US3668125A - Block copolymers as viscosity index improvers for lubricating oils - Google Patents
Block copolymers as viscosity index improvers for lubricating oils Download PDFInfo
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- US3668125A US3668125A US884720A US3668125DA US3668125A US 3668125 A US3668125 A US 3668125A US 884720 A US884720 A US 884720A US 3668125D A US3668125D A US 3668125DA US 3668125 A US3668125 A US 3668125A
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- hydrogenated
- lubricating
- viscosity index
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- viscosity
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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
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
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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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
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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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
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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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
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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
- C10N2040/02—Bearings
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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
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- Mineral lubricating oils have been modified by a vast array of additives for purposes of improving viscosity index, thermal stability, oxidation stability, detergency, and other properties.
- the viscosity index is highly important especially in multigrade oils to provide lubricating oil compositions having much flatter viscosity-temperature curve than the unmodified oil. It is especially vital that the lubricating oil compositions exhibit specified maximum viscosities at relatively low temperatures and specified minimum viscosities at relatively elevated temperatures.
- the viscosity index of mineral lubricants has been altered by the presence of high molecular weight polymeric additives such as polymethacrylates.
- additives are found to be sensitive to thermal or oxidative degradation and particularly to degradation under the degree of shear which is experienced during dynamic utilization of the lubricant in machinery and the like.
- the additive may be promising as a viscosity index improver in mineral lubricants prior to its exposure to shear forces, in many instances it is found that many of the compositions rapidly lose their initial beneficial properties and gradually revert to the undesirable viscosity-temperature relationships of unmodified oil.
- any potential lubricating oil additives In addition to the properties of improving viscosity index and of being stable under conditions of high shear, it is necessary for any potential lubricating oil additives to have two other important properties, namely, compatibility with the lubricating oil and stability under conditions of oxidation which would be reasonably expected to be encountered under conditions of storage and use of such compositions.
- improved lubricating compositions comprising a mineral oil and as a viscosity index improver therefor 075-5 .0 percent by weight of a block copolymer having at least three polymer blocks C and D, blocks C being hydrogenated monovinyl arene polymers, having average molecular weights of 5,000-50,000 and blocks D are polymer blocks of the group consisting of alpha olefin polymers and hydrogenated conjugated diene polymers wherein at least 50 percent of the original olefinic double bonds have been reduced by hydrogenation said block having average molecular weight between about 10,000 and 1,000,000.
- an improved process of lubrication comprising lubricating relatively moving metallic surfaces with the mineral oil compositions just described.
- the mineral oils particularly contemplated for use in the present compositions particularly useful for engine lubricants generally have viscosities between about 150 and about 250 SSU at F. and generally are described as having SAE grades of 5-50. These are usually mineral oil distillates but may comprise or contain mineral oil residuals as long as the compositions has lubricating properties. While low viscosity index mineral lubricants are employed, it is much more desirable to utilize those having viscosity indexes between about and about 200, the higher the better, especially when multigrade lubricants are being compounded. Multi-grade lubricams are especially contemplated such as 10/30 or 20/40 oils either for summer or winter use. Oils suitable in greases, hydraulic oils, open gear lubricants and other lubricating situations also are contemplated.
- the essence thereof lies primarily in the discovery that certain and only certain hydrogenated block copolymers are not only compatible with mineral oillubricants but-also substantially improve the viscosity indexes thereof and exhibit a surprising and unaccountable degree of stability under the rates of shear expected and encountered during lubricated operations. Moreover, due to the substantial degree of hydrogenation as more particularly described hereinafter, the polymers are especially stable even under oxidizing conditions. Furthermore, one of the aspects of the present invention lies in the relative low molecular weight of the polymers utilized therein as compared with the substantially higher molecular weight polymers utilized by the prior art.
- the stability of the polymers of this invention under degrees of thermal stress, oxidative influences and particularly under shear is not only highly unexpected but essential to their success in lubricating processes. Contrary to the scission which may occur when a random copolymer or homopolymer degrades, the permanent scission of a block copolymer will result in catastrophic degradation of its physical properties as well as of its molecular structure.
