EP0119069A2 - Composition lubrifiante comprenant un copolymère d'éthylène-alphaoléfine - Google Patents

Composition lubrifiante comprenant un copolymère d'éthylène-alphaoléfine Download PDF

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Publication number
EP0119069A2
EP0119069A2 EP84301568A EP84301568A EP0119069A2 EP 0119069 A2 EP0119069 A2 EP 0119069A2 EP 84301568 A EP84301568 A EP 84301568A EP 84301568 A EP84301568 A EP 84301568A EP 0119069 A2 EP0119069 A2 EP 0119069A2
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EP
European Patent Office
Prior art keywords
viscosity
ethylene
lubricants
shear
low
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.)
Withdrawn
Application number
EP84301568A
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German (de)
English (en)
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EP0119069A3 (fr
Inventor
Frederick C. Loveless
Raymond F. Watts
Walter Nudenberg
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.)
Uniroyal Inc
Original Assignee
Uniroyal Inc
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Publication date
Application filed by Uniroyal Inc filed Critical Uniroyal Inc
Publication of EP0119069A2 publication Critical patent/EP0119069A2/fr
Publication of EP0119069A3 publication Critical patent/EP0119069A3/fr
Withdrawn legal-status Critical Current

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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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic 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
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/04—Fatty oil fractions
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/06—Well-defined hydrocarbons aromatic
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/34—Esters of monocarboxylic acids
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy compounds
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/04—Polyethene
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
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    • C10M127/00—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon
    • C10M127/04—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon well-defined aromatic
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    • 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
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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    • 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
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/42—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms polycarboxylic
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
    • C10M129/95—Esters
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/44—Five-membered ring containing nitrogen and carbon only
    • C10M133/46—Imidazoles
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    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
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    • 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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    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
    • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
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    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
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    • C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
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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
    • C10M145/10—Macromolecular 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
    • C10M145/12—Macromolecular 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
    • C10M145/14—Acrylate; Methacrylate
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    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/02—Monomer containing silicon
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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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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Definitions

  • This invention relates to compositions useful as lubricating oils having high viscosity index, improved resistance to oxidative degradation and resistance to viscosity losses caused by permanent or temporary shear.
  • a lubricating composition comprising (1) a high viscosity ethylene-alphaolefin oligomer having a viscosity of 1000-3500 centistokes at 100°C; (2) a low viscosity synthetic hydrocarbon, such as alkylated benzene or low viscosity polyalphaolefin; optionally, (3) a low viscosity ester, such as monoesters, diesters, polyesters and, optionally (4) an additive package.
  • a high viscosity ethylene-alphaolefin oligomer having a viscosity of 1000-3500 centistokes at 100°C
  • a low viscosity synthetic hydrocarbon such as alkylated benzene or low viscosity polyalphaolefin
  • a low viscosity ester such as monoesters, diesters, polyesters and, optionally (4) an additive package.
  • An object of the invention is to provide a lubricating composition with properties not obtainable with conventional polymeric thickeners.
  • a further object of the invention is to provide lubricating compositions exhibiting improved shear stability, oxidative stability and excellent temperature-viscosity properties.
  • the viscosity-temperature relationship of a lubricating oil is one of the critical criteria which must be considered when selecting a lubricant for a particular application.
  • the mineral oils commonly used as a base for single and multigraded lubricants exhibit a relatively large change in viscosity with a change in temperature. Fluids exhibiting such a relatively large change in viscosity with temperature are said to have a low viscosity index.
  • the viscosity index of a common paraffinic mineral oil is usually given a value of about 100.
  • Viscosity index (VI) is determined according to ASTM Method D 2770-74 wherein the VI is related to kinematic viscosities measured at 40°C and 1000C.
  • Lubricating oils composed mainly of mineral oil are said to be single graded.
  • SAE grading requires that oils have a certain minimum viscosity at high temperatures and, to be multigraded, a certain maximum viscosity at low temperatures.
