DE4237501A1 - Use of water insol. di:alkyl ethers - as oil phase in metal surface treating agents. - Google Patents
Use of water insol. di:alkyl ethers - as oil phase in metal surface treating agents.Info
- Publication number
- DE4237501A1 DE4237501A1 DE4237501A DE4237501A DE4237501A1 DE 4237501 A1 DE4237501 A1 DE 4237501A1 DE 4237501 A DE4237501 A DE 4237501A DE 4237501 A DE4237501 A DE 4237501A DE 4237501 A1 DE4237501 A1 DE 4237501A1
- Authority
- DE
- Germany
- Prior art keywords
- metal surface
- surface treatment
- use according
- water
- emulsions
- 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- Withdrawn
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- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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Abstract
Description
Gegenstand der Erfindung ist die Verwendung von Dialkylethern als Ölphase in Metalloberflächen-Behandlungsmitteln.The invention relates to the use of dialkyl ethers as Oil phase in metal surface treatment agents.
Metalloberflächen-Behandlungsmittel, wie beispielsweise Kühl schmierstoffe sowie Reinigungs- und Korrosionsschutzemulsionen, sind in der Regel O/W-Emulsionen auf der Basis von Mineralöl. Die verwendeten Mineralölqualitäten sind überwiegend Kombinationen von paraffinischen, naphthenischen und aromatischen Kohlenwasserstoff verbindungen. Neben den Mineralölen haben auch sogenannte synthe tische Schmiermittel ("synthetische Öle"), wie Polyolefine, Polyalkylenglykole und Polyglykolether, natürliche Esteröle sowie synthetische Ester und ihre Derivate Bedeutung. Daneben enthalten die genannten Metalloberflächen-Behandlungsmittel spezielle Wirk stoff-Additive zur Einstellung der gewünschten Gebrauchseigen schaften.Metal surface treatment agents, such as cooling lubricants as well as cleaning and corrosion protection emulsions, are usually O / W emulsions based on mineral oil. The used mineral oil qualities are predominantly combinations of paraffinic, naphthenic and aromatic hydrocarbons links. In addition to the mineral oils also have so-called synthe lubricants ("synthetic oils"), such as polyolefins, Polyalkylene glycols and polyglycol ethers, natural ester oils and synthetic esters and their derivatives meaning. In addition included said metal surface treatment agents have a specific action Substance additives for adjusting the desired properties companies.
Insbesondere stellt jedoch die Verwendung von Mineralölen einen ökologischen Nachteil dieser Metalloberflächen-Behandlungsmittel dar, da eben diese Mineralöle beim Einsatz der Mittel in mehr oder weniger starkem Maße in die Umwelt gelangen und außerordentlich schwer biologisch abbaubar sind.In particular, however, the use of mineral oils provides one ecological disadvantage of these metal surface treatment agents because these mineral oils are more or less used when the agents are used to a lesser extent into the environment and greatly are difficult to biodegrade.
Zur Entgiftung und Verminderung der damit geschaffenen ökologischen Problematik ist zwar aus dem Bereich der Bohrspülmittel die Ver wendung von weitgehend aromatenfreien Kohlenwasserstoff-Fraktionen - heute auch als "non-polluting oils" bezeichnet - in diesem speziellen Einsatzgebiet bekannt, wobei diese weitgehend aromatenfreien Kohlenwasserstoff-Fraktionen als geschlossene Öl phase eingesetzt werden. Siehe hierzu beispielsweise die Veröf fentlichungen E.A. Boyd et al. "New Base Oil Used in Low Toxicity Oil Muds", Journal of Petroleum Technology, 1985, S. 137-143 sowie R.B. Bennet "New Drilling fluid Technology - Mineral Oil Mud", Journal of Petroleum Technology, 1984, S. 975-981 sowie die darin zitierte Literatur. Diese als "non-polluting oils" bezeichneten Ölphasen sind jedoch auch bei ihrer Freigabe in die Umwelt nicht vollkommen unbedenklich. Eine Minderung der Umweltproblematik - ausgelöst durch die flüssigen Ölphasen der hier betroffenen Art - erscheint daher auch auf dem Gebiet der Metalloberflächen-Behand lungsmittel dringend erforderlich.To detoxify and reduce the environmental created Problem is indeed in the field of Bohrspülmittel Ver use of largely aromatic-free hydrocarbon fractions - today also referred to as "non-polluting oils" - in this known special application, these being largely aromatic-free hydrocarbon fractions as a closed oil phase are used. See, for example, the Veröf publications E.A. Boyd et al. "New Base Oil Used in Low Toxicity Oil Muds ", Journal of Petroleum Technology, 1985, pp. 137-143 as well R. B. Bennet "New Drilling Fluid Technology - Mineral Oil Mud", Journal of Petroleum Technology, 1984, pp. 975-981, and therein quoted literature. These are called "non-polluting oils" However, oil phases are not released when released into the environment completely harmless. A reduction of the environmental problem - triggered by the liquid oil phases of the species concerned - therefore also appears in the field of metal surface treatment urgently needed.
Die vorliegende Erfindung geht daher von der Aufgabe aus, Metall oberflächen-Behandlungsmittel mit bisher unbekannter ökologischer Verträglichkeit zu schaffen, die gleichzeitig gute Gebrauchseigen schaften auf den verschiedensten Gebieten aufweisen und eine be friedigende Verwendung, insbesondere auch in Problemgebieten, ge währleisten.The present invention is therefore based on the task of metal Surface treatment agent with previously unknown ecological To create compatibility, the good at the same time have a variety of areas and a be peaceful use, especially in problem areas, ge währleisten.
In einem weiteren Ansatz will die Erfindung auch den weiteren Pro blemkreis der Wirkstoff-Additive in Metalloberflächen-Behandlungs mitteln dadurch ökologisch verbessern, daß aus dem großen Bereich der an sich im Stand der Technik bekannten Zusatzstoffe und Hilfs mittel wenigstens überwiegend und vorzugsweise durchgängig solche Zusatzstoffe und Hilfsmittel ausgewählt werden, die sich durch ökologische Unbedenklichkeit oder wenigstens ökologische Vorteile auszeichnen.In a further approach, the invention also wants the other Pro loop of drug additives in metal surface treatment thereby improving ecologically that out of the big area the additives and auxiliaries known per se in the prior art medium at least predominantly and preferably consistently such Additives and adjuvants are selected which are ecological safety or at least environmental benefits distinguished.