- block copolymers it is essential for the block copolymers to be compatible with the mineral oils in which they are utilized if they are to be successful viscosity index improving additives. For this purpose its necessary to carefully select the block molecular weights and type of block which in the entire structure of the block copolymer will be compatible with the lubricating oil. This may of course vary to a certain degree depending upon the aromatic and aliphatic contents of such oils. However, the generic aspect of the present invention broadly contemplates the several types of block copolymers which will be suitable in this respect.
- the block copolymers as represented hereinbefore may be either linear or branched in its structure, the linear species represented by the general formula C(DC),, while the branched configuration is represented by the general configuration CD(DC),,.
- C is a hydrogenated monovinyl arene polymer block wherein at least 50 percent of the original aromatic double bonds are reduced by hydrogenation, having an average molecular weight between about 5,000 and 50,000.
- Blocks D are either aliphatic mono-alphaolefin polymer blocks or hydrogenated conjugated diene polymer blocks in which at least 50 percent of the original diene unsaturation is reduced by hydrogenation; said blocks D having average molecular weights of 10,000-1,000,000, preferably 15,000-200,000.
- the most simple linear block copolymer of this type is hydrogenated polystyrenehydrogenated polyisoprene-hydrogenated polystyrene or polyvinylcyclohexane-EPR-polyvinylcyclohexane and their counterparts wherein the center block is hydrogenated polybutadiene, preferably having a 1,2 content of 30-60 percent.
- EPR refers to an ethylene/propylene random copolymeric block.
- the conjugated dienes which may be employed in forming TABLEI the block polymers to be later hydrogenated include especially butadiene and isoprene as well as mixtures thereof.
- the Block Lengths monovinyl arenes to be used in the block copolymer forma- Sample p tion include. particularly styrene as well as ring alkylated styrenes'and their mixtures.
- lf block copolymers are formed 10 1 polyvinylcyclohexanbhydmgenated 13444 5 incorporating alpha olefin blocks as the blocks D, the polybutadienepolyvinylcyclohexane al
- copolyrner blocks of monovinyl p y p -p y y y n arenes with conjugated dienes may be employed in any or all 4 plysltyrne'hydrgnated 23402-23 of blocks C or D as described above.
- the blocks p0 ystyrene should predominate prior to hydrogenation in the previously described monomers.
- a typical polymer of this type prior to hydrogenation will have the structure polystyrene-random Samples 2 and 4 were found to be incompatible with the B' T term SBR, refers a Styrene/bu lubricating oil to the extend that lumpy gels were formed at tadlene copolymenc block" 0.2 percent by weight of polymer in the oil.
- Their contribublock copPlymers are hydrogenated to reduce their tions to the viscosity of the oil were too small for. them to be olefinic unsaturation by at least 50 percent and preferably at 25 useful as VI improves.
- the remaining two polymers f d least 80 Percent of the original olefin: double bondssuitable solutions in oil and their concentrations were adjusted Moreoven y of the block copolymers having mom than a to give kinematic viscosity values measured at 210 F.
- Moreoven y of the block copolymers having mom than a to give kinematic viscosity values measured at 210 F.
- the shear stabilities of the polymers in solution were deterp and Preferably at least 80 Percent Hydrogenation is mined by the kinematic viscosity loss of the solution measured Preferably carried n in Solution utilizing either nomogene' at 210 F.
- Catalysts V, V F such as cobalt or nickel salts or alkoxides reduced with aluloss: V V X 100 minum alkyl compounds are employed preferably as catalysts.
- a..- Suitablecatalysts include nickel acetate, nickel octoate, or where V,, V and V refers to viscosities of the initial solution nickel acetyl acetonate reduced with aluminum alkyl combefore shear, of the solution after shear, and of the base oil pounds such as aluminum triethyl, aluminum triisobutyl, or blend less VI improver, respectively. The results are given in aluminum trioctyl. the table below.
