EP2138556B1 - Stabiliser and additive compound for combustion engines - Google Patents

Stabiliser and additive compound for combustion engines Download PDF

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Publication number
EP2138556B1
EP2138556B1 EP09008342.9A EP09008342A EP2138556B1 EP 2138556 B1 EP2138556 B1 EP 2138556B1 EP 09008342 A EP09008342 A EP 09008342A EP 2138556 B1 EP2138556 B1 EP 2138556B1
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EP
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Prior art keywords
component
oil
weight
carbodiimide
fatty acid
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EP09008342.9A
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German (de)
French (fr)
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EP2138556A1 (en
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Volker Dr. Schäfer
Otto Heinrich Botz
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Botz Otto Heinrich
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/042—Epoxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/2805—Esters used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/14—Containing carbon-to-nitrogen double bounds, e.g. guanidines, hydrazones, semicarbazones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants

Definitions

  • the invention relates to an additive composition for stabilizing crude oil, at least partially refined oil or synthetic esters, an additive composition containing this stabilizer and their use as lubricants in internal combustion engines and the stabilized crude oil, at least partially refined oil or synthetic ester itself.
  • polyesters-based plastics are subject to hydrolytic degradation due to aging processes. During the aging of these ester-group-containing plastics, carboxyl groups are released which accelerate the degradation of the plastics autocatalytically.
  • Anti-hydrolysis agents of various kinds are added as additives in order to intercept the autocatalytic free acid and render it ineffective.
  • the property of the NCN group of the carbodiimide is exploited, preferably to react with the carboxyl group to form acylated ureas.
  • carbodiimides as hydrolysis protection leads to good results, but is also associated with disadvantages. These include the toxicity of such compounds and the relatively high cost associated with the use of carbodiimides.
  • This hydrolysis protection agent is composed of epoxidized natural oils or fatty acid esters of unsaturated fatty acids and at least one epoxidized fatty acid glyceride, supplemented by bis [-2,6-diisopropylphenyl] carbodiimide.
  • Suitable natural oils include vegetable oils such as rapeseed oil, linseed oil, soybean oil and sunflower oil. In addition, as a natural oil and fish oil can be used.
  • the hydrolysis protection agent has a correspondingly markedly reduced carbodiimide content.
  • Vegetable oils themselves as they have become known as part of the said hydrolysis protection agent, are more and more used as environmentally friendly, biodegradable fluids in industrial applications.
  • this desirable use of vegetable oils in practice does not always succeed quite smoothly, because their property profile still has disadvantages for the particular application, so they must be modified.
  • suitable for hydraulic purposes lubricating oil u. a. containing at least one, already mentioned vegetable triglyceride oil, the selected pour point depressant, a metal deactivator performance additive and at least one aminophenol.
  • the present invention was based on the object of providing novel lubricant uses and, in addition, expanding the field of use of technical fluids based on plants.
  • component a1 epoxidized natural fatty acid ester
  • component a2 epoxidized natural fatty acid glyceride
  • component a3 epoxidized natural fatty acid glyceride
  • component B epoxidized natural fatty acid glyceride
  • component C preferably vegetable oil having an oleic acid content of at least 85%, preferably of at least 90%
  • component C for stabilizing crude oil, at least partially refined oil or synthetic esters, wherein component A has an epoxide content of at least 1.5% by weight.
  • component A being present in an amount of 10 to 50% by weight, preferably 30 to 40% by weight
  • component B in an amount of 10 to 50% by weight.
  • % more preferably from 30 to 40% by weight
  • component C in an amount of from 10 to 40% by weight, preferably from 10 to 30% by weight, in the additive system is.
  • the inventively proposed stabilizer is suitable for use in internal combustion engines.
  • the component A which is composed at least of the subcomponents a1 and a2, serves to bind the free acid which forms or basically exists in the case of the natural oils.
  • the written opinion on the search report refers to Figure 4a, which I do not have. To refute this citation, various approaches are conceivable. First of all, the written statement also considered claim 13, which concerns the high oleic acid content of vegetable oil, to be novelty-prone by D1 . However, the different oleic acid content of vegetable oils, depending on their type and quality, was not problematized in the D1 abstract. This ignored the search report.
  • the autocatalysis can be effectively prevented. It has been found that the component A forms a depot, which can adequately buffer further acid.
  • the further component B serves as an antioxidant and thus additionally stabilizes the oil or the synthetic ester.
  • the carbodiimide having component A as partial component a3 is preferably bis [-2,6-diisopropylphenyl] carbodiimide.
  • the invention is not limited to the use of this particular carbodiimide.
  • Other carbodiimides can also be used.
  • Another industrially used carbodiimide in this connection is exemplified by poly (2,4,6-triisopropylbenzene-1,3-carbodiimide).
  • sunflower seed oil can be used as the vegetable oil for the component C.
  • a lubricant is obtained, which shows very good lubricating properties, especially in the automotive sector and can significantly reduce the wear on the injection pump and in the engine.
  • component A has an overall epoxide content of at least 1.5% by weight a substantially complete interception of formed free acid can be ensured.
  • the natural oil as such or as the basis for the fatty acid ester according to (component a1) and / or the fatty acid glyceride according to (component a2) is preferably selected from rapeseed oil or rapeseed oil, linseed oil, soybean oil, sunflower seed oil or fish oil and mixtures thereof.
  • the epoxidized fatty acid esters are formed from the fatty acids mainly contained in the oils.
  • the oleic acid, stearic acid, palmitic acid, linoleic acid and ⁇ -linolenic acid are exemplary and not restrictive. In principle, however, the entire range of natural oils and thus not only the range of vegetable oils is available for the selection of the oil and thus according to the fatty acid esters and the fatty acid glyceride.
  • an excellent stabilizing effect results when components A and B together in an amount of 5 to 20% by weight, preferably 5 to 15% by weight, more preferably 5 to 10% by weight. are included.
  • the invention also relates to an additive composition
  • an epoxidized natural fatty acid ester (component a1), at least one epoxidized natural fatty acid glyceride (component a2) and a carbodiimide (component a3) as component A and a sterically hindered phenol as component B and additionally a natural, preferably a vegetable oil having an oleic acid content of at least 85%, more preferably of at least 90% as component C, wherein the component A in an amount of 10 to 50 wt .-%, preferably from 30 to 40 wt .-%, component B in from 10 to 50% by weight, preferably from 30 to 40% by weight, and component C in an amount of 10 - 40 wt .-%, preferably from 10 to 30 wt .-%, is contained in the additive system.
  • the percentages by weight are based on the additive system as used or added. It results in an excellent stabilizing activity.
  • the carbodiimide which contains component A of the additive composition according to the invention as component a3 may preferably, but not necessarily, be a bis [-2,6-diisopropylphenyl] carbodiimide.
  • the natural, preferably vegetable oil as component C is preferably, but not necessarily, a sunflower oil.
  • inventive additive composition is to be seen in its suitability as a lubricant for internal combustion engines.
  • the invention further relates to a crude oil, an at least partially refined oil or a synthetic ester which comprise the additive system having a composition and properties as further explained above with respect to the additive composition of the invention.
  • Component A of the stabilizer according to the invention contains, for the purposes of the experiments carried out here, the three components a1 in the form of an epoxidized fatty acid ester, a2 in the form of an epoxidized natural fatty acid glyceride and a3 in the form of bis [-2,6-diisopropylphenyl] carbodiimide.
  • the preparation of the composite component A can be carried out as in the DE-B-103 49 168 described in more detail.
  • component A a product obtainable in the above-mentioned manner but commercially available under the name LUBIO Hystab 9 from Shufer Additivsysteme GmbH, Ludwigshafen, was used.
  • component B a sterically hindered phenol which is likewise commercially available under the name LUBIO AO 17 from Shufer Additivsysteme GmbH, Ludwigshafen, was used.
  • Component C is preferably a sunflower seed oil having an oleic acid content of about 90.92%.
  • composition of the stabilizer or additive system used is a composition of the stabilizer or additive system used:
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • component A The sub-components of component A are generally mixed together by stirring at elevated temperature of about 50-70 ° C over a period of about 3 h and acting as an antioxidant component B is added after stirring and briefly mixed with the component A. Components A and B are then also added to component C by stirring.
  • test medium and the catalyst are filled together in a glass, which is introduced into the rotating container (so-called "rotary bomb") and this is then closed.
  • rotary bomb rotating container
  • the test medium is aged at the specified, constant speed and temperature for a fixed period of time as indicated above under test duration.
  • test parameters are the same as indicated under I. in the aging resistance test.
  • performance of the test procedure is the same as stated under I.
  • Acid value fresh oil in mg KOH / g oil Acid value used oil in mg KOH / g oil Change d. Acid number in% Trial 1 0.1 0.18 + 80 Trial 2 0.07 0.08 + 1 Trial 3 0.06 0.07 +/- 0 Kin. Viscous. [40 ° C] fresh oil in cstokes Kin. Viscous. [40 ° C] waste oil in cstokes Kin. Viscous. [40 ° C] in% Trial 1 29.61 29.61 +/- 0 Trial 2 29.29 29.48 +/- 0 Trial 3 29,45 29.12 +/- 0
  • Acid value fresh oil in mg KOH / g oil Acid value used oil in mg KOH / g oil Change d. Acid number in% Trial 3 0.08 0.28 + 250 Trial 4 0.06 0.10 + 17 Trial 5 0.04 0.04 +/- 0 Kin. Viscous. [40 ° C] fresh oil in cstokes Kin. Viscous. [40 ° C] waste oil in cstokes Kin. Viscous. [40 ° C] in% Trial 3 21.68 23.78 + 10 Trial 4 22.17 22,49 +/- 0 Trial 5 22.65 22.46 +/- 0
  • the change in the acid number represents the hydrolytic stability of a tribosystem.
  • High acid numbers can lead to decomposition of the oil by autocatalysis, whose cleavage products in turn lead to corrosion, deteriorated Elastomerver joskeit etc.
  • the classic oil-based SAE 10W40 motor oil is hydrolytically most stable, but shows an increase in acid number of 80% after aging due to decomposition. By adding the additive system, the acid number is gradually reduced before and after aging.
  • the FAME-added motor oil shows in the non-additive state, especially after aging, a drastic increase in acid number by 250%.
  • the unadditiere motor oil naturally shows a relatively high acid number, which increases even after aging up to 45%.
  • the acid number is reduced in fresh oil. After aging, little or no change in the acid number is observed.
  • the change in viscosity represents the thermal and oxidative stability of a tribosystem. High viscosity changes lead to increased pressures, poorer lubricating properties, etc. Responsible for this are polymerization and decomposition processes.
  • the FAME-added or contaminated engine oil already shows a viscosity increase of 10% in the unadditivated state.
  • the addition of the additive system causes a stabilization and thus also after aging no change in viscosity.
  • inventive additive system causes a significant improvement in hydrolytic, thermal and oxidative stability both in pure and contaminated with FAME engine oil and in vegetable engine oil.

