EP0318848A2 - Schmieröl, enthaltend hydrierte Polydiolefinblockpolymere - Google Patents

Schmieröl, enthaltend hydrierte Polydiolefinblockpolymere Download PDF

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Publication number
EP0318848A2
EP0318848A2 EP88119638A EP88119638A EP0318848A2 EP 0318848 A2 EP0318848 A2 EP 0318848A2 EP 88119638 A EP88119638 A EP 88119638A EP 88119638 A EP88119638 A EP 88119638A EP 0318848 A2 EP0318848 A2 EP 0318848A2
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EP
European Patent Office
Prior art keywords
block
lubricating oil
hydrogenated
polybutadiene
block polymers
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.)
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Application number
EP88119638A
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English (en)
French (fr)
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EP0318848B1 (de
EP0318848A3 (en
Inventor
Hans Peter Dr. Rath
Hans-Michael Dr. Walter
Daniel Dr. Wagner
Helmut Dr. Mach
Klaus Dr. Bronstert
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BASF SE
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BASF SE
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Publication of EP0318848A3 publication Critical patent/EP0318848A3/de
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    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/12—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing conjugated diene
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    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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Definitions

  • the invention relates to the use of hydrogenated polydiolefin block polymers as viscosity index-improving additives for mineral lubricating oils.
  • the viscosity index (VI) of mineral oil-based lubricants is conventionally set by polymer additives. It is known that the viscosity index of mineral lubricating oils can be improved by adding ethylene / butene (1) copolymers.
  • DE-OS 23 58 764 describes hydrogenated polydiolefins as additives to mineral lubricating oils in which 30 to 95, preferably 40 to 65% of the double bonds have a 1,2-configuration before the hydrogenation.
  • these polymers are not yet satisfactory in terms of the viscosity index-improving effect and durability in the engine.
  • mineral lubricating oils which, as VI improvers, contain a hydrogenated block (co) polymer of the formal structure AB, the polymer block A - before the hydrogenation - a polybutadiene with a 1,2 content between 7 and 20%, the polymer block B - before the hydrogenation - a polybutadiene or a copolymer of butadiene and isoprene has a 1,2 content of more than 35%, or the polymer block B is a homopolymer of isoprene.
  • the polymers are advantageously prepared by anionic polymerization of the monomers in the presence of a catalyst system from organolithium compounds in inert solvents. It is known that in the polymerization of butadiene in the presence of Lewis bases, block copolymers are obtained if either Lewis bases are added in the course of the polymerization, or if the polymerization is carried out in several stages, the amount being added with each addition of monomers on Lewis bases is changed (US Pat. No. 3,140,278).
  • Suitable organolithium initiators are, for example, methyl lithium, ethyl lithium, n-, sec-butyllithium or isopropyllithium. N- or sec-butyllithium is preferably used.
  • straight-chain and branched aliphatic hydrocarbons such as n-octane or n-hexane, and simple or substituted cycloaliphatic and aromatic hydrocarbons such as cyclohexane, methylcyclohexane, toluene, and any mixture of aliphatic, cycloaliphatic and aromatic hydrocarbons are used as solvents for the polymerization .
  • Cyclohexane is preferred as the solvent.
  • Suitable Lewis bases are ethers, such as diethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, or tertiary amines, such as tetramethylethylene diamine, pyridine, N-methylmorpholine or 1,2-dipiperidinoethane.
  • All feed materials must be freed from oxygen and proton-active impurities; this can e.g. by contact with metal organyls or by adsorptive cleaning e.g. on alumina.
  • the polymerization is carried out under inert gas conditions at temperatures from -20 to 140 ° C, preferably at 25 to 80 ° C at pressures at which the monomers and solvents do not evaporate at the polymerization temperature.
  • a sufficient amount of water, methanol or isopropanol is added to the polymerization mixture in order to deactivate the active end groups or excess initiator.
  • the active end groups of the polymers can also be functionalized by reaction with suitable reagents such as ethylene oxide, ethylene sulfide or Schiff bases.
