WO2003064572A1 - Lubricating oil compositions with improved friction properties - Google Patents

Lubricating oil compositions with improved friction properties Download PDF

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Publication number
WO2003064572A1
WO2003064572A1 PCT/US2003/002935 US0302935W WO03064572A1 WO 2003064572 A1 WO2003064572 A1 WO 2003064572A1 US 0302935 W US0302935 W US 0302935W WO 03064572 A1 WO03064572 A1 WO 03064572A1
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WO
WIPO (PCT)
Prior art keywords
hydrocarbyl
group
esters
oils
base
Prior art date
Application number
PCT/US2003/002935
Other languages
English (en)
French (fr)
Inventor
Mark D. Winemiller
Douglas Edward Deckman
William L. Maxwell
William H. Buck
David J. Baillargeon
Original Assignee
Exxonmobil Research And Engineering Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxonmobil Research And Engineering Company filed Critical Exxonmobil Research And Engineering Company
Priority to MXPA04006250A priority Critical patent/MXPA04006250A/es
Priority to KR10-2004-7011678A priority patent/KR20040077895A/ko
Priority to EP03710807A priority patent/EP1481044A1/en
Priority to CA002471886A priority patent/CA2471886A1/en
Priority to JP2003564169A priority patent/JP2006503926A/ja
Priority to NZ533412A priority patent/NZ533412A/en
Publication of WO2003064572A1 publication Critical patent/WO2003064572A1/en

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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
    • 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
    • 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
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
    • C—CHEMISTRY; METALLURGY
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    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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    • C10M127/00—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon
    • C10M127/06—Alkylated aromatic hydrocarbons
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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
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    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
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    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
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    • C10M2203/065—Well-defined aromatic compounds used as base material
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    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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    • C10M2203/1025—Aliphatic fractions used as base material
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    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • This invention relates to lubricating oil compositions suitable for use in internal combustion engines.
  • Lubricating oils for internal combustion engines contain in addition to at least one base lubricating oil, additives which enhance the performance of the lubricating oil.
  • additives such as detergents, dispersants, friction reducers, viscosity index improvers, antioxidants, corrosion inhibitors, antiwear additives, pour point depressants, seal compatibility additives, and antifoam agents are used in lubricating oil compositions.
  • Friction reducers often include mixtures of two or more of the above classes of components. Several of the above prior art friction reducing compositions are found to have significant and often undesirable side-effects. It is thus desirable to have several improved fuel economy components and/or systems to be able to choose from in the formulation of high quality fuel economy improving lubricants.
  • the present invention concerns friction reducers for use in lubricating oil compositions which comprise certain groups of aromatic compounds, esters, narrow mixtures of base stocks, and/or amorphous polymers such as amorphous olefin copolymers. These compositions can provide substantial reductions in the coefficient of friction and fuel economy improving benefits when admixed to lubricating oils without deleterious effects such as instability, undesirable high viscosities and deposits.
  • pentaerythritol esters and optionally triol esters are added to lubricating oil compositions to provide reduced friction and improved fuel economy.
  • similar results are obtained by adding hydrocarbyl aromatics to a lubricating oil composition containing one or more of Group II base stock, Group III base stock, and wax isomerate base stock.
  • the invention concerns a lubricating oil composition comprising an amorphous olefin copolymer and one or more of Group II base stock, Group III base stock, and wax isomerate base stock.
  • the third aspect also includes one or more of hydrocarbyl aromatics and polyol esters as part of the composition.
  • moderate concentrations of hydrocarbyl aromatics are used in a lubricating oil composition comprising paraffinic base oil stocks and preferably a borated polyisobutenyl succinimide ashless dispersant.
  • Figure 1 is a plot of coefficient of friction as a function of temperature for various compositions.
  • Engine oils contain a base lube oil and a variety of additives. These additives include detergents, dispersants, friction reducers, viscosity index improvers, antioxidants, corrosion inhibitors, antiwear additives, pour point depressants, seal compatibility additives, and antifoam agents. To be effective, these additives must be oil-soluble or oil-dispersible. By oil-soluble, it is meant that the compound is soluble in the base oil or lubricating oil composition under normal blending conditions.
  • the instant invention concerns certain groups of aromatic compounds, esters, mixtures of base stocks, and/or amorphous polymers such as amorphous olefin copolymers that can provide substantial reductions in the coefficient of friction and fuel economy improving benefits when admixed to lubricating oils without deleterious effects such as instability, undesirable high viscosities and deposits.
  • the present invention concerns certain pentaerythritol esters which are found to provide unexpected and significant fuel economy improving (friction reducing) benefits when formulated into lubricants containing hydrocarbyl aromatic compositions. This fuel economy improvement enhancement can be further improved with the addition of certain esters to the above-mentioned pentaerythritol esters.
  • this additional fuel economy improvement is seen with a mixed triol ester and pentaerythritol ester system in the presence of a relatively low concentration of hydrocarbyl aromatics such as alkylated naphthalene.
  • Useful concentrations of hydrocarbyl aromatics range from about 1% or more. We believe that about 2% to about 45% of such hydrocarbyl aromatics is often preferred, more preferably about 2% to about 30%, even more preferably about 3% to about 15%.
  • Desirable esters include pentaerythritol esters, derived from mono-, di-, and poly pentaerythritol polyols reacted with mixed hydrocarbyl acids (RC0 2 H), and where a substantial amount of the available -OH groups are converted to esters.
  • the substituent hydrocarbyl groups, R, of the acid moiety and ester comprise from about C 6 to about C 16 or more, with preferable ranges being about C 6 to about Cj 4 , and may comprise alkyl, alkenyl, cycloalkyl, cycloalkenyl, linear, branched, and related hydrocarbyl groups, and can optionally contain S, N, and/or O groups.
  • Pentaerythritol esters with mixtures of substituent hydrocarbyl groups, R are often preferred.
  • substituent hydrocarbyl groups, R may comprise a substantial amount of C 8 and Cio hydrocarbyl moieties in the proportions of about 1 :4 to 4: 1.
  • a preferred pentaerythritol ester has R groups comprising approximately about 55% C 8 , about 40% C 10 , and the remainder approximately 5% C 6 and C ⁇ 2+ moieties.
  • one useful pentaerythritol ester has a viscosity index of about 148, a pour point of about 3°C and a kinematic viscosity of about 5.9 cSt at 100°C.
  • the pentaerythritol esters can be used in lubricant compositions at concentrations of about 3% to about 30%, preferably about 4% to about 20%, and more preferably about 5% to about 15%.
  • Esters may also include esters of trimethylolpropane and trimethylolethane and the like.
  • the hydrocarbyl aromatics that can be used can be any hydrocarbyl molecule that contains at least about 5% of its weight derived from an aromatic moiety such as a benzenoid moiety or naphthenoid moiety, or their derivatives.
