DE1053699B - Schmieroel - Google Patents

Schmieroel

Info

Publication number
DE1053699B
DE1053699B DEN12754A DEN0012754A DE1053699B DE 1053699 B DE1053699 B DE 1053699B DE N12754 A DEN12754 A DE N12754A DE N0012754 A DEN0012754 A DE N0012754A DE 1053699 B DE1053699 B DE 1053699B
Authority
DE
Germany
Prior art keywords
lubricating oil
oil according
unsaturated
carbon atoms
copolymer
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.)
Pending
Application number
DEN12754A
Other languages
English (en)
Inventor
Roland Frederick Bergstrom
John Avery Edgar
Robert Caldwell Jones
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.)
Bataafsche Petroleum Maatschappij NV
Original Assignee
Bataafsche Petroleum Maatschappij NV
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 Bataafsche Petroleum Maatschappij NV filed Critical Bataafsche Petroleum Maatschappij NV
Publication of DE1053699B publication Critical patent/DE1053699B/de
Pending legal-status Critical Current

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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M165/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic compounds
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
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    • C10M2207/02—Hydroxy compounds
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  • Chemical & Material Sciences (AREA)
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Description

C 1OM ί69/00A40
DEUTSCHES
kl. 23 c 1/01
INTERNAT. Kl. C 10 Ml
PATENTAMT
N12754IVc/23c
ANMELDETAG: 24. SEPTEMBER 1956
BEKANNTMACHUNG
DER ANMELDUNG
UND AUSGABE DEB
ÄUSLEGESCHRIFT: 26. MÄRZ 3959
Die Erfindung bezieht sich auf Schmieröle, welche eine reinigende oder dispergierende Wirkung sowie gute Hochdruckeigenschaften besitzen und gleichzeitig verschleißhindernd wirken, insbesondere unter schwierigen Bedingungen bei Stillsetzen und Anlaufen von Motoren bei niedrigen Temperaturen.
Die bisher als Reinigungsmittel in Schmierölen verwendeten Salze mehrwertiger Metalle oder Seifen organischer Carbonsäuren, organischer Naphthensäuren oder organischer Sulfonsäuren zeigen unter solchen Bedingungen keine befriedigende Wirkung.
Es ist bereits bekannt, gewisse öllösliche und keine aschebildende Mischpolymerisate mit einem Molgewicht von mindestens 1000 den Schmierölen an Stelle solcher metallhaltiger Reinigungsmittel einzuverleiben, doch können diese Mischpolymerisate trotz einer guten Reinigungswirkung innerhalb eines weiten Temperaturbereiches den Verschleiß der Motoren bei starker Belastung und unter extrem hohen Drükken bei niedrigen bzw. hohen Temperaturen nicht verhindern oder wenigstens in ausreichendem Maße herabsetzen.
Solche reinigend wirkenden Schmiermittel können beispielsweise Ideine Anteile von Mischpolymerisaten aus einer polymerisierbaren basischen heterocyclischen Stickstoffverbindung und einem weiteren polymerisierbaren ungesättigten Material enthatlen, wie sie bei der Umsetzung von Laurylmethacrylat und 2-Methyl-5-vinylpyridin in Anwesenheit eines Katalysators erhalten werden. Neben diesen Mischpolymerisaten können in den betreffenden Schmierölen auch noch gebräuchliche Modifizierungsmittel vorliegen, welche beispielsweise als Antioxydationsmittel wirken.
Auch Mischpolymerisate mit einem Molgewicht über 1000 aus einem a-Olefin mit mindestens 10 Kohlenstoffatomen im Molekül und einer anderen ungesättigten polymerisierbaren Verbindung, welche polare Gruppen enthält, wie die alkoholische OH-Gruppe, dieSH-Gruppe und dieCONR2-Gruppe (R=H oder 1 Kohlenwasserstoffrest), sind schon als Schmierölzusatzstoffe in Vorschlag gebracht worden. Neben diesen aus einem ct-Olefin hergestellten Mischpolymerisaten können die betreffenden Schmiermittel auch noch öllösliche Phosphor und/oder Schwefel enthaldende Verbindungen aufweisen, wobei diese Kombination zu besonderen Effekten Anlaß geben kann.
Es ist ferner vorgeschlagen worden, mineralischen und synthetischen Schmierölen Mischpolymerisate aus 75 bis 99 Gewichtsteüen eines Acrylsäureester von gesättigten aliphatischen Alkoholen mit mindestens 8 Kohlenstoffatomen im Alkoholrest und 1 bis 25 Gewichtsteilen einer äthylenisch ungesättigten, eine basische tertiäre Aminogruppe enthaltenden Verbin Schmieröl