Description

Die Erfindung betrifft eine Additivzusammensetzung zur Stabilisierung von Rohöl, von zumindest teilweise raffiniertem Öl oder von synthetischen Estern, eine Additivzusammensetzung, die diesen Stabilisator enthält sowie deren Verwendung als Schmiermittel in Verbrennungsmotoren und das stabilisierte Rohöl, zumindest teilweise raffiniertem Öl oder synthetischen Ester selbst.The invention relates to an additive composition for stabilizing crude oil, at least partially refined oil or synthetic esters, an additive composition containing this stabilizer and their use as lubricants in internal combustion engines and the stabilized crude oil, at least partially refined oil or synthetic ester itself.

Es ist ein weithin bekanntes Problem, daß Kunststoffe auf der Basis von Polyestern aufgrund von Alterungsprozessen einem hydrolytischen Abbau unterliegen. Bei der Alterung dieser estergruppenhaltigen Kunststoffe werden Carboxylgruppen frei, die den Abbau der Kunststoffe autokatalytisch beschleunigen.It is a well-known problem that polyesters-based plastics are subject to hydrolytic degradation due to aging processes. During the aging of these ester-group-containing plastics, carboxyl groups are released which accelerate the degradation of the plastics autocatalytically.

Hydrolyseschutzmittel verschiedenster Art werden als Additive zugefügt, um die durch Autokatalyse entstehende freie Säure abzufangen und unwirksam zu machen. Insbesondere ist bekannt, sterisch gehinderte monomere Carbodiimide als Hydrolyseschutzmittel für polyesterbasierende PUR-Gießelastomere oder sterisch gehinderte polymere Carbodiimide als Hydrolyseschutzmittel für polyesterbasierende PUR-Systeme und thermoplastische Polyesterpolyurethane einzusetzen.Anti-hydrolysis agents of various kinds are added as additives in order to intercept the autocatalytic free acid and render it ineffective. In particular, it is known to employ sterically hindered monomeric carbodiimides as hydrolysis protectants for polyester-based PUR cast elastomers or sterically hindered polymeric carbodiimides as hydrolysis protectants for polyester-based PUR systems and thermoplastic polyester polyurethanes.

Dabei wird die Eigenschaft der NCN-Gruppe des Carbodiimids zunutze gemacht, bevorzugt mit der Carboxylgruppe unter Bildung acylierter Harnstoffe zu reagieren.In this case, the property of the NCN group of the carbodiimide is exploited, preferably to react with the carboxyl group to form acylated ureas.

Der Einsatz von Carbodiimiden als Hydrolyseschutzmittel führt zu guten Ergebnissen, ist aber auch mit Nachteilen verbunden. Dazu gehören die Toxizität solcher Verbindungen und die mit dem Einsatz von Carbodiimiden verbundenen relativ hohen Kosten.The use of carbodiimides as hydrolysis protection leads to good results, but is also associated with disadvantages. These include the toxicity of such compounds and the relatively high cost associated with the use of carbodiimides.

Aus der DE-A-103 49 168 ist daher ein Hydrolyseschutzmittel bekanntgeworden, mit dem der Carbodiimidgehalt und damit auch das toxische Potential der Carbodiimide deutlich reduziert werden kann. Dieses Hydrolyseschutzmittel setzt sich zusammen aus epoxidierten natürlichen Ölen bzw. Fettsäureestern ungesättigter Fettsäuren und zumindest einem epoxidierten Fettsäureglycerid, ergänzt durch Bis[-2,6-diisopropylphenyl]-carbodiimid.From the DE-A-103 49 168 Therefore, a hydrolysis protection agent has become known, with which the carbodiimide content and thus also the toxic potential of the carbodiimides can be significantly reduced. This hydrolysis protection agent is composed of epoxidized natural oils or fatty acid esters of unsaturated fatty acids and at least one epoxidized fatty acid glyceride, supplemented by bis [-2,6-diisopropylphenyl] carbodiimide.

Als in Frage kommende natürliche Öle sind dabei Pflanzenöle, wie Rüböl, Leinöl, Sojabohnenöl und Sonnenblumenöl genannt. Außerdem kann als natürliches Öl auch Fischöl eingesetzt werden. Das Hydrolyseschutzmittel weist einen entsprechend deutlich verringerten Carbodiimid-Gehalt auf.Suitable natural oils include vegetable oils such as rapeseed oil, linseed oil, soybean oil and sunflower oil. In addition, as a natural oil and fish oil can be used. The hydrolysis protection agent has a correspondingly markedly reduced carbodiimide content.