  • the block polymers are generally prepared in such a way that in a first stage a partial amount of the diene hydrocarbon to form the A block is completely polymerized in the inert solvent, in the second polymerization step the second partial amount of diene hydrocarbon to form the B block is completely reacted . In both polymerization stages, just as much Lewis base is added to the reaction mixture as is required for the desired 1,2-incorporation of the diene, taking into account the polymerization temperature.
  • the polymers are then hydrogenated. This can be done either in a homogeneous phase using catalysts based on salts, especially carboxylates, alkoxides or enolates of cobalt, nickel or iron, which are combined with metal alkyls, especially aluminum alkyls, at temperatures from 40 to 130 ° C and hydrogen pressures from 1 to 100 bar respectively.
  • catalysts based on salts especially carboxylates, alkoxides or enolates of cobalt, nickel or iron, which are combined with metal alkyls, especially aluminum alkyls, at temperatures from 40 to 130 ° C and hydrogen pressures from 1 to 100 bar respectively.
  • the hydrogenation can also be carried out in a heterogeneous phase over suspended or fixedly arranged lumpy catalysts.
  • nickel or platinum metals are used as catalysts at hydrogen pressures of 20 to 300 bar and temperatures between 40 and 300 ° C (e.g. according to DE-AS 1 106 961 or DE-OS 1 595 345).
  • the polymerization mixture can be heated directly to dryness or treated with steam by known methods, the solvent being distilled off. It can also be precipitated with an excess of a precipitant such as ethanol, mechanically separated and dried or worked up by extruder degassing.
  • a precipitant such as ethanol
  • the number average molecular weight of the hydrogenated block polymer to be used according to the invention can be within a wide range, but the average molecular weight should advantageously be between 30,000 and 150,000.
  • the weight ratio of blocks A and B to one another can also vary very greatly, but a ratio between 0.25 and 4 is preferred.
  • the hydrogenated block polymers are dissolved in amounts of 0.5 to 6, preferably 1 to 5% by weight in the mineral oil at 80 to 130 ° C.
  • Suitable mineral lubricants are conventional hydrocarbons used for lubricating oils, which are obtained from naturally occurring, paraffinic or naphthenic petroleum by distillation and subsequent refining.
  • the mineral lubricating oil compositions can also contain other known additives, for example antioxidants, agents for lowering the pour point, dyes, detergents, etc.
  • the diene microstructure of the polymers is determined by Fourier analysis of the infrared spectra.
  • the AB block polymer has the following structure: Molecular weight A block: 44,000 g / mol Molecular weight AB block: 65,000 g / mol Microstructure A block: 8.2% (1,2-vinyl) Microstructure B block: 38% (1,2-vinyl)
  • the block polymer obtained is hydrogenated by adding a catalyst solution of 1.4 g of nickel (II) acetylacetonate in 80 g of toluene, mixed with 30 ml of a 20% by weight solution of aluminum triisobutyl in hexane at a hydrogen pressure of 15 bar and 80 ° C. Hydrogenation temperature.
  • the hydrogenated block polymer is precipitated by adding ethanol, isolated and dried at 60 ° C. in vacuo.
  • the polymers according to Examples 1 and 2 are dissolved in a mineral oil at 115 ° C.
  • the base oil has a viscosity of 41.00 mm2 / s at 37.8 ° C and a viscosity of 6.25 mm2 / s at 98.9 ° C.
  • Some lubricant-related data are listed in Table 1.
  • Table 1 Polymer conc. in the solution (% by weight) Viscosity at 98.9 ° C (mm2 / s) Viscosity at 37.8 ° C (mm2 / s) VI (according to DIN 51 564) example 1 1.5 15.74 83.95 201
  • Example 2 1 11.34 58.92 190
  • the polybutadiene obtained in this way has the following structure: Molecular weight: 38,000 g / mol Microstructure: 52% (1,2-vinyl)
  • Example 2 The hydrogenation and workup is carried out analogously to Example 1. It still contains about 0.8% olefinic double bonds.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Lubricants (AREA)

Abstract

Verwendung von hydrierten Polydienblockpolymeren, die vor der Hydrierung eine AB-Blockstruktur aufweisen, wobei der A-Block ein Polybutadien mit einem Gehalt von höchstens 20 % 1,2-Struktureinheiten ist, der B-Block ein Polybutadien oder ein Copolymer aus Butadien und Isopren mit einem Gehalt von 1,2-Struktureinheiten von mehr als 35 % oder ein Polyisopren ist, das Gewichtsverhältnis von Block A zu Block B 0,25 bis 4 und das mittlere Molgewicht 30.000 bis 150.000 beträgt als Viskositätsindex verbesserndes Additiv für Schmieröle.