  • These hydrocarbyl aromatics include alkyl benzenes, alkyl naphthalenes, alkyl diphenyl oxides, alkyl naphthols, alkyl diphenyl sulfides, alkylated bis-phenol A, alkylated thiodiphenol, and the like.
  • the aromatic can be mono-alkylated, dialkylated, polyalkylated, and the like.
  • the aromatic can be mono- or poly- functionalized.
  • the hydrocarbyl groups can also be comprised of mixtures of alkyl groups, alkenyl groups, alkynyl, cycloalkyl groups, cycloalkenyl groups and other related hydrocarbyl groups.
  • the hydrocarbyl groups can range from about C 6 up to about C 6 o with a range of about C 8 to about C 0 often being preferred. A mixture of hydrocarbyl groups is often preferred.
  • the hydrocarbyl group can optionally contain sulfur, oxygen, and/or nitrogen containing substituents.
  • the aromatic group can also be derived from natural (petroleum) sources, provided at least about 5% of the molecule is comprised of an above- type aromatic moiety.
  • Viscosities at 100 °C of approximately 3 cSt to about 50 cSt are preferred, with viscosities of approximately 3.4 cSt to about 20 cSt often being more preferred for the hydrocarbyl aromatic component.
  • an alkyl naphthalene where the alkyl group is primarily comprised of 1-hexadecene is used.
  • Other alkylates of aromatics can be advantageously used.
  • Naphthalene for example, can be alkylated with olefins such as octene, decene, dodecene, tetradecene or higher, mixtures of similar olefins, and the like.
  • Useful concentrations of hydrocarbyl aromatic in a lubricant oil composition can be about 2% to about 25%, preferably about 4% to about 20%, and more preferably about 4% to about 15%, depending on the application.
  • Alkylated aromatics such as the hydrocarbyl aromatics of the present invention may be produced by well-known Friedel-Crafts alkylation of aromatic compounds. See Friedel-Crafts and Related Reactions, Olah, G.A. (ed), Interscience Publishers, New York, 1963.
  • an aromatic compound such as benzene or naphthalene
  • an olefin, alkyl halide or alcohol in the presence of a Friedel-Crafts catalyst. See Friedel-Crafts and Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, See Olah, G.A. (ed), Interscience Publishers, New York, 1964.
  • catalysts are known to one skilled in the art.
  • the choice of catalyst depends on the reactivity of the starting materials and product quality requirements.
  • strong acids such as A1C1 3 , BF 3 , or HF may be used.
  • milder catalysts such as FeCl 3 or SnCL* are preferred.
  • Other alkylation technology uses zeolites or solid super acids.
  • Fuel economy enhancements are seen with synergistic mixtures of (a) Group II or Group III paraffinic oil blends, including wax isomerate base oils, and (b) hydrocarbyl aromatics.
  • the above mentioned base stocks comprising certain hydroprocessed base oils, in the presence of low concentrations of polyol based esters (such as those derived from trimethylolpropane and mixed hydrocarbyl acids), and hydrocarbyl aromatics (such as alkylated naphthalene) are found to provide unexpected and significant fuel economy improving (friction reducing) benefits when directly compared to lubricants containing relatively high quantities of about 40% of high quality synthetic fluids derived from olefin oligomers such as oligomers of 1-decene.
  • both groups of base stocks have viscosities of about 4 to about 50 cSt at 100 °C and similar viscosity indices of approximately 110 to approximately 150 or greater.
  • certain amorphous olefin copolymers are found to provide unexpected and significant fuel economy improving (friction reducing) benefits when formulated into lubricants, especially those containing significant amounts of Group II or Group III base oils, including wax isomerates, having viscosity indices of about 110 to about 150 or greater.
  • Such olefin copolymers are not predominantly crystalline.
  • Copolymers used in this invention have molecular weights in the range of about 20,000 or higher, preferably 60,000 or higher, more preferably 100,000 or higher and even more preferably 150,000 or higher.
  • amorphous etheylene-propylene copolymers comprising significant to major amounts of propylene-derived copolymers have molecular weights in the range of about 20,000 or higher.
  • a traditional ester and/or hydrocarbyl aromatic such as alkyl naphthalene at concentrations of about 1% to about 30% or more, preferably about 2% to about 25%, or more preferably about 3% to about 20% in the finished formulated lubricant.
  • significant fuel economy enhancements are attained with the use of moderate concentrations of hydrocarbyl aromatics, preferably in the presence of at least a minor concentration of Group II or Group III hydrocracked and/or hydrotreated base stocks, including wax isomerates.
  • hydrocarbyl aromatics are described above.
  • Group II and Group III base stocks and wax isomerate base stocks are described below. We also believe that the presence of certain ashless dispersants can significantly contribute to the fuel economy enhancements observed.
  • one preferred composition comprising about 20% hydrocarbyl aromatic, about 40% Group II paraffinic base stock, about 3 weight percent borated polyisobutyl succinimide ashless dispersant is found to be particularly useful.
  • Useful ashless dispersants are described below.
  • Group II and/or Group III hydroprocessed or hydrocracked base stocks including wax isomerates, or their synthetic counterparts such as polyalphaolefin lubricating oils are preferred as lubricating base stocks when used in conjunction with the components of each of the aspects of the present invention.
  • At least about 20% of the total composition should comprise such Group II or Group III base stocks, including wax isomerates, with at least about 30% on occasion being more preferable, with at least about 50% on occasion being more preferable and more than about 80% on occasion being even more preferable.
  • Gas-to-Liquids base stocks can also be preferentially used with the components of this invention as a portion or all of the base stocks used to formulate the finished lubricant.
  • a mixture of all or some of such base stocks can be used to advantage and can often be preferred.
  • the components of this invention are added to lubricating systems comprised of primarily Group II and or Group III base stocks, including wax isomerates, with up to lesser quantities of alternate fluids such as the above described hydrocarbyl aromatics as exemplified by C ⁇ 2 , C ⁇ , 6 , and/or Cis alkylated naphthalenes.
  • hydrocarbyl aromatics products comprising substantially mono-alkylated naphthalene can be preferred.
  • Other components, including effective amounts of co-base stocks, and various performance additives can be advantageously used with the components of this invention.
  • co-base stocks include polyalphaolefin oligomeric low- and moderate- and high-viscosity oils, dibasic acid esters, polyol esters, other hydrocarbon oils such as those derived from gas to liquids type technology, supplementary hydrocarbyl aromatics and the like.
  • co-base stocks can also include some quantity of decene-derived trimers and tetramers, and also some quantity of Group I base stocks, provided that the above Group II and/or Group III type base stocks, including wax isomerates, predominate and make up at least about 50% of the total base stocks contained in fluids comprised of the elements of the above invention requiring a substantial portion of such stocks.
  • the base stocks, co-base stocks and other performance additives are discussed in more detail below.
