DE1263960B - Schmiermittel - Google Patents

Schmiermittel

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Publication number
DE1263960B
DE1263960B DES80181A DES0080181A DE1263960B DE 1263960 B DE1263960 B DE 1263960B DE S80181 A DES80181 A DE S80181A DE S0080181 A DES0080181 A DE S0080181A DE 1263960 B DE1263960 B DE 1263960B
Authority
DE
Germany
Prior art keywords
separation
calcium
dispersion
calcium acetate
oil
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.)
Granted
Application number
DES80181A
Other languages
English (en)
Other versions
DE1263960C2 (de
Inventor
Robert Hall Davis
Green Fields Village
Richard George Ramge
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.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
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
Priority claimed from US141580A external-priority patent/US3206399A/en
Application filed by Mobil Oil Corp filed Critical Mobil Oil Corp
Publication of DE1263960B publication Critical patent/DE1263960B/de
Application granted granted Critical
Publication of DE1263960C2 publication Critical patent/DE1263960C2/de
Expired legal-status Critical Current

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Description

BUNDESREPUBLIK DEUTSCHLAND
Int. Cl.:
ClOm
DEUTSCHES
PATENTAMT
AUSLEGESGHRIFT
DeutscheKI.: 23 c-1/01
Nummer: 1263 960
Aktenzeichen: S 80181IV c/23 c
Anmeldetag: 29. Juni 1962
Auslegetag: 21. März 1968
Schmiermittel
Es ist bekannt, daß Calciumacetat bei der Dispergierung in einem Schmieröl diesem wünschenswerte Verbesserungen verleiht, wie Lasttragfahigkeit und Anti-Abnutzungseigenschaften. Auch auf Grund seiner Eigenschaft, Säure zu neutralisieren, ist Calciumacetat ein besonders erwünschter Zusatz für Schmieröle, welche in mit sehr schwefelhaltigen Brennstoffen betriebenen Maschinen verwendet werden, wie Schiffsdieselmaschinen.
Einfache Dispersionen von Calciumacetat in Schmieröl sind jedoch instabil, so daß sich das Calciumacetat ausscheidet. Um diese Schwierigkeit zu überwinden, war es üblich, öle vom Emulsionstyp, d. h. solche, welche durch Emulgierung einer Wasserlösung von Calciumacetat mit Schmieröl gebildet wurden, zu verwenden. Diese Emulsionsöle waren jedoch nicht völlig zufriedenstellend. Sie neigen so auf Grund ihres Wassergehalts zur Steigerung des Korrosionsproblems, und sie sind unter den verschiedenen, bei Lagerung und Verwendung auftretenden Bedingungen nicht stabil. Beispielsweise besteht bei den hohen Temperaturen, welche während der Lagerung in den Maschinenräumen von Schiffen auftreten, die Neigung zur Zersetzung der Emulsion. Andererseits kann unter den niedrigen Temperaturbedingungen, welche in kaltem Klima häufig auftreten, die wäßrige Phase zur Ausfrierung kommen, so daß die Emulsion zerstört wird.
Es wurde nun gefunden, daß Schmiermittel diese Nachteile nicht besitzen, wenn sie ein Gemisch aus Calciumacetat und einem N-acylsubstituierten Sarkosin der Formel
R — C — N — CH2COOH
CH3
enthalten, worin R einen aliphatischen Kohlenwasserstoffrest mit 8 bis 24 Kohlenstoffatomen, der sowohl gesättigt als auch ungesättigt sein kann, darstellt.
Die Schmiereigenschaften von Schmierölen mit der erfindungsgemäßen Kombination können durch den Zusatz eines öllöslichen, kohlensäurehaltigcn., sulfurierten, basischen CalciumaIkylphenolats noch weiter verbessert werden.
Die erfindungsgemäße Kombination eignet sich auch für Schmierfette.
Die N-acylsubstituierten Sarkosine besitzen die Formel ()
ti
R C N CIL COOH
CIL
Anmelder:
Mobil OiI Corporation,
New York, N. Y. (V. St. A.)
Vertreter:
Dr. E. Wiegand und Dipl.-Ing. W. Niemann, Patentanwälte,
8000 München 15, Nußbaumstr. 10
Als Erfinder benannt:
Robert Hall Davis,
Green Fields Village, Woodbury, Ν. J.; Richard George Ramge,
Sewell, N. J. (V. St. A.)
Beanspruchte Priorität:
V. St. v. Amerika vom 30. Juni 1961 (120 938), vom 29. September 1961 (141 580), ■
vom 28. Mai 1962 (197 866)
in welcher R einen aliphatischen Kohlenwasserstoffrest mit 8 bis 24 Kohlenstoffatomen, der sowohl gesättigt als auch ungesättigt sein kann, darstellt. Beispiele für Sarkosinderivate sind;
N-Pelargonoylsarkosin,
N-Undecyloylsarkosin,
N-Lauroylsarkosin,
N-Myristoylsarkosin,
N-Palmitoylsarkosin,
N-Stearoylsarkosin,
N-Oleoylsarkosin,
N-Linoleoylsarkosin,
N-Arachidoylsarkosin,
N-Behenoylsarkosin,
N-HyenoyIsarkosin.
Es kann sowohl wasserfreies als auch hydratisiertes Calciumacetat verwendet werden. Das Calciuniacetat kanu entweder vorgebildet sein, oder es kann in situ gebildet werden. Bei Verwendung von \ orgebildetem Calciumacetat wird die Dispersion hergestellt, indem man eine Mischung aus dem Calciumacetat, dem N-Acvlsarkosin und der ülgitmdlage bildet und die
«89 519/5*2