  • an oil having a viscosity of 10 cSt. at 100°C would be an SAE 30 and if that oil had a viscosity of 3400 cP. at -20°C, the oil would be graded 10W-30.
  • the viscosity requirements for qualification as multigrade engine oils are described by the SAE Engine Oil Viscosity Classification - SAE J300 SEP80, which became effective April 1, 1982.
  • the low temperature (W) viscosity requirements are ' determined by ASTM D 2602, Method of Test for Apparent Viscosity of Motor Oils at Low Temperature Using the Cold Cranking Simulator, and the results are reported in centipoise (cP).
  • the higher temperature (100°C) viscosity is measured according to ASTM D445, Method of Test for Kinematic Viscosity of Transparent and Opaque Liquids, and the results are reported in centistokes (cSt.).
  • the following table outlines the high and low temperature requirements for the recognized SAE grades for engine oils.
  • the 40°C viscosity estimated by linearly connecting the 100°C and -25°C viscosities would be about 70 cSt.
  • V.I. improved oils have viscosities at -25°C, which are considerably greater than predicted by linear extrapolation of the K.V. 100 and K.V. 40 values. Therefore, even having a V.I. of 180 does not guarantee the blend would be a 5W-40 oil.
  • V.I. improvers are traditionally high molecular weight rubbers whose molecular weights may vary from 10,000 to 1,000,000. Since the thickening power and V.I. increase are related to the molecular weight of the V.I. improver, most of these polymers normally have a molecular weight of at least 100,000.
  • Temporary shear is the result of the non-Newtonian viscometrics associated with solutions of high molecular weight polymers. It is caused by an alignment of the polymer chains with the shear field under high shear rates with a resultant decrease in viscosity. The decreased viscosity reduces the wear protection associated with viscous oils. Newtonian fluids maintain their viscosity regardless of shear rate.
  • Certain specific blends of high viscosity synthetic hydrocarbons, low viscosity synthetic hydrocarbons and optionally low viscosity esters form base fluids from which superior crankcase or gear oils can be produced by the addition of the proper additive "packages". Besides exhibiting a broad range of viscosity, the finished oils thus prepared exhibit an improved stability to permanent shear and, because of their Newtonian nature, reduced temporary shear and still maintain nearly the viscosity required for proper wear protection.
  • the oils of this invention have better stability toward oxidative degradation than those of the prior art.
  • the high viscosity indices produced from our base fluid blends permit the preparation of broadly multigraded crankcase fluids, such as 5W-40 and gear oils such as 75W-140.
  • the high viscosity synthetic hydrocarbon having viscosities of 1000 to 3500 cSt. is an ethylene-alphaolefin oligomer (EAO).
  • the high viscosity ethylene-alphaolefin oligomers of this invention are conveniently prepared by Ziegler catalysis. Many references exist covering methods of producing liquid oligomers of ethylene and alphaolefins (particularly propylene).
  • Polymerization is typically performed by subjecting the monomer mixture usually in a solvent to the combination of an organo aluminum compound and a vanadium or titanium compound.
  • the products formed can range from materials having viscosities as low as 20 cSt. to rubbery semi-solids depending on the choice of catalyst, the addition of molecular weight regulating species, temperature of polymerization and, especially, imposed hydrogen pressure.
  • low viscosity oligomers are prepared by the pyrolysis of high viscosity oligomers or rubbery solids.
  • Typical preparations of liquid ethylene-alphaolefin copolymers can be found in references, such as:
  • oligomers of ethylene and at least one other alphaolefin of this invention may be hydrogenated to increase their stability toward oxidation, the proper choice of polymerization catalysts in the presence of hydrogen often produces oligomers having very low levels of unsaturation directly.
  • the alphaolefins which can be used, singly or in combinations, with ethylene include linear alphaolefins of C 3 (propylene) to C 14 (tetradecene) and branched alphaolefins of the same molecular weight range, provided that the branch point is at least in the beta-position to the double bond (e.g. 4-methyl pentene-1).
