DE2530562C2 - Use of a concentrated solution of methyl benzotriazole as a corrosion protection agent - Google Patents
Use of a concentrated solution of methyl benzotriazole as a corrosion protection agentInfo
- Publication number
- DE2530562C2 DE2530562C2 DE2530562A DE2530562A DE2530562C2 DE 2530562 C2 DE2530562 C2 DE 2530562C2 DE 2530562 A DE2530562 A DE 2530562A DE 2530562 A DE2530562 A DE 2530562A DE 2530562 C2 DE2530562 C2 DE 2530562C2
- Authority
- DE
- Germany
- Prior art keywords
- oil
- acid
- corrosion
- iso
- decylamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
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- C10M2203/06—Well-defined aromatic compounds
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Description
Metalloberflächen sind häufig chemischen und elektrochemischen Angriffen ausgesetzt, die diese Oberflächen zerstören. Um diese Korrosion zu verhindern, kann man auf der Metalloberfläche mit Methyibenzotriazol eine monomolekulare Chelatkomplexschicht aufbauen, die sehr fest haftet, chemisch inert ist, und so die Metalloberfläche korrodierenden Einflüssen entzieht. Metal surfaces are often exposed to chemical and electrochemical attacks that affect these surfaces destroy. To prevent this corrosion, one can apply methyibenzotriazole on the metal surface build up a monomolecular chelate complex layer that adheres very firmly, is chemically inert, and so on the metal surface removes corrosive influences.
In der Praxis steht man meist vor dem Problem, Maschinenteile, die mit Schmiermitteln in Beziehung stehen, z.B. Lagerschalen, gegen die korrodierende Wirkung des Schmiermittels (z. B. aktive Schwefelverbindungen im Schmieröl) zu schützen. Dies gelingt aber nur sehr schwer, denn Methyibenzotriazol löst sich in Mineralölen in praktisch vertretbarer Zeit erst bei höheren Temperaturen und auch dann nur in geringen Mengen.In practice, one usually faces the problem of machine parts that are related to lubricants stand, e.g. bearing shells, against the corrosive Effect of the lubricant (e.g. active sulfur compounds in the lubricating oil). However, this is very difficult because methyl benzotriazole dissolves in Mineral oils in a practically acceptable time only at higher temperatures and then only at low temperatures Amounts.
Ein Teil dieser Schwierigkeiten kann vermieden werden, wenn man Thiodiazole als Korrosionsinhibitoren einsetzt. Diese Produkte sind bei 20" C flüssig, lassen sicä leicht in öl einmischen, sind aber erheblich weniger wirksam als Methylbenzotriazoi.Some of these difficulties can be avoided by using thiodiazoles as corrosion inhibitors begins. These products are liquid at 20 "C. Let go They mix easily in oil, but are considerably less effective as methylbenzotriazoi.
Aufgabe der Erfindung ist es, ein flüssiges Korrosionsschutzmittel auf Methylbenzotriazolbasis zur Verfugung zu stellen, das sich leicht in Schmieröle einarbeiten läßtThe object of the invention is to provide a liquid anti-corrosion agent based on methylbenzotriazole, which is easily converted into lubricating oils can be incorporated
Die US-Patentschrift 29 71 912 beschreibt auf Spalte 2, Zeilen 5—21, ein synthetisches Schmiermittel auf Basis Esteröl, welches ein Antioxidant in Kombination mit Benzotriazol enthält. Als weiteres Hilfsmittel können Phosphorsäureester zugesetzt werden, die die Hochdruckeigenschaften verbessern (Spalte 6, Zeilen « 5—27). Demgegenüber bezieht sich die Erfindung darauf, Methylbenzotriazoi, welches als schwer löslich bekannt ist, in eine in Schmierölen lösliche Form zu überführen. Dies geschieht dadurch, daß dem dem Methyibenzotriazol z. B. ein Phosphatester als Lösungsmittel zugegeben wird. Diese erfinderische Lösung unterscheidet sich von der entgegengehaltenen US-Patentschrift darin, daß die dort beschriebenen Phosphatester einer anderen Funktion dienen.U.S. Patent 2,971,912 describes on Column 2, lines 5-21, a synthetic ester oil based lubricant which is an antioxidant in combination with benzotriazole contains. As a further aid, phosphoric acid esters can be added, which the Improve high pressure properties (column 6, lines «5-27). In contrast, the invention relates sought to convert methylbenzotriazoi, which is known to be sparingly soluble, into a form soluble in lubricating oils convict. This is done by the fact that the methyibenzotriazole z. B. a phosphate ester as a solvent is admitted. This inventive solution differs from the cited US patent in that the phosphate esters described there serve a different function.