Gegenstand der Erfindung ist somit in einer ersten Ausführungsform die Verwendung von wenigstens weitgehend wasserunlöslichen, bei Arbeitstemperatur flüssigen Dialkylethern ein- und/oder mehrfunk tioneller Alkohole natürlichen oder synthetischen Ursprungs als Ölphase in Metalloberflächen-Behandlungsmitteln.The invention is thus in a first embodiment the use of at least substantially water-insoluble, at Working temperature liquid dialkyl ethers and / or mehrfunk traditional alcohols of natural or synthetic origin Oil phase in metal surface treatment agents.
Die Vorteile der erfindungsgemäßen Verwendung der Dialkylether ge genüber Formulierungen des Standes der Technik auf Mineralölbasis bestehen insbesondere in der biologischen Abbaubarkeit der Dialkylether. Darüber hinaus tritt auch keine Akkumulation von Kohlenwasserstoffen im Abwasser von Prozeßkreisläufen und in der Umwelt auf. Die Entsorgung gebrauchter Metalloberflächen- Behandlungsmittel vereinfacht sich stark. Darüber hinaus resultiert eine mindestens vergleichbare, überwiegend jedoch eine verbesserte Materialverträglichkeit gegenüber Metalloberflächen- Behandlungsmitteln auf der Basis von Mineralölen.The advantages of the use according to the invention of the dialkyl ethers ge compared with prior art mineral oil based formulations exist in particular in the biodegradability of Dialkyl. In addition, there is no accumulation of Hydrocarbons in the wastewater of process circuits and in the Environment up. Disposal of used metal surfaces Treatment agent simplifies greatly. In addition results at least comparable, but mostly improved Material compatibility with metal surface Treatment agents based on mineral oils.
Die Verwendung der Ether als Ölphase, aber auch gegebenenfalls ihre Mitverwendung als mengenmäßig untergeordneter oder übergeordneter Anteil der Ölphase fordert die hinreichende Wasserunlöslichkeit dieser Ether. Im allgemeinen sollte die Wasserlöslichkeit der Ether im Bereich von weniger als 1 Gew.-% und bevorzugt bei weniger als etwa 0.5 Gew.-% liegen.The use of the ethers as oil phase, but also optionally their Co-use as quantitatively subordinate or superior Proportion of the oil phase requires sufficient water insolubility this ether. In general, the water solubility of the ether in the range of less than 1% by weight and preferably less than about 0.5 wt .-% are.
Generell geeignet sind Ether monofunktioneller und/oder mehrfunk tioneller Alkohole. Hierbei kommen neben den Ethern insbesondere monofunktioneller Alkohole auch solche in Betracht, die sich von difunktionellen Alkoholen ableiten. Die Alkohole selbst sollen ökologisch verträglich sein und weisen dementsprechend in bevor zugten Ausführungsformen keine aromatischen Bestandteile auf. Geradkettige und/oder verzweigtkettige, aliphatische oder auch entsprechende ungesättigte, insbesondere ein- und/oder mehrfach olefinisch ungesättigte Alkohole sind die bevorzugten Ether bildenden Ausgangsverbindungen. Darüber hinaus können auch cycloaliphatische Alkohole als Ausgangsverbindungen in Betracht gezogen werden.Ether are generally suitable monofunctional and / or mehrfunk of conventional alcohols. Here come in addition to the Ethern in particular monofunctional alcohols are also those which are different from derive difunctional alcohols. The alcohols themselves are supposed to be environmentally friendly and therefore have in advance ferred embodiments no aromatic constituents. Straight-chain and / or branched-chain, aliphatic or also corresponding unsaturated, especially one and / or multiple Olefinically unsaturated alcohols are the preferred ethers forming starting compounds. In addition, also can Cycloaliphatic alcohols as starting compounds into consideration to be pulled.
Die erfindungsgemäß hergestellten Metalloberflächen-Behandlungs mittel, beispielsweise Kühlschmierstoffe, müssen in der Regel gut hautverträglich sein, da die Bediener der Maschinen häufig in di rekten Kontakt mit den Flüssigkeiten geraten. Ein wichtiges all gemeines Erfordernis im Sinne der vorliegenden Erfindung ist daher, daß sowohl die zugrundeliegenden Alkohole als auch die Ether selbst nicht nur ökologisch verträglich sind, sondern darüber hinaus auch keine sonstigen toxikologischen, insbesondere keine inhalations toxikologischen Gefährdungen der Bediener und Anwender auslösen.The metal surface treatment produced according to the invention Medium, for example cooling lubricants, usually have to be good be tolerated by the skin, as the operators of the machines often in di direct contact with the liquids. An important all common requirement in the sense of the present invention is therefore that both the underlying alcohols and the ethers themselves not only ecologically sound, but also beyond no other toxicological, in particular no inhalations cause toxicological hazards to operators and users.
Aus dem an sich breiten Bereich geeigneter Ether, bevorzugt wenig stens anteilweise auf Basis ausgeprägt oleophiler Alkohole, kommen insbesondere Ether von Alkoholen mit geradkettiger und/oder ver zweigtkettiger Kohlenwasserstoffstruktur in Betracht. Im Rahmen entsprechender monofunktioneller Alkohole sind entsprechende Ver bindungen mit wenigstens 6 C-Atomen geeignete Verbindungen, wobei besonders brauchbar entsprechende Alkohole mit wenigstens 8 C-Ato men im Molekül sind. Die Obergrenze der Kettenlänge wird durch die technische Zugänglichkeit der Alkohole bestimmt und liegt daher beispielsweise im Bereich bis etwa 36, vorzugsweise bei etwa 20 bis 24, insbesondere bevorzugt bei 18 C-Atomen. Die etherbildenden Al kohole selbst können dabei geradkettig und/oder verzweigtkettig sein, sie können aliphatisch gesättigt oder auch ein- und/oder mehrfach olefinisch ungesättigt sein.From the wide range of suitable ethers, preferably little proportionately based on pronounced oleophilic alcohols in particular ethers of alcohols having straight-chain and / or ver branched-chain hydrocarbon structure. As part of corresponding monofunctional alcohols are corresponding Ver compounds with at least 6 C-atoms suitable compounds, wherein particularly suitable corresponding alcohols having at least 8 C-Ato are in the molecule. The upper limit of the chain length is determined by the technical accessibility of the alcohols is and therefore is for example in the range up to about 36, preferably at about 20 to 24, particularly preferably 18 C atoms. The ether-forming Al Alcohols themselves can be straight-chain and / or branched-chain be, they can be aliphatic saturated or even on and / or be multiple olefinically unsaturated.
