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US3198739A - Lubricants and polymeric additives therefor - Google Patents

Lubricants and polymeric additives therefor Download PDF

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Publication number
US3198739A
US3198739A US71403A US7140360A US3198739A US 3198739 A US3198739 A US 3198739A US 71403 A US71403 A US 71403A US 7140360 A US7140360 A US 7140360A US 3198739 A US3198739 A US 3198739A
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US
United States
Prior art keywords
methacrylate
copolymer
vinyl
oil
stearyl
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 - Lifetime
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US71403A
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English (en)
Inventor
Harry F Richards
Jr Stephen A Herbert
Robert J Moore
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Shell USA Inc
Original Assignee
Shell Oil Co
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Filing date
Publication date
Application filed by Shell Oil Co filed Critical Shell Oil Co
Priority to US71403A priority Critical patent/US3198739A/en
Priority to FR879828A priority patent/FR1306897A/fr
Priority to DES76807A priority patent/DE1237721B/de
Priority to GB41977/61A priority patent/GB947800A/en
Application granted granted Critical
Publication of US3198739A publication Critical patent/US3198739A/en
Anticipated expiration legal-status Critical
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/005Macromolecular compounds, e.g. macromolecular compounds composed of alternatively specified monomers not covered by the same main group
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/08Lubricating 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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    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14Acrylate; Methacrylate
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    • C10M151/00Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
    • C10M151/02Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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    • C10M153/02Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic 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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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/024Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
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    • C10M2207/02Hydroxy compounds
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    • C10M2207/026Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084Acrylate; Methacrylate
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064Di- and triaryl amines
    • C10M2215/065Phenyl-Naphthyl amines
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    • C10M2217/02Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
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    • C10M2217/02Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024Macromolecular 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
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    • C10M2217/02Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/026Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrile group
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    • C10M2217/02Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028Macromolecular 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
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    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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    • C10M2223/04Phosphate esters
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08Resistance to extreme temperature
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/14Electric or magnetic purposes
    • C10N2040/16Dielectric; Insulating oil or insulators
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    • C10N2040/17Electric or magnetic purposes for electric contacts

