DE832787C - Lubricating greases - Google Patents
Lubricating greasesInfo
- Publication number
- DE832787C DE832787C DEP49907A DEP0049907A DE832787C DE 832787 C DE832787 C DE 832787C DE P49907 A DEP49907 A DE P49907A DE P0049907 A DEP0049907 A DE P0049907A DE 832787 C DE832787 C DE 832787C
- Authority
- DE
- Germany
- Prior art keywords
- oil
- acid
- grease
- greases
- oxidized
- 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
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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/026—Butene
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/14—Synthetic waxes, e.g. polythene waxes
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/16—Paraffin waxes; Petrolatum, e.g. slack wax
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- C10M2205/17—Fisher Tropsch reaction products
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- C10M2205/20—Natural rubber; Natural resins
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- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- 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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- C10M2207/128—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 containing hydroxy groups; Ethers thereof
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- 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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- C10M2207/16—Naphthenic acids
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- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
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- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/10—Groups 5 or 15
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/04—Oxidation, e.g. ozonisation
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Description
(WlGBL S. 175)(WlGBL p. 175)
AUSGEGEBEN AM 28. FEBRUAR 1952ISSUED FEBRUARY 28, 1952
ρ 49907 IVd123 c Dρ 49907 IVd123 c D
SchmierfetteLubricating greases
Die Erfindung bezieht sich auf verbesserte Schmierfette. Spezieller ausgedrückt, führt die Erfindung ziu neuen ' Schmierfetten, die gegenüber Bluten und Verhärten durch Altern widerstandsfähig sind und die eine außerordentliche mechanische und thermische Stabilität besitzen.The invention relates to improved lubricating greases. More specifically, the invention performs ziu new 'lubricating greases that are resistant to bleeding and hardening due to aging and which have an extraordinary mechanical and thermal stability.
Es steht fest, daß die Oxydation eine schwerwiegend schädigende Wirkung auf Schmierfette hat. Die Schnelligkeit dieser Zerstörung ist bei den verschiedenen Schmierfetten verschieden und hängt zum Teil von der ölbasis, der Gegenwart von Zusatzstoffen und auch von den Bedingungen ab, denen das Schmierfett ausgesetzt ist. Wenn einmal die Oxydation in einem Schmierfett begonnen hat, scheint die dadurch 'bewirkte Zerstörung eine autokatalytische Erscheinung zu sein, die zu weiterer Zerstörung des Schmierfettes führt.It is clear that oxidation has a seriously damaging effect on lubricating greases Has. The speed at which this destruction occurs is different for the various lubricating greases and depends on it partly on the oil base, the presence of additives and also on the conditions, to which the grease is exposed. Once oxidation has begun in a grease, the destruction caused thereby seems to be an autocatalytic phenomenon leading to further Destruction of the grease leads.
Das Bluten ist eine bei Schmierfetten häufig auftretende Erscheinung, die sich in einer unerwünschten Trennung der Seife und des Schmierstoffes in ein flüssiges öl und einen an Seifen reicheren Teil äußert. Diese Wirkung ist vermutlich die Folge von Änderungen, die tkirch eine gewisse Instabilität der Struktur des Seife-Kohlenwasserstoff-Gemische-s bedingt werden.Bleeding is a common occurrence with greases and results in an undesirable Separation of the soap and the lubricant into a liquid oil and a part richer in soaps expresses. This effect is presumably the result of changes that tkirch a certain instability the structure of the soap-hydrocarbon mixture.
Im allgemeinen werden zur Verhinderung des Blutens und zur Verbesserung der Struktur der Schmierfette spezielle Vorsichtsmaßnahmen getroffen, wie die Anwendung langsamer oder schneller Kühlung oder umfassende Bearbeitung desGenerally used to prevent bleeding and improve the structure of the Special precautions are taken, such as slowing down or applying greases faster cooling or extensive processing of the
Schmierfettes in besonderen Homogenisierapparaten, zum. Beispiel im Cornell-Homogenisator. Solche Verfahren benötigen meist Zeit und tragen erheblich zu den Kosten des Fettes bei. Andere Wege der Herstellung von stabilen, niohtblutendenLubricating grease in special homogenizers, for. Example in the Cornell homogenizer. Such procedures usually take time and add significantly to the cost of the fat. Other Ways of producing stable, non-bleeding
. Schmierfetten sind versucht worden, entweder durch Verminderung des Seifengehaltes im allgemeinen auf weniger als ungefähr 5 Gewichtsprozent oder durch Erhöhen des Seifengehaltes bis zu einem Maximum. Diese Verfahren zur Stabilisierung von Schmierfetten gegenüber dem Bluten haben nicht befriedigt, da in dem Falle der Verminderung des Seifengehaltes auf weniger als 5°/o der Anwendungsbereich der Schmierfette infolge des niedrigen Seifengehaltes eingeschränkt wird, während die Erhöhung des Seifengehaltes auf ein Maximum das Schmierfett zu kostspielig macht und solche Produkte für gewöhnlich eine nichtemvünschte Konsistenz besitzen.. Lubricating greases have been tried either by reducing the soap content in general to less than about 5 percent by weight or by increasing the soap content up to one Maximum. These methods of stabilizing greases against bleeding do not have satisfied, since in the case of reducing the soap content to less than 5% the area of application the grease is restricted due to the low soap content, while the increase maximum soap content makes grease too expensive and such products usually have an undesirable consistency.
Der Grund oder die Gründe für das Verhärten durch Altern sind bisher noch nicht bekannt. Es scheint dadurch verursacht zu werden, daß die fadenförmigen Seifenteilchen während des Lagerns zur Rekristallisation an den Kontaktpunkten unter Bildung eines starreren Gefüges neigen und so eine erhöhte Konsistenz bewirken. Ein solches Erhärten ist außerordentlich unerwünscht, da es verschiedene Schwierigkeiten beim Schmieren hervorruft, so bei Pumpen u. dgl.The cause or reasons for hardening due to aging are not yet known. It appears to be caused by the thread-like soap particles during storage tend to recrystallize at the contact points to form a more rigid structure, and so on cause increased consistency. Such hardening is extremely undesirable because it is various Causes difficulties in lubrication, so with pumps and the like.
Ein Ziel der Erfindung ist die Schaffung von Schmierfetten, die gegen Bluten und Erhärten durch Alterung widerstandsfähig sind. Ein weiterer Gegenstand der Erfindung sind Schmierfette, die auf irgendwelche bekannte Weise hergestellt wurden und Zusatzmittel enthalten, die das Erhärten durch Alterung und Bluten dieser Schmierfette verhindern. Außerdem ist es ein Ziel der Erfindung, für alle Zwecke brauchbare nichtblutende und nicht durch Alterung verhärtende, eine Minimalmenge Seife enthaltende Schmierfette zu schaffen.An object of the invention is to provide lubricating greases that are resistant to bleeding and hardening are resistant to aging. Another object of the invention are lubricating greases that made in any known manner and containing additives that promote hardening prevent these greases from aging and bleeding. It is also an aim of the invention non-bleeding and non-hardening through aging, usable for all purposes, a minimum amount To create greases containing soap.
Die obenerwähnten und andere Vorteile der Erfindung können erhalten werden durch Zusetzen einer oxydierten, an Aromaten reichen Erdölfraktion, das heißt von solchen mit einem Anilinpunkt von 75° oder weniger, vorzugsweise einem Anilinpunkt von 650 oder weniger, in einer Menge von zwischen 1 und 20 Gewichtsprozent, bezogen auf die gesamte Komposition, zu den Schmierfetten.The above mentioned and other advantages of the invention can be obtained by adding an oxidized, aromatics rich petroleum fraction, that is, those having an aniline point of 75 ° or less, preferably an aniline point of 65 0 or less, in an amount of 1 to 20 Percentage by weight, based on the total composition, of the lubricating greases.