- a lubricating composition comprising a mineral oil and as a viscosity index improver therefor 0.75-5 percent by weight of a hydrogenated block copolymer having at least three essentially uniform blocks C and D, blocks C being hydrogenated polymer blocks of styrene wherein at least 50 percent of the original aromatic unsaturation has been reduced by hydrogenation of the polymer, said blocks C hav ing an average molecular weight between about 5,000 and 50,000, and blocks D being hydrogenated polymer blocks of conjugated dienes wherein at least 50 percent of the original unsaturation has been reduced by hydrogenation of the polymer, said blocks D having average molecular weights between about 10,000 and 1,000,000.
- composition according to claim 1 where the oil is a lubricating oil is a lubricating oil.
- a lubricating composition according to claim 1 comprising a mineral lubricating oil and 1.0-4.5 percent by weight of a three-block copolymer of a hydrogenated polystyrene block and a hydrogenated polyisoprene block.
- a lubricating composition according to claim 1 comprising a mineral lubricating oil and l.04.5 percent by weight of a block copolymer of alternating hydrogenated polystyrene blocks and hydrogenated conjugated diene polymer blocks.
- a lubricating composition according to claim 1 having a viscosity no greater than about 2,600 cp at 0 F. and a viscosity ofat least about 50 cp at 210 F.
- a lubricating composition according to claim 1 containing in addition a stabilizing proportion of lubricating oil detergent.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US88472069A | 1969-12-12 | 1969-12-12 |
Publications (1)
Publication Number | Publication Date |
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US3668125A true US3668125A (en) | 1972-06-06 |
Family
ID=25385236
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US884720A Expired - Lifetime US3668125A (en) | 1969-12-12 | 1969-12-12 | Block copolymers as viscosity index improvers for lubricating oils |
Country Status (10)
Country | Link |
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US (1) | US3668125A (xx) |
JP (1) | JPS4937564B1 (xx) |
BE (1) | BE759715A (xx) |
CA (1) | CA923112A (xx) |
DE (1) | DE2060864A1 (xx) |
FR (1) | FR2070827B1 (xx) |
GB (1) | GB1329000A (xx) |
NL (1) | NL7018019A (xx) |
SE (1) | SE368025B (xx) |
ZA (1) | ZA708338B (xx) |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4081390A (en) * | 1975-05-22 | 1978-03-28 | Orobis Limited | Viscosity index improver composition |
US4116917A (en) * | 1976-02-10 | 1978-09-26 | Shell Oil Company | Hydrogenated star-shaped polymer |
US4141847A (en) * | 1977-05-11 | 1979-02-27 | Shell Oil Company | Star-shaped polymer reacted with dicarboxylic acid and amine as dispersant viscosity index improver |
US4156673A (en) * | 1976-02-10 | 1979-05-29 | Shell Oil Company | Hydrogenated star-shaped polymer |
US4728578A (en) * | 1986-08-13 | 1988-03-01 | The Lubrizol Corporation | Compositions containing basic metal salts and/or non-Newtonian colloidal disperse systems and vinyl aromatic containing polymers |
US4788361A (en) * | 1987-10-30 | 1988-11-29 | Shell Oil Company | Polymeric viscosity index improver and oil composition comprising the same |
US4849481A (en) * | 1987-07-10 | 1989-07-18 | Shell Oil Company | Star shaped asymmetric block copolymer of monoalkenyl aromatic hydrocarbon and conjugated diene |
US4877836A (en) * | 1988-05-24 | 1989-10-31 | Shell Oil Company | Viscosity index improver and composition containing same |