Pflanzliche Öle selbst, wie sie als Bestandteil des genannten Hydrolyseschutzmittels bekanntgeworden sind, werden darüber hinaus immer mehr als umweltfreundliche, biologisch abbaubare Fluide in industriellen Anwendungen eingesetzt. Allerdings gelingt dieser an sich erwünschte Einsatz der pflanzlichen Öle in der Praxis noch nicht immer ganz reibungslos, weil ihr Eigenschaftsprofil noch Nachteile für den jeweiligen Einsatzzweck aufweist, so dass sie modifiziert werden müssen.Vegetable oils themselves, as they have become known as part of the said hydrolysis protection agent, are more and more used as environmentally friendly, biodegradable fluids in industrial applications. However, this desirable use of vegetable oils in practice does not always succeed quite smoothly, because their property profile still has disadvantages for the particular application, so they must be modified.

So ist aus der EP-A-93 310 680 der Lubrizol Corp. das Problem bekannt, dass die Niedrigtemperatur-Viskosimetrie der pflanzlichen Öle verbessert werden und insbesondere ihr Stockpunkt erniedrigt werden muss. Gemäß diesem Dokument soll ein Schmieröl für hydraulische Zwecke auf der Basis eines pflanzlichen Triglyceridöls bereitgestellt werden. Dort besteht das Problem einer natürlichen Verdikkung der Triglyceride bei niedrigen Temperaturen. Dadurch kann ihre Giess- bzw. Fliessfähigkeit nicht mehr aufrechterhalten werden. Entsprechend soll gemäss der EP-Schrift ein spezieller Stockpunkt-Erniedriger für solche hoch einfach ungesättigten pflanzlichen Öle und für biologisch abbaubare Mischungen von Flüssigkeiten mit diesen hoch einfach ungesättigten pflanzlichen Ölen eingesetzt werden.So is out of the EP-A-93 310 680 the Lubrizol Corp. the problem is known that the low-temperature viscometry of vegetable oils to be improved and in particular their pour point must be lowered. According to this document, a lubricating oil for hydraulic purposes based on a vegetable triglyceride oil is to be provided. There is the problem of natural thickening of the triglycerides at low temperatures. As a result, their Giess- or flowability can no longer be maintained. Accordingly, according to the EP document, a special pour point depressant for such highly monounsaturated vegetable oils and biodegradable mixtures of liquids with these highly monounsaturated vegetable oils are used.

Insgesamt sind in dem vorgeschlagenen, für hydraulische Zwecke geeigneten Schmieröl u. a. das zumindest eine, schon genannte pflanzliche Triglyceridöl, der ausgewählte Stockpunkt-Erniedriger, ein Metall-Desaktivator-Leistungsadditiv und mindestens ein Aminophenol enthalten.Overall, in the proposed, suitable for hydraulic purposes lubricating oil u. a. containing at least one, already mentioned vegetable triglyceride oil, the selected pour point depressant, a metal deactivator performance additive and at least one aminophenol.

Des weiteren betrifft eine Veroffeutlichung aus den Chemical Abstracts,
Database CA No. 2007:0663862 XP-002550840,
die chemische Veränderung pflanzlicher Öle zur Herstellung bioabbaubarer Schmiermittel. Dabei wird der Einfluß ihrer Epoxidierung und /oder trans-Veresterung auf die Oxidationsstabilität anhand von Sojabohnen- und Rapsöl untersucht. Es wurden auch Untersuchungen an Mischungen von Mineralöl mit den chemisch veränderten pflanzlichen Ölen durchgeführt und der Einfluß von Antioxidantien wurde getestet. Eines der genannten Antioxidantien ist ein sterisch gehindertes Phenol.Furthermore, a disclosure from the Chemical Abstracts,
Database CA No. 2007: 0663862 XP-002550840,
the chemical modification of vegetable oils to produce biodegradable lubricants. The influence of their epoxidation and / or trans esterification on the oxidation stability is examined using soybean oil and rapeseed oil . Investigations were also carried out on mixtures of mineral oil with the chemically modified vegetable oils and the influence of antioxidants was tested. One of the antioxidants mentioned is a sterically hindered phenol.

Perez et al., verwendet in dem Aufsatz "Proceedings of ASME ICES2003-657 , XP-002SS0839,
eine spezielle calorimetrische Analysemethode (PDSC), um den Einfluß von Additiven in Schmiermitteln auf Pflanzenölbasis zu untersuchen. Dabei wird aus geführt daß die Oxidationsstabilität von pflanzlichen Ölen verbessert werden muß, damit sie als Ersatz von Mineralölen in Schmiermitteln eingesetzt werden können. Hierfür wurde mittels der speziellen calorimetrischen PDSC-Methode Sojabohnenöl unterschiedlicher Zusammensetzung untersucht, wobei der Ölsäuregehalt im Bereich von 23 - 83 % lag. Außerdem wurde ein epoxidiertes Sojabohnenöl, das keine Doppelbindungen enthielt, untersucht. Der Oxidationsgrad wurde jeweils mit und ohne Additiv untersucht, wobei fünf Additive überprüft worden sind. Perez et al., Used in the article "Proceedings of ASME ICES2003-657 , XP-002SS0839,
a special calorimetric analysis method (PDSC) to investigate the influence of additives in vegetable oil based lubricants. It is carried out that the oxidation stability of vegetable oils must be improved so that they can be used as a replacement of mineral oils in lubricants. For this purpose soybean oil of different composition was investigated by means of the special calorimetric PDSC method, the oleic acid content being in the range of 23-83%. In addition, an epoxidized soybean oil containing no double bonds was examined. The degree of oxidation was investigated with and without additive, with five additives being checked.

Ausgehend von diesem Stand der Technik lag der vorliegenden Erfindung die Aufgabe zugrunde, neuartige Schmiermittelverwendungen bereitzustellen und zusätzlich das Einsatzgebiet technischer Fluide auf pflanzlicher Basis zu erweitern.Based on this prior art, the present invention was based on the object of providing novel lubricant uses and, in addition, expanding the field of use of technical fluids based on plants.

Gelöst wird diese Aufgabe durch die Verwendung von zumindest einem epoxidierten natürlichen Fettsäureester (Komponente a1), zumindest einem epoxidierten natürlichen Fettsäureglycerid (Komponente a2) und einem Carbodiimid (Komponente a3) als Komponente A, zusammen mit einem sterisch gehinderten Phenol als Komponente B und einem natürlichen, vorzugsweise pflanzlichen Öl mit einem Ölsäuregehalt von zumindest 85%, bevorzugt von zumindest 90% als weitere Komponente C zur Stabilisierung von Rohöl, von zumindest teilweise raffiniertem Öl oder von synthetischen Estern, wobei die Komponente A einen Epoxidgehalt von zumindest 1,5 Gew.% aufweist und die Komponenten A, B und C zusammen ein Additivsystem bilden, wobei Komponente A in einer Menge von 10 - 50 Gew.-%, bevorzugt von 30 - 40 Gew.%, Komponente B in einer Menge von 10 - 50 Gew.-%, besonders bevorzugt von 30 - 40 Gew.% und Komponente C in einer Menge von 10 - 40 Gew.%, bevorzugt von 10 - 30 Gew.-%, in dem Additivsystem enthalten ist.This object is achieved by the use of at least one epoxidized natural fatty acid ester (component a1), at least one epoxidized natural fatty acid glyceride (component a2) and a carbodiimide (component a3) as component A, together with a sterically hindered phenol as component B and a natural , preferably vegetable oil having an oleic acid content of at least 85%, preferably of at least 90% as further component C for stabilizing crude oil, at least partially refined oil or synthetic esters, wherein component A has an epoxide content of at least 1.5% by weight. and components A, B and C together form an additive system, component A being present in an amount of 10 to 50% by weight, preferably 30 to 40% by weight, component B in an amount of 10 to 50% by weight. %, more preferably from 30 to 40% by weight, and component C in an amount of from 10 to 40% by weight, preferably from 10 to 30% by weight, in the additive system is.

