US20090156442A1 - Lubricant Compositions With Low HTHS for a Given SAE Viscosity Grade - Google Patents

Lubricant Compositions With Low HTHS for a Given SAE Viscosity Grade Download PDF

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US20090156442A1
US20090156442A1 US11/957,627 US95762707A US2009156442A1 US 20090156442 A1 US20090156442 A1 US 20090156442A1 US 95762707 A US95762707 A US 95762707A US 2009156442 A1 US2009156442 A1 US 2009156442A1
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lubricant composition
polymer
composition according
equal
percent
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Laurent Chambard
Jai G. Bansal
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Priority to US11/957,627 priority Critical patent/US20090156442A1/en
Priority to EP08105939A priority patent/EP2077316A3/en
Priority to CA002646858A priority patent/CA2646858A1/en
Priority to KR1020080127717A priority patent/KR20090065449A/en
Priority to SG200809286-8A priority patent/SG153772A1/en
Priority to CNA2008101871396A priority patent/CN101463286A/en
Priority to JP2008321494A priority patent/JP2009144162A/en
Priority to AU2008258192A priority patent/AU2008258192B2/en
Publication of US20090156442A1 publication Critical patent/US20090156442A1/en
Abandoned 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
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/047—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and macromolecular compounds
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/019—Shear stability
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
    • 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

