DE4435548A1 - Stabilisierte Schmierstoff-Grundsubstanz - Google Patents

Stabilisierte Schmierstoff-Grundsubstanz

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Publication number
DE4435548A1
DE4435548A1 DE4435548A DE4435548A DE4435548A1 DE 4435548 A1 DE4435548 A1 DE 4435548A1 DE 4435548 A DE4435548 A DE 4435548A DE 4435548 A DE4435548 A DE 4435548A DE 4435548 A1 DE4435548 A1 DE 4435548A1
Authority
DE
Germany
Prior art keywords
lubricant base
acid
carbodiimides
test
base substance
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Withdrawn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
DE4435548A
Other languages
English (en)
Inventor
Armin Dipl Chem Dr Fesenbecker
Joachim Dipl Chem Dr Korff
Hans-Juergen Dipl Chem Dr Kres
Volker Mueller
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.)
Rhein Chemie Rheinau 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 DE4435548A priority Critical patent/DE4435548A1/de
Priority to EP95114956A priority patent/EP0705898A3/de
Priority to US08/534,703 priority patent/US5614483A/en
Priority to CA002159696A priority patent/CA2159696A1/en
Priority to JP7276174A priority patent/JPH08209169A/ja
Publication of DE4435548A1 publication Critical patent/DE4435548A1/de
Withdrawn legal-status Critical Current

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    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/22Lubricating 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
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Description