Die FR-PS 15 38 431 beschreibt ein Trockenreini- S5 gungsmittel, bestehend aus Benzotriazol, einem Detergens und einem Lösungsmittel. Als Lösungsmittel werden beispielsweise auf der linken Seite, zweiter Absatz der Seite 2, chlorhaltige Kohlenwasserstoffe aufgeführt. Als Detergentien können beispielsweise Aminalkylbenzolsuifonate zugegeben werden. Wie im 3. Absatz der linken Spalte auf Seite 2 beschrieben, bewirken diese Sulfonate eine starke Korrosion der Metalloberfläche, wenn sie in Kombination mit einem Lösungsmittel benutzt werden. Die vorliegende Erfindung betrifft im Gegensatz hierzu z. B. eine Lösung von Methyibenzotriazol in dem Sulfonat als Lösungsmittel, welches als Korrosionsschutzmittel in Schmieröl wirkt.The FR-PS 15 38 431 describes a dry cleaning S5 agent consisting of benzotriazole, a detergent and a solvent. As a solvent for example, on the left-hand side, second paragraph on page 2, chlorine-containing hydrocarbons listed. Amine alkylbenzenesulfonates, for example, can be added as detergents. As in the 3rd Described in the first paragraph of the left column on page 2, these sulfonates cause severe corrosion of the Metal surface when used in combination with a solvent. The present invention in contrast, concerns z. B. a solution of methyl benzotriazole in the sulfonate as a solvent, which acts as an anti-corrosive agent in lubricating oil.
Wenn nun, wie die französische Patentschrift lehrt, das Sulfonat eine stark korrodierende Wirkung besitzt, wird ein Durchschnittsfachmann diese Verbindung nicht als Lösungsmittel für Methyibenzotriazol benutzen, um es als Korrosionsschutzmittel einzusetzen. Dieser Fachmann entnimmt der französischen Patentschrift, daß die Sulfonat-Verbindungen stark korrodierend wirken und somit als Lösungsmittel für einen Korrosionsinhibitor nicht näher in Betracht kommen.If now, as the French patent teaches, that Sulphonate has a highly corrosive effect, one of ordinary skill in the art will not consider this compound Use solvent for methyl benzotriazole to use it as a corrosion protection agent. This professional takes from the French patent that the sulfonate compounds are highly corrosive and thus, as a solvent for a corrosion inhibitor, it cannot be considered.
Die GB-PS 811675 erwähnt Benzotriazol als Korrosionsinhibitor in Frostschutzmitteln auf Basis EthylenglykoL Wie auf Seite 1, rechte Spalte im ersten Absatz beschrieben, vermeidet das weiterhin zugesetzte Cyclohexylamin einen Anstieg des pH-Wertes während des Gebrauchs. Methyibenzotriazol ist, wie dem Fachmann geläufig, gut in Glykolen löslich. Die Verwendung eines speziellen Lösungsmittelsystems zur Bereitstellung einer löslichen Form von Methyibenzotriazol auf dem Frostschuztmittelgebiet erübrigt sich daher.GB-PS 811675 mentions benzotriazole as Corrosion inhibitor in antifreeze based on ethylene glycol As on page 1, right column in the first Paragraph described, avoids the addition of cyclohexylamine a rise in pH during of use. As the person skilled in the art is familiar with, methyl benzotriazole is readily soluble in glycols. the Use of a special solvent system to provide a soluble form of methyl benzotriazole there is therefore no need for antifreeze.
