EP0082574B1 - Produkt verwendbar als Dispergiermittel und Viskositätsindexverbesserer - Google Patents

Produkt verwendbar als Dispergiermittel und Viskositätsindexverbesserer Download PDF

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Publication number
EP0082574B1
EP0082574B1 EP82201623A EP82201623A EP0082574B1 EP 0082574 B1 EP0082574 B1 EP 0082574B1 EP 82201623 A EP82201623 A EP 82201623A EP 82201623 A EP82201623 A EP 82201623A EP 0082574 B1 EP0082574 B1 EP 0082574B1
Authority
EP
European Patent Office
Prior art keywords
polymer
product
nitrogen
nucleus
hydrogenated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82201623A
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English (en)
French (fr)
Other versions
EP0082574A2 (de
EP0082574A3 (en
Inventor
Michael Kent Martin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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Filing date
Publication date
Priority claimed from US06/332,690 external-priority patent/US4427834A/en
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP0082574A2 publication Critical patent/EP0082574A2/de
Publication of EP0082574A3 publication Critical patent/EP0082574A3/en
Application granted granted Critical
Publication of EP0082574B1 publication Critical patent/EP0082574B1/de
Expired legal-status Critical Current

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Classifications

    • 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
    • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
    • C10M151/02—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/10—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aromatic monomer, e.g. styrene
    • 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
    • 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
    • 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
    • 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
    • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • 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
    • 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
    • C10M149/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • 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
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/02—Macromolecular compounds obtained by reactions of monomers involving only carbon-to-carbon unsaturated bonds

Definitions

  • the star-shaped polymers prepared in reaction step (b) are characterized by having a dense centre or nucleus of cross-linked poly(polyalkenyl coupling agent) and a number of arms of substantially linear unsaturated polymers extending outwardly therefrom.
  • the number of arms may vary considerably but is typically between 3 and 25, preferably from about 7 to about 15.
  • Star-shaped homopolymers may be represented by the formula A-X-4-A),
  • star-shaped copolymers may be represented by the formula A ⁇ B ⁇ x-(B ⁇ A) n wherein n is an integer, usually between 2 and 24 and x is the poly(polyalkenyl coupling agent)nucleus.
  • step (c) the star-shaped polymer is contacted with a nitrogen-containing polar compound monomer, resulting in the attachment of at least one polymer arm directly to the poly(polyvinyl aromatic)nucleus.
  • the nitrogen containing polar compound is preferably selected from the group consisting of 2-vinylpyridine and 4-vinylpyridine, with 2-vinylpyridine being most preferred.
  • the molecular weights of the star-shaped polymer to be hydrogenated may vary between relatively wide limits. However, an important aspect of the present invention is that polymers possessing good shear stability may. be produced even though the polymers have very high molecular weights. It is possible to produce star polymers having peak molecular weights between about 25,000 and about 1,250,000. Preferred molecular weights are 100,000 to 500,000. These peak molecular weights are determined by gel permeation chromotography (GPC) on a polystyrene scale.
  • GPC gel permeation chromotography
  • the star-shaped polymers are hydrogenated by any suitable technique.
  • at least 80%, preferably 90 to about 98% of the original olefinic unsaturation is hydrogenated.
  • the star-shaped polymer is partly derived from a monoalkenyl arene compound, then the amount of aromatic unsaturation which is hydrogenated, if any, will depend on the hydrogenation conditions used. However, preferably less than 20%, more preferably less than 5% of such aromatic unsaturation is hydrogenated.
  • the poly(polyalkenyl coupling agent)nucleus is a poly(polyalkenyl aromatic coupling agent)nucleus, then the aromatic unsaturation of the nucleus may or may not be hydrogenated again depending upon the hydrogenation conditions used.
  • the molecular weights of the hydrogenated star-shaped polymers correspond to those of the unhydrogenated star-shaped polymers.
  • a much preferred hydrogenation process is the selective hydrogenation process shown in U.S. Patent No. 3,595,942.
  • hydrogenation is conducted, preferably in the same solvent in which the polymer was prepared, utilizing a catalyst comprising the reaction product of an aluminium alkyl and a nickel or cobalt carboxylate or alkoxide.
  • a favoured catalyst is the reaction product formed from triethyl aluminium and nickel octoate.
  • compositions or concentrates other conventional additives may also be present, including dyes, pour point depressants, antiwear, e.g., tricresyl phosphate, zinc dialkyl dithiophosphates of 3 to 8 carbon atoms, antioxidants such as phenyl-alpha-naphthyl-amine, tert-octylphenol sulphide, bisphenols such as 4,4'-methylene bis(3,6-di-tert-butylphenol), viscosity index improvers such as the ethylene-higher olefin copolymer, polymethylacrylates, polyisobutylene, alkyl fumaratevinyl acetate copolymers, and the like as well as other ashless dispersants or detergents such as overbased sulphonates.
  • dyes e.g., tricresyl phosphate, zinc dialkyl dithiophosphates of 3 to 8 carbon atoms
  • antioxidants such as pheny
  • the reactor was charged with 1170 grams of cyclohexane and heated to 35°C. A small amount of 1,1-diphenylethylene was then added to serve as an indicator for the subsequent tritration.
  • the reaction was allowed to continue overnight resulting in a final degree of hydrogenation of 98.4%.
  • the polymer cement was subjected to several citric-acid wash cycles to remove the residual nickel from the polymer. Analysis of the polymer by an atomic absorption technique indicated the remaining nickel concentration to be on the order of 155-160 ppm nickel based on the weight of neat polymer. lonol anti-oxidant was added to the cement and the polymer cement was stored until needed. The polymer could be easily isolated by coagulation into isopropanol, followed by vacuum drying.
  • the kinematic viscosity data as measured at both high and low temperatures indicate the polymer has good thickening capability, qualifying this polymer as a suitable VI-improver as well as a dispersant.