Eine Reihe von Schmierstoff-Grundsubstanzen, z. B. natürliche Triglyceride, syn­ thetische Carbonsäureester, Phosphorsäuretriester Olefin-Dicarbonsäure- Copolymere und Silikonöle werden durch Wasser hydrolytisch angegriffen unter Bildung von sauren Spaltprodukten und Alkoholen. 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 Schmierstoff-Grundsubstanzen dient (Säurezahl ist die Menge KOH in mg, die zur Neutralisation von 1 g Substanz erforderlich ist).
Die Anwesenheit von Säuren oder sauren Spaltprodukten beschleunigt die Hydrolyse autokatalytisch. Da Wasser unter technischen Bedingungen immer min­ destens in geringen Mengen anwesend ist, ist also die Nutzungsdauer von Schmierstoffen auf der Basis von solchen Estergruppen enthaltenden Schmierstoff- Grundsubstanzen beschränkt.
Bisher ist es nicht gelungen, diesen entscheidenden Nachteil der Estergruppen enthaltenden Schmierstoff-Grundsubstanzen durch Zusätze zu beheben. Man war auch der Ansicht, daß dies aufgrund der Natur der Esterbindung gar nicht möglich ist. Man hat versucht, den anfänglichen Säuregehalt solcher Substanzen durch besondere Reinigungsverfahren herabzusetzen. Jedoch wird hierdurch der Abbau lediglich anfänglich verzögert. Ebenso hat man langkettige öllösliche Amine zuge­ setzt, die mit denen in den Grundstoffen enthaltenden oder entstandenen Säuren unter Salzbildung reagieren. Diese Salze dissoziieren aber sehr leicht (sie werden z. B. bei der Bestimmung der Säurezahl mit erfaßt), so daß die sauren Verunreini­ gungen (im wesentlichen Carboxylationen) nicht dauerhaft aus der Zubereitung entfernt werden.
Der Erfindung liegt die Erkenntnis zugrunde, daß ein Zusatz von 0,05 bis 5 Gew.-%, bevorzugt 0,1 bis 3 Gew.-% eines darin löslichen Carbodiimids zu einer Estergruppen enthaltenden Schmierstoff-Grundsubstanz die hydrolytische Zersetzung wirksam verhindert. Carbodiimide reagieren sowohl mit Säuren, z. B. den Spaltprodukten der Estergruppen enthaltenden Schmierstoff-Grundsubstanz als auch mit Wasser. In beiden Fällen entstehen stabile Harnstoffderivate. Die Reak­ tion mit den sauren Bestandteilen ist schnell, die mit Wasser sehr langsam. Es werden also sowohl vorhandene oder entstandene saure Bestandteile dauerhaft entfernt als auch in das Produkt gelangtes Wasser.
Bisher hat man Carbodiimide zur Stabilisierung thermoplastischer Kunststoffe ver­ wendet. Diese liegen aber nach einmaliger Verformung im allgemeinen als feste unveränderliche Formkörper vor, die lediglich an der Oberfläche mit der Umge­ bung in Kontakt treten. Schmierstoffe dagegen werden bei Dauertemperaturen von z. B. 60 bis 120°C ständig umgewälzt, so daß ständig neue Oberflächen gebildet werden und mit der Umgebung in Berührung kommen. Die thermische und mecha­ nische Belastung ist also ganz entscheidend stärker als in Kunststoffen. Es war nicht vorhersehbar, daß Carbodiimide auch unter diesen wesentlich stringenteren Bedingungen die Stabilität von Schmierstoff-Grundsubstanzen dramatisch ver­ bessern und daß hierzu nur geringe Mengen erforderlich sind.
Gegenstand der Erfindung sind Estergruppen enthaltende Schmierstoff-Grundsub­ stanzen, die als Stabilisatoren 0,05 bis 5 Gew.-%, bevorzugt 0,1 bis 3 Gew.-% Carbodiimid enthalten.
Schmierstoffgrundsubstanzen im Sinne der Erfindung sind insbesondere langkettige Carbonsäureester, hergestellt aus ein- und mehrwertigen, gesättigten und unge­ sättigten, verzweigten und unverzweigten, offenkettigen und cyclischen aliphati­ schen, substituierten und unsubstituierten ein- und mehrwertigen aromatischen Carbonsäuren mit ein- und mehrwertigen, gesättigten und ungesättigten, ver­ zweigten und unverzweigten, offenkettigen und cyclischen aliphatischen, sub­ stituierten, sterisch gehinderten und ungehinderten, sowie unsubstituierten ein- und mehrwertigen aromatischen Alkoholen. Hierzu zählen natürliche Fette, Öle und Wachse, d. h. Triglyceride von Fettsäuren und ebenso künstlich hergestellte Ester, z. B. von Methanol, 2-Ethylhexanol, Glykol, Glycerin, Trimethylolpropan (im folgenden kurz TMP) Pentaerythritol, Neopentylglykol mit Carbonsäuren wie z. B. Sterinsäure, Ölsäure, Adipinsäure, Terephthalsäure und Trimellitsäure. Alkohol­ komponenten und Carbonsäuren enthalten 1 bis 100, bevorzugt 1 bis 36 Kohlenstoff­ atome.
Beispiele für geeignete Schmierstoffgrundsubstanzen auf Basis organischer Säuren und Alkohole sind: Rapsölmethylester (im folgenden kurz: RME genannt), Rapsölraffinat, Trimethylolpropantrioleat (im folgenden kurz TMP-Oleat genannt), Diisotridecyladipat.
