10% bis 90% niedriger liegt, als die einer vollständig flüssigen Referenz der gleichen Zusammensetzung bei entsprechend höherer Temperatur. Der Feststoffanteil wird dabei vorzugsweise so gewählt, dass die Lichttransmission um 10% bis 50%, idealerweise um 10% bis 20%, niedriger liegt als die der Referenz. Methoden zur Bestimmung der Lichttransmission sind beispielsweise Photometer oder Messgeräte, die nach dem TURBISCAN®-Prinzip arbeiten.The occurrence of the solid phase (solids content) is characterized by the fact that the light transmission of the mixture is 10% to 90% lower than that of a completely liquid reference of the same composition at a correspondingly higher temperature. The proportion of solids is preferably selected in such a way that the light transmission is 10% to 50%, ideally 10% to 20%, lower than that of the reference. Methods for determining the light transmission are, for example, photometers or measuring devices that work according to the TURBISCAN ® principle.

Die erfindungsgemäße schmierend wirkende Mischung, im Folgenden auch als Schmierstoff bezeichnet, erfüllt somit die Schmierwirkung von zwei Systemen auf einmal, in dem die Eigenschaften von Schmierölen (flüssige Phase) und Schmierfetten (feste Phase) kombiniert werden. Die Mischung weist eine überwiegend flüssige Konsistenz auf, der Volumenanteil an Flüssigkeit in der Mischung beträgt also >40%, vorteilhaft >80%, besonders vorteilhaft >90%. Die Mischung kann dabei auch vollständig aus nachwachsenden Rohstoffen, insbesondere pflanzlichen Ölen und Fetten, gebildet sein bzw. hergestellt werden.The lubricating mixture according to the invention, also referred to below as lubricant, thus fulfills the lubricating effect of two systems at once by combining the properties of lubricating oils (liquid phase) and lubricating greases (solid phase). The mixture has a predominantly liquid consistency, so the volume fraction of liquid in the mixture is >40%, advantageously >80%, especially advantageously >90%. The mixture can also be formed or produced entirely from renewable raw materials, in particular vegetable oils and fats.

Überraschenderweise beeinträchtigt der Anteil an Feststoffen die Eigenschaften des Schmierstoffs nicht oder nur unwesentlich, führt aber zu einer verbesserten chemischen Beständigkeit des Schmierstoffs als beim Einsatz reiner Pflanzenöle. Der Schmierstoff kann daher problemlos in technischen Schmieranwendungen zum Einsatz kommen.Surprisingly, the proportion of solids does not impair the properties of the lubricant, or only insignificantly, but leads to better chemical resistance of the lubricant than when using pure vegetable oils. The lubricant can therefore be used in technical lubrication applications without any problems.

Die Größe der Feststoffpartikel, die den Feststoffanteil der vorgeschlagenen Mischung bilden, weisen eine Kantenlänge im Bereich zwischen 4 µm und 5 mm auf. Sie zeigen dabei eine gute Schmierwirkung, da sie zum Beispiel in Getrieben in den Platz zwischen den Zahnrädern gelangen und dort eine vorteilhaft schmierende Wirkung entfalten können. Dies reduziert den Verschleiß zwischen den Metalloberflächen im Vergleich zu anderen nicht schmierend wirkenden Feststoffpartikeln im Schmierstoff ganz erheblich und hindert abrasive Komponenten daran, zwischen die Zahnräder oder in Spalten einzudringen und dort ihre abrasive Wirkung zu entfalten.The size of the solid particles that form the solids content of the proposed mixture have an edge length in the range between 4 μm and 5 mm. They show a good lubricating effect, since they get into the space between the gear wheels in transmissions, for example, and can develop an advantageous lubricating effect there. This significantly reduces the wear between the metal surfaces compared to other non-lubricating solid particles in the lubricant and prevents abrasive components from penetrating between the gears or into gaps and developing their abrasive effect there.