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

Claims (14)

1. Ein öllösliches, sternförmig ausgebildetes Produkt mit den Eigenschaften sowohl eines Verbesserungsmittels für den Viskositätsindex als auch eines Dispergiermittels, welches öllösliche Produkt die nachstehenden Struktureinheiten umfaßt:
(a) einen Poly(polyalkenylaromatischen)Kern;
(b) mindestens drei hydrierte polymere Arme, welche mit besagtem Kern verknüpft sind, wobei besagte hydrierte polymere Arme ausgewählt sind aus der Gruppe, bestehend aus:
i) hydrierten Homopolymeren und hydrierten Copolymeren von konjugierten Dienen;
ii) hydrierten Copolymeren von konjugierten Dienen und Monoalkenylarenen und
iii) Mischungen daraus, und wobei mindestens etwa 80% der aliphatischen Ungesättigtheit der polymeren Arme durch Hydrierung reduziert sind, während vorzungsweise weniger als 20% der aromatischen Ungesättigtheit reduziert worden sind;
(c) mindestens einen aus einer polymerisierten stickstoffhaltigen polaren Verbindung aufgebauten Arm, der mit besagtem Kern verknüpft ist.
2. Ein Produkt wie in Anspruch 1 beansprucht, in weichem besagter Poly(polyalkenylaromatischer)-Kern ein Poly(divinylbenzol)Kern ist.
3. Ein Produkt wie in Anspruch 1 oder 2 beansprucht, in welchem das Zahlenmittel des Molekulargewichts jedes hydrierten polymeren Arms zwischen 1000 und 100 000 liegt..
4. Ein Produkt wie in irgendeinem der Ansprüche 1 bis 3 beansprucht, in welchem der Gewichtsprozentsatz an der stickstoffhaltigen polaren Verbindung zwischen 0,1 und 10,0 liegt.
5. Ein Produkt wie in irgendeinem der Ansprüche 1 bis 4 beansprucht, in welchem besagte stickstoffhaltige polare Verbindung 2-Vinylpyridin oder 4-Vinylpyridin ist.
6. Ein Verfahren zur Herstellung eines Produktes wie in irgendeinem der Ansprüche 1 bis 5 beansprucht, umfassend:
(a) eine Lösungspolymerisation eines oder mehrerer konjugierten(r) Diens(e) und gegebenenfalls eines oder mehrerer Monoalkenylarenmonomer(e) unter Polymerisationsbedingungen mit einer Organolithiumverbindung unter Bildung reaktionsfähiger (living) polymerer Arme;
(b) Kontaktieren besagter reaktionsfähiger polymerer Arme mit einem polyalkenylaromatischen Kupplungsmittel unter Bildung eines gekuppelten Polymeren mit einem Poly(polyalkenylaromatischen)-Kern und daran gebundenen polymeren Armen;
(c) Kontaktieren besagten gekuppelten Polyumers mit einer monomeren stick-stoffhaltigen polaren Verbindung, unter Anknüpfung von Armen, aufgebaut aus der polymeren stickstoffhaltigen polaren Verbindung, an besagten Kern und
(d) Reduzieren von mindestens 80% der aliphatischen Ungesättigtheit der polymeren Arme durch Hydrieren und vorzugsweise Reduzieren von weniger als 20% der aromatischen Ungesättigheit.
7. Ein Verfahren wie in Anspruch 6 beansprucht, in welchem die Monomeren der Verfahrensstufe (a) Butadien und/oder Isopren und wahlweise Styrol sind.
8. Ein Verfahren wie in Anspruch 6 oder 7 beansprucht, in welchem besagte stickstoffhaltige polare Verbindung 2-Vinylpyridin oder 4-Vinylpyridin ist.
9. Ein Verfahren wie in irgendeinem der Ansprüche 6 bis 8 beansprucht, in welchem besagte stickstoffhaltige polare Verbindung mit besagtem gekuppeltem Polymer bei einer Temperatur zwischen -78°C und +80°C kontaktiert wird.
10. Ein Verfahren wie in irgendeinem der Ansprüche 6 bis 9 beansprucht, in welchem in Verfahrensstufe (d) das erhaltene Polymer mit Wasserstoff und einem Hydrierungskatalysator unter Hydrierungsbedingungen kontaktiert wird.
11. Ein Verfahren wie in Anspruch 10 beansprucht, in welchem besagter Hydrierungskatalysator das Reaktionsprodukt eines Aluminiumalkyls und eines Nickelcarboxylates oder Nickelalkoxyds umfaßt.
12. Ein Verfahren wie in irgendeinem der Ansprüche 6 bis 9 beansprucht, in weichem in Verfahrensstufe (d) das erhaltene Polymer mit einem Hydrazin- oder p-Toluolsulfonylhydrazid- Reaktionsmittel unter Bildung der Verbindung N2H2 kontaktiert wird, welche das Polymer durch Hydrierung reduziert.
13. Ein Verfahren wie in Anspruch 12 beansprucht, in welchem das molare Verhältnis der Reaktionsmittels zu den Einheiten des konjugierten Diens zwischen etwa 5:1 und etwa 1:1 liegt.
14. Eine Schmiermittelzusammensetzung, enthaltend ein Schmieröl und 0,1 bis 45 Gewichtsprozent eines Produktes, wie in irgendeinem der Ansprüche 1 bis 5 beansprucht.
EP82201623A 1981-12-21 1982-12-17 Produkt verwendbar als Dispergiermittel und Viskositätsindexverbesserer Expired EP0082574B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US33269281A 1981-12-21 1981-12-21
US332690 1981-12-21
US332692 1981-12-21
US06/332,690 US4427834A (en) 1981-12-21 1981-12-21 Dispersant-VI improver product