Definitions

  • the present invention relates to lubricant compositions which exhibit certain performance characteristics; particularly a low High-Temperature, High-Sheer viscosity measurement.
  • Lubricant compositions are well known in the art. Lubricant compositions are typically made up of base oil and various additives. Lubricant compositions must met specific performance characteristics such as, but not limited to, kinematic viscosity and High-Temperature, High-Shear viscosity measurement (HTHS), depending on their end use.
  • kinematic viscosity and High-Temperature High-Temperature
  • HTHS High-Shear viscosity measurement
  • the present invention provides a lubricant composition comprising base oil having a viscosity index equal to or greater than 120 that exhibits an HTHS at or near the minimum for its SAE Viscosity Grade.
  • the present invention is a lubricant composition comprising base oil having a viscosity index equal to or greater than 120 and a first polymer having a kinematic viscosity ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent.
  • SSI shear stability index
  • the present invention is a lubricant composition
  • a lubricant composition comprising: a first polymer having a kinematic viscosity as defined later in the specification ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent; and a base oil having a viscosity index equal to or greater than 120.
  • SSI shear stability index
  • the present invention is a lubricant composition
  • a lubricant composition comprising: a polymer having a kinematic viscosity ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent; and a base oil having a viscosity index equal to or greater than 120, wherein the concentration of phosphorus in the lubricant composition is less than 0.08 weight percent and the concentration of sulfur is less than 0.5 weight percent.
  • SSI shear stability index
  • a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 5.5 to 10.
  • the polymer in solution is prepared by diluting the viscosity modifier concentrate in an API Group I solvent neutral 100 base stock between 60° C. and 70° C. for 45 minutes.
  • the kv100 and kv150 are measured according to ASTM D445.
  • Table 1 below shows the composition of three different polymer concentrates in solution as used herein as well as the kv100, kv150 and the kinematic viscosity ratios of the polymer solutions.
  • the three polymer concentrates are commercially available.
  • Polymer Concentrate 1 is commercially available from Infineum USA as SV145;
  • Polymer Concentrate 2 is commercially available from Infineum USA as SV265;
  • Polymer Concentrate 3 is commercially available from Chevron Corporation as Paratone 8451.
  • kv is kv100 of the polymer solution
  • kv(oil) is kv100 of the oil. kv is measured according ASTM D445.
  • the present invention is a lubricant composition
  • base oil having a viscosity index ranging of equal to or greater than 120 and a first polymer having a kinematic viscosity ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent.
  • SSI shear stability index
  • the base oil comprises a Group III basestock.
  • Group III basestocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 120.
  • the base oil comprises a Group IV basestock.
  • the base oil comprises a Group III basestock and a Group IV basestock.
  • the base oil comprises Group IV and Group V basestocks.
  • the base oil comprises Group II, Group IV and Group V basestocks.
  • the basestock is made using gas-to-liquids (“GTL”) process.
  • GTL gas-to-liquids
  • GTL is a refinery process used to convert natural gas or other gaseous hydrocarbons into longer-chain hydrocarbons.
  • GTL can be used to convert methane-rich gases into liquid fuels either via direct conversion or via syngas as an intermediate using the Fischer Tropsch process.
  • isomerization catalyst can be used with GTL to make Group III basestock.
  • the lubricant composition comprises at least one polymer (a “first polymers”) having a kinematic viscosity ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent, for example, equal to or greater than 35 percent or equal to or greater than 45 percent.
  • first polymers having a kinematic viscosity ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent, for example, equal to or greater than 35 percent or equal to or greater than 45 percent.
  • the first polymer comprises a minimum of 5 weight percent styrene.
  • the first polymer has a thickening efficiency (TE) equal to or greater than 2.0, for example, equal to or greater than 2.4 or equal to or greater than 2.8.
  • TE thickening efficiency
  • suitable first polymers comprise a normal block copolymer (i.e., true block copolymer) or a random block copolymer.
  • the normal block copolymer can be made from (1) conjugated dienes having from 4 to 10 carbon atoms, for example, from 4 to 6 carbon atoms or (2) from vinyl substituted aromatics having from 8 to 12 carbon atoms, for example, 8 or 9 carbon atoms.
  • the block copolymer is made from conjugated dienes.
  • Suitable conjugated dienes include piperylene, 2,3-dimethyl-1,3-butadiene, chloroprene, isoprene and 1,3-butadiene, with isoprene and 1,3-butadiene being particularly preferred. Mixtures of such conjugated dienes are useful.
  • the block copolymer is made from vinyl substituted aromatics.
  • Suitable vinyl substituted aromatics include styrene, alpha-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-tertiary-butylstyrene.
  • the normal block copolymers has a total of from 2 to 5, for example, from 2 or 3, polymer blocks of the vinyl substituted aromatic and the conjugated diene with at least one polymer block of said vinyl substituted aromatic and at least one polymer block of said conjugated diene being present.
  • the conjugate diene block is hydrogenated as more fully set forth hereinbelow.
  • the normal block copolymers can be linear block copolymers wherein a substantially long sequence of one monomeric unit (Block I) is linked with another substantially long sequence of a second (Block II), third (Block III), fourth (Block IV), or fifth (Block V) monomeric unit.
  • the vinyl substituted aromatic content of these copolymers i.e., the total amount of vinyl substituted aromatic blocks in the normal block copolymer
  • the aliphatic conjugated diene content (i.e., the total diene block content) of these copolymers is in the range of from 30 percent to 80 percent by weight, for example, from 40 percent to 60 percent by weight.
  • the described normal block copolymers can be prepared by conventional methods which are well known in the art.
  • the copolymers are prepared by anionic polymerization using, for example, an alkali metal hydrocarbon (e.g., sec-butyllithium) as a polymerization catalyst.
  • an alkali metal hydrocarbon e.g., sec-butyllithium
  • Infineum SV140 is a hydrogenated styrene-isoprene block available from Infineum U.S.A (Linden, N.J.).
  • the polymers of the invention will be introduced into lubricant compositions in the form of a concentrate as is well known in the art.
  • Concentrates comprise one or more components in oil.
  • Typical concentrates contain from 3 to 25 weight percent of the polymer.
  • the composition comprises more than one polymer.
  • the composition comprises a first polymer as described above and a “second polymer”.
  • Suitable examples of the second polymer include, but are not limited to, olefin polymers such as polybutene; hydrogenated polymers and copolymers and terpolymers of styrene with isoprene and/or butadiene; polymers of alkyl acrylates or alkyl methacrylates; copolymers of alkyl methacrylates with N-vinyl pyrrolidone or dimethylaminoalkyl methacrylate; post-grafted polymers of ethylenepropylene with an active monomer such as maleic anhydride; styrene-maleic anhydride polymers post-reacted with alcohols and amines. These can be used to provide the desired viscosity in the lubrication composition.
  • lubricant compositions for specific SAE Viscosity Grades exhibit lower HTHS values closer to the minimum HTHS than conventional lubricant compositions for that Grade.
  • the minimum HTHS for a 5W30 lubricant composition is 2.9. See Table 2 below for the SAE Engine Oil Viscosity Requirements Classifications which include minimum HTHS requirements.
  • ASTM D5293 (4) ASTM D4684: Note that the presence of any yield stress detectable by this method constitutes a failure regardless of viscosity. (5) ASTM D445 (6) ASTM D4683, CEC L-36-A-90 (ASTM D4741) or D5481 “Reprinted with permission form SAE J300 ⁇ 1999 Society of Automotive Engineers, Inc.”
  • the lubricant composition of the present invention encompasses different SAE J300 viscosity grades.
  • the lubricant composition of the present invention satisfies the requirements for SAE J300 viscosity grade 0Wx or 5Wx where x is 10, 20, 30 or 40.
  • the lubricant composition comprises a detergent inhibitor package.
  • the detergent inhibitor package comprises one or more of the following: metal or ash-containing detergents, antioxidants, anti-wear agents, rust inhibitors, anti-foaming agents, demulsifiers, pour point depressants, etc.
  • Metal-containing or ash-forming detergents function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
  • Detergents generally comprise a polar head with a long hydrophobic tail, with the polar head comprising a metal salt of an acidic organic compound.
  • the salts may contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts, and would typically have a total base number or TBN (as may be measured by ASTM D2896) of from 0 to 80. It is possible to include large amounts of a metal base by reacting an excess of a metal compound such as an oxide or hydroxide with an acidic gas such as carbon dioxide.
  • the resulting overbased detergent comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle, Such overbased detergents may have a TBN of 150 or greater, and typically of from 250 to 450 or more.
  • Detergents that can be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., sodium, potassium, lithium, calcium, and magnesium (With the constraints noted herein).
  • a metal particularly the alkali or alkaline earth metals, e.g., sodium, potassium, lithium, calcium, and magnesium (With the constraints noted herein).
  • the most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium an or magnesium with sodium.
  • Common metal detergents include overbased calcium sulfonates having a TBN greater than or equal to 250, for example, a TBN from 250 to 450: neutral and overbased calcium phenates having a TBN greater than or equal to 50; and sulfurized phenates having a TBN greater than or equal to 50.
  • Sulfonates can be prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene.
  • the alkylation can be carried out in the presence of a catalyst with alkylating agents having from 3 to more than 70 carbon atoms.
  • the alkaryl sulfonates usually contain from 9 to 80 or more carbon atoms per alkyl substituted aromatic moiety.
  • the oil soluble sulfonates or alkyl aryl sulfonic acids can be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates and ethers of the metal.
  • the amount of metal compound is chosen having regard to the desired TBN of the final product but typically ranges from 100 to 220 wt. percent of the stoichiometrically required.
  • Dihydrocarbyl dithiophosphate metal salts are frequently used as anti-wear and antioxidant agents.
  • the metal can be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper.
  • the zinc salts are typically used in lubricating oil in amounts of 0.1 to 10 wt. percent, for example, from 0.2 to 2 wt. percent, based upon the total weight of the lubricating oil composition. They can be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohol or a phenol with P 2 S 5 and then neutralizing the formed DDPA with a zinc compound.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid can be made by reacting mixtures of primary and secondary alcohols.
  • multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character.
  • any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most generally employed.
  • Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralization reaction.
  • Zinc dihydrocarbyl dithiophosphates are oil soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula:
  • R and R′ may be the same or different hydrocarbyl radicals containing from 1 to 18, for example, from 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals.
  • R and R′ groups are alkyl groups of 2 to 8 carbon atoms.
  • the radicals can, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.
  • the total number of carbon atoms (i.e. R and R′) in the dithiophosphoric acid will generally be 5 or greater.
  • the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates. Conveniently at least 50 (mole) percent of the alcohols used to introduce hydrocarbyl groups into the dithiophosphoric acids are secondary alcohols.
  • the alcohols used to introduce the hydrocarbyl groups can be more than 60 mole percent secondary or more than 90 mole percent secondary.
  • Metal dithiophosphates that are secondary in character give better wear control in tests such as the Sequence VE (ASTM D5302) and the GM 6.2L tests,
  • the high levels of nitrogenous TBN required by the present invention to control soot related viscosity may increase wear and corrosion performance.
  • Oxidation inhibitors or antioxidants reduce the tendency of mineral oils to deteriorate in service which deterioration can be evidence by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth.
  • oxidation inhibitors include hindered phenols, oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, phosphorous esters, metal thiocarbamates, oil soluble copper compounds as described in U.S. Pat. No. 4,867,890, and molybdenum containing compounds. Such compounds are utilized within the constraints noted herein.
  • the lubricant includes at least 0.0008 mole percent hindered phenol antioxidant.
  • hindered phenols are oil soluble phenols substituted at one or both ortho positions.
  • Suitable compounds include monohydric and mononuclear phenols such as 2,6-di-tertiary alkylphenols (e.g. 2,6 di-t-butylphenol, 2,4,6 tri-t-butyl phenol, 2-t-butyl phenol, 4-alkyl, 2,6, t-butyl phenol, 2,6 di-isopropylphenol, and 2,6 dimethyl, 4 t-butyl phenol).
  • hindered phenols include polyhydric and polynuclear phenols such as alkylene bridged hindered phenols (4,4 methylenebis(6 tert butyl-o-cresol), 4,4′-methylenebis(2-tert-amyl-o-cresol), and 2,2′-methylenebis(2,6-di-t-butylphenol).
  • alkylene bridged hindered phenols (4,4 methylenebis(6 tert butyl-o-cresol), 4,4′-methylenebis(2-tert-amyl-o-cresol), and 2,2′-methylenebis(2,6-di-t-butylphenol).
  • the hindered phenol can be borated or sulfurized.
  • Rust inhibitors selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkyene phenols, and anionic alkyl sulfonic acids can be used.
  • Copper and lead bearing corrosion inhibitors can be used.
  • such compounds are thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof.
  • Derivatives of 1, 3, 4 thiadiazoles such as those described in U.S. Pat. Nos. 2,719,125; 2,719,126; and 3,087,932; are typical.
  • Other similar materials are described in U.S. Pat. Nos. 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043; 4,188,299; and 4,193,882.
  • Other additives are the thio and polythio sulfenamides of thiadiazoles such as those described in UK. Patent Specification No. 1,560,830. Benzotriazoles derivatives also fall within this class of additives. When these compounds are included in the lubricating composition, they are typically present in an amount not exceeding 0.2 wt. percent active ingredient.
  • a small amount of a demulsifying component can be used.
  • a suitable demulsifying component is described in EP 330,522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol. A treat rate of 0.001 to 0.05 mass percent active ingredient is typical.
  • pour point depressants otherwise known as lube oil flow improvers, lower the minim temperature at which the fluid will flow or can be poured.
  • Such additives are well known. Typical of those additives which improve the low temperature fluidity of the fluid are C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers and polyalkylmethacrylates. Likewise, dialkyl fumarate and vinyl acetate can be used as compatibilizing agents.
  • Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • additives can provide a multiplicity of effects; thus for example, a single additive can act as a dispersant-oxidation inhibitor. This approach is well known and does not require further elaboration. It is important to note that addition of the other components noted above must comply with the limitations set forth herein.
  • the invention comprises one or more ashless dispersants.
  • the ashless dispersants can include the polyalkenyl or borated polyalkenyl succinimide where the alkenyl group is derived from a C 3 -C 4 olefin, especially polyisobutenyl having a number average molecular weight of about 700 to 5,000.
  • Other well known dispersants include the oil soluble polyol esters of hydrocarbon substituted succinic anhydride, e.g. polyisobutenyl succinic anhydride, and the oil soluble oxazoline and lactone oxazoline dispersants derived from hydrocarbon substituted succinic anhydride and di-substituted amino alcohols.
  • lubricant composition contains 0.5 to 5 wt. percent of ashless dispersant.
  • the present invention comprises ashless detergent.
  • ashless detergents and dispersants are so called despite the fact that, depending on their constitution, they may upon combustion yield a non-volatile material such as boric oxide or phosphorus pentoxide; however, they do not ordinarily contain metal and therefore do not yield a metal-containing ash on combustion.
  • a non-volatile material such as boric oxide or phosphorus pentoxide
  • Many types are known in the art, and are suitable for use in lubricating compositions. These include the following:
  • Interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates. Examples of these are described in the following patents which are hereby incorporated by reference: U.S. Pat. Nos. 3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; and 3,702,300.
  • the detergent inhibitor package of the present invention can contain phosphorus, sulfur, chlorine, ash, etc.
  • the lubricant composition comprises less than 0.08 weight percent of phosphorus.
  • the lubricant composition comprises less than 0.5 weight percent of sulfur.
  • the lubricant composition comprises less than 150 PPM, for example, less than 50 PPM of chlorine.
  • the lubricant composition comprises 0.35 to 2 mass percent of ash.
  • Examples 1-12 illustrate the present invention.
  • Various concentrates made by blending a first polymer concentrate and a commercially available SN 100 Group I base stock at a temperature between 60° C. and 70° C. for 45 minutes were used to formulate the different examples.
  • Different first polymer concentrates, Polymer Concentrates 1-3 were used to formulate the different examples.
  • Polymer Concentrate 1 is commercially available from Infineum USA as SV145;
  • Polymer Concentrate 2 is commercially available from Infineum USA as SV265;
  • Polymer Concentrate 3 is commercially available from Chevron Corporation as Paratone 8451.
  • the kinematic viscosity ratios and the shear stability indices (SSI) of the first polymer concentrates used in the examples are shown in Table 12.
  • Component 1 is a detergent inhibitor package commercially available from Infineum USA as P5224;
  • Component 2 is a pour point depressant commercially available from Infineum USA as V385; and
  • Component 3 is a detergent inhibitor package commercially available from Infineum USA as P6000.
  • Examples 1-3 are representative of 5W20 lubricant compositions. Compositional information for Examples 1-3 is shown in Table 3. Examples 4-6 are representative of 5W30 lubricant compositions. Compositional information for Examples 1-3 is shown in Table 5. Examples 7-9 are representative of 0W30 PAO lubricant compositions. Compositional information for Examples 7-9 is shown in Table 7. Examples 10-12 are representative of 0W20 PAO lubricant compositions. Compositional information for Examples 10-19 is shown in Table 9.
  • the kinematic viscosity of the exemplary compositions was measured at 100° C. and 150° C. was measured according to ASTM D445.
  • the HTHS of the lubricant compositions were made according to ASTM D4741. Results for the various examples are shown in Tables 4, 6, 8 and 10.
  • Examples 1-3 are illustrative of 5W20 lubricant compositions with Example 1 being illustrative of the present invention. As expected, Example 1 has the lowest HTHS of the exemplary 5W20 lubricant compositions.
  • Examples 4-6 are illustrative of 5W30 lubricant compositions with Example 4 being illustrative of the present invention. As expected, Example 4 has the lowest HITHS of the exemplary 5W30 lubricant compositions.
  • Examples 7-9 are illustrative of 0W30 PAO lubricant compositions with Example 7 being illustrative of the present invention. As expected, Example 7 has the lowest HTHS of the exemplary 5W30 PAO lubricant compositions.
  • Examples 10-12 are illustrative of 0W20 PAO lubricant compositions with Example 10 being illustrative of the present invention. As expected, Example 10 has the lowest HTHS of the exemplary 5W20 PAO lubricant compositions.
  • Basestock 1 19.70 4.26 125
  • Basestock 2 44.49 7.36 130
  • Basestock 3 19.64 4.03
  • Basestock 4 54.95 2.69
  • Basestock 5 17.61 3.98
  • Basestock 6 47.44 7.95
  • Basestock 7 18.79 4.26 138
  • the shear stability indices of the Polymer Concentrates in Table 12 were determined according to ASTM D6278 using polymer solutions prepared by blending Polymer Concentrates 1, 2 and 3, respectively, and a Group I basestock having a kv100 of 4.70 cSt. The kv100 of the solution was 15.0 ⁇ 0.2 cSt.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Lubricants (AREA)