  • the instant invention can be used with additional lubricant components in effective amounts in lubricant compositions, such as for example polar and/or non-polar lubricant base oils, and performance additives such as for example, but not limited to, oxidation inhibitors, metallic and non-metallic dispersants, metallic and non-metallic detergents, corrosion and rust inhibitors, metal deactivators, anti-wear agents (metallic and non-metallic, phosphorus- containing and non-phosphorus, sulfur-containing and non-sulfur types), extreme pressure additives (metallic and non-metallic, phosphonis-containing and non-phosphorus, sulfur-containing and non-sulfur types), anti-seizure agents, pour point depressants, wax modifiers, viscosity modifiers, seal compatibility agents, friction modifiers, lubricity agents, anti-staining agents, chromophoric agents, def amants, demulsifiers, and others.
  • performance additives such as for example, but not limited to, oxidation
  • Lubricating oils that are useful in the present invention are both natural oils and synthetic oils. Natural and synthetic oils (or mixtures thereof) can be used unrefined, refined, or rerefined (the latter is also known as reclaimed or reprocessed oil). Unrefined oils are those obtained directly from a natural or synthetic source and used without added purification. These include shale oil obtained directly from retorting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from an esterification process. Refined oils are similar to the oils discussed for unrefined oils except refined oils are subjected to one or more purification steps to improve the at least one lubricating oil property. One skilled in the art is familiar with many purification processes. These processes include solvent extraction, secondary distillation, acid extraction, base extraction, filtration, and percolation. Rerefined oils are obtained by processes analogous to refined oils but using an oil that has been previously used.
  • Groups I, II, III, IV and V are broad categories of base oil stocks developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base oils.
  • Group I base stock generally have a viscosity index of between about 80 to 120 and contains greater than about 0.03% sulfur and/or less than about 90% saturates.
  • Group II base stocks generally have a viscosity index of between about 80 to 120, and contain less than or equal to about 0.03 % sulfur and greater than or equal to about 90% saturates.
  • Group III stock generally has a viscosity index greater than about 120 and contain less than or equal to about 0.03 % sulfur and greater than about 90% saturates.
  • Group IV includes polyalphaolefins (POA).
  • Group V base stock includes base stocks not included in Groups I-IV. The table below summarizes properties of each of these five groups.
  • Natural oils include animal oils, vegetable oils (castor oil and lard oil, for example), and mineral oils. Animal and vegetable oils possessing favorable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful in the present invention. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight run or cracked, hydrorefined, or solvent extracted.
  • Synthetic oils include hydrocarbon oil.
  • Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (polybutylenes, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alphaolefin copolymers, for example).
  • Polyalphaolefin (PAO) oil base stocks are a commonly used synthetic hydrocarbon oil.
  • PAOs derived from C 8 , Cio, C ]2 , C olefins or mixtures thereof may be utilized. See U.S. Patents 4,956,122; 4,827,064; and 4,827,073, which are incorporated herein by reference in their entirety.
  • the number average molecular weights of the PAOs typically vary from about 250 to about 3,000, although PAO's may be made in viscosities up to about 100 cSt (100°C).
  • the PAOs are typically comprised of relatively low molecular weight hydrogenated polymers or oligomers of alphaolefins which include, but are not limited to, C 2 to about C 32 alphaolefins with the C 8 to about C 16 alphaolefins, such as 1-octene, 1 -decene, 1-dodecene and the like, being preferred.
  • alphaolefins include, but are not limited to, C 2 to about C 32 alphaolefins with the C 8 to about C 16 alphaolefins, such as 1-octene, 1 -decene, 1-dodecene and the like, being preferred.
  • the preferred polyalphaolefins are poly- 1-octene, poly-1-decene and poly- 1-dodecene and mixtures thereof and mixed olefin-derived polyolefins.
  • the dimers of higher olefins in the range of C 1 to C J8 may be used to provide low viscosity basestocks of acceptably low volatility.
  • the PAOs may be predominantly trimers and tetramers of the starting olefins, with minor amounts of the higher oligomers, having a viscosity range of 1.5 to 12 cSt.
  • the PAO fluids may be conveniently made by the polymerization of an alphaolefin in the presence of a polymerization catalyst such as the Friedel- Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel- Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel- Crafts catalysts including, for example, aluminum trichloride, boron triflu
  • the alkyl substituents are typically alkyl groups of about 8 to 25 carbon atoms, usually from 10 to 18 carbon atoms and up to three such substituents may be present, as described for the alkyl benzenes in ACS Petroleum Chemistry Preprint 1053-1058, "Poly n-Alkylbenzene Compounds: A Class of Thermally Stable and Wide Liquid Range Fluids", Eapen et al, Phila. 1984. Tri-alkyl benzenes may be produced by the cyclodimerization of 1-alkynes of 8 to 12 carbon atoms as described in U.S. Patent No. 5,055,626.
  • alkylbenzenes are described in European Patent Application No. 168534 and U.S. Patent No. 4,658,072.
  • Alkylbenzenes are used as lubricant basestocks, especially for low-temperature applications (arctic vehicle service and refrigeration oils) and in papermaking oils. They are commercially available from producers of linear alkylbenzenes (LABs) such as Vista Chem. Co, Huntsman Chemical Co., Chevron Chemical Co., and Nippon Oil Co.
  • LABs linear alkylbenzenes
  • the linear alkylbenzenes typically have good low pour points and low temperature viscosities and VI values greater than 100 together with good solvency for additives.
  • alkylated aromatics which may be used when desirable are described, for example, in “Synthetic Lubricants and High Performance Functional Fluids", Dressier, H., chap 5, (R. L. Shubkin (Ed.)), Marcel Dekker, N.Y. 1993.
  • Other useful lubricant oil base stocks include wax isomerate base stocks and base oils, comprising hydroisomerized waxy stocks (e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.), hydroisomerized Fischer-Tropsch waxes, Gas-to-Liquids (GTL) base stocks and base oils, and other wax isomerate hydroisomerized base stocks and base oils, or mixtures thereof.
  • hydroisomerized waxy stocks e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.
  • hydroisomerized Fischer-Tropsch waxes e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.
  • Fischer-Tropsch waxes the high boiling point residues of Fischer- Tropsch synthesis, are highly paraffinic hydrocarbons with very low sulfur content.
  • the hydroprocessing used for the production of such base stocks may use an amorphous hydrocracking hydroisomerization catalyst, such as one of the specialized lube hydrocracking (LHDC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • an amorphous hydrocracking hydroisomerization catalyst such as one of the specialized lube hydrocracking (LHDC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • LHDC specialized lube hydrocracking
  • a zeolitic catalyst preferably ZSM-48 as described in U.S. ' Patent 5,075,269, the disclosure of which is incorporated herein by reference in its entirety.
  • Processes for making hydrocracked/hydroisomerized distillates and hydrocracked/hydroisomerized waxes are described, for example, in U.S. Patents Nos.
  • Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and other wax-derived hydroisomerized (wax isomerate) base oils be advantageously used in the instant invention, and may have useful kinematic viscosities at 100°C of about 3 cSt to about 50 cSt, preferably about 3 cSt to about 30 cSt, more preferably about 3.5 cSt to about 25 cSt, as exemplified by GTL 4 with kinematic viscosity of about 4.0 cSt at 100°C and a viscosity index of about 141.
  • Gas-to-Liquids (GTL) base oils may have useful pour points of about -20°C or lower, and under some conditions may have advantageous pour points of about -25 °C or lower, with useful pour points of about -30°C to about -40°C or lower.
  • Useful compositions of Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and wax-derived hydroisomerized base oils are recited in U.S. Patent Nos. 6,080,301; 6,090,989, and 6, 165,949 for example, and are incorporated herein in their entirety by reference.
  • Gas-to-Liquids (GTL) base oils have a beneficial kinematic viscosity advantage over conventional Group II and Group III base oils, which may be very advantageously used with the instant invention.
  • Gas-to-Liquids (GTL) base oils can have significantly higher kinematic viscosities, up to about 20-50 cSt at 100°C, whereas by comparison commercial Group II base oils can have kinematic viscosities, up to about 15 cSt at 100°C, and commercial Group III base oils can have kinematic viscosities, up to about 10 cSt at 100°C.
  • the higher kinematic viscosity range of Gas-to- Liquids (GTL) base oils, compared to the more limited kinematic viscosity range of Group II and Group III base oils, in combination with the instant invention can provide additional beneficial advantages in formulating lubricant compositions.
  • the exceptionally low sulfur content of Gas-to-Liquids (GTL) base oils, and other wax-derived hydroisomerized base oils, in combination with the low sulfur content of suitable olefin oligomers and/or alkyl aromatics base oils, and in combination with the instant invention can provide additional advantages in lubricant compositions where very low overall sulfur content can beneficially impact lubricant performance.
  • Alkylene oxide polymers and interpolymers and their derivatives containing modified terminal hydroxyl groups obtained by, for example, esterification or etherification are useful synthetic lubricating oils.
  • these oils may be obtained by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (methyl-polyisopropylene glycol ether having an average molecular weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about 500-1000, and the diethyl ether of polypropylene glycol having a molecular weight of about 1000 to 1500, for example) or mono- and polycarboxylic esters thereof (the acidic acid esters, mixed C 3 . 8 fatty acid esters, or the C ⁇ 3 Oxo acid diester of tetraethylene glycol, for example).
  • Esters comprise a useful base stock. Additive solvency and seal compatibility characteristics may be secured by the use of esters such as the esters of dibasic acids with monoalkanols and the polyol esters of monocarboxylic acids.
  • Esters of the former type include, for example, the esters of dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc., with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc.
  • dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, etc.
  • Particularly useful synthetic esters are those which are obtained by reacting one or more polyhydric alcohols, preferably the hindered polyols (such as the neopentyl polyols e.g. neopentyl glycol, trimethylol ethane, 2-methyl-2- propyl-l,3-propanediol, trimethylol propane, pentaerythritol and dipenta- erythritol) with alkanoic acids containing at least about 4 carbon atoms (preferably Cs to C 30 acids such as saturated straight chain fatty acids including caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic acid, or the corresponding branched chain fatty acids or unsaturated fatty acids such as oleic acid, or mixtures of any of these materials).
  • the hindered polyols such as the neopentyl polyols
  • Suitable synthetic ester components include the esters of trimethylol propane, trimethylol butane, trimethylol ethane, pentaerythritol and/or dipentaerythritol with one or more monocarboxylic acids containing from about 5 to about 10 carbon atoms. These esters are widely available commercially, for example, the Mobil P-41 and P-51 esters ExxonMobil Chemical Company).
  • Silicon-based oils are another class of useful synthetic lubricating oils. These oils include polyalkyl-, polyaryl-, polyalkoxy-, and polyaryloxy-siloxane oils and silicate oils. Examples of suitable silicon-based oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl- hexyl)silicate, tetra-(p-tert-butylphenyl) silicate, hexyl-(4-methyl-2-pentoxy) disiloxane, poly(methyl) siloxanes, and poly-(methyl-2-mehtylphenyl) siloxanes.
  • esters of phosphorous- containing acids include, for example, tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid.
  • Another class of oils includes polymeric tetrahydrofurans and the like.
  • ZDDP zinc dialkyldithio- phosphate
  • ZDDP compounds generally are of the formula Zn[SP(S)(OR 1 )(OR 2 )] 2 where R 1 and R 2 are alkyl groups, preferably C 2 -C 12 alkyl groups. These alkyl groups may be straight chain or branched.
  • the ZDDP is typically used in amounts of from about 0.4 to 1.4 weight percent of the total lube oil composition, although more or less can often be used advantageously.
  • Sulfurized olefins are useful as antiwear and EP additives.
  • Sulfur- containing olefins can be prepared by sulfurization or various organic materials including aliphatic, arylaliphatic or alicyclic olefinic hydrocarbons containing from about 3 to 30 carbon atoms, preferably 3-20 carbon atoms.
  • the olefinic compounds contain at least one non-aromatic double bond. Such compounds are defined by the formula
  • R 3 R 4 C CR 5 R 6 where each of R -R are independently hydrogen or a hydrocarbon radical.
  • Preferred hydrocarbon radicals are alkyl or alkenyl radicals. Any two of R 3 -R 6 may be connected so as to form a cyclic ring. Additional information concerning sulfurized olefins and their preparation can be found in U.S. Patent No. 4,941,984, incorporated by reference herein in its entirety.
  • alkylthiocarbamoyl compounds bis(dibutyl)thiocarbamoyl, for example
  • a molybdenum compound oxymolybdenum diisopropylphosphorodithioate sulfide, for example
  • a phosphorous ester dibutyl hydrogen phosphite, for example
  • U.S. Patent No. 4,758,362 discloses use of a carbamate additive to provide improved antiwear and extreme pressure properties.
  • the use of thiocarbamate as an antiwear additive is disclosed in U.S. Patent No. 5,693,598.
  • Thiocarbamate/molybdenum complexes such as moly- sulfur alkyl dithiocarbamate trimer complex alkyl are also useful antiwear agents.
  • Esters of glycerol may be used as antiwear agents.
  • mono-, di, and tri-oleates, mono-palmitates and mono-myristates may be used.
  • ZDDP is combined with other compositions that provide antiwear properties.
  • U.S. Patent No. 5,034, 141 discloses that a combination of a thiodixanthogen compound (octylthiodixanthogen, for example) and a metal thiophosphate (ZDDP, for example) can improve antiwear properties.
  • U.S. Patent No. 5,034, 142 discloses that use of a metal alkyoxyalkylxanthate (nickel ethoxyethylxanthate, for example) and a dixanthogen (diethoxyethyl dixanthogen, for example) in combination with ZDDP improves antiwear properties.
