EP2912151A1 - Associations de modificateur de viscosité de réserve de base d'huile de graissage à haut indice de viscosité et huiles de graissage issues de celles-ci - Google Patents

Associations de modificateur de viscosité de réserve de base d'huile de graissage à haut indice de viscosité et huiles de graissage issues de celles-ci

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Publication number
EP2912151A1
EP2912151A1 EP13773574.2A EP13773574A EP2912151A1 EP 2912151 A1 EP2912151 A1 EP 2912151A1 EP 13773574 A EP13773574 A EP 13773574A EP 2912151 A1 EP2912151 A1 EP 2912151A1
Authority
EP
European Patent Office
Prior art keywords
viscosity
group
lubricating
lubricating composition
base stock
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13773574.2A
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German (de)
English (en)
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EP2912151B1 (fr
Inventor
Willie A. GIVENS
Percy Rohinton Kanga
Jared Michael ROBILLARD
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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Publication of EP2912151A1 publication Critical patent/EP2912151A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/16—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
    • 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
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
    • 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
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/019—Shear stability
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/06—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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/68—Shear stability
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions

Definitions

  • This disclosure relates to high viscosity index lubricating oil base stock (e.g., metallocene catalyzed polyalphaolefm and polyalphaolefm fluid) and viscosity modifier (e.g., ester-containing copolymer) combinations, lubricating oils derived therefrom, processes for preparing same, and methods of use thereof.
  • This disclosure relates to lubricating driveline devices, e.g., gears and transmissions, using the lubricating oils to improve fuel efficiency without sacrificing driveline device durability.
  • Lubricants in commercial use today are prepared from a variety of natural and synthetic base stocks admixed with various additive packages and solvents depending upon their intended application.
  • the base stocks typically include mineral oils. polyalphaolefms (PAO), gas-to-liquid base oils (GTL), silicone oils, phosphate esters, diesters, polyol esters, and the like.
  • Viscosity index improvers are known to be added to lubricating oil compositions to reduce the change in viscosity of the lubricant as a function of temperature.
  • the most conventional types of viscosity index improvers used in axle and transmission oil applications include polyisobutylene and polymers of methacrylates.
  • More recent viscosity index improver technologies consist of olefins (such as copolymers of alpha-olefins and maleic anhydride and esterified derivatives thereof). These viscosity index improvers tend to incorporate ester functional groups in pendant/grafted/branched groups.
  • the ester functional groups may be derived from linear alkyl alcohols with 1 to 40 carbon atoms.
  • Lubricants capable of performing at lower viscosity typically provide increased fuel economy (thus improving corporate average fuel efficiency (CAFE), NEDC (European Driving Cycle), or FTP-75 (Federal Test Procedure), or Japanese test cycle (JC-08)). Conversely, higher viscosity fluids contribute to elevated gear and transmission operating temperatures, which are believed to reduce fuel economy and diminish durability.
  • CAFE corporate average fuel efficiency
  • NEDC European Driving Cycle
  • FTP-75 Federal Test Procedure
  • JC-08 Japanese test cycle
  • Driveline power transmitting devices such as axles and transmissions-present highly complex technological challenges for axle and manual transmission lubricants. These lubricants are required to ensure hardware durability in the form wear protection and high load-carrying capacity, while delivering enhanced fuel efficiency benefits over extended periods. Additionally, transmissions typically require specific frictional characteristics of fluids that are compatible with synchronizer material or design.
  • One of the important parameters influencing performance is lubricant viscosity. Lubricants capable of performing at lower viscosity typically provide increased fuel economy. However viscosity that is too low to maintain sufficient and stable oil film between surface asperities results in elevated gear and transmission operating temperatures, which are believed to reduce fuel economy due to higher friction in contact zones. Therefore, increasing lubricant viscosity is conventionally believed to provide better wear protection and durability to gears and transmissions.
  • This disclosure relates in part to a lubricating composition
  • a lubricating composition comprising: a first base stock component comprising one or more metaliocene catalyzed polyalphaolefins (mPAOs), each mPAO having a kinematic viscosity (Kvioo) from 40 cSt to 155 cSt and a viscosity index (VI) from 150 to 207; a second base stock comprising one or more polyalphaolefins (PAOs), each PAO having a kinematic viscosity (Kvioo) ess than 10 cSt and a VI from 130 to 145; and a viscosity modifier comprising a copolymer having units derived from monomers of (i) an a-olefm and (ii) an ethylenieally unsaturated carboxylic acid or derivatives thereof esterified.
