EP2994522A1 - Methods for producing oil formulations by means of certain carbodiimides - Google Patents

Methods for producing oil formulations by means of certain carbodiimides

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Publication number
EP2994522A1
EP2994522A1 EP14724675.5A EP14724675A EP2994522A1 EP 2994522 A1 EP2994522 A1 EP 2994522A1 EP 14724675 A EP14724675 A EP 14724675A EP 2994522 A1 EP2994522 A1 EP 2994522A1
Authority
EP
European Patent Office
Prior art keywords
oil
carbodiimide
oils
formula
oil formulations
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14724675.5A
Other languages
German (de)
French (fr)
Inventor
Wilhelm Laufer
Armin Eckert
Siegfried KÜNZEL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
Original Assignee
Rhein Chemie Rheinau GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhein Chemie Rheinau GmbH filed Critical Rhein Chemie Rheinau GmbH
Priority to EP14724675.5A priority Critical patent/EP2994522A1/en
Publication of EP2994522A1 publication Critical patent/EP2994522A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0042—Preserving by using additives, e.g. anti-oxidants containing nitrogen
    • C11B5/005—Amines or imines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/22—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms containing a carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C10M2203/106—Naphthenic fractions
    • C10M2203/1065—Naphthenic fractions 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
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds 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
    • C10M2207/401—Fatty vegetable or animal oils 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
    • 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
    • C10N2030/66—Hydrolytic stability
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/12—Gas-turbines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/16—Dielectric; Insulating oil or insulators
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention relates to novel processes for the preparation of stabilized oil formulations by means of certain carbodiimides.
  • a range of base oils and lubricant base substances e.g. Triglycerides, synthetic carboxylic acid esters, phosphoric acid triesters, olefin-dicarboxylic acid copolymers and silicone oils are attacked by water or oxidants to form acidic cleavage products and alcohols.
  • These acidic fission products are a measure of the degree of decomposition. They can be given quantitatively in the form of the acid number, so that this serves as a measure of the aging state of the lubricating oils.
  • the presence of acids or acidic cleavage products accelerates the hydrolysis autocatalytically. Since water is always present in small quantities under technical conditions, the useful life of lubricants is accordingly limited.
  • the object of the present invention was therefore to provide methods which do not have the disadvantages of the prior art.
  • the present invention thus provides a novel process for the preparation of oil formulations, according to which at least one carbodiimide of the formula (I) With
  • the carbodiimides of formula (I) are commercial compounds which are e.g. can be obtained from Rhein Chemie Rheinau GmbH under the trade name Stabaxol® or Additin®.
  • the oil according to the invention is preferably mineral oils, more preferably naphthenic low sulfur base oils and / or natural fats, oils or waxes, triglycerides preferably soybean oil, rapeseed or sunflower oil and also artificially produced esters e.g. starting from methanol, 2-ethylhexanol, glycol, glycerol, trimethylpropanol (TMP), pentaerythritol, neopentylglycol esterified with e.g. Stearic acid, oleic acid, adipic acid, terephthalic acid and trimellitic acid.
  • mineral oils more preferably naphthenic low sulfur base oils and / or natural fats, oils or waxes, triglycerides preferably soybean oil, rapeseed or sunflower oil and also artificially produced esters e.g. starting from methanol, 2-ethylhexanol, glycol, glycerol, trimethylpropanol
  • the oil is a trimethylolpropane ester (TMP) of the general formula (II)
  • radicals R 3 , R 4 and R 5 each of which may be the same or different, have a linear or branched alkyl group having 5 to 22 carbon atoms.
  • the radicals R 3 , R 4 and R 5 which may each be identical or different, define a linear or branched alkyl group having 7 to 18 carbon atoms.
  • TMP oleate Trimethylolpropane trioleate
  • the artificially produced esters based on methanol are preferably rapeseed oil methyl ester.
  • the oil formulations stabilized by the process according to the invention may furthermore comprise further additives customary for this field of application.
  • they may be antioxidants or metal deactivators.
  • the oil formulation therefore additionally contains 0.005 to 1.0% by weight of an antioxidant and / or 0.01 to 2.0% by weight of a metal deactivator, in each case based on the oil formulation.
  • the preferred amount of antioxidant is between 0.1 and 0.5% by weight, and more preferably 0.1-0.2% by weight, based on the oil formulation.
