DE1075254B - Mineral oil-based lubricating oil mixture - Google Patents
Mineral oil-based lubricating oil mixtureInfo
- Publication number
- DE1075254B DE1075254B DENDAT1075254D DE1075254DA DE1075254B DE 1075254 B DE1075254 B DE 1075254B DE NDAT1075254 D DENDAT1075254 D DE NDAT1075254D DE 1075254D A DE1075254D A DE 1075254DA DE 1075254 B DE1075254 B DE 1075254B
- Authority
- DE
- Germany
- Prior art keywords
- lubricating oil
- oil mixture
- mixture according
- copolymer
- weight
- 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
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/16—Ethers
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
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- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
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- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/08—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
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- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of a saturated carboxylic or carbonic acid
- C10M145/08—Vinyl esters of a saturated carboxylic or carbonic acid
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- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/20—Condensation polymers of aldehydes or ketones
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- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/36—Polyoxyalkylenes etherified
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- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
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- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
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- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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- C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
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- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/087—Boron oxides, acids or salts
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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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- 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
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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- C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
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- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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Description
Die Erfindung bezieht sich auf eine Schmierölmischung auf Mineralölbasis, die ein Gemisch dreier jeweils einzeln als Zusatzstoffe zu Mineralschmierölen bekannten Verbindungen enthält und durch die Kombination vonThe invention relates to a lubricating oil mixture based on mineral oil, which is a mixture of three each individually contains compounds known as additives to mineral lubricating oils and through the combination of
(a) öllöslichen stickstoffhaltigen Polymeren mit(a) with oil-soluble nitrogen-containing polymers
(b) öllöslichen mehrwertigen Metallsalzen mit Antischlammeigenschaften und(b) oil-soluble polyvalent metal salts with anti-sludge properties and
(c) öllöslichen wasserunlöslichen polymeren Alkoholen als Zusatzstoffe gekennzeichnet ist.(c) oil-soluble, water-insoluble polymeric alcohols are labeled as additives.
Es ist bekannt, Schmierölmischungen reinigende und verschleißverhindernde öllösliche Mischpolymerisate aus einer polymerisierbaren stickstoffhaltigen Verbindung, insbesondere mit basischem Stickstoffatom, mit einer polymerisierbaren ungesättigten Verbindung, gegebenenfalls mit polyvalenten Metallsalzen, zuzusetzen.It is known to consist of oil-soluble copolymers which clean lubricating oil mixtures and prevent wear a polymerizable nitrogen-containing compound, in particular with a basic nitrogen atom, with a add polymerizable unsaturated compound, optionally with polyvalent metal salts.
Weiterhin ist es bekannt, Schmierölen öllösliche mehrwertige Metallsalze mit Antischlammeigenschaften gegebenenfalls mit polymeren Alkoholen als Verschleißinhibitoren und Reinigungsmittel zuzusetzen.It is also known to use oil-soluble polyvalent metal salts with anti-slurry properties in lubricating oils with polymeric alcohols as wear inhibitors and cleaning agents.
Auch wurde vorgeschlagen, Schmiermitteln polymere, reinigend wirkende Alkohole zuzusetzen.It has also been proposed to add polymeric alcohols with a cleaning effect to lubricants.
Zwar stellen die öllöslichen polyvalenten Metallsalze wirksame Verschleißinhibitoren dar, doch geben sie zu einer Erhöhung der Verschlammungsneigung des Schmieröls während der Verwendung sowohl unter niedrigen wie hohen Temperaturbedingungen Anlaß. Es wurde festgestellt, daß diese unerwünschte Verschlammungsneigung besonders deutlich hervortritt, wenn der polymere Schlamminhibitor ein stickstoffhaltiges Polymer ist. Diese Erscheinung ist insofern überraschend, als man nach allgemeiner Ansicht die Verschlammung von Schmierölen am wirksamsten dadurch bekämpfen zu können glaubte, daß man als Schlamminhibitor ein keine Asche bildendes stickstoffhaltiges Polymer oder ein öllösliches polyvalentes Metallsalz, z. B. ein polyvalentes Metallsulfonat, zusetzte.Although the oil-soluble polyvalent metal salts are effective wear inhibitors, they give rise to an increase in the tendency of the lubricating oil to sludge during use under both low and high temperature conditions. It has been found that this undesirable tendency to sludge becomes particularly pronounced when the polymeric sludge inhibitor is a nitrogen-containing polymer. This phenomenon is surprising insofar as it is generally believed that the most effective way of combating sludging of lubricating oils is to use a non-ash-forming nitrogenous polymer or an oil-soluble polyvalent metal salt, e.g. B. a polyvalent metal sulfonate added.
Es wurde nun festgestellt, daß man Schmieröle, die als Zusatzstoffe bekannte öllösliche stickstoffhaltige Polymere und öllösliche mehrwertige Metallsalze mit Antischlammeigenschaften enthalten, durch Zusatz eines öllöslichen wasserunlöslichen polymeren Alkohols stabilisieren kann.It has now been found that lubricating oils containing the oil-soluble nitrogen-containing additives known as additives Contain polymers and oil-soluble polyvalent metal salts with anti-slurry properties by adding a Oil-soluble, water-insoluble polymeric alcohol can stabilize.
Vorzugsweise enthält der polymere Alkohol mehrere nichtsaure Hydroxylgruppen und mindestens eine Alkylgruppe mit 4 oder mehr Kohlenstoffatomen. Es wurde festgestellt, daß man den polymeren Alkohol auch in Form einer Komplexverbindung mit einem öllöslichen polyvalenten Metallsalz verwenden kann.The polymeric alcohol preferably contains several non-acidic hydroxyl groups and at least one alkyl group with 4 or more carbon atoms. It was found that the polymeric alcohol can also be used in Can use the form of a complex compound with an oil-soluble polyvalent metal salt.