Die DE-AS 12 85 835 beschreibt auf Spalte 1, Zeilen 34—41, ein Korrosionsschutzmittel für Metalloberflächen, enthaltend neben Methyibenzotriazol ein Aminsalz einer gesättigten Dicarbonsäure. Das Korrosionsschutzmittel kann gemäß Spalte 2, Zeilen 3—12, Wasser oder ein organisches Lösungsmittel, wie beispielsweise Alkohole, enthalten. Ähnlich wie in der bereits abgehandelten britischen Patentschrift besteht auch hier nicht das Problem, das Benzotriazol in eine öllösliche Form zu überführen. Die auf Spalte 2, Zeilen 45—52, beschriebenen Anwendungsformen des Korrosionsschutzmittels beziehen sich nicht auf den Einsatz eines Schmiermittels auf Basis Mineral- oder Syntheseöl, welches Methyibenzotriazol als Korrosionsinhibitor enthält.DE-AS 12 85 835 describes in column 1, lines 34-41, a corrosion protection agent for metal surfaces, containing, in addition to methyl benzotriazole, an amine salt of a saturated dicarboxylic acid. According to column 2, lines 3-12, the anti-corrosion agent can be water or an organic solvent such as alcohols. Similar to the one already Discussed British patent there is no problem here either, the benzotriazole in a to convert oil-soluble form. The forms of application of the anti-corrosion agent described in column 2, lines 45-52 do not refer to the use of a lubricant based on mineral or synthetic oil, which contains methyl benzotriazole as a corrosion inhibitor.
Gegenstand der Erfindung ist demnach die Verwendung einer konzentrierten Lösung von Methyibenzotriazol in einem Aminsalz einer Carbonsäure, einem Aminsalz einer Phosphorsäure, einem Phosphorsäuretrialkylester, einem Aminalkylbenzolsulfonat oder deren Mischungen als Korrosionsschutzmittel in Schmierölen. The invention accordingly relates to the use of a concentrated solution of methyl benzotriazole in an amine salt of a carboxylic acid, an amine salt of a phosphoric acid, a phosphoric acid trialkyl ester, an amine alkylbenzenesulfonate or mixtures thereof as a corrosion protection agent in lubricating oils.
Diese Lösungen besitzen eine Reihe von unerwarteten Vorteilen. So ist Methyibenzotriazol in den genannten Lösungsmitteln auch bei Zimmertemperatur (200C) leicht (bis zu 40%) löslich. Die Lösungen sind flüssig. Sie können bei Zimmertemperatur in Schmiermittel eingearbeitet werden. Auch dabei wirkt das Lösungsmittel als Lösungsvermittler und erhöht die Löslichkeit des Methylbenzotriazots in öl erheblich (etwa auf das Neunfache). Gleichzeitig wird durch das Lösungsmittel auch die korrosionsinhibierende Wirkung des Methylbenzotriazols gesteigert, so daß für den gleichen Effekt eine erheblich herabgesetzte Menge ausreicht.These solutions have a number of unexpected advantages. Thus Methyibenzotriazol is slightly (up to 40%) soluble in the solvents mentioned also at room temperature (20 0 C). The solutions are liquid. They can be incorporated into lubricants at room temperature. Here, too, the solvent acts as a solubilizer and increases the solubility of the methylbenzotriazot in oil considerably (about nine times). At the same time, the solvent also increases the corrosion-inhibiting effect of the methylbenzotriazole, so that a considerably reduced amount is sufficient for the same effect.
Bei der erfindungsgemäßen Verwendung wirkt das Korrosionsschutzmittel besonders gegen die Korrosion von Buntmetallen, wie Kupfer und Kupferlegierungen, durch Schwefelverbindungen, wie aktiven Schwefel enthaltende Schmierölzusätze. Deshalb wird es bevorzugt für diesen Zweck eingesetzt.When used according to the invention, the anti-corrosion agent acts particularly against corrosion of non-ferrous metals, such as copper and copper alloys, through sulfur compounds, such as active sulfur containing lubricating oil additives. Therefore it is preferred for this purpose.