  • a metal alkyoxyalkylxanthate nickel ethoxyethylxanthate, for example
  • a dixanthogen diethoxyethyl dixanthogen, for example
  • Preferred antiwear additives include phosphorus and sulfur compounds such as zinc dithiophosphates and/or sulfur, nitrogen, boron, molybdenum phosphorodithioates, molybdenum dithiocarbamates and various organo-molybdenum derivatives including heterocyclics, for example dimercaptothiadiazoles, mercaptobenzothiadiazoles, triazines, and the like, alicyclics, amines, alcohols, esters, diols, triols, fatty amides and the like can also be used. Such additives may be used in an amount of about 0.01 to 6 weight percent, preferably about 0.01 to 4 weight percent. Viscositv Index Improvers
  • Viscosity index improvers also known as VI improvers, viscosity modifiers, and viscosity improvers
  • VI improvers also known as VI improvers, viscosity modifiers, and viscosity improvers
  • Viscosity index improvers provide lubricants with high and low temperature operability. These additives impart shear stability at elevated temperatures and acceptable viscosity at low temperatures.
  • Suitable viscosity index improvers include high molecular weight hydrocarbons, polyesters and viscosity index improver dispersants that function as both a viscosity index improver and a dispersant.
  • Typical molecular weights of these polymers are between about 10,000 to 1,000,000, more typically about 20,000 to 500,00, and even more typically between about 50,000 and 200,000.
  • suitable viscosity index improvers are polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes.
  • Polyisobutylene is a commonly used viscosity index improver.
  • Another suitable viscosity index improver is polymethacrylate (copolymers of various chain length alkyl methacrylates, for example), some formulations of which also serve as pour point depressants.
  • Other suitable viscosity index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chain length acrylates, for example). Specific examples include styrene-isoprene or styrene- butadiene based polymers of 50,000 to 200,000 molecular weight.
  • Viscosity index improvers may be used in an amount of about 0.01 to 8 weight percent, preferably about 0.01 to 4 weight percent.
  • Antioxidants may be used in an amount of about 0.01 to 8 weight percent, preferably about 0.01 to 4 weight percent.
  • Antioxidants retard the oxidative degradation of base oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in the lubricant.
  • oxidation inhibitors that are useful in lubricating oil compositions. See, Klamann in Lubricants and Related Products, op cite, and U.S. Patent Nos. 4,798,684 and 5,084,197, for example, each of which is incorporated by reference herein in its entirety.
  • Useful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are the hindered phenolics which are the ones which contain a sterically hindered hydroxyl group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p- position to each other. Typical phenolic antioxidants include the hindered phenols substituted with C 6 + alkyl groups and the alkylene coupled derivatives of these hindered phenols.
  • phenolic materials of this type 2-t-butyl- 4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t- butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4- heptyl phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol.
  • Other useful hindered mono-phenolic antioxidants may include for example hindered 2,6-di-alkyl- phenolic proprionic ester derivatives.
  • Bis-phenolic antioxidants may also be advantageously used in combination with the instant invention.
  • ortho coupled phenols include: 2,2'-bis(6-t-butyl-4-heptyl phenol); 2,2'-bis(6-t- butyl-4-octyl phenol); and 2,2'-bis(6-t-butyl-4-dodecyl phenol).
  • Para coupled bis phenols include for example 4,4'-bis(2,6-di-t-butyl phenol) and 4,4'- methylene-bis(2, 6-di-t-butyl phenol).
  • Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants and these may be used either as such or in combination with phenolics.
  • non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines such as aromatic monoamines of the formula R R R J where R is an aliphatic, aromatic or substituted aromatic group, R 9 is an aromatic or a substituted aromatic group, and R 10 is H, alkyl, aryl or R S(0) ⁇ R 12 where R 11 is an alkylene, alkenylene, or aralkylene group, R 12 is a higher alkyl group, or an alkenyl, aryl, or alkaryl o group , and x is 0, 1 or 2.
  • the aliphatic group R may contain from 1 to about 20 carbon atoms, and preferably contains from about 6 to 12 carbon atoms.
  • the aliphatic group is a saturated aliphatic group.
  • both R and R are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl.
  • Aromatic groups R and R may be joined together with other groups such as S.
  • Typical aromatic amines antioxidants have alkyl substituent groups of at least about 6 carbon atoms.
  • Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than about 14 carbon atoms.
  • the general types of amine antioxidants useful in the present compositions include diphenylamines, phenyl naphthyl- amines, phenothiazines, imidodibenzyls and diphenyl phenylene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used.
  • aromatic amine antioxidants useful in the present invention include: p,p' -dioctyl diphenylamine; t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; and p-octylphenyl-alpha-naphthylamine.
  • Sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof also are useful antioxidants. Low sulfur peroxide decomposers are useful as antioxidants.
  • Another class of antioxidant used in lubricating oil compositions is oil-soluble copper compounds. Any oil-soluble suitable copper compound may be blended into the lubricating oil.
  • suitable copper antioxidants include copper dihydrocarbyl thio or dithio-phosphates and copper salts of carboxylic acid (naturally occurring or synthetic).
  • suitable copper salts include copper dithiocarbamates, sulphonates, phenates, and acetylacetonates.
  • Basic, neutral, or acidic copper Cu(I) and or Cu(II) salts derived from alkenyl succinic acids or anhydrides are know to be particularly useful.
  • Preferred antioxidants include hindered phenols, arylamines, low sulfur peroxide decomposers and other related components. These antioxidants may be used individually by type or in combination with one another. Such additives may be used in an amount of about 0.01 to 5 weight percent, preferably about 0.01 to 1.5 weight percent.
  • Detergents are commonly used in lubricating compositions.
  • a typical detergent is an anionic material that contains a long chain oleophillic portion of the molecule and a smaller anionic or oleophobic portion of the molecule.
  • the anionic portion of the detergent is typically derived from an organic acid such as a sulfur acid, carboxylic acid, phosphorous acid, phenol, or mixtures thereof.
  • the counter ion is typically an alkaline earth or alkali metal.
  • Salts that contain a substantially stoichiometric amount of the metal are described as neutral salts and have a total base number (TBN, as measured by ASTM D2896) of from 0 to 80.
  • compositions are overbased, containing large amounts of a metal base that is achieved by reacting an excess of a metal compound (a metal hydroxide or oxide, for example) with an acidic gas (such as carbon dioxide).
  • a metal compound a metal hydroxide or oxide, for example
  • an acidic gas such as carbon dioxide
  • the overbased material has a ratio of metallic ion to anionic portion of the detergent of about 1.05: 1 to 50: 1 on an equivalent basis. More preferably, the ratio is from about 4: 1 to about 25: 1.
  • the resulting detergent is an overbased detergent that will typically have a TBN of about 150 or higher, often about 250 to 450 or more.
  • the overbasing cation is sodium, calcium, or magnesium.