Ebenfalls geeignet als Schmierstoff-Grundsubstanzen im Sinne der Erfindung sind Ester von anorganischen Säuren mit Alkoholen. Beispiele für anorganische Säuren sind Phosphorige Säure (H₂PO₃), Phosphorsäure (H₃PO₄), Phosphonsäure (RP(OH)₃), Borsäure (B(OH)₃), Kieselsäure (Si(OH)₄), "Silikonsäure" (R₂Si(OH)₂) (R = Kohlen­ wasserstoff) und deren oligomeren und polymeren Anhydride. Alkohole können sein ein- und mehrwertig, gesättigt und ungesättigt, verzweigt und unverzweigt, offenkettig und cyclisch aliphatisch sowie substituiert und unsubstituiert ein- und mehrwertig aromatisch. Beispiele für Alkohole sind Methanol, Ethanol, Dodecanol, 2-Ethylhexanol, Isotridecylalkohol, Oleylalkohol, Isopropylphenol, Nonylphenol und 2,4-Dimethylphenol.
Beispiele für Vertreter von Schmierstoff-Grundsubstanzen auf Basis anorganischer Ester sind z. B. Triisopropylphenylphosphat, Trinonylphenylphosphat, Tetraethylsili­ kat, Diethylpolysilikat, Dimethylpolysiloxan, Silikone.
Eine weitere Gruppe von Schmierstoff-Grundsubstanzen im Sinne der Erfindung sind die Olefin-Dicarbonsäure-Copolymere (Handelsname: Ketjenlube; Hersteller AKZO)
Geeignete Carbodiimide sind solche der Formel (I)
(X)m-[-N=C=N-Y-]p-N=C=N-Y (I)
in der
X und Y aromatische oder araliphatische Kohlenwasserstoffreste mit 6 bis 20 C- Atomen bedeuten, die in mindestens einer Orthostellung zur Carbodiimidgruppe aromatische, aliphatische und/oder cycloaliphatische Substituenten mit mindestens 2 C-Atomen, bevorzugt verzweigte oder cyclische aliphatische Reste mit minde­ stens 3 C-Atomen tragen, und die Carbodiimidgruppe(n) an aromatischen Kohlen­ stoff gebunden ist (sind), p = 0 bis 100, bevorzugt 0 bis 50 (im Mittel) ist, wobei X noch freie Isocyanat-Gruppen enthalten kann.
Bevorzugt sind Carbodiimide der Formel (I), deren aromatische Reste X und Y, beispielsweise Phenyl, in beiden Orthostellungen und gegebenenfalls in Parastel­ lung zur Carbodiimidgruppe durch (cyclo-)aliphatische und/oder aromatische Reste, beispielsweise C₁-C₆-Alkyl oder Phenyl substituiert sind, wobei einer dieser orthoständigen Substituenten eine Methylgruppe sein kann. Besonders bevorzugt sind Verbindungen, deren aromatische Ringe X und Y in beiden Nachbar­ stellungen zur Carbodiimidgruppe durch (cyclo)aliphatische Reste substituiert sind, wobei einer dieser orthoständigen Substituenten eine Methylgruppe sein kann, der andere mindestens 2 C-Atome enthält.
Ganz besonders bevorzugt sind Carbodiimide, die in Orthostellung bzw. Ortho- und Parastellung zur Carbodiimidgruppe 2 bzw. 3 Substituenten tragen, von denen mindestens einer eine verzweigte aliphtische Kette mit mindestens 3 C-Atomen, oder ein Cycloaliphat mit 5 oder 6 C-Atomen ist. p ist vorzugsweise 0 bis 40.
Die Carbodiimide können als Dimere, oligomere oder polymere Verbindungen oder aus Gemischen daraus eingesetzt werden. Vorzugsweise werden dimere und polymere Carbodiimide (p 11) eingesetzt.
Erfindungsgemäß geeignete zur Carbodiimidgruppe benachbarte Substituenten am aromatischen Ring sind C₂-C₂₀-Alkyl- und/oder Cycloalkylgruppen, wie Ethyl-, Propyl-, Isopropyl-, sek. Butyl-, tert.-Butyl, Cyclohexyl-, Dodecyl-, oder auch Aryl- und Aralkylreste mit 6 bis 15 C-Atomen, wie Phenyl-, Tolyl-, Benzyl-, Naphthylreste usw.
Besonders geeignet sind solche Carbodiimide, die in den Ortho-Stellungen zur Carbodiimidgruppe durch iso-Propyl substituiert sind, und die gegebenenfalls in der para-Stellung zur Carbodiimidgruppe ebenfalls durch iso-Propyl substituiert sind.
Beispielhaft seien die folgenden Carbodiimide genannt:
Die Carbodiimide der Formel (I) können nach an sich bekannten Verfahren herge­ stellt werden. Ein mögliches Herstellungsverfahren ist z. B. in der DAS 25 37 685 beschrieben. Nach der Lehre dieser Patentschrift werden organische Polyisocyanate in Gegenwart einer geeigneten Phosphorverbindung bis zum gewünschten Grad teilweise umgesetzt und der Katalysator anschließend mit einem geeigneten Halogenid, z. B. einem Säurehalogenid, desaktiviert.
Polycarbodiimide können außerdem, wenn sie aus Isocyanaten hergestellt worden sind, noch reaktionsfähige NCO-Gruppen und komplex gebundene monomere Iso­ cyanate enthalten. Polycarbodiimide lassen sich beispielsweise nach der französi­ schen Patentschrift 1 180 370 aus Polyisocyanaten mit katalytischen Mengen an Phospholinen, Phospholidinen und deren Oxiden und Sulfiden herstellen. Weitere geeignete Polycarbodiimide lassen sich herstellen aus aromatischen Di- und Poly­ isocyanaten, die in o-Stellung zu allen NCO-Gruppen einen oder zwei Aryl-, Alkyl- bzw. Aralkylsubstituenten tragen, wobei wenigstens einer der Substituenten mindestens zwei Kohlenstoffatome aufweisen soll, unter Einwirkung von tertiären Aminen, basisch reagierenden Metallverbindungen, carbonsauren Metallsalzen und nicht basischen Organometallverbindungen. NCO-Gruppen-haltige Polycarbodi­ imide können in der Weise modifiziert werden, daß die noch vorhandenen Iso­ cyanatgruppen mit reaktionsfähigen, Wasserstoff enthaltenden Verbindungen wie Alkoholen, Phenolen oder Aminen beseitigt werden (vgl. DE-AS 11 56 401 und DE-OS 24 19 968).