Der erfindungsgemäße Schmierstoff besteht zu überwiegenden Anteilen aus Tri- und Partialglyceriden natürlicher Öle und Fette sowie Fettsäurealkylestern mit 1 bis 4 C-Atomen in der Alkylgruppe. Besonders vorteilhafte Eigenschaften ergeben sich, wenn der Massenanteil der Triglyceride im Schmierstoff >30%, vorzugsweise >40%, idealerweise >50% beträgt. In einer besonders vorteilhaften Ausgestaltung der Erfindung beträgt der Massenanteil an Fettsäurealkylestern >10%, idealerweise >15%. Besonders vorteilhafte Eigenschaften ergeben sich, wenn der Anteil an Diglyceriden >10% idealerweise >15%, der an Monoglyceriden >5% beträgt.The lubricant according to the invention consists predominantly of triglycerides and partial glycerides natural oils and fats and fatty acid alkyl esters with 1 to 4 carbon atoms in the alkyl group. Particularly advantageous properties result when the mass fraction of the triglycerides in the lubricant is >30%, preferably >40%, ideally >50%. In a particularly advantageous embodiment of the invention, the mass fraction of fatty acid alkyl esters is >10%, ideally >15%. Particularly advantageous properties result when the proportion of diglycerides is >10%, ideally >15%, and that of monoglycerides is >5%.

In einer Ausgestaltung der Erfindung enthält der Schmierstoff einen Anteil an ungebundenem ein- oder mehrwertigen Alkohol. Vorzugsweise liegt dieser Anteil zwischen 0,1 und 4%, idealerweise zwischen 0,1 und 2%.In one embodiment of the invention, the lubricant contains a proportion of unbound monohydric or polyhydric alcohol. This proportion is preferably between 0.1 and 4%, ideally between 0.1 and 2%.

Der Feststoffanteil wird vorteilhaft aus Komponenten bestehen, die im natürlichen Rohstoff (Fett, Öl), aus dem die Glyceride für die Mischung gewonnen werden, enthalten sind oder die aus diesem Rohstoff gewonnen werden. In einer besonders vorteilhaften Ausgestaltung der Erfindung enthält der Schmierstoff neben den o.g. Feststoffen auf Basis von Fetten und Ölen und/oder Fettsäurealkylester noch weitere organische oder anorganische Bestandteile, die nicht aus dem natürlichen Rohstoff stammen und die auch bei hohen Temperaturen von wenigstens 90°C noch immer fest sind. Diese Partikel weisen vorzugsweise einen Durchmesser von 0,1 bis 1,5 µm, idealerweise 0,2 bis 1 µm, auf und verbessern überraschenderweise die Einlaufeigenschaften von Getrieben. Der Anteil dieser Feststofffraktion am Schmierstoff beträgt vorzugsweise zwischen 0,1 und 3%, idealerweise zwischen 0,15 und 2%. Beispiele für derartige Fremdpartikel sind nichtoxidativ wirkende Metalle und Metallverbindungen wie Eisen- oder Aluminiumoxide, inerte Verbindungen auf Basis von Silizium, wie Siliziumoxid, sowie synthetische und natürliche Polymere wie Polystyrol, Polyethylen, Polyethylenterephtalat, Polypropylen, Polycarbonat, Polyhydroxyalkanoate, Polymilchsäure, Proteine, Stärken, Cellulosen sowie deren Derivate.The solids content will advantageously consist of components that are contained in the natural raw material (fat, oil) from which the glycerides for the mixture are obtained or that are obtained from this raw material. In a particularly advantageous embodiment of the invention, the lubricant contains, in addition to the above-mentioned solids based on fats and oils and/or fatty acid alkyl esters, other organic or inorganic components which do not come from the natural raw material and which remain active even at high temperatures of at least 90°C are always fixed. These particles preferably have a diameter of 0.1 to 1.5 μm, ideally 0.2 to 1 μm, and surprisingly improve the running-in properties of gears. The proportion of this solid fraction in the lubricant is preferably between 0.1 and 3%, ideally between 0.15 and 2%. Examples of such foreign particles are non-oxidative metals and metal compounds such as iron or aluminum oxides, inert silicon-based compounds such as silicon oxide, and synthetic and natural polymers such as polystyrene, polyethylene, polyethylene terephthalate, polypropylene, polycarbonate, polyhydroxyalkanoates, polylactic acid, proteins, starches, Celluloses and their derivatives.