Lösungsmittel für Methyibenzotriazol im Sinne der Erfindung sind:Solvents for methyl benzotriazole within the meaning of the invention are:
1. Aminsalze von Carbonsäuren1. Amine salts of carboxylic acids
Die den Salzen zugrunde liegenden Carbonsäuren sind insbesondere aliphatische Monocarbonsäuren mit 6—18 Kohlenstoffatomen. Besonders bevor-The carboxylic acids on which the salts are based are, in particular, aliphatic monocarboxylic acids with 6-18 carbon atoms. Particularly preferred
zugt sind gesättigte aliphatische Monocarbonsäuren mit 6—10 Kohlenstoffatomen und ungesättigte aliphatische Monocarbonsäuren mit 6—14 Kohlenstoffatomen. Saturated aliphatic monocarboxylic acids with 6-10 carbon atoms and unsaturated ones are added aliphatic monocarboxylic acids with 6-14 carbon atoms.
Die den Salzen zugrunde liegenden Amine sind aliphatische, cycloaliphatische und aromatische Mono-, Di- und Triamine. Besonders bevorzugt sind Mono-, Di- und Trialkylamine, deren Alkylgruppen insgesamt 6—18 Kohlenstoffatome enthalten. The amines on which the salts are based are aliphatic, cycloaliphatic and aromatic Mono-, di- and triamines. Mono-, di- and trialkylamines and their alkyl groups are particularly preferred contain a total of 6-18 carbon atoms.
Neben diesen Salzen kann auch ein Oberschuß der Säure vorhanden sein, wobei das Molverhältnis
Amin : Säure bevorzugt 1 :1 nicht übersteigt.
Beispiele für geeignete Carbonsäuren sind Capronsäure,
Caprinsäure, Isononansäure, Isopalmitinsäure, Ölsäure.In addition to these salts, there may also be an excess of the acid, the amine: acid molar ratio preferably not exceeding 1: 1.
Examples of suitable carboxylic acids are caproic acid, capric acid, isononanoic acid, isopalmitic acid and oleic acid.
Beispiele für geeignete Amine sind n-Hexylamin, tert-Octylamin, tert-Isotetradecylamin, Oleylamin, Dicyclohexylamin, Anilin.Examples of suitable amines are n-hexylamine, tert-octylamine, tert-isotetradecylamine, oleylamine, Dicyclohexylamine, aniline.
2. Aminsalze von Phosphorsäuren2. Amine salts of phosphoric acids
1010
1515th
2020th
3030th
Hier sind die gleichen Amine geeignet, die zur Bildung d^r Carbonsäuresalze benutzt werden.
Phosphorsäuren sind Phosphorsäure selbst oder ihre Mono- und Dialkylester. Bevorzugt wird aus
diesen Phosphorsäuren ein neutrales Salz gebildet, d.h., sämtliche vorhandenen aziden Wasserstoffatome
werden umgesetzt Auch hier ist ein Oberschuß der Phosphorsäure möglich.
Besonders bevorzugt sind Salze aus Alkylaminen und Phosphonsäuren oder deren Mono- oder
Dialkylestern. In diesen Salzen ist die Gesamtzahl an Kohlenstoffatomen in alten Alkylgruppen
bevorzugt 10—40.The same amines that are used to form the carboxylic acid salts are suitable here. Phosphoric acids are phosphoric acid itself or its mono- and dialkyl esters. A neutral salt is preferably formed from these phosphoric acids, ie all acidic hydrogen atoms present are converted. Here, too, an excess of phosphoric acid is possible.
Salts of alkylamines and phosphonic acids or their mono- or dialkyl esters are particularly preferred. In these salts the total number of carbon atoms in old alkyl groups is preferably 10-40.
Beispiele fijr geeignete Verbindungen sind Monobutylphosphat,
Di-butylphosphat, Di-2-ethylhexylphosphatMono-octadecenylphosphat
Phosphorsädretrjalkylester, gegebenenfalls im Gemisch mit einem der unter 1. genannten Amine. Das
Molverhältnis Phosphorsäureester: Amin soli 1 :1
nicht übersteigen. Phosphorsäuretrialkylester enthalten bevoteugt insgesamt 10—40 Kohlenstoffatome
in den Alkylgruppen.