Mischungen dieser oxydierten, aromatenreichen Erdölkohlenwasserstoffe und/oder oxydierten stickstoffhaltigen aus aromatenreichen Erdölfraktionen stammenden Fraktionen und/oder oxydierten von aromatenreichen Erdölfraktionen stammenden schwefelhaltigen Fraktionen können ebenfalls verwendet werden. Diese hochatomatischen Kohlenwasserstoffe können aus verschiedenen aromatenreichen Erdölfraktionen durch Behandlung mit selektiven Lösungsmitteln gewonnen werden, wobei die für die Behandlung eines geeigneten Ausgangsöles verwendeten Lösungsmittel geeignet sind, die aromatischen Bestandteile von den in dem öl enthaltenen nichtaromatischen Bestandteilen zu trennen. Geeignete Lösungsmittel sind /.. B. Schwefeldioxyd, Phenol, Furfurol, Nitrobenzol, Kresol, Anilin, ß, ß-Dichlordiäthyläther. Erdölkohlenwasserstoffe, die für die Behandlung mit den obengenannten Arten von Lösungsmitteln und ihren Mischungen besonders geeignet sind, sind die Schmieröle, das heißt Erdölfraktionen, die über ungefähr 371° sieden, wie aus aromatenreichen Roherdölen erhaltene Mineralschmieröle. Besonders bevorzugt sind als Ausgangsstoffe für die Schmierfettzusätze Aromaten, die durch Schwefeldioxydoder Furfurolbehandlung eines Erdöldestillats mit einer Saybolt-Universal-Viskosität (SUS) von ungefähr 60 bei 990 erhalten wurden.Mixtures of these oxidized, aromatic-rich petroleum hydrocarbons and / or oxidized nitrogen-containing fractions originating from aromatic-rich petroleum fractions and / or oxidized sulfur-containing fractions originating from aromatic-rich petroleum fractions can also be used. These highly aromatic hydrocarbons can be obtained from various aromatic-rich petroleum fractions by treatment with selective solvents, the solvents used for the treatment of a suitable starting oil being suitable for separating the aromatic components from the non-aromatic components contained in the oil. Suitable solvents are / .. B. sulfur dioxide, phenol, furfural, nitrobenzene, cresol, aniline, ß, ß-dichlorodiethyl ether. Petroleum hydrocarbons which are particularly suitable for treatment with the above-mentioned types of solvents and their mixtures are the lubricating oils, that is to say petroleum fractions which boil above approximately 371 °, such as mineral lubricating oils obtained from crude oils rich in aromatic compounds. Aromatics obtained by sulfur dioxide or furfural treatment of a petroleum distillate with a Saybolt Universal Viscosity (SUS) of approximately 60 at 99 0 are particularly preferred as starting materials for the lubricating grease additives.
Ein Destillat, das nach der Lösungsmittelbehandlung zwecks Extraktion der Aromaten und nachfolgender Oxydation dieser Aromaten einen besonders geeigneten Zusatzstoff ergibt, hat die folgenden Eigenschaften:A distillate that, after solvent treatment, for the extraction of aromatics and subsequent ones Oxidation of these aromatics results in a particularly suitable additive, has the following Characteristics:
Viskosität bei 990 C (SUS) ... 60,Viscosity at 99 0 C (SUS) ... 60,
Anilinpunkt in 0C 64,8,Aniline point in 0 C 64.8,
Viskositätindex — 53,Viscosity index - 53,
Molekulargewicht 364,Molecular weight 364,
Brechungszahl η 2£ 1,5319,Refractive index η 2 £ 1.5319,
. Sp. Disp. (Dispersion) 155.. Sp. Disp. (Dispersion) 155.
Die charakteristischen Daten der aus dem obigen Destillat durch SO2- oder Furfurolextraktion erhaltenen Aromaten sind folgende:The characteristic data of the aromatics obtained from the above distillate by SO 2 or furfural extraction are as follows:
Spezifisches Gewicht 1,04,Specific weight 1.04,
Viskosität bei 990 C (SSU) . . . 106,Viscosity at 99 0 C (SSU). . . 106,
Jodzahl, Wijs 100 bis 120,Iodine number, Wijs 100 to 120,
Flammpunkt 0C 202,Flash point 0 C 202,
Brennpunkt 0C 249,Focus 0 C 249,
Anilinpunkt in 0C o,Aniline point in 0 C o,
Anilinpunkt, gemischt ° C (mitAniline point, mixed ° C (with
2 Vol. Anilin und 1 Vol.2 vol. Aniline and 1 vol.
«-Heptan und 1 Vol. Extrakt«-Heptane and 1 vol. Extract
bestimmt) 23,certain) 23,
Neutralisationszahl 0,3,Neutralization number 0.3,
Verseifungszahl 0,9,Saponification number 0.9,
Brechungszahl 1,597, l°5 Refractive index 1.597, l ° 5
Anfangssiedepunkt 1 mm abs. 0C 83,Initial boiling point 1 mm abs. 0 C 83,
Endsiedepunkt 1 mm abs. 0C .. 145.Final boiling point 1 mm abs. 0 C .. 145.
Aromaten, die oxydiert und danach als Bestandteil der Schmierfette der Erfindung benutzt werden no können, können auch auf andere Weise als Lösungsmittelextraktion von Erdöldestillaten erhalten werden. So können Aromaten erhalten werden durch katalytisohe Umwandlung von Erdölkohlenwasserstoffen, wie sie aus den bei dem katalytischen Spalten erhaltenen Rückständen gewonnen werden.Aromatics which are oxidized and then used as a component of the lubricating greases of the invention no can also be obtained in ways other than solvent extraction of petroleum distillates. So aromatics can be obtained by catalytic conversion of petroleum hydrocarbons, how they are obtained from the residues obtained in the catalytic cracking.
An Stelle der Verwendung der gesamten aromatischen Komponente, wie sie aus dem Erdöldestillat in der oben beschriebenen Weise erhalten wird, kann die Stickstoff oder Schwefel enthaltende an heterocyclischen Verbindungen reiche Fraktion daraus, wie die stickstoffhaltigen Basen, benutzt werden. Die so erhaltenen stickstoffhaltigen Fraktionen bestehen aus Mischungen von Verbindungen aus Kohlenstoff, Wasserstoff und Stickstoff und sind wahrscheinlich Verbindungen, wie substituier-Instead of using the entire aromatic component as it is from the petroleum distillate obtained in the manner described above, the nitrogen or sulfur-containing an A fraction of them rich in heterocyclic compounds, such as the nitrogenous bases, is used will. The nitrogen-containing fractions thus obtained consist of mixtures of compounds made of carbon, hydrogen and nitrogen and are probably compounds such as substitute
tes Pyridin, Chinolin, Piperidin, Indol, Carbazol, Pyrazin, Cinnolin, Naphthyridin und Homologe davon. Auch schwefelhaltige Fraktionen, die in den • durch das Edeleanuverfahren oder dergleichen aus Erdöldestillaten erhaltenen aromatischen Fraktionen enthalten sind, können als Zusätze zu Schmierfetten gemäß der Erfindung verwendet werden, wie substituiertes Tiopben, Benzotiophen, Dibenzotiophen und deren Homologe.tes pyridine, quinoline, piperidine, indole, carbazole, Pyrazine, cinnoline, naphthyridine and homologues thereof. Also sulfur-containing fractions that are in the • Aromatic fractions obtained from petroleum distillates by the Edeleanu process or the like are contained, can be used as additives to lubricating greases can be used according to the invention, such as substituted tiopbene, benzotiophene, dibenzotiophene and their homologues.