  • propylene and the lower molecular weight olefins are the preferred monomers in the preparation of the oligomers of ethylene and at least one other alphaolefin of this invention.
  • oligomeric ethylene- alpha olefin polymers which contain controlled amounts of unsaturation introduced by copolymerization with certain non-conjugated diene such as dicyclopentadiene, ethylidene norbornene and 1,4-hexadiene.
  • certain non-conjugated diene such as dicyclopentadiene, ethylidene norbornene and 1,4-hexadiene.
  • the introduction of unsaturation is sometimes desired if the oligomer is to be treated in any way to produce polar functionality thus giving the oligomer dispersant properties.
  • the low viscosity synthetic hydrocarbons of the present invention having viscosities of from 1 to 10 cSt., consist primarily of oligomers of alphaolefins and/or alkylbenzenes.
  • Low molecular weight oligomers of alphaolefins from C 8 (octene) to C 12 (dodecene) or mixtures of the olefins can be utilized.
  • Low viscosity alphaolefin oligomers can be produced by Ziegler catalysis, thermal polymerization, free radically catalyzed polymerization and, preferably, BF 3 catalyzed polymerization.
  • BF 3 catalyzed polymerization preferably, BF 3 catalyzed polymerization.
  • a host of similar processes involving BF 3 in conjunction with a cocatalyst is known in the patent literature.
  • a typical polymerization technique is described in United States Patent No. 4,045,508.
  • the alkyl benzenes may be used in the present invention alone or in conjunction with low viscosity polyalphaolefins in blends with high viscosity synthetic hydrocarbons and low viscosity esters.
  • the alkyl benzenes prepared by Friedel-Crafts alkylation of benzene with olefins are usually predominantly dialkyl benzenes wherein the alkyl chain may be 6 to 14 carbon atoms long.
  • the alkylating olefins used in the preparation of alkyl benzenes can be straight or branched chain olefins or combinations. These materials may be prepared as shown in U.S.P. 3,909,432.
  • the low viscosity esters of this invention having viscosities of from 1 to 10 cSt. can be selected from classes of esters readily available commercially, e.g., monoesters prepared from monobasic acids such as pelargonic acid and alcohols; diesters prepared from dibasic acids and alcohols or from diols and monobasic acids or mixtures of acids; and polyol esters prepared from diols, triols (especially trimethylol propane), tetraols (such as pentaerythritol), hexaols (such as dipentaerythritol) and the like reacted with monobasic acids or mixtures of acids.
  • monoesters prepared from monobasic acids such as pelargonic acid and alcohols
  • diesters prepared from dibasic acids and alcohols or from diols and monobasic acids or mixtures of acids
  • esters examples include tridecyl pelargonate, di-2 ethylhexyl adipate, di-2 ethylhexyl azelate, trimethylol propane triheptanoate and pentaerythritol tetraheptanoate.
  • esters and mixtures of esters derived from natural sources, plant or animal are those esters and mixtures of esters derived from natural sources, plant or animal. Examples of these materials are the fluids produced from jojoba nuts, tallows, safflowers and sperm whales.
  • esters used in our blends ought to be carefully selected to insure compatibility of all components in finished lubricants of this invention. If esters having a high degree of polarity (roughly indicated by oxygen content) are blended with certain combinations of high viscosity synthetic hydrocarbons and low viscosity synthetic hydrocarbons, phase separation can occur at low temperatures with a resultant increase in apparent viscosity. Such phase separation is, of course, incompatible with long term storage of lubricants under a variety of temperature conditions.
  • the additive "packages" mixed with the recommended base oil blend for the production of multigraded crankcase fluids or gear oils are usually combination of various types of chemical additives so chosen to operate best under the use conditions which the particular formulated fluid may encounter.