  • the preferred amount of metal deactivator is between 0.1 and 1, 0 wt .-% and in particular 0.1 to 0.2 wt .-%, based on the oil formulation.
  • the antioxidants are preferably selected from the group consisting of bishydroxytoluene, hydroquinone, 4-tert-butylcatechol, naphthol, phenylnaphthylamines, diphenylamines, phenolic thioethers, tocopherols and mixtures of the listed substances.
  • the metal deactivator is preferably selected from the group consisting of organic heteroatom compounds, more preferably triazoles, toluyltriazoles, Dimercaptothiadiazolen and mixtures of the listed substances.
  • concentrations of 0.05-2% by weight of carbodiimide preferably 0.1-1% by weight and more preferably 0.2-0.5% by weight, based on the oil formulation, are used .
  • the addition of the carbodiimide preferably takes place in a mixing or storage container, particularly preferably directly in the container, preferably in a drum or container.
  • the carbodiimide is poured into the oil or pumped in via a line.
  • this can be additionally reinforced by stirrers, such as blade, coil or anchor agitator, dispersants, drum or container stirrers.
  • the carbodiimide in the mixing or storage container more preferably directly in the container, preferably presented in a barrel or container, and then poured the oil.
  • pouring the oil usually enters a sufficient mixing.
  • Another object of the invention are also Olformulierungen prepared by the novel process and their use as process oils, propellants, heat transfer oils, engine oils, greases, metalworking fluids, turbine and transformer oils.
  • the following examples serve to illustrate the invention without being limiting.
  • SXL I Stabaxol ® I, a solid monomeric carbodiimide based on 2,6-diisopropyl Rhein Chemie Rheinau GmbH phenyl isocyanate.
  • TMP-oleate Synative ® ES TMP 05 from BASF SE.
  • RME Rapeseed oil methyl ester
  • the toast test ASTM D 2619 (“Beverage bottle test”) is part of internationally recognized oil formulation specifications and is used to test the hydrolytic resistance of liquids and tracks the acid number increase as a measure of the hydrolytic stability of the oil.
  • test oil rapeseed oil methyl ester
  • Table 1 show that the hydrolytic stability of the oil formulations prepared by the process according to the invention is already given when using low carbodiimide concentrations.
  • the temperature must be raised to 80 ° C. in order to be able to produce any solution at all, which is complicated and involves undesired decomposition processes with liberation of toxic substances.
  • Table 2 decrease in the acid value at 30 ° C: comparison between Stabaxol ® MTC (ERF) and SXL I (V) Experimental procedure:

Abstract

The invention relates to novel methods for producing stabilised oil formulations by means of certain carbodiimides.

Description

Verfahren zur Herstellung von Ölformulierungen mittels bestimmter Carbodiimide  Process for the preparation of oil formulations by means of certain carbodiimides
Die vorliegenden Erfindung betrifft neue Verfahren zur Herstellung von stabilisierten Ölformulierungen mittels bestimmter Carbodiimide. The present invention relates to novel processes for the preparation of stabilized oil formulations by means of certain carbodiimides.