ίο Die obigen aromatischen Destillate und Fraktionen und/oder deren Derivate können auf irgendeine geeignete Weise entweder vor oder während ihrer Zugal>e zu Schmierfetten oxydiert werden. So kann ein voroxydierter Edeleanuextrakt einem Schmierfett während des Verfahrens seiner Herstellung oder nach der Fertigung des Schmierfettes zugege-] >en werden, oder es kann ein Edeleanuextrakt eines Schmierfettes während einer geeigneten Stufe seiner Herstellung zugegeben und in ihr oxydiert werden.ίο The above aromatic distillates and fractions and / or their derivatives can be used in any suitable manner either before or during their In addition, they are oxidized to form lubricating greases. So can a pre-oxidized noble anu extract to a lubricating grease during the process of its manufacture or after the production of the lubricating grease, or a noble anu extract of one can be added Grease can be added and oxidized in it during a suitable stage of its manufacture.
ao Dieses Oxydieren kann durch einfaches Aussetzen der Luft oder Durchblasen von Luft durch ein einen Edeleanuextrakt enthaltendes Schmierfett während ihrer Herstellung geschehen.ao This oxidizing can be accomplished by simply exposing to air or bubbling air through a one Grease containing noble anu extract happen during their production.
Wenn das aromatische Destillat oder Fraktionen daraus vor der Zugabe zu einem Schmierfett oxydiert werden, so können sie durch Verblasen mit einem oxydierenden Gas oxydiert werden, wie Luft, mit Sauerstoff angereicherte Luft, reiner Sauerstoff, ferner mittels Wasserstoffsuperoxyd, Mangandioxyd, Permanganaten, Chloraten, Perchloraten, Perboraten, Chromaten, Chromsäuren usw., vorzugsweise unter Bedingungen, bei denen keine Bildung von organischen Peroxyden stattfindet.When the aromatic distillate or fractions thereof oxidize prior to being added to a grease they can be oxidized by blowing with an oxidizing gas, such as air, air enriched with oxygen, pure oxygen, also by means of hydrogen peroxide, manganese dioxide, Permanganates, chlorates, perchlorates, perborates, chromates, chromic acids, etc., preferably under conditions in which no formation of organic peroxides takes place.
Die Menge der gemäß der Erfindung zu benutzenden oxydierten Produkte kann innenhalb weiter Grenzen variieren und hängt von vielen Faktoren, wie dem zur Schmierfettherstellung benutzten Schmieröl, der Menge und der Art der Seife und anderen verwendeten Verdickungsmitteln ab. Im allgemeinen variiert die Menge des verwendeten oxydierten Produktes zwischen ungefähr 1 %> und ungefähr 20%, vorzugsweise von ungefähr 4% bis ungefähr io°/o, der Gesamtfette.The amount of the oxidized products to be used according to the invention can be varied within Limits vary and depend on many factors, such as the one used to make grease Lubricating oil, the amount and type of soap and other thickeners used. in the in general, the amount of oxidized product used will vary between about 1% and about 20%, preferably from about 4% to about 10% of the total fats.
Die für die Herstellung der Schmierfette der Erfindung, die das oben l>eschriel>ene oxydierte Produkt enthalten müssen, verwendete Seife kann durch Verseifung von verschiedenen Fetten, Fettsäuren, Derivaten von Fetten und ölen, z. B. von Fettsäuren aus vegetabilischen, tierischen Fisdhölen, hydrierten Fettsäuren daraus, vorzugsweise 8 bis 40 Kohlenstoffatome enthaltenden, synthetischen Fettsäuren, hergestellt aus Kohlenwasserstoffen, z. B. durch Oxydieren von natürlichen ölen oder synthetischen Erdölprodukten, von Naphthensäuren, Harzsäuren, Tallölsäuren oder auch von Säuren der oben angegebenen Art, die -polare Gruppen, wie Hydroxylgruppen, Ketogruppen, Halogengruppen, Aminogruppen, enthalten, hergestellt werden.Those used in the manufacture of the lubricating greases of the invention containing the above oxidized product must contain, the soap used can be saponified by various fats, fatty acids, Derivatives of fats and oils, e.g. B. of fatty acids from vegetable, animal fish halls, hydrogenated fatty acids made therefrom, preferably containing 8 to 40 carbon atoms, synthetic Fatty acids made from hydrocarbons, e.g. B. by oxidizing natural oils or synthetic petroleum products, naphthenic acids, resin acids, tall oil acids or even of Acids of the type indicated above, the polar Groups such as hydroxyl groups, keto groups, halogen groups, amino groups, are prepared will.
Speziell können die natürlichen Fette und aus ihnen abstammende Fettsäuren zur Bildung der
Seifen verwendet werden, und zwar folgende:
I. Tierischer Herkunft: Talg (Rind, Hammel, Ziege) usw., Schmalzöl, Knochenöl, Klauenöl,
Wollfett, Pferdefettöl usw.;In particular, natural fats and fatty acids derived from them can be used to form the soaps, namely the following:
I. Animal origin: tallow (beef, mutton, goat), etc., lard oil, bone oil, foot oil, wool fat, horse fat oil, etc .;
IT. vegetabilische öle: Rizinusöl, Elefantenläuseöl (Acajouöl), Erdnußöl, Kokosöl, Jojobasamenöl, Olivenöl, Palmöl, Maisöl, Baumwollsamenöl, Rapsöl, Ravisonöl, Sesamöl, Sojabohnenöl, Leinöl usw.;IT. vegetable oils: castor oil, elephant lice oil (Cashew oil), peanut oil, coconut oil, jojoba seed oil, olive oil, palm oil, corn oil, cottonseed oil, Rapeseed oil, ravison oil, sesame oil, soybean oil, linseed oil, etc .;
III. Fisdhöle: Dorschöl, Lebertran (Dorschleberöl), Delphintran, Heringsöl, Menhadentran, Meerschweintran, Laohsöl, Sardinenöl, Robbentran, Haifischöl, Walöl usw.;III. Fisdhöle: Cod oil, cod liver oil (cod liver oil), dolphin oil, herring oil, menhad oil, guinea pig oil, Laoh oil, sardine oil, seal oil, shark oil, whale oil, etc .;
iV. hydrierte Rückstands- oder Destillatfraktioneu, erhalten aus irgendeinem öl der obigen Liste;iV. hydrogenated residue or distillate fractions eu obtained from any oil in the above list;
V. spezielle Fettsäuren, die bei der Bildung der Seife verwendet werden können, sind gesättigte aliphatisch« Monocarbonsäuren: Caprinsäure, Undecylsäure\ Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, Arachinsäure, Lignocerinsäure, Montansäure, Melissinsäure usw.;V. Special fatty acids that can be used in the formation of the soap are saturated aliphatic «monocarboxylic acids: capric acid, undecylic acid \ Lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, lignoceric acid, Montanic acid, melissic acid, etc .;
Va. ungesättigte alip'hatischeMonocarbonsäuren: ölsäure, Linolsäure, Erucasäure, Clupanodonsäure, Linolensäure, Brassidinsäure, Elaidinsäure, Eläo-Stearinsäure, Stearolsäure usw.;Va. Unsaturated aliphatic monocarboxylic acids: oleic acid, linoleic acid, erucic acid, clupanodonic acid, linolenic acid, brassidic acid, elaidic acid, elaeostearic acid, Stearolic acid, etc .;
Vb. aliphatische Oxycarbonsäuren: Dimetfhyloxycaprylsäure, Dimethyloxycapronsäure, Rizinusölsäure, Ricinelaidinsäure, 12-Oxystearinsäure, 10, ii-Dioxystearinsäure, 4-Oxypalmitinsäure, Linusinsäur«, Sativinsäure, Lanocerinsäure, Dioxybehensäure usw. Die bevorzugten Oxyfettsäuren sind die, bei denen die Hydroxylgruppe mindestens 12 Kohlenstoffatome von der Carboxylgruppe entfernt ist;Vb aliphatic oxycarboxylic acids: dimethyl oxycaprylic acid, Dimethyloxycaproic acid, castoroleic acid, ricinelaidic acid, 12-oxystearic acid, 10, ii-dioxystearic acid, 4-oxypalmitic acid, linusic acid «, Sativic acid, lanoceric acid, dioxybehenic acid, etc. The preferred oxy fatty acids are those in which the hydroxyl group is at least 12 carbon atoms away from the carboxyl group is;
Vc. Katosäuren: Licansäure, 12-Ketostearinsäure, 13-Ketobehensäure, Jojöbaölfettsäure usw.;Vc. Kato acids: licanic acid, 12-ketostearic acid, 13-keto-behenic acid, jojoba oil fatty acid, etc .;
VI. gemischte Säuren: Säuren, die durch Oxydation von Kohlenwasserstoffen, z. B. Paraffin entstehen, Mercaptoölsäure, Mercaptostearinsäure, Aminofettsäuren usw.VI. mixed acids: acids produced by the oxidation of hydrocarbons, e.g. B. Paraffin arise, Mercaptooleic acid, mercaptostearic acid, amino fatty acids, etc.