Die öllöslichen stickstoffhaltigen Polymere, die als Zusatzstoff (a) in der Kombination verwendet werden 5" können, sind in der deutschen Auslegeschrift 1 003 896 beschrieben. Sie leiten sich von mindestens zwei verschiedenen polymerisierbaren Verbindungen ab, erstens einer Verbindung, die im Molekül einen ungesättigten Schmierölmisctmng auf MineralölbasisThe oil-soluble nitrogen-containing polymers used as additive (a) in the combination 5 " are described in the German Auslegeschrift 1 003 896. They derive from at least two different ones polymerizable compounds, firstly a compound that has an unsaturated compound in the molecule Mineral oil based lubricating oil mixing
Anmelder:Applicant:
N. V. De Bataafsche Petroleum
Maatschappij, Den HaagNV De Bataafsche Petroleum
Maatschappij, The Hague
Vertreter: Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. PulsRepresentative: Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse
und Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Pechmann,and Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Bad luck man,
Patentanwälte, München 9, Schweigerstr. 2Patent Attorneys, Munich 9, Schweigerstr. 2
Beanspruchte Priorität:
V. St. v. Amerika vom 26. November 1957Claimed priority:
V. St. v. America November 26, 1957
Pratt Lavaur Greer, Pleasant Hill, Calif.,Pratt Lavaur Greer, Pleasant Hill, Calif.,
Roland Frederick Bergstrom, Martinez, Calif.,Roland Frederick Bergstrom, Martinez, Calif.,
und John Sayler Coon, East Alton, 111. (V. St. A.),and John Sayler Coon, East Alton, 111. (V. St. A.),
sind als Erfinder genannt wordenhave been named as inventors
Rest enthält, der über ein Sauerstoffatom an eine Alkylgruppe mit mindestens 8, vorzugsweise 8 bis 22 und insbesondere 12 bis 20 Kohlenstoffatomen gebunden ist, sowie zweitens von einer ungesättigten stickstoffhaltigen Verbindung.Contains the remainder that is attached to an alkyl group via an oxygen atom is bonded with at least 8, preferably 8 to 22 and in particular 12 to 20 carbon atoms, and second, from an unsaturated nitrogenous compound.
In den folgenden Beispielen soll die Herstellung von zwei weiter unten als polymere Zusatzstoffe (a) in den Zubereitungen angeführten stickstoffhaltigen Mischpolymeren beschrieben werden, wobei diese Herstellung im Rahmen vorliegender Erfindung nicht unter Schutz gestellt wird.In the following examples, the preparation of two below as polymeric additives (a) in the Preparations listed nitrogen-containing copolymers are described, this preparation in The scope of the present invention is not protected.
Eine Mischung von 2 Mol Methacrylsäurelaurylester, 1 Mol N-Vinylpyrrolidon und 0,5 Gewichtsprozent Benzoylperoxyd wird 10 Stunden lang bei 65° C gehalten. Das Polymer wird in Benzol aufgenommen und anschließend mit Aceton—Methanol gefällt. Die Fällungsoperation wird wiederholt und ein Mischpolymer mit einem Stickstoffgehalt von 2,20 Gewichtsprozent und einem Molekulargewicht von mehr als 250 000 isoliert. Das Polymer enthält die Monomereinheiten im eingesetzten Verhältnis.A mixture of 2 moles of lauryl methacrylate, 1 mole of N-vinylpyrrolidone and 0.5 percent by weight of benzoyl peroxide is kept at 65 ° C for 10 hours. The polymer is taken up in benzene and then precipitated with acetone-methanol. The precipitation operation is repeated and a mixed polymer with a nitrogen content of 2.20 percent by weight and a molecular weight of more than 250,000. The polymer contains the monomer units in the ratio used.
Eine Mischung von 2,52 Mol Methacrylsäurestearylester, 5,04 Mol Methacrylsäurelaurylester, 0,83 Mol Methacrylsäuremethylester, 1 Mol 2-Methyl-5-vinylpyridin undA mixture of 2.52 moles of stearyl methacrylate, 5.04 moles of lauryl methacrylate, 0.83 moles of methyl methacrylate, 1 mole of 2-methyl-5-vinylpyridine and
909 729/403909 729/403
1 U /O Ü041 U / O Ü04
3 43 4
0,2 Gewichtsprozent Azoisobuttersäurenitril, in wenig sich z. B. nach den in den USA.-Patentschriften 2356043,0.2 percent by weight azoisobutyronitrile, in little z. B. according to the US patents 2356043,
Aceton gelöst, wird in einem Kolben 36 Stunden lang 2 409 687, 2 616 904, 2 616 905 und 2 616 910 beschrie-Dissolved acetone, 2 409 687, 2 616 904, 2 616 905 and 2 616 910 are written in a flask for 36 hours.
unter Stickstoff und Rühren bei 65° C zur Reaktion ge- benen Verfahren herstellen.Prepare the process indicated for the reaction under nitrogen and stirring at 65 ° C.
bracht. Das Polymer wird hierauf in einer gleichen Der dritte entscheidende Zusatzstoff (c), der in derbrings. The polymer is then in an equal The third crucial additive (c), which is in the
Volumenmenge Benzol aufgenommen und danach mit 5 erfindungsgemäßen Kombination verwendet wird, ist einAmount of volume of benzene added and then used with 5 combination according to the invention is a
10 \Tolumteilen einer Aceton-Methanol-Mischung gefällt. öllöslicher wasserunlöslicher polymerer Alkohol, der10 \ T olumteilen an acetone-methanol mixture like. oil-soluble water-insoluble polymeric alcohol, the
Dies wird wiederholt und das Tetrapolymer mit einem mehrere nichtsaure sauerstoffhaltige Reste, z. B. Hydro-This is repeated and the tetrapolymer with one several non-acidic oxygen-containing residues, e.g. B. Hydro
Stickstoffgehalt von 0,60 Gewichtsprozent und einem xyl- oder Oxyalkylengruppen, sowie mindestens eineNitrogen content of 0.60 percent by weight and one xyl or oxyalkylene group, as well as at least one
Molekulargewicht von mehr als 750 000 isoliert. Alkylgruppe mit mindestens 4 Kohlenstoffatomen ent-Molecular weight greater than 750,000 isolated. Alkyl group with at least 4 carbon atoms
Auch die folgenden Mischpolymere eignen sich als io hält, wobei das Polymer in Form einer Komplexverbin-The following copolymers are also suitable as holds, the polymer being in the form of a complex compound
Schmierölzusatzstoffe (a) gemäß der Erfindung: Meth- dung mit einer polyvalenten Metallverbindung vorliegenLubricating oil additives (a) according to the invention: method with a polyvalent metal compound
acrylsäurelaurylester—Styrol—2-Methyl-5-vinylpyridin, kann.lauryl acrylic ester — styrene — 2-methyl-5-vinylpyridine, may.