Abstract

A lubricant composition that exhibits low high temperature high shear viscosity is disclosed. The lubricant composition is made up of a first polymer having a kinematic viscosity ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent and base oil having a viscosity index equal to or greater than 120.

Description

    FIELD OF THE INVENTION
  • The present invention relates to lubricant compositions which exhibit certain performance characteristics; particularly a low High-Temperature, High-Sheer viscosity measurement.
    • BACKGROUND OF THE INVENTION
  • Lubricant compositions are well known in the art. Lubricant compositions are typically made up of base oil and various additives. Lubricant compositions must met specific performance characteristics such as, but not limited to, kinematic viscosity and High-Temperature, High-Shear viscosity measurement (HTHS), depending on their end use.
  • It is known in the art that fuel economy of vehicles and the HTHS values of the lubricant composition used in the vehicle are related. Vehicles using lubricant compositions having lower HTHS values exhibit improved fuel economy. For every SAE Viscosity Grade, a minimum HTHS of the lubricant composition is specified in the SAE J300 Engine Oil Viscosity Classification. Therefore, a lubricant composition that has an HTHS that is at or near the minimum required for the SAE Viscosity Grade is expected to provide the best fuel economy.
  • The present invention provides a lubricant composition comprising base oil having a viscosity index equal to or greater than 120 that exhibits an HTHS at or near the minimum for its SAE Viscosity Grade. The present invention is a lubricant composition comprising base oil having a viscosity index equal to or greater than 120 and a first polymer having a kinematic viscosity ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent.
    • SUMMARY OF THE INVENTION
  • In a non-limiting embodiment, the present invention is a lubricant composition comprising: a first polymer having a kinematic viscosity as defined later in the specification ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent; and a base oil having a viscosity index equal to or greater than 120.
  • In another non-limiting embodiment, the present invention is a lubricant composition comprising: a polymer having a kinematic viscosity ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent; and a base oil having a viscosity index equal to or greater than 120, wherein the concentration of phosphorus in the lubricant composition is less than 0.08 weight percent and the concentration of sulfur is less than 0.5 weight percent.
    • DETAILED DESCRIPTION OF THE INVENTION
  • Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, dimensions, physical characteristics, processing parameters, and the like, used in the specification and claims are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Moreover, all ranges disclosed herein are to be understood to encompass the beginning and ending range values and any and all subranges subsumed therein. For example, a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 5.5 to 10. Any mentioning of a U.S. patent or patent document or literature reference in the following description also incorporates by reference that document herein and is to be understood to be incorporated in its entirety.
  • The following terms used herein are defined below.
  • (A) base oil-mixtures of one or more basestocks.
    (B) kinematic viscosity-temperature specific property measured according to ASTM D445.
    (C) kinematic viscosity ratio of a polymer—the kinematic viscosity of the polymer in solution at 150° C. (kv150) divided by the kinematic viscosity of the polymer in solution at 100° C. (kv100). The polymer in solution is prepared by diluting the viscosity modifier concentrate in an API Group I solvent neutral 100 base stock between 60° C. and 70° C. for 45 minutes. The kv100 and kv150 are measured according to ASTM D445.
  • Table 1 below shows the composition of three different polymer concentrates in solution as used herein as well as the kv100, kv150 and the kinematic viscosity ratios of the polymer solutions. The three polymer concentrates are commercially available. Polymer Concentrate 1 is commercially available from Infineum USA as SV145; Polymer Concentrate 2 is commercially available from Infineum USA as SV265; and Polymer Concentrate 3 is commercially available from Chevron Corporation as Paratone 8451.
  • TABLE 1
    Polymer Polymer Polymer
    Concentrate Concentrate Concentrate
    in Solution 1 in Solution 2 in Solution 3
    Component
    Polymer Concentrate 1 24.4
    Polymer Concentrate 2 23.0
    Polymer Concentrate 3 27.0
    API Group I 75.6 77.0 73.0
    solvent neutral 100 basestock
    Performance
    kv100 [cSt] 30.48 30.50 29.96
    kv150 [cSt] 4.65 12.44 11.65
    kv150/kv100 0.15 0.41 0.39