Eine Reihe von Grundölen und Schmierstoff-Grundsubstanzen, z.B. Triglyceride, synthetische Carbonsäurester, Phosphorsäuretriester, Olefin-Dicarbonsäure-Copolymere und Silikonöle werden durch Wasser oder Oxidationsmittel unter Bildung von sauren Spaltprodukten und Alkoholen angegriffen. Diese sauren Spaltprodukte sind ein Maß für den Zersetzungsgrad. Sie können in Form der Säurezahl quantitativ angegeben werden, so dass diese als Maß für den Alterungszustand der Schmieröle dient. Die Anwesenheit von Säuren oder sauren Spaltprodukten beschleunigt die Hydrolyse autokatalytisch. Da Wasser unter technischen Bedingungen immer in geringen Mengen anwesend ist, ist dementsprechend die Nutzungsdauer von Schmierstoffen beschränkt. Wie in DE 4435548 A1 beschrieben kann der Zusatz von Öl-löslichen Carbodiimiden die hydrolytische Zersetzung wirksam verhindern. Die im Stand der Technik beschriebenen Verfahren zur Herstellung der mit Carbodiimid stabilisierten Ölformulierungen haben jedoch den Nachteil, dass feste Carbodiimide eingesetzt werden. Diese müssen erst aufgeschmolzen und anschließend in die erwärmte Ölformulierung eingerührt werden. Diese Vorgehensweise ist sehr aufwändig und darüber hinaus unwirtschaftlich. Idealerweise sollen die Carbodiimide bei niedrigen Temperaturen eingerührt werden. Weiterhin neigen die Carbodiimide bei diesem Vorgang zur Abspaltung von giftigen und bei den angewandten Temperaturen flüchtigen Isocyanaten. A range of base oils and lubricant base substances, e.g. Triglycerides, synthetic carboxylic acid esters, phosphoric acid triesters, olefin-dicarboxylic acid copolymers and silicone oils are attacked by water or oxidants to form acidic cleavage products and alcohols. These acidic fission products are a measure of the degree of decomposition. They can be given quantitatively in the form of the acid number, so that this serves as a measure of the aging state of the lubricating oils. The presence of acids or acidic cleavage products accelerates the hydrolysis autocatalytically. Since water is always present in small quantities under technical conditions, the useful life of lubricants is accordingly limited. As described in DE 4435548 A1, the addition of oil-soluble carbodiimides can effectively prevent the hydrolytic decomposition. However, the processes described in the prior art for preparing the carbodiimide-stabilized oil formulations have the disadvantage that solid carbodiimides are used. These must first be melted and then stirred into the heated oil formulation. This procedure is very complex and beyond uneconomical. Ideally, the carbodiimides should be stirred in at low temperatures. Furthermore, the carbodiimides tend in this process to cleave off toxic and volatile at the temperatures used isocyanates.
Die Aufgabe der vorliegenden Erfindung bestand somit darin, Verfahren bereitzustellen, die die Nachteile des Standes der Technik nicht aufweisen. The object of the present invention was therefore to provide methods which do not have the disadvantages of the prior art.
Überraschenderweise wurde nun gefunden, dass mit dem erfindungsgemäßen Verfahren auf einfache Weise Ölformulierungen stabilisiert werden können und dadurch diese für die Schmierstoffindustrie wirtschaftlich machen. Weiterhin trägt das erfindungsgemäße Verfahren auch einen deutlichen Beitrag zur Verbesserung der Arbeitshygiene und zum Umweltschutz bei. Surprisingly, it has now been found that oil formulations can be stabilized in a simple manner with the process according to the invention and thereby make them economical for the lubricant industry. Furthermore, the method according to the invention also makes a significant contribution to the improvement of occupational hygiene and environmental protection.
Gegenstand der vorliegenden Erfindung ist somit ein neues Verfahren zur Herstellung von Ölformulierungen, wonach mindestens ein Carbodiimid der Formel (I) mit The present invention thus provides a novel process for the preparation of oil formulations, according to which at least one carbodiimide of the formula (I) With
R1 = CH3 oder CH(CH3)2 und R2 = H oder CH(CH3)2, bei Temperaturen von 10 - 40°C, bevorzugt 15 - 30 °C, mindestens einem Öl zugesetzt wird. R 1 = CH 3 or CH (CH 3 ) 2 and R 2 = H or CH (CH 3 ) 2 , at temperatures of 10 - 40 ° C, preferably 15 - 30 ° C, at least one oil is added.
In einer besonders bevorzugten Ausführungsform der Erfindung ist R1 = CH3 und R2 = H. In a particularly preferred embodiment of the invention, R 1 = CH 3 and R 2 = H.
In einer weiteren bevorzugten Ausführungsform der Erfindung ist R1 = R2 = CH(CH3)2. In a further preferred embodiment of the invention, R 1 = R 2 = CH (CH 3 ) 2 .
Bei den Carbodiimiden der Formel (I) handelt es sich um handelsübliche Verbindungen, die z.B. bei der Rhein Chemie Rheinau GmbH unter dem Handelsnamen Stabaxol® oder Additin® erhältlich sind. The carbodiimides of formula (I) are commercial compounds which are e.g. can be obtained from Rhein Chemie Rheinau GmbH under the trade name Stabaxol® or Additin®.
Besonders bevorzugt ist das Bis-o-Tolylcarbodiimid, kommerziell erhältlich bei der Rhein Chemie Rheinau GmbH unter dem Handelsnamen Stabaxol®MTC. Particularly preferred is the bis-o-Tolylcarbodiimid, commercially available from Rhein Chemie Rheinau GmbH under the trade name Stabaxol®MTC.