Grundsätzlich sind Ether aus Alkoholen natürlichen und/oder syn thetischen Ursprungs geeignet. Insbesondere Synthesealkohole des hier besonders interessierenden Bereichs von etwa C8-18, die auch ungesättigte Anteile enthalten können, sind häufig preiswerte Komponenten des Marktes und als Ausgangsstoffe für Ether im Sinne der Erfindung verwertbar.Basically, ethers are suitable from alcohols of natural and / or synthetic origin. In particular, synthetic alcohols of the here particularly interesting range of about C 8-18 , which may also contain unsaturated portions, are often inexpensive components of the market and as starting materials for ethers in the context of the invention utilizable.
Die Flammpunkte der Ether sollten vorzugsweise wenigstens 80°C, insbesondere wenigstens 100°C und weiter bevorzugt wenigstens 120°C betragen. Dementsprechend kommen hier neben den genannten Ethern auf der Basis von monofunktionellen Alkoholen mit insbesondere we nigstens 8 C-Atomen auch Ether ausgewählter Polyole in Betracht. Für die Etherbildung geeignete Polyole sind insbesondere niedere Diole, wie Ethylenglykol und/oder Dipropylenglykole, aber auch ge gebenenfalls verzweigtkettige Diole mit einem höheren oleophilen Kohlenwasserstoffrest im Molekül. Geeignet sind beispielsweise oleophile Diole mit Hydroxylgruppen in α,ω-Stellung und/oder längerkettige Diole, die ihre Hydroxylgruppen an benachbarten Koh lenstoffatomen aufweisen. Charakteristische Beispiele für die Ver bindungen dieser Art sind etwa das 2,2-Dimethyl-1,3-propandiol (Neopentylglykol) oder die Verseifungsprodukte von epoxidierten Olefinen.The flash points of the ethers should preferably be at least 80 ° C, in particular at least 100 ° C and more preferably at least 120 ° C amount. Accordingly, here come next to the mentioned ethers on the basis of monofunctional alcohols with in particular we at least 8 C atoms also ethers of selected polyols into consideration. Polyols which are suitable for ether formation are in particular lower ones Diols, such as ethylene glycol and / or dipropylene glycols, but also ge optionally branched-chain diols with a higher oleophilic Hydrocarbon radical in the molecule. Suitable, for example oleophilic diols with hydroxyl groups in α, ω-position and / or longer chain diols that have their hydroxyl groups on adjacent Koh have lenstoffatomen. Characteristic examples of the Ver Compounds of this type are about the 2,2-dimethyl-1,3-propanediol (Neopentyl glycol) or the saponification products of epoxidized Olefins.
Neben symmetrischen Dialkylethern, die aus zwei Alkoholresten gleicher Kettenlänge hergestellt werden, sind in gleicher Weise auch nicht symmetrische Dialkylether, die aus Gemischen von Alko holen unterschiedlicher Kettenlängen hergestellt werden können, im Sinne der vorliegenden Erfindung einsetzbar. Im Sinne der vorlie genden Erfindung werden jedoch vorzugsweise solche Dialkylether verwendet, die zwei gleiche Alkylreste aufweisen, d. h. symmetrische Dialkylether. Bevorzugt sind hierbei insbesondere solche symme trische Dialkylether, die zwei geradkettige, gesättigte Alkylreste mit je 8 C-Atomen aufweisen.In addition to symmetrical dialkyl ethers consisting of two alcohol radicals same chain length are produced in the same way also non-symmetrical dialkyl ethers, which consist of mixtures of Alko pick different chain lengths can be made in the Can be used according to the present invention. For the purposes of the present However, the invention preferably such dialkyl ethers used having two identical alkyl radicals, d. H. symmetrical Dialkyl. In this case, in particular, such symme are preferred trical dialkyl ethers, the two straight-chain, saturated alkyl radicals each having 8 carbon atoms.
Gegenüber vergleichbaren Formulierungen auf der Basis von Mineral ölen entsteht auch bei der Verwendung der Dialkylether gemäß der vorliegenden Erfindung bei Umwälzung der Metalloberflächen-Behand lungsmittel in der Regel kein störender Schaum; der Anstrich und die Dichtungen der Maschinen werden nicht angegriffen. Ferner wurde festgestellt, daß die Emulsionsstabilität auch über eine längere Gebrauchszeit gewährleistet ist. Rückstände auf den Maschinen las sen sich leicht mit Wasser abwaschen.Compared to similar formulations based on mineral Oils also arise when using the dialkyl ethers according to the present invention in circulation of the metal surface treatment usually no disturbing foam; the painting and The seals of the machines are not attacked. Further became found that the emulsion stability over a longer Period of use is guaranteed. Residues on the machines read It is easy to wash off with water.
Die Menge der in den Metalloberflächen-Behandlungsmitteln einzu setzenden Dialkylether richtet sich insbesondere nach dem jewei ligen Anwendungszweck. Hierbei ist im allgemeinen davon auszugehen, daß die gleichen Mengen an Dialkylether einzusetzen sind, wie auch an Mineralölen in vergleichbaren Produkten. Im Sinne der vorlie genden Erfindung ist es jedoch bevorzugt, daß die Dialkylether in Mengen von 20 bis 90 Gew.-%, insbesondere von 30 bis 70 Gew.-%, in den Metalloberflächen-Behandlungsmitteln vorliegen, wobei diese zusätzlich Wirkstoff-Additive und gegebenenfalls Wasser enthalten.To enter the amount of metal surface treatment agents Setting dialkyl ether depends in particular on the jewei long-term use. It is generally assumed that that the same amounts of dialkyl ethers are to be used, as well of mineral oils in comparable products. For the purposes of the present However, it is preferred that the dialkyl ethers in Amounts of 20 to 90 wt .-%, in particular from 30 to 70 wt .-%, in the metal surface treatment agents are present, these additionally contain active substance additives and optionally water.