Die Zusammensetzung der Feststoffpartikel aus den Glyceriden unterscheidet in einer vorteilhaften Ausführung der Erfindung von der Zusammensetzung der Flüssigphase. So ist der Monoglyceridanteil in der Feststoffphase idealerweise um einen Faktor >1,5, vorteilhaft um einen Faktor >2, besonders vorteilhaft um einen Faktor >5 höher als in der Flüssigphase.In an advantageous embodiment of the invention, the composition of the solid particles from the glycerides differs from the composition of the liquid phase. Thus, the monoglyceride content in the solid phase is ideally higher by a factor of >1.5, advantageously by a factor of >2, particularly advantageously by a factor of >5, than in the liquid phase.

Zur Herstellung der vorgeschlagenen Mischung bieten sich unterschiedliche Verfahren an, wobei als Rohstoff zumindest zu einem Teil Fette zum Einsatz kommen, die einen hohen Anteil gesättigter Fettsäuren enthalten. Diese können pflanzliche Fette wie Palmöl, Palmkernöl oder Kokosfett oder andere Fette sein, die einen hohen Anteil gesättigter Fettsäuren >30 Mass.-%, besonders vorteilhaft >80 Mass.-% enthalten und bei einer Temperatur von 20°C noch fest sind. Durch Umwandlung eines Teils der Triglyceride dieser Fette in Mono- und/oder Diglyceride wird ein sehr oxidationsstabiler Schmierstoff erhalten, der bei einer Temperatur von 20°C zu einem großen Anteil flüssig ist, so dass ein Pumpen möglich wird und eine überraschend hohe Schmierwirkung erzielt wird. Dies ist bei einem unbehandelten pflanzlichen Fett nicht gegeben.Various methods are available for producing the proposed mixture, with fats containing a high proportion of saturated fatty acids being used at least in part as the raw material. These can be vegetable fats such as palm oil, palm kernel oil or coconut fat or other fats that contain a high proportion of saturated fatty acids >30% by mass, particularly advantageously >80% by mass and are still solid at a temperature of 20°C. By converting some of the triglycerides of these fats into mono- and/or diglycerides, a very oxidation-stable lubricant is obtained, which is largely liquid at a temperature of 20°C, so that pumping is possible and a surprisingly high lubricating effect is achieved . This is not the case with untreated vegetable fat.

Die Verwendung unraffinierter bzw. nur teilweise raffinierter Pflanzenöle und -fette als Rohstoff ist besonders vorteilhaft. Der daraus gewonnene Schmierstoff weist eine besonders gute Oxidationsstabilität auf.The use of unrefined or only partially refined vegetable oils and fats as raw material is particularly advantageous. The lubricant obtained from this has particularly good oxidation stability.

Weiterhin weist der Schmierstoff besonders vorteilhafte Eigenschaften auf, wenn im Raffinationsprozess lediglich die hydratisierbaren Phospholipide entfernt werden oder wenn Fettbestandteile, die üblicherweise bei der Pflanzenölraffiniation abgetrennt werden, nicht entfernt bzw. wieder zugesetzt werden. Beispiele für derartige Verbindungen sind Carotinoide, nicht-hydratisierbare Lecithine, Phenole und Phenolsäuren, Tocopherole, Phorbolester etc.Furthermore, the lubricant has particularly advantageous properties if only the hydratable phospholipids are removed in the refining process or if fat components, which are usually separated off in vegetable oil refining, are not removed or added back. Examples of such compounds are carotenoids, non-hydratable lecithins, phenols and phenolic acids, tocopherols, phorbol esters, etc.