Description

  • Die Erfindung betrifft die Verwendung von hydrierten Polydiolefin­blockpolymeren als Viskositätsindex verbessernde Additive für Mineralschmieröle.
  • Der Viskositätsindex (VI) von Schmierstoffen auf Mineralölbasis wird herkömmlich durch polymere Zusatzstoffe eingestellt. Es ist bekannt, daß der Viskositätsindex von Mineralschmierölen durch Zusatz von Ethylen/Buten-(1)-Copolymerisaten verbessert werden kann. So werden in DE-OS 23 58 764 hydrierte Polydiolefine als Zusätze zu Mineralschmierölen beschrieben, bei denen vor der Hydrierung 30 bis 95, vorzugsweise 40 bis 65 % der Doppelbindungen 1,2-Konfiguration aufweisen. Diese Polymere befriedigen jedoch im Hinblick auf die Viskositätsindex verbessernde Wirkung und Beständigkeit im Motor noch nicht.
  • Es war daher Aufgabe der Erfindung, Schmieröladditive zur Verfügung zu stellen, die eine zum Stand der Technik deutlich erhöhte VI-verbessernde Wirkung entfalten und darüber hinaus eine hervorragende Beständigkeit gegenüber Scherwirkung, Oxidation und thermischer Beanspruchung aufweisen.
  • Diese Aufgabe wird erfindungsgemäß durch Mineralschmieröle gelöst, die als VI-Verbesserer ein hydriertes Block(co)polymeres der formalen Struktur AB enthalten, wobei der Polymerblock A - vor der Hydrierung - ein Polybutadien mit einem 1,2-Gehalt zwischen 7 und 20 %, der Polymerblock B - vor der Hydrierung - ein Polybutadien- oder ein Copolymeres aus Butadien und Isopren einen 1,2-Gehalt von mehr als 35 %, oder der Polymerblock B ein Homopolymerisat des Isoprens darstellt.
  • Verfahren zur Herstellung hydrierter Blockcopolymerer ausgehend von 1,3-Butadien, die vor der Hydrierung einen Block mit überwiegend 1,4 und einen zweiten Block mit erhöhter 1,2-Mikrostruktur aufweisen, sind bekannt und werden z.B. in EP-A1 0 024 314 beschrieben.
  • Die Polymerisate werden zweckmäßig durch anionische Polymerisation der Monomeren in Gegenwart eines Katalysatorsystems aus lithiumorganischen Verbindungen in inerten Lösungsmitteln hergestellt. Es ist bekannt, daß bei der Polymerisation von Butadien in Gegenwart von Lewis-Basen Block­copolymere erhalten werden, wenn entweder im Verlauf der Polymerisation Lewis-Basen zugesetzt werden, oder aber die Polymerisation in mehreren Stufen erfolgt, wobei bei jeder Zugabe von Monomeren auch die Menge an Lewis-Basen verändert wird (US-PS 3 140 278).
  • Als lithiumorganische Initiatoren kommen beispielsweise Methyllithium, Ethyllithium, n-, sek-Butyllithium oder Isopropyllithium in Betracht. Bevorzugt wird n- oder sek-Butyllithium eingesetzt.
  • Als Lösungsmittel für die Polymerisation werden in der Regel geradkettige und verzweigte aliphatische Kohlenwasserstoffe wie n-Oktan oder n-Hexan, sowie einfache oder substituierte cycloaliphatische und aromatische Kohlenwasserstoffe wie Cyclohexan, Methylcyclohexan, Toluol, sowie jede beliebige Mischung der aliphatischen, cycloaliphatischen und aromatischen Kohlenwasserstoffe verwendet.
  • Cyclohexan ist als Lösungsmittel bevorzugt.
  • Als Lewis-Basen kommen Ether, wie Diethylether, Tetrahydrofuran, Diethylenglykoldimethylether, oder tertiäre Amine, wie Tetramethylethylen­diamin, Pyridin, N-Methylmorpholin oder 1,2-Dipiperidinoethan in Betracht.
  • Alle Einsatzstoffe müssen von Sauerstoff und protonenaktiven Verunreini­gungen befreit werden; dies kann z.B. durch Kontaktieren mit Metall­organylen oder durch adsorptive Reinigung z.B. an Aluminiumoxid erfolgen. Die Durchführung der Polymerisation erfolgt unter Inertgasbedingungen bei Temperaturen von -20 bis 140°C, vorzugsweise bei 25 bis 80°C bei Drücken, bei denen die Monomeren und Lösungsmittel bei der Polymerisations­temperatur nicht verdampfen. Nach beendeter Polymerisation wird das Polymerisationsgemisch mit einer ausreichenden Menge Wasser, Methanol oder Isopropanol versetzt, um die aktiven Endgruppen bzw. überschüssigen Initiator zu desaktivieren.