Bei dem Öl im Sinne der Erfindung handelt es sich vorzugsweise um Mineralöle, besonders bevorzugt naphthenische schwefelarme Grundöle und/oder natürliche Fette, Öle oder Wachse, - Triglyceride bevorzugt Sojaöl, Raps- oder Sonnenblumenöl und ebenso künstlich hergestellte Ester z.B. ausgehend von Methanol, 2-Ethylhexanol, Glykol, Glycerin, Trimethylpropanol (TMP), Pentaerythritol, Neopenthylglykol verestert mit z.B. Stearinsäure, Ölsäure, Adipinsäure, Terephtalsäure und Trimellitsäure handelt. The oil according to the invention is preferably mineral oils, more preferably naphthenic low sulfur base oils and / or natural fats, oils or waxes, triglycerides preferably soybean oil, rapeseed or sunflower oil and also artificially produced esters e.g. starting from methanol, 2-ethylhexanol, glycol, glycerol, trimethylpropanol (TMP), pentaerythritol, neopentylglycol esterified with e.g. Stearic acid, oleic acid, adipic acid, terephthalic acid and trimellitic acid.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung handelt es sich bei dem Öl um ein Trimethylolpropanester (TMP) der allgemeinen Formel (II) In a preferred embodiment of the present invention, the oil is a trimethylolpropane ester (TMP) of the general formula (II)
Entsprechende Trimethylolpropanester sind aus der deutschen Patentanmeldung DE 10 2004 025 939 A bekannt. In der vorstehenden allgemeinen Formel (II) weisen die Reste R3, R4 und R5, die jeweils gleich oder verschieden sein können, eine lineare oder verzweigte Alkylgruppe mit 5 bis 22 Kohlenstoffatomen auf. In einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung definieren die Reste R3, R4 und R5, die jeweils gleich oder verschieden sein können, eine lineare oder verzweigte Alkylgruppe mit 7 bis 18 Kohlenstoffatomen. Corresponding trimethylolpropane esters are known from German patent application DE 10 2004 025 939 A. In the above general formula (II), the radicals R 3 , R 4 and R 5 , each of which may be the same or different, have a linear or branched alkyl group having 5 to 22 carbon atoms. In a further preferred embodiment of the present invention, the radicals R 3 , R 4 and R 5 , which may each be identical or different, define a linear or branched alkyl group having 7 to 18 carbon atoms.
Besonders bevorzugt ist dabei Trimethylolpropantrioleat (TMP-Oleat). Trimethylolpropane trioleate (TMP oleate) is particularly preferred.
Bei den künstlich hergestellten Ester auf Basis von Methanol handelt sich bevorzugt um Rapsölmethylester. The artificially produced esters based on methanol are preferably rapeseed oil methyl ester.
In einer weiteren bevorzugten Ausführungsform der Erfindung wird eine Mischungen aus Ölen eingesetzt. In a further preferred embodiment of the invention, a mixture of oils is used.
Die nach dem erfindungsgemäßen Verfahren stabilisierten Ölformulierungen können darüber hinaus weitere, für dieses Anwendungsgebiet übliche Additive umfassen. Beispielsweise kann es sich um Antioxidantien oder Metalldeaktivatoren handeln. The oil formulations stabilized by the process according to the invention may furthermore comprise further additives customary for this field of application. For example, they may be antioxidants or metal deactivators.
In einer weiteren Ausführungsform enthält die Ölformulierung daher zusätzlich 0,005 bis 1 ,0 Gew.-% eines Antioxidans und/oder 0,01 bis 2,0 Gew.-% eines Metalldeaktivators, jeweils bezogen auf die Ölformulierung. In a further embodiment, the oil formulation therefore additionally contains 0.005 to 1.0% by weight of an antioxidant and / or 0.01 to 2.0% by weight of a metal deactivator, in each case based on the oil formulation.
Die bevorzugte Menge an Antioxidans liegt zwischen 0,1 und 0,5 Gew.-% und insbesondere bei 0,1 - 0,2 Gew.-%, bezogen auf die Ölformulierung. The preferred amount of antioxidant is between 0.1 and 0.5% by weight, and more preferably 0.1-0.2% by weight, based on the oil formulation.