Mischungen von Fettstoffen und Derivaten daraus können zur Bildung von Seife benutzt werden. So kann eine ausgezeichnete Seife für Schmierfette hergestellt werden aus einer Mischung von hydrierten Fischölfettsäuren und hydriertem Rizinusöl. Bei Benutzung von Mischungen von Fettstoffen zur Bildung einer Seife können die Fettstoffe zum Beispiel von ungefähr io°/0 einer Oxyfettsäure und 90V0 hydrierten Fettöls und/oder dessen Fettsäurederivaten bis ungefähr90V0 Oxyfettsäure und 10% hydriertes Fettölprodukt variieren. Bei Benutzung von Oxyfettsäuren in einer Mischung von Fettstoffen wird vorzugsweise die Oxyfettsäure in einem Bereich von zwischen ungefähr 50 und 90 Gewichtsprozent gehalten. Die benutzten Anteile bestimmen sich zum Teil nadh der Art der zur Bildung der Schmierfette verwendeten Mineralöle und nach der beabsichtigten Verwendung.Mixtures of fatty substances and derivatives thereof can be used to form soap. An excellent soap for greases can be made from a mixture of hydrogenated fish oil fatty acids and hydrogenated castor oil. When using mixtures of fatty substances to form a soap, the fatty substances, for example, can io ° / vary 0 of an oxy fatty acid and 90V 0 hydrogenated fatty oil and / or its fatty acid derivatives to ungefähr90V 0 oxy fatty acid and 10% hydrogenated fat oil product of approximately. When oxy fatty acids are used in a mixture of fatty substances, the oxy fatty acid is preferably kept in a range of between approximately 50 and 90 percent by weight. The proportions used are determined in part by the type of mineral oils used to form the lubricating greases and the intended use.
Die Seife kann durch Verseifung der obenge- iao nannten Fettstoffe bzw. ihrer Mischungen mit Metalloxyd, -hydroxyden, -carbonaten usw. oder in Gegenwart verschiedener Metallverbindungen oder organischer Basen hergestellt werden.The soap can be made by saponifying the above ge iao named fatty substances or their mixtures with metal oxides, hydroxides, carbonates, etc. or in Presence of various metal compounds or organic bases can be produced.
A. Metalle des periodischen Systems, zum Bei- ias spiel:A. Metals of the periodic table, for example game:
Gruppe I: Lithium, Natrium, Kalium, Rubidium, Cäsium,Group I: lithium, sodium, potassium, rubidium, cesium,
Gruppe II: Calcium, Strontium, Barium, Beryllium, Magnesium, Zink, Cadmium,
Gruppe III: Aluminium, Gallium, Indium,
Gruppe IV: Zirconium, Zinn, Blei,
Gruppe V: Wismut,
Gruppe VI: Chrom,
Gruppe VII: Mangan,
ίο Gruppe VIII: Eisen, Kobalt, Nickel.Group II: calcium, strontium, barium, beryllium, magnesium, zinc, cadmium,
Group III: aluminum, gallium, indium,
Group IV: zirconium, tin, lead,
Group V: bismuth,
Group VI: chromium,
Group VII: Manganese,
ίο Group VIII: iron, cobalt, nickel.
B. Organische Basen, wie organische Stickstoff-B. Organic bases, such as organic nitrogen
basen, z. B. Cyclohexylamin, Trimethylcyclohexylamin, Äthanolamin, Dodecylamin, Amylhexylamin, Dicydohexylamin, Triamylamin, quaternäre Ammoniumbasen. bases, e.g. B. cyclohexylamine, trimethylcyclohexylamine, Ethanolamine, dodecylamine, amylhexylamine, dicydohexylamine, triamylamine, quaternary ammonium bases.
Schmierfette, welche Fettsäuresalze der Alkali- und Erdalkalimetalle, z. B. Natrium,' Lithium, Calcium, Barium, Strontium und Magnesium enthalten, ebenso wie die Aluminium- und Zinkseifenao schmiermittel sind !besonders beständig gegen das Bluten und Verhärten durch Alterung bei dem Zusatz der oxydierten Produkte gemäß der Erfindung. Das für die Herstellung der Schmierfette der Erfindung verwendete Mineralöl kann einen weiten Viskositätsbereich haben, von ungefähr 150 Saybolt-Universal-Viskosität bei 380 bis 2000 Saybolt-Universal-Viskosität bei 380. Der Viskositätsindex des Öls kann von unter Null bis ungefähr 100 variieren, und das mittlere Molekulargewicht kann von ungefähr 250 bis 600 betragen. Es kann hochraffiniert und auf irgendeine bekannte Weise mit Lösungsmitteln behandelt sein. Ein bevorzugtes Mineralöl ist eines mit einer Viskosität zwischen ungefähr 300 und 700 SUS bei 380, einem Viskositätsindex von ungefähr 40 bis 70 und einem mittleren Molekulargewicht von zwischen 350 und 550. An Stelle der Verwendung von durch Destillation aus Erdöl erzeugten Schmieröl als ölgrundlage kann es ganz oder teilweise duroh synthetische öle und Schmiermittel ersetzt sein. Als synthetische Schmiermittel können verwendet werden: Polymerisierte Olefine, organische Ester, z. B. 2-Äthylhexylsebacinsäureester, Dioctylphthalsäureester, Trioctylphosphat, polymeres Tetrahydrofuran. Unter manchen Bedingungen des Schmieren« können geringe Mengen eines fetten Öles, wie Rizinusöl, Sohmalzöl dem Kohlenwasserstofföl und/oder dem synthetischen öl, das bei der Herstellung der Schmierfette der Erfindung verwendet wird, zugemischt werden.Lubricating greases which contain fatty acid salts of the alkali and alkaline earth metals, e.g. B. sodium, 'lithium, calcium, barium, strontium and magnesium, as well as the aluminum and zinc soaps are also lubricants! Particularly resistant to bleeding and hardening due to aging with the addition of the oxidized products according to the invention. The mineral oil used in making the greases of the invention can have a wide range of viscosities, from about 150 Saybolt Universal Viscosity at 38 0 to 2000 Saybolt Universal Viscosity at 38 0 . The viscosity index of the oil can vary from below zero to about 100, and the average molecular weight can be from about 250 to 600. It can be highly refined and treated with solvents in any known manner. A preferred mineral oil is one having a viscosity between about 300 and 700 SUS at 38 0 , a viscosity index of about 40 to 70 and an average molecular weight of between 350 and 550. Instead of using lubricating oil produced by distillation from petroleum as an oil base, it can fully or partially replaced by synthetic oils and lubricants. As synthetic lubricants, there can be used: polymerized olefins, organic esters, e.g. B. 2-ethylhexyl sebacic acid ester, dioctylphthalic acid ester, trioctyl phosphate, polymeric tetrahydrofuran. Under some lubrication conditions, small amounts of a fatty oil, such as castor oil, salty malt oil, may be admixed with the hydrocarbon oil and / or synthetic oil used in making the greases of the invention.