Die erfindungsgemäßen stabilisierten Schmierstoff-Grundsubstanzen können herge­ stellt werden durch Vermischen der Grundstoffe mit den Carbodiimiden in übli­ chen Mischaggregaten.
Die erfindungsgemäßen Mischungen können beispielsweise eingesetzt werden für folgende Anwendungen: Prozeßöle, Treibstoffe, Wärmeträgeröle, Motorenöle, Fette, Metallbearbeitungsflüssigkeiten und Flugturbinenöle. Besonders geeignet sind die erfindungsgemäßen Mischungen für Kraftübertragungsflüssigkeiten (Hydrauliköle) und Kältemaschinenöle.
Die erfindungsgemäßen stabilisierten Schmierstoff-Grundsubstanzen können in Verbindung mit neutralen oder alkalischen Korrosionsschutz-Additiven z. B. Cal­ cium-Sulfonat (RC 4220, Rheinchemie Rheinau GmbH), aminischen und phenoli­ schen Oxidationsinhibitoren, Buntmetalldesaktivatoren, metallhaltigen und metall­ freien Verschleiß- und Hochdruckzusätzen sowie Stockpunktverbesserern, Ent­ schäumern und Demulgatoren, Dispersants, Detergentien und Viskositätsindexver­ besserern eingesetzt werden.
Ausführungsbeispiele
Durch einfaches Vermischen bei ca. 50°C wurden die erfindungsgemäßen Mischungen von Carbodiimiden mit Schmierstoff-Grundsubstanzen hergestellt. Diese Lösungen wurden genormten Schmierstoffprüfungen unterzogen und hinsichtlich der hydrolytischen Beständigkeit untersucht. Hauptbewertungs­ kriterium dieser Hydrolyseprüfungen ist der Anstieg der Säurezahl über den Versuchszeitraum. Nachfolgend beschrieben sind die Testmethoden und Ergebnisse.
TOST-Test ASTM-D 943 (DIN 51587)
Der TOST-Test ist Bestandteil vieler verschiedener Industrieölspezifikationen. Es wird der Säurezahlanstieg als Maßzahl für den Alterungszustand des Öles verfolgt bis die kritische Zahl von 2 mg KOH/g Öl überschnitten wird.
Einerseits trägt der Sauerstoff über einen radikalischen Sauerstoff-Oxidations­ mechanismus und andererseits das Wasser über die Hydrolyse (Spaltung des Esters in Säure und Alkoholen) zum Anstieg bei. Um die beiden Einflüsse getrennt bewerten zu können, wurde bei einigen Prüfungen ein Gemisch von Alterungs­ stabilisatoren und Korrosionsschutzprodukten (im folgenden abgekürzt AO/CI- Paket) eingesetzt, die bekanntermaßen die Sauerstoffalterung unterdrücken. Die Tabelle macht deutlich, daß durch Zugabe eines Carbodiimids (Handelsname: Stabaxol 1; Hersteller: Rhein Chemie) der Säurezahlanstieg in den Prüfölen bei Anwesenheit von ca. 17% Wasser zeitlich wesentlich verzögert werden kann.
Prüfbedingungen:
300 ml Öl → Prüfsubstanz
60 ml Wasser (dest.) → Hydrolyse
Cu-Spirale → Oxidationskatalysatoren
Eisen-Spirale → Oxidationskatalysatoren
Sauerstoff 3 l/h → Oxidation
95°C → Temperaturbelastung
Bewertung:
Zeit [h] bis Säurezahl < 2 mg KOWg
Tabelle 1
ASTM-D 2619 ("Beverage bottle test" oder auch "Coca-Cola-Test")
Dieser Test ist Teil von international anerkannten Hydrauliköl-Spezifikationen und wird zur Überprüfung der hydrolytischen Beständigkeit von Flüssigkeiten heran­ gezogen. Das wichtigste Prüfkriterium im ASTM-D 2619 ist der Anstieg der Säurezahl in der wäßrigen Phase.
Prüfbedingungen:
75 g Öl → Prüfsubstanz
25 g Wasser → Hydrolyse
Cu-Blech → Katalysator
93°C → Prüftemperatur
48 h → Prüfdauer (rotierende Flaschen)
Bewertung:
Anstieg der Acidität der Wasserphase nach Ablauf der Prüfzeit
Tabelle 2
Hydrolytische Stabilisierung von Schmierstoff-Grundsubstanzen mit Carbodiimiden
ASTM-D 2619 ("Beverage bottle test" oder "Coca-Cola-Test")
Die Zugabe von Carbodiimiden zu unterschiedlichen Schmierstoff-Grundsub­ stanzen hat jeweils einen deutlich geringen Säurezahlanstieg der wäßrigen Phase über den Versuchszeitraum zur Folge: Die Schmierstoff-Grundsubstanzen werden bei Anwesenheit von Carbodiimiden wesentlich langsamer durch Wasser zersetzt.

Claims (1)

  1. Estergruppen enthaltende Schmierstoff-Grundsubstanzen, die als Stabilisatoren 0,05 bis 5 Gew.-% Carbodiimid enthalten.
DE4435548A 1994-10-05 1994-10-05 Stabilisierte Schmierstoff-Grundsubstanz Withdrawn DE4435548A1 (de)

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US08/534,703 US5614483A (en) 1994-10-05 1995-09-27 Stabilized lubricant base material
CA002159696A CA2159696A1 (en) 1994-10-05 1995-10-02 Stabilised lubricant base material
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