DE1003900B - Grease - Google Patents
GreaseInfo
- Publication number
- DE1003900B DE1003900B DEN12137A DEN0012137A DE1003900B DE 1003900 B DE1003900 B DE 1003900B DE N12137 A DEN12137 A DE N12137A DE N0012137 A DEN0012137 A DE N0012137A DE 1003900 B DE1003900 B DE 1003900B
- Authority
- DE
- Germany
- Prior art keywords
- lubricating grease
- grease according
- acid
- salt
- lubricating
- 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
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M5/00—Solid or semi-solid compositions containing as the essential lubricating ingredient mineral lubricating oils or fatty oils and their use
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M7/00—Solid or semi-solid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single solid or semi-solid substances
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/063—Peroxides
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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- C10M2215/065—Phenyl-Naphthyl amines
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- C10N2050/10—Semi-solids; greasy
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Description
Die Erfindung bezieht sich auf Schmierfette, welche einen verbesserten Korrosionsschutz ergeben und verbesserte mechanische Beständigkeit besitzen.The invention relates to lubricating greases which give and improved corrosion protection have mechanical resistance.
Schmierfette, welche als Bestandteile ein Schmieröl und Seifen enthalten, sind hauptsächlich zwei abbauenden Einflüssen unterworfen, nämlich einerseits der Oxydation und der Einwirkung von dabei gebildeten schädlichen Produkten sowie andererseits auch dem thermischen Abbau und der Schädigung durch die dabei entstehenden Abbauprodukte. Es ist eine große Vielzahl von Zusatzstoffen in bezug auf ihre Wirkung auf die verschiedenen Schmierfetteigenschaften, wie Aufrechterhaltung der Konsistenz, Vermeidung korrodierender Eigenschaften, Stabilisierung gegen Oxydation und thermische Zersetzung, geprüft worden. Eine Eigenschaft, welche die meisten Schmierfette neben den vorstehend angegebenen Nachteilen aufweisen, ist ihre Empfindlichkeit gegenüber Wasser. Die meisten Seifen und daher auch die auf Seifengrundlage aufgebauten Schmierfette neigen in größerem oder geringerem Maße zum Emulgieren oder zum Lösen in Wasser. Da Radlager und ähnliche Schmierstellen der benetzenden Wirkung von Wasser ausgesetzt sind, insbesondere bei feuchtem Wetter, ist es erforderlich, daß Schmierfette so aufgebaut werden, daß sie gegenüber übermäßiger Emulgierung oder Lösungswirkung in Wasser oder ähnlichen Lösungsmitteln widerstandsfähig sind.Lubricating greases, which contain as components a lubricating oil and soaps, are mainly two degradative agents subjected, namely on the one hand to oxidation and the action of harmful products formed in the process and on the other hand also the thermal degradation and the damage caused by the degradation products. There is a wide variety of additives in terms of their effect on the various lubricating grease properties, such as maintaining consistency, avoiding corrosive properties, stabilization against oxidation and thermal decomposition. A property that most greases do in addition to the disadvantages indicated above, is their sensitivity to water. the Most soaps, and therefore also the soap-based greases, tend to be greater or lesser Dimensions for emulsifying or for dissolving in water. Since wheel bearings and similar lubrication points of the wetting Effects of water, especially in damp weather, it is necessary that greases so be built up against excessive emulsification or dissolving action in water or the like Solvents are resistant.
Zusätzlich zu der Empfindlichkeit eines Schmierfettes kann das Schmierfett in der zu schmierenden Maschine der Einwirkung korrodierender Mittel, wie organischer Säuren u. dgl., ausgesetzt sein. Dies ist z. B. der Fall in Konservenfabriken. Hierbei wirken sowohl viele Frucht- und Gemüsesäfte, wie Spinatsaft, allein als auch, da die Konservierung oft in schwacher Salzlösung erfolgt, die Kombination von Frucht- bzw. Gemüsesäften und Salzlösung oft stark korrodierend auf die verwendeten Einrichtungen. Infolgedessen müssen Schmierfette verwendet werden, welche die Konserviereinrichtungen gegen Korrosion schützen.In addition to the sensitivity of a grease, the grease in the machine to be lubricated be exposed to corrosive agents such as organic acids and the like. This is e.g. B. the case in Canning factories. Many fruit and vegetable juices, such as spinach juice, work on their own as well as because the Preservation often takes place in a weak salt solution, the combination of fruit or vegetable juices and salt solution often highly corrosive to the equipment used. As a result, greases must be used which protect the preservation devices against corrosion.