  • Gegebenenfalls können die aktiven Endgruppen der Polymeren auch funktionalisiert werden durch Umsetzung mit geeigneten Reagentien wie Ethylenoxid, Ethylensulfid oder Schiff'schen Basen.
  • Die Darstellung der Blockpolymerisate erfolgt im allgemeinen in der Weise, daß in einer ersten Stufe eine Teilmenge des Dienkohlenwasserstoffs zur Bildung des A-Blocks in dem inerten Lösungsmittel vollständig auspoly­merisiert wird, im zweiten Polymerisationsschritt die zweite Teilmenge Dienkohlenwasserstoffs zur Bildung des B-Blocks vollständig umgesetzt wird. In beiden Polymerisationsstufen werden dem Reaktionsgemisch gerade soviel an Lewis-Basen zugesetzt, wie - unter Berücksichtigung der Polymerisationstemperatur - für den gewünschten 1,2-Einbau des Diens erforderlich ist.
  • Anschließend werden die Polymerisate hydriert. Dies kann entweder in homogener Phase mit Katalysatoren auf Basis von Salzen, insbesondere von Carboxylaten, Alkoxiden oder Enolaten des Kobalts, Nickels oder Eisens, die mit Metallalkylen, insbesondere Aluminiumalkylen kombiniert sind bei Temperaturen von 40 bis 130°C und Wasserstoffdrücken von 1 bis 100 bar erfolgen. Derartige Verfahren werden u.a. in den Druckschriften US-PS 3 113 986 oder der DE-AS 1 222 260, auf die hiermit Bezug genommen wird, beschrieben.
  • Die Hydrierung kann auch in heterogener Phase an suspendierten oder fest angeordneten stückigen Katalysatoren durchgeführt werden. Man verwendet dazu Nickel- oder Platinmetalle als Katalysatoren bei Wasserstoffdrücken von 20 bis 300 bar und Temperaturen zwischen 40 und 300°C, (z.B. nach den Angaben der DE-AS 1 106 961 oder DE-OS 1 595 345).
  • Zur Isolierung der hydrierten Polymeren kann das Polymerisationsgemisch nach bekannten Verfahren wahlweise direkt zur Trockene erhitzt oder mit Wasserdampf behandelt werden, wobei das Lösungsmittel abdestilliert wird. Es kann gleichfalls mit einem Überschuß eines Fällungsmittels wie Ethanol gefällt, mechanisch abgetrennt und getrocknet oder durch Extruderentgasung aufgearbeitet werden.
  • Das Zahlenmittel des Molekulargewichts des erfindungsgemäß zu verwendenden hydrierten Blockpolymerisats kann innerhalb eines breiten Bereiches liegen, jedoch soll das durchschnittliche Molekulargewicht vorteilhaft zwischen 30 000 und 150 000 betragen.
  • Das Gewichtsverhältnis der Blöcke A und B zueinander kann gleichfalls sehr stark varriert werden, bevorzugt wird jedoch ein Verhältnis, das zwischen 0,25 und 4 liegt.
  • Die hydrierten Blockpolymerisate werden in Mengen von 0,5 bis 6, vorzugs­weise 1 bis 5 Gew.% im Mineralöl bei 80 bis 130°C gelöst.
  • Als Mineralschmierstoffe kommen übliche für Schmieröle verwendete Kohlen­wasserstoffe in Betracht, die aus natürlich vorkommenden, paraffinischen oder naphthenischem Erdöl durch Destillation und anschließende Raffination gewonnen werden.
  • Außer den erfindungsgemäß zu verwendenden Zusätzen können die Mineral­schmierölzusammensetzungen noch andere bekannte Additive, z.B. Antioxidantien, Mittel zur Senkung des Stockpunktes, Farbstoffe, Detergentien usw. enthalten.
  • Die Polymerisate werden zur Einstellung der geforderten Parameter mit folgenden Methoden charakterisiert:
  • Das mittlere Molekulargewicht (Zahlenmittel M w) wird durch Gelpermeationschromatographie anhand von Eichkurven für Polybutadien (Eichsubstanzen M w/M n = ca. 1) bei 23°C in 0,125 gew.%iger Tetrahydrofuranlösung bei einer Durchflußgeschwindigkeit von 1,5 ml/min ermittelt.
  • Die Dienmikrostruktur der Polymerisate wird durch Fourier-Analyse der Infrarot-Spektren bestimmt.
    • Beispiel 1