Methacrylsäurelaurylester — Styrol — Methacrylsäure- Zwei Gruppen dieser als Zusatzstoffe (c) verwendetenLauryl methacrylate - styrene - methacrylic acid - Two groups of these used as additives (c)
2-methyl-5-octylester—X-vinylpyrrolidon, Methacryl- polymeren Alkohole werden besonders vorgezogen. Zur2-methyl-5-octyl ester-X-vinylpyrrolidone, methacrylic polymeric alcohols are particularly preferred. To the
säurelaurylester— Vinyl-ß-aminoäthyläther, N-Vinyl- 15 ersten Gruppe gehören die Mischpolymere von a-Olefinenacid lauryl ester - vinyl-ß-aminoethyl ether, N-vinyl- 15 The first group includes the copolymers of α-olefins
pyrrolidon—Methacrylsäureoctylester, X-Vinyl-3-methyl- mit mindestens 10 Kohlenstoffatomen im Molekül mitpyrrolidone - octyl methacrylate, X-vinyl-3-methyl- with at least 10 carbon atoms in the molecule
pyrrolidon—Methacrylsäurecetylester, N -Vinylpyrroli- ungesättigten Alkoholen, insbesondere Vinylalkohol,pyrrolidone-methacrylic acid cetyl ester, N -Vinylpyrroli- unsaturated alcohols, especially vinyl alcohol,
don—Methacrylsäurestearylester, X-Vinylpyrrolidon— Diese Mischpolymere lassen sich nach den in der USA,-don — stearyl methacrylate, X-vinylpyrrolidone— These copolymers can be prepared according to the US, -
Acrylsäurestearylester, X-Vinyl-3,3-dimethylpyrrolidon— Patentschrift 2 800 453 beschriebenen Verfahren her-Acrylic acid stearyl ester, X-vinyl-3,3-dimethylpyrrolidone - patent specification 2,800,453.
Methacrylsäurelaurylester, X - Vinylpyrrolidon—Meth- 20 stellen, wobei im wesentlichen ein a-Olefin mit einemLauryl methacrylate, X - vinylpyrrolidone — meth- 20, where essentially an α-olefin with a
acrylsäurestearylester — Methacrylsäurecetylester, Vinylester mischpolymerisiert wird und anschließend diestearyl acrylic ester - cetyl methacrylate, vinyl ester is copolymerized and then the
X-Vinyl-3-methylpyrrolidon—Methacrylsäurestearyl- Estergruppen durch Hydrolyse oder Alkoholyse inX-vinyl-3-methylpyrrolidone — methacrylic acid stearyl ester groups by hydrolysis or alcoholysis in
ester—Methacrylsäurelaurylester, X - Vinylpiperidon— Hydroxylgruppen umgewandelt werden.ester — lauryl methacrylate, X — vinylpiperidone — hydroxyl groups.
Methacrylsäurelaurylester. X-Vinyl-3-methyrpiperidon— Geeignete a-Olefine sind diejenigen, die 10 bis 40, vor-Lauryl methacrylate. X-vinyl-3-methyrpiperidone - Suitable α-olefins are those containing 10 to 40, pre-
Methacrylsäurestearylester. 25 zugsweise 12 bis 30 Kohlenstoffatome im Molekül ent-Stearyl methacrylate. 25 preferably 12 to 30 carbon atoms in the molecule
Der zweite Zusatzstoff (b) in den erfindungsgemäßen halten, wie a-Decen, a-Hexadecen, a-Tetradecen, a-Penta-The second additive (b) keep in the invention, such as a-decene, a-hexadecene, a-tetradecene, a-penta-
Zubereitungen ist ein öllösliches mehrwertiges Metallsalz decen, α - Heptadecen, a-Octadecen, a-Xonadecen,Preparations is an oil-soluble polyvalent metal salt decene, α - heptadecene, a-octadecene, a-xonadecene,
mit Antischlammeigenschaften. Bevorzugte Salze sind a-Eikosen, a-Dokosen, a-Triakonten und deren Mischun-with anti-sludge properties. Preferred salts are a-eicoses, a-docoses, a-triacconts and their mixtures
die Sulfonate, Phenolate und die Salze von Carbonsäuren. gen. Mischungen von a-Olefmen mit 12 bis 20 und ins-the sulfonates, phenates and the salts of carboxylic acids. gen.Mixtures of α-olefins with 12 to 20 and ins-
Es können sowohl neutrale wie basische Salze verwendet 30 besondere 16 bis 18 Kohlenstoffatomen eignen sich beson-Both neutral and basic salts can be used. 30 special 16 to 18 carbon atoms are particularly suitable
werden. ders. Diese Olefine werden durch thermische Zersetzungwill. ders. These olefins are produced by thermal decomposition
Die Sulfonate sind vorzugsweise Petroleumsulfonate von Paraffinwachsen erhalten und stellen ein billiges Aus-The sulfonates are preferably petroleum sulfonates obtained from paraffin waxes and are an inexpensive option
der Metalle der II. Gruppe des Periodensystems mit gangsmaterial dar.of the metals of group II of the periodic table with common material.
Ordnungszahlen von 12 bis 56, insbesondere die Erd- Die Vinylester leiten sich vorzugsweise von Carbonalkalimetalle,
z. B. die neutralen oder basischen Calcium-, 35 säuren mit bis zu 5 Kohlenstoffatomen im Molekül ab,
Barium- und Magnesiumsalze von öllöslichen Petroleum- z. B. Vinylacetat, Vinylpropionsäureester, Vinylisobuttersulfonsäuren
mit einem Molekulargewicht von 350 bis 550 säureester und Vinylisovaleriansäureester.
und vorzugsweise von 400 bis 500. Im allgemeinen werden diese AusgangsverbindungenOrdinal numbers from 12 to 56, especially the earth. The vinyl esters are preferably derived from carbon alkali metals, eg. B. the neutral or basic calcium, 35 acids with up to 5 carbon atoms in the molecule, barium and magnesium salts of oil-soluble petroleum z. B. vinyl acetate, vinyl propionic acid ester, vinyl isobutyric acid ester with a molecular weight of 350 to 550 and vinyl isovaleric acid ester.
and preferably from 400 to 500. In general, these starting compounds
Die Phenolate sind vorzugsweise Salze von Polypheno- in Gegenwart eines Katalysators mischpolymerisiert.The phenates are preferably salts of polypheno- in the presence of a catalyst copolymerized.
len. Unter Polyphenolen sind Verbindungen verstanden, 40 Hierfür geeignete Katalysatoren sind verschiedene orga-len. Polyphenols are compounds, 40 Catalysts suitable for this purpose are various organic
die mehrere Phenolreste durch Kohlenwasserstoffketten nische Peroxyde, wie aliphatische, aromatische, hetero-the several phenol residues through hydrocarbon chains niche peroxides, such as aliphatic, aromatic, hetero-
miteinander verknüpft enthalten, z.B. Verbindungen, cyclische und alicyclische Peroxyde, z. B. Diäthylperoxyd,contain linked to one another, e.g. compounds, cyclic and alicyclic peroxides, e.g. B. diethyl peroxide,
bei denen mehrere einfache Phenole in ortho-Stellung tert.-Butylhydroperoxyd, Dibenzoylperoxyd, Dimethyl-in which several simple phenols in the ortho position tert-butyl hydroperoxide, dibenzoyl peroxide, dimethyl
und oder para-Stellung zur phenolischen Hydroxylgruppe thienylperoxyd, Dicyclohexylperoxyd, Dilauroylperoxyd,and or para position to the phenolic hydroxyl group thienyl peroxide, dicyclohexyl peroxide, dilauroyl peroxide,
über Alkylenreste, z. B. Methylengruppen, miteinander 45 Ditert.-butylperoxyd und Harnstoffperoxyd.via alkylene radicals, e.g. B. methylene groups, together 45 di-tert-butyl peroxide and urea peroxide.