Beispiele für geeignete Phosphorsäureester sind Tributylphosphat, Tri-2-ethylhexylphosphat, TridodecyIphosphatlDibutyl-2-ethylhexylphosphat.
Amin-Alkylbenzolsulfonale sind bevorzugt Salze
der unter L1 genannten Amine mit Alkylbenzolsulfonsäuren,
die, 1 — 18 Kohlenstoffatome in der .Q
Alkylgruppe enthalten.Examples of suitable compounds are monobutyl phosphate, di-butyl phosphate, di-2-ethylhexyl phosphate, mono-octadecenyl phosphate
Phosphorsädretrjalkylester, optionally in a mixture with one of the amines mentioned under 1. The molar ratio of phosphoric ester: amine should not exceed 1: 1. Trialkyl phosphorates contain a total of 10-40 carbon atoms in the alkyl groups by preference.
Examples of suitable phosphoric acid esters are tributyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate / dibutyl-2-ethylhexyl phosphate.
Amine-alkylbenzenesulfonals are preferably salts of the amines mentioned under L 1 with alkylbenzenesulfonic acids which have 1-18 carbon atoms in the . Q contain alkyl group.
Beispiele sind p-Toluolsulfonsäure, Isooctadecenylbenzolsulfonsäure. Examples are p-toluenesulfonic acid, isooctadecenylbenzenesulfonic acid.
Es ist möglich, beliebige Kombinationen dieser Lösungsmittel zy verwenden.It is possible to use any combination of these solvents.
Alle drese Lösungsmittel lösen Methylbenzotriazol zu sehr konzentrierten Lösungen bei Zimmertemperatur. Diese Lösungen können ohne weiteres ebenfalls bei Zimmertemperatur, in das Schmiermittel eingearbeitet werden. Insbesondere werden sie Mineralschmierölen zugefügt, die korrodierende Bestandteile, z. B. aktive Schwefelverbindungen enthalten. Dabei genügt im Schmieröl i. a. eine Konzentration des Methylbenzotriazols von 0,01 b,is 0,1 Gew.-%, um die Korrosion von Kupfer oder Kupferverbindungen zu verhindern, die mit dem öl in Berührung stehen. Diese Konzentration ist erheblich niedriger als die bei Abwesenheit derAll these solvents dissolve methylbenzotriazole very concentrated solutions at room temperature. These solutions can also be used without further ado Room temperature into which lubricants are incorporated. In particular, they become mineral lubricating oils added, the corrosive components, e.g. B. contain active sulfur compounds. The im Lubricating oil i. a. a concentration of the methylbenzotriazole from 0.01 to 0.1% by weight to prevent corrosion of copper or copper compounds associated with are in contact with the oil. This concentration is considerably lower than that in the absence of
4040
45 Lösungsmittel für denselben Effekt erforderliche. Da dem öl flüssige Korrosionsinhibitoren zugesetzt werden, deren Lösungsmittel die Löslichkeit der Methylbenzotriazole im Öl erhöht, besteht auch keine Gefahr der Entmischung. 45 solvents required for the same effect. Since liquid corrosion inhibitors are added to the oil, the solvents of which increase the solubility of the methylbenzotriazoles in the oil, there is also no risk of separation.
Grundsätzlich kann jedes Schmiermittel auf diese Weise korrosionshemmend ausgerüstet werden.In principle, any lubricant can be given a corrosion-inhibiting finish in this way.
Beispiele für besonders geeignete Schmiermittel sind Mineralöle auf paraffinischer, naphthenischer, arcnatischer oder gemischter Basis mit den üblichen Viskositäten von 2,8—150mm2/s bei 50°C, Syntheseöle, z.B. Esteröle, Alkylbenzole und deren Gemische mit Mineralölen, Schmierfette, z. B. Lithiumfette, Calchimfette. Examples of particularly suitable lubricants are mineral oils on a paraffinic, naphthenic, arcnatic or mixed basis with the usual viscosities of 2.8-150mm 2 / s at 50 ° C, synthetic oils, for example ester oils, alkylbenzenes and their mixtures with mineral oils, lubricating greases, e.g. B. lithium fats, calchim fats.