Überraschenderweise weist die erfindungsgemäße Mischung aus Tri- und Partialglyceriden und Fettsäureestern im Vergleich zu den unbehandelten Ölen und Fetten einen höheren Viskositätsindex von >200 auf.Surprisingly, the mixture of triglycerides and partial glycerides and fatty acid esters according to the invention has a higher viscosity index of >200 compared to the untreated oils and fats.

Besonders vorteilhaft sind dabei Mischungen, bei denen ein Teil der Glyceride bei Temperaturen von wenigstens 20°C als feste Phase vorliegt.Mixtures in which some of the glycerides are present as a solid phase at temperatures of at least 20° C. are particularly advantageous.

Zur weiteren Verbesserung des Viskositätsindexes der Mischungen ist es vorteilhaft, neben den Fettbestandteilen, die bei einer Temperatur von 20° noch fest sind, auch Bestandteile von pflanzlichen Ölen zu verwenden, die bei dieser Temperatur flüssig sind und langkettige ungesättigte Fettsäuren enthalten. Dies kann durch Zugabe von Ölen erreicht werden, die einen hohen Gehalt an ungesättigten Fettsäuren enthalten wie z.B. Raps- oder Sonnenblumenöl, wobei der Anteil dieser Öle zum Erhalt der Oxidationsstabilität keiner als 50 Mass-%, vorteilhaft kleiner 10 Mass-% gewählt werden sollte. Dabei ist es sowohl möglich, das niedrigviskose Öl vor der Umwandlung der Triglyceride oder nach der Umwandlung zuzugeben.To further improve the viscosity index of the mixtures, it is advantageous to use components of vegetable oils that are liquid at this temperature and contain long-chain unsaturated fatty acids in addition to the fat components that are still solid at a temperature of 20°. This can be achieved by adding oils that a contain a high content of unsaturated fatty acids, such as rapeseed or sunflower oil, with the proportion of these oils being selected to be less than 50% by mass, advantageously less than 10% by mass, in order to maintain oxidation stability. It is possible to add the low-viscosity oil before the conversion of the triglycerides or after the conversion.

In einer besonders einfachen Ausführungsform der Erfindung kann es zum Erhalt der vorteilhaften Eigenschaften ausreichend sein, eine Mischung aus Fetten und Ölen herzustellen, die bei Raumtemperatur pumpbar ist. Auch mit derartigen Mischungen ergibt sich eine erstaunlich gute Schmierwirkung in Getrieben oder Motoren.In a particularly simple embodiment of the invention, it may be sufficient to obtain the advantageous properties to produce a mixture of fats and oils that can be pumped at room temperature. A surprisingly good lubricating effect in gears or engines is also achieved with such mixtures.

Derartige Mischungen können auch Fraktionen von pflanzlichen Ölen in Form pumpbarer Rückstände sein, die als Minorkomponente bei der Winterisierung von Ölen abgetrennt werden. Diese enthalten bei einer Temperatur von 20°C sowohl flüssige als auch feste Bestandteile, die eine überraschend gute Schmierwirkung zeigen. Weitere Ausgestaltungen können Mischungen aus diesen Winterisierungsrückständen mit Fetten oder Ölen sein, die optional auch einer Teilumesterung unterworfen werden.Such mixtures can also be fractions of vegetable oils in the form of pumpable residues which are separated off as minor components during the winterization of oils. At a temperature of 20°C, these contain both liquid and solid components, which have a surprisingly good lubricating effect. Further configurations can be mixtures of these winterization residues with fats or oils, which are optionally also subjected to a partial transesterification.