\erbunden sind. Derartige Verbindungen lassen sich Der Anteil des jeweils ausgewählten Katalysators und\ are bound. Such compounds can be The proportion of the selected catalyst and
durch Kondensation eines Alkylphenols, ζ. B. p-Octoyl- die bei der Mischpolymerisation angewendete Temperaturby condensation of an alkylphenol, ζ. B. p-Octoyl- the temperature used in the copolymerization
phenol, mit einem Aldehyd, wie Formaldehyd, Acetalde- kann zur Herstellung von Produkten mit verschiedenenphenol, with an aldehyde such as formaldehyde, acetaldehyde- can be used to manufacture products with various
hyd oder Benzaldehyd, herstellen. Die bevorzugten poly- Molekulargewichten variiert werden,hyd or benzaldehyde. The preferred poly- molecular weights are varied,
valenten Metalle in den Phenolaten sind die gleichen 50 Die Monomere werden vorzugsweise in derartigenvalent metals in the phenates are the same 50. The monomers are preferably in such
wie bei den Sulfonaten. Calcium- und Bariumsalze von Mengenverhältnissen verwendet, daß das Molverhältnisas with the sulfonates. Calcium and barium salts used in proportions that the molar ratio
Octylphenol-Formaldehyd-Kondensationsprodukten mit von a-Olefin zum Vinylester im Mischpolymer zwischenOctylphenol-formaldehyde condensation products with from α-olefin to vinyl ester in the copolymer between
einem Molekulargewicht von 500 bis 1100 eignen sich 1 : 1 und 1 : 5 beträgt.a molecular weight of 500 to 1100 are 1: 1 and 1: 5 are suitable.
ganz besonders. Zu den carbonsauren Salzen gehören Xach der Mischpolymerisation wird ein beträchtlicher
die neutralen oder basischen polyvalenten Metallsalze 55 Anteil der Estergruppen in Hydroxylgruppen verwandelt,
λ'οη Carbonsäuren, ζ. B. aromatischen Carbonsäuren, wie Vorzugsweise werden mindestens 80°/0 und insbesondere
die stark basischen Erdalkalisalze (Magnesium, Calcium, mindestens 90°/0 der Estergruppen in Hydroxylgruppen
Barium) von alkylierten Benzoe-, Salicyl-, Resorcyl-, umgewandelt. Der Anteil an umgewandelten Ester-Anthranil-
und Xaphthoesäuren, insbesondere die basi- gruppen kann bis zu 99 oder sogar 100° 0 betragen,
sehen Calciumsalze von C3- bis C22-Alkylbenzoesäuren und 60 Das durchschnittliche Molekulargewicht des End-C12-bis
Cjg-Alkylsalicylsäuren. Andere basische poly- produktes beträgt vorzugsweise zwischen 4000 und 50000.
valente Metallsalze sind die cycloaliphatischen carbon- Die folgenden Beispiele sollen die Herstellung der polysauren
Salze, z. B. die basischen Calcium- und Barium- meren Alkohole näher erläutern, die jedoch im Rahmen
salze von Xaphthensäuren. der vorliegenden Erfindung nicht unter Schutz gestelltmost notably. The carboxylic acid salts include X After the copolymerization, a considerable proportion of the neutral or basic polyvalent metal salts is converted into hydroxyl groups, λ'οη carboxylic acids, ζ. B. aromatic carboxylic acids, such as, preferably at least 80 ° / 0 and in particular the strongly basic alkaline earth metal salts (magnesium, calcium, at least 90 ° / 0 of the hydroxyl groups in Estergruppen barium) converted from alkylated benzoic, salicylic, Resorcyl-. The proportion of converted ester-anthranilic and xaphthoic acids, in particular the basic groups, can be up to 99 or even 100 ° 0 ,
See calcium salts of C 3 to C 22 alkyl benzoic acids and 60 The average molecular weight of the end C 12 to C 18 alkyl salicylic acids. Other basic polyproducts are preferably between 4000 and 50,000. Valent metal salts are the cycloaliphatic carbon- The following examples are intended to illustrate the preparation of the polyacid salts, e.g. B. explain the basic calcium and barium alcohols in more detail, but the salts of xaphthenic acids. of the present invention is not protected
Die in den erfindungsgemäßen Zubereitungen verwen- 65 wird.Which is used in the preparations according to the invention.
deten Salze besitzen eine Basizität von 2 bis 1000°/0, Beispiel I
vorzugsweise von 50 bis 800°/0. Die neutralen polyvalenten
Metallsalze aromatischer Carbonsäuren werden 2,5 Mol Vinylacetat und 1 Mol einer Mischung von
nach üblichen \rerfahren hergestellt und sind im Handel C16- bis C18-a-Olefinen, vorwiegend C18-a-Olefinen, sowie
erhältlich. Die entsprechenden basischen Salze lassen 70 1 Gewichtsprozent Ditert.-butylperoxyd werden in einenDeten salts have a basicity of 2 to 1000 ° / 0 , Example I.
preferably from 50 to 800 ° / 0 . The neutral polyvalent metal salts of aromatic carboxylic acids are vinyl acetate and 2.5 moles of 1 mole of a mixture of r out by customary \ prepared and are commercially available C 16 - to C 18 a-olefins, predominantly C 18 -a-olefins, as well as available. The corresponding basic salts allow 70 1 percent by weight of di-tert-butyl peroxide to be in one
nichtrostenden Autoklav gegeben, in dem die Luft durch Stickstoff verdrängt wird. Der Autoklav wird auf 115° C erhitzt, bis die Umwandlung etwa 90%ig ist. Nicht umgesetzte Ausgangsverbindungen werden bei 185° C und 1 mm Hg abdestilliert.in a stainless autoclave in which the air is displaced by nitrogen. The autoclave is set to 115 ° C heated until the conversion is about 90%. Unreacted starting compounds are at 185 ° C and 1 mm Hg distilled off.