  • Additives can be classified as materials which either impart or enhance a desirable property of the base lubricant blend into which they are incorporated. While the general nature of the additives might be the same for various types or blends of the base lubricants, the specific additives chosen will depend on the particular type of service in which the lubricant is employed and the characteristics of the base lubricants.
  • a finished lubricant will contain several and possibly most or all of the above types of additives in what is commonly called an "additive package.”
  • the development of a balanced additive package involves considerably more work than the casual use of each of the additive types. Quite often functional difficulties arising from combinations of these materials show up under actual operating conditions. On the other hand, certain unpredictable synergistic effects of a desirable nature may also become evident. The only methods currently available for obtaining such data are from extensive full scale testing both in the laboratory and in the field. Such testing is costly and time-consuming.
  • Dispersants have been described in the literature as “detergents”. Since their function appears to be one of effecting a dispersion of particulate matter, rather than one of "cleaning up” any existing dirt and debris, it is more appropriate to categorize them as dispersants.
  • Materials of this type are generally molecules having a large hydrocarbon "tail” and a polar group head.
  • the tail section an oleophilic group, serves as a solubilizer in the base fluid while the polar group serves as the element which is attracted to particulate contaminants in the lubricant.
  • the dispersants include metallic and ashless types.
  • the metallic dispersants include sulfonates (products of the neutralization of a sulfonic acid with a metallic base), thiophosphonates (acidic components derived from the reaction between polybutene and phosphous pentasulfide) and phenates and phenol sulfide salts (the broad class of metal phenates includes the salts of alkylphenols, alkylphenol sulfides, and alkyl phenol aldehyde products).
  • the ashless type dispersants may be categorized into two broad types: high molecular weight polymeric dispersants for the formulation of multigrade oils and lower molecular weight additives for use where viscosity improvement is not necessary.
  • the compounds useful for this purpose are again characterized by a "polar" group attached to a relatively high molecular weight hydrocarbon chain.
  • the "polar” group generally contains one or more of the elements-nitrogen, oxygen, and phosphorus.
  • the solubilizing chains are generally higher in molecular weight than those employed in the metallic types; however, in some instances they may be quite similar.
  • Some examples are N-substituted long chain alkenyl succinimides, high molecular weight esters, such as products formed by the esterification of mono or polyhydric aliphatic alcohols with olefin substituted succinic acid, and Mannich bases from high molecular weight alkylated phenols.
  • the high molecular weight polymeric ashless dispersants have the general formula:
  • an oxidation inhibitor is the prevention of a deterioration associated with oxygen attack on the lubricant base fluid. These inhibitors function either to destroy free radicals (chain breaking) or to interact with peroxides which are involved in the oxidation mechanism.
  • oxidation inhibitors include the phenolic types (chain-breaking) e.g., 2,6-di-tert.-butyl para cresol and 4,4 1 methylenebis(2,6-di-tert.-butylphenol), and the zinc dithiophosphates (peroxide-destroying).
  • Wear is loss of metal with subsequent change in clearance between surfaces moving relative to each other. If continued, it will result in engine or gear malfunction.
  • the principal factors causing wear are metal-to-metal contact, presence of abrasive particulate matter, and attack of corrosive acids.
  • Metal-to-metal contact can be prevented by the addition of film-forming compounds which protect the surface either by physical absorption or by chemical reaction.
  • the zinc dithiophosphates are widely used for this purpose. These compounds were described under anti-oxidant and anti-bearing corrosion additives. Other effective additives contain phosphorus, sulfur or combinations of these elements.
  • Abrasive wear can be prevented by effective removal of particulate matter by filtration while corrosive wear from acidic materials can be controlled by the use of alkaline additives such as basic phenates and sulfonates.
  • conventional viscosity improvers are often used in "additive packages" their use should not be necessary for the practice of this invention since our particular blends of high and low molecular weight base lubricants produce the same effect.