Beispiel 1 1) MethylbenzotriazolExample 1 1) Methylbenzotriazole
400 g Isononansäure und 250 g Isododecylamin werden unter Rühren und Kühlen gemischt In dieser Mischung werden 350 g Methylbenzotriazol langsam aufgelöst und die Lösung filtriert Es wird eine 35%ige Methylbenzotriazollösung erhalten.400 g of isononanoic acid and 250 g of isododecylamine are mixed in this with stirring and cooling 350 g of methylbenzotriazole are slowly dissolved in the mixture and the solution is filtered. It becomes 35% strength Obtain methylbenzotriazole solution.
2) Löslichkeit in Mineralöl2) solubility in mineral oil
In je 100 g paraffinbasischem Spindelöl werden bei 22° C eingerührt:In each 100 g of paraffin-based spindle oil are stirred at 22 ° C:
(A) 10 mg der Lösung gemäß 1),(A) 10 mg of the solution according to 1),
(B) 30 mg der Lösung gemäß 1),(B) 30 mg of the solution according to 1),
(C) 10 mg Methylbenzotriazol.(C) 10 mg methylbenzotriazole.
Die so erhaltenen Schmieröle enthalten:The lubricating oils obtained in this way contain:
(A) 0,003 Gew.-% Methylbenzotriazol(A) 0.003 wt% methylbenzotriazole
(B) 0,01 Gew.-% Methylbenzotriazol(B) 0.01 wt% methylbenzotriazole
(C) 0,01 Gew.-% Methylbenzotriazo!.(C) 0.01 wt% methylbenzotriazo !.
Bei der Herstellung waren die Schmieröle A und B nach einer Minute vollständig klar, während sich bei C auch nach einer Stunde der Zusatz noch nicht gelöst hatte. In C löste sich der Zusatz erst beim Erwärmen auf 700C.During production, lubricating oils A and B were completely clear after one minute, while in the case of C the additive had not yet dissolved after one hour. In C, the additive did not dissolve until it was heated to 70 ° C.
In demselben Schmieröl lösten sich bei 22" C 0,02 Gew.-% Methylbenzotriazol, aber 0,3% (entsprechend 0,1 Gew.-% Methylbenzotriazol) der Lösung nach 1).In the same lubricating oil, 0.02% by weight of methylbenzotriazole dissolved at 22 ° C., but 0.3% (corresponding to 0.1% by weight methylbenzotriazole) of the solution according to 1).
3) Korrosionstest 1.) Cu-AktivitätnachASTM-D-lSO3) Corrosion test 1.) Cu activity according to ASTM-D-ISO
Geprüft wurde in einem handelsüblichen paraffinischen Mineralöl mit einer Viskosität von 6,0 mm2/s bei 500C.The test was carried out in a commercially available paraffinic mineral oil with a viscosity of 6.0 mm 2 / s at 50 ° C.
In diesem öl wurden 0,5% Di-tert-Nonylpentasulfid
mit. 38% Gesamtschwefel und 26% aktivem Schwefel gelöst.
Zu je 100 ml dieser Lösung wurden dannIn this oil were 0.5% di-tert-nonyl pentasulfide with. 38% total sulfur and 26% active sulfur dissolved.
To 100 ml of this solution were then
a) 30 mg Methylbenzotriazol bei 900C in einer halben Stunde eingerührt;a) 30 mg of methylbenzotriazole are stirred in at 90 ° C. in half an hour;
b) 30' mg Produkt aus Beispiel 1 bei 25°C in 10 min eingerührt.b) 30 mg of product from Example 1 are stirred in at 25 ° C. in 10 minutes.