Hierbei ist es jedoch möglich, die Dialkylether im Rahmen der Er findung mit weiteren geeigneten Ölkomponenten, die an sich im Stand der Technik bekannt sind, abzumischen. Besonders bevorzugt im Sinne der Erfindung sind dabei im wesentlichen aromatenfreie aliphatische und/oder cycloaliphatische Kohlenwasserstoff-Fraktionen. Auf den einschlägigen druckschriftlichen Stand der Technik und die auf dem Markt befindlichen Handelsprodukte wird verwiesen. Sofern er wünscht, können somit beispielsweise Paraffinöle und auch Mineral öle als Mischungskomponente neben den Dialkylethern in der Ölphase vorliegen.It is possible, however, the dialkyl ethers in the context of Er finding with other suitable oil components, the stand in itself The technique is known to mix. Particularly preferred in the sense The invention are essentially aromatic-free aliphatic and / or cycloaliphatic hydrocarbon fractions. On the relevant prior art and printed on the Marketed commercial products are referenced. Unless he wishes, thus, for example, paraffin oils and mineral Oils as a mixture component in addition to the dialkyl ethers in the oil phase available.
Besonders wichtige Mischungskomponenten im Sinne der vorliegenden Erfindung sind jedoch umweltverträgliche oleophile Alkohole und/oder Esteröle. Derartige Alkohole bzw. Esteröle sollten bei Umgebungstemperatur, aber auch unter Einsatzbedingungen fließfähig sein. Dementsprechend werden bevorzugt solche Alkohole und Esteröle eingesetzt, deren Erstarrungswerte (Fließ- und Stockpunkt) unter halb 10°C und zweckmäßigerweise unterhalb 0°C liegen.Particularly important mixture components in the sense of the present Invention, however, are environmentally compatible oleophilic alcohols and / or ester oils. Such alcohols or ester oils should be included Ambient temperature, but also in service conditions flowable his. Accordingly, preferred are those alcohols and ester oils used their solidification values (flow and pour point) under half 10 ° C and conveniently below 0 ° C.
Aus Gründen der Betriebssicherheit sollten auch diese Mischungs komponenten Flammpunkte im Bereich der oben genannten Dialkylether aufweisen. Besonders wichtig im Sinne der vorliegenden Erfindung ist die biologisch und ökologisch verträgliche Konstitution der einzusetzenden Alkohole und Esteröle, die somit frei von uner wünscht toxischen Bestandteilen sein sollten. Entsprechende Alko hole und/oder Esteröle sind beispielsweise aus der WO-A-90/14400 bekannt. Sofern ein Einsatz derartiger Mischungskomponenten neben den erfindungsgemäß zu verwendenden Dialkylethern in der Ölphase aus technischen oder sonstigen Gründen erwünscht ist, können der artige Mischungskomponenten die Dialkylether bis zu 50 Gew.-%, be zogen auf die Ölphase, ersetzen.For reasons of operational safety, this mixture should also be used components flash points in the range of the above dialkyl ethers respectively. Especially important in the context of the present invention is the biologically and ecologically compatible constitution of to be used alcohols and ester oils, thus free from uner desires to be toxic ingredients. Corresponding Alko hole and / or ester oils are known, for example, from WO-A-90/14400 known. If a use of such mixture components in addition the dialkyl ethers to be used according to the invention in the oil phase is desired for technical or other reasons, the like mixture components, the dialkyl ethers up to 50 wt .-%, be moved to the oil phase, replacing.
Die Metalloberflächen-Behandlungsmittel im Sinne der vorliegenden Erfindung können einerseits in Form von Öl-basierten Konzentraten sowie andererseits in Form von Öl-in-Wasser-Emulsionen (O/W-Emul sionen) vorliegen. Im ersteren Fall bestehen die Metalloberflächen-Behandlungsmittel aus der Ölphase - den Dialkylethern -, die in der Regel nur Wirkstoff-Additive, die dem jeweiligen Anwendungszweck entsprechen, enthält. Im zweiten Falle bilden die Dialkylether die disperse Ölphase einer Wasser-basierten O/W-Emulsion, die dann gleichfalls die entsprechenden Wirkstoff- Additive enthält.The metal surface treatment agents according to the present On the one hand, the invention can be in the form of oil-based concentrates and on the other hand in the form of oil-in-water emulsions (O / W Emul sions). In the former case, the Metal surface treatment agents from the oil phase - the Dialkyl ethers - which are usually only drug additives that the corresponding application. In the second case The dialkyl ethers form the water-based disperse oil phase O / W emulsion, which then also contains the corresponding active ingredient Contains additives.
Metalloberflächen-Behandlungsmittel im Sinne der vorliegenden Er findung umfassen auch sogenannte Phaseninversions-Emulsionen (PIT-Emulsionen). Diese werden dadurch hergestellt, daß man zu nächst die Phaseninversions-Temperatur bestimmt, indem man eine Probe der auf übliche Weise hergestellten Emulsion unter Verwendung eines Leitfähigkeit-Meßgerätes erhitzt und die Temperatur bestimmt, bei der die Leitfähigkeit stark abnimmt. Nachdem nun der Phasenin versions-Temperaturbereich für eine bestimmte Zusammensetzung einer Emulsion bekannt ist, wird zunächst wie üblich eine Emulsion, die alle wesentlichen Komponenten enthält, auf eine Temperatur erhitzt, die innerhalb oder oberhalb des Phaseninversions-Temperaturbe reiches liegt. Eine weitere Herstellungsmöglichkeit besteht darin, daß man bereits bei der Herstellung einer bestimmten Emulsion eine solche Temperatur wählt, die innerhalb oder oberhalb des Phasenin versions-Temperaturbereiches liegt. Anschließend wird das Gemisch durch intensives Rühren emulgiert. Man kühlt oder läßt die Emulsion auf die gewünschte Temperatur abkühlen. Die Herstellung entspre chender stabiler O/W-Rostschutzemulsionen wird beispielsweise in der DE-A-39 33 137 beschreiben.Metal surface treatment agent according to the present Er also include so-called phase inversion emulsions (PIT emulsions). These are made by allowing one to next determines the phase inversion temperature by adding a Sample of conventionally prepared emulsion using of a conductivity meter heated and the temperature determined in which the conductivity decreases sharply. Now that the Phasenin version temperature range for a particular composition of a Emulsion is known, first as usual, an emulsion, the contains all the essential components, heated to a temperature, those within or above the phase inversion temperature rich lies. Another production possibility is that one already in the production of a particular emulsion a selects those temperatures which are within or above the phase version temperature range is. Subsequently, the mixture emulsified by intensive stirring. Cool or leave the emulsion Cool to the desired temperature. The production correspond The stable O / W antirust emulsions are described, for example, in US Pat DE-A-39 33 137 describe.