Mit dieser erfindungsgemässen Verwendung wird ein weites Anwendungsgebiet eröffnet. Insbesondere bei Motorenölen geht der Trend immer mehr in Richtung von Ölen auf pflanzlicher Basis. Biodiesel oder Bioethanol werden zunehmend verwendet. Hier besteht aber das Problem, dass die Kraftfahrzeugmotoren oft durch die entsprechenden Abbau- und Nebenprodukte der Kraftstoffe und Öle auf biologischer bzw. pflanzlicher Basis verunreinigt und in ihrer Leistungsfähigkeit zumindest vermindert werden. Die aus dem Bereich der hydraulischen Systeme bekannten Stabilisatoren und Additive können im Kraftfahrzeugbereich nicht zur Anwendung kommen, weil sie nicht für die in Verbrennungsmotoren viel höheren Temperaturen ausgelegt sind.This use according to the invention opens up a wide field of application. Especially with motor oils, the trend is increasingly in the direction of plant-based oils. Biodiesel or bioethanol are increasingly being used. Here, however, there is the problem that the motor vehicle engines are often contaminated by the corresponding degradation and by-products of fuels and oils on a biological or plant basis and at least reduced in their performance. The known from the field of hydraulic systems stabilizers and additives can not be used in the automotive sector, because they are not designed for the much higher temperatures in internal combustion engines.

Der hier erfindungsgemäss vorgeschlagene Stabilisator ist zur Anwendung in Verbrennungsmotoren geeignet. Dabei dient die Komponente A, die sich zumindest aus den Teilkomponenten a1 und a2 zusammensetzt, dazu, die sich bei den natürlichen Ölen bildende bzw. grundsätzlich vorhandene freie Säure zu binden.
Die schriftliche Stellungnahme zu dem Recherchenbericht weist noch auf eine Abbildung 4a hin, die mir aber nicht vorliegt.
Um diese Entgegenhaltung zu entkräften, sind verschiedene Ansatzpunkte denkbar.
Zunächst hat die schriftliche Stellungnahme pauschal auch Anspruch 13, der den hohen Ölsäuregehalt des pflanzlichen Öls betrifft, als durch D1 neuheitsschädlich vorweggenommen angesehen. Der unterschiedliche Ölsäuregehalt der pflanzlichen Öle, je nach ihrer Art und Qualität, wurde aber in dem Abstract von D1 nicht problematisiert. Dies hat der Recherchenbericht außer acht gelassen.
Die Verwendung der besonderen Additivzusammensetzung gemäß einem der Ansprüche 8-10, d.h. unter Beanspruchung näherer gewichtsprozentualer Anteile speziell als Schmiermittel für Verbrennungsmotoren könnte in Ihrer Anmeldung eine weitere Abgrenzung zu dem Stand der Technik sein.
Und schließlich ist es auch möglich, die Neuheit und das Vorliegen einer erfinderischen Tätigkeit der Additivzusammensetzung durch besondere Vorteile bei der zusätzlichen Verwendung von Sonnenblumenkernöl eines hohen Ölsäuregehalts anhand von Vergleichsversuchen zu belegen. Hier muß allerdings die Offenbarung in D2 (siehe meine Erläuterungen unter II., dort letzter Absatz) sorgfältig berücksichtigt werden.The inventively proposed stabilizer is suitable for use in internal combustion engines. The component A, which is composed at least of the subcomponents a1 and a2, serves to bind the free acid which forms or basically exists in the case of the natural oils.
The written opinion on the search report refers to Figure 4a, which I do not have.
To refute this citation, various approaches are conceivable.
First of all, the written statement also considered claim 13, which concerns the high oleic acid content of vegetable oil, to be novelty-prone by D1 . However, the different oleic acid content of vegetable oils, depending on their type and quality, was not problematized in the D1 abstract. This ignored the search report.
The use of the particular additive composition according to any one of claims 8-10, that is to say using closer weight percentages especially as a lubricant for internal combustion engines, could be a further delimitation from the prior art in your application.
Finally, it is also possible to demonstrate the novelty and the presence of an inventive step of the additive composition by particular advantages in the additional use of high oleic sunflower seed oil by comparative experiments. Here, however, the revelation in D2 (see my remarks under II., Last paragraph) must be carefully considered.

Damit kann auch die Autokatalyse wirksam unterbunden werden. Es hat sich gezeigt, dass die Komponente A ein Depot bildet, das in ausreichender Weise weitere Säure abpuffern kann.
Die weitere Komponente B dient als Antioxidans und stabilisiert damit das Öl oder den synthetischen Ester zusätzlich.Thus, the autocatalysis can be effectively prevented. It has been found that the component A forms a depot, which can adequately buffer further acid.
The further component B serves as an antioxidant and thus additionally stabilizes the oil or the synthetic ester.

Das Carbodiimid welches die Komponente A als Teilkomponente a3 aufweist, ist vorzugsweise ein Bis[-2,6-diisopropylphenyl]-carbodiimid. Allerdings ist die Erfindung nicht auf die Verwendung dieses speziellen Carbodiimids beschränkt. Es können auch andere Carbodiimide eingesetzt werden. Als ein weiteres technisch verwendetes Carbodiimid sei in diesem Zusammenhang exemplarisch Poly(2,4,6-triisopropylbenzol-1,3-carbodiimid) genannt.The carbodiimide having component A as partial component a3 is preferably bis [-2,6-diisopropylphenyl] carbodiimide. However, the invention is not limited to the use of this particular carbodiimide. Other carbodiimides can also be used. Another industrially used carbodiimide in this connection is exemplified by poly (2,4,6-triisopropylbenzene-1,3-carbodiimide).

Als pflanzliches Öl für die Komponente C kann Sonnenblumenkernöl verwendet werden.As the vegetable oil for the component C, sunflower seed oil can be used.

Auf diese Weise wird ein Schmiermittel erhalten, das insbesondere im Kfz-Bereich sehr gute Schmiereigenschaften zeigt und den Verschleiss an der Einspritzpumpe sowie im Motor erheblich reduzieren kann.In this way, a lubricant is obtained, which shows very good lubricating properties, especially in the automotive sector and can significantly reduce the wear on the injection pump and in the engine.

Auch ist auf neue Entwicklungen im Kraftstoffbereich zu verweisen, die es zur Auflage machen, dem konventionellen, mineralischen Dieselkraftstoff einen geringen Anteil an Bio-Diesel zuzusetzen. Dies ist ein ganz besonders bevorzugtes Verwendungsgebiet des aus den Komponenten A, B bestehenden Stabilisators bzw. des aus den Komponenten A, B und C bestehenden Additivsystems.There are also new developments in the field of fuel that make it necessary to add a small amount of biodiesel to conventional mineral diesel fuel. This is a very particularly preferred field of use of the stabilizer consisting of components A, B or of the additive system consisting of components A, B and C.

Dadurch, daß die Komponente A insgesamt einen Epoxidgehalt von zumindest 1,5 Gew.-% aufweist, kann ein im wesentlichen vollständiges Abfangen von gebildeter freier Säure gewährleistet werden.Characterized in that component A has an overall epoxide content of at least 1.5% by weight a substantially complete interception of formed free acid can be ensured.

Das natürliche Öl als solches oder als Grundlage für den Fettsäureester gemäss (Komponente a1) und/oder das Fettsäureglycerid gemäss (Komponente a2) ist vorzugsweise ausgewählt aus Rüböl oder Rapsöl, Leinöl, Sojabohnenöl, Sonnenblumenkernöl oder Fischöl sowie Mischungen davon. Entsprechend der genannten Öle werden die epoxidierten Fettsäureester aus den hauptsächlich in den Ölen enthaltenen Fettsäuren gebildet. Als solche Fettsäuren sind die Ölsäure, Stearinsäure, Palmitinsäure, Linolsäure und α-Linolensäure exemplarisch und nicht beschränkend zu nennen. Grundsätzlich steht aber für die Auswahl des Öls und damit entsprechend der Fettsäureester und des Fettsäureglycerids der gesamte Bereich der natürlichen Öle und damit nicht nur der Bereich der pflanzlichen Öle zur Verfügung.The natural oil as such or as the basis for the fatty acid ester according to (component a1) and / or the fatty acid glyceride according to (component a2) is preferably selected from rapeseed oil or rapeseed oil, linseed oil, soybean oil, sunflower seed oil or fish oil and mixtures thereof. According to the said oils, the epoxidized fatty acid esters are formed from the fatty acids mainly contained in the oils. As such fatty acids, the oleic acid, stearic acid, palmitic acid, linoleic acid and α-linolenic acid are exemplary and not restrictive. In principle, however, the entire range of natural oils and thus not only the range of vegetable oils is available for the selection of the oil and thus according to the fatty acid esters and the fatty acid glyceride.