    (D) CCS at −30° C. [cp]—measured according to ASTM D5293.
    (E) HTHS at 150-C [cp]—measured according to ASTM D4741.
    (F) Shear Stability Index—determined according to ASTM D6278.
    (G) thickening efficiency—
  • TE = 1 c ln ( 2 ) 2 ln ( kv polymer + oil kv oil )
  • where c is wt % polymer, kv(polymer+oil) is kv100 of the polymer solution, and kv(oil) is kv100 of the oil. kv is measured according ASTM D445.
  • Various groups of base oils and basestocks are discussed herein. Definitions for the basestocks are the same as those found in the American Petroleum Institute (API) publication “Engine Oil Licensing and Certification System”, Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998.
  • The present invention is a lubricant composition comprising base oil having a viscosity index ranging of equal to or greater than 120 and a first polymer having a kinematic viscosity ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent.
  • In a non-limiting embodiment of the invention, the base oil comprises a Group III basestock. Group III basestocks contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 120. In another non-limiting embodiment of the invention, the base oil comprises a Group IV basestock. In yet another non-limiting embodiment of the invention, the base oil comprises a Group III basestock and a Group IV basestock. In another non-limiting embodiment of the invention, the base oil comprises Group IV and Group V basestocks. In yet another non-limiting embodiment of the invention, the base oil comprises Group II, Group IV and Group V basestocks.
  • In a non-limiting embodiment of the invention, the basestock is made using gas-to-liquids (“GTL”) process. GTL is a refinery process used to convert natural gas or other gaseous hydrocarbons into longer-chain hydrocarbons. For example, GTL can be used to convert methane-rich gases into liquid fuels either via direct conversion or via syngas as an intermediate using the Fischer Tropsch process. As is well known in the art, isomerization catalyst can be used with GTL to make Group III basestock.
  • According to the present invention, the lubricant composition comprises at least one polymer (a “first polymers”) having a kinematic viscosity ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent, for example, equal to or greater than 35 percent or equal to or greater than 45 percent.
  • In a non-limiting embodiment of the invention, the first polymer comprises a minimum of 5 weight percent styrene.
  • In yet another non-limiting embodiment of the invention, the first polymer has a thickening efficiency (TE) equal to or greater than 2.0, for example, equal to or greater than 2.4 or equal to or greater than 2.8.
  • In a non-limiting embodiment of the invention, suitable first polymers comprise a normal block copolymer (i.e., true block copolymer) or a random block copolymer. The normal block copolymer can be made from (1) conjugated dienes having from 4 to 10 carbon atoms, for example, from 4 to 6 carbon atoms or (2) from vinyl substituted aromatics having from 8 to 12 carbon atoms, for example, 8 or 9 carbon atoms.
  • In a non-limiting embodiment of the invention, the block copolymer is made from conjugated dienes. Suitable conjugated dienes include piperylene, 2,3-dimethyl-1,3-butadiene, chloroprene, isoprene and 1,3-butadiene, with isoprene and 1,3-butadiene being particularly preferred. Mixtures of such conjugated dienes are useful.
  • In another non-limiting embodiment of the invention, the block copolymer is made from vinyl substituted aromatics. Suitable vinyl substituted aromatics include styrene, alpha-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-tertiary-butylstyrene.
  • In a non-limiting embodiment of the invention, the normal block copolymers has a total of from 2 to 5, for example, from 2 or 3, polymer blocks of the vinyl substituted aromatic and the conjugated diene with at least one polymer block of said vinyl substituted aromatic and at least one polymer block of said conjugated diene being present. The conjugate diene block is hydrogenated as more fully set forth hereinbelow. The normal block copolymers can be linear block copolymers wherein a substantially long sequence of one monomeric unit (Block I) is linked with another substantially long sequence of a second (Block II), third (Block III), fourth (Block IV), or fifth (Block V) monomeric unit.
  • The following references disclose suitable copolymers and are hereby
  • incorporated by reference: U.S. Pat. No. 5,429,758; U.S. Pat. No. 5,429,758.
  • In this embodiment, the vinyl substituted aromatic content of these copolymers (i.e., the total amount of vinyl substituted aromatic blocks in the normal block copolymer) is in the range of from 20 percent to 70 percent by weight, for example, from 40 percent to 60 percent by weight. Thus, the aliphatic conjugated diene content (i.e., the total diene block content) of these copolymers is in the range of from 30 percent to 80 percent by weight, for example, from 40 percent to 60 percent by weight.
  • The described normal block copolymers can be prepared by conventional methods which are well known in the art. In a non-limiting embodiment of the invention, the copolymers are prepared by anionic polymerization using, for example, an alkali metal hydrocarbon (e.g., sec-butyllithium) as a polymerization catalyst.
  • A commercial example of a normal block copolymer as described above is Infineum SV140 which is a hydrogenated styrene-isoprene block available from Infineum U.S.A (Linden, N.J.).
  • Typically, the polymers of the invention will be introduced into lubricant compositions in the form of a concentrate as is well known in the art. Concentrates comprise one or more components in oil. Typical concentrates contain from 3 to 25 weight percent of the polymer.
  • In a non-limiting embodiment of the invention, the composition comprises more than one polymer. In his embodiment, the composition comprises a first polymer as described above and a “second polymer”. Suitable examples of the second polymer include, but are not limited to, olefin polymers such as polybutene; hydrogenated polymers and copolymers and terpolymers of styrene with isoprene and/or butadiene; polymers of alkyl acrylates or alkyl methacrylates; copolymers of alkyl methacrylates with N-vinyl pyrrolidone or dimethylaminoalkyl methacrylate; post-grafted polymers of ethylenepropylene with an active monomer such as maleic anhydride; styrene-maleic anhydride polymers post-reacted with alcohols and amines. These can be used to provide the desired viscosity in the lubrication composition.
  • According to the present invention, lubricant compositions for specific SAE Viscosity Grades exhibit lower HTHS values closer to the minimum HTHS than conventional lubricant compositions for that Grade. For example, the minimum HTHS for a 5W30 lubricant composition is 2.9. See Table 2 below for the SAE Engine Oil Viscosity Requirements Classifications which include minimum HTHS requirements.
  • TABLE 2
    SAE J300 Engine Oil Viscosity Requirements
    SAE Viscosity Grades For Engine Oils(1)(2)
    Low
    Temperature
    Low (° C.)
    Temperature Pumping Low-Shear- Low-Shear- High-Shear-
    (° C.) Viscosity(4), Rate Rate Rate
    Cranking cP Kinematic Kinematic Viscosity(6)
    SAE Viscosity(3), Max with Viscosity(5)(cSt) Viscosity(5)(cSt) (cP)
    Viscosity cP No Yield at 100° C. at 100° C. at 150° C.
    Grade Max Stress(4) Min Max Min
     0W 6200 at −35 60000 at −40 3.8 — —
     5W 6600 at −30 60000 at −35 3.8 — —
    10W 7000 at −25 60000 at −30 4.1 — —
    15W 7000 at −20 60000 at −25 5.6 — —
    20W 9500 at −15 60000 at −20 5.6 — —
    25W 13000 at −10  60000 at −15 9.3 — —
    20 — — 5.6 <9.3 2.6
    30 — — 9.3 <12.5 2.9
    40 — — 12.5 <16.3 2.9 (0W-40,
    5W-40, 10W-
    40 grades)
    40 — — 12.5 <16.3 3.7 (15W-40,
    20W-40, 25W-
    40, 40 grades)
    50 — — 16.3 <21.9 3.7
    60 — — 21.9 <26.1 3.7
    (1)Notes-1 cP = 1 mPa * s; 1 cSt = 1 mm2/S
    (2)All values are critical specifications as defined by ASTM D3244 (see text, Section 3).
    (3)ASTM D5293
    (4)ASTM D4684: Note that the presence of any yield stress detectable by this method constitutes a failure regardless of viscosity.
    (5)ASTM D445
    (6)ASTM D4683, CEC L-36-A-90 (ASTM D4741) or D5481
    “Reprinted with permission form SAE J300 © 1999 Society of Automotive Engineers, Inc.”
  • The lubricant composition of the present invention encompasses different SAE J300 viscosity grades. In various non-limiting embodiments, the lubricant composition of the present invention satisfies the requirements for SAE J300 viscosity grade 0Wx or 5Wx where x is 10, 20, 30 or 40.
  • In a non-limiting embodiment of the invention, the lubricant composition comprises a detergent inhibitor package. The detergent inhibitor package comprises one or more of the following: metal or ash-containing detergents, antioxidants, anti-wear agents, rust inhibitors, anti-foaming agents, demulsifiers, pour point depressants, etc.
  • Metal-containing or ash-forming detergents function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally comprise a polar head with a long hydrophobic tail, with the polar head comprising a metal salt of an acidic organic compound. The salts may contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts, and would typically have a total base number or TBN (as may be measured by ASTM D2896) of from 0 to 80. It is possible to include large amounts of a metal base by reacting an excess of a metal compound such as an oxide or hydroxide with an acidic gas such as carbon dioxide. The resulting overbased detergent comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle, Such overbased detergents may have a TBN of 150 or greater, and typically of from 250 to 450 or more.
  • Detergents that can be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., sodium, potassium, lithium, calcium, and magnesium (With the constraints noted herein). The most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium an or magnesium with sodium. Common metal detergents include overbased calcium sulfonates having a TBN greater than or equal to 250, for example, a TBN from 250 to 450: neutral and overbased calcium phenates having a TBN greater than or equal to 50; and sulfurized phenates having a TBN greater than or equal to 50.
  • Sulfonates can be prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene. The alkylation can be carried out in the presence of a catalyst with alkylating agents having from 3 to more than 70 carbon atoms. The alkaryl sulfonates usually contain from 9 to 80 or more carbon atoms per alkyl substituted aromatic moiety.
  • The oil soluble sulfonates or alkyl aryl sulfonic acids can be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates and ethers of the metal. The amount of metal compound is chosen having regard to the desired TBN of the final product but typically ranges from 100 to 220 wt. percent of the stoichiometrically required.
  • Dihydrocarbyl dithiophosphate metal salts are frequently used as anti-wear and antioxidant agents. The metal can be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. The zinc salts are typically used in lubricating oil in amounts of 0.1 to 10 wt. percent, for example, from 0.2 to 2 wt. percent, based upon the total weight of the lubricating oil composition. They can be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohol or a phenol with P2S5 and then neutralizing the formed DDPA with a zinc compound. For example, a dithiophosphoric acid can be made by reacting mixtures of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character. To make the zinc salt any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralization reaction.
  • Zinc dihydrocarbyl dithiophosphates are oil soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula:
  • Figure US20090156442A1-20090618-C00001
  • wherein R and R′ may be the same or different hydrocarbyl radicals containing from 1 to 18, for example, from 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. In a non-limiting embodiment, R and R′ groups are alkyl groups of 2 to 8 carbon atoms. Thus, the radicals can, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl. In order to obtain oil solubility, the total number of carbon atoms (i.e. R and R′) in the dithiophosphoric acid will generally be 5 or greater. The zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates. Conveniently at least 50 (mole) percent of the alcohols used to introduce hydrocarbyl groups into the dithiophosphoric acids are secondary alcohols.
  • Greater percentages of secondary alcohols can be used. In some instances, high nitrogen systems may be required. Thus, the alcohols used to introduce the hydrocarbyl groups can be more than 60 mole percent secondary or more than 90 mole percent secondary. Metal dithiophosphates that are secondary in character give better wear control in tests such as the Sequence VE (ASTM D5302) and the GM 6.2L tests, The high levels of nitrogenous TBN required by the present invention to control soot related viscosity may increase wear and corrosion performance.
  • Oxidation inhibitors or antioxidants reduce the tendency of mineral oils to deteriorate in service which deterioration can be evidence by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth. Such oxidation inhibitors include hindered phenols, oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, phosphorous esters, metal thiocarbamates, oil soluble copper compounds as described in U.S. Pat. No. 4,867,890, and molybdenum containing compounds. Such compounds are utilized within the constraints noted herein.