Im Stand der Technik sind eine Reihe von Metalloberflächen-Behand lungsmitteln auf der Basis von Mineralölen bekannt. Im Sinne der vorliegenden Erfindung sind diese insbesondere ausgewählt aus Rei nigungs- und Korrosionsschutzemulsionen sowie Kühlschmierstoffen. Im weitesten Sinne können derartige Mittel unter Verwendung der wäßrigen Anwendungsemulsionen zum Reinigen und Korrosionsschutz (Passivieren) sowie zum Kühlen und Schmieren beim Zerspanen, Schleifen, Honen oder Fräsen von Metalloberflächen aber auch son stiger harter Oberflächen, wie lackierten Oberflächen, Kunststoff- oder Glasoberflächen, dienen.The prior art includes a number of metal surface treatments agents based on mineral oils. In the sense of the In the present invention, these are especially selected from Rei anti-corrosive and anti-corrosive emulsions and cooling lubricants. In the broadest sense, such agents can be made using the aqueous application emulsions for cleaning and corrosion protection (Passivieren) and for cooling and lubricating during machining, Grinding, honing or milling metal surfaces but also son hard surfaces, such as painted surfaces, plastic or glass surfaces, serve.
Um die Anforderungen der Praxis erfüllen zu können, müssen die Me talloberflächen-Behandlungsmittel neben den Dialkylethern meist verschiedene Wirkstoff-Additive enthalten. Die wichtigsten Wirk stoff-Additive im Sinne der vorliegenden Erfindung sind, je nach Einsatzzweck, Emulgatoren, Korrosionsinhibitoren, Biozide, EP-Zusätze, Schmiermittelzusätze, Antinebelzusätze, Alterungs schutzstoffe, Lösevermittler, Entschäumer und pH-Regulatoren.To meet the requirements of the practice, the Me tallow surface treatment agents in addition to the dialkyl ethers usually contain various active ingredient additives. The main effects Substance additives in the context of the present invention are, depending on Intended use, emulsifiers, corrosion inhibitors, biocides, EP additives, lubricant additives, anti-fog additives, aging protective agents, solubilizers, defoamers and pH regulators.
Emulgatoren, z. B. nichtionische Tenside, Petroleumsulfonate, Al kaliseifen, Alkanolaminseifen, stabilisieren die feine Verteilung von Öltröpfchen in der wäßrigen Arbeitsflüssigkeit, die eine Öl- in-Wasser-Emulsion darstellt. Die Emulgatoren stellen mengenmäßig eine wichtige Gruppe an Zusatzstoffen bei den wassermischbaren Kühlschmierstoffen dar. Die Metalloberflächen-Behandlungsmittel enthalten vorzugsweise an sich im Stand der Technik bekannte Emulgatoren, insbesondere solche, die ausgewählt sind aus a) anio nischen Emulgatoren, insbesondere Seifen, Sulfonaten und Phosphor säureestern und deren Salze, und b) nichtionischen Emulgatoren, insbesondere Fettalkoholethoxylaten, Fettalkoholpropoxylaten und Zuckerestern. Die Einsatzmengen an Emulgatoren lassen sich hier aus dem Gebiet der mineralölbasierten Metalloberflächen- Behandlungsmittel übertragen.Emulsifiers, e.g. Nonionic surfactants, petroleum sulfonates, Al Kaliseifen, alkanolamine soaps, stabilize the fine distribution of oil droplets in the aqueous working fluid containing an oil represents in-water emulsion. The emulsifiers provide in quantity an important group of additives in the water-miscible Cooling lubricants. The metal surface treatment agents preferably contain per se known in the art Emulsifiers, in particular those selected from a) anio niche emulsifiers, especially soaps, sulfonates and phosphorus acid esters and their salts, and b) nonionic emulsifiers, in particular fatty alcohol ethoxylates, fatty alcohol propoxylates and Zuckerestern. The quantities of emulsifiers can be used here the field of mineral oil-based metal surfaces Transfer treatment agent.