  • a mixture of detergents of differing TBN can be used in the present invention.
  • Preferred detergents include the alkali or alkaline earth metal salts of sulfates, phenates, carboxylates, phosphates, and salicylates.
  • Sulfonates may be prepared from sulfonic acids that are typically obtained by sulfonation of alkyl substituted aromatic hydrocarbons.
  • Hydrocarbon examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl and their halogenated derivatives (chlorobenzene, chlorotoluene, and chloronaphthalene, for example).
  • the alkylating agents typically have about 3 to 70 carbon atoms.
  • the alkaryl sulfonates typically contain about 9 to about 80 carbon or more carbon atoms, more typically from about 16 to 60 carbon atoms.
  • Klamann in Lubricants and Related Products, op cit discloses a number of overbased metal salts of various sulfonic acids which are useful as detergents and dispersants in lubricants.
  • Alkaline earth phenates are another useful class of detergent. These detergents can be made by reacting alkaline earth metal hydroxide or oxide (CaO, Ca(OH) 2 , BaO, Ba(OH) 2 , MgO, Mg(OH) 2 , for example) with an alkyl phenol or sulfurized alkylphenol.
  • alkyl phenol or sulfurized alkylphenol Useful alkyl groups include straight chain or branched C ⁇ -C 3 o alkyl groups, preferably, C -C 20 . Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, 1-ethyldecylphenol, and the like.
  • starting alkylphenols may contain more than one alkyl substituent that are each independently straight chain or branched.
  • the sulfurized product may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and sulfurizing agent (including elemental sulfur, sulfur halides such as sulfur dichloride, and the like) and then reacting the sulfurized phenol with an alkaline earth metal base.
  • Metal salts of carboxylic acids are also useful as detergents. These carboxylic acid detergents may be prepared by reacting a basic metal compound with at least one carboxylic acid and removing free water from the reaction product. These compounds may be overbased to produce the desired TBN level.
  • Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids.
  • Usef l salicylates include long chain alkyl salicylates.
  • One useful family of compositions is of the formula
  • R is a hydrogen atom or an alkyl group having 1 to about 30 carbon atoms
  • n is an integer from 1 to 4
  • M is an alkaline earth metal.
  • Preferred R groups are alkyl chains of at least Cn, preferably C ⁇ 3 or greater. R may be optionally substituted with substituents that do not interfere with the detergent's function.
  • M is preferably, calcium, magnesium, or barium. More preferably, M is calcium.
  • Hydrocarbyl-substituted salicylic acids may be prepared from phenols by the Kolbe reaction. See U.S. Patent No. 3,595,791, which is incorporated herein by reference in its entirety, for additional information on synthesis of these compounds.
  • the metal salts of the hydrocarbyl-substituted salicylic acids may be prepared by double decomposition of a metal salt in a polar solvent such as water or alcohol.
  • Alkaline earth metal phosphates are also used as detergents.
  • Detergents may be simple detergents or what is known as hybrid or complex detergents. The latter detergents can provide the properties of two detergents without the need to blend separate materials. See U.S. Patent No. 6,034,039 for example.
  • Preferred detergents include calcium phenates, calcium sulfonates, calcium salicylates, magnesium phenates, magnesium sulfonates, magnesium salicylates and other related components (including borated detergents).
  • the total detergent concentration is about 0.01 to about 6.0 weight percent, preferably, about 0.1 to 0.4 weight percent.
  • Dispersants help keep these byproducts in solution, thus diminishing their deposit on metal surfaces.
  • Dispersants may be ashless or ash-forming in nature.
  • the dispersant is ashless.
  • So called ashless dispersants are organic materials that form substantially no ash upon combustion.
  • non-metal-containing or borated metal-free dispersants are considered ashless.
  • metal-containing detergents discussed above form ash upon combustion.
  • Suitable dispersants typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain.
  • the polar group typically contains at least one element of nitrogen, oxygen, or phosphorous.
  • Typical hydrocarbon chains contain 50 to 400 carbon atoms.
  • dispersants may be characterized as phenates, sulfonates, sulfurized phenates, salicylates, naphthenates, stearates, carbamates, thiocarbamates, phosphorus derivatives.
  • a particularly useful class of dispersants are the alkenylsuccinic derivatives, typically produced by the reaction of a long chain substituted alkenyl succinic compound, usually a substituted succinic anhydride, with a polyhydroxy or polyamino compound.
  • the long chain group constituting the oleophilic portion of the molecule which confers solubility in the oil is normally a polyisobutylene group.
  • Exemplary U.S. patents describing such dispersants are 3,172,892; 3,2145,707; 3,219,666; 3,316, 177; 3,341,542; 3,444, 170; 3,454,607; 3,541,012; 3,630,904; 3,632,511; 3,787,374 and 4,234,435.
  • Other types of dispersant are described in U.S. Patents Nos.
  • Hydrocarbyl-substituted succinic acid compounds are popular dispersants.
  • succinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid compound preferably having at least 50 carbon atoms in the hydrocarbon substituent, with at least one equivalent of an alkylene amine are particularly useful.
  • Succinimides are formed by the condensation reaction between alkenyl succinic anhydrides and amines. Molar ratios can vary depending on the polyamine. For example, the molar ratio of alkenyl succinic anhydride to TEPA can vary from about 1: 1 to about 5: 1. Representative examples are shown in U.S. Pat. Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800; and Canada Pat. No. 1,094,044, which are incorporated herein in their entirety by reference.
  • Succinate esters are formed by the condensation reaction between alkenyl succinic anhydrides and alcohols or polyols. Molar ratios can vary depending on the alcohol or polyol used. For example, the condensation product of an alkenyl succinic anhydride and pentaerythritol is a useful dispersant.
  • Succinate ester amides are formed by condensation reaction between alkenyl succinic anhydrides and alkanol amines.
  • suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpoly- amines and polyalkenylpolyamines such as polyethylene polyamines.
  • propoxylated hexamethylenediamine Representative examples are shown in U.S. Pat. No. 4,426,305, incorporated herein by reference.
  • the molecular weight of the alkenyl succinic anhydrides used in the preceding paragraphs will typically range between 800 and 2,500.
  • the above products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid, and boron compounds such as borate esters or highly borated dispersants.
  • the dispersants can be borated with from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.
  • Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. See U.S. Patent No. 4,767,551, which is incorporated herein by reference. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part of the reaction mixture. Molecular weights of the alkylphenols range from 800 to 2,500. Representative examples are shown in U.S. Pat. Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; and 3,803,039, which are incorporated herein in their entirety by reference.
  • Typical high molecular weight aliphatic acid modified Mannich condensation products useful in this invention can be prepared from high molecular weight alkyl-substituted hydroxyaromatics or HN(R) 2 group- containing reactants.
  • Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenol, polybutylphenol, and other polyalkylphenols.