Gemäß der vorliegenden Erfindung können dieAccording to the present invention, the
oxydierten aromatenreichenVerbindungen und/oder ihre Derivate dem Schmierstoff zu irgendeiner Zeit während oder nach dem Kochprozeß zugegeben werden. Wenn andere Zusätze zugegeben werden, • so können sie ebenfalls zu irgendeiner geeigneten Zeit vor, während oder nach dem Zusatz des oxydierten aromatenreichen Zusatzstoffes und/oder der Derivate zu dem Schmierstoff zugegeben werden.oxidized aromatic-rich compounds and / or their derivatives to the lubricant at any time be added during or after the cooking process. If other additives are added, • You can also do so at any convenient time before, during, or after the addition of the oxidized aromatic-rich additive and / or the derivatives added to the lubricant will.
Wertvolle Schmierfette können unter Verwendung der Rezepte in den folgenden Bereichen hergestellt werden:Valuable greases can be made using the recipes in the following areas will:
Seife soap
Oxydierte Produkte gemäß
der Erfindung, z. B. oxydierter Edeleanuextrakt,
herrührend von einem
, 60 SUS bei 99° C Erdöldestillat
Oxidized products according to
of the invention, e.g. B. oxidized Edeleanu extract,
originating from one
, 60 SUS at 99 ° C petroleum distillate
! Polyalkylenglykolund oder
seine Derivate ! Polyalkylene glycol and or
its derivatives
Kohlenwasserstofföl (Viskosität 150 bis 2000 (SSU)
bei 380 C) Hydrocarbon oil (viscosity 150 to 2000 (SSU)
at 38 0 C)
Allgemeiner BereichGeneral area
5 bis 25 °/o5 to 25 ° / o
1-20 °/o1-20 ° / o
C) - 15%C) - 15%
54 - 94°/°54-94 ° / °
Bevorzugter , BereichPreferred, area
7 bis 14%7 to 14%
4-IO4-IO
0,01 - 0,1 %0.01 - 0.1%
BestandteileComponents
Hydrierte Fischölsäuren Hydrogenated fish oleic acids
Hydriertes Rizinusöl Hydrogenated castor oil
Polyäthylenglykol mit einem mittleren Molekulargewicht von 600 Polyethylene glycol with an average molecular weight of 600
Natriumhydroxyd (gelöst in 2 kgWassei)Sodium hydroxide (dissolved in 2 kg water egg)
Oxydierter Edeleanuextrakt, herrührend aus einem 60 SUS bei 90° C Erdöldestillat Oxidized Edeleanu extract, derived from a 60 SUS at 90 ° C petroleum distillate
Mineralschmieröl 600 SUS bei 38 C. . .Mineral lubricating oil 600 SUS at 38 C.. .
1,01.0
0,045 · 1,120.045 x 1.12
5.0 86,35.0 86.3
75,9-88,990/075.9-88.990 / 0
Schmierfette nach der Erfindung können unter Benutzung von beispielsweise den folgenden Verbindungen hergestellt werden:Lubricating greases according to the invention can be prepared using, for example, the following compounds getting produced:
kg/100 kg Schmierfettkg / 100 kg of grease
Die Säuren und Glyceride werden geschmolzen mit ungefähr der zweifachen Gewichtsmenge öl bei ungefähr 80°, und es wird eine alkalische Lösung zugegeben. Die ausgefällte Seife wird kräftig unter Bildung eines Breies gerührt und zum Abtreiben des Wassers erhitzt. Während des Erhitzens und Rührens kann zur Verhinderung des Schäumens eine geringe Menge eines polymeren Silicons, z. B. ein polymeres Dimethylsilicon, zugegeben werden. Das Erhitzen wird unter kräftigem Rühren fortgesetzt, bis eine Temperatur von ungefähr 1700 erreicht ist. Dann wird heißes (121 °) öl, welches oxydierten Edeleanuextrakt enthält, langsam in den Öl-Seifen-Brei eingemischt, und die ganze Mischung wird bis zur Erzielung der Seife-Öl-Mischung in gelatiniertem Zustand erhitzt. Wenn der Edeleanuextrakt nicht vor seiner Zugabe zu der Seife-Öl-Mischung oxydiert ist, so soll das gesamte Gemisch der Atmosphäre ausgesetzt werden, so daß der Edeleanuextrakt während der Bildung des Schmiermittels oxydiert werden kann. Das Polyäthylenglykol wird üblicherweise während des Zusetzens des heißen Öles zu der Seife-Öl-Mischung zugefügt. Das endgültige Gemisch wird auf eine Temperatur unterhalb ungefähr 210°, vorzugsweise 1820, erhitzt und dann in einen geeigneten Behälter gefüllt zwecks Nachbehandlung in der Wärme.The acids and glycerides are melted with about twice the weight of oil at about 80 °, and an alkaline solution is added. The precipitated soap is stirred vigorously to form a pulp and heated to drive off the water. During the heating and stirring, a small amount of a polymeric silicone, e.g. B. a polymeric dimethyl silicone may be added. The heating is continued with vigorous stirring until a temperature of approximately 170 0 is reached. Then hot (121 °) oil, which contains oxidized noble anu extract, is slowly mixed into the oil-soap pulp, and the whole mixture is heated in a gelatinized state until the soap-oil mixture is obtained. If the noble anu extract is not oxidized prior to its addition to the soap-oil mixture, the entire mixture should be exposed to the atmosphere so that the noble anu extract can be oxidized during the formation of the lubricant. The polyethylene glycol is usually added to the soap-oil mixture during the addition of the hot oil. The final mixture is heated to a temperature below about 210 °, preferably 182 0 and then filled into a suitable container for subsequent treatment in the heat.
ITm den Unterschied der Wirkung bei Verwendung von oxydiertem Edeleanuextrakt und nichtoxydiertem Edeleanuextrakt auf die Altershärtung von Schmierfetten zu zeigen, wurde der folgende Versuch angestellt, dessen Resultate in der folgenden Tabelle aufgezeigt und in dem Diagramm dargestellt sind. Eine Probe eines Natriumseifenschmierfettes, wie oben beschrieben, wurde in einem offenen Kessel hergestellt, so daß der Edeleanuextrakt oxydiert werden konnte, und die andere Probe eines Natriumseifenschmierfettes aus den gleichen Materialien wurde in einer Atmosphäre von Stickstoff hergestellt, so daß eine Oxydierung des Edeleanuextraktes verhindert wurde. In beiden Fällen wurde eine ausgezeichnete mechanische Stabilität beobachtet.In the difference in effect when using oxidized noble anu extract and non-oxidized To show the age hardening of lubricating greases noble anu extract became the following Attempt made, the results of which are shown in the following table and shown in the diagram are. A sample of sodium soap grease as described above was in a open kettle so that the Edeleanu extract could be oxidized, and the other sample a sodium soap grease made from the same materials was placed in an atmosphere of nitrogen produced so that oxidation of the Edeleanu extract was prevented. In both cases excellent mechanical stability was observed.