  • In one aspect of the invention the lubricant includes at least 0.0008 mole percent hindered phenol antioxidant. Generally, hindered phenols are oil soluble phenols substituted at one or both ortho positions. Suitable compounds include monohydric and mononuclear phenols such as 2,6-di-tertiary alkylphenols (e.g. 2,6 di-t-butylphenol, 2,4,6 tri-t-butyl phenol, 2-t-butyl phenol, 4-alkyl, 2,6, t-butyl phenol, 2,6 di-isopropylphenol, and 2,6 dimethyl, 4 t-butyl phenol). Other suitable hindered phenols include polyhydric and polynuclear phenols such as alkylene bridged hindered phenols (4,4 methylenebis(6 tert butyl-o-cresol), 4,4′-methylenebis(2-tert-amyl-o-cresol), and 2,2′-methylenebis(2,6-di-t-butylphenol). The hindered phenol can be borated or sulfurized.
  • Rust inhibitors selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkyene phenols, and anionic alkyl sulfonic acids can be used.
  • Copper and lead bearing corrosion inhibitors can be used. Typically such compounds are thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof. Derivatives of 1, 3, 4 thiadiazoles such as those described in U.S. Pat. Nos. 2,719,125; 2,719,126; and 3,087,932; are typical. Other similar materials are described in U.S. Pat. Nos. 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043; 4,188,299; and 4,193,882. Other additives are the thio and polythio sulfenamides of thiadiazoles such as those described in UK. Patent Specification No. 1,560,830. Benzotriazoles derivatives also fall within this class of additives. When these compounds are included in the lubricating composition, they are typically present in an amount not exceeding 0.2 wt. percent active ingredient.
  • A small amount of a demulsifying component can be used. A suitable demulsifying component is described in EP 330,522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol. A treat rate of 0.001 to 0.05 mass percent active ingredient is typical.
  • Pour point depressants, otherwise known as lube oil flow improvers, lower the minim temperature at which the fluid will flow or can be poured. Such additives are well known. Typical of those additives which improve the low temperature fluidity of the fluid are C8 to C18 dialkyl fumarate/vinyl acetate copolymers and polyalkylmethacrylates. Likewise, dialkyl fumarate and vinyl acetate can be used as compatibilizing agents.
  • Incompatibility can occur when certain types of polymers for use in the manufacture of motor oil viscosity modifiers are dissolved in basestock. An uneven molecular dispersion of polymer which gives the mixture either a tendency to separate or a grainy appearance ensues. The problem is solved by using a compatibility agent having a hydrocarbon group attached to a functional group that serves to break up or prevent packing.
  • Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • Some of the above-mentioned additives can provide a multiplicity of effects; thus for example, a single additive can act as a dispersant-oxidation inhibitor. This approach is well known and does not require further elaboration. It is important to note that addition of the other components noted above must comply with the limitations set forth herein.
  • In a non-limiting embodiment, the invention comprises one or more ashless dispersants. The ashless dispersants can include the polyalkenyl or borated polyalkenyl succinimide where the alkenyl group is derived from a C3-C4 olefin, especially polyisobutenyl having a number average molecular weight of about 700 to 5,000. Other well known dispersants include the oil soluble polyol esters of hydrocarbon substituted succinic anhydride, e.g. polyisobutenyl succinic anhydride, and the oil soluble oxazoline and lactone oxazoline dispersants derived from hydrocarbon substituted succinic anhydride and di-substituted amino alcohols.
  • In a non-limiting embodiment, lubricant composition contains 0.5 to 5 wt. percent of ashless dispersant.
  • In a non-limiting embodiment, the present invention comprises ashless detergent. These ashless detergents and dispersants are so called despite the fact that, depending on their constitution, they may upon combustion yield a non-volatile material such as boric oxide or phosphorus pentoxide; however, they do not ordinarily contain metal and therefore do not yield a metal-containing ash on combustion. Many types are known in the art, and are suitable for use in lubricating compositions. These include the following:
  • (1) Reaction products of carboxylic acids (or derivatives thereof) containing at least 34 with nitrogen containing compounds such as amines, organic hydroxy compounds such as phenols and alcohols and, or basic inorganic materials. Examples of these are described in the following patents: U.S. Pat. Nos. 3,219,666; 4,234,435; 4,904,401; and 6,165,235 which are hereby incorporated by reference.
  • (2) Reaction products of relatively high molecular weight aliphatic or alicyclic halides with amines such as oxyalkylene polyamines. Examples of these are described for in the following patents which are hereby incorporated by reference: U.S. Pat. Nos. 3,275,554; 3,438,757; 3,454,555; and 3,565,804.
  • (3) Reaction products of alkyl phenols in which the alkyl group contains at least 30 carbon atoms with aldehydes and amines which may be characterized as “Mannich dispersants.” Examples of these are described in the following patents which are hereby incorporated by reference: U.S. Pat. Nos. 3,649,229; 3,697,574; 3,725,277; 3,725,480; 3,726,882; and 3,980,569.
  • (4) Products obtained by post-treating the mine or Mannich dispersants with such reagents as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like. Examples of these are described in the following patents which are hereby incorporated by reference: U.S. Pat. Nos. 3,639,242; 3,649,229; 3,649,659; 3,658,836; 3,697,574; 3,702,757; 3,703,536; 3,704,308; and 3,708,422.
  • (5) Interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates. Examples of these are described in the following patents which are hereby incorporated by reference: U.S. Pat. Nos. 3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; and 3,702,300.
  • The detergent inhibitor package of the present invention can contain phosphorus, sulfur, chlorine, ash, etc. In a non-limiting embodiment of the invention, the lubricant composition comprises less than 0.08 weight percent of phosphorus. In another non-limiting embodiment of the invention, the lubricant composition comprises less than 0.5 weight percent of sulfur. In yet another non-limiting embodiment of the invention, the lubricant composition comprises less than 150 PPM, for example, less than 50 PPM of chlorine. And, in another non-limiting embodiment of the invention, the lubricant composition comprises 0.35 to 2 mass percent of ash.
    • EXAMPLES
  • The following non-limiting examples, Examples 1-12, illustrate the present invention. Various concentrates made by blending a first polymer concentrate and a commercially available SN 100 Group I base stock at a temperature between 60° C. and 70° C. for 45 minutes were used to formulate the different examples. Different first polymer concentrates, Polymer Concentrates 1-3, were used to formulate the different examples. Polymer Concentrate 1 is commercially available from Infineum USA as SV145; Polymer Concentrate 2 is commercially available from Infineum USA as SV265; and Polymer Concentrate 3 is commercially available from Chevron Corporation as Paratone 8451. The kinematic viscosity ratios and the shear stability indices (SSI) of the first polymer concentrates used in the examples are shown in Table 12.
  • Several different grades of lubricant compositions were prepared by blending various base stocks with the concentrates described above according to well known methods and techniques. The viscometric properties of the different basestocks, Basestock 1-7, used to make the examples are described in Table 11.
  • In the various examples, Component 1 is a detergent inhibitor package commercially available from Infineum USA as P5224; Component 2 is a pour point depressant commercially available from Infineum USA as V385; and Component 3 is a detergent inhibitor package commercially available from Infineum USA as P6000.
  • Examples 1-3 are representative of 5W20 lubricant compositions. Compositional information for Examples 1-3 is shown in Table 3. Examples 4-6 are representative of 5W30 lubricant compositions. Compositional information for Examples 1-3 is shown in Table 5. Examples 7-9 are representative of 0W30 PAO lubricant compositions. Compositional information for Examples 7-9 is shown in Table 7. Examples 10-12 are representative of 0W20 PAO lubricant compositions. Compositional information for Examples 10-19 is shown in Table 9.
  • The kinematic viscosity of the exemplary compositions was measured at 100° C. and 150° C. was measured according to ASTM D445. The HTHS of the lubricant compositions were made according to ASTM D4741. Results for the various examples are shown in Tables 4, 6, 8 and 10.
  • TABLE 3
    Compositional Information for Exemplary 5W20 Lubricants
    Component Ex. 1 [wt %] Ex. 2 [wt %] Ex. 3 [wt %]
    Component 1 9.60 9.60 9.60
    Basestock 1 38.36 39.31 39.95
    Basestock 2 46.90 47.90 46.63
    Polymer Concentrate 1 4.93 0.00 0.00
    Polymer Concentrate 2 0.00 2.99 0.00
    Polymer Concentrate 3 0.00 0.00 3.61
    Component 2 0.20 0.20 0.20
  • TABLE 4
    Performance Information for Exemplary 5W20 Lubricants
    Ex. 1 Ex. 2 Ex. 3
    Kv100 [cSt] 8.56 8.66 8.73
    CCS at −30° C. [cp] 5570 5620 5440
    HTHS at 150° C. [cp] 2.61 2.71 2.77
    • Conclusion
  • Examples 1-3 are illustrative of 5W20 lubricant compositions with Example 1 being illustrative of the present invention. As expected, Example 1 has the lowest HTHS of the exemplary 5W20 lubricant compositions.
  • TABLE 5
    Compositional Information for Exemplary 5W30 Ultra Lubricants
    Component Ex. 4 [wt %] Ex. 5 [wt %] Ex. 6 [wt %]
    Component 1 9.60 9.60 9.60
    Basestock 1 30.85 32.68 32.12
    Basestock 2 50.35 52.00 51.64
    Polymer Concentrate 1 9.00 0.00 0.00
    Polymer Concentrate 2 0.00 5.52 0.00
    Polymer Concentrate 3 0.00 0.00 6.44
    Component 2 0.20 0.20 0.20
  • TABLE 6
    Performance Information for Exemplary 5W30 Ultra Lubricants
    Ex. 4 Ex. 5 Ex. 6
    kv100 [cSt] 10.82 10.81 10.86
    CCS at −30° C. [cp] 6250 6510 6470
    HTHS at 150° C. [cp] 2.93 3.12 3.22
    • Conclusion
  • Examples 4-6 are illustrative of 5W30 lubricant compositions with Example 4 being illustrative of the present invention. As expected, Example 4 has the lowest HITHS of the exemplary 5W30 lubricant compositions.
  • TABLE 7
    Compositional Information for Exemplary 0W30 PAO Lubricants
    Component Ex. 7 [wt %] Ex. 8 [wt %] Ex. 9 [wt %]
    Component 3 12.00 12.00 12.00
    Polymer Concentrate 1 9.71 0.00 0.00
    Polymer Concentrate 2 0.00 6.09 0.00
    Polymer Concentrate 3 0.00 0.00 6.91
    Basestock 7 2.00 2.00 2.00
    Basestock 5 45.05 48.26 47.55
    Basestock 6 31.04 31.45 31.34
    Component 2 0.20 0.20 0.20
  • TABLE 8
    Performance Information for Exemplary 0W30 PAO Lubricants
    Ex. 7 Ex. 8 Ex. 9
    kv100 [cSt] 10.69 10.82 10.82
    CCS at −35° C. [cp] 5930 5870 5670
    HTHS at 150° C. [cp] 2.93 3.14 3.28
    • Conclusion
  • Examples 7-9 are illustrative of 0W30 PAO lubricant compositions with Example 7 being illustrative of the present invention. As expected, Example 7 has the lowest HTHS of the exemplary 5W30 PAO lubricant compositions.
  • TABLE 9
    Compositional Information for Exemplary 0W20 PAO Lubricants
    Component Ex. 10 [wt %] Ex. 11 [wt %] Ex. 12 [wt %]
    Component 3 12.00 12.00 12.00
    Polymer Concentrate 1 5.30 0.00 0.00
    Polymer Concentrate 2 0.00 3.23 0.00
    Polymer Concentrate 3 0.00 0.00 3.68
    Basestock 7 2.00 2.00 2.00
    Basestock 4 46.85 48.92 48.47
    Basestock 5 33.65 33.65 33.65
    Component 2 0.20 0.20 0.20
  • TABLE 10
    Performance Information for Exemplary 0W20 PAO Lubricants
    Ex. 10 Ex. 11 Ex. 12
    kv100 [cSt] 8.83 8.91 8.93
    CCS at −35° C. [cp] 5720 5620 5540
    HTHS at 150° C. [cp] 2.70 2.80 2.87
    • Conclusion
  • Examples 10-12 are illustrative of 0W20 PAO lubricant compositions with Example 10 being illustrative of the present invention. As expected, Example 10 has the lowest HTHS of the exemplary 5W20 PAO lubricant compositions.
  • TABLE 11
    Viscosities of the Basestocks
    Basestock kv at 40° C. kv at 100° C. VI
    Basestock 1 19.70 4.26 125
    Basestock 2 44.49 7.36 130
    Basestock 3 19.64 4.03 103
    Basestock 4 54.95 2.69 104
    Basestock 5 17.61 3.98 126
    Basestock 6 47.44 7.95 139
    Basestock 7 18.79 4.26 138
  • TABLE 12
    Description of Polymer Concentrates 1-3
    Kinematic Viscosity Shear Stability Index
    Ratio [%]
    Polymer Concentrate 1 0.15 52.8
    Polymer Concentrate 2 0.41 7.0
    Polymer Concentrate 3 0.39 49.7
  • The shear stability indices of the Polymer Concentrates in Table 12 were determined according to ASTM D6278 using polymer solutions prepared by blending Polymer Concentrates 1, 2 and 3, respectively, and a Group I basestock having a kv100 of 4.70 cSt. The kv100 of the solution was 15.0±0.2 cSt.