Anmelder:
N. V. De Bataafsche Petroleum
Maatschappij, Den Haag
Vertreter: Dr. K. Schwarzhans, Patentanwalt,
München 19, Romanplatz 9
Beanspruchte Priorität:
V. St. v. Amerika vom 26. September 1955
John Avery Edgar, Martinez,
Roland Frederick Bergstrom, Martinez,
und Robert Caldwell Jones, Berkeley, Calif. (V. St. Α.),
sind als Erfinder genannt worden
dung hinzuzusetzen, in welcher Verbindung der tertiäre Aminostickstoff acyclisch oder Glied eines hetreocyclischen Ringes ist. Im letzteren Fall muß sich die polymerisierbare Äthylendoppelbindung aber außerhalb des Ringes befinden. Zusätzlich können diese Schmiermittel noch bekannte Antioxydationsmittel, wie Alkylphenole und Amine, enthalten.
Es wurde nun gefunden, daß insbesondere die durch den Verschleiß des Motors bei hoher Belastung auftretenden Schwierigkeiten überwunden werden können, wenn man idem betreffenden Schmieröl eine synergetisch wirkende Mischung von Zusatzstoffen in kleinen Mengen zusetzt, welche aus a) einem oder mehreren öllöslichen Mischpolymerisaten mit einem Molgewicht über 1000 und einer Mehrzahl von Seitenketten COOR oder R, wobei R einen Kohlenwasserstoffrest mit mindestens 8 Kohlenstoffatomen bedeutet, und b) einem als Schmiermittelzusatz an sich bekannten basischen Metallsalz einer organischen V5ulfonsäure besteht.
* Das Mischpolymerisat wird aus (1) einem oder mehreren ct-Olefinen mit mindestens 10 Kohlenstoffatomen und/oder einem bzw. mehreren Estern einer ungesättigten Carbonsäure mit einem aliphatischen Alkohol mit mindestens 8 Kohlenstoffatomen und (2) einem ungesättigten Alkohol und/oder einer ungesättigten Carbonsäure und/oder einer ungesättigten Stickstoffverbindung hergestellt.
Das Mischpolymerisat liegt in den neuen Schmierölen vorzugsweise in Mengen von 0,5 bis 10 Gewichtsso» 787/507
tätsindex und Stockpunktserniedriger, wie die Polymerisate von Alkylmethacrylaten; Kondensationsprodukte aus chloriertem festem Paraffin und Naphthalin; Hochdruckzusatzmittel, wie öllösliehe Polyhalogenalkanphosphonkomponenten, z. B. Trkhlormethan-P'basphonsäure, lister, Amide oder Aminsalze der seligen, z. B. das Di-2-äthylhexylaminsalz der Trichlormethanphosphonsäure; organische Sulfide und Gemische derselben.
Die außergewöhnlichen Eigenschaften der erim- *° dungsgemäßen Gemische zeigen sich bei der Prüfung einer Mischung A in einem Chevrolet-Motor nach dem EX-3-Test. Am Ende der Prüfung war die Maschine sauber, es waren keine Anzeichen von Verschleiß oder Korrosion festzustellen, es trat kein KIeben von Kolbenringen auf, und der Motor war in ausgezeichnetem Zustand. Wenn man dagegen das basische CalciumerdölsuJfonat aus der Mischung A wegließ oder durch eine gleiche Menge von neutralem Calciumerdölsulfonat ersetzte (bezeichnet als Mischun- ao gen X und Y) und die Prüfung unter entsprechenden Bedingungen durchführte, >var der Motor in jedem Fall in schlechtem Zustand, wie sich durch das Kleben mehrerer Ringe und wesentlichen Verschleiß von Motorteilen zeigte. 2S
Ähnliche Ergebnisse wie mit der Mischung A können mit den Mischungen B, C oder D oder anderen erfindungsgemäßen Gemischen bei dem Test imEX-3-Motor erhalten werden.
Die synergetische Wirkung der erfmdungsgemäßen Kombination von Zusatzstoffen wird aus den folgenden Vergleichsversuchen ersichtlich, die in einem fiüssigkeifrsgekühl+en l-Zylrnd'er-CFR-Bemzinmotor durchgeführt wurden. (Ausbolirung. Takt:8,255-11.430cm).
ng
Yerstjchsbedingungen:
Geschwindigkeit 1 (.00 ITpM
Belastung BMEl' 5Ai kg /cm2
Verbuch flauer 4(1 Siunden
Mantellemperatur 25C C
("^temperatur 2(',44- C
Kovnpres^nnsverbnltnis .... 6
40
Zusammensetzung
J. Mineralöl
2. Mineralöl -f- 5 Gewichtsprozent Mischpolymerisat aus Stearylmethacrylat-2-Methy 1-5-vinylpyridin (Molverhpltnis 4,3/J) ...'
3 Mineralöl -!- 0.5 Gewichtsprozent basisches Calciumerdölnilfonat, !berechnet als SulfatasclK'
4. Mineralöl ~ 5 Gewichtsprozent Mischpolymerisat 2 -^ 0.5 Gewichtsprozent Suifonat 3
Versdileii?
in 0Zo,
be/.ogen auf das Basisö)
100
137
143
92
55
6o
Diese Ergebnisse zeigen sehr deutlich, daß keiner der beiden Arten von Zusatzstoffen an sich den Verschleiß des Motors verringert, verglichen mit dem reinen Mineralöl, während die kombinierte Anwendung zu einer wesentlichen Herabsetzung des Verschleißes führt.