Diese Lösungen wurden dann zusammen mit einer Probe c) = ohne Zusatz von Korrosionsinhibitoren nach ASTM-D-130 im Cu-Streifentest geprüft. Hierbei bedeutet la keine,4cstarke Korrosion.These solutions were then used together with a sample c) = without the addition of corrosion inhibitors tested in accordance with ASTM-D-130 in the Cu strip test. Here, la means no, 4c strong corrosion.
LosungSolution
Cu-Aktivität nach ASTM-D-130 bei 130°C inCu activity according to ASTM-D-130 130 ° C in
ASTM-D-130, siehe oben, für Eisen, rostfrei, Rostpunkte, Flächenrost.ASTM-D-130, see above, for iron, rust-free, rust spots, surface rust.
3Std.3 hours.
5Std.5h
Lösungsolution
a
b
ca
b
c
3a3a
Ia-IbIa-Ib
4c4c
3a Ib 4c3a Ib 4c
Korrosion nach 48 StcL/1000 C auf
Cu FeCorrosion after 48 StcL / 100 0 C
Cu Fe
2.) V-W-Ringrfllentest gemäß VW-P-14012.) V-W ring test according to VW-P-1401
a
b
ca
b
c
3a/3b
3a/3b
4a3a / 3b
3a / 3b
4a
Flächenrost
Rostpunkte
FlächenrostSurface grate
Rust spots
Surface grate
In einem Becherglas werden 98 ml des zu prüfenden Öles mit 2 ml dest. Wassers 1 min mit einem Rührwerk gemischt Je ein Prüfkörper aus Stahl, 1A des Innenringes eines Ringrillenlagers, und ein Kupferstreifen, Elektrolytkupfer mit den Abmessungen 50 χ 5 χ 1 mm, werden anschließend ohne Berührung in das Becherglas gelegt Das Becherglas wird mit einem Uhrglas bedeckt und für 48 Std. bei 100—2° C in einen Trockenschrank gestellt Nach Ablauf der Testzeit werden die Prüfkörper entnommen. Die Beurteilung erfolgt für Kupfer nach ASTM-D-130, für Eisen, rostfrei, Rostpunkte, Flächenrost98 ml of the oil to be tested are mixed with 2 ml of distilled water in a beaker. Water mixed for 1 min with a stirrer. A steel test specimen, 1 A of the inner ring of an annular groove bearing, and a copper strip, electrolytic copper with dimensions of 50 5 1 mm, are then placed in the beaker without touching the beaker.The beaker is covered with a watch glass and placed in a drying cabinet at 100-2 ° C for 48 hours. After the test time has elapsed, the test specimens are removed. The assessment is carried out for copper according to ASTM-D-130, for iron, rust-free, rust spots, surface rust
Geprüft wurde wieder in einem handelsüblichen paraffinischen Mineralöl mit einer Viskosität von 6,0mm2/sbei50°C.The test was carried out again in a commercially available paraffinic mineral oil with a viscosity of 6.0 mm 2 / s at 50 ° C.
In je 100 g dieses Öls wurden 0,9 g Zinkdialkyldithiophosphat undIn every 100 g of this oil there was 0.9 g of zinc dialkyldithiophosphate and
a) 30 mg Methylbenzotriazol,a) 30 mg methylbenzotriazole,
b) 30 mg Produkt aus Beispiel 1b) 30 mg of product from Example 1
eingerührt und gelöst und 2 g Wasser einemulgiert Diese Emulsionen wurden zusammen mit einer Probe c) = ohne Korrosionsschutz gemäß VW-P-1401 geprüft. Die Bewertung erfolgt für Cu nach Beispiele 2bis29stirred in and dissolved and 2 g of water emulsified in. These emulsions were combined with a Sample c) = tested without corrosion protection according to VW-P-1401. The evaluation is carried out for Cu according to Examples 2-29
Nach der Methode des Beispiels 1 wurden mit verschiedenen Lösungsmitteln die Löslichkeit des Methylbenzotriazols in diesen Lösungsmitteln, die Löslichkeit der erhaltenen Lösungen in Schmierölen und die Wirkung dieser Schmieröle gegen die Korrosion von Kupfer geprüft Die Ergebnisse zeigt die Tabelle t. Als Schmieröl wurde verwende-:'.According to the method of Example 1, the solubility of the were with various solvents Methylbenzotriazole in these solvents, the solubility of the resulting solutions in lubricating oils and the effect of these lubricating oils against the corrosion of copper was tested. The results are shown in Table t. The lubricating oil used was: '.