Altersverhärtung eines Schmierfettes
auf NatriumbasisAge hardening of a grease
based on sodium
Zusammensetzungcomposition
A. Schmierfett auf Natriumbasis,
enthaltend 5 % oxydierten
Edeleanuextrakt, herrührend
von einem Destillat mit 60 S SU
bei 99° A. Sodium-based grease,
containing 5% oxidized
Edeleanu extract, derived
from a distillate with 60 S SU
at 99 °
B. Schmierfett auf Natriumbasis,
enthaltend 5 % nichtoxydierten Edeleanuextrakt, herrührend von einem Destillat
mit 60 SSU bei 99° B. Sodium-based grease,
containing 5% non-oxidized Edeleanu extract, derived from a distillate
with 60 SSU at 99 °
ASTM
Penetration ASTM
penetration
352352
295295
Penetrationsänderung Change in penetration
nach
8 Wochenafter
8 weeks
1919th
4040
Schmierfette gemäß der Erfindung können auf beliebige andere bekannte Arten kontinuierlich oder diskontinuierlich hergestellt und entweder langsam oder schnell abgekühlt werden, entsprechend der für die Herstellung des Schmierfettes benutzten Art der Seife. So können, wenn Natrium- oder Erdalkaliseife enthaltende Schmierfette hergestellt werden, diese in dem Kessel langsam gekühlt werden, während wenn Lithium- oder Aluminium-Seifen-Schmierfette gemäß der Erfindung hergestellt werden, diese vorzugsweise gleichmäßig und schnell entweder in Rohren von geringem Durchmesser oder durch Aufgeben des heißen Schmierfettes in dünnen Schichten auf ein Stahlband und Behandeln des Schmierfettes mit einem Luftstrom oder einem anderen Kühlmedium zwecks gleichförmiger Kühlung des Schmierfettes ohne Scher-• spannungen gekühlt werden.Lubricating greases according to the invention can be continuous or in any other known manner produced discontinuously and cooled either slowly or quickly, according to the kind of soap used for making grease. So can if sodium or Greases containing alkaline earth soap are produced, these are slowly cooled in the kettle, while when lithium or aluminum soap greases are made according to the invention preferably evenly and quickly in either small diameter pipes or by applying the hot grease in thin layers to a steel belt and Treat the grease with a stream of air or other cooling medium to make it more uniform Cooling of the grease can be cooled without • shear stresses.
Besonders erwünschte Stabilisierungsmittel, die mit Schmierfetten der Erfindung benutzt werden können, sind die Alkylenglykol- und/oder Alkylenthioglykolpolymere und ihre Monoester- und Ätherderivate. Die Alkylenglykolpolymere können durch die folgende allgemeine Strukturformel dargestellt werden:Particularly desirable stabilizers used with lubricating greases of the invention are the alkylene glycol and / or alkylene thioglycol polymers and their monoester and ether derivatives. The alkylene glycol polymers can be represented by the following general structural formula will:
HO (CnH2n-O-C7nH2J0-OH (I)
in der m und η und ο ganze Zahlen sind. Vorzugsweise
sollen die polymeren Alkylenglykole, dargestellt durch die obige allgemeine Formel, derart
sein, daß der Faktor ο multipliziert mit der Zähl
der Kohlenstoffatome in der Klammer mindestens 6 ist.HO (C n H 2n -OC 7n H 2 J 0 -OH (I)
in which m and η and ο are integers. Preferably, the polymeric alkylene glycols represented by the above general formula should be such that the factor ο multiplied by the number of carbon atoms in the brackets is at least 6.
Die polymeren Alkylenglykole können durch Polymerisieren von Äthylen-, Propylen-, Isobutylen-, n-Butylenoxyden und/oder ihren Mischungen in Gegenwart eines Katalysators, wie z. B. Jod oder Jodwasserstoffsäure, hergestellt werden. Solche Polymere können auch durch Umsetzen eines einwertigen Alkohols mit einem Alkylenoxyd hergestellt werden. So kann ein geeignetes Produkt ·75 durch Umsetzung von n-Butanol mit Propylenoxyd bei Temperaturen zwischen ungefähr 100 und iio° unter Druck und in Gegenwart eines Alkalikatalysators erhalten werden.The polymeric alkylene glycols can be prepared by polymerizing ethylene, propylene, isobutylene, n-butylene oxides and / or their mixtures in the presence of a catalyst, such as. B. iodine or Hydriodic acid. Such polymers can also be converted into a monovalent Alcohol can be produced with an alkylene oxide. So a suitable product can · 75 by reacting n-butanol with propylene oxide at temperatures between about 100 and iio ° can be obtained under pressure and in the presence of an alkali catalyst.
Die polymerisierten höheren Polyalkylenglykole mit zwischen 2 und 6 Kohlenstoffatomen in der Alkylengruppe sind besonders wirksam als Zusatzstoffe gemäß der Erfindung, und bevorzugt sind Polyäthylen- und Polypropylenglykole. Das mittlere Molekulargewicht der Polyalkylenglykole kann von ungefähr 200 bis ungefähr 7000 betragen, und das bevorzugte Molekulargewicht liegt im Bereidh von ungefähr 1000 bis 6000.The polymerized higher polyalkylene glycols having between 2 and 6 carbon atoms in the Alkylene groups are particularly effective as additives according to the invention, and are preferred Polyethylene and polypropylene glycols. The average molecular weight of the polyalkylene glycols can from about 200 to about 7,000 and the preferred molecular weight is within the range from about 1000 to 6000.
Es soll ausgeführt werden, daß die höheren Polyalkylenglykole aus Mischungen von mehreren Polymeren bestehen, z. B. besteht ein Polyäthylenglykol mit einem mittleren Molekulargewicht von 400 aus verschiedenen Glykolen, angefangen von einer geringen Menge Monoäthylenglykol bis herauf zum Penteadecaäthylenglykol. Infolgedessen ist es das mittlere Molekulargewicht, das hier in der Beschreibung gemeint ist und auf das sich die Angaben betreffend der Polyalkylenglykole oder PoIyäthylenglykole beziehen; die höheren Glykole besitzen ein mittleres Molekulargewicht oberhalb 200 und vorzugsweise oberhalb 400; die mit einem mittleren Molekulargewicht von zwischen 1000 und 1500 sind bei der Durchführung der vorliegenden Erfindung sehr wirksam.It should be stated that the higher polyalkylene glycols are made from mixtures of several polymers exist, e.g. B. consists of a polyethylene glycol with an average molecular weight of 400 various glycols, from a small amount of monoethylene glycol up to Penteadecaethylene glycol. As a result, it is the average molecular weight that is here in the description is meant and to which the information relating to the polyalkylene glycols or polyethylene glycols relate; the higher glycols have an average molecular weight above 200 and preferably above 400; those with an average molecular weight of between 1000 and 1500 are very effective in practicing the present invention.
An Stelle der Polyalkylenglykole können die Ester- und Ätherderivate verwendet werden. Die Ester können aus einer Anzahl von Säuren mit zwischen 1 und ungefähr 22 Kohlenstoffatomen und vorzugsweise zwischen ungefähr 10 und 18 Kohlenstoffatomen erzeugt werden. Die verwendbaren Säuren sind die aliphatischen, aromatischen, cyclischen Carbonsäuren, Sulfonsäuren u. dgl. Fett- ' säuren, und insbesondere die höheren Fettsäuren sind bevorzugt, z. B. folgende Säuren: Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, Arachinsäure, Behensäure, ölsäure, Ricinolsäure, Oxystearinsäure, Phenylessigsäure oder Phenylstearinsäure. Auch .können zur Bildung der Ester andere Säuren verwendet werden, wie Naphthensäure, öllösliche Erdölsulfonsäuren, Tallölfettsäuren, aromatische Säuren, z. B. Salicylsäure und Phthalsäure. Besondere Beispiele von Estern dieser Art sind Polyäthylenglykolmonostearat, PoIyäthylenglykolmonooleat. The ester and ether derivatives can be used in place of the polyalkylene glycols. the Esters can be selected from a number of acids having between 1 and about 22 carbon atoms and preferably between about 10 and 18 carbon atoms be generated. The acids that can be used are aliphatic, aromatic, cyclic Carboxylic acids, sulfonic acids and the like fatty acids, and especially the higher fatty acids are preferred e.g. B. the following acids: lauric acid, myristic acid, palmitic acid, stearic acid, Arachidic acid, behenic acid, oleic acid, ricinoleic acid, oxystearic acid, phenylacetic acid or phenylstearic acid. Other acids can also be used to form the esters, such as naphthenic acid, oil-soluble petroleum sulfonic acids, tall oil fatty acids, aromatic acids, e.g. B. salicylic acid and Phthalic acid. Particular examples of esters of this type are polyethylene glycol monostearate and polyethylene glycol monooleate.