Das Polymer wird abschließend mit einer Lösung von Natriummethylat in Methanol vermischt, um 95°/0 der Acetatgruppen zu verseifen. Dies wird durch Zugabe von 10 Teilen Methanol, 35 Teilen Isopropanol und 1 Teil Natriummethylat je 50 Teile Polymer erreicht, wobei die Mischung 8 Stunden bei 70° C gerührt wird. Natriumacetat wird hierauf durch zweimaliges Waschen mitThe polymer is finally mixed with a solution of sodium methylate in methanol / 0 to saponify at 95 ° of the acetate groups. This is achieved by adding 10 parts of methanol, 35 parts of isopropanol and 1 part of sodium methylate per 50 parts of polymer, the mixture being stirred at 70 ° C. for 8 hours. Sodium acetate is then washed with twice
1 Teil einer 33%igen Isopropanol-Wasser-Mischung entfernt. Nach dem Absitzen wird die untere Schicht abgelassen und alle niedrigsiedenden Bestandteile bei einer Temperatur von 110° C bei 90 mm Hg abdestilliert. Das entstehende Mischpolymer ist eine klebrige gelbe feste Masse. Verhältnis der Acetat- und Alkoholgruppen zu olefinischen C14- bis C16-Alkylgruppen 5:1, Molekulargewicht 2700; Verhältnis von Hydroxyl- zu Acetatgruppen 19:1.1 part of a 33% isopropanol-water mixture removed. After settling, the lower layer is drained and all low-boiling constituents are distilled off at a temperature of 110 ° C. at 90 mm Hg. The resulting copolymer is a sticky yellow solid mass. Ratio of acetate and alcohol groups to olefinic C 14 to C 16 alkyl groups 5: 1, molecular weight 2700; Ratio of hydroxyl to acetate groups 19: 1.
Analog der im Beispiel I gegebenen Vorschrift werden die Beispiele II bis XXI (s. die folgende Tabelle) hergestellt. Examples II to XXI (see the following table) are prepared analogously to the procedure given in Example I.
temperaturReaction
temperature
Olefin
Molverhältnis
in der
ReaktionsVinyl ester--
Olefin
Molar ratio
in the
Reaction
a-Olefin
MolverhältnisVinyl ester--
α-olefin
Molar ratio
Umwandlung
von Ester
gruppen inpercent
conversion
from Ester
groups in
gewicht 2)Molecular
weight 2 )
Im Beispiel XIX ist der Vinylester Vinylbuttersäureester; in allen anderen Beispielen wird als Vinylester Vinylacetat verwendet. Bestimmt nach der Lichtstreuungsmethode.In Example XIX, the vinyl ester is vinyl butyric acid ester; in all other examples vinyl acetate is used as the vinyl ester. Determined by the light scattering method.
Die Komplexverbindungen dieser Mischpolymere mit polyvalenten Metallverbindungen lassen sich nach bekannten Verfahren herstellen, z. B. durch Umsetzung des Polymers mit einem Überschuß eines polyvalenten Metalloxydes, -hydroxydes oder -carbonates, vorzugsweise in Gegenwart von Kohlendioxyd bei Temperaturen von etwa 50 bis 250° C, oder nach den in den USA.-Patentschriften 2 736 701 und 2 751 359 bzw. britischen Patentschriften 599 729 und 744 942 beschriebenen Verfahren. Das folgende Beispiel erläutert die Herstellung derartiger Komplexverbindungen:The complex compounds of these copolymers with polyvalent metal compounds can be prepared according to known methods Manufacture processes, e.g. B. by reacting the polymer with an excess of a polyvalent Metal oxide, hydroxide or carbonate, preferably in the presence of carbon dioxide at temperatures from about 50 to 250 ° C, or as described in U.S. Patents 2,736,701 and 2,751,359 or British Methods described in U.S. Patents 599,729 and 744,942. The following example explains the production such complex compounds:
Beispiel XXIIExample XXII
200 Gewichtsteile des Mischpolymers des Beispiels I wurden in 1200 Gewichtsteilen Xylol gelöst, 120 Gewichtsteile Calciumhydroxyd in 220 Gewichtsteilen Methanol zugefügt und die Mischung bei einer Temperatur von etwa 55° C kräftig gerührt. Innerhalb einer Stunde wurden hierbei 32 Gewichtsteile Kohlendioxyd in die Mischung eingeleitet. Die Reaktionsmischung ließ man hierauf absitzen und trennte von den festen Bestandteilen ab. Das Produkt wies eine Basenzahl von 15 auf.200 parts by weight of the mixed polymer of Example I were dissolved in 1200 parts by weight of xylene, 120 parts by weight Calcium hydroxide in 220 parts by weight of methanol was added and the mixture at a temperature vigorously stirred from about 55 ° C. Within one hour, 32 parts by weight of carbon dioxide were here in the Mixture initiated. The reaction mixture was then allowed to settle and separated from the solid constituents away. The product had a base number of 15.
Auf folgende Weise ließ sich zeigen, daß die mit dem Mischpolymer komplex verbundene Menge an Calciumcarbonat erhöht werden kann. Das oben erhaltene Reaktionsprodukt wurde mit einer weiteren Menge von 100 Gewichtsteilen Calciumhydroxyd und 50 Gewichtsteilen Methanol vermischt, erneut unter Rühren auf etwa 55° C erhitzt und mit weiteren 36 Gewichtsteilen Kohlendioxyd über einen Zeitraum von einer Stunde behandelt. Das Rohprodukt wies eine Basenzahl von 50 auf. Das Produkt wurde abfiltriert und vom Lösungsmittel befreit. Man erhielt eine klare gelbe Masse mit einer Basenzahl von 274.It was shown in the following way that the amount of calcium carbonate complexed with the copolymer can be increased. The reaction product obtained above was with a further amount of 100 parts by weight of calcium hydroxide and 50 parts by weight of methanol mixed, again with stirring to about Heated to 55 ° C and treated with a further 36 parts by weight of carbon dioxide over a period of one hour. The crude product had a base number of 50. The product was filtered off and freed from the solvent. A clear yellow mass with a base number of 274 was obtained.