EP0351964A1 (en) | 1988-06-24 | 1990-01-24 | Exxon Chemical Patents Inc. | Synergistic combination of additives useful in power transmitting compositions |
US4900875A (en) * | 1987-07-10 | 1990-02-13 | Shell Oil Company | Polymeric viscosity index additive and oil composition comprising the same |
US4927889A (en) * | 1981-08-13 | 1990-05-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer and a process for producing the same |
US4992529A (en) * | 1987-10-29 | 1991-02-12 | Shell Oil Company | Method for separating metal contaminants from organic polymers |
US5118875A (en) * | 1990-10-10 | 1992-06-02 | Exxon Chemical Patents Inc. | Method of preparing alkyl phenol-formaldehyde condensates |
US5209862A (en) * | 1991-01-30 | 1993-05-11 | Shell Oil Company | Vi improver and composition containing same |
US5262508A (en) * | 1990-10-10 | 1993-11-16 | Exxon Chemical Patents Inc. | Process for preparing alkyl phenol-sulfur condensate lubricating oil additives |
US5272209A (en) * | 1981-08-13 | 1993-12-21 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer composition |
US5272208A (en) * | 1981-08-13 | 1993-12-21 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer composition |
US5278246A (en) * | 1981-08-13 | 1994-01-11 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer and a process for producing the same |
US5310814A (en) * | 1991-03-15 | 1994-05-10 | Exxon Chemical Patents Inc. | Viscosity modifier polybutadiene polymers |
US5310490A (en) * | 1991-03-13 | 1994-05-10 | Exxon Chemical Products Inc. | Viscosity modifer polymers |
EP0611818A1 (en) | 1990-07-31 | 1994-08-24 | Exxon Chemical Patents Inc. | Low pressure derived mixed phosphorous- and sulfur-containing reaction products useful in power transmitting compositions and process for preparing the same |
WO1999036491A1 (en) | 1998-01-13 | 1999-07-22 | Exxon Chemical Patents Inc. | Automatic transmission fluids of improved viscometric properties |
US20050130853A1 (en) * | 2003-12-11 | 2005-06-16 | Mishra Munmaya K. | Lubricating oil compositions |
US20070105731A1 (en) * | 2005-11-04 | 2007-05-10 | Chin Chu | Lubricating oil compositions |
US20130324447A1 (en) * | 2012-06-01 | 2013-12-05 | Exxonmobil Research And Engineering Company | Lubricant compositions and processes for preparing same |
WO2015159249A1 (en) | 2014-04-17 | 2015-10-22 | Eni S.P.A. | Hydrogenated polymers with a radial structure having a core based on calixarenes and use thereof in lubricant compositions |
IT201900013836A1 (it) | 2019-08-02 | 2021-02-02 | Eni Spa | Copolimeri lipofili comprendenti multi-blocchi polari, procedimento per la loro preparazione e loro utilizzo in composizioni lubrificanti. |
US11078437B2 (en) | 2014-04-17 | 2021-08-03 | Eni S.P.A. | Hydrogenated polymers with a radial structure having a core based on calixarenes and use thereof in lubricant compositions |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3772196A (en) * | 1971-12-03 | 1973-11-13 | Shell Oil Co | Lubricating compositions |
FR2245758B1 (xx) * | 1973-10-01 | 1978-04-21 | Lubrizol Corp | |
DE2603034C3 (de) * | 1976-01-28 | 1982-04-15 | Basf Ag, 6700 Ludwigshafen | Mineralschmierölgemische |
JP4361516B2 (ja) * | 2005-06-10 | 2009-11-11 | キヤノンマシナリー株式会社 | ウェーハ分割方法 |
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US3060120A (en) * | 1956-02-23 | 1962-10-23 | Exxon Research Engineering Co | Lubricating oil compositions |
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US3338877A (en) * | 1963-12-09 | 1967-08-29 | Shell Oil Co | Copolymers of ethylene/stilbene |
US3509056A (en) * | 1963-05-28 | 1970-04-28 | Princeton Chemical Res Inc | Viscosity index improvers |