Claims (13)

1. A lubricant composition comprising:
a first polymer having a kinematic viscosity ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent; and
base oil having a viscosity index equal to or greater than 120.
2. A lubricant composition according to claim 1 where the first polymer comprises a minimum of 5 weight percent styrene.
3. A lubricant composition according to claim 1 where the first polymer comprises a normal block copolymer (i.e., true block copolymer) or a random block copolymer.
4. A lubricant composition according to claim 1 further comprising a second polymer.
5. A lubricant composition according to claim 4 wherein the second polymer is selected from a group comprising olefin polymers; hydrogenated polymers and copolymers and terpolymers of styrene with isoprene and/or butadiene; polymers of alkyl acrylates or alkyl methacrylates; copolymers of alkyl methacrylates with N-vinyl pyrrolidone or dimethylaminoalkyl methacrylate; post-grafted polymers of ethylenepropylene with an active monomer such as maleic anhydride; styrene-maleic anhydride polymers post-reacted with alcohols and amines.
6. A lubricant composition according to claim 1 comprising a detergent inhibitor package comprising one or more of the following: metal or ash-containing detergents, antioxidants, anti-wear agents, rust inhibitors, anti-foaming agents, demulsifiers, rust inhibitors, ashless detergents and pour point depressants.
7. A lubricant composition according to claim 6 having a concentration of phosphorus less than 0.08 weight percent.
8. A lubricant composition according to claim 6 having a concentration of sulfur less than 0.5 weight percent.
9. A lubricant composition according to claim 6 having a concentration of chlorine less than 150 PPM.
10. A lubricant composition according to claim 6 having an ash content ranging from 0.35 to 2 mass percent.
11. A lubricant composition according to claim 1 that satisfies the requirements for SAE J300 viscosity grade 0Wx or 5Wx where x is 10, 20, 30 or 40.
12. A lubricant composition comprising:
a polymer having a kinematic viscosity ratio less than or equal to 0.25 and a shear stability index (SSI) equal to or greater than 20 percent; and
a. base oil having a viscosity index equal to or greater than 120,
wherein the concentration of phosphorus in the lubricant composition is less than 0.08 weight percent and the concentration of sulfur is less than 0.5 weight percent.
13. A lubricant composition according to claim 12 wherein the base oil comprises a Group III base stock and/or a Group IV base stock.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468347A (en) * 2013-08-03 2013-12-25 龚金玉 Viscosity index improver for recombined type lubrication oil
US20220081641A1 (en) * 2020-09-17 2022-03-17 Exxonmobil Research And Engineering Company Diluent oils for viscosity modifiers and additive packages