Es ist ein Ziel der vorliegenden Erfindung, Schmierfette zu schaffen, welche ausreichenden Schutz gegen Korrosion bieten und eine verbesserte mechanische Beständigkeit aufweisen.It is an object of the present invention to provide lubricating greases which provide adequate protection against corrosion offer and have an improved mechanical resistance.
Erfindungsgemäß werden Schmierfette, welche in überwiegender Menge aus einem Schmieröl bestehen, das mit einer Metallseife einer Fettsäure zur Schmierfettkonsistenz verdickt worden ist, in unerwarteter Weise verbessert durch die synergetische Kombination von Monoestern von Polyoxyalkylenglykolen mit aliphatischen Carbonsäuren (wobei jedes Oxyalkylenradikal 2 bis 6 Kohlenstoffatome enthält) und Erdalkalikohlenwasserstoffsulfonaten. Beide Komponenten sind an sich als Bestandteile von Schmiermitteln bekannt. Es ist jedoch gefunden worden, daß die Kombination dieser speziellen Zusätze, besonders wenn sie in Mengen zwischen 0,1 und etwa 5 Gewichts-Schmierfett According to the invention, lubricating greases which consist predominantly of a lubricating oil with a metallic soap of a fatty acid has been thickened to a grease consistency, unexpectedly improved through the synergetic combination of monoesters of polyoxyalkylene glycols with aliphatic carboxylic acids (each oxyalkylene radical containing 2 to 6 carbon atoms) and alkaline earth hydrocarbon sulfonates. Both components are known per se as constituents of lubricants. However, it has been found that the combination of these special additives, especially when they are in amounts between 0.1 and about 5 weight grease
Anmelder:Applicant:
N. V. De Bataafsctie Petroleum
Maatschappij, Den HaagNV De Bataafsctie Petroleum
Maatschappij, The Hague
Vertreter: Dr. K. Schwarzhans, Patentanwalt,
München 38, Romanplatz 9Representative: Dr. K. Schwarzhans, patent attorney,
Munich 38, Romanplatz 9
Beanspruchte Priorität:
V. St. v. Amerika vom 22. April 1955Claimed priority:
V. St. v. America April 22, 1955
Harold Albert Woods und Harvey Milton Trowbridger Harold Albert Woods and Harvey Milton Trowbridge r
Emeryville, Calif. (V. St. Α.),
sind als Erfinder genannt wordenEmeryville, Calif. (V. St. Α.),
have been named as inventors
prozent (für jeden Stoff einzeln, berechnet nach der Gesamtmenge der Schmierfettes) vorliegen, eine unerwartete Verlängerung der ausnutzbaren Lebensdauer des Schmierfettes im Lager ergibt und ein ausgezeichnetes Widerstandsvermögen schafft gegen die Korrosion metallischer Flächen, welche mit diesen Fetten geschmiert worden sind. Die Polyalkylenglykolmonoester haben die allgemeine Formelpercent (for each substance individually, calculated based on the total amount of lubricating grease), an unexpected one Extension of the useful life of the grease in the bearing results in an excellent resistance creates against the corrosion of metallic surfaces which have been lubricated with these greases. The polyalkylene glycol monoesters have the general formula
IlIl
H-(-O —R-^O-C-R1,H - (- O --R- ^ OCR 1 ,
in welcher R ein Alkylenrest mit etwa 2 bis etwa 6 Kohlenstoffatomen, vorzugsweise zwischen 2 und 4 Kohlenstoffatomen, Ri ein organischer Rest, vorzugsweise ein Alkylrest mit 8 bis 24 Kohlenstoffatomen, insbesondere zwischen 12 und 20 Kohlenstoffatomen, und η eine ganze Zahl, vorzugsweise zwischen 5 und 20, bedeuten. Vorzugsweise haben die Polyoxyalkylenglykole Molgewichte zwischen 150 und 2000, und die davon abgeleiteten Monoester haben ein ausreichend hohes Molgewicht, um öllöslich zu sein. Geeignete Glykole sind u. a. Polyäthylenglykol, PoIypropylenglykol, Polybutylenglykol, Polyamylenglykol und Polyhexylenglykol sowie Kombinationen derselben, wie die Heteropolymeren von Äthylenglykol und Propylenglykol. Die als Bestandteil der Monoester angesetzten Säuren umfassen sowohl gesättigte als auch ungesättigte aliphatische