Für die zu stabilisierende Gesamtzusammensetzung ergibt sich ein ausgezeichneter stabilisierender Effekt, wenn die Komponenten A und B zusammen in einer Menge von 5 - 20 Gew.-%, vorzugsweise 5 - 15 Gew.-%, besonders bevorzugt von 5 - 10 Gew.-% enthalten sind.For the overall composition to be stabilized, an excellent stabilizing effect results when components A and B together in an amount of 5 to 20% by weight, preferably 5 to 15% by weight, more preferably 5 to 10% by weight. are included.

Die Erfindung betrifft auch eine Additivzusammensetzung, enthaltend einen epoxidierten natürlichen Fettsäureester (Komponente a1), zumindest ein epoxidiertes natürliches Fettsäureglycerid (Komponente a2) und ein Carbodiimid (Komponente a3) als Komponente A und ein sterisch gehindertes Phenol als Komponente B und zusätzlich ein natürliches, vorzugsweise ein pflanzliches Öl mit einem Ölsäuregehalt von zumindest 85%, besonders bevorzugt von zumindest 90% als Komponente C, wobei die Komponente A in einer Menge von 10 - 50 Gew.-%, bevorzugt von 30 - 40 Gew.-%, Komponente B in einer Menge von 10 - 50 Gew.-%, bevorzugt von 30 - 40 Gew.-% und Komponente C in einer Menge von 10 - 40 Gew.-%, bevorzugt von 10 - 30 Gew.-%, in dem Additivsystem enthalten ist. Die gewichtsprozentualen Angaben sind auf das Additivsystem bezogen sind, wie es eingesetzt bzw. zugesetzt wird. Es ergibt sich eine ausgezeichnete stabilisierende Wirksamkeit.The invention also relates to an additive composition comprising an epoxidized natural fatty acid ester (component a1), at least one epoxidized natural fatty acid glyceride (component a2) and a carbodiimide (component a3) as component A and a sterically hindered phenol as component B and additionally a natural, preferably a vegetable oil having an oleic acid content of at least 85%, more preferably of at least 90% as component C, wherein the component A in an amount of 10 to 50 wt .-%, preferably from 30 to 40 wt .-%, component B in from 10 to 50% by weight, preferably from 30 to 40% by weight, and component C in an amount of 10 - 40 wt .-%, preferably from 10 to 30 wt .-%, is contained in the additive system. The percentages by weight are based on the additive system as used or added. It results in an excellent stabilizing activity.

Das Carbodiimid, welches Komponente A der erfindungsgemässen Additivzusammensetzung als Teilkomponente a3 enthält, kann vorzugsweise, aber nicht zwingend ein Bis[-2,6-diisopropylphenyl]-carbodiimid sein.The carbodiimide which contains component A of the additive composition according to the invention as component a3 may preferably, but not necessarily, be a bis [-2,6-diisopropylphenyl] carbodiimide.

Das natürliche, vorzugsweise pflanzliche Öl als Komponente C ist vorzugsweise, aber nicht zwangsläufig ein Sonnenblumenkemöl.The natural, preferably vegetable oil as component C is preferably, but not necessarily, a sunflower oil.

Eine besonders hervorzuhebende Verwendung der erfindungsgemässen Additivzusammensetzung ist in seiner Eignung als Schmiermittel für Verbrennungsmotoren zu sehen.A particularly noteworthy use of the inventive additive composition is to be seen in its suitability as a lubricant for internal combustion engines.

Die Erfindung betrifft ausserdem ein Rohöl, ein zumindest teilweise raffiniertes Öl oder einen synthetischen Ester, welche das Additivsystem mit einer Zusammensetzung und Eigenschaften aufweisen, wie weiter oben in bezug auf die erfindungsgemässe Additivzusammensetzung näher erläutert.The invention further relates to a crude oil, an at least partially refined oil or a synthetic ester which comprise the additive system having a composition and properties as further explained above with respect to the additive composition of the invention.

Im folgenden soll die Erfindung anhand von Ausführungsbeispielen näher erläutert werden.In the following, the invention will be explained in more detail with reference to embodiments.

Ausgangsverbindungen:Starting Compounds:

Die Komponente A des erfindungsgemässen Stabilisators enthält für die Zwecke der hier durchgeführten Versuche die drei Teilkomponenten a1 in Form eines epoxidierten Fettsäureesters, a2 in Form eines epoxidierten natürlichen Fettsäureglycerids und a3 in Form von Bis[-2,6-diisopropylphenyl]-carbodiimid.
Die Herstellung der so zusammengesetzten Komponente A kann erfolgen, wie in der DE-B-103 49 168 näher beschrieben.
Für die Zwecke der nachfolgenden Versuche wurde als Komponente A ein auf die genannte Weise herstellbares, aber handelsüblich unter dem Namen LUBIO Hystab 9 von der Schäfer Additivsysteme GmbH, Ludwigshafen, erhältliches Produkt eingesetzt.
Als Komponente B wurde ein ebenfalls handelsüblich unter dem Namen LUBIO AO 17 von der Schäfer Additivsysteme GmbH, Ludwigshafen, erhältliches sterisch gehindertes Phenol verwendet.
Komponente C ist vorzugsweise ein Sonnenblumenkernöl mit einem Ölsäuregehalt von ca. 90,92%. Vorliegend wurde ein unraffiniertes Sonnenblumenkernöl "90 plus" von der Dr. Frische GmbH, erhältlich über die T+T Oleochemie GmbH, Deutschland, eingesetzt.
Nachfolgend sind die genannten Komponenten noch einmal als Übersicht unter Angabe ihrer gewichtsprozentualen Anteile angegeben:Component A of the stabilizer according to the invention contains, for the purposes of the experiments carried out here, the three components a1 in the form of an epoxidized fatty acid ester, a2 in the form of an epoxidized natural fatty acid glyceride and a3 in the form of bis [-2,6-diisopropylphenyl] carbodiimide.
The preparation of the composite component A can be carried out as in the DE-B-103 49 168 described in more detail.
For the purposes of the following experiments, as component A, a product obtainable in the above-mentioned manner but commercially available under the name LUBIO Hystab 9 from Schäfer Additivsysteme GmbH, Ludwigshafen, was used.
As component B, a sterically hindered phenol which is likewise commercially available under the name LUBIO AO 17 from Schäfer Additivsysteme GmbH, Ludwigshafen, was used.
Component C is preferably a sunflower seed oil having an oleic acid content of about 90.92%. In the present case, an unrefined sunflower seed oil "90 plus" from Dr. Ing. Frische GmbH, available through T + T Oleochemie GmbH, Germany.
The following components are given again as an overview stating their percentages by weight:

Zusammensetzung des eingesetzten Stabilisators bzw. Additivsystems:Composition of the stabilizer or additive system used: Komponente A:Component A:

30 Gew.-%30% by weight Carbodiimid/Epoxid-System, Handelsname LUBIO Hystab 9 der Firma Schäfer-Additivsysteme GmbH, DeutschlandCarbodiimide / epoxy system, trade name LUBIO Hystab 9 from Schäfer-Additivsysteme GmbH, Germany

Komponente B:Component B:

30 Gew.-%30% by weight Antioxidanssystem LUBIO AO 17, erhältlich über die Firma Schäfer-Additivsysteme GmbH, DeutschlandAntioxidant system LUBIO AO 17, available from Schäfer-Additivsysteme GmbH, Germany

Komponente C:Component C:

40 Gew.-%40% by weight Sonnenblumenkernöl, Dr. Frische GmbH, "90 plus" über die T+T Oleochemie GmbHSunflower seed oil, Dr. med. Frische GmbH, "90 plus" via T + T Oleochemie GmbH

Die genannten Teilkomponenten der Komponente A werden grundsätzlich durch Rühren bei erhöhter Temperatur von ca. 50 - 70°C über einen Zeitraum von etwa 3 h miteinander vermischt und die als Antioxidans wirkende Komponente B wird nach dem Rühren zugegeben und kurz mit der Komponente A vermischt. Die Komponenten A und B werden dann der Komponente C ebenfalls durch Rühren hinzugefügt.The sub-components of component A are generally mixed together by stirring at elevated temperature of about 50-70 ° C over a period of about 3 h and acting as an antioxidant component B is added after stirring and briefly mixed with the component A. Components A and B are then also added to component C by stirring.