Übliche Korosionsinhibitoren, z. B. Alkanolamine und ihre Salze, Sulfonate, organische Borverbindungen, Fettsäureamide, Aminodicar bonsäuren, Phosphorsäureester, Thiophosphonsäureester, Dialkyldi thiophosphate, Mono- und Dialkylarylsulfonate, Benzotriazole, Polyisobutenbernsteinsäurederivate, sollen das Rosten von Metall oberflächen verhindern. Früher wurde als Korrosionsschutzmittel häufig Nitrit verwendet, das jedoch heute wegen der Toxizität und Umweltschädlichkeit, besonders auch wegen der Gefahr der Bildung carcinogener Nitrosamine verpönt ist. Einige Korrosionsinhibitoren haben gleichzeitig emulgierende Eigenschaften und finden deshalb auch als Emulgator ihre Anwendung. Biozide, z. B. Phenol-Derivate, Formaldehydabkömmlinge, Kathon MW, sollen das Wachstum von Bakte rien und Pilzen verhindern. EP-Zusätze, z. B. geschwefelte Fette und Öle, phosphorhaltige Verbindungen, chlororganische Verbindungen, sollen Mikroverschweißungen zwischen Metalloberflächen bei hohen Drücken und Temperaturen verhindern. Schmiermittelzusätze, z. B. natürliche Fette und Öle, synthetische Ester, erhöhen die Schmie rungseigenschaften. Alterungsschutzstoffe, z. B. organische Sul fide, Zinkdithiophosphate, aromatische Amine, gewährleisten eine lange Gebrauchsdauer der Metalloberflächen-Behandlungsmittel. Antinebelzusätze verhindern eine Vernebelung der Metalloberflächen-Behandlungsmittel bei deren Anwendung, bei spielsweise ataktisches Polypropylen, Polyisobuten, Poly-n-buten, Polymethacrylat und insbesondere klarwasserlösliche Polymerverbin dungen (MG<106) auf Basis von Polyalkylenoxiden, Polyacrylamiden, Polymethacrylamiden und Copolymeren von Acrylamid und/oder Methacrylamid und ungesättigten Carbonsäuren mit 3 bis 5 C-Atomen (DE-A-42 17 859). Als Entschäumer können die in derartigen Pro dukten üblicherweise verwendeten Substanzen eingesetzt werden, beispielsweise nichtionische Tenside, insbesondere endgruppenverschlossene Fettalkoholpolyethylenglykolether.Usual corrosion inhibitors, eg. As alkanolamines and their salts, sulfonates, organic boron compounds, fatty acid amides, aminodicarboxylic acids, phosphoric acid esters, thiophosphonic acid esters, Dialkyldi thiophosphate, mono- and dialkylarylsulfonates, benzotriazoles, Polyisobutenbernsteinsäurederivate to prevent the rusting of metal surfaces. In the past, nitrite was often used as a corrosion inhibitor, but today it is frowned upon because of its toxicity and environmental damage, especially because of the risk of the formation of carcinogenic nitrosamines. Some corrosion inhibitors have simultaneously emulsifying properties and therefore find their application as an emulsifier. Biocides, e.g. As phenol derivatives, Formaldehydabkömmlinge, Kathon MW, to prevent the growth of bacteria and fungi. EP additives, eg. As sulfurized fats and oils, phosphorus compounds, organochlorine compounds, microwelding between metal surfaces at high pressures and temperatures to prevent. Lubricant additives, eg. As natural fats and oils, synthetic esters, increase the lubrication properties. Anti-aging agents, eg. As organic Sul fide, zinc dithiophosphates, aromatic amines, ensure a long service life of the metal surface treatment agents. Anti-fogging additives prevent atomization of the metal surface treatment agents in their application, for example, atactic polypropylene, polyisobutene, poly-n-butene, polymethacrylate and especially clear water-soluble Polymerverbin applications (MW <10 6 ) based on polyalkylene oxides, polyacrylamides, polymethacrylamides and copolymers of acrylamide and / or methacrylamide and unsaturated carboxylic acids having 3 to 5 carbon atoms (DE-A-42 17 859). Defoamers which can be used are the substances customarily used in such products, for example nonionic surfactants, in particular end-capped fatty alcohol polyethylene glycol ethers.
Der pH-Wert-Konstanz der Metalloberflächen-Behandlungsmittel kommt hinsichtlich der Emulsionsstabilität und des Korrosionsschutzes eine wesentliche Bedeutung zu. Üblicherweise ist es nicht erfor derlich, den pH-Wert der Metalloberflächen-Behandlungsmittel eigens einzustellen. Bevorzugterweise wird jedoch, um einen ausreichenden Korrosionsschutz zu gewährleisten, der pH-Wert im Bereich von neu tral bis alkalisch eingestellt. Besonders bevorzugt im Sinne der vorliegenden Erfindung ist die Einstellung des pH-Wertes im Bereich von 7 bis 11, insbesondere pH 8 bis 9,5. Die Einstellung des pH- Wertes kann beispielsweise durch Alkalimetallhydroxid vorgenommen werden. Die Verwendung von Magnesium- oder Calciumhydroxid ist we niger bevorzugt, da gegebenenfalls schwerlösliche Salze gebildet werden könnten. Dementsprechend ist der Einsatz von Kalium- und/oder Natriumhydroxid im Sinne der vorliegenden Erfindung besonders bevorzugt.The pH consistency of the metal surface treatment agents comes in terms of emulsion stability and corrosion protection an essential meaning too. Usually it is not required specifically, the pH of the metal surface treatment agents specifically adjust. Preferably, however, to a sufficient To ensure corrosion protection, the pH in the range of new tral to alkaline. Particularly preferred in the sense of present invention is the adjustment of the pH in the range from 7 to 11, especially pH 8 to 9.5. The adjustment of the pH Value can be made for example by alkali metal hydroxide become. The use of magnesium or calcium hydroxide is we niger preferred because optionally formed sparingly soluble salts could become. Accordingly, the use of potassium and / or Sodium hydroxide in the context of the present invention particularly prefers.
Auch Alkanolamine und Alkanolaminderivate können als Korrosionsin hibitoren verwendet werden. Außerdem garantieren sie in Verbindung mit Carbonsäuren durch ihre gute Pufferkapazität eine pH-Wert-Kon stanz der wäßrigen Anwendungsemulsionen. Ferner wirken Umsetzungs produkte von Alkanolaminen mit Borsäure wachstumshemmend auf Bak terien und Schimmelpilze und verbessern deshalb die Gebrauchsdauer von Kühlschmierstoffen. Ein gravierender Nachteil der Alkanolamine und Alkanolaminderivate ist, daß sie während des Praxiseinsatzes mit nitrosierenden Substanzen, z. B. bakteriell gebildetem Nitrit oder Stickoxiden in der Luft, reagieren können und dabei in Ni trosamine umgewandelt werden. Z. B. kann in wassergemischten Kühl schmierstoffen, die Ethanolamine enthalten, Nitrosodiethanolamin (NDELA) gebildet werden. Nitrosamine können nach Tierversuchen Krebs an verschiedenen Organen (z. B. Magen, Lunge, Blase, Leber, Speiseröhre) auslösen. Deshalb sind einige Nitrosamine, z. B. auch NDELA, in der deutschen Gefahrstoffverordnung als krebserzeugend eingestuft. Zur Vermeidung von gesundheitlichen Gefahren für die Bediener von Metallbearbeitungsmaschinen muß deshalb die Bildung von Nitrosaminen vermieden werden. Trotz der an sich hervorragenden anwendungstechnischen Eigenschaften der Alkanolamine ist es aus den vorstehenden Gründen erfindungsgemäß bevorzugt, daß die Metalloberflächen-Behandlungsmittel keine Alkanolamine enthalten, d. h. aminfrei sind. Generell liegen Alkanolamine und Alkanolaminderivate als Wirkstoff-Additive jedoch durchaus im Rah men der vorliegenden Erfindung.Alkanolamines and alkanolamine derivatives can also be used as corrosion inks hibitors are used. In addition, they guarantee in conjunction With its good buffering capacity, it has a pH-value with carboxylic acids stamping of the aqueous application emulsions. Furthermore, implementation products of alkanolamines with boric acid growth inhibiting to Bak and molds and therefore improve the service life of cooling lubricants. A serious disadvantage of alkanolamines and alkanolamine derivatives is that during practical use with nitrosating substances, eg. B. bacterial nitrite or nitrogen oxides in the air, and can react in Ni trosamine be converted. For example, in water-mixed refrigeration lubricants containing ethanolamines, nitrosodiethanolamine (NDELA) are formed. Nitrosamines can be used after animal experiments Cancer of various organs (eg stomach, lung, bladder, liver, Esophagus). Therefore, some nitrosamines, eg. Belly NDELA, in the German Hazardous Substances Ordinance as carcinogenic classified. To avoid health hazards for the Therefore, operators of metalworking machines must be educated be avoided by nitrosamines. Despite the outstanding in itself technical properties of the alkanolamines it is from the above reasons preferred according to the invention that the Metal surface treatment agents do not contain alkanolamines, d. H. are amine free. Generally, there are alkanolamines and However, alkanolamine derivatives as active ingredient additives are well within reach men of the present invention.