  • These materials are usually oil-soluble organic polymers with molecular weights ranging from approximately 10,000 to 1,000,000. The polymer molecule in solution is swollen by the lubricant. The volume of this swollen entity determines the degree to which the polymer increases its viscosity.
  • pour point depressants prevent the congelation of the oil at low temperatures. This phenomenon is associated with the crystallization of waxes from the lubricants. Chemical structures of representative commercial pour point depressants are:
  • Chemicals employed as rust inhibitors include sulfonates, alkenyl succinic acids, substituted imidazolines, amines, and amine phosphates.
  • the anti-foam agents include the silicones and miscellaneous organic copolymers.
  • Additive packages known to perform adequately for their recommended purpose are prepared and supplied by several major manufacturers. The percentage and type of additive to be used in each application is recommended by the suppliers. Typically available packages are:
  • a typical additive package for an automotive gear lubricant would normally contain antioxidant, corrosion inhibitor, anti-wear agents, anti-rust agents, extreme pressure agent and foam inhibitor.
  • a typical additive package for a crankcase lubricant would normally be comprised of a dispersant, antioxidant, corrosion inhibitor, anti-wear agent, anti-rust agent and foam inhibitor.
  • An additive package useful for formulating a compressor fluid would typically contain an anti-oxidant, anti-wear agent, an anti- rust agent and foam inhibitor.
  • This invention describes blends of high viscosity synthetic hydrocarbons, having a viscosity range of 1000 to 3500 cSt. with one or more synthetic hydrocarbon fluids having viscosities in the range of 1 to 10 cSt. and, optionally, one or more compatible ester fluids having a viscosity ,range of 1 to 10 cSt.
  • Such blends when treated with a properly chosen additive "package" can be formulated in a broad range multigraded crankcase or gear oil having improved shear stability, improved oxidative stability, and more Newtonian viscometric properties.
  • the blends of this invention also find uses in certain applications where no additive need be employed.
  • the low viscosity synthetic hydrocarbon fluid is frequently the main ingredient in the base oil blend, particularly in finished lubricants having an SAE viscosity grade of 30 or 40. While certain low viscosity esters are insoluble in high viscosity synthetic hydrocarbons, the presence of low viscosity synthetic hydrocarbon ; being a better solvent for low viscosity esters, permits greater variations in the type of esters used in base oil blends of high viscosity synthetic hydrocarbons, low viscosity synthetic hydrocarbons, and low viscosity esters.
  • the high viscosity ethylene-alphaolefin oligomers of this invention provide thickening and viscosity index improvement to the base oil blend.
  • the third component, low viscosity esters may or may not be added to produce the superior lubricants of this invention.
  • High viscosity synthetic hydrocarbons and low viscosity synthetic hydrocarbons can be used alone to produce multigraded lubricants.
  • low levels of low viscosity esters usually 1-25% results in a base oil blend superior to blends of high viscosity synthetic hydrocarbons and low viscosity synthetic hydrocarbons alone in low temperature fluidity.
  • low viscosity esters usually constitute 10-25% of the synthetic base oil blend, more or less can be used in specific formulations. When the final application involves exposure to moisture elimination or limitation of the amount of ester in blends may be advantageous.
  • the components of the finished lubricants of this invention can be admixed in any convenient manner or sequence.
  • An important aspect of the present invention is in the use of the properly constituted base oil blend in combination with the proper compatible additive package to produce finished broad range multigrade lubricants having:
  • the lubricants of this invention when properly formulated, display viscometrics close to Newtonian fluids. That is, their viscosities are minimally changed over a wide range of shear rates. While the high viscosity synthetic hydrocarbons of the invention may, in themselves, display non-Newtonian characteristics, particularly at low temperatures, the final lubricant products utilizing low viscosity oils as diluents are nearly Newtonian.
  • the high viscosity synthetic hydrocarbons of this invention all have molecular weights below 5000, and shear thinning of their solutions is minimal, i.e., they will display nearly Newtonian character.