Auch wenn die erfindungsgemäße Mischung aufgrund eines hohen Anteils gesättigter Fettsäuren bereits ohne weitere Komponenten oder Zusätze eine gute Beständigkeit und Stabilität aufweist, ist es dennoch von Vorteil, antioxidative Stoffe zur weiteren Steigerung der Oxidationsstabilität zuzusetzen. Dafür kommen vorteilhaft Pflanzeninhaltsstoffe zum Einsatz, die auch in natürlichen Fetten enthalten und auch dort löslich sind. Dies können Carotine, Tocopherole, Tocotrienole und weitere antioxidativ wirksame öllösliche Substanzen sein. Für die technische Anwendung sollten je nach dem Anteil der ungesättigten Fettsäuren Gehalte zwischen 0,1 und 10 Mass-% an antioxidativen Pflanzenstoffen zum Einsatz kommen.Even if the mixture according to the invention has good resistance and stability even without further components or additives due to a high proportion of saturated fatty acids, it is still advantageous to add antioxidant substances to further increase the oxidation stability. For this plant ingredients are used to advantage, which are also contained in natural fats and are also soluble there. These can be carotenes, tocopherols, tocotrienols and other oil-soluble substances with an antioxidant effect. Depending on the proportion of unsaturated fatty acids, between 0.1 and 10% by mass of antioxidant plant substances should be used for technical applications.

Überraschenderweise zeigt sich, dass der Schmierstoff besonders vorteilhafte Eigenschaften aufweist wenn er geringe Anteile an anorganischen Partikeln (<1,5µm) aufweist. Diese dienen der Fettkristallisation als Keime und beschleunigen die Bildung der festen Phase.Surprisingly, it turns out that the lubricant has particularly advantageous properties if it has a low proportion of inorganic particles (<1.5 μm). These serve as nuclei for fat crystallization and accelerate the formation of the solid phase.

Ausführungsbeispielexample

Nachfolgend werden die Zusammensetzung und die Anwendung des vorgeschlagenen Schmierstoffes anhand eines Beispiels dargestellt.The composition and application of the proposed lubricant are shown below using an example.

Beispielexample

57 Mass-% nicht raffiniertes Palmöl, 22 Mass-% Fettsäureethylester aus Palmöl, 16 Mass-% Palm-Diglyceride und 5 Mass-% Palm-Monoglyceride werden bei einer Temperatur von 50°C gemischt. Die resultierende Mischung weist nach dem Abkühlen auf eine Temperatur von 20°C einen Feststoffanteil von >40 Vol-% auf.57% by mass of unrefined palm oil, 22% by mass of fatty acid ethyl esters from palm oil, 16% by mass of palm diglycerides and 5% by mass of palm monoglycerides are mixed at a temperature of 50°C. After cooling to a temperature of 20° C., the resulting mixture has a solids content of >40% by volume.

In einem Zahnradkurztest nach DIN ISO 14635-1 wird mit dem nicht additivierten Schmiermittel Schadenskraftstufe 7 erreicht. Die Schmiereigenschaften des palmbasierten Mediums sind somit mit schwach additivierten Schmierstoffen auf Mineralölbasis vergleichbar.In a short gear test according to DIN ISO 14635-1, damage load level 7 is achieved with the additive-free lubricant. The lubricating properties of the palm-based medium are thus comparable with lightly additive-based lubricants based on mineral oil.

Claims (18)