  • polyalkylphenols can be obtained by the alkylation, in the presence of an alkylating catalyst, such as BF 3 , of phenol with high molecular weight polypropylene, polybutylene, and other polyalkylene compounds to give alkyl substituents on the benzene ring of phenol having an average 600-100,000 molecular weight.
  • an alkylating catalyst such as BF 3
  • HN(R) 2 group-containing reactants are alkylene polyamines, principally polyethylene polyamines.
  • Other representative organic compounds containing at least one HN(R) 2 group suitable for use in the preparation of Mannich condensation products are well known and include the mono- and di-amino alkanes and their substituted analogs, e.g., ethylamine and diethanol amine; aromatic diamines, e.g., phenylene diamine, diamino naphthalenes; heterocyclic amines, e.g., morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and their substituted analogs.
  • alkylene polyamide reactants include ethylenediamine, diethylene triamine, triethylene tetraamine, tetraethylene pentaamine, pentaethylene hexamine, hexaethylene heptaamine, heptaethylene octaamine, octaethylene nonaamine, nonaethylene decamine, and decaethylene undecamine and mixture of such amines having nitrogen contents corresponding to the alkylene polyamines, in the formula H 2 N-(Z-NH-) n H, mentioned before, Z is a divalent ethylene and n is 1 to 10 of the foregoing formula.
  • propylene polyamines such as propylene diamine and di-, tri-, terra-, pentapropylene tri-, terra-, penta- and hexaamines are also suitable reactants.
  • the alkylene polyamines are usually obtained by the reaction of ammonia and dihalo alkanes, such as dichloro alkanes.
  • the alkylene polyamines obtained from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of dichloro alkanes having 2 to 6 carbon atoms and the chlorines on different carbons are suitable alkylene polyamine reactants.
  • Aldehyde reactants useful in the preparation of the high molecular products useful in this invention include the aliphatic aldehydes such as formaldehyde (also as paraformaldehyde and formalin), acetaldehyde and aldol (b-hydroxybutyraldehyde). Formaldehyde or a formaldehyde-yielding reactant is preferred.
  • Hydrocarbyl substituted amine ashless dispersant additives are well known to one skilled in the art; see, for example, U.S. Patent Nos. 3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209, and 5,084,197, which are incorporated herein in their entirety by reference.
  • Preferred dispersants include borated and non-borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having a Mn of from about 500 to about 5000, preferably from about 1000 to 3000, more preferably from about 1000 to 2000, and even more preferably from about 1000 to 1600 or a mixture of such hydrocarbylene groups.
  • Other preferred dispersants include succinic acid-esters and amides, alkylphenol-polyamine coupled Mannich adducts, their capped derivatives, and other related components. Such additives may be used in an amount of about 0.1 to 20 weight percent, preferably about 0.1 to 8 weight percent.
  • Conventional pom * point depressants may be added to the compositions of the present invention if desired. These pour point depressant may be added to lubricating compositions of the present invention to lower the minimum temperature at which the fluid will flow or can be poured.
  • suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.
  • 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655,479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pour point depressants and/or the preparation thereof.
  • Such additives may be used in an amount of about 0.01 to 5 weight percent, preferably about 0.01 to 1.5 weight percent.
  • Corrosion inhibitors are used to reduce the degradation of metallic parts that are in contact with the lubricating oil composition.
  • Suitable corrosion inhibitors include thiadizoles. See, for example, U.S. Patent Nos. 2,719,125; 2,719, 126; and 3,087,932, which are incorporated herein by reference in their entirety.
  • Such additives may be used in an amount of about 0.01 to 5 weight percent, preferably about 0.01 to 1.5 weight percent.
  • Seal compatibility agents help to swell elastomeric seals by causing a chemical reaction in the fluid or physical change in the elastomer.
  • Suitable seal compatibility agents for lubricating oils include organic phosphates, aromatic esters, aromatic hydrocarbons, esters (butylbenzyl phthalate, for example), and polybutenyl succinic anhydride. Such additives may be used in an amount of about 0.01 to 3 weight percent, preferably about 0.01 to 2 weight percent.
  • Anti-foam agents may advantageously be added to lubricant compositions. These agents retard the formation of stable foams. Silicones and organic polymers are typical anti-foam agents. For example, polysiloxanes, such as silicon oil or polydimethyl siloxane, provide antifoam properties. Anti-foam agents are commercially available and may be used in conventional minor amounts along with other additives such as demulsifiers; usually the amount of these additives combined is less than 1 percent and often less than 0.1 percent.
  • Antirust additives are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants.
  • a wide variety of these are commercially available; they are referred to in Klamann in Lubricants and Related Products, op cite.
  • antirust additive is a polar compound that wets the metal surface preferentially, protecting it with a film of oil.
  • Another type of antirust additive absorbs water by incorporating it in a water-in-oil emulsion so that only the oil touches the metal surface.
  • Yet another type of antirust additive chemically adheres to the metal to produce a non-reactive surface.
  • suitable additives include zinc dithiophosphates, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of about 0.01 to 5 weight percent, preferably about 0.01 to 1.5 weight percent.
  • a friction modifier is any material or materials that can alter the coefficient of friction of any lubricant or fluid containing such material(s).
  • Friction modifiers also known as friction reducers, or lubricity agents or oiliness agents, and other such agents that change the coefficient of friction of lubricant base oils, formulated lubricant compositions, or functional fluids, may be effectively used in combination with the base oils or lubricant compositions of the present invention if desired. Friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this invention. Friction modifiers may include metal-containing compounds or materials as well as ashless compounds or materials, or mixtures thereof.
  • Metal-containing friction modifiers may include metal salts or metal- ligand complexes where the metals may include alkali, alkaline earth, or transition group metals. Such metal-containing friction modifiers may also have low-ash characteristics. Transition metals may include Mo, Sb, Sn, Fe, Cu, Zn, and others.
  • Ligands may include hydrocarbyl derivative of alcohols, polyols, glycerols, partial ester glycerols, thiols, carboxylates, carbamates, thiocarbamates, dithiocarbamates, phosphates, thiophosphates, dithiophosphates, amides, imides, amines, thiazoles, thiadiazoles, dithiazoles, diazoles, triazoles, and other polar molecular functional groups containing effective amounts of O, N, S, or P, individually or in combination.
  • Mo-containing compounds can be particularly effective such as for example Mo- dithiocarbamates, Mo(DTC), Mo-dithiophosphates, Mo(DTP), Mo-amines, Mo (Am), Mo-alcoholates, Mo-alcohol-amides, etc.
  • Ashless friction modifiers may have also include lubricant materials that contain effective amounts of polar groups, for example hydroxyl-containing hydrocaryl base oils, glycerides, partial glycerides, glyceride derivatives, and the like.
  • Polar groups in friction modifiers may include hyrdocarbyl groups containing effective amounts of O, N, S, or P, individually or in combination.