Monocarbonsäuren, einschließlich der Fettsäuren und auch der Oxyfettsäuren. Ausdrücklich werdenin which R is an alkylene radical with about 2 to about 6 carbon atoms, preferably between 2 and 4 carbon atoms, Ri is an organic radical, preferably an alkyl radical with 8 to 24 carbon atoms, in particular between 12 and 20 carbon atoms, and η is an integer, preferably between 5 and 20, mean. The polyoxyalkylene glycols preferably have molecular weights between 150 and 2000, and the monoesters derived therefrom have a sufficiently high molecular weight to be oil-soluble. Suitable glycols include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyamylene glycol and polyhexylene glycol and combinations thereof, such as the heteropolymers of ethylene glycol and propylene glycol. The acids used as a constituent of the monoesters include both saturated and unsaturated aliphatic monocarboxylic acids, including the fatty acids and also the oxy fatty acids. Be explicit
609 838/367609 838/367
als zu dieser Gruppe gehörend genannt: Caprinsäure, Laurinsäure, Myristin-, Palmitin- und Stearinsäure sowie die entsprechenden ungesättigten Säuren, für welche Ölsäure als typischer und bevorzugt verwendeter Vertreter genannt wird. Es können auch die entsprechenden Oxyfettsäuren, wie 12-Oxystearinsäure, verwendet werden oder die Gemische von Säuren, die von hydriertem Ricinusöl oder natürlich vorkommenden Ölen abgeleitet sind. Typische Vertreter geeigneter Monoester sind die Ölsäurefettzusammensetzung keine Erhöhung der Rollstabilität oder höchstens eine geringe Verbesserung ergeben. Dieses Ergebnis ist besonders deutlich ersichtlich aus dem nachstehenden Beispiel 1, und die Wirkung ist am stärksten ausgeprägt bei höherer Temperatur in der Größenordnung von etwa 65° und darüber. Selbst bei Raumtemperatur ist aber festgestellt worden, daß die Kombination der Zusatzstoffe im wesentlichen eine Verdopplung der nutzbaren Lebensdauer der Schmierfettnamed as belonging to this group: capric acid, lauric acid, myristic, palmitic and stearic acid as well as the corresponding unsaturated acids, for which oleic acid is mentioned as a typical and preferred representative will. The corresponding oxyfatty acids, such as 12-oxystearic acid, can also be used or the mixtures of acids derived from hydrogenated castor oil or naturally occurring oils. Typical representatives of suitable monoesters are the oleic acid fat composition no increase in rolling stability or at most a slight improvement. This result is particularly evident from the following Example 1, and the effect is most pronounced at higher temperature in the order of magnitude of about 65 ° and above. However, even at room temperature it has been found that the combination The additives essentially double the useful life of the grease
ester von Polyäthylenglykol, die Stearinsäureester von 10 mischung unter starker mechanischer Beanspruchungester of polyethylene glycol, the stearic acid ester of 10 mixture under heavy mechanical stress
Polypropylenglykol sowie Polyäthylenglykolmonolaureat. Die öllöslichen Erdalkalikohlenwasserstoffsulfonate werden vorzugsweise aus Erdöl erhalten und stellen die bekannten Erdölsulfonate dar. Sie können in bekannter Weise aus dem mit Säure behandelten Erdöl erhalten werden oder durch geeignete Lösungsmittel aus dem Säureschlamm gewonnen werden. Vorzugsweise haben die Sulfonsäuren Molgewichte in der Größenordnung von etwa 400 bis 750.Polypropylene glycol and polyethylene glycol monolaurate. The oil-soluble alkaline earth hydrocarbon sulfonates are preferably obtained from petroleum and are the known petroleum sulfonates. They can be obtained in a known manner from the petroleum treated with acid or obtained from the acid sludge using suitable solvents. Preferably they have Sulphonic acids molecular weights on the order of about 400 to 750.
ergibt.results.