Ätherderivate von Polyalkylenglykolen können 1*5 auf übliche Weise hergestellt werden; die aroma-Ether derivatives of polyalkylene glycols can be 1 * 5 be made in the usual way; the aroma
tischen Äther von Polyalkylenglykolen haben die allgemeine Formel:Table ethers of polyalkylene glycols have the general formula:
HO(CnH2n-O-CmH21n-O)2Ar-R'; (Π)HO (CnH 2n -O-CmH 21n -O) 2 Ar-R '; (Π)
in der Ar ein aromatisches Radikal ist mit einem ihm verbundenen Alkylradikal, dargestellt durch R',in which Ar is an aromatic radical with an alkyl radical linked to it, represented by R ',
ίο das von ι bis ungefähr 8 Kohlenstoffatome besitzt, und in der Y ein Fettsäureradikal ist, während n, m und α ganze Zahlen sind wie in (I) und q ο oder ι ist.ίο which has from ι to about 8 carbon atoms, and in which Y is a fatty acid radical, while n, m and α are integers as in (I) and q is ο or ι.
Thioalkylenglykolpolymere können durch folgende allgemeine Formel dargestellt werden:Thioalkylene glycol polymers can be represented by the following general formula:
-(O —R)m— (S-R)n—I— (III)- (O —R) m - (SR) n —I— (III)
in der m , n' und r ganze Zahlen sind und R ein organisches Radikal, vorzugsweise ein Kohlenwasserstoffradikal ist. Diese Stoffe können durch Umsetzung eines Alkylenglykols oder eines Alkylenoxyds mit einem Alkylensulfid, z. B. Äthlen-, Propylen-, Amylensulftd, Thioglykol oder Merkaptane, hergestellt werden.in which m, n ' and r are integers and R is an organic radical, preferably a hydrocarbon radical. These substances can be obtained by reacting an alkylene glycol or an alkylene oxide with an alkylene sulfide, e.g. B. Äthlen-, propylene, amylensulftd, thioglycol or mercaptans are produced.
Das mittlere Molekulargewicht der Polyalkylenglykolderivate kann unterhalb 400 und bis ungefähr 7000 sein, wobei Derivate mit einem mittleren Molekulargewicht von zwischen 700 und ungefähr 7000 bevorzugt sind.The average molecular weight of the polyalkylene glycol derivatives can be below 400 and up to about 7000, with derivatives having an average molecular weight of between 700 and approximately 7000 are preferred.
Die Menge der Polyalkylenglykolderivate oder anderer benutzbarer, das Bluten verhindernder Mittel hängt von der Seifenkonzentration und zum Teil von der Art des verwendeten Öles ab. Im allgemeinen werden gute Wirkungen erzielt mit Konzentrationen im Bereich von 0,01 bis ungefähro,5 °/o und vorzugsweise innerhalb des Bereiches von zwischen ungefähr 0,05 und ungefähr 0,25 Gewichtsprozent. The amount of polyalkylene glycol derivatives or other useful bleeding preventive agents Medium depends on the soap concentration and, in part, on the type of oil used. In general Good effects are obtained with concentrations ranging from 0.01 to about 5% and preferably within the range of between about 0.05 and about 0.25 weight percent.
Zur weiteren Verdeutlichung der Erfindung diene das folgende Beispiel.The following example serves to further illustrate the invention.
In einem offenen Kessel zur Scbmierfettherstellung werden ungefähr 3,7 Teile hydrierte Fisdhölfettsäuren und 3,7 Teile hydrierte Rizinusölfettsäuren, 1 Teil Lithiumhydroxydlösung und ungefähr 10 Teile Paraffinöl mit 100 SUS bei 38 ° zusammengemischt und unter Rühren auf eine Temperatur von ungefähr 193 bis 2050 erhitzt. In dieser Mischung werden ungefähr 35 bis 40 Teile Paraffinöl mit 100 SUS bei 38 °, 30 Teile Coastal Pale öl von 2000 SUS bei 38 ° und ungefähr 5 bis 15 Teile eines oxydierten Edeleanuextraktes aus einem Destillat von 60 SUS bei 99 ° sehr langsam zugegeben, und die Temperatur des Gemisches wird auf ungefähr 193 bis 1960 gehalten. Nach Bildung einer homogenen Masse wurde dem Schmierfett ungefähr 0,01 Teil Polyäthylenglykol zugegeben. Die heiße flüssige Masse wurde in flache Pfannen mit einer Schichtdicke von weniger als 2,5 cm gegössen und einem Strom von Kühlluft ausgesetzt, so daß das Schmierfett in weniger als 30 Minuten auf rund 65 ° heruntergekühlt wurde. Das gekühlte Schmierfett wurde zerrieben unter Bildung eines verbesserten nichtblutenden Lithium-Seife-Schmierfettes. In an open vessel for Scbmierfettherstellung be about 3.7 parts hydrogenated Fisdhölfettsäuren and 3.7 parts of hydrogenated castor oil fatty acids, 1 part of lithium hydroxide and about 10 parts of paraffin oil having 100 SUS mixed together at 38 ° and heated with stirring to a temperature of about 193-205 0 . About 35 to 40 parts of paraffin oil with 100 SUS at 38 °, 30 parts of Coastal Pale oil of 2000 SUS at 38 ° and about 5 to 15 parts of an oxidized noble anu extract from a distillate of 60 SUS at 99 ° are added very slowly to this mixture, and the temperature of the mixture is maintained at about 193 to 196 degrees Celsius. When a homogeneous mass was formed, approximately 0.01 part of polyethylene glycol was added to the grease. The hot liquid mass was poured into shallow pans with a layer thickness of less than 2.5 cm and exposed to a stream of cooling air, so that the grease was cooled down to around 65 ° in less than 30 minutes. The chilled grease was ground to form an improved non-bleeding lithium soap grease.
Das Verfahren zur Herstellung des obigen Schmierfettes wurde unter Weglassung des oxydierten Edeleanuextraktes wiederholt.The procedure for preparing the above grease was carried out omitting the oxidized one Edeleanu extract repeated.
Dies Lithium-Seife-Schmierfett wurde auf Bluten nach den Vorschriften der Army-Navy-Aeronautical Specification for gresses AN-G-25 vom 10. April 1946 untersucht. Die den oxydierten Edeleanuextrakt enthaltende Probe zeigte keine Tendenz zu Muten, während die Probe, aus der der oxydierte Edeleanuextrakt fortgelassen war, eine merkliche Tendenz zum Bluten zeigte.This lithium-soap-grease was made to bleed according to the regulations of the Army-Navy-Aeronautical Specification for gresses AN-G-25 of April 10, 1946. The oxidized ones The sample containing noble anu extract showed no tendency to mute, while the sample from which the oxidized Edeleanu extract was omitted, showed a noticeable tendency to bleed.
