EP0082574B1 - Produit utilisable comme agent dispersant et agent améliorant l'indice de viscosité - Google Patents

Produit utilisable comme agent dispersant et agent améliorant l'indice de viscosité 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
Other languages
German (de)
English (en)
Other versions
EP0082574A2 (fr
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
Priority date (The priority date 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 date listed.)
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/fr
Publication of EP0082574A3 publication Critical patent/EP0082574A3/en
Application granted granted Critical
Publication of EP0082574B1 publication Critical patent/EP0082574B1/fr
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. Un produit en étoile, soluble dans l'huile, ayant les propriétés à la fois d'un agent améliorant l'indice de viscosité et d'un dispersant, ce produit soluble dans l'huile comprenant:
(a) un noyau poly(polyalcényl aromatique);
(b) au moins trois branches polymères hydrogénées liées à ce noyau, ces branches polymères hydrogénées étant choisies dans le groups constitué par:
(1) des homopolymères hydrogénés et des copolymères hydrogénés de diènes conjugués;
(2) des compolymères hydrogénés de diènes conjugués et de monoalcényi arènes; et
(3) leurs mélanges; et où au moins environ 80% de l'insaturation aliphatique des branches polymères a été réduit par hydrogénation tandis que de préeférence moins de 20% de l'insaturation aromatique a été réduite; et
(c) au moins une branche de composé polaire azoté polymérisé liée au noyau.
2. Un produit selon la revendication 1, dans lequel le noyau poly(polyalcényl aromatique) est un noyau poly(divinyl benzène).
3. Un produit selon la revendication 1 ou 2, dans lequel le poids moléculaire moyen en nombre de chaque branche polymère hydrogénée est compris entre 1 000 et 100 000.
4. Un produit selon l'une quelconque des revendications 1-3, dans lequel le pourcentage en poids de composé polaire azoté est compris entre 0,1 et 10,0.
5. Un produit selon l'une quelconque des revendications 1-4, dans lequel le composé polaire azoté est de la 2-vinylpyridine ou de la 4-vinylpyridine.
6. Un procédé pour la préparation d'un produit tel que revendiqué dans l'une quelconque des revendications 1-5, comprenant:
(a) la polymérisation en solution d'un ou plusieurs monomères diènes conjugués et éventuellement d'un ou plusieurs monomères monoalcényle arènes dans des conditions de polymérisation avec un composé organo-lithium, formant des branches polymères vivantes;
(b) la mise en contact de ces branches polymères vivantes avec un agent de couplage polyalcényl aromatique formant un polymère couplé ayant un noyau poly(polyalcényi aromatique) et des branches polymères attachées;
(c) la mise en contact de ce polymère couplé avec un monomère polaire contenant de l'azote attachant des branches de poly(composé polaire azoté) au noyau, et
(d) la réduction par hydrogénation d'au moins 80% de l'insaturation aliphatique des branches polymères tout en réduisant de préférence moins de 20% de linsaturation aromatique.
7. Un procédé selon la revendication 6, dans lequel les monomères de l'étape (a) sont du butadiène et/ou de l'isoprène et éventuellement du styrène.
8. Un procédé selon la revendication 6 ou 7, dans lequel le composé polaire azoté est de la 2-vinylpyridine ou de la 4-vinylpyridine.
9. Un procédé selon l'une quelconque des revendications 6―8, dans lequel le composé polaire azoté est mis en contact avec le polymère couplé à une température comprise entre -78°C et +80°C.
10. Un procédé selon l'une quelconque des revendications 6-9, dans lequel dans l'étape (d) le polymère résultant est mis en contact avec de l'hydrogène et un catalyseur d'hydrogénation dans des conditions d'hydrogénation.
11. Un procédé selon la revendication 10, dans lequel le catalyseur d'hydrogénation comprend le produit de réaction d'un aluminium-alcoyle et d'un carboxylate de nickel ou alcoolate de nickel.
12. Un procédé selon l'une quelconque des revendications 6-9, dans lequel dans l'étape (d) le polymère résultant est mis en contact avec un corps en réaction hydrazine ou p-toluènesulfonylhydrazide formant N2H2, qui réduit le polymère par hydogénation.
13. Un procédé selon la revendication 12, dans lequel le rapport molaire du corps en réaction aux mailles de diène conjugué est compris entre environ 5:1 et environ 1:1.
14. Une composition lubrifiante comprenant une huile lubrifiante et 0,1-45% en poids d'un produit selon l'une quelconque des revedications 1-5.
EP82201623A 1981-12-21 1982-12-17 Produit utilisable comme agent dispersant et agent améliorant l'indice de viscosité Expired EP0082574B1 (fr)

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 (fr) 1983-06-29
EP0082574A3 EP0082574A3 (en) 1983-08-03
EP0082574B1 true EP0082574B1 (fr) 1985-07-17

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP82201623A Expired EP0082574B1 (fr) 1981-12-21 1982-12-17 Produit utilisable comme agent dispersant et agent améliorant l'indice de viscosité

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

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 (fr) 1983-06-29
CA1205590A (fr) 1986-06-03
EP0082574A3 (en) 1983-08-03

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