Beim Studium der verschiedenen möglichen Wirkungen der allgemeinen Klasse von hier in Betracht gezogenen Zusammensetzungen wurde die Anwendung der entsprechenden Natriumsulfonate genau geprüft. Wie aber die Vergleichszahlen im Beispiel 1 zeigen, sind die Alkalisulfonate höchst unerwünscht, da bei Anwendung in Mengen, die auch nur einen schwachen Grad von Korrosionsschutz in den SchmierfettzusammensetzungenIn studying the various possible effects of the general class from here considered Compositions, the use of the appropriate sodium sulfonates was carefully examined. But how The comparative figures in Example 1 show that the alkali metal sulfonates are highly undesirable because when used in Amounts that provide even a weak level of corrosion protection in the grease compositions
Die Erdalkalisalze der Sulfonsäuren können neutrale 20 ergeben, ihre Anwesenheit eine starke Wasserempfindlichoder basische Sulfonate sein. keit verursacht, wie aus dem Prozentsatz des durchThe alkaline earth salts of sulfonic acids can give neutral 20, their presence a strong water-sensitive or be basic sulfonates. speed caused as from the percentage of by
Emulgierung oder auf andere Weise bei dem Test für Wasserbeständigkeit verlorengegangenen Schmierfettes ersichtlich ist. In dem Maße, wie der Anteil von Natriumsulfonat zwecks Steigerung des Korrosionsschutzes erhöht wird, nimmt die Wasserbeständigkeit des Schmierfettes drastisch ab. So steigt bei Erhöhung des Anteils von Natriumsulfonat von etwa 2% auf etwa 21J2 0J0 in dem gleichen Lithium-^-oxystearat-Mineralöl-Schmierfett derEmulsification or otherwise lost grease is evident in the test for water resistance. As the proportion of sodium sulfonate is increased for the purpose of increasing the corrosion protection, the water resistance of the lubricating grease decreases drastically. Thus, increasing the proportion of sodium sulfonate from about 2% to about 2 1 J 2 0 J 0 in the same lithium - ^ - oxystearate mineral oil grease increases the
daß das Molgewicht der Sulfonsäure dem vorstehend ge- 30 Prozentualverlust an Schmierfett beim Wasserbeständigforderten
entspricht. Es besteht die Möglichkeit, daß das keitstest von 32% auf etwa 55%. Es wurde mithin
basische Sulfonat ein kolloidales Gemisch aus neutralem
Sulfonat und Erdalkalihydroxyd darstellt.that the molecular weight of the sulfonic acid corresponds to the 30 percent loss of lubricating grease required for water resistance. There is a possibility that the speed test went from 32% to about 55%. It thus became a colloidal mixture of neutral basic sulfonate
Represents sulfonate and alkaline earth hydroxide.
Die in den Gemischen nach der Erfindung verwendeten Seifen können Alkali- oder Erdalkaliseifen von Fettsäuren oder Oxyfettsäuren, einschließlich besonders von Calcium- oder Lithiumseifen der Stearinsäure oder der 12-Oxystearinsäure sein. Andere für die Bildung geeigneter Schmierfette verwendete Seifen, welche erfindungsgemäßThe soaps used in the mixtures according to the invention can be alkali or alkaline earth soaps of fatty acids or oxy fatty acids, including especially calcium or lithium soaps of stearic acid or 12-oxystearic acid be. Other soaps used in the formation of suitable greases which are in accordance with the invention
Bevorzugt werden die basischen Sulfonate, von welchen man annimmt, daß sie der allgemeinen FormelPreferred are the basic sulfonates which are believed to have the general formula
(RSO3)M-OH(RSO 3 ) M-OH
entsprechen, in welcher M ein Erdalkalimetall und R ein Kohlenwasserstoffrest, gewöhnlich ein Naphthenyl-, Alkylnaphthenyl-, Alkaryl- oder Naphthenylarylrest ist, socorrespond, in which M an alkaline earth metal and R a hydrocarbon radical, usually a naphthenyl, alkylnaphthenyl, Is alkaryl or naphthenylaryl, so
einverleibt werden können, sind in der Technik bekannt. Calcium- und Lithiumstearat oder -oxystearat haben eine gewisse ihnen eigentümliche Wasserbeständigkeit und werden aus diesem Grunde vorgezogen. Die Erfindung umfaßt aber auch die Anwendung von wasserempfindlicheren Seifen, wie der Natriumseifen geeigneter Fettsäuren. Die verwendbaren Fett- (oder Oxyfett-) Säuren sind solche mit 12 bis 24 Kohlenstoffatomen pro Molekül, vorzugsweise zwischen 16 und 20 Kohlenstoffatomen pro Molekül. Gewöhnlich werden solche Ausgangsstoffe für die Säuren verwendet, welche überwiegend Säuren mit einem Durchschnitt von etwa 18 Kohlenstoffatomen pro Molekül liefern, wie Ricinusöl oder tierische Fette.are known in the art. Calcium and lithium stearate or oxystearate have one certain water resistance peculiar to them and are preferred for this reason. The invention but also includes the use of soaps that are more sensitive to water, such as the sodium soaps of suitable fatty acids. The fatty (or oxyfatty) acids that can be used are those with 12 to 24 carbon atoms per molecule, preferably between 16 and 20 carbon atoms per molecule. Usually such starting materials are used for the acids used, which are predominantly acids with an average of about 18 carbon atoms per Supply molecule, such as castor oil or animal fats.