  • the shear rate developed in pistons and gears (equal to or greater than 10 6 sec 1 ) is such that, depending on the polymeric thickener used, the apparent viscosity of the oils approaches that of the unthickened base fluids resulting in loss of hydrodynamic films. Since wear protection of moving parts has been correlated with oil viscosity, it is apparent that the wear characteristics of a lubricant can be downgraded as a result of temporary shear. The nearly Newtonian fluids of the current invention maintain their viscosity under these use conditions better and therefore afford more protection to and longer lifetime for the machinery being lubricated.
  • the advantages a Newtonian fluid brings to such a grading system are obvious to anyone skilled in the art.
  • the viscosity of a Newtonian fluid can be directly extrapolated to 150°C under high shear conditions.
  • a polymer thickened fluid will invariably have a viscosity lower than the extrapolated value, frequently close to the base fluid itself.
  • polymer thickened oils will require a more viscous base fluid.
  • the use of thicker base fluids will produce higher viscosities at low temperature making it more difficult to meet the low temperature (e.g. 5W for crankcase or 75W for gear oil) requirements for broadly multigraded oils.
  • V.I. improvers "artificially" improve the viscosity index, since realistic high temperature high shear measurements are not utilized in determining V.I. Viscosity index is determined by low shear viscosity measurements at 40°C and 100°C.
  • the nearly Newtonian lubricants of this invention not only produce high viscosity index multigraded fluids which stay "in grade", but the VI and multigrade ratings are more realistic since they are essentially insensitive to shear.
  • the invention uses a high viscosity ethylene-alphaolefin oligomer having a viscosity of from 1000 to 3500 cSt. As the viscosity increases the oxidation and shear stability decreases. None the less, the high viscosity oligomers of the invention still represent an improvement of the VI improvers of the prior art. This is particularly true for broadly graded lubricants such as 75W-140 gear oils and 5W-40 crankcase oil. While the specific compositions exemplified in this patent are fairly precise, it should be obvious to anyone skilled in the art to produce even further combinations within the scope of this invention which will be valuable lubricants.
  • the lubricants had the properties shown:
  • the lubricants had the properties shown:

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EP84301568A 1983-03-09 1984-03-08 Composition lubrifiante comprenant un copolymère d'éthylène-alphaoléfine Withdrawn EP0119069A3 (fr)

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EP0276320A1 (fr) * 1986-07-11 1988-08-03 Mitsui Petrochemical Industries, Ltd. Composition de polymere liquide et son utilisation
EP0496486A1 (fr) * 1991-01-11 1992-07-29 Mobil Oil Corporation Compositions de lubrifiant
WO1995006700A1 (fr) * 1993-08-31 1995-03-09 Henkel Corporation Lubrifiant pour engrenages soumis a des pressions extremes
WO2002064709A2 (fr) * 2001-02-13 2002-08-22 The Lubrizol Corporation Lubrifiants synthetiques pour moteurs diesel contenant un dispersant-agent modificateur de viscosite et un detergent phenol fonctionnalise
US7683013B2 (en) 2005-06-07 2010-03-23 Exxonmobil Research And Engineering Company Base stock lubricant blends for enhanced micropitting protection
EP2449068A1 (fr) * 2009-07-03 2012-05-09 Total Raffinage Marketing Fluides de laminage
US8247358B2 (en) 2008-10-03 2012-08-21 Exxonmobil Research And Engineering Company HVI-PAO bi-modal lubricant compositions
US8318993B2 (en) 2002-03-05 2012-11-27 Exxonmobil Research And Engineering Company Lubricant blend composition
US8394746B2 (en) 2008-08-22 2013-03-12 Exxonmobil Research And Engineering Company Low sulfur and low metal additive formulations for high performance industrial oils