Publications (3)

Publication Number Publication Date
EP0082574A2 EP0082574A2 (de) 1983-06-29
EP0082574A3 EP0082574A3 (en) 1983-08-03
EP0082574B1 true EP0082574B1 (de) 1985-07-17

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP82201623A Expired EP0082574B1 (de) 1981-12-21 1982-12-17 Produkt verwendbar als Dispergiermittel und Viskositätsindexverbesserer

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EP (1) EP0082574B1 (de)
CA (1) CA1205590A (de)
DE (1) DE3264798D1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2144430B (en) * 1983-08-04 1986-11-19 Shell Int Research Hydrogenated modified star-shaped polymers
DE3517281A1 (de) * 1985-05-14 1986-11-20 Bayer Ag, 5090 Leverkusen Elektroviskose fluessigkeiten
AU754496B2 (en) * 1999-09-17 2002-11-21 Lubrizol Corporation, The Dispersant-viscosity improvers for lubricating oil compositions
US6472353B1 (en) 2000-09-14 2002-10-29 The Lubrizol Corporation Dispersant-viscosity improvers for lubricating oil compositions

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1575507A (en) * 1976-02-10 1980-09-24 Shell Int Research Hydrogenated star-shaped polymers and oil compositions thereof
US4221872A (en) * 1977-11-28 1980-09-09 Ici Australia Limited Process for removing unsaturation from ion exchange resins containing unquaternized amino groups by hydrogenation with imine
DE3068707D1 (en) * 1979-11-16 1984-08-30 Shell Int Research Modified hydrogenated star-shaped polymer, its preparation and a lubricating oil composition containing the polymer

Also Published As

Publication number Publication date
DE3264798D1 (en) 1985-08-22
EP0082574A2 (de) 1983-06-29
CA1205590A (en) 1986-06-03
EP0082574A3 (en) 1983-08-03

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