Zur zweiten Gruppe der öllöslichen wasserunlöslichen polymeren Alkohole gehören Polyätheralkohole der allgemeinen FormelThe second group of oil-soluble, water-insoluble polymeric alcohols includes polyether alcohols of the general type formula
R— -!!—(OR')»—OR"—OHR - - !! - (OR ') "- OR" -OH
worin η eine ganze Zahl von mindestens 2 bis 6, R eine Alkylgruppe mit 4 bis 20, vorzugsweise 4 bis 12 Kohlenstoffatomen ist und R' sowie R" gleiche oder verschiedene, jedoch vorzugsweise gleiche Alkylengruppen sind, insbesondere Äthylen- und Propylengruppen, wobei jedoch die Äthylengruppen vorgezogen werden. Diese Verbindungen können als C4-bis C20-Alkylphenoxy-(alkoxy)2_6-alkanole bezeichnet werden. Als Beispiele seien Octylphenoxy-(äthoxy)4-äthanol, Butylphenoxy-(äthoxy)2-äthanol, Diisobutylphenoxy-(äthoxy)4-äthanol, Dodecylphenoxy-where η is an integer of at least 2 to 6, R is an alkyl group with 4 to 20, preferably 4 to 12 carbon atoms and R 'and R "are the same or different, but preferably the same alkylene groups, in particular ethylene and propylene groups, but with the ethylene groups are preferred. These compounds may be referred to as C 4 to C 20 -Alkylphenoxy- (alkoxy) 2 _ 6 alkanols. as examples octylphenoxy (ethoxy) 4 were -ethanol, butylphenoxy (ethoxy) -ethanol 2, Diisobutylphenoxy - (ethoxy) 4 -ethanol, dodecylphenoxy-
(äthoxy)4-äthanol, Butylphenoxy- (propoxy)2-propanol und Butylphenoxy-(äthoxy)4-propanol genannt.(ethoxy) 4 ethanol, butylphenoxy (propoxy) 2 propanol and butylphenoxy (ethoxy) 4 propanol.
Der Befund, daß die hydroxylgruppenhaltigen Mischpolymere der Gruppe 1, die normalerweise als Reinigungsmittel wirken, und die Polyätheralkohole der Gruppe 2, die normalerweise als Korrosionsschutzmittel wirken, beide als Schlamminhibitoren bei Schmierölen wirken, die die Zusatzstoffe (a) und (b) enthalten, ist überraschend, da sie diese Eigenschaft in Kombination mit anderen Typen von Reinigungsmitteln, wie Sulfonaten und Phenolaten, nicht zeigen.The finding that the hydroxyl-containing copolymers of group 1, which normally act as cleaning agents, and the polyether alcohols of group 2, which normally act as corrosion inhibitors, both act as sludge inhibitors in lubricating oils, which contain the additives (a) and (b) is surprising since they combine this property with others Types of detergents, such as sulfonates and phenates, do not show.
Die in den erfindungsgemäßen Zubereitungen verwendeten Mineralschmieröle leiten sich von paraffinischen, naphthenischen, asphaltischen und oder deren Mischungen ab. Die Viskosität dieser Öle kann in einem weiten Bereich schwanken, z. B. von etwa 21 cSt (100 SUS) bei 37,8° C bis 21 cSt (100 SUS) bei 98,9° C. Die Kohlenwasserstofföle können mit anderen Ölen verschnitten werden, z. B. Castoröl, Specköl (lardoil) und ähnlichem oder mit künstlichen Schmierölen, wie polymerisierten Olefinen, Mischpolymeren und Alkylenglycolen und Alkylenoxyden, Silikonpolymeren, z. B. Dimethylsilikonpolymeren.The mineral lubricating oils used in the preparations according to the invention are derived from paraffinic, naphthenic, asphaltic and or their mixtures. The viscosity of these oils can be in a wide range fluctuate, e.g. B. from about 21 cSt (100 SUS) at 37.8 ° C to 21 cSt (100 SUS) at 98.9 ° C. The hydrocarbon oils can be blended with other oils, e.g. B. castor oil, bacon oil (lardoil) and the like or with artificial lubricating oils such as polymerized olefins, copolymers and alkylene glycols and alkylene oxides, Silicone polymers, e.g. B. dimethyl silicone polymers.
Besonders geeignete Mineralschmieröle zur Verwendung in den erfindungsgemäßen Zubereitungen lassen sich aus West - Texas - Ellenburger - Rohöl, Ost -Texas- Rohölen, Oklahoma- und kalifornischen Rohölen erhalten. Ein brauchbares lösungsmittelraffiniertes Ost-Texas-Mineralschmieröl wies folgende Eigenschaften aus:Particularly suitable mineral lubricating oils for use in the preparations according to the invention can be omitted West Texas Ellenburger Crude, East Texas Crude, Oklahoma, and California Crude. A useful East Texas solvent-refined mineral lubricating oil had the following properties:
Stockpunkt, 0C — 12,2Pour point, 0 C - 12.2
Viskosität, cSt bei 37,8° C 27Viscosity, cSt at 37.8 ° C 27
Viskositätsindex 95Viscosity index 95
Die drei Zusatzstoffe (a), (b) und (c) werden im allgemeinen in Mengen von 0,1 bis 10°/0, vorzugsweise in Mengen von je 0,5 bis 6 Gewichtsprozent, bezogen auf die gesamte Schmierölzubereitung, verwendet.The three additives (a), (b) and (c) are generally used in amounts of 0.1 to 10 ° / 0, preferably in amounts of 0.5 to 6 weight percent, based on the total lubricating oil composition is used.