Zusätzlich zu den gewöhnlichen Mineralölen, welche, wie in der Technik bekannt ist, für die Erzeugung von Schmierfetten verwendet werden, können auch synthetische Schmiermittel angewandt werden, einschließlich der aliphatischen Ester von Dicarbonsäuren, der flüssigen Polyoxyalkylenglykole und -oxyde, flüssiger phosphorhaltiger Ester und Silicate. Typische Beispiele für diese Gruppen sind Trikresylphosphat, Tri-(2-äthylhexyl)-phosphat, Bis-(2-äthylhexyl)-sebazat oder -adipat, Tetrahexylsilicat und Heteromischpolymere von Äthylenoxyd und Propylenoxyd.In addition to the common mineral oils known in the art for the production of If lubricating greases are used, synthetic lubricants can also be applied, including the aliphatic esters of dicarboxylic acids, the liquid polyoxyalkylene glycols and oxides, liquid phosphorus Esters and silicates. Typical examples of these groups are tricresyl phosphate, tri- (2-ethylhexyl) phosphate, Bis (2-ethylhexyl) sebacate or adipate, tetrahexyl silicate and hetero copolymers of ethylene oxide and propylene oxide.
Eines der unerwarteten Ergebnisse der vorliegenden Erfindung liegt in der ganz beträchtlichen Erhöhung der mechanischen Beständigkeit der Schmierfette, welche die erfindungsgemäße Kombination der Zusatzstoffe enthalten. Dies ist besonders unerwartet im Hinblick auf die Tatsache, daß die verwendeten einzelnen Stoffe beim festgestellt, daß Natriumsulfonate in den hier behandelten Zusammenstellungen infolge ihrer unvorteilhaften Neigung zur Herbeiführung hoher Wasserempfindlichkeit des Schmierfettes nicht verwendet werden können. Aus diesem Grund und auch wegen der überlegenen stabilisierenden Eigenschaften der Erdalkalisulfonate in mechanischer Hinsicht werden die Alkalisulfonate nicht in den Bereich der vorliegenden Erfindung einbezogen.One of the unexpected results of the present invention is the very substantial increase in mechanical resistance of the lubricating greases which contain the combination of additives according to the invention. This is particularly unexpected in view of the fact that the individual substances used in found that sodium sulfonates in the compositions discussed here because of their unfavorable tendency cannot be used to make the grease highly water-sensitive. For this Reason and also because of the superior stabilizing properties of the alkaline earth metal sulfonates in mechanical terms In regard to this, the alkali sulfonates are not included in the scope of the present invention.
Die in diesem Beispiel verwendete »Schmierfettbasis« bestand aus einem mineralischen Schmieröl mittlerer Viskosität, das mit Lithium-12-oxystearat geliert war.The "grease base" used in this example consisted of a medium viscosity mineral lubricating oil gelled with lithium 12-oxystearate.