  1. Lubricating mixture, particularly for use in transmissions and engines, containing at least
    - a mass fraction of ≥ 50% glycerides of natural origin, wherein at least a part of the glycerides is obtained from vegetable fats which contain a mass fraction of at least 30% saturated fatty acids and are solid at a temperature of 20 °C, and
    - a proportion of fatty acid alkyl esters having 1 to 4 C atoms in the alkyl group,
    wherein
    - at least a part of the glycerides are mono- and/or diglycerides which form a mass fraction of ≥ 10% in the mixture, and
    - the mixture has a liquid phase with a solids content of ≥ 1% by volume in a temperature range from > 10 °C to at least 15 °C,
    - which is formed from a proportion of the glycerides and/or the fatty acid alkyl esters, and is formed by solid particles having an expansion in the range between 4 µm and 5 mm, and
    - wherein a proportion of liquid in the mixture amounts to > 40% by volume in the temperature range from > 10 °C to at least 15 °C.
  2. Lubricating mixture according to Claim 1,
    characterized in that
    the mixture contains the liquid phase with the solids content of ≥ 1% by volume in the temperature range from > 10 °C to at least 20 °C.
  3. Lubricating mixture according to Claim 1 or 2, characterized in that
    in the temperature range from > 10 °C to at least 15 °C or to at least 20 °C the mixture contains a liquid phase having a solids content of ≥ 50% by volume.
  4. Lubricating mixture according to Claim 1 or 2, characterized in that
    in the temperature range from > 10 °C to at least 15 °C or to at least 20 °C the liquid phase has a proportion of ≥ 80% by volume of the mixture.
  5. Lubricating mixture according to any one of Claims 1 to 4,
    characterized in that
    the mixture contains a mass fraction of ≥ 30% triglycerides.
  6. Lubricating mixture according to any one of Claims 1 to 5,
    characterized in that
    the mixture contains a mass fraction of > 10% diglycerides and a mass fraction of > 5% monoglycerides.
  7. Lubricating mixture according to Claim 5 or 6, characterized in that
    the mass fraction of triglycerides amounts to > 40%, preferably > 50%.
  8. Lubricating mixture according to Claim 6 or 7, characterized in that
    the mass fraction of diglycerides amounts to > 15%.
  9. Lubricating mixture according to any one of Claims 1 to 8,
    characterized in that
    the mixture contains a mass fraction of > 10%, preferably > 15% of the fatty acid alkyl esters.
  10. Lubricating mixture according to any one of Claims 1 to 9,
    characterized in that
    the mixture contains a mass fraction between 0.1% and 4% of unbound monohydric or polyhydric alcohol.
  11. Lubricating mixture according to any one of Claims 1 to 10,
    characterized in that
    in addition to the solids content of the glycerides and/or fatty acid alkyl esters the mixture also contains solid particles of other organic and/or inorganic substances, which are still solid even at a temperature of at least 90 °C.
  12. Lubricating mixture according to Claim 11, characterized in that
    the solid particles from the other organic and/or inorganic substances are contained in the mixture with a mass fraction between 0.1% and 3%.
  13. Lubricating mixture according to Claim 11 or 12, characterized in that
    the solid particles from the other organic and/or inorganic substances have an expansion in the range between 0.1 µm and 1.5 µm.
  14. Lubricating mixture according to any one of Claims 1 to 13,
    characterized in that
    the glycerides in the solids content have a proportion of monoglycerides which is at least 1.5 greater than that of the glycerides in the liquid phase.
  15. Lubricating mixture according to any one of Claims 1 to 14,
    characterized in that
    at least a part of the glycerides is derived from palm butter and/or coconut oil.
  16. Lubricating mixture according to any one of Claims 1 to 15, characterized in that
    a part of the glycerides is derived from vegetable oils which are liquid at a temperature of 20 °C.
  17. Use of the lubricating mixture according to one or more of the preceding claims as a lubricant.
  18. Use according to Claim 17 as a lubricant for transmissions or engines.
EP16754476.6A 2015-08-31 2016-08-16 Lubricating mixture having glycerides Active EP3344734B1 (en)

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DE102019210061A1 (en) * 2019-07-09 2021-01-14 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. System subjected to sliding friction

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ES2933622T3 (en) 2023-02-10
JP7053454B2 (en) 2022-04-12
MY191237A (en) 2022-06-10
CN108138065B (en) 2021-01-12
AU2016315409A1 (en) 2018-03-08
EP3344734A1 (en) 2018-07-11
JP2018526511A (en) 2018-09-13
CA2992150C (en) 2023-06-27
BR112018002095A2 (en) 2018-09-18
RU2018111249A (en) 2019-10-04
RU2018111249A3 (en) 2019-10-04
AU2016315409B2 (en) 2019-07-18
MX2018002472A (en) 2018-06-15
PH12018500243A1 (en) 2018-07-30
CN108138065A (en) 2018-06-08
WO2017036785A1 (en) 2017-03-09
CA2992150A1 (en) 2017-03-09
US10640722B2 (en) 2020-05-05
BR112018002095B1 (en) 2020-11-24

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