Beispiel 1 —23Example 1-23
28—30 ein paraffinbasisches Spindelöl mit einer Viskosität von 6,0 mm2/s bei28-30 a paraffin-based spindle oil with a viscosity of 6.0 mm 2 / s
500C.50 0 C.
Beispiel 24—25 ein paraffinbasisches Getriebeöl mit einer Viskosität von 122,6 mm2/s bei 500C.Example 24-25 a paraffin-based gear oil with a viscosity of 122.6 mm 2 / s at 50 ° C.
Beispiel 26—27 ein naphthenbasisch^ Spindelöl mit einer Viskosität von 8,22 mm2/s bei 50° C.Example 26-27 a naphthenic spindle oil with a viscosity of 8.22 mm 2 / s at 50 ° C.
Beispiel 31 Syntheseöl Alkylbenzol mit einer Viskosität von 17,2 mm2/s bei 50"C.Example 31 Synthetic oil alkylbenzene with a viscosity of 17.2 mm 2 / s at 50 "C.
Beispiel 32 Syntheseöl, handelsübliches Esteröl auf Sebazinsäurebasis mit einer Viskosität von 12,1 mm2/sbei50°C.Example 32 Synthetic oil, commercially available ester oil based on sebacic acid with a viscosity of 12.1 mm 2 / s at 50 ° C.
Octadecylphosphat Octadecyl phosphate
Di-2-äthylhexylphosphat Di-2-ethylhexyl phosphate
Tri-2-äthylhexylphosphat Tri-2-ethylhexyl phosphate
Tri-n-butylphpsphat Tri-n-butylphphosphate
p-Toluolsulfonsäure + i-Tetradecylamin p-toluenesulfonic acid + i-tetradecylamine
i-Octadecenylbenzolsulfunsäure + t-Octy1 amin i-Octadecenylbenzenesulfunic acid + t-Octy 1 amine
3535
0,40.4
0,140.14
7,07.0
1 : 11: 1
1 : 11: 1
2525th
0,20.2
0,050.05
2,52.5
Claims (1)
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FR2414547A1 (en) * | 1978-01-11 | 1979-08-10 | Exxon Research Engineering Co | Synthetic ester lubricants - contg. ammonium phosphate ester and ammonium organo-sulphonate, esp. useful as aircraft turbine lubricants |
FR2414548B1 (en) * | 1978-01-13 | 1985-06-21 | Exxon Research Engineering Co | OIL COMPOSITION BASED ON SYNTHETIC ESTER CONTAINING AMMONIUM SALTS OF ORGANIC SULFONIC ACIDS |
EP0088724B1 (en) * | 1982-02-26 | 1988-05-18 | Ciba-Geigy Ag | Mixtures of benzotriazoles, process for their preparation and their use as metal passivators |
US4511481A (en) * | 1983-08-31 | 1985-04-16 | Mobil Oil Corporation | Multifunctional additives |
US6180575B1 (en) * | 1998-08-04 | 2001-01-30 | Mobil Oil Corporation | High performance lubricating oils |
WO2012102944A1 (en) | 2011-01-24 | 2012-08-02 | Dow Global Technologies Llc | Composite polyamide membrane |
WO2013048763A1 (en) * | 2011-09-29 | 2013-04-04 | Dow Global Technologies Llc | Method for solubilizing carboxylic acid-containing compound in hydrocarbon solvent |
US9051227B2 (en) | 2013-03-16 | 2015-06-09 | Dow Global Technologies Llc | In-situ method for preparing hydrolyzed acyl halide compound |
US9051417B2 (en) | 2013-03-16 | 2015-06-09 | Dow Global Technologies Llc | Method for solubilizing carboxylic acid-containing compound in hydrocarbon solvent |
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