Die bevorzugte Menge an Metalldeaktivator liegt zwischen 0,1 und 1 ,0 Gew.-% und insbesondere bei 0,1 - 0,2 Gew.-%, bezogen auf die Ölformulierung. The preferred amount of metal deactivator is between 0.1 and 1, 0 wt .-% and in particular 0.1 to 0.2 wt .-%, based on the oil formulation.
Die Antioxidantien werden vorzugsweise ausgewählt aus der Gruppe, bestehend aus Bishydroxytoluol, Hydrochinon, 4-tert.-Butylkatechol, Naphthol, Phenylnaphthylaminen, Diphenylaminen, phenolischen Thioethern, Tocopherolen und Mischungen der aufgeführten Substanzen. The antioxidants are preferably selected from the group consisting of bishydroxytoluene, hydroquinone, 4-tert-butylcatechol, naphthol, phenylnaphthylamines, diphenylamines, phenolic thioethers, tocopherols and mixtures of the listed substances.
Der Metalldeaktivator wird vorzugsweise ausgewählt aus der Gruppe, bestehend aus organischen Heteroatomverbindungen, besonders bevorzugt Triazolen, Toluyltriazolen, Dimercaptothiadiazolen und Mischungen der aufgeführten Substanzen. Zur Stabilisierung der nach dem erfindungsgemäßen Verfahren hergestellten Olformulierungen werden Konzentrationen von 0,05 - 2 Gew.% Carbodiimid, bevorzugt 0,1 - 1 Gew.% und besonders bevorzugt 0,2 - 0,5 Gew.%, bezogen auf die Ölformulierung verwendet. Die Zugabe des Carbodiimids erfolgt bevorzugt in einem Misch- oder Lagerbehälter, besonders bevorzugt direkt im Gebinde, vorzugsweise in einem Fass oder Container. The metal deactivator is preferably selected from the group consisting of organic heteroatom compounds, more preferably triazoles, toluyltriazoles, Dimercaptothiadiazolen and mixtures of the listed substances. To stabilize the oil formulations prepared by the process according to the invention, concentrations of 0.05-2% by weight of carbodiimide, preferably 0.1-1% by weight and more preferably 0.2-0.5% by weight, based on the oil formulation, are used , The addition of the carbodiimide preferably takes place in a mixing or storage container, particularly preferably directly in the container, preferably in a drum or container.
In einer bevorzugten Ausführungsform der Erfindung wird das Carbodiimid in das Öl eingegossen oder über eine Leitung eingepumpt. Bei der Eindosierung tritt in der Regel bereits eine Durchmischung ein, diese kann aber zusätzlich durch Rühraggregate, wie beispielsweise Blatt-, Wendel- oder Ankerrührer, Dispergatoren, Fass- oder Containerrührer, verstärkt werden. In a preferred embodiment of the invention, the carbodiimide is poured into the oil or pumped in via a line. In the metering usually already mixed, but this can be additionally reinforced by stirrers, such as blade, coil or anchor agitator, dispersants, drum or container stirrers.
In einer weiteren bevorzugten Ausführungsform der Erfindung wird das Carbodiimid im Misch- oder Lagerbehälter, besonders bevorzugt direkt im Gebinde, vorzugsweise in einem Fass oder Container, vorgelegt und anschließend das Öl eingegossen. Beim Eingießen des Öls tritt in der Regel bereits eine ausreichende Durchmischung ein. In a further preferred embodiment of the invention, the carbodiimide in the mixing or storage container, more preferably directly in the container, preferably presented in a barrel or container, and then poured the oil. When pouring the oil usually enters a sufficient mixing.
Weiterer Gegenstand der Erfindung sind ebenso Olformulierungen hergestellt nach dem erfindungsgemäßen Verfahren sowie deren Einsatz als Prozessöle, Triebstoffe, Wärmeträgeröle, Motorenöle, Fette, Metallbearbeitungsflüssigkeiten, Turbinen- und Transformatorenöle. Die nachfolgenden Beispiele dienen der Erläuterung der Erfindung, ohne dabei limitierend zu wirken. Another object of the invention are also Olformulierungen prepared by the novel process and their use as process oils, propellants, heat transfer oils, engine oils, greases, metalworking fluids, turbine and transformer oils. The following examples serve to illustrate the invention without being limiting.