Bevorzugte Schmierölmischungen nach der Erfindung zeichnen sich durch folgende Zusammensetzung aus:Preferred lubricating oil mixtures according to the invention are characterized by the following composition:
Schmieröl ALube Oil A
Zusatz des Beispiels II 5 GewichtsprozentAddition of Example II 5 percent by weight
Basisches Calciumsalz einer Petroleumsulfonsäure 1 0Q SulfatrestBasic calcium salt of a petroleum sulfonic acid 1 0 Q sulfate residue
Diisobutylphenoxy-(äthoxy)4-Diisobutylphenoxy- (ethoxy) 4 -
äthanol 0,2 Gewichtsprozent ethanol 0.2 percent by weight
Zinkdialkyldithiophosphat 0,9 Gewichtsprozent
Mineralschmieröl (lOW-30) RestZinc dialkyldithiophosphate 0.9 weight percent
Mineral lubricating oil (LOW-30) rest
Schmieröl BLubricating oil B
Znsatz des Beispiels II 5 GewichtsprozentAddition of Example II 5 percent by weight
Basisches Calciumsalz einer Petroleumsulfonsäure 1 °o SulfatrestBasic calcium salt of a petroleum sulfonic acid 1 ° o sulfate residue
Znsatz des Beispiels XXII 0,2 Gewichtsprozent Addition of Example XXII 0.2 percent by weight
Zinkdialkyldithiophosphat 0,9 Gewichtsprozent Zinc dialkyldithiophosphate 0.9 weight percent
Mineralschmieröl (10W-30) RestMineral lubricating oil (10W-30) rest
Schmieröl CLubricating oil C
Zusatz des Beispiels I 5 GewichtsprozentAddition of Example I 5 percent by weight
Basisches Calciumsalz einerBasic calcium salt of a
Petroleumsulfonsäure 1 ° 0 SulfatrestPetroleum sulfonic acid 1 ° 0 sulfate residue
Diisobutylphenoxy-(äthoxy)4 Diisobutylphenoxy (ethoxy) 4
äthanol 0,2 Gewichtsprozent ethanol 0.2 percent by weight
Zinkdialkyldithiophosphat 0,9 Gewichtsprozent
Mineralschmieröl (10 W-30) RestZinc dialkyldithiophosphate 0.9 weight percent
Mineral lubricating oil (10 W-30) rest
Schmieröl DLubricating oil D
Mischpolymer des Methacrylsäurelaurylesters—Methacrylsäure- Mixed polymer of methacrylic acid lauryl ester - methacrylic acid
ß-diäthylaminoäthylester (90:10) 5 Gewichtsprozent Basisches Calciumsalz einerß-diethylaminoethyl ester (90:10) 5 percent by weight Basic calcium salt of a
Petroleumsulfonsäure 1 ° 0 SulfatrestPetroleum sulfonic acid 1 ° 0 sulfate residue
Butylphenoxy-(propoxy)2-propanol 0,2 Gewichtsprozent Butylphenoxy (propoxy) 2 propanol 0.2 percent by weight
Zinkdialkyldithiophosphat 0,8 Gewichtsprozent
Mineralschmieröl (SAE 30) RestZinc dialkyldithiophosphate 0.8 weight percent
Mineral lubricating oil (SAE 30) rest
Andere Beispiele von erfindungsgemäßen Schmierölmischungen sind Mineralschmieröle des SAE-Typs 10, 20, 30 oder des 10 W-30-Typs mit etwa 1 bis 6 Gewichtsprozent folgender Mischpolymerer: Methacrylsäurelaurylester—Styrol—Methacrylsäuredibutylaminoäthylester, Methacrylsäurelaurylester—4-Dimethyl-aminocyclohexylmethacrylsäureamid, Methacrylsäurelaurylester—2-Methyl-5-vinylpyridin, Methacrylsäurelaurylester—3-Äthyl-5-vinylpyridin, Laurylmethacrylsäureamid—2-Methyl-5-vinylpyridin, etwa 0,5 bis 5 Gewichtsprozent öllösliches neutrales und oder basisches Calcium- oder Bariumsalz einer Petroleumsulfonsäure, Dialkylbenzolsulfonat, Cetylphenolat, Octylphenol-Formaldehyd-Kondensationsprodukt, C12- bis C22 - alkylsalicylsaure Salze sowie 0,01 bis 0,5 Gewichtsprozent Butylphenoxy-(äthoxy)4-äthanol, Butylphenoxy-(äthoxy)2-äthanol, Dodecylphenoxy-(äthoxy)4-äthanol, Butylphenoxy-(äthoxy)4-propanol.Other examples of lubricating oil mixtures according to the invention are mineral lubricating oils of the SAE type 10, 20, 30 or of the 10 W-30 type with about 1 to 6 percent by weight of the following copolymers: lauryl methacrylate — styrene — dibutylaminoethyl methacrylate, lauryl methacrylate, 4-dimethylaminocyclohexidyl methacrylate — 2-dimethyl-aminocyclohexidyl methacrylate -Methyl-5-vinylpyridine, lauryl methacrylate, 3-ethyl-5-vinylpyridine, lauryl methacrylic acid amide, 2-methyl-5-vinylpyridine, about 0.5 to 5 percent by weight, oil-soluble, neutral and or basic calcium or barium salt of a petroleum sulfonic acid, dialkylbenzenesulfonate, cetylbenzenesulfonate, Octylphenol-formaldehyde condensation product, C 12 - to C 22 - alkyl salicylic acid salts and 0.01 to 0.5 percent by weight of butylphenoxy (ethoxy) 4 -ethanol, butylphenoxy- (ethoxy) 2 -ethanol, dodecylphenoxy- (ethoxy) 4 -ethanol , Butylphenoxy (ethoxy) 4 propanol.
Die überragenden Eigenschaften der erfindungsgemäßen Schmierölgemische zeigten sich deutlich, wenn diese Massen in einem Chevroletmotor unter den Bedingungen des EX-3-Versuchs geprüft wurden. Der EX-3-Versuch ist im CRC Progress-Report, Nr. 3, Juni 1957, beschrieben.The outstanding properties of the lubricating oil mixtures according to the invention were clearly shown when these Masses in a Chevrolet engine were tested under the conditions of the EX-3 experiment. The EX-3 attempt is described in CRC Progress Report, No. 3, June 1957.
Die Ergebnisse sind in der Tabelle 1 angeführt.The results are shown in Table 1.
in der Reinheit
im EX-3-
Yersuch*)Improvements
in purity
in the EX-3-
Yersuch *)
A Lubricating oils:
A.
80
80
69
68
71
73
73
54
64 bis 65
5479
80
80
69
68
71
73
73
54
64 to 65
54
2 (2-Methyl-5-vinylpyridin)
3 (Cetvlalkohol)
4 (öllösliches Oxim)
5 (Caprolactam)
Mineralöl ohne Zusätze
6 (Schmieröl A — 5 Gewichtsprozent
Zusatz des Beispiels XI + 1 %
(Sulfatrest) basisches Calciumsalz
einer Petroleumsulfonsäure
+ 0,9 Gewichtsprozent Zinkdialkyl
dithiophosphat)
7 (Schmieröl -f 0,2 Gewichtsprozent
Diisobutylphenoxy - (äthoxy) 4-
äthanol -4- 0,9 Gewichtsprozent
Zinkdialkvldithiophosphat) 1 **) (monooleic acid ester of glycerine)
2 (2-methyl-5-vinylpyridine)
3 (cetyl alcohol)
4 (oil soluble oxime)
5 (caprolactam)
Mineral oil without additives
6 (lubricating oil A - 5 percent by weight
Addition of example XI + 1%
(Sulfate residue) basic calcium salt
a petroleum sulfonic acid
+ 0.9 percent by weight zinc dialkyl
dithiophosphate)
7 (lubricating oil -f 0.2 percent by weight
Diisobutylphenoxy - (ethoxy) 4 -
ethanol -4- 0.9 percent by weight
Zinc dialkvldithiophosphate)
*) 100 = sehr gut; reines Mineralöl (54).
**) Die Schmieröle 1 bis 5 sind die gleichen wie Schmieröl A, jedoch wird das Diisobutylphenoxy-(äthoxy)4-äthanol durch die
"5 angegebenen Zusätze ausgetauscht.*) 100 = very good; pure mineral oil (54).
**) Lubricating oils 1 to 5 are the same as lubricating oil A, but the diisobutylphenoxy (ethoxy) 4 -ethanol is replaced by the additives indicated in "5".