Definitions

  • Polymers of this type may be represented by the Formula I where R and R are alkyl radicals as defined above, Y may be a C alkyl radical or a polar radical such as an ester, amide, amine, or phosphate radical or the like, m and m; are Whole numbers of at least 2 each and u may be zero or a Whole number, the ratio of m to m may vary from 1:10 to :1, preferably from 5:1 to 2:1 and the ratio of m+m to n when n is a whole number may vary from 10:1 to 5:1, respectively.
  • the molecular weight of the polymer varies from about one thousand to about one million, preferably from 10,000 to 500,000.
  • the first polymerizable monomer group includes acrylic and alkacrylic esters of aliphatic alcohols of at least 8 carbon atoms, preferably of from 10 to 20 carbon atoms, and include, inter alia, decyl acrylate, lauryl acrylate, stearyl acrylate, eicosanyl acrylate, docosanyl acrylate, decyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, and the like, and mixtures thereof.
  • the other polymerizable group includes omega-hydroxyesters of acrylic or alkacrylic acid and dihydroxy alkanes which may be straight or branch-chain, preferably alpha,
  • vinyl ethers vinyl dodecyl ether, vinyl tridecyl ether, vinyl tetracosyl ether, vinyl hexacosyl ether; allyl esters or ethers, allyl stearate, allyl dodecyl ether; amido esters, e.g., N-lauryl methacrylamide, N-stearyl methacrylamide, N,N'-di-.stearyl methacrylamide; vinylpyridines, e.g., 4- vinylpyridine, 2-methyl-5-vinylpyridine, vinylpyrrolidone, vinyl phosphonates and allyl phosphates, e.g., tn'methallyl phosphate, bis-chloroethyl vinyl phosphonate and and mixtures thereof.
  • vinylpyridines e.g., 4- vinylpyridine, 2-methyl-5-vinylpyridine, vinylpyrrolidone, vinyl phosphonates and allyl phosphates, e
  • the polymerization may be effected in the presence of a substantially inert liquid and in the presence of an oxygen-yielding catalyst at a temperature in the range of 50 to C., preferably between 6090 C.
  • Suitable liquid reaction media are various classes of hydrocarbons or their mixtures which are liquid and substantially inert under the polymerization conditions of the present process.
  • Certain classes of aliphatic hydrocarbons can be employed as'a liquid hydrocarbon reaction medium in the present process.
  • various saturated hydrocarbons alkanes and cycloalkanes
  • Either pure alkanes or cycloalkanes or commercially available mixtures, freed of catalyst poisons, may be employed.
  • liquid or liquefied alkanes such as n-pentane, n-hexane, 2,3-dimethylbutane, n-octane, isooctane (2,2,4- trimethylpentane), n-decane, n-dodecane, cyclohexane, methylcyclohexane, dimethylcyclopentane, ethylcyclohexane, decalin, methyldecalins, dimethyldecalins and the like.
  • alkanes such as n-pentane, n-hexane, 2,3-dimethylbutane, n-octane, isooctane (2,2,4- trimethylpentane), n-decane, n-dodecane, cyclohexane, methylcyclohexane, dimethylcyclopentane, ethylcyclohexane
  • aromatic hydrocarbon series particularly the mononuclear aromatic hydrocarbons, viz., benzene, toluene, xylenes, mesitylene and xylene-p-cymene mixtures can also be employed.
  • aromatic hydrocarbons as ethylbenzene, isopropylbenzene, sec-butylbenzene, t-butylbenzene, ethyltoluene, ethylxylenes, hemimellitene, pseudocumene, prehnitene, isodurene, diethylbenzenes, isoamylbenzene and the like.
  • Suitable aromatic hydrocarbon fractions can be obtained by the selective extraction of aromatic naphthas from hydroforming operations as distillates or bottoms, from cyclo stock fractions of cracking operations, etc.
  • alkyl naphthalenes which are liquid under the polymerization reaction con recovered and the copolymer exhibited excellent detergent properties.
  • acry a VIII do ..do Triallyl phosphate" Heptene. do 80 100,000 IX w-Hydlrotxyamyl methdo Vinyl pyrrolidone..- Benzene do 80 200, 000
  • an oil-soluble copolymer of stearyl methacrylate/ 2 methyl-S-vinylpyridine/ omega hydroxyamyl methacrylate having a moiecular weight of 100,000 was
  • additional improvements with respect to oxidation stability and scufiing inhibition can be imparted to the oil compositions containing the copolymers of this invention by incorporating small amounts (0.01%- 2%, preferably 0.1%-1%) of phenolic antioxidants such as alkylphenols, e.g., 2,6-ditertbutyl-4-methylphenol or p,p'-methylene bisphenols such as 4,4-rnethylene bis (2,6-ditertbutylphenol) or arylamines such as phenylalpha-naphthylamine and mixtures thereof.
  • phenolic antioxidants such as alkylphenols, e.g., 2,6-ditertbutyl-4-methylphenol or p,p'-methylene bisphenols such as 4,4-rn
  • Anti-scuifing agents include organic phosphites, phosphates, phosphonates and their thio-derivatives, such as C alkyl phosphites, or phosphonates, e.g., diand tributyl, octyl, lauryl, stearyl, cyclohexyl, benzyl, cresyl, phenyl, phosphites or phosphates, as well as their thio-derivatives, P S -terpene reaction product, e.g., P S -pine oil reaction product and alkali metal salts thereof such as a potassium salt of a P S -terpene reaction product, phosphonates such as dibutyl methanephosphonate, dibutyl trichloromethanephosphonate, dibutyl monochloromethanephosphonate, dibutyl chlorobenzenephosphonate, and the like.
  • the polymeric additives of this invention improve various mineral oil products by the incorporation of a minor amount (0.01% to 5%, preferably 0.1% to 3% by weight) of the additive.
  • they may be used to improve transformer oils, turbine oils, mineral lubricating oils, industrial oils and the like.
  • lubricating oils range from SAE 5W viscosity grade .to SAE 140 grade and are derived from parafiinic, naphthenic or asphaltic base crudes.
  • Representative oils are refined high viscosity index mineral oils having a viscosity of F of 100 to 250 SUS.
  • a typical mineral lubricating oil (X) of this type had the following properties:
  • Lubricating compositions of this invention are particularly applicable for high temperature, high speed use as in aviation engines, automotive engines, truck engines
  • Composition A Percent wt. 11 d 1
  • a mineral lubricating oil composition consisting es- 1e c 01 mer 2 sentially of a major amount of mineral lubricating oil Mineral lubricgfig on 6 Balance and from about 0.01% to by weight of an oil-soluble Com osition copolymer of a C1240 alkyl methacrylate and an ester of g 1e Co 01 mar 2 methacrylic acid and an alpha, omega C alkanediol in Minergl z z oil Balance the ratio of 1:10 to 10: 1, respectively, said copolyiner hav- Com osition ing a molecular weight of from 10,000 to 500,000.
  • a mineral lubricating oil composition consisting es- Minergl lubricagny on Balance sentially of major amount of mineral lubricating Oil and Com osition g 1 from about 0.01% to 5% by weight of an oil-soluble g 1e co olymer 2 copolymer of a C1240 alkyl methacrylate and an ester of Mineral lubricgfing oil Balance methacrylic acid and 1,5-pentanediol in the ratio of 1:10 Composition to 10:1, respectively, said copolymer having a molecular Example copolymer 3 weight of from 10,000 to 500,000.
  • a mineral lubricating oil composition consistlng es- Mineml lubricating (aviation oil 65 sentially of a major amount of mineral lubricating oil grade) Balance and from about 0.01% to 5% by weight of an oil-soluble comnosifion copolymer of stearyl methacrylate and an ester of methajixamnle I'copdymer 5 crylic acid and 1,5-pentanediol in the ratio of 1:10 to 4 4, methy1ene his, g ';gg g gfl ggf 0 5 10:1, respectively, said copolymer having a molecular Tricresyl phosphate weight of from 10,000 to 500,000.
  • a mineral lubricating oil composition consisting esi "f "i sentially of a major amount of mineral lubricating oil in order to demonstrate the utility and nnproved propand from about 0.01% to 5% by weight of an oil-soluble erties of this invention, the c0mpos1t1ons identified in copolymer of stearyl methacrylate, lauryl methacrylate, Table I were tested in the Chevrolet V8 Sludgmg Test, an ester of methacrylic acid and 1,5-pentanediol in the modified EX-3 test described in CRC Progress Report ratio of 1:10 to 10:1, respectively, said copolymer having No. 3, June 1, 1957, and the results were as follows: a molecular weight of from 10,000 to 500,000.