Ausführungsbeispiele: EXAMPLES
In den nachfolgenden Beispielen wurden die folgenden Substanzen eingesetzt: In the following examples, the following substances were used:
SXL MTC= Stabaxol®MTC, ein flüssiges Carbodiimid der Formel (I) mit R1= CH3, R2 = H der Rhein Chemie Rheinau GmbH SXL I Liq = Stabaxol® I Liq, ein Carbodiimid der Formel (I) mit R1 = R2 = CH(CH3)2. SXL MTC = Stabaxol ® MTC, a liquid carbodiimide of the formula (I) with R 1 = CH 3, R 2 = H Rhein Chemie Rheinau GmbH SXL I Liq = Stabaxol ® I Liq, a carbodiimide of the formula (I) with R 1 = R 2 = CH (CH 3 ) 2 .
SXL I = Stabaxol® I, ein festes monomeres Carbodiimid auf Basis von 2,6-Diisopropyl- phenylisocyanat der Firma Rhein Chemie Rheinau GmbH. SXL I = Stabaxol ® I, a solid monomeric carbodiimide based on 2,6-diisopropyl Rhein Chemie Rheinau GmbH phenyl isocyanate.
TMP-Oleat = Synative® ES TMP 05 der Firma BASF SE. TMP-oleate = Synative ® ES TMP 05 from BASF SE.
Rapsölmethylester (RME) der Firma ADM Hamburg AG. Beispiel 1 : Rapeseed oil methyl ester (RME) from ADM Hamburg AG. Example 1 :
Der Toast-Test ASTM D 2619 („Beverage bottle test") ist Teil von international anerkannten Ölformulierung-Spezifikationen und wird zur Überprüfung der hydrolytischen Beständigkeit von Flüssigkeiten herangezogen. Es wird der Säurezahlanstieg als Maßzahl für die hydrolytische Beständigkeit des Öles verfolgt. Prüfbedingungen:  The toast test ASTM D 2619 ("Beverage bottle test") is part of internationally recognized oil formulation specifications and is used to test the hydrolytic resistance of liquids and tracks the acid number increase as a measure of the hydrolytic stability of the oil.
75 ml Testöl (Rapsölmethylester), nachstehend als RME abgekürzt 75 ml of test oil (rapeseed oil methyl ester), abbreviated hereafter as RME
25 ml destilliertes Wasser 25 ml of distilled water
Temperatur: 95 °C. Bewertungskriterien in Abhängigkeit der Zeit (h): - Säurezahl (SZ) der Ölphase (mg KOH/g) Temperature: 95 ° C. Evaluation criteria as a function of time (h): acid number (SZ) of the oil phase (mg KOH / g)
Acidität der Wasserphase (mg KOH/25ml). Tabelle 1 : Acidity of the water phase (mg KOH / 25ml). Table 1 :
Für die erfindungsgemäßen Beispiele wurden 0,5 Gew.% bzw. 1 Gew % SXL MTC über 1 Stunde bei 30°C in den Rapsölmethylester eingerührt. Für die Vergleichsbeispiele musste die Temperatur auf 80°C erhöht werden, um SXL I aufzuschmelzen und so überhaupt im Öl lösen zu können. Dementsprechend wurden 0,5 Gew % bzw. 1 % Gew SXL I über 1 Stunde bei 80°C eingerührt. For the examples according to the invention, 0.5% by weight and 1% by weight SXL MTC were stirred into the rapeseed oil methyl ester at 30 ° C. for 1 hour. For the comparative examples, the temperature had to be raised to 80 ° C. in order to be able to melt SXL I and thus dissolve it in the oil at all. Accordingly, 0.5% by weight or 1% by weight of SXL I was stirred in at 80 ° C. for 1 hour.
(V) = Vergleichsbeispiel; (E) = Erfindungsgemäß. (V) = Comparative Example; (E) = According to the invention.