Neben den drei wesentlichen Zusatzstoffen (a), (b) undIn addition to the three essential additives (a), (b) and
(c) können die erfindungsgemäßen Schmierölgemische kleinere Anteile, z. B. 0,1 bis 3 Gewichtsprozent, anderer bekannter Zusätze, wie Metalldithiophosphate, z. B.(c) the lubricating oil mixtures according to the invention can contain smaller proportions, e.g. B. 0.1 to 3 percent by weight, others known additives such as metal dithiophosphates, e.g. B.
Zinkalkyldithiophosphate, Amine, ζ. B. Plienyl-cc-naphthylamin, Octadecylamin, Alkylphenole, Viskositätsindexverbesserer und Stockpunkterniedriger enthalten, z. B. die in der USA.-Patentschrift2 710842beschriebenen Mischpolymeren von N-Vinylpyrrolidon und Laurylmethacrylat, Kondensationsprodukte von chloriertem Paraffinwachs und Naphthalin sowie Hochdruckzusätze, wie organische Sulfide und Aminsalze von Trichlormethan-Phosphinsäuren. Zinc alkyldithiophosphates, amines, ζ. B. Plienyl-cc-naphthylamine, Contain octadecylamine, alkylphenols, viscosity index improvers and pour point depressants, z. Those described in U.S. Patent 2,710,842 Mixed polymers of N-vinylpyrrolidone and lauryl methacrylate, Condensation products of chlorinated paraffin wax and naphthalene as well as extreme pressure additives, such as organic sulfides and amine salts of trichloromethane phosphinic acids.
Die erfindungsgemäßen Schmierölgemische werden als Maschinenöle, Turbinenöle und Getriebeöle und in verschiedenen anderen Gebieten der Schmierung verwendet, bei denen Verhinderung der Schlammbildung und Abnützung als wesentliche Eigenschaften gefordert werden.The lubricating oil mixtures according to the invention are used as machine oils, turbine oils and gear oils and in various other areas of lubrication where sludge prevention and wear and tear are used are required as essential properties.
Claims (13)
Deutsche Patentschriften Xr. 947 186, 960 756, 896 560, 496, 909 021, 920 864;Considered publications:
German patents Xr. 947 186, 960 756, 896 560, 496, 909 021, 920 864;
französische Patentschriften Nr. 1 061 771, 1 101 147,German Auslegeschriften Nos. 1 003 896, 1 003 897, 026;
French patents nos. 1 061 771, 1 101 147,
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US853535XA | 1957-11-26 | 1957-11-26 |
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---|---|
DE1075254B true DE1075254B (en) | 1960-02-11 |
Family
ID=22191045
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DENDAT1075254D Pending DE1075254B (en) | 1957-11-26 | Mineral oil-based lubricating oil mixture |
Country Status (4)
Country | Link |
---|---|
DE (1) | DE1075254B (en) |
FR (1) | FR1217095A (en) |
GB (1) | GB853535A (en) |
NL (1) | NL104534C (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3431062A (en) * | 1964-10-26 | 1969-03-04 | Chevron Res | Antievaporant process and composition |
GB8714922D0 (en) * | 1987-06-25 | 1987-07-29 | Shell Int Research | Lubricating oil composition |
DE59708189D1 (en) * | 1997-01-07 | 2002-10-17 | Clariant Gmbh | Improving the flowability of mineral oils and mineral oil distillates using alkylphenol-aldehyde resins |
EP0965680A1 (en) * | 1998-06-18 | 1999-12-22 | Clariant International Ltd. | Aqueous dispersions, their preparation and use thereof |
US6605572B2 (en) | 2001-02-07 | 2003-08-12 | The Lubrizol Corporation | Lubricating oil composition |
US6583092B1 (en) * | 2001-09-12 | 2003-06-24 | The Lubrizol Corporation | Lubricating oil composition |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE896560C (en) * | 1946-08-31 | 1953-11-12 | Bataafsche Petroleum | Process for the production of lubricants or lubricant components |
DE903496C (en) * | 1941-09-20 | 1954-02-08 | Basf Ag | Lubricants that are exposed to high temperatures and / or must have high load capacities |
DE909021C (en) * | 1943-07-07 | 1954-04-12 | Basf Ag | lubricant |
FR1061771A (en) * | 1951-03-09 | 1954-04-15 | Du Pont | Improvements to lubricating compositions |
DE920864C (en) * | 1951-03-07 | 1954-12-02 | Basf Ag | lubricant |
FR1101147A (en) * | 1953-05-25 | 1955-09-28 | Bataafsche Petroleum | Oilseed compositions |
FR1111338A (en) * | 1953-05-18 | 1956-02-24 | Bataafsche Petroleum | Lubricating composition |
DE947186C (en) * | 1951-03-09 | 1956-08-09 | Du Pont | Additive to lubricating oils and heating oils |
FR1131152A (en) * | 1954-05-10 | 1957-02-18 | Bataafsche Petroleum | Oilseed compositions |
-
0
- NL NL104534D patent/NL104534C/xx active
- DE DENDAT1075254D patent/DE1075254B/en active Pending
-
1958
- 1958-11-24 GB GB37735/58A patent/GB853535A/en not_active Expired
- 1958-11-24 FR FR779897A patent/FR1217095A/en not_active Expired
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE903496C (en) * | 1941-09-20 | 1954-02-08 | Basf Ag | Lubricants that are exposed to high temperatures and / or must have high load capacities |
DE909021C (en) * | 1943-07-07 | 1954-04-12 | Basf Ag | lubricant |
DE896560C (en) * | 1946-08-31 | 1953-11-12 | Bataafsche Petroleum | Process for the production of lubricants or lubricant components |
DE920864C (en) * | 1951-03-07 | 1954-12-02 | Basf Ag | lubricant |
FR1061771A (en) * | 1951-03-09 | 1954-04-15 | Du Pont | Improvements to lubricating compositions |
DE947186C (en) * | 1951-03-09 | 1956-08-09 | Du Pont | Additive to lubricating oils and heating oils |
FR1111338A (en) * | 1953-05-18 | 1956-02-24 | Bataafsche Petroleum | Lubricating composition |
DE1003896B (en) * | 1953-05-18 | 1957-03-07 | Bataafsche Petroleum | Lubricating oil mixture |
FR1101147A (en) * | 1953-05-25 | 1955-09-28 | Bataafsche Petroleum | Oilseed compositions |
DE960756C (en) * | 1953-05-25 | 1957-03-28 | Bataafsche Petroleum | lubricant |
FR1131152A (en) * | 1954-05-10 | 1957-02-18 | Bataafsche Petroleum | Oilseed compositions |
DE1003897B (en) * | 1954-05-10 | 1957-03-07 | Bataafsche Petroleum | lubricant |
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FR1217095A (en) | 1960-05-02 |
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