Während des Kochens des obigen Lithiumschmierfettes können kleine Mengen von Seifen oder Salzen, im allgemeinen in Mengen von weniger als 2°/0 zur Erreichung zusätzlicher Effekte zügefügt werden. Zum Beispiel können in ein Lithium-Seife-Schmierfett, wie oben beschrieben, eine geringe Menge Aluminium- oder Natriumseife oder Alkali- und Erdalkalinaphthenate, -acetate usw. zugegeben werden.During cooking, the above lithium grease may contain small amounts of soaps or salts, generally in amounts less / 0 to achieve additional effects are trains added as 2 °. For example, in a lithium soap grease as described above, a small amount of aluminum or sodium soap or alkali and alkaline earth naphthenates, acetates, etc. can be added.
Geringe Mengen von Oxydationsschutzmitteln können den Schmierfetten der Erfindung zugegeben werden, wie n-Butyl-p-phenyldiamin, α- oder /J-Naphthylamin, Phenyl-a- oder /3-Naphthylamin, a, et, ß, ß, oder ot, /3-Dinaphthylamin, Diphenylamin, Tetramethyldiaminodiphenylmethan, Erdölalkylphenole und 2, 4-Ditert.-buty]-6-methylphenol.Small amounts of antioxidants can be added to the lubricating greases of the invention, such as n-butyl-p-phenyldiamine, α- or / J-naphthylamine, phenyl-a- or / 3-naphthylamine, a, et, ß, ß, or ot, / 3-dinaphthylamine, diphenylamine, tetramethyldiaminodiphenylmethane, petroleum alkylphenols and 2,4-di-tert-buty] -6-methylphenol.
Korrosionsschutzmittel, die bei Schmierfetten gemäß der Erfindung besonders anwendbar sind, sind N-primäre Amine mit mindestens 6 bis zu mehr als 18 Kohlenstoffatomen im Molekül, wie Hexylamin, Octylamin, Decylamin, Dodecylamin, Octadecylamin, heterocyclische, Stickstoff enthaltende organische Verbindungen, wie alkylsubstituierte Oxazoline, und Oxazolinsalze von Fettsäuren. Corrosion protection agents which are particularly applicable to lubricating greases according to the invention, are N-primary amines with at least 6 to more than 18 carbon atoms in the molecule, such as Hexylamine, octylamine, decylamine, dodecylamine, octadecylamine, heterocyclic, nitrogen containing organic compounds such as alkyl-substituted oxazolines and oxazoline salts of fatty acids.
Dem Schmierfett nach d-er Erfindung können auch Mittel zugegeben werden, die eine verbesserte Brauchbarkeit bei hohen Drucken verleihen. Die hierfür bevorzugten Mittel umfassen Phosphorsäureester, wie Triaryl-, Alkyloxy-, Aryl- oder Aralkylphosphate, Thiophosphate oder Phosphite, neutrale aromatische Schwefelverbindungen, wie Diarylsulfide und Polysulfide, z. B. Diphenylsulfid, Dikresolsulfid, Dibenzylsulrid, Methylbutyldiphenolsulfid, Diphenylselenid und -diselenid, Dikresolselenid, und Polyselenid, geschwefelte fette öle oder Ester von Fettsäuren und einwertigen Alkoholen, z. B. Walratöl, Jojobaöl, in denen der Schwefel fest gebunden ist; geschwefelte langkettige Olefine, erhalten durch Dehydrierung oder Spaltung von Paraffin, geschwefelte und phosphorierte fette öle, Säuren, Ester und Ketone, Phosphorsäureester mit geschwefelten organischen Radikalen, wie Ester der phosphorigen Säure oder der Phosphorsäure mit geschwefelten Oxyfettsäuren, ferner chlorierte Kohlenwasserstoffe, wie chlorierte Paraffine, aromatische Kohlenwasserstoffe,Terpene, Mineralschmieröle, oder chlorierte Ester von Fettsäuren, die das Chlor in anderen Stellungen als der α-Stellung enthalten. *The lubricating grease according to the invention can also be added agents that improve Give utility at high pressures. The preferred agents for this include phosphoric acid esters, such as triaryl, alkyloxy, aryl or aralkyl phosphates, thiophosphates or phosphites, neutral aromatic sulfur compounds such as diaryl sulfides and polysulfides, e.g. B. Diphenyl sulfide, Dicresol sulfide, dibenzyl sulfide, methylbutyldiphenol sulfide, Diphenyl selenide and diselenide, dicresol selenide, and polyselenide, sulfurized fatty oils or esters of fatty acids and monohydric alcohols, e.g. B. Walratöl, Jojobaöl, in which the sulfur is tightly bound; sulfurized long chain olefins obtained by dehydrogenation or cleavage of paraffin, sulphurized and phosphorized fatty oils, acids, esters and ketones, phosphoric acid esters with sulfurized organic radicals, such as esters of phosphorous acid or phosphoric acid with sulfurized oxy fatty acids, also chlorinated hydrocarbons, such as chlorinated ones Paraffins, aromatic hydrocarbons, terpenes, mineral lubricating oils, or chlorinated esters of fatty acids, which contain the chlorine in positions other than the α-position. *
Claims (3)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US669206XA | 1948-07-26 | 1948-07-26 |
Publications (1)
Publication Number | Publication Date |
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DE832787C true DE832787C (en) | 1952-02-28 |
Family
ID=22072573
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEP49907A Expired DE832787C (en) | 1948-07-26 | 1949-07-26 | Lubricating greases |
Country Status (2)
Country | Link |
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DE (1) | DE832787C (en) |
GB (1) | GB669206A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE943487C (en) * | 1952-06-21 | 1956-05-24 | Deutsche Erdoel Ag | Reversible universal grease |
DE1075777B (en) * | 1956-11-20 | 1960-02-18 | Socony Mobil Oil Company, Inc., New York, N. Y. (V. St. A.) | Mineral oil-based lubricating grease with a content of metal soaps of higher fatty acids |
DE1123421B (en) * | 1959-02-11 | 1962-02-08 | Shell Int Research | High temperature grease |
DE1128069B (en) * | 1959-02-11 | 1962-04-19 | Shell Int Research | Grease |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE927820C (en) * | 1952-08-25 | 1955-05-16 | Huels Chemische Werke Ag | Additives for lubricants |
DE926681C (en) * | 1952-08-25 | 1955-04-21 | Huels Chemische Werke Ag | Additives for lubricants |
DE926680C (en) * | 1952-08-25 | 1955-04-21 | Huels Chemische Werke Ag | Additives for lubricants |
DE929384C (en) * | 1952-08-25 | 1955-06-27 | Huels Chemische Werke Ag | Additives for lubricants |
DE1086514B (en) * | 1954-10-06 | 1960-08-04 | Prod Chim Ind Et Organiques So | N-polyglycol ether derivatives as corrosion protection agents |
DE1076299B (en) * | 1956-08-18 | 1960-02-25 | Basf Ag | Lubricating oils |
-
1949
- 1949-07-13 GB GB18474/49A patent/GB669206A/en not_active Expired
- 1949-07-26 DE DEP49907A patent/DE832787C/en not_active Expired
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE943487C (en) * | 1952-06-21 | 1956-05-24 | Deutsche Erdoel Ag | Reversible universal grease |
DE1075777B (en) * | 1956-11-20 | 1960-02-18 | Socony Mobil Oil Company, Inc., New York, N. Y. (V. St. A.) | Mineral oil-based lubricating grease with a content of metal soaps of higher fatty acids |
DE1123421B (en) * | 1959-02-11 | 1962-02-08 | Shell Int Research | High temperature grease |
DE1128069B (en) * | 1959-02-11 | 1962-04-19 | Shell Int Research | Grease |
Also Published As
Publication number | Publication date |
---|---|
GB669206A (en) | 1952-03-26 |
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