  • In einem thermostatisierbaren Rührkessel werden unter Reinstickstoff 5400 g gereinigtes, wasserfreies Cyclohexan und 420 g gereinigtes 1,3-Butadien vorgelegt und die Mischung auf 56°C aufgeheizt. Die im Reaktionsgemisch noch vorhandenen Verunreinigungen werden durch Zugabe geringer Mengen einer 0,8 %igen Lösung von sek.-Butyllithium in Cyclohexan entfernt, bis die Temperatur anzusteigen beginnt. Anschließend werden 9,5 mmol sek.-Butyllithium (0,8 %ige Lösung in Cyclohexan) als Initiator zugesetzt und die Temperatur der Polymerisation wird etwa 1 Stunde zwischen 60 und 70°C zur Bildung des ersten Blocks aus Polybutadienyl­lithium eingestellt. Sodann werden dem Reaktionsgefäß 300 mmol Tetrahydro­furan, das zur Reinigung frisch über Natrium/Benzophenon abdestilliert wurde, und weitere 180 g 1,3-Butadien zugeführt. Die Bildung des zweiten Blocks ist bei isothermer Reaktionsführung bei 70°C nach 2 h vollständig abgeschlossen. Danach werden 5 ml Isopropanol zugesetzt, um den Abbruch der lebenden Kettenenden sicherzustellen. Nach jeder Polymerisationsstufe werden dem Reaktionsgefäß Probemengen für analytische Zwecke entnommen.
  • Das AB-Blockpolymere weist folgende Struktur auf:
    Molekulargewicht A-Block : 44 000 g/mol
    Molekulargewicht AB-Block : 65 000 g/mol
    Mikrostruktur A-Block : 8,2 % (1,2-Vinyl)
    Mikrostruktur B-Block : 38 % (1,2-Vinyl)
  • Die Hydrierung des erhaltenen Blockpolymeren erfolgt durch Zugabe einer Katalysatorlösung aus 1,4 g Nickel(II)acetylacetonat in 80 g Toluol, versetzt mit 30 ml einer 20 gew.%igen Lösung von Aluminiumtriisobutyl in Hexan bei einem Wasserstoffdruck von 15 bar und 80°C Hydriertemperatur.
  • Nach 8 Stunden wird ein Restdoppelbindungsgehalt von weniger als 3 % der ursprünglich vorhandenen Doppelbindungen erreicht.
  • Das hydrierte Blockpolymerisat wird durch Zusatz von Ethanol gefällt, isoliert und bei 60°C im Vakuum getrocknet.
    • Beispiel 2
  • Man verfährt wie in Beispiel 1 beschrieben, verwendet jedoch zur Herstellung des AB-Blockpolymeres die folgende Rezeptur:
    5 000 g Cyclohexan
    480 g 1,3-Butadien 1. Polymerisationsstufe
    10 mmol sek.-Butyllithium
    500 mmol Tetrahydrofuran
    120 g 1,3-Butadien 2. Polymerisationsstufe
    • Charakterisierung:
  • Molekulargewicht A-Block : 42 000 g/mol
    Molekulargewicht AB-Block : 54 000 g/mol
    Mikrostruktur
    A-Block : 9,3 % (1,2-Vinyl)
    B-Block : 48,8 % (1,2-Vinyl)
  • Hydrierung und Aufarbeitung erfolgen gemäß den Angaben des Beispiels 1.
  • Die Polymerisate gemäß Beispiel 1 und 2 werden in einem Mineralöl bei 115°C gelöst. Das Grundöl weist bei 37,8°C eine Viskosität von 41,00 mm²/s, bei 98,9°C eine Viskosität von 6,25 mm²/s auf. In Tabelle 1 sind einige schmierstofftechnische Daten aufgeführt. Tabelle 1
    Polymerkonz. in der Lösung (Gew.%) Viskosität bei 98,9°C (mm²/s) Viskosität bei 37,8°C (mm²/s) VI (nach DIN 51 564)
    Beispiel 1 1,5 15,74 83,95 201
    Beispiel 2 1 11,34 58,92 190
    • Scherverlust (Schertest nach DIN 51 382)
  • Beispiel 1 3,0 %
    Beispiel 2 0,5 %
    • Vergleichsversuch
  • In 5200 g Cyclohexan und 800 mmol Tetrahydrofuran werden 1000 g gereinigtes 1,3-Butadien vorgelegt und auf 60°C aufgeheizt. Als Initiator werden 30 mmol sek.-Butyllithium (0,8 %ige Lösung in Cyclohexan) zugesetzt, und man läßt bei 60 bis 70°C 3 Stunden polymerisieren.
  • Das so erhaltene Polybutadien weist folgende Struktur auf:
    Molekulargewicht: 38 000 g/mol
    Mikrostruktur: 52 % (1,2-vinyl)
  • Die Hydrierung und Aufarbeitung erfolgt analog Beispiel 1. Es enthält noch ca. 0,8 % olefinische Doppelbindungen.
  • Eine 4 gew.%ige Lösung des Polymerisats im gleichen Mineralöl ergibt einen Viskositätsindex von 140 (DIN 51 564). Im Schertest nach DIN 511 382 ergibt sich ein Scherverlust von 4,3 %.