US8535514B2 (en) 2006-06-06 2013-09-17 Exxonmobil Research And Engineering Company High viscosity metallocene catalyst PAO novel base stock lubricant blends
US8598103B2 (en) 2010-02-01 2013-12-03 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low, medium and high speed engines by reducing the traction coefficient
US8642523B2 (en) 2010-02-01 2014-02-04 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
US8716201B2 (en) 2009-10-02 2014-05-06 Exxonmobil Research And Engineering Company Alkylated naphtylene base stock lubricant formulations
US8728999B2 (en) 2010-02-01 2014-05-20 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
US8748362B2 (en) 2010-02-01 2014-06-10 Exxonmobile Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed gas engines by reducing the traction coefficient
US8759267B2 (en) 2010-02-01 2014-06-24 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
EP2714865B1 (fr) * 2011-06-01 2019-12-11 ExxonMobil Research and Engineering Company Composition lubrifiante à haute efficacité

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EP0088453A1 (fr) * 1982-03-10 1983-09-14 UNIROYAL CHEMICAL COMPANY, Inc. Composition lubrifiante

Cited By (23)

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Publication number Priority date Publication date Assignee Title
EP0276320A4 (fr) * 1986-07-11 1988-11-22 Mitsui Petrochemical Ind Composition de polymere liquide et son utilisation.
US4922046A (en) * 1986-07-11 1990-05-01 Mitsui Petrochemical Industries, Ltd. Liquid polymer composition and use thereof
EP0276320A1 (fr) * 1986-07-11 1988-08-03 Mitsui Petrochemical Industries, Ltd. Composition de polymere liquide et son utilisation
EP0496486A1 (fr) * 1991-01-11 1992-07-29 Mobil Oil Corporation Compositions de lubrifiant
WO1995006700A1 (fr) * 1993-08-31 1995-03-09 Henkel Corporation Lubrifiant pour engrenages soumis a des pressions extremes
US6399550B1 (en) 1993-08-31 2002-06-04 Cognis Corporation Extreme pressure lubricant
WO2002064709A2 (fr) * 2001-02-13 2002-08-22 The Lubrizol Corporation Lubrifiants synthetiques pour moteurs diesel contenant un dispersant-agent modificateur de viscosite et un detergent phenol fonctionnalise
WO2002064709A3 (fr) * 2001-02-13 2003-02-20 Lubrizol Corp Lubrifiants synthetiques pour moteurs diesel contenant un dispersant-agent modificateur de viscosite et un detergent phenol fonctionnalise
US6610637B2 (en) 2001-02-13 2003-08-26 The Lubrizol Corporation Synthetic diesel engine lubricants containing dispersant-viscosity modifier and functionalized phenol detergent
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US7683013B2 (en) 2005-06-07 2010-03-23 Exxonmobil Research And Engineering Company Base stock lubricant blends for enhanced micropitting protection
US8535514B2 (en) 2006-06-06 2013-09-17 Exxonmobil Research And Engineering Company High viscosity metallocene catalyst PAO novel base stock lubricant blends
US8394746B2 (en) 2008-08-22 2013-03-12 Exxonmobil Research And Engineering Company Low sulfur and low metal additive formulations for high performance industrial oils
US8247358B2 (en) 2008-10-03 2012-08-21 Exxonmobil Research And Engineering Company HVI-PAO bi-modal lubricant compositions
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US8716201B2 (en) 2009-10-02 2014-05-06 Exxonmobil Research And Engineering Company Alkylated naphtylene base stock lubricant formulations
US8598103B2 (en) 2010-02-01 2013-12-03 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low, medium and high speed engines by reducing the traction coefficient
US8642523B2 (en) 2010-02-01 2014-02-04 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
US8728999B2 (en) 2010-02-01 2014-05-20 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
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EP0119069A3 (fr) 1986-07-16
BR8401057A (pt) 1984-10-16
IN160834B (fr) 1987-08-08
IN160835B (fr) 1987-08-08
KR840007895A (ko) 1984-12-11

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