DE942584C - Antioxydationsmittel fuer Mineraloele, fette OEle, Wachse und synthetische Schmiermittel - Google Patents

Antioxydationsmittel fuer Mineraloele, fette OEle, Wachse und synthetische Schmiermittel

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Publication number
DE942584C
DE942584C DEN6494A DEN0006494A DE942584C DE 942584 C DE942584 C DE 942584C DE N6494 A DEN6494 A DE N6494A DE N0006494 A DEN0006494 A DE N0006494A DE 942584 C DE942584 C DE 942584C
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DE
Germany
Prior art keywords
oils
waxes
antioxidant
oil
synthetic lubricants
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
Application number
DEN6494A
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English (en)
Inventor
Aldo De Benedicits
Walter Richard Haefele
Daniel Benjamin Luten
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
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Bataafsche Petroleum Maatschappij NV
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Publication of DE942584C publication Critical patent/DE942584C/de
Expired legal-status Critical Current

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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00Preserving by using additives, e.g. anti-oxidants
    • C11B5/0021Preserving by using additives, e.g. anti-oxidants containing oxygen
    • C11B5/0035Phenols; Their halogenated and aminated derivates, their salts, their esters with carboxylic acids
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
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    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
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    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/182Organic compounds containing oxygen containing hydroxy groups; Salts thereof
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    • C10M1/00Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
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Description