Daneben können die Metalloberflächen-Behandlungsmittel weiterhin auch Lösevermittler enthalten, beispielsweise Alkohole, Glykole und Glykolether. Besides, the metal surface treatment agents may continue also contain solubilizers, for example, alcohols, glycols and Glycol ethers.
Die Einsatzmengen aller vorgenannten Bestandteile sind dem Fachmann aus dem Fachgebiet der mineralölbasierten Metalloberflächen- Behandlungsmittel bekannt und bedürfen keiner weiteren Erläuterung.The quantities used of all the above-mentioned components are those skilled in the art from the field of mineral oil-based metal surface Treatment agents known and require no further explanation.
Beispielsweise enthalten übliche Korrosionsschutzemulsionen im Sinne der vorliegenden Erfindung, d. h. O/W-Emulsions-Konzentrate, 20 bis 60 Gew.-% Ölphase (Dialkylether), 1 bis 20 Gew.-% Emulgatorkomponente und 1 bis 10 Gew.-% eines Korrosionsinhibitors, wobei der Rest aus Wasser besteht.For example, conventional anti-corrosive emulsions in the Meaning of the present invention, d. H. O / W-emulsion concentrates, 20 to 60% by weight of oil phase (dialkyl ether), 1 to 20% by weight Emulsifier component and 1 to 10% by weight of a corrosion inhibitor, the remainder being water.
Die gemäß der vorliegenden Erfindung erhältlichen Metalloberflä chen-Behandlungsmittel können sowohl in der Form der Konzentrate als auch in der mit Wasser verdünnten Form Verwendung finden. Üb licherweise werden sie jedoch in Form von mit Wasser verdünnten O/W-Emulsionen angewendet. Sowohl die Konzentrate, als auch die mit Wasser verdünnten Emulsionen gewährleisten einen sehr guten Korro sionsschutz für Metalloberflächen aus Eisen und Stahl.The metal surfaces obtainable according to the present invention chen treatment agents can be used both in the form of concentrates as well as in the form diluted with water. Ov Unfortunately, they are diluted in the form of water O / W emulsions applied. Both the concentrates, as well as those with Water-diluted emulsions ensure a very good corro sion protection for metal surfaces made of iron and steel.
In derartigen, mit Wasser verdünnten O/W-Emulsionen liegt die Kon zentration der Metalloberflächen-Behandlungsmittel (Konzentrate) vorzugsweise im Bereich von 1 bis 10 Gew.-%, insbesondere im Be reich von 2 bis 4 Gew.-% (Anwendungskonzentration).In such, diluted with water O / W emulsions Kon concentration of metal surface treatment agents (concentrates) preferably in the range of 1 to 10 wt .-%, in particular in Be rich from 2 to 4 wt .-% (application concentration).
In den nachstehenden Beispielen bedeutet die Abkürzung "EO" Ethylenoxid-einheiten.In the examples below, the abbreviation "EO" Ethylene oxide units.
Herstellung einer aminfreien Korrosionsschutzemulsion ausPreparation of an amine-free corrosion protection emulsion
Propylenglykol, Tallölfettsäure und Wasser wurden im Reaktor vor gelegt und gerührt. Anschließend wurden die festen Kaliumhydroxid- Plätzchen eingestreut (exotherme Reaktion) und ca. 30 min nachge rührt. Die Temperatur der Lösung wurde zwischen 50 und 70°C ge halten. Die restlichen Komponenten (Dioctylether, Fettalkoholethoxylate, Petrolsulfonat und Caprylsäure) wurden an schließend in der oben genannten Reihenfolge zudosiert. Es wurde etwa 1 h nachgerührt, bis eine klare braune Lösung vorlag. Propylene glycol, tall oil fatty acid and water were in the reactor laid and stirred. Subsequently, the solid potassium hydroxide Cookies sprinkled (exothermic reaction) and nachge about 30 min stir. The temperature of the solution was between 50 and 70 ° C ge hold. The remaining components (dioctyl ether, Fatty alcohol ethoxylates, petroleum sulfonate and caprylic acid) were added closing dosed in the above order. It was Stirred for about 1 h until a clear brown solution was present.
Analog Beispiel 1 wurde unter Verwendung von 54,6 Gew.-% Mineralöl (Shell Gravex® 915) anstelle des Dioctylethers eine entsprechende Korrosionsschutzemulsion auf der Basis von Mineralöl hergestellt.Analogously to Example 1, using 54.6 wt .-% mineral oil (Shell Gravex® 915) instead of the dioctyl ether a corresponding Anticorrosion emulsion based on mineral oil.
Unter Verwendung vonUnder the use of
wurde eine aminhaltige Korrosionsschutzemulsion hergestellt.An amine-containing anticorrosive emulsion was prepared.
Propylenglykol und Tallölfettsäure wurden im Reaktor vorgelegt und gerührt. Die restlichen Komponenten (Dioctylether, Fettalkoholeth oxylate, Petrolsulfonat, Caprylsäure und Monoethanolamin/Trietha nolamin) wurden danach in der genannten Reihenfolge zudosiert (exotherme Reaktion). Es wurde 1 h bei 40 bis 50°C nachgerührt, bis eine klare braune Lösung vorlag. Propylene glycol and tall oil fatty acid were placed in the reactor and touched. The remaining components (dioctyl ether, fatty alcohol eth oxylate, petroleum sulfonate, caprylic acid and monoethanolamine / trietha nolamin) were then added in the order mentioned (exothermic reaction). It was stirred for 1 h at 40 to 50 ° C, until a clear brown solution was present.