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  • General Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US71403A 1960-11-25 1960-11-25 Lubricants and polymeric additives therefor Expired - Lifetime US3198739A (en)

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US71403A US3198739A (en) 1960-11-25 1960-11-25 Lubricants and polymeric additives therefor
FR879828A FR1306897A (fr) 1960-11-25 1961-11-23 Composés polymères convenant comme additifs pour huile lubrifiante, et huiles lubrifiantes contenant ces composés
DES76807A DE1237721B (de) 1960-11-25 1961-11-23 Schmiermittel
GB41977/61A GB947800A (en) 1960-11-25 1961-11-23 Polymeric compounds suitable as lubricating oil additives and lubricating oils containing them

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Cited By (8)

* Cited by examiner, † Cited by third party
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US3377285A (en) * 1965-05-07 1968-04-09 Shell Oil Co Non-thickening oil concentrates
JPS5830357B1 (de) * 1971-03-05 1983-06-28 Shell Int Research
EP0418610A1 (de) * 1989-09-09 1991-03-27 Röhm Gmbh Dispergierwirksame ViskositÀ¤ts-Index-Verbesserer
EP0570093A1 (de) * 1992-03-20 1993-11-18 Rohm And Haas Company Aschefreie Dispersante Poly(Meth)Acrylat-Polymere
EP0569639A1 (de) * 1992-03-20 1993-11-18 Rohm And Haas Company Dispergierende Polymethacrylat-Viskositätsverbesserer
US5726136A (en) * 1994-10-19 1998-03-10 Agip Petroli S.P.A. Multifunctional additive for lubricating oils compatible with fluoroelastomers
US6475964B1 (en) * 1994-08-03 2002-11-05 Roehm Gmbh & Co. Kg Motor oil with high dispersivity and good wear protection characteristics
WO2009095483A3 (en) * 2008-01-30 2009-10-29 Shell Internationale Research Maatschappij B.V. Lubricating composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE791942R (fr) * 1971-05-05 1973-05-28 Sun Oil Co Pennsylvania Lubrification par