BUNDESREPUBLIK DEUTSCHLAND
AUSGEGEBEN AM 3. MAI 1956
DEUTSCHES PATENTAMT
PATENTSCHRIFT
KLASSE 23c GRUPPE 1oi
N O494 IVc/23 c
Aldo de Benedictis, Daniel Benjamin Luten und Walter Richard Haefele,
Emeryville, Calif. (V. St. A.)
sind als Erfinder genannt worden
N. V. De Bataafsche Petroleum Maatschappij, Den Haag
Antioxydationsmittel für Mineralöle, fette öle, Wachse und synthetische
Schmiermittel
Patentiert im Gebiet der Bundesrepublik Deutschland vom 16. Dezember 1952 an Patentanmeldung bekanntgemacht am 27. Oktober 195$
Patenterteilung bekanntgemacht am 12. April 1956
Die Priorität der Anmeldung in den V. St. v. Amerika vom 17. Dezember 1951 ist in Anspruch genommen
Die Erfindung bezieht sich auf die Verwendung einer besonderen Gruppe von Zusatzstoffen als Antioxydationsmittel in Mineralölen, beispielsweise leichte bis hochviskose Mineralöle, fetten Ölen, Wachsen und synthetischen Schmiermitteln. Diese Produkte neigen infolge Oxydation zu einer Verschlechterung ihrer Eigenschaften, da die Oxydation zur Bildung unerwünschter und schädlicher Stoffe führt, welche sie für ihren Zweck innerhalb verhältnismäßig kurzer Zeit unbrauchbar machen. So neigen natürliche fette Öle zum Ranzigwerden, und Erdölfraktionen neigen zur Verfärbung und zur Bildung unerwünschter gummiartiger Stoffe, Schlämme und Harzabscheidungen.
Es ist gefunden worden, daß 2,2'-Dioxy-3,5,3', 5'-tetramethyldiphenylrnethan von folgender Struktur- 15 formel
unerwartet günstige Eigenschaften als Antioxydations- 25 mittel aufweist, insbesondere für Erdölprodukte, wie
Benzin, Dieseltreibstoffe, mineralische Schmieröle und Wachse, z. B. die verschiedensten Paraffinsorten, mikrokristaUine Wachse, Bienenwachs, Karnaubawachs. Das Antioxydationsmittel gemäß vorliegender Erfindung ist besonders gut brauchbar in hochraffinierten Mineralölen, aus welchen -etwa von Natur aus vorhandene Oxydationsverhinderer durch scharfe Raffination entfernt worden sind.
2, 2'-Dioxy-3, 5, 3', 5'-tetramethyldiphenylmethan kann hergestellt werden durch Umsetzung von 2, 4-Dimethylphenol mit Salzsäure und Formaldehyd oder durch Kochen von o-Oxymesithylalkohol mit einer verdünnten wäßrigen Ätzalkalilösung und Ansäuern des Reaktionsgemisches.
Das erfindungsgemäße Antioxydationsmittel kann auch in Salzform verwendet werden. Geeignete Salze können durch die nachfolgende Formel dargestellt werden,
OH
CH,-
-CH3
in welcher Y den kationischen Anteil des Salzes darstellt und η der Valenz von Y entspricht.
Besonders bevorzugt sind die Sake mehrwertiger Metalle, z. B. von Ca, Ba, Mg, Sr, Sn, Co, Cd, Zn und Al, insbesondere die Ca- und Ba-Salze.
Das neue Antioxydationsmittel bzw. seine Salze werden in Mengen verwendet, die die Oxydation der Mineralöle, fetten Öle, Wachse und synthetischen Schmiermittel in ausreichendem Maß verhindern. Im allgemeinen werden für diesen Zweck 0,0001 bis 1 Gewichtsprozent, berechnet auf das Gesamtgemisch, des Zusatzstoffes zugegeben, doch sind die angegebenen Konzentrationsgrenzen nicht kritisch.
Die ausgeprägte überlegene Wirkung der erfindungsgemäßen Antioxydationsmittel gegenüber anderen bekannten Antioxydationsmitteln wird in den nachfolgenden Beispielen aufgezeigt.
Beispiel 1
20 g eines Mineralöls wurden dem Dornte-Oxydationstest unterworfen, wie er in Industrial and Engineering Chemistry, Bd. 28 (1936), S. 26, beschrieben ist. Bei dieser Prüfung wird Sauerstoff bei konstantem Druck und konstanter Temperatur in Blasenform durch eine bestimmte Menge Öl hindurchgeleitet und das Maß der Sauerstoffabsorption gemessen. Das Maß der Sauerstoff absorption wird ausgedrückt durch die Zeit; welche notwendig ist, um eine bestimmte Menge Sauerstoff im Öl zu absorbieren.
Das Mineralöl, welches in den Mustern verwendet würde, auf welche sich die Spalte 2 der Tabelle I bezieht, war ein Weißöl, welches aus einem kalifornischen Rohöl hergestellt war und folgende Eigenschaften aufwies:
Spezifisches Gewicht (0API) 30,4 ■
Farbe nach Say bolt +30
Stockpunkt —150
Flammpunkt nach Cleveland, offenes
Gefäß 220,9°
Brennpunkt 254,2°
Viskosität in Saybolt-Sekunden bei 37,8° 348 Kohlenstoffrückstand nach Conradson
Gewichtsprozent 0,01
Säurezahl (TAN — C) neutral
Schwefel Gewichtsprozent 0,01
unsulfonierter Rückstand Volumprozent 99
Geruch bei normaler Temperatur .... kein
Elektrische Festigkeit Volt 35.000
Änfangssiedepunkt 292°
TabeUe I
Zusatz
0,1 Gewichtsprozent Zeit für die Absorption
von 2000 ecm Sauerstoff
bei 1560
(Stunden)
Cu-Katalysator
Zeit für die Absorption
von 1500 ecm Sauerstoff
bei 1500 (Stunden)
Cu-Katalysator
Kurbelwannenkatalysator
kein
2, 6-ditert.-Butyl-p-kresol
Bis-(2-hydroxy-3-tert.-butyl-5-methylphenyl)-methan Dioctylphenol
2, 2-Bis-(2-hydroxy-3-tert.-butyl-5-methylphenyl)-
Pr°Pan ···· '
2, 2-Bis-(4-hydroxy-3, 5-dimethylphenyl)-propan
2, 2'-Dioxy-3, 5, 3', 5'-tetramethyldiphenyhnethan...
0,6
2.4 8,0
o,8
1.7
2,0
32,0
22,6
25.7
37.3
4,8
18,8
49.1
Das Mineralöl, welches in den Mustern verwendet wurde, auf welche sich die Spalten 3 und 4 der Tabelle I beziehen, war ein mineralisches Schmieröl mit einem spezifischen Gewicht (0API) von 25,3, einem Stockpunkt von — 29° und einer Viskosität in Saybolt-Sekunden bei 99° von 61,5.
Das Öl wurde in Anwesenheit eines Katalysators untersucht. Die Prüfbedingungen und die Ergebnisse sind in Tabelle I zusammengestellt.
Unter der Bezeichnung »Kurbelwannenkatalysator« wird das ölunlösliche Material verstanden, welches sich in einem Schmiermittel während des Laufens eines Motors anreichert.
Beispiel 2
Specköl wurde dem im Beispiel 1 erwähnten Dornte-Oxydationstest unterworfen. Es wurde eine Probe von 100 g geprüft, und die Zusätze wurden in einer Menge von 0,1 Gewichtsprozent zugegeben. Es wurde kein Katalysator verwendet. Die Prüfbedingungen und die Ergebnisse sind in Tabelle II zusammengestellt.
Tabelle II
Zusatz
o,i Gewichtsprozent
kein
2, 6-ditert.-Butyl-p-kresol ..
2, 2'-Dioxy-3, 5, 3', 5'-tetra-
methyldiphenylmethan...
Zeit für die Absorption
von 1500 ecm Sauerstoff
bei 100° (Stunden)
7.6
68,6
126,0
Beispiel 3
Ein Mineralschmieröl mit einem spezifischen Gewicht (0APL) von 37,7, einem Stockpunkt von —120 und einer Viskosität in Saybolt-Sekunden bei 99° von 122 wurde einer Hochtemperaturoxydationsprüfung in dem in Industrial and Engineering Chemistry, Bd. 44 (1952), S. 1834, beschriebenen Apparat unterworfen. Bei dieser Prüfung wird der Boden eines Behälters mit einer Schicht des zu prüfenden Öls bedeckt und das Öl unter einer Sauerstoff atmosphäre von konstantem Druck und konstanter Temperatur gehalten. Die Geschwindigkeit der Sauerstoffabsorption wird gemessen und ausgedrückt durch die Zeit, welche notwendig ist, eine bestimmte Menge Sauerstoff pro 100 cm2 der der Sauerstoffatmosphäre ausgesetzten Ölobernäche zu absorbieren. Die geprüfte Ölmenge betrug 100 g. Die Prüfbedingungen und die Ergebnisse sind in Tabelle III zusammengestellt.
Tabelle III
Zusatz
ι Gewichtsprozent
kein
2, 2'-Dioxy-3, 5, 3', 5'-tetramethyldiphenylmethan..,
Zeit zur Absorption
von 250 ecm Sauerstoff
bei 260° Minuten
Cu-Katalysator
Kurbelwannen katalysator
6,6
17.5
Beispiel 4
Verschiedene Proben von Paraffin mit einem Schmelzpunkt über 59 bis 6o° wurden bei etwa 1480 der Oxydation unterworfen. Bei der Prüfung wurde die Veränderung in der Peroxydzahl der Proben bestimmt. Die Ergebnisse sind in der Zeichnung festgehalten, in welcher die horizontale Achse die Prüfzeit in Minuten und die vertikale Achse die Peroxydzahl der Proben darstellt. Es wurden folgende Proben untersucht: Paraffin ohne Antioxydationsmittel (Kurve 1); Paraffin mit 0,0001 Gewichtsprozent 2, 6-ditert.-Butyl-p-kresol (Kurve 2); Paraffin mit 0,0001 Gewichtsprozent 2, 2'-Dioxy-3, 5, 3', 5'-tetramethyldiphenylmethan (Kurve 3).
Die erfindungsgemäß in ihrer Oxydationsbeständigkeit verbesserten Mineralöle, fetten Öle, Wachse und synthetischen Schmiermittel können auch noch andere Zusätze enthalten, beispielsweise Reinigungsmittel, Korrosionsverhinderer, Rostschutzmittel, Stockpunkterniedriger.
Mit den erfindungsgemäßen Antioxydationsmitteln besonders gut verträgliche Reinigungszusätze sind die Calciumsalze von öllöslichen Erdölsulfonsäuren und die Erdalkalisalze von Alkylphenolaldehydkondensationsprodukten.
Solche weiteren Zusätze können je nach der besonderen Art derselben sowie den speziellen Verwendungsbedingungen in Mengen von 0,01 bis 2 Gewichtsprozent, vorzugsweise von 0,1 bis 0,5 Gewichtsprozent, vorliegen.