Analog Beispiel 2 wurde unter Verwendung von 51,8 Gew.-% Mineralöl (Shell Gravex® 915) anstelle des Dioctylethers eine entsprechende Mineralöl enthaltende Korrosionsschutzemulsion hergestellt.Analogously to Example 2, using 51.8 wt .-% mineral oil (Shell Gravex® 915) instead of the dioctyl ether a corresponding Mineral oil-containing anticorrosive emulsion made.
Versuche mit verdünnten wäßrigen O/W-Emulsionen (5-gew.-%ig) der Beispiele 1 und 2 sowie Vergleichsbeispiele 1 und 2 auf der Basis von Dioctylether bzw. Mineralöl wurden an verschiedenen Nitrilbutadientkautschuk-Typen mit unterschiedlichem Acrylnitril- Gehalt (Perbunan®-N Handelsprodukte, Bayer AG) im Lagertest bei 50°C (Testdauer 26 Tage) durchgeführt. Es wurde dabei festgestellt, daß aminfreie Produkte nach Sichtprüfung die Dichtungen im allge meinen weniger angreifen, als Produkte, die Mono- und Triethanolamin enthalten. Dioctylether zeigt im Vergleich zu Mine ralöl eine mindestens vergleichbare, überwiegend jedoch eine bes sere Materialverträglichkeit.Experiments with dilute aqueous O / W emulsions (5 wt .-%) of Examples 1 and 2 and Comparative Examples 1 and 2 on the basis Of dioctyl ether or mineral oil were used at various Nitrile butadiene rubber grades with different acrylonitrile Content (Perbunan®-N Handelsprodukte, Bayer AG) in the storage test 50 ° C (test period 26 days) performed. It was found that amine-free products after visual inspection, the seals in general my less attack than products mono- and Contain triethanolamine. Dioctyl ether shows in comparison to mine at least comparable, but mainly a bes Material compatibility.
Nach DIN 51360/2 wurde die Korrosionsschutzwirkung von wäßrigen Emulsionen gemäß den Beispielen 1 und 2 sowie den Vergleichsbei spielen 1 und 2 geprüft, indem Gußspäne auf Filterpapier mit der Emulsion benetzt wurden. Nach 2 h wurden die Korrosionsabzeich nungen auf dem Filterpapier entsprechend einer Vergleichsskala be wertet, wobei "Korrosionsgrad O" bedeutet, daß keine Korrosion be obachtet wurde, der "Korrosionsgrad 6" hingegen, daß eine sehr starke Korrosion beobachtet wurde. Die Anwendungskonzentrationen sind der folgenden Tabelle zu entnehmen und variieren von 2 bis 5 Gew.-%. According to DIN 51360/2, the corrosion protection effect of aqueous Emulsions according to Examples 1 and 2 and the comparative example Play 1 and 2 tested by placing cast chips on filter paper with the Emulsion were wetted. After 2 hours, the corrosion marks were removed on the filter paper according to a comparison scale evaluates, where "degree of corrosion O" means that no corrosion be was observed, the "degree of corrosion 6", however, that a very strong corrosion was observed. The application concentrations are given in the following table and vary from 2 to 5 Wt .-%.
Die nachfolgende Tabelle gibt den pH-Wert der jeweiligen Emulsionen sowie den Korrosionsgrad einer abgestuften Skala im Bereich von 0 bis 6 wieder.The following table gives the pH of the respective emulsions and the degree of corrosion of a graduated scale in the range of 0 to 6 again.
Insbesondere zeigt die Emulsion gemäß Beispiel 2 bei niedriger Konzentration ein verbessertes Korrosionsverhalten als die Ver gleichsbeispiele 1 und 2.In particular, the emulsion of Example 2 shows at lower Concentration an improved corrosion behavior than the Ver Examples 1 and 2.
Claims (10)
Priority Applications (3)
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DE4237501A DE4237501A1 (en) | 1992-11-06 | 1992-11-06 | Use of water insol. di:alkyl ethers - as oil phase in metal surface treating agents. |
PCT/EP1993/002990 WO1994011469A1 (en) | 1992-11-06 | 1993-10-28 | Dialkyl esters for use in agents for treating metal surfaces |
EP93923564A EP0667891A1 (en) | 1992-11-06 | 1993-10-28 | Dialkyl esters for use in agents for treating metal surfaces |
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DE4237501A DE4237501A1 (en) | 1992-11-06 | 1992-11-06 | Use of water insol. di:alkyl ethers - as oil phase in metal surface treating agents. |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996012054A1 (en) * | 1994-10-14 | 1996-04-25 | Henkel Kommanditgesellschaft Auf Aktien | Use of guanidine salts of unsaturated fatty acids as anticorrosive active substances |
EP3067463A1 (en) | 2015-03-10 | 2016-09-14 | Sasol Wax GmbH | Water based wax dispersion comprising a hydrocarbon wax and a dialkylether for the coating of paper products |
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1992
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1996012054A1 (en) * | 1994-10-14 | 1996-04-25 | Henkel Kommanditgesellschaft Auf Aktien | Use of guanidine salts of unsaturated fatty acids as anticorrosive active substances |
US5749947A (en) * | 1994-10-14 | 1998-05-12 | Henkel Kommanditgesellschaft Auf Aktien | Use of guanidinium salts of unsaturated fatty acids as corrosion inhibitors |
EP3067463A1 (en) | 2015-03-10 | 2016-09-14 | Sasol Wax GmbH | Water based wax dispersion comprising a hydrocarbon wax and a dialkylether for the coating of paper products |
WO2016142068A1 (en) | 2015-03-10 | 2016-09-15 | Sasol Wax Gmbh | Water based wax dispersion comprising a hydrocarbon wax and a dialkylether for the coating paper products |
US10676870B2 (en) | 2015-03-10 | 2020-06-09 | Sasol Wax Gmbh | Water based wax dispersion comprising a hydrocarbon wax and a dialkylether for coating paper products |
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