Claims (1)

  1. Mischung während eines IcurzentZeitraums, d. h. von einigen Sekunden bis zu 30 Minuten, bei einer Temperatur von 25 bis 200°C und vorzugsweise von 50 bis 150°C rührt. Obgleich stabile Dispersionen bei Raumtemperatur mit nur einem kurzen Mischen zu Beginn des Calciumacetats, der Sarkosinverbindung und des Öls und mehrstündigem Stehenlassen der Mischung gebildet werden können, wird ihre Bildung beträchtlich durch Erhitzen und Rühren der- Mischung beschleunigt.
    Das Calciumacetat kann in situ hergestellt werden, indem man Calciumoxyd oder Calciumhydroxyd mit entweder Essigsäureanhydrid oder Essigsäure in Gegenwart des Öls neutralisiert und anschließend die Mischung zur Entfernung des Wassers erhitzt.
    Die sulfurierten, basischen Calciumalkylphenolate, welche, noch dem. erfindungsgemäßen Schmieröl zugesetzt werden können, sind in den USA.-Patentschriften 2 680 096 und 3 036 971 beschrieben.
    Die erfindungsgemäßen Schmiermittel können weitere übliche Zusätze, z. B. Seifen- oder Geliermittel, enthalten.
    Als Schmierölgrundlage können natürliche oder synthetische öle, z. B. Mineralöle, polymerisierte Olefine, Silicone, Fluorkohlenstoffe, Perfluoralkyläther, Esteröle, Silicatester od. dgl. verwendet werden. Die öle sollen eine Viskosität (SUS) von mehr als 40 Sekunden bei 38 °C, vorzugsweise von 60 bis 6000 Sekunden bei 38°C, besitzen.
    '
    Beispiell
    Bei dieser Versuchsreihe wurde Calciumacetat in einem lösungsmittelraffinierten Coastalöl mit einer Viskosität von 60 SUS bei 99° C dispergiert. Die Menge des dispergierten Calciumacetats betrug 10 Gewichtsprozent, bezogen auf die gesamte Dispersion.
    Es wurden verschiedene bekannte Dispergiermittel und oberflächenaktive Stoffe- mit Oleylsarkosin verglichen. Die zugesetzte ,Menge betrug in jedem Falle 2,5 Gewichtsprozent. .
    Die Dispersionen wurden hergestellt, indem ein Brei aus Calciumacetat und 35 Gewichtsprozent des Öls unter Rühren bereitet-wurde. Dann wurde das Dispergiermittel zugesetzt, und das sich ergebende Gemisch wurde auf eine. Temperatur von etwa 132°C erhitzt. Nachfolgend wurde der Re-st des Öles eingemischt und die sich ergebende Dispersion wurde unter fortgesetztem Rühren auf 2-10C abgekühlt und 24 Stunden bei dieser Temperatur gehalten. Die erzielten Ergebnisse sind in .der Tabelle I angegeben:
    Tabelle I '
    Beisp i e 1 2
    Bei dieser Versuchsreihe wurden verschiedene Metallsalze von organischen Säuren, einschließlich Calciumacetat, in dem Mineralöl dispergiert, das vorstehend in Verbindung mit dem Beispiel 1 beschrieben wurde. Es wurde Oleylsarkosin als Dispergiermittel verwendet. Die Menge des Salzes in der Dispersion betrug in allen Fällen 10 Gewichtsprozent, bezogen auf die gesamte Dispersion, und die Dispersion enthielt jeweils 2,5 Gewichtsprozent Oleylsarkosin, bezogen auf die gesamte Dispersion.
    Die Arbeitsweise, die zum Dispergieren der Salze und zum Prüfen der Stabilität der Dispersionen Anwendung fand, war die1 gleiche wie bei dem vorstehenden Beispiel 1. Die erzielten Ergebnisse sind in der Tabelle II- aufgeführt.
    Tabelle II
    SaJz· Verhalten der Dispersion Calciumacetat keine. Trennung Magnesiumacetat Trennung Calciumformiat. Trennung Calciumpropionat Trennung
    Dispergiermittel Verhalten der Dispersion Oleylsarkosin keine Trennung . . CalciumsuIfonat Trennung DioIeyImalat Trennung Hexadecylamin Trennung I-Octadecanol Trennung
    55
    60 Aus den vorstehenden Versuchswerten geht hervor, daß Oleylsarkosin Calciumacetat-Öl-Dispersionen wesentlich besser stabilisiert als andere bekannte oberflächenaktive Mittel. Gemäß Tabelle I tritt nur bei Verwendung von Oleylsarkosin keine Trennung der Dispersion ein, während mit den anderen bekannten oberflächenaktiven Mitteln eine Trennung stattfindet.
    Aus der Tabelle II ist ersichtlich, daß Oleylsarkosin die Calciumacetatdispersion stabilisiert, während andere eng verwandte organische CaIciumsalze und Magnesiumacetät unwirksam sind.
    Die überraschende Wirkung der beanspruchten Kombination ist somit offensichtlich.
    Patentanspruch:
    ' Schmiermittel, enthaltend· ein Gemisch aus zwei einzeln als Schmierölzusätze bekannten Verbindungen sowie gegebenenfalls weitere übliche Zusätze, dadurch gekennzeichnet, daß es ein Gemisch aus Calciumacetat und einem N-acylsubstituierten Sarkosin der Formel
    II "
    ■ R — C — N —CHsCOOH
    r ■
    CH3
    in der R ein gesättigter oder ungesättigter Cs-21-Alkylrest ist, enthält.
    In Betracht gezogene Druckschriften: USA.-Patentschrift 'Nr. 2 841 555.
DE1962S0080181 1961-06-30 1962-06-29 Schmiermittel Expired DE1263960C2 (de)