Claims (6)

1. Schmierölzusammensetzung, bestehend aus einem Kohlenwasserstoffgrundöl und Schmieröladditiven, dadurch gekennzeichnet, daß sie als Viskosi­tätsindex verbesserndes Additiv geringe Mengen eines hydrierten Poly­dienblockpolymeren enthält, das vor der Hydrierung eine AB-Block­struktur aufweist, wobei der A-Block ein Polybutadien mit einem Gehalt von höchstens 20 % 1,2-Struktureinheiten ist, der B-Block ein Poly­butadien oder ein Copolymer aus Butadien und Isopren mit einem Gehalt von 1,2-Struktureinheiten von mehr als 35 % oder ein Polyisopren ist, das Gewichtsverhältnis von Block A zu Block B 0,25 bis 4 und wobei das mittlere Molgewicht 30.000 bis 150.000 beträgt.
2. Schmierölzusammensetzung gemäß Anspruch 1, dadurch gekennzeichnet, daß der Gehalt der hydrierten Polydienblockpolymeren 0,5 bis 6 Gew.%, be­zogen auf die Schmierölzusammensetzung beträgt.
3. Schmierölzusammensetzung gemäß Ansprüchen 1 und 2, dadurch gekenn­zeichnet, daß die hydrierten Blockpolymere noch höchstens 5 % der ur­sprünglich vorhandenen Doppelbindungen enthalten.
4. Verwendung von hydrierten Polydienblockpolymeren, die vor der Hydrierung eine AB-Blockstruktur aufweisen, wobei der A-Block ein Polybutadien mit einem Gehalt von höchstens 20 % 1,2-Struktureinheiten ist, der B-Block ein Polybutadien oder ein Copolymer aus Butadien und Isopren mit einem Gehalt von 1,2-Struktureinheiten von mehr als 35 % oder ein Polyisopren ist, das Gewichtsverhältnis von Block A zu Block B 0,25 bis 4 und wobei das mittlere Molgewicht 30.000 bis 150.000 beträgt als Viskositätsindex verbesserndes Additiv für Schmieröle.
5. Verwendung von hydrierten Polydienblockpolymeren gemäß Anspruch 4 in Mengen von 0,5 bis 6 Gew.%, bezogen auf das fertige Schmieröl.
6. Verwendung von hydrierten Polydienblockpolymeren gemäß Ansprüchen 4 und 5, dadurch gekennzeichnet, daß die hydrierten Polydienblock­polymeren noch höchstens 5 % der ursprünglichen Doppelbindungen enthalten.
EP88119638A 1987-12-04 1988-11-25 Schmieröl, enthaltend hydrierte Polydiolefinblockpolymere Expired - Lifetime EP0318848B1 (de)

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DE19873741097 DE3741097A1 (de) 1987-12-04 1987-12-04 Schmieroel, enthaltend hydrierte polydiolefinblockpolymere

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992016567A1 (en) * 1991-03-13 1992-10-01 Exxon Chemical Patents Inc. Improved viscosity modifier polymers
WO1992016568A1 (en) * 1991-03-15 1992-10-01 Exxon Chemical Patents Inc. Improved viscosity modifier polybutadiene polymers
WO1996028523A1 (en) * 1995-03-14 1996-09-19 Exxon Chemical Patents Inc. Fuel oil additives and compositions
EP0837921A1 (de) * 1995-06-07 1998-04-29 Mobil Oil Corporation Dispergiermittel sowie mittel zur verbesserung des viskositätindexes aus selektiv hydrierten polymeren.