Claims (1)

  1. PATENTANSPRUCH:
    Verwendung von 2, 2'-Dioxy-3, 5, 3',"5'-tetramethyldiphenylmethan oder eines Salzes dieser Verbindung, insbesondere des Calcium- oder Bariumsalzes als oxydationshemmender Zusatz zu Mineralölen, fetten Ölen, Wachsen und synthetischen Schmiermitteln in Mengen von vorzugsweise 0,0001 bis ι Gewichtsprozent, berechnet auf das Gesamtgemisch.
    Angezogene Druckschriften: USA.-Patentschrift Nr. 2 574 994; französische Patentschrift Nr. 968 596; deutsche Patentschrift Nr. 857 846.
    Hierzu 1 Blatt Zeichnungen
    509 706 4.
DEN6494A 1951-12-17 1952-12-16 Antioxydationsmittel fuer Mineraloele, fette OEle, Wachse und synthetische Schmiermittel Expired DE942584C (de)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1257777B (de) * 1959-12-31 1968-01-04 Shell Int Research Stabilisieren von fetten OElen, Mineraloelen, Wachsen oder synthetischen Schmiermitteln gegen oxydative Zersetzung

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE550337A (de) * 1955-09-22
DE1126055B (de) * 1958-03-14 1962-03-22 Basf Ag Schmiermittel auf Mineraloelbasis
US3043775A (en) * 1959-07-24 1962-07-10 Thomas H Coffield Organic material containing a 4, 4'-methylenebis phenol

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR968596A (fr) * 1947-07-01 1950-11-30 Bataafsche Petroleum Composition lubrifiante
US2574994A (en) * 1947-10-24 1951-11-13 Shell Dev Lubricating composition
DE857846C (de) * 1948-12-03 1952-12-01 Bataafsche Petroleum Schmier- und Rostschutzmittel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR968596A (fr) * 1947-07-01 1950-11-30 Bataafsche Petroleum Composition lubrifiante
US2574994A (en) * 1947-10-24 1951-11-13 Shell Dev Lubricating composition
DE857846C (de) * 1948-12-03 1952-12-01 Bataafsche Petroleum Schmier- und Rostschutzmittel

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1257777B (de) * 1959-12-31 1968-01-04 Shell Int Research Stabilisieren von fetten OElen, Mineraloelen, Wachsen oder synthetischen Schmiermitteln gegen oxydative Zersetzung

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FR1067709A (fr) 1954-06-17
NL77073C (de)
NL174660B (nl)

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