Eine weitere Untersuchung der erfindungsgemäßen Schmierfettzusammenstellungen ergab, daß die Kombination von Monoestern und Erdalkalisulfonaten beiA further examination of the grease compositions according to the invention revealed that the combination of monoesters and alkaline earth sulfonates
einer höchst unerwarteten Steigerung in der mechani-Fehlen der übrigen sogar in der gleichen Art von Schmier- 70 sehen Beständigkeit des Schmierfettes gleichzeitig dazua most unexpected increase in the mechani-lack of the rest even in the same kind of lubricating grease at the same time
führte, daß das Schmierfett gegenüber Oxydation etwas empfindlicher wurde. Wenn diese Eigenschaft auch ohne Bedeutung ist, wenn das Schmierfett dem Angriff von Sauerstoff nicht oder wenig ausgesetzt ist, ist es jedoch oft erwünscht, diese negative Eigenschaft zu beseitigen. Es hat sich nun gezeigt, daß ein weiterer Zusatz von als Schmiermittelbestandteil bekannten öllöslichen Salzen aus mehrwertigen Metallen und der Dithiocarbaminsäuren nicht nur die ursprüngliche Oxydationsbeständigkeit des Schmierfettes wieder herstellt, sondern sogar unerwartet steigert. Typische Vertreter aus dieser Klasse von Zusatzstoffen sind Zink-, Aluminium-, Blei-, Eisen-, Calcium-, Barium- und Natriumdialkyldithiocarbamate, wie Zinkdibutyldithiocarbamat, Calciumdiäthyldithiocarbamat, Bariumdimethyldithiocarbamat, Bleidimethyldithiocarbamat, Zinkdihexyldithiocarbamat, Bariumdiamyldithiocarbamat und die entsprechenden Dioctyl-, Dipropyl-, Propyl-, Butyl- und Äthylphenyldithiocarbamate. Diese Verbindungen werden im allgemeinen in einer Menge zwischen etwa 0,01 und etwa 1,5 Gewichtsprozent, berechnet auf das gesamte Schmierfett, angewendet.resulted in the grease becoming somewhat more sensitive to oxidation. If this property also without It is important if the grease is little or no exposure to oxygen, but it is often desired to remove this negative quality. It has now been shown that a further addition of as Lubricant component known oil-soluble salts from polyvalent metals and dithiocarbamic acids not only restores the original oxidation resistance of the grease, but even unexpectedly increases. Typical representatives from this class of additives are zinc, aluminum, lead, iron, Calcium, barium and sodium dialkyldithiocarbamates, such as zinc dibutyldithiocarbamate, calcium diethyldithiocarbamate, bariumdimethyldithiocarbamate, lead dimethyldithiocarbamate, Zinc dihexyldithiocarbamate, bariumdiamyldithiocarbamate and the corresponding dioctyl, Dipropyl, propyl, butyl and ethylphenyldithiocarbamates. These compounds are generally in an amount between about 0.01 and about 1.5 percent by weight, calculated on the total grease, applied.
Wie das nachstehende Beispiel 2 zeigt, wird durch die Anwendung von Zinkdibutyldithiocarbamat nicht nur die Oxydationsbeständigkeit der Schmierfettzusammen-Setzung wieder hergestellt, nachdem sie durch Zugabe von Calciumerdölsulfonat und Polyäthylenglykolmonooleat etwas herabgesetzt worden war, sondern in dieser Hinsicht tatsächlich eine Verbesserung des Schmierfettes erreicht.As Example 2 below shows, the use of zinc dibutyldithiocarbamate not only the oxidation resistance of the grease composition is restored after it has been added by Calcium petroleum sulfonate and polyethylene glycol monooleate had been lowered somewhat, but in this regard actually achieved an improvement in the grease.
Erst das Zusammenwirken der beiden Komponenten der synergistischen Zusatzmischung führt zu einer bedeutenden Steigerung in der mechanischen Beständigkeit der Schmierfettbasis und zur Beseitigung der Korrosionserscheinungen. Only the interaction of the two components of the synergistic additional mixture leads to a significant one Increase in the mechanical resistance of the grease base and to eliminate the signs of corrosion.
raturtempe
rature
Rollendated
roll
3030th
3535
4040
4545
Zusammensetzung in GewichtsprozentComposition in percent by weight
Nr. 1 Nr. 2 Nr. 3 Schmierfettbasis 100 96,0 95,5No. 1 No. 2 No. 3 Grease Base 100 96.0 95.5
Poly-(äthylenglykol)-monooleat — 1,0 1,0Poly (ethylene glycol) monooleate - 1.0 1.0
Calciumerdölsulfonate*) .... —■ 3,0 3,0Calcium petroleum sulfonates *) .... - ■ 3.0 3.0
Zinksalz von Dibutyl-Zinc salt of dibutyl
dithiocarbamat — — 0,5dithiocarbamate - - 0.5
*) Zugesetzt als Lösung in Mineralöl, welche 33 Gewichtsprozent des Salzes enthielt.*) Added as a solution in mineral oil, which contained 33 percent by weight of the salt.