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3378877B1 (de) 2017-02-28 2019-06-19 Evonik Oil Additives GmbH Als schmiermitteladditive nützliche hydrierte polybutadiene

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US3312621A (en) * 1964-09-28 1967-04-04 Exxon Research Engineering Co Lubricants having a high viscosity index
DE2358764A1 (de) * 1973-11-26 1975-06-05 Basf Ag Mineralschmieroeladditive
FR2346439A1 (fr) * 1976-04-02 1977-10-28 Exxon Research Engineering Co Copolymeres sequences en degrade hydrogenes de dienes conjugues et d'un compose vinyl aromatique convenant comme additifs pour huiles lubrifiantes
EP0024314A1 (de) * 1979-08-20 1981-03-04 The Firestone Tire & Rubber Company Hydrierte Blockcopolymere von Butadien, die einen Block mit 1,4-Mikrostruktur und einen Block mit 1,2-Mikrostruktur enthalten

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Publication number Priority date Publication date Assignee Title
US3312621A (en) * 1964-09-28 1967-04-04 Exxon Research Engineering Co Lubricants having a high viscosity index
DE2358764A1 (de) * 1973-11-26 1975-06-05 Basf Ag Mineralschmieroeladditive
FR2346439A1 (fr) * 1976-04-02 1977-10-28 Exxon Research Engineering Co Copolymeres sequences en degrade hydrogenes de dienes conjugues et d'un compose vinyl aromatique convenant comme additifs pour huiles lubrifiantes
EP0024314A1 (de) * 1979-08-20 1981-03-04 The Firestone Tire & Rubber Company Hydrierte Blockcopolymere von Butadien, die einen Block mit 1,4-Mikrostruktur und einen Block mit 1,2-Mikrostruktur enthalten

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5310490A (en) * 1991-03-13 1994-05-10 Exxon Chemical Products Inc. Viscosity modifer polymers
US5543469A (en) * 1991-03-13 1996-08-06 Exxon Chemical Patents Inc. Viscosity modifier polymers
WO1992016567A1 (en) * 1991-03-13 1992-10-01 Exxon Chemical Patents Inc. Improved viscosity modifier polymers
CN1048506C (zh) * 1991-03-13 2000-01-19 埃克森化学专利公司 制备改进的粘度调节剂聚合物的方法
US5945485A (en) * 1991-03-15 1999-08-31 Exxon Chemical Patents Inc Viscosity modifier polybutadiene polymers
WO1992016568A1 (en) * 1991-03-15 1992-10-01 Exxon Chemical Patents Inc. Improved viscosity modifier polybutadiene polymers
US5310814A (en) * 1991-03-15 1994-05-10 Exxon Chemical Patents Inc. Viscosity modifier polybutadiene polymers
AU657319B2 (en) * 1991-03-15 1995-03-09 Exxon Chemical Patents Inc. Improved viscosity modifier polybutadiene polymers
US5703171A (en) * 1991-03-15 1997-12-30 Exxon Chemical Patents Inc Viscosity modifier polybutadiene polymers
CN1050142C (zh) * 1991-03-15 2000-03-08 埃克森化学专利公司 制备改进的粘度调节剂聚丁二烯聚合物的方法
WO1996028523A1 (en) * 1995-03-14 1996-09-19 Exxon Chemical Patents Inc. Fuel oil additives and compositions
EP0837921A4 (de) * 1995-06-07 1998-10-07 Mobil Oil Corp Dispergiermittel sowie mittel zur verbesserung des viskositätindexes aus selektiv hydrierten polymeren.
EP0837921A1 (de) * 1995-06-07 1998-04-29 Mobil Oil Corporation Dispergiermittel sowie mittel zur verbesserung des viskositätindexes aus selektiv hydrierten polymeren.

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EP0318848B1 (de) 1991-05-08
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EP0318848A3 (en) 1989-08-16

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