Claims (9)

Patentansprüche.·
1. Schmieröl mit einem Gehalt an einem oder mehreren öllöslichen Mischpolymerisaten mit einem Molgewicht über 1000 und einer Mehrzahl von Seitenketten COOR oder R, wobei R einen Kohlenwasserstoffrest mit mindestens 8 C-Atomen bedeutet, aus 1. einem oder mehreren ct-Olefinen mit mindestens 10 Kohlenstoffatomen und/oder einem bzw. mehreren Estern einer ungesättigten Carbonsäure mit einem aliphatischen Alkohol mit mindestens 8 Kohlenstoffatomen und 2. einem ungesättigten Alkohol und/oder einer ungesättigten Carbonsäure und/od«r 'einer ungesättigten Stickstoffverbindung, gekennzeichnet durch einen Gehalt an einer synergistechen Mischung aus a) Kleineren Mengen, vorzugsweise 0,5 bis 10 Gewichtsprozent, bezogen auf die Gesamtmischung, b) einer kleineren Menge, vorzugsweise 0,1 bis 10 Gewichtsprozent, bezogen auf die Gesamtmischung, eines an sich als Schmiermittelzusatz bekannten basischen Metallsalze« einer organischen Sulfonsäure.
2. Schmieröl nach Anspruch 1, dadurch gekennzeichnet, daß das Mischpolymerisat ein Molgewicht zwischen 30 000 und 500000 aufweist.
3. Schmieröl nach Anspruch 1 und 2, dadurch gekennzeichnet, daß die ungesättigte Stickstoffverbindung für das Mischpolymerisat heterocyclisch ist, wie 4-\'inylpyridin oder 2-Methyl-5-vinylpyridin.
4. Schmieröl nach Anspruch 1 und 2, dadurch gekennzeichnet, daß die ungesättigte Stickstoffverbindung für das Mischpolymerisat ein Acrylsäurenitril oder Acrylsäureamid oder der Ester einer Acrylsäure und eines Aniinoalkohols, wie Diäthykiminoätihyhnethacrylat, ist.
5. Schmieröl nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß die ungesättigten Komponenten 1 und 2 in dem Mischpoylmerisat in einem molaren Verhältnis zwischen 1:10 und 10:1, vorzugsweise zwischen 1 : 1 und 4: 1. vorliegen.
o. Schmieröl nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß das basische Sulfonat von einer alkylsubstituierten aromatischen Sulfonsäure mit oder ohne polaren Substituenten und insbesondere von einer Erdölsulfonsäure abgeleitet ist.
7. Schmieröl nach Anspruch 1 bis 6, dadurch gekennzeichnet, daß es als basisches Sulfonat ein Calciumsalz enthält.
8. Schmieröl nach Anspruch 1 bis 7, dadurch gekennzeichnet, daß das Basisöl ein mineralisches Schmieröl ist.
9. Schmieröl nach Anspruch 1 bis 8, dadurch gekennzeichnet, daß es zusätzlich kleinere Mengen an sich bekannter Zusatzstoffe, wie eines Antioxydationsmittels, eines Korrosionsinhibitors, eines Viskositätsindexverbesserers und/oder eines Stockpunkt>erniedrigers, enthält.
In Betracht gezogene Druck.schriften:
Französische Patentschrift Nr. 1 061 771;
In Betracht gezogene ältere Patente:
Deutsche Patente Nr. 947 186, 960 756, 1 003 896, 003 897.
Bei der Bekanntmachung der Anmeldung ist ein Prioritätsbeleg ausgelegt worden.
© 80S 787/507 3.59
DEN12754A 1955-09-26 1956-09-24 Schmieroel Pending DE1053699B (de)