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2154230A1 (en) * 2008-08-08 2010-02-17 Afton Chemical Corporation Lubricant additive compositions having improved viscosity index increasing properties
WO2014031508A1 (en) * 2012-08-20 2014-02-27 The Lubrizol Corporation Lubricating composition including esterified copolymer and diene rubber polymer

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3775329A (en) * 1970-11-13 1973-11-27 Shell Oil Co Lubricant compositions containing a viscosity index improver
US4594378A (en) * 1985-03-25 1986-06-10 The Lubrizol Corporation Polymeric compositions, oil compositions containing said polymeric compositions, transmission fluids and hydraulic fluids
US5068047A (en) * 1989-10-12 1991-11-26 Exxon Chemical Patents, Inc. Visosity index improver
US5146021A (en) * 1991-04-17 1992-09-08 Mobil Oil Corporation VI enhancing compositions and Newtonian lube blends
US5458791A (en) * 1994-07-01 1995-10-17 Shell Oil Company Star polymer viscosity index improver for oil compositions
US5458792A (en) * 1994-08-11 1995-10-17 Shell Oil Company Asymmetric triblock copolymer viscosity index improver for oil compositions
US6232279B1 (en) * 1996-11-25 2001-05-15 Exxon Research And Engineering Company Fuel-economy lubrication-effective engine oil composition
US20030013623A1 (en) * 2001-05-01 2003-01-16 Kwok-Leung Tse Olefin copolymer viscocity index improvers
US20030073785A1 (en) * 2001-05-31 2003-04-17 Keiji Okada Olefin block copolymer, viscosity index improver for lubricating oils and lubricating oil composition
US20030186824A1 (en) * 2001-09-25 2003-10-02 Pennzoil-Quaker State Company Environmentally friendly lubricants
US20040129603A1 (en) * 2002-10-08 2004-07-08 Fyfe Kim Elizabeth High viscosity-index base stocks, base oils and lubricant compositions and methods for their production and use
US20040154957A1 (en) * 2002-12-11 2004-08-12 Keeney Angela J. High viscosity index wide-temperature functional fluid compositions and methods for their making and use
US20060211586A1 (en) * 2005-03-16 2006-09-21 The Lubrizol Corporation Viscosity improver compositions providing improved low temperature characteristics to lubricating oil
US20070105731A1 (en) * 2005-11-04 2007-05-10 Chin Chu Lubricating oil compositions