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US3333024A (en) * | 1963-04-25 | 1967-07-25 | Shell Oil Co | Block polymers, compositions containing them and process of their preparation |
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0
- BE BE759715D patent/BE759715A/nl unknown
-
1969
- 1969-12-12 US US884720A patent/US3668125A/en not_active Expired - Lifetime
-
1970
- 1970-12-10 NL NL7018019A patent/NL7018019A/xx not_active Application Discontinuation
- 1970-12-10 ZA ZA708338A patent/ZA708338B/xx unknown
- 1970-12-10 JP JP45109041A patent/JPS4937564B1/ja active Pending
- 1970-12-10 FR FR707044519A patent/FR2070827B1/fr not_active Expired
- 1970-12-10 DE DE19702060864 patent/DE2060864A1/de active Pending
- 1970-12-10 GB GB5861870A patent/GB1329000A/en not_active Expired
- 1970-12-10 CA CA100309A patent/CA923112A/en not_active Expired
- 1970-12-10 SE SE16713/70A patent/SE368025B/xx unknown
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US2478843A (en) * | 1946-02-26 | 1949-08-09 | Monsanto Chemicals | Mineral oil composition |
US2798853A (en) * | 1954-05-27 | 1957-07-09 | Exxon Research Engineering Co | Lubricant containing hydrogenated liquid polymer oils |
US3060120A (en) * | 1956-02-23 | 1962-10-23 | Exxon Research Engineering Co | Lubricating oil compositions |
US3509056A (en) * | 1963-05-28 | 1970-04-28 | Princeton Chemical Res Inc | Viscosity index improvers |
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Cited By (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4081390A (en) * | 1975-05-22 | 1978-03-28 | Orobis Limited | Viscosity index improver composition |
US4116917A (en) * | 1976-02-10 | 1978-09-26 | Shell Oil Company | Hydrogenated star-shaped polymer |
US4156673A (en) * | 1976-02-10 | 1979-05-29 | Shell Oil Company | Hydrogenated star-shaped polymer |
US4141847A (en) * | 1977-05-11 | 1979-02-27 | Shell Oil Company | Star-shaped polymer reacted with dicarboxylic acid and amine as dispersant viscosity index improver |
US4927889A (en) * | 1981-08-13 | 1990-05-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer and a process for producing the same |
US5278246A (en) * | 1981-08-13 | 1994-01-11 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer and a process for producing the same |
US5272208A (en) * | 1981-08-13 | 1993-12-21 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer composition |
US5272209A (en) * | 1981-08-13 | 1993-12-21 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer composition |
US4972020A (en) * | 1981-08-13 | 1990-11-20 | Asahi Kasei Kogyo Kabushiki Kaisha | Modified block copolymer composition |
US4728578A (en) * | 1986-08-13 | 1988-03-01 | The Lubrizol Corporation | Compositions containing basic metal salts and/or non-Newtonian colloidal disperse systems and vinyl aromatic containing polymers |
US4900875A (en) * | 1987-07-10 | 1990-02-13 | Shell Oil Company | Polymeric viscosity index additive and oil composition comprising the same |
US4849481A (en) * | 1987-07-10 | 1989-07-18 | Shell Oil Company | Star shaped asymmetric block copolymer of monoalkenyl aromatic hydrocarbon and conjugated diene |
US4992529A (en) * | 1987-10-29 | 1991-02-12 | Shell Oil Company | Method for separating metal contaminants from organic polymers |
AU608087B2 (en) * | 1987-10-30 | 1991-03-21 | Shell Internationale Research Maatschappij B.V. | Polymeric viscosity index improver and oil composition comprising the same |
US4788361A (en) * | 1987-10-30 | 1988-11-29 | Shell Oil Company | Polymeric viscosity index improver and oil composition comprising the same |