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DE1145289B (de) * 1958-06-26 1963-03-14 Monsanto Chemicals Zusaetze zu Mineralschmieroelen, Brennstoffoelen und anderen Kohlenwasserstoffgemischen aus Mineraloelen
US3205170A (en) * 1958-08-08 1965-09-07 Universal Oil Prod Co Stabilization of organic compounds
NL127317C (de) * 1958-09-22
US3397145A (en) * 1958-12-29 1968-08-13 Universal Oil Prod Co Hydrocarbon oils containing alkylthiophosphoric acid salts of polymeric condensation products
US3159578A (en) * 1960-02-26 1964-12-01 Shell Oil Co Organic functional fluids and polymeric amine salt additives therefor
BE604945A (de) * 1960-06-15
US3192158A (en) * 1962-04-18 1965-06-29 Shell Oil Co Lubricating compositions containing a detergent copolymer and an alkaline earth petroleum sulfonate-trialkyl amine complex
US3211652A (en) * 1962-12-03 1965-10-12 Ethyl Corp Phenolic compositions
US3336237A (en) * 1963-05-16 1967-08-15 Shell Oil Co Lubricating oil composition
NL6404814A (de) * 1964-04-29 1965-11-01
DE2926474C2 (de) * 1979-06-30 1984-08-30 Chemische Fabriek Servo B.V., Delden Acrylester-Mischpolymerisate und ihre Verwendung als Kristallisationsinhibitoren für paraffinhaltige Rohöle
GB2056482A (en) * 1979-08-13 1981-03-18 Exxon Research Engineering Co Lubricating oil compositions

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FR1061771A (fr) * 1951-03-09 1954-04-15 Du Pont Perfectionnements aux compositions lubrifiantes
DE947186C (de) * 1951-03-09 1956-08-09 Du Pont Zusatz zu Schmieroelen und Heizoelen
DE960756C (de) * 1953-05-25 1957-03-28 Bataafsche Petroleum Schmiermittel

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BE526487A (de) * 1953-02-17
BE538017A (de) * 1954-05-10
NL97884C (de) * 1954-07-12
GB786167A (en) * 1954-09-27 1957-11-13 Shell Res Ltd Improvements in or relating to the preparation of basic oil-soluble polyvalent metalsalts of organic acids and solutions of said basic salts in oils, and the resultingsalts
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DE947186C (de) * 1951-03-09 1956-08-09 Du Pont Zusatz zu Schmieroelen und Heizoelen
DE960756C (de) * 1953-05-25 1957-03-28 Bataafsche Petroleum Schmiermittel

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DE1237721B (de) * 1960-11-25 1967-03-30 Shell Int Research Schmiermittel

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GB799037A (en) 1958-07-30
NL102108C (de)
FR1158245A (fr) 1958-06-12
NL102109C (de)
GB810685A (en) 1959-03-18
DE1058187B (de) 1959-05-27
US2958660A (en) 1960-11-01
NL102110C (de)

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