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US120938A US3182020A (en) 1961-06-30 1961-06-30 Stabilized calcium acetate oil dispersions
US141580A US3206399A (en) 1961-09-29 1961-09-29 Diesel lubricating oil
US19786662A 1962-05-28 1962-05-28

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US3259577A (en) * 1963-02-19 1966-07-05 Socony Mobil Oil Co Inc Lubricant and additives therefor
US3278426A (en) * 1964-11-05 1966-10-11 Chevron Res Carboxylic acid amine salts or carboxylic acid amides-calcium acetate complexes
US3278432A (en) * 1965-03-23 1966-10-11 Mobil Oil Corp Extreme pressure lubricants containing sulfur
US3437594A (en) * 1966-11-25 1969-04-08 Mobil Oil Corp Alkaline earth metal carboxylate dispersions
US3506573A (en) * 1968-05-29 1970-04-14 Mobil Oil Corp Greases containing a hydrogenated olefin polymer vehicle,organophilic clay thickener and calcium acetate dispersion
US3909426A (en) * 1973-10-03 1975-09-30 Mobil Oil Corp Extreme pressure grease composition
US4052322A (en) * 1976-06-24 1977-10-04 Texaco Inc. Corrosion-inhibited grease compositions
DE4222185A1 (de) * 1992-07-06 1994-01-13 Schaeffler Waelzlager Kg Wälzlagerkäfig aus elastischem Kunststoff

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US2790779A (en) * 1953-07-27 1957-04-30 Geigy Chem Corp Rust preventive compositions containing monoamidocarboxylic acids
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US2940932A (en) * 1957-10-01 1960-06-14 Exxon Research Engineering Co Lubricants containing stabilized dispersions of fatty acid salts
US2929783A (en) * 1957-10-24 1960-03-22 Exxon Research Engineering Co Lubricating oil compositions containing stabilized salt suspension

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E77 Valid patent as to the heymanns-index 1977