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US2892819A (en) * 1956-03-29 1959-06-30 California Research Corp Detergent copolymers
US2892790A (en) * 1956-02-03 1959-06-30 California Research Corp Lubricant composition
US2892792A (en) * 1956-02-03 1959-06-30 California Research Corp Lubricant composition
US2913439A (en) * 1955-12-01 1959-11-17 Shell Dev Hydroxy-containing copolymers and their preparation
CA590443A (en) * 1960-01-12 T. Stewart William Lubricant composition
US2927013A (en) * 1956-03-29 1960-03-01 California Research Corp Fuel composition
US2949445A (en) * 1958-05-06 1960-08-16 Du Pont Methyl methacrylate polymers containing amino residues
US2980658A (en) * 1956-05-14 1961-04-18 Baker Chem Co J T Copolymer of an alkyl methacrylate and an alpha-acyloxystyrene, and method for preparing same
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GB770771A (en) * 1953-05-18 1957-03-27 California Research Corp Copolymeric dispersants and lubricant compositions containing them
NL91489C (de) * 1953-05-25
BE538017A (de) * 1954-05-10
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CA590443A (en) * 1960-01-12 T. Stewart William Lubricant composition
US2913439A (en) * 1955-12-01 1959-11-17 Shell Dev Hydroxy-containing copolymers and their preparation
US2892790A (en) * 1956-02-03 1959-06-30 California Research Corp Lubricant composition
US2892792A (en) * 1956-02-03 1959-06-30 California Research Corp Lubricant composition
US2892819A (en) * 1956-03-29 1959-06-30 California Research Corp Detergent copolymers
US2927013A (en) * 1956-03-29 1960-03-01 California Research Corp Fuel composition
US2980658A (en) * 1956-05-14 1961-04-18 Baker Chem Co J T Copolymer of an alkyl methacrylate and an alpha-acyloxystyrene, and method for preparing same
US2949445A (en) * 1958-05-06 1960-08-16 Du Pont Methyl methacrylate polymers containing amino residues
US2994663A (en) * 1959-08-10 1961-08-01 California Research Corp Lubricant containing copolymer viscosity index improver

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3377285A (en) * 1965-05-07 1968-04-09 Shell Oil Co Non-thickening oil concentrates
JPS5830357B1 (de) * 1971-03-05 1983-06-28 Shell Int Research
EP0418610A1 (de) * 1989-09-09 1991-03-27 Röhm Gmbh Dispergierwirksame ViskositÀ¤ts-Index-Verbesserer
US5188770A (en) * 1989-09-09 1993-02-23 Rphm GmbH Viscosity index improver having detergent properties
EP0570093A1 (de) * 1992-03-20 1993-11-18 Rohm And Haas Company Aschefreie Dispersante Poly(Meth)Acrylat-Polymere
EP0569639A1 (de) * 1992-03-20 1993-11-18 Rohm And Haas Company Dispergierende Polymethacrylat-Viskositätsverbesserer
US6475964B1 (en) * 1994-08-03 2002-11-05 Roehm Gmbh & Co. Kg Motor oil with high dispersivity and good wear protection characteristics
US5726136A (en) * 1994-10-19 1998-03-10 Agip Petroli S.P.A. Multifunctional additive for lubricating oils compatible with fluoroelastomers
WO2009095483A3 (en) * 2008-01-30 2009-10-29 Shell Internationale Research Maatschappij B.V. Lubricating composition

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GB947800A (en) 1964-01-29

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