Family Cites Families (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2719126A (en) 1952-12-30 1955-09-27 Standard Oil Co Corrosion inhibitors and compositions containing same
US2719125A (en) 1952-12-30 1955-09-27 Standard Oil Co Oleaginous compositions non-corrosive to silver
DE1248643B (en) 1959-03-30 1967-08-31 The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) Process for the preparation of oil-soluble aylated amines
US3087932A (en) 1959-07-09 1963-04-30 Standard Oil Co Process for preparing 2, 5-bis(hydrocarbondithio)-1, 3, 4-thiadiazole
US3449250A (en) 1962-05-14 1969-06-10 Monsanto Co Dispersency oil additives
US3329658A (en) 1962-05-14 1967-07-04 Monsanto Co Dispersency oil additives
NL137371C (en) 1963-08-02
US3658836A (en) 1964-04-16 1972-04-25 Monsanto Co Hydroxyboroxin-amine salts
NL145565B (en) 1965-01-28 1975-04-15 Shell Int Research PROCESS FOR PREPARING A LUBRICANT COMPOSITION.
US3574576A (en) 1965-08-23 1971-04-13 Chevron Res Distillate fuel compositions having a hydrocarbon substituted alkylene polyamine
US3697574A (en) 1965-10-22 1972-10-10 Standard Oil Co Boron derivatives of high molecular weight mannich condensation products
US3704308A (en) 1965-10-22 1972-11-28 Standard Oil Co Boron-containing high molecular weight mannich condensation
US3413347A (en) 1966-01-26 1968-11-26 Ethyl Corp Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines
US3702757A (en) 1967-03-09 1972-11-14 Chevron Res Phosphate ester amine salts useful as fuel detergents and anti-icing agents
US3519565A (en) 1967-09-19 1970-07-07 Lubrizol Corp Oil-soluble interpolymers of n-vinylthiopyrrolidones
US3703536A (en) 1967-11-24 1972-11-21 Standard Oil Co Preparation of oil-soluble boron derivatives of an alkylene polyamine-substituted phenol-formaldehyde addition product
GB1244435A (en) 1968-06-18 1971-09-02 Lubrizol Corp Oil-soluble graft polymers derived from degraded ethylene-propylene interpolymers
US3726882A (en) 1968-11-08 1973-04-10 Standard Oil Co Ashless oil additives
US3725480A (en) 1968-11-08 1973-04-03 Standard Oil Co Ashless oil additives
US3702300A (en) 1968-12-20 1972-11-07 Lubrizol Corp Lubricant containing nitrogen-containing ester
US3649229A (en) 1969-12-17 1972-03-14 Mobil Oil Corp Liquid hydrocarbon fuels containing high molecular weight mannich bases
US3639242A (en) 1969-12-29 1972-02-01 Lubrizol Corp Lubricating oil or fuel containing sludge-dispersing additive
US3649659A (en) 1970-03-24 1972-03-14 Mobil Oil Corp Coordinated complexes of mannich bases
US3708422A (en) 1971-01-29 1973-01-02 Cities Service Oil Co Electric discharge machining fluid
US3904537A (en) 1972-05-03 1975-09-09 Lubrizol Corp Novel disulfides derived from 1,2,4-thiadiazole
US3821236A (en) 1972-05-03 1974-06-28 Lubrizol Corp Certain 2-halo-1,2,4-thiadiazole disulfides
US4193882A (en) 1973-07-06 1980-03-18 Mobil Oil Corporation Corrosion inhibited lubricant composition
US4136043A (en) 1973-07-19 1979-01-23 The Lubrizol Corporation Homogeneous compositions prepared from dimercaptothiadiazoles
US3980569A (en) 1974-03-15 1976-09-14 The Lubrizol Corporation Dispersants and process for their preparation
GB1560830A (en) 1975-08-08 1980-02-13 Exxon Research Engineering Co Sulphenamides
US4097387A (en) 1976-09-03 1978-06-27 Standard Oil Company (Indiana) Olefin-dimercapto-thiadiazole compositions and process
US4107059A (en) 1977-06-27 1978-08-15 Pennwalt Corporation Polymer of 1,2,4-thiadiazole and lubricants containing it as an additive
US4188299A (en) 1978-05-17 1980-02-12 Standard Oil Company (Indiana) Oil soluble dithiophosphoric acid derivatives of mercaptothiadiazoles
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
GB2056482A (en) 1979-08-13 1981-03-18 Exxon Research Engineering Co Lubricating oil compositions
CA1339430C (en) 1985-12-19 1997-09-02 Katsumi Hayashi Graft copolymers prepared from solvent-free reactions and dispersant derivatives thereof
IL89210A (en) 1988-02-26 1992-06-21 Exxon Chemical Patents Inc Lubricating oil compositions containing demulsifiers
US4904401A (en) 1988-06-13 1990-02-27 The Lubrizol Corporation Lubricating oil compositions
EP0425027B1 (en) * 1989-10-26 1995-06-14 Shell Internationale Researchmaatschappij B.V. Star shaped polymer, its preparation and lubricating compositions containing it
US6165235A (en) 1997-08-26 2000-12-26 The Lubrizol Corporation Low chlorine content compositions for use in lubricants and fuels
US6713438B1 (en) * 1999-03-24 2004-03-30 Mobil Oil Corporation High performance engine oil
ES2584163T3 (en) * 2003-03-28 2016-09-26 The Lubrizol Corporation Viscosity enhancing compositions that provide the lubricating oil with improved low temperature characteristics
ATE552328T1 (en) * 2005-11-03 2012-04-15 Infineum Int Ltd LINEAR DIBLOCK COPOLYMERS AS ANTI-WEAR ADDITIVES FOR LUBRICANTS IN COMBUSTION ENGINE CRANKCASES
EP2380952A1 (en) * 2006-10-24 2011-10-26 Total Raffinage Marketing Multi-functional lubricating fluid

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3775329A (en) * 1970-11-13 1973-11-27 Shell Oil Co Lubricant compositions containing a viscosity index improver
US4594378A (en) * 1985-03-25 1986-06-10 The Lubrizol Corporation Polymeric compositions, oil compositions containing said polymeric compositions, transmission fluids and hydraulic fluids
US5068047A (en) * 1989-10-12 1991-11-26 Exxon Chemical Patents, Inc. Visosity index improver
US5146021A (en) * 1991-04-17 1992-09-08 Mobil Oil Corporation VI enhancing compositions and Newtonian lube blends
US5458791A (en) * 1994-07-01 1995-10-17 Shell Oil Company Star polymer viscosity index improver for oil compositions
US5458792A (en) * 1994-08-11 1995-10-17 Shell Oil Company Asymmetric triblock copolymer viscosity index improver for oil compositions
US6232279B1 (en) * 1996-11-25 2001-05-15 Exxon Research And Engineering Company Fuel-economy lubrication-effective engine oil composition
US20030013623A1 (en) * 2001-05-01 2003-01-16 Kwok-Leung Tse Olefin copolymer viscocity index improvers
US20030073785A1 (en) * 2001-05-31 2003-04-17 Keiji Okada Olefin block copolymer, viscosity index improver for lubricating oils and lubricating oil composition
US20030186824A1 (en) * 2001-09-25 2003-10-02 Pennzoil-Quaker State Company Environmentally friendly lubricants
US20040129603A1 (en) * 2002-10-08 2004-07-08 Fyfe Kim Elizabeth High viscosity-index base stocks, base oils and lubricant compositions and methods for their production and use
US20040154957A1 (en) * 2002-12-11 2004-08-12 Keeney Angela J. High viscosity index wide-temperature functional fluid compositions and methods for their making and use
US20060211586A1 (en) * 2005-03-16 2006-09-21 The Lubrizol Corporation Viscosity improver compositions providing improved low temperature characteristics to lubricating oil
US20070105731A1 (en) * 2005-11-04 2007-05-10 Chin Chu Lubricating oil compositions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468347A (en) * 2013-08-03 2013-12-25 龚金玉 Viscosity index improver for recombined type lubrication oil
CN103468347B (en) * 2013-08-03 2016-04-27 深圳昆油石化技术有限公司 A kind of recombinant type lubricating oil viscosity index improver
US20220081641A1 (en) * 2020-09-17 2022-03-17 Exxonmobil Research And Engineering Company Diluent oils for viscosity modifiers and additive packages
US11505761B2 (en) * 2020-09-17 2022-11-22 Exxon Mobil Technology and Engineering Company Diluent oils for viscosity modifiers and additive packages

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