Die Ergebnisse in der Tabelle 1 zeigen, dass die hydrolytische Stabilität der nach dem erfindungsgemäßen Verfahren hergestellten Olformulierungen bereits beim Einsatz geringer Carbodiimid-Konzentrationen gegeben ist. Zudem muss bei den Verbindungen des Standes der Technik die Temperatur auf 80°C erhöht werden, um überhaupt eine Lösung herstellen zu können, was aufwändig ist und mit unerwünschten Zersetzungsprozessen unter Freisetzung giftiger Substanzen einhergeht. Tabelle 2 Abnahme der Säurezahl bei 30°C: Vergleich zwischen Stabaxol® MTC (erf) und SXL I (V) Versuchsdurchführung: The results in Table 1 show that the hydrolytic stability of the oil formulations prepared by the process according to the invention is already given when using low carbodiimide concentrations. In addition, in the case of the compounds of the prior art, the temperature must be raised to 80 ° C. in order to be able to produce any solution at all, which is complicated and involves undesired decomposition processes with liberation of toxic substances. Table 2 decrease in the acid value at 30 ° C: comparison between Stabaxol ® MTC (ERF) and SXL I (V) Experimental procedure:
298,5 g TMP-Oleat wurden auf 30°C erwärmt. Danach erfolgte die Zugabe von entweder 1 ,5 g (0,5 Gew %) SXL MTC oder 1 ,5 g (0,5 Gew %) SXL I Pulver und das Gemisch wurde 48 h lang bei 30°C gerührt. Jeweils nach 0, 6, 24 und 48 h wurde eine Probe genommen und deren Säurezahl bestimmt. 298.5 g of TMP oleate were heated to 30 ° C. Thereafter, either 1.5 g (0.5% by weight) of SXL MTC or 1.5 g (0.5% by weight) of SXL I powder was added and the mixture was stirred at 30.degree. C. for 48 hours. After each 0, 6, 24 and 48 h, a sample was taken and their acid number was determined.
Es zeigte sich, dass die erfindungsgemäße Mischung bereits bei Temperaturen von 30°C zu einer deutlich reduzierten Säurezahl führte. It was found that the mixture according to the invention already resulted in a significantly reduced acid number at temperatures of 30 ° C.

Claims

Patentansprüche claims
Verfahren zur Herstellung von Olformulierungen, dadurch gekennzeichnet, dass mindestens ein Carbodiimid der Formel (I) Process for the preparation of oil formulations, characterized in that at least one carbodiimide of the formula (I)
R' = CH3 oder CH(CH3)2 und R2 = H oder CH(CH3)2, bei Temperaturen von 10 - 40°C, bevorzugt 15 - 30 °C, mindestens einem Öl zugesetzt wird. 2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass es sich bei dem Öl um Öl auf Basis von naphthenischem Mineralöl und/oder auf Basis von Estern handelt. R '= CH 3 or CH (CH 3 ) 2 and R 2 = H or CH (CH 3 ) 2 , at temperatures of 10 - 40 ° C, preferably 15 - 30 ° C, at least one oil is added. 2. The method according to claim 1, characterized in that it is the oil to oil based on naphthenic mineral oil and / or based on esters.
Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass es sich bei dem Öl auf Basis von Estern um Triglyceride, Trimethylolpropanester (TMP) und/oder ein Pentaerythritester handelt. Process according to Claim 2, characterized in that the oil based on esters is triglycerides, trimethylolpropane ester (TMP) and / or a pentaerythritol ester.
Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass es sich bei dem Öl auf Basis von Estern um Rapsölmethylester handelt. Process according to Claim 2, characterized in that the oil based on esters is rapeseed oil methyl ester.
Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass als Carbodiimid eine Verbindung der Formel I Method according to one of claims 1 to 4, characterized in that as carbodiimide, a compound of formula I.
eingesetzt wird. is used.
Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass als Carbodiimid eine Verbindung der Formel I Method according to one of claims 1 to 4, characterized in that as carbodiimide, a compound of formula I.
Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Carbodiimid der Formel I in Konzentrationen von 0,1 - 0,5 % zugesetzt wird. Method according to one of claims 1 to 6, characterized in that the carbodiimide of the formula I is added in concentrations of 0.1 - 0.5%.
Olformulierungen, hergestellt nach dem Verfahren der Ansprüche 1 bis 7. Olformulations prepared by the process of claims 1 to 7.
Verwendung der Olformulierungen nach Anspruch 8 als Prozessöle, Triebstoffe, Wärmeträgeröle, Motorenöle, Fette, Metallbearbeitungsflüssigkeiten, Turbinen- und Transformatorenöle. Use of the Olformulierungen according to claim 8 as process oils, propellants, heat transfer oils, motor oils, fats, metalworking fluids, turbine and transformer oils.
EP14724675.5A 2013-05-07 2014-05-06 Methods for producing oil formulations by means of certain carbodiimides Withdrawn EP2994522A1 (en)

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