Die nachfolgend in den beschriebenen Testverfahren eingesetzte Beispielmischung V219 wurde wie folgt hergestellt:

  • 30g LUBIO Hystab 9
  • 30g LUBIO AO 17
  • 40g "90 plus" der Dr. Frische GmbH
wurden in einem 200ml Becherglas unter Rühren bei Raumtemperatur vorgelegt und bei 60°C 180 min lang gerührt.The example mixture V219 used in the described test procedure was prepared as follows:
  • 30g LUBIO Hystab 9
  • 30g LUBIO AO 17
  • 40g "90 plus" the Dr. Fresh GmbH
were placed in a 200ml beaker with stirring at room temperature and stirred at 60 ° C for 180 minutes.

Es wurde eine klare, gelbe Flüssigkeit erhalten, die als Additivsystem zur Stabilisierung von Ölen eingesetzt werden kann.It was obtained a clear, yellow liquid, which can be used as an additive system for the stabilization of oils.

Wenn, wie vorliegend, handelsüblich erhältliche, fertige Produkte eingesetzt werden, entfällt das Rühren der Teilkomponenten a1, a2, a3. Es wird lediglich noch das Vermischen der Komponenten A und B und das Hinzufügen zu der Komponente C erforderlich.If, as in this case, commercially available, finished products are used, the stirring of the subcomponents a1, a2, a3 is omitted . It only requires the mixing of the components A and B and the addition to the component C is required.

Durch das Vorhandensein der Teilkomponente a3, d.h. des Carbodiimids, haben sich während der Versuchsdurchführungen synergistische Effekte ergeben, wenn ein Öl untersucht wurde, das entweder ganz oder teilweise ein Mineralöl war. Es hat sich dabei gezeigt, dass die Carbodiimid-Komponente besonders geeignet für den mineralischen Anteil des Öls war, während insbesondere auch durch den Zusatz der Komponente B eine Langzeitstabilisierung des Anteil an natürlicher Ölkomponente ermöglicht wurde.The presence of the sub-component a3, ie the carbodiimide, gave rise to synergistic effects during the experimental procedures when an oil which was either totally or partly a mineral oil was investigated. It It has been shown that the carbodiimide component was particularly suitable for the mineral portion of the oil, while in particular by the addition of component B, a long-term stabilization of the proportion of natural oil component was made possible.

Durchgeführte Testverfahren:Test procedures performed: I. Prüfung der Alterungsbeständigkeit in einem rotierenden Behälter in Anlehnung an "Beverage Bottle Test" gemäß der ASTM D2619-95I. Aging resistance test in a rotating container based on "Beverage Bottle Test" according to ASTM D2619-95

Prüfparameter:Parameters: Drehzahl:Rotation speed: 150 U/min150 rpm Temperatur:Temperature: 93°C93 ° C Dauer:duration: 360 min360 min Prüfmedium:Test medium: 75g Prüf-Flüssigkeit und 25g destilliertes Wasser75g test liquid and 25g distilled water Katalysator:Catalyst: Kupferplättchen 13x51x1 mmCopper plate 13x51x1 mm

Das Prüfmedium und der Katalysator werden zusammen in ein Glas gefüllt, das in den rotierenden Behälter (sogen. "Rotationsbombe") eingebracht und dieser anschliessend verschlossen wird. Im erwärmten Ölbad wird das Prüfmedium bei der angegebenen, konstanten Drehzahl und Temperatur über eine festgelegte Zeitspanne, wie oben unter Versuchsdauer angegeben, gealtert.The test medium and the catalyst are filled together in a glass, which is introduced into the rotating container (so-called "rotary bomb") and this is then closed. In the heated oil bath, the test medium is aged at the specified, constant speed and temperature for a fixed period of time as indicated above under test duration.

Anschliessend wird das in dem Glas befindliche Prüfmedium (hier das Öl) nach den Kriterien:

  • Zunahme Säurezahl
  • Viskositätsänderung
ausgewertet.Subsequently, the test medium in the glass (here the oil) according to the criteria:
  • Increase in acid number
  • viscosity change
evaluated.

II. Prüfung der Hydrolysebeständigkeit in einem rotierenden Behälter in Anlehnung an "Beverage Bottle Test" gemäß der ASTM D2619-95II. Hydrolysis resistance test in a rotating container based on "Beverage Bottle Test" according to ASTM D2619-95

Die Prüfparameter sind dieselben, wie unter I. bei der Prüfung der Alterungsbeständigkeit angegeben. Auch die Durchführung des Prüfverfahrens ist dieselbe, wie unter I. angegeben.The test parameters are the same as indicated under I. in the aging resistance test. The performance of the test procedure is the same as stated under I.

Die Prüfkriterien sind hier:

  • Zunahme Säurezahl des Öls
  • Verfärbungsgrad des Kupferstreifens
  • Viskositätsänderung des Öls
  • Verfärbungen des Öl
The test criteria are here:
  • Increase acid number of the oil
  • Degree of discoloration of the copper strip
  • Viscosity change of the oil
  • Discoloration of the oil

Ergebnisse bei der Bestimmung der SäurezahlResults in the determination of the acid number

Untersuchte Schmierstoffe:

  1. 1. P160 der Puralube GmbH, Tröglitz, Deutschland
  2. 2. P160/FAME (90% P160; 10% FAME)
  3. 3. unraffiniertes Sonnenblumenkernöl "90 plus" der Dr. Frische GmbH
  4. 4. Motorenöl SAE10W40
  5. 5. P160 + 1 Gew.-% V219
  6. 6. P160/FAME +1 Gew.-% V219
  7. 7. Sonnenblumenkernöl "90 plus" der Dr. Frische GmbH +1 Gew.-% V219
  8. 8. P160 + 5 Gew.-% V219
  9. 9. P160/FAME + 5 Gew.-% V219
  10. 10. Sonnenblumenkernöl "90 plus" der Dr. Frische GmbH + 5 Gew.-% V219
Tabelle 1: Produkt Säurezahl Frischöl in mg KOH/g Öl Säurezahl Altöl in mg KOH/g Öl Änderung Säurezahl 1 0,10 0,18 + 80 % 2 0,08 0,28 + 250 % 3 0,83 0,87 +5 % 4 0,70 1,68 + 140 % 5 0,07 0,08 + 1 % 6 0,06 0,10 + 17 % 7 0,35 0,36 + 3 % 8 0,13 0,13 +0 % 9 0,15 0,15 +0 % 10 0,31 0,31 +0 % Examined lubricants:
  1. 1. P160 of Puralube GmbH, Tröglitz, Germany
  2. 2. P160 / FAME (90% P160; 10% FAME)
  3. 3. unrefined sunflower seed oil "90 plus" Dr. Ing. Fresh GmbH
  4. 4. Engine oil SAE10W40
  5. 5. P160 + 1 wt% V219
  6. 6. P160 / FAME +1 wt% V219
  7. 7. Sunflower seed oil "90 plus" Dr. Ing. Fresh GmbH +1% by weight V219
  8. 8. P160 + 5% by weight V219
  9. 9. P160 / FAME + 5% by weight V219
  10. 10. Sunflower seed oil "90 plus" Dr. Ing. Fresh GmbH + 5% by weight V219
<b><u> Table 1: </ u></b> product Acid value fresh oil in mg KOH / g oil Acid value used oil in mg KOH / g oil Change in acid number 1 0.10 0.18 + 80% 2 0.08 0.28 + 250% 3 0.83 0.87 +5% 4 0.70 1.68 + 140% 5 0.07 0.08 + 1% 6 0.06 0.10 + 17% 7 0.35 0.36 + 3% 8th 0.13 0.13 +0% 9 0.15 0.15 +0% 10 0.31 0.31 +0%