US4877836A (en) * | 1988-05-24 | 1989-10-31 | Shell Oil Company | Viscosity index improver and composition containing same |
EP0351964A1 (en) | 1988-06-24 | 1990-01-24 | Exxon Chemical Patents Inc. | Synergistic combination of additives useful in power transmitting compositions |
EP0611818A1 (en) | 1990-07-31 | 1994-08-24 | Exxon Chemical Patents Inc. | Low pressure derived mixed phosphorous- and sulfur-containing reaction products useful in power transmitting compositions and process for preparing the same |
US5118875A (en) * | 1990-10-10 | 1992-06-02 | Exxon Chemical Patents Inc. | Method of preparing alkyl phenol-formaldehyde condensates |
US5262508A (en) * | 1990-10-10 | 1993-11-16 | Exxon Chemical Patents Inc. | Process for preparing alkyl phenol-sulfur condensate lubricating oil additives |
US5209862A (en) * | 1991-01-30 | 1993-05-11 | Shell Oil Company | Vi improver and composition containing same |
US5543469A (en) * | 1991-03-13 | 1996-08-06 | Exxon Chemical Patents Inc. | Viscosity modifier polymers |
US5310490A (en) * | 1991-03-13 | 1994-05-10 | Exxon Chemical Products Inc. | Viscosity modifer polymers |
US5310814A (en) * | 1991-03-15 | 1994-05-10 | Exxon Chemical Patents Inc. | Viscosity modifier polybutadiene polymers |
US5945485A (en) * | 1991-03-15 | 1999-08-31 | Exxon Chemical Patents Inc | Viscosity modifier polybutadiene polymers |
WO1999036491A1 (en) | 1998-01-13 | 1999-07-22 | Exxon Chemical Patents Inc. | Automatic transmission fluids of improved viscometric properties |
US7407918B2 (en) | 2003-12-11 | 2008-08-05 | Afton Chemical Corporation | Lubricating oil compositions |
US20050130853A1 (en) * | 2003-12-11 | 2005-06-16 | Mishra Munmaya K. | Lubricating oil compositions |
US20070105731A1 (en) * | 2005-11-04 | 2007-05-10 | Chin Chu | Lubricating oil compositions |
US20090291871A1 (en) * | 2005-11-04 | 2009-11-26 | Chin Chu | Lubricating Oil Compositions |
US8188021B2 (en) | 2005-11-04 | 2012-05-29 | Infineum International Limited | Lubricating oil compositions |
US20130324447A1 (en) * | 2012-06-01 | 2013-12-05 | Exxonmobil Research And Engineering Company | Lubricant compositions and processes for preparing same |
US8703666B2 (en) * | 2012-06-01 | 2014-04-22 | Exxonmobil Research And Engineering Company | Lubricant compositions and processes for preparing same |
WO2015159249A1 (en) | 2014-04-17 | 2015-10-22 | Eni S.P.A. | Hydrogenated polymers with a radial structure having a core based on calixarenes and use thereof in lubricant compositions |
US10584299B2 (en) | 2014-04-17 | 2020-03-10 | Eni S.P.A. | Hydrogenated polymers with a radial structure having a core based on calixarenes and use thereof in lubricant compositions |
US11078437B2 (en) | 2014-04-17 | 2021-08-03 | Eni S.P.A. | Hydrogenated polymers with a radial structure having a core based on calixarenes and use thereof in lubricant compositions |
IT201900013836A1 (it) | 2019-08-02 | 2021-02-02 | Eni Spa | Copolimeri lipofili comprendenti multi-blocchi polari, procedimento per la loro preparazione e loro utilizzo in composizioni lubrificanti. |
Also Published As
Publication number | Publication date |
---|---|
ZA708338B (en) | 1971-09-29 |
FR2070827B1 (xx) | 1973-04-27 |
JPS4937564B1 (xx) | 1974-10-09 |
CA923112A (en) | 1973-03-20 |
GB1329000A (en) | 1973-09-05 |
FR2070827A1 (xx) | 1971-09-17 |
BE759715A (nl) | 1971-06-02 |
NL7018019A (xx) | 1971-06-15 |
SE368025B (xx) | 1974-06-17 |
DE2060864A1 (de) | 1971-06-24 |
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