  • friction modifiers that may be particularly effective include, for example, salts (both ash-containing and ashless derivatives) of fatty acids, fatty alcohols, fatty amides, fatty esters, hydroxyl-containing carboxylates, and comparable synthetic long-chain hydrocarbyl acids, alcohols, amides, esters, hydroxy carboxylates, and the like.
  • salts both ash-containing and ashless derivatives
  • fatty acids fatty alcohols, fatty amides, fatty esters, hydroxyl-containing carboxylates
  • fatty alcohols, amides, esters hydroxy carboxylates
  • comparable synthetic long-chain hydrocarbyl acids alcohols, amides, esters, hydroxy carboxylates, and the like.
  • fatty organic acids, fatty amines, and sulfurized fatty acids may be used as suitable friction modifiers.
  • Useful concentrations of friction modifiers may range from about 0.01 wt% to 10-15 wt% or more, often with a preferred range of about 0.1 wt% to 5 wt%. Concentrations of molybdenum containing materials are often described in terms of Mo metal concentration. Advantageous concentrations of Mo may range from about 10 ppm to 3000 ppm or more, and often with a preferred range of about 20-2000 ppm, and in some instances a more preferred range of about 30-1000 ppm. Friction modifiers of all types may be used alone or in mixtures with the materials of this invention. Often mixtures of two or more friction modifiers, or mixtures of friction modifiers(s) with alternate surface active material(s), are also desirable.
  • lubricating oil compositions contain one or more of the additives discussed above, the additive(s) are blended into the composition in an amount sufficient for it to perform its intended function. Typical amounts of such additives useful in the present invention are shown in the table below. [0096] Note that many of the additives are shipped from the manufacturer and used with a certain amount of base oil solvent in the formulation. Accordingly, the weight amounts in the table below, as well as other amounts mentioned in this patent, are directed to the amount of active ingredient (that is the non- solvent or non-diluent portion of the ingredient). The weight percents indicated below are based on the total weight of the lubricating oil composition.
  • kinematic viscosity at 40°C or 100°C is determined according to ASTM test method D 445, viscosity index is determined by ASTM test method D 2270, pour point is determined by ASTM test method D 97, and TBN by ASTM test method number D 2896.
  • the hydrocarbyl aromatic in the following examples is alkylated naphthalene (primarily mono-alkylated) having a kinematic viscosity of approximately 4.6 cSt at 100 °C.
  • the primarily mono-alkylated naphthalene is prepared by the alkylation of naphthalene with an olefin primarily comprised of 1-hexadecene.
  • PE ester pentaerythritol ester
  • the admixture of 9.4% of such PE ester to a SAE 10W-30 automotive engine oil exhibited a surprising 44% fuel economy enhancement.
  • the admixture of 12% of such PE ester to a SAE 10W-30 automotive engine oil exhibited a surprising 65% fuel economy enhancement.
  • the admixture of 15% of such PE ester to a SAE 10W-30 automotive engine oil exhibited a smprising 77% fuel economy enhancement. It is found that increasing concentrations of such PE ester resulted in greater fuel economy enhancements.
  • Each of these test oils contained a hydrocarbyl aromatic base oil, and it is believed that the presence of such hydrocarbyl aromatic may have contributed to the favorable results obtained.
  • Preferred amounts may be from about 4% to about 15% hydrocarbyl aromatic, about 30% to about 50% Group II type paraffinic base stocks and about 1% to about 4% borated polyisobutenyl succinimide ashless dispersant as received by weight that correspond with HFRR testing of dispersants in Figure 1.
  • the neat borated polyisobutenyl succinimide ashless dispersant is approximately two- thirds active ingredient and provides about 2% active ingredient when added to the oil blends.
  • the inventors also note that a mixture of about 70 wt% Group III base stock, about 8 to 9 wt% Pentaerythritol derived ester and about 5 to 6 wt % Hydrocarbyl Aromatics, with the remainder being a Performance Additive package will also achieve the same surprising Fuel Economy increases.
  • Certain amorphous olefin copolymers are found to provide unexpected and significant fuel economy improving (friction reducing) benefits when formulated into lubricants, especially those containing significant amounts of Group II or Group III base oils having viscosity indices of about 110 to about 150 or greater.
  • a series of industry-sanctioned Sequence VIB fuel economy engine tests is performed to determine the effect of compositional changes upon fuel economy of the test lubricants. Comparative Example 5.1 is used as the reference engine test formulation to establish the base-line FEI value used in subsequent calculations as described above.
  • the inventors have found that the fuel economy benefit can be further enhanced when the above amorphous olefin copolymer is used in the presence of about 1% to about 10% or more of any traditional polyol ester and/or hydrocarbyl aromatic such as alkyl naphthalene and/or other co-base oils in the finished formulated lubricant.
  • Sequence VIB engine testing shows that significant fuel economy enhancements can be attained with the use of moderate concentrations of hydrocarbyl aromatics, preferably in the presence of at least a minor concentration of Group II or Group III, or hydrocracked and/or hydrotreated base stocks, including wax isomerate base oils.
  • the presence of certain ashless dispersants also can significantly contribute to the fuel economy enhancements observed.
  • a series of industry-sanctioned Sequence VIB fuel economy engine tests is performed to determine the effect of compositional changes upon fuel economy of the test lubricants. Comparative Example 6.1 is used as the reference engine test formulation to establish the base-line FEI value used in subsequent calculations as described above.
  • Preferred amounts may be from about 4% to about 15% hydrocarbyl aromatic, about 30% to about 50% Group II type paraffinic base stocks and about 1% to about 4% borated polyisobutenyl succinimide ashless dispersant as received by weight that correspond with HFRR testing of dispersants in Figure 1.
  • the Sequence VIB fuel economy engine test results clearly show the unexpected advantages obtainable by using the components of this invention.

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PCT/US2003/002935 2002-01-31 2003-01-31 Lubricating oil compositions with improved friction properties WO2003064572A1 (en)

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WO2024104822A1 (en) 2022-11-16 2024-05-23 Basf Se Substituted tetrahydrobenzodiazepine as fungicides
WO2024104823A1 (en) 2022-11-16 2024-05-23 Basf Se New substituted tetrahydrobenzoxazepine
WO2024165343A1 (en) 2023-02-08 2024-08-15 Basf Se New substituted quinoline compounds for combatitng phytopathogenic fungi
WO2024194038A1 (en) 2023-03-17 2024-09-26 Basf Se Substituted pyridyl/pyrazidyl dihydrobenzothiazepine compounds for combatting phytopathogenic fungi

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EP1481044A1 (en) 2004-12-01
KR20040077895A (ko) 2004-09-07
NZ533412A (en) 2006-09-29
MXPA04006250A (es) 2004-09-27
JP2006503926A (ja) 2006-02-02
US20060079411A1 (en) 2006-04-13
US20030166476A1 (en) 2003-09-04
CA2471886A1 (en) 2003-08-07

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