Ergebnisse der ViskositätsmessungenResults of the viscosity measurements Schmierstoffe:lubricants:

  1. 1. P160 der Puralube GmbH, Tröglitz, Deutschland 1. P160 of Puralube GmbH, Tröglitz, Germany
  2. 2. P160/FAME (90% P160; 10% FAME) 2. P160 / FAME (90% P160; 10% FAME)
  3. 3. Sonnenblumenkernöl "90 plus" der Dr. Frische GmbH 3. Sunflower seed oil "90 plus" Dr. Ing. Fresh GmbH
  4. 4. Motorenöl SAE10W40 4. Engine oil SAE10W40
  5. 5. P160 + 1 Gew.-% V219 5. P160 + 1 wt% V219
  6. 6. P160/FAME +1 Gew.-% V219 6. P160 / FAME +1 wt% V219
  7. 7. Sonnenblumenkernöl "90 plus" der Dr. Frische GmbH +1 Gew.-% V219 7. Sunflower seed oil "90 plus" Dr. Ing. Fresh GmbH +1% by weight V219
  8. 8. P160 + 5 Gew.-% V219 8. P160 + 5% by weight V219
  9. 9. P160/FAME + 5 Gew.-% V219 9. P160 / FAME + 5% by weight V219
  10. 10. Sonnenblumenkernöl "90 plus" der Dr. Frische GmbH + 15Gew.-% V219 10. Sunflower seed oil "90 plus" Dr. Ing. Fresh GmbH + 15Gew .-% V219
Tabelle 2:Table 2: Produktproduct Kin. Viskosität [40°C] Frischöl in mm2/sKin. Viscosity [40 ° C] Fresh oil in mm 2 / s Kin. Viskosität [40°C] Altöl in mm2/sKin. Viscosity [40 ° C] Used oil in mm 2 / s Änderung Kin. ViskositätChange Kin. viscosity 11 29,6129.61 29,6129.61 ± 0 %± 0% 22 21,6821.68 23,7823.78 + 10 %+ 10% 33 40,4540.45 58,5758.57 + 45 %+ 45% 44 91,7491.74 Nicht messbarNot measurable ----------------
-------------------
--- 55 29,2929.29 29,4829.48 ± 0 %± 0% 66 22,1722.17 22,4922,49 ± 0 %± 0% 77 39,9639.96 39,9839,98 ± 0 %± 0% 88th 29,4529,45 29,1229.12 ± 0 %± 0% 99 22,6522.65 22,4622.46 ± 0 %± 0% 1010 39,8039,80 39,3239.32 ± 0 %± 0% Versuchsreihe 1:Test series 1: Stabilisierung von Motorenöl SAE 10W40 auf der Basis von klassischem MineralölStabilization of engine oil SAE 10W40 based on classic mineral oil

Additivsystemadditive system Motorenölmotor oil Versuch 1:Trial 1: 0 Gew.-%0% by weight 100 Gew.-%100% by weight Versuch 2:Trial 2: 1 Gew.-%1% by weight 99 Gew.-%99% by weight Versuch 3:Trial 3: 5Gew.-%5 wt .-% 95 Gew.-%95% by weight

Versuchsreihe 2:Test series 2: Stabilisierung von Motorenöl SAE 10W40 auf der Basis von klassischem Mineralöl, versetzt mit 10% FAME (Fettsäuremethylester)Stabilization of motor oil SAE 10W40 based on classic mineral oil, mixed with 10% FAME (fatty acid methyl ester)

Additivsystemadditive system Motorenöl/FAMEEngine oil / FAME Versuch 4:Trial 4: 0 Gew.-%0% by weight 100 Gew.-%100% by weight Versuch 5:Trial 5: 1 Gew.-%1% by weight 99 Gew.-%99% by weight Versuch 6:Trial 6: 5Gew.-%5 wt .-% 95 Gew.-%95% by weight

Versuchsreihe 3:Trial 3: Stabilisierung von pflanzlichem Motorenöl auf der Basis von FettsäureglyceridenStabilization of vegetable oil based on fatty acid glycerides

Additivsystemadditive system Pflanzliches MotorenölVegetable engine oil Versuch 7:Trial 7: 0 Gew.-%0% by weight 100 Gew.-%100% by weight Versuch 8:Trial 8: 1 Gew.-%1% by weight 99 Gew.-%99% by weight Versuch 9:Trial 9: 5Gew.-%5 wt .-% 95 Gew.-%95% by weight

ErgebnisseResults Versuchsreihe 1Test series 1

Säurezahl Frischöl in mg KOH/g ÖlAcid value fresh oil in mg KOH / g oil Säurezahl Altöl in mg KOH/g ÖlAcid value used oil in mg KOH / g oil Änderung d. Säurezahl in %Change d. Acid number in% Versuch 1Trial 1 0,10.1 0,180.18 + 80+ 80 Versuch 2Trial 2 0,070.07 0,080.08 + 1+ 1 Versuch 3Trial 3 0,060.06 0,070.07 +/- 0+/- 0 Kin. Viskos. [40°C] Frischöl in cstokesKin. Viscous. [40 ° C] fresh oil in cstokes Kin. Viskos. [40°C] Altöl in cstokesKin. Viscous. [40 ° C] waste oil in cstokes Kin. Viskos. [40°C] in %Kin. Viscous. [40 ° C] in% Versuch 1Trial 1 29,6129.61 29,6129.61 +/- 0+/- 0 Versuch 2Trial 2 29,2929.29 29,4829.48 +/- 0+/- 0 Versuch 3Trial 3 29,4529,45 29,1229.12 +/- 0+/- 0

Versuchsreihe 2Series 2

Säurezahl Frischöl in mg KOH/g ÖlAcid value fresh oil in mg KOH / g oil Säurezahl Altöl in mg KOH/g ÖlAcid value used oil in mg KOH / g oil Änderung d. Säurezahl in %Change d. Acid number in% Versuch 3Trial 3 0,080.08 0,280.28 + 250+ 250 Versuch 4Trial 4 0,060.06 0,100.10 + 17+ 17 Versuch 5Trial 5 0,040.04 0,040.04 +/- 0+/- 0 Kin. Viskos. [40°C] Frischöl in cstokesKin. Viscous. [40 ° C] fresh oil in cstokes Kin. Viskos. [40°C] Altöl in cstokesKin. Viscous. [40 ° C] waste oil in cstokes Kin. Viskos. [40°C] in %Kin. Viscous. [40 ° C] in% Versuch 3Trial 3 21,6821.68 23,7823.78 + 10+ 10 Versuch 4Trial 4 22,1722.17 22,4922,49 +/- 0+/- 0 Versuch 5Trial 5 22,6522.65 22,4622.46 +/- 0+/- 0

Versuchsreihe 3Trial Series 3

Säurezahl Frischöl in mg KOH/g ÖlAcid value fresh oil in mg KOH / g oil Säurezahl Altöl in mg KOH/g ÖlAcid value used oil in mg KOH / g oil Änderung d. Säurezahl in %Change d. Acid number in% Versuch 6Trial 6 0,830.83 1,221.22 + 47+ 47 Versuch 7Trial 7 0,350.35 0,360.36 + 3+ 3 Versuch 8Trial 8 0,310.31 0,310.31 +/- 0+/- 0 Kin. Viskos. [40°C] Frischöl in cstokesKin. Viscous. [40 ° C] fresh oil in cstokes Kin. Viskos. [40°C] Altöl in cstokesKin. Viscous. [40 ° C] waste oil in cstokes Kin. Viskos. [40°C] in %Kin. Viscous. [40 ° C] in% Versuch 6Trial 6 40,4540.45 58,5758.57 + 45+45 Versuch 7Trial 7 39,9639.96 39,9839,98 +/- 0+/- 0 Versuch 8Trial 8 39,8039,80 39,3239.32 +/- 0+/- 0

Interpretation der ErgebnisseInterpretation of the results

Die Veränderung der Säurezahl steht für die hydrolytische Stabilität eines Tribosystems. Hohe Säurezahlen können zur Zersetzung des Öls durch Autokatalyse führen, deren Spaltprodukte wiederum zu Korrosion, verschlechterte Elastomerverträglichkeit etc. führen.The change in the acid number represents the hydrolytic stability of a tribosystem. High acid numbers can lead to decomposition of the oil by autocatalysis, whose cleavage products in turn lead to corrosion, deteriorated Elastomerverträglichkeit etc.