Navy EES LagertestNavy EES bearing test
(121°, 10 000 Umdrehungen(121 °, 10,000 revolutions
pro Minute)per minute)
Zeit bis zum Versagen inTime to failure in
Stunden 653 483 925Hours 653 483 925
Die Schmierfette können weiterhin Zusätze von bekannten Antioxydationsmitteln vom Amintyp, wie aromatischen Aminen, einschließlich Phenyl-a-naphthylamin und anderer Naphthylamine, sowie von Guanidin-•derivaten, wie Mono- und Dicarbonsäuresalzen von l-(o-oxyaryliden)-aminoguanidin, enthalten.The lubricating greases can also contain additives of known antioxidants of the amine type, such as aromatic amines, including phenyl-a-naphthylamine and other naphthylamines, as well as of guanidine • derivatives, such as mono- and dicarboxylic acid salts of l- (o-oxyarylidene) aminoguanidine.
Um den erfindungsgemäß erzielbaren synergistischen Effekt augenscheinlich zu machen, wurde das im Beispiel 1 verwendete Lithium-12-Oxystearat-Schmierfett jeweils mit 4 Gewichtsprozent der einzelnen Komponenten der Zusatzmischung versetzt und die Ergebnisse bezüglich der Korrosion und der Rollstabilität der so modifizierten Schmierfettbasis mit einer erfindungsgemäßen Zusammensetzung verglichen, welche 2 Gewichtsprozent jeder Komponente enthielt. Die in der folgenden Tabelle zusammengefaßten Versuchsergebnisse lassen erkennen, •daß jeder Zusatzstoff für sich die Stabilität des Schmierfettes wesentlich verschlechtert und seine Korrosionsfähigkeit gar nicht oder nur unwesentlich verbessert. In order to make the synergistic effect achievable according to the invention apparent, this was done in Example 1 used lithium 12 oxystearate grease each with 4 percent by weight of the individual components of the Additional mixture added and the results regarding the corrosion and the rolling stability of the modified Comparing grease base with a composition according to the invention which is 2 percent by weight each Component included. The test results summarized in the following table show that • that each additive in itself enhances the stability of the grease significantly worsened and its corrosion resistance is not improved at all or only insignificantly.
Claims (18)
gekennzeichnet, daß die Metallseife einer
eine Lithiumseife ist.4. Lubricating grease according to claim 1
characterized that the metal soap one
is a lithium soap.
gekennzeichnet, daß die Metallseife5. Lubricating grease according to claim 1 to
marked that the metal soap
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US503340A US2820008A (en) | 1955-04-22 | 1955-04-22 | Lubricating grease composition |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1003900B true DE1003900B (en) | 1957-03-07 |
Family
ID=24001678
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEN12137A Pending DE1003900B (en) | 1955-04-22 | 1956-04-20 | Grease |
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US (1) | US2820008A (en) |
BE (1) | BE547163A (en) |
DE (1) | DE1003900B (en) |
FR (1) | FR1149565A (en) |
GB (1) | GB818328A (en) |
NL (1) | NL94582C (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2916450A (en) * | 1957-12-11 | 1959-12-08 | Exxon Research Engineering Co | Lubricating oil containing an alkaline earth metal sulfonate, a co-neutralized nonyl phenate, and a metal diamyldithiocarbamate |
US3462367A (en) * | 1966-10-31 | 1969-08-19 | Shell Oil Co | Lubricating oils containing an antioxidant mixture of zinc and antimony dialkyl dithiocarbamates |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE23243E (en) * | 1950-06-20 | Lubricating grease composition | ||
US2352811A (en) * | 1941-06-27 | 1944-07-04 | Standard Oil Co | Lubricant |
US2450633A (en) * | 1944-10-31 | 1948-10-05 | California Research Corp | Compounded oil |
-
0
- NL NL94582D patent/NL94582C/xx active
- BE BE547163D patent/BE547163A/xx unknown
-
1955
- 1955-04-22 US US503340A patent/US2820008A/en not_active Expired - Lifetime
-
1956
- 1956-04-20 DE DEN12137A patent/DE1003900B/en active Pending
- 1956-04-20 FR FR1149565D patent/FR1149565A/en not_active Expired
- 1956-04-20 GB GB12183/56A patent/GB818328A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
US2820008A (en) | 1958-01-14 |
BE547163A (en) | |
NL94582C (en) | |
GB818328A (en) | 1959-08-12 |
FR1149565A (en) | 1957-12-27 |
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