Ein Vergleich der Ergebnisse der Versuchsreihen 1 bis 3 zeigt folgendes:A comparison of the results of the test series 1 to 3 shows the following:

Das Motorenöl SAE 10W40 auf der Basis von klassischem Mineralöl ist hydrolytisch am stabilsten, zeigt aber nach der Alterung infolge von Zersetzung einen Anstieg der Säurezahl um 80%. Durch Zugabe des Additivsystems wird die Säurezahl vor und nach der Alterung sukzessiv reduziert.The classic oil-based SAE 10W40 motor oil is hydrolytically most stable, but shows an increase in acid number of 80% after aging due to decomposition. By adding the additive system, the acid number is gradually reduced before and after aging.

Das mit FAME versetzte Motorenöl zeigt im nicht additivierten Zustand, besonders nach der Alterung, einen drastischen Säurezahlanstieg um 250 %. Durch Zugabe des Additivsystems erkennt man, dass die Säurezahl sowohl im Frischöl als auch im Altöl wirksam gesenkt wird und der Säurezahlanstieg bis zu 0 % reduziert werden kann.The FAME-added motor oil shows in the non-additive state, especially after aging, a drastic increase in acid number by 250%. By adding the additive system, it can be seen that the acid value is effectively lowered both in the fresh oil and in the waste oil and the acid number increase can be reduced up to 0%.

Das unadditivierte pflanzliche Motorenöl zeigt naturgemäß eine relativ hohe Säurezahl, die auch nach der Alterung bis zu 45% ansteigt. Durch Zugabe des erfindungsgemässen Additivsystems wird die Säurezahl im Frischöl reduziert. Nach der Alterung beobachtet man eine geringe bzw. keine Veränderung der Säurezahl.The unadditierte vegetable motor oil naturally shows a relatively high acid number, which increases even after aging up to 45%. By adding the inventive additive system, the acid number is reduced in fresh oil. After aging, little or no change in the acid number is observed.

Die Veränderung der Viskosität steht für die thermische und oxidative Stabilität eines Tribosystems. Hohe Viskositätsänderungen führen zur erhöhten Drücken, schlechteren Schmiereigenschaften etc. Verantwortlich dafür sind Polymerisations- und Zersetzungsprozesse.The change in viscosity represents the thermal and oxidative stability of a tribosystem. High viscosity changes lead to increased pressures, poorer lubricating properties, etc. Responsible for this are polymerization and decomposition processes.

Aufgrund des gesättigten Charakters des Motorenöls auf der Basis von klassischem Mineralöl beobachtet man sowohl mit als auch ohne Zugabe des erfindungsgemässen Additivsystems keine Viskositätsänderung.Due to the saturated character of the engine oil on the basis of classic mineral oil observed both with and without the addition of the inventive additive system no change in viscosity.

Das mit FAME versetzte bzw. verunreinigte Motorenöl zeigt im unadditivierten Zustand bereits eine Viskositätszunahme von 10%. Die Zugabe des Additivsystems bewirkt eine Stabilisierung und somit auch nach der Alterung keine Viskositätsveränderung.The FAME-added or contaminated engine oil already shows a viscosity increase of 10% in the unadditivated state. The addition of the additive system causes a stabilization and thus also after aging no change in viscosity.

Im pflanzlichen Motorenöl hingegen beobachtet man erwartungsgemäß eine starke Viskositätsveränderung von bis 45%. Die Zugabe des Additivsystems stabilisiert auch hier das Motorenöl signifikant. Es wird keine Viskositätsänderung beobachtet.In vegetable oil, on the other hand, as expected, a strong viscosity change of up to 45% is observed. The addition of the additive system also stabilizes the engine oil significantly. No change in viscosity is observed.

Daraus folgt, dass das erfindungsgemässe Additivsystem sowohl im reinen und mit FAME verunreinigten Motorenöl als auch im pflanzlichen Motorenöl eine deutliche Verbesserung der hydrolytischen, thermischen und oxidativen Stabilität bewirkt.It follows that the inventive additive system causes a significant improvement in hydrolytic, thermal and oxidative stability both in pure and contaminated with FAME engine oil and in vegetable engine oil.

Claims (9)

  1. Use of at least one epoxidized natural fatty acid ester (component a1), at least one epoxidized natural fatty acid glyceride (component a2) and a carbodiimide (component a3) as component A together with a sterically hindered phenol as component B and a natural preferably vegetable oil having an oleic acid content of at least 85% preferred of at least 90% as a further component C, for the stabilisation of crude oil, of at least partially refined oil or of synthetic esters, wherein component A has an epoxid content of at least 1,5 % by weight and components A, B and C together form an additive system, containing component A in an amount of 10 - 50 % by weight, preferred 30 - 40 % by weight, component B in an amount of 10 - 50 % by weight, particularly preferred 30 - 40 % by weight, and component C in an amount of 10 - 40 % by weight, preferred 10 - 30 % by weight.
  2. The use of claim 1, wherein the carbodiimide is bis(2,6-diisopropylphenyl)carbodiimide.
  3. The use of claim 1 or 2, wherein the component C is sunflower seed oil.
  4. The use of any of claims 1 - 3, wherein the natural oil as a basis for the fatty acid ester of (component a1) and/or the fatty acid glyceride of (component a2) are selected from the group consisting of rape seed oil, lin seed oil, soybean oil, sunflower seed oil or fish oil and mixtures thereof.
  5. The use of any of claims 1 - 4, containing the component A together with component B in an amount of 5 - 20 % by weight, preferably 5 - 15 % by weight, particularly preferred 5 - 10 % by weight in the total stabilizing composition.
  6. An additive composition containing an epoxidized natural fatty acid ester (component a1) at least one epoxidized natural fatty acid glyceride (component a2) and a carbodiimide (component a3) as component A, a sterically hindered phenol as component B and further a natural preferably vegetable oil having an oleic acid content of at least 85%, particularly preferred of at least 90% as component C, wherein the component A is contained in the additive system in an amount of 10 - 50 % by weight, preferred 30 - 40 % by weight, component B is contained in an amount of 10 - 50 % by weight, particularly preferred 30 - 40 % by weight, and component C is contained in an amount of 10 - 40 % by weight, preferred 10 - 30 % by weight.
  7. The additive composition of claim 6, wherein the carbodiimide is bis(2,6-diisopropyl-phenyl)carbodiimide.
  8. The use of the additive composition of claim 6 or 7 as a lubricant for combustion engines.
  9. Crude oil, at least partially refined oil or synthetic esters, containing an additive composition of claims 6 or 7.
EP09008342.9A 2008-06-26 2009-06-25 Stabiliser and additive compound for combustion engines Active EP2138556B1 (en)

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CH01004/08A CH703950B1 (en) 2008-06-26 2008-06-26 Stabilizer and additive composition for internal combustion engines.

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US9464256B2 (en) * 2013-05-07 2016-10-11 Rhein Chemie Rheinau Gmbh Methods for producing oil formulations by means of certain carbodiimides
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