  • mPAOs metaliocene cat
  • wear control as determined by ASTM D4172
  • load carrying capacity as determined by ASTM D2783
  • traction reduction as determined by Mini-Traction Machine (MTM) Ball-on-Dise apparatus
  • wear control as determined by ASTM D4172
  • load carrying capacity as determined by ASTM D2783
  • traction reduction as determined by Mini-Traction Machine (MTM) Ball-on-Dise apparatus
  • MTM Mini-Traction Machine
  • This disclosure also relates in part to a process for producing the above lubricating composition, said process comprising: providing a first base stock component comprising one or more metailocene catalyzed polyalphaolefins (mPAOs), each mPAO having a kinematic viscosity (KVJOO) from 40 cSt to 155 cSt and a viscosity index ( VI) from 150 to 207; providing a second base stock comprising one or more polyalphaolefins ( AOs), each PAO having a kinematic viscosity (KVJOO) ess than 10 cSt and a VI from 130 to 145; providing a viscosity modifier comprising a copolymer having units derived from monomers of (i) an a-olefin and (ii) an ethylenically unsaturated carboxy!ic acid or derivatives thereof esterified with an alcohol; and blending the first base stock component compris
  • This disclosure further relates in part to a lubricant comprising the above lubricating composition, e.g., axle fluids and manual transmission fluids (MTFs).
  • a lubricant comprising the above lubricating composition, e.g., axle fluids and manual transmission fluids (MTFs).
  • This disclosure yet further relates in part to a method of lubricating a mechanical device comprising supplying to the device the above lubricating composition.
  • the mechanical device comprises a driveline device, e.g., gears or transmissions.
  • This disclosure further relates in part to a method for improving fuel efficiency, while maintaining or improving wear control, load carrying capacity and/or traction reduction in a driveline device, e.g., gears or transmissions, lubricated with a lubricating composition, by using a lubricating composition comprising: a first base stock component comprising one or more metallocene catalyzed polyalphaolefins (mPAOs), each mPAO having a kinematic viscosity ( vioo) from 40 cSt to 155 cSt and a viscosity index (VI) from 150 to 207; a second base stock comprising one or more polyalphaolefins (PAOs), each AO having a kinematic viscosity (Kv 100 ) less than 10 cSt and a VI from 130 to 145; and a viscosity modifier comprising a copolymer having units derived from monomers of (i) an a
  • the lubricating compositions of this disclosure exhibit improved wear control (as determined by ASTM D4172), load carrying capacity (as determined by ASTM D2783) and/or traction reduction (as determined by Mini-Traction Machine (MTM) Ball-on-Disc apparatus) with said lubricating composition as compared to wear control, load earning capacity and traction reduction achieved, at an equal or lower kinematic viscosity ( v@100°C), with a lubricating composition containing a viscosity modifier other than a viscosity modifier comprising a copolymer having units derived from monomers of (i) an a-olefin and (ii) an ethylenically unsaturated carboxylic acid or derivatives thereof esterified with an alcohol.
  • FIG. 1 depicts Four-Ball Wear Scar (ASTM D4172) results for lubricating compositions in Example 1. Consistently lower wear is achieved by incorporating a viscosity modifier comprising a copolymer having units derived from monomers of (i) an ⁇ -olefin and (ii) an ethylenicaliy unsaturated carboxylic acid or derivatives thereof esterified with an alcohol.
  • a viscosity modifier comprising a copolymer having units derived from monomers of (i) an ⁇ -olefin and (ii) an ethylenicaliy unsaturated carboxylic acid or derivatives thereof esterified with an alcohol.
  • Fig. 2 depicts LWI results which are a measure of the relative ability of a lubricant to prevent wear under applied loads. LWI is calculated from data obtained from the Four Ball EP Method (ASTM D2783) in Example 2. Across a broad range of finished lubricant kinematic viscosity at 100°C (Kv 100 ), the combination of viscosity modifier and mPAO 65 showed surprisingly higher LWI than either the Meridian VM or the mPAO 65 alone.
  • Fig. 3 depicts average friction coefficient measurements for lubricating compositions in Example 2.
  • the combination of mPAO 65 and Meridian show surprisingly higher friction than other base oil and/or VM combinations indicating the possibility to control friction of lubricants designed for automotive transmission applications such at continuously variable transmissions (CVT) or infinitely variable transmissions (IVT).
  • CVT continuously variable transmissions
  • IVT infinitely variable transmissions
  • Fig. 4 depicts average traction coefficient for lubricating compositions in Example 1. Improved traction coefficients are observed over a range of finished lubricant kinematic viscosity at 100°C for these compositions compared to conventional PIB-based viscosity modifier.
  • Fig. 5 is a tabular listing of tapered roller bearing 40-hr shear stability test results for lubricating compositions in Example 3.
  • Fig. 7 depicts FZG scuffing testing results for lubricating compositions in Example 4. Results indicate unexpected directional improvement in wear protection with higher concentration of Meridian viscosity modifier even at lower finished fluid viscosity.
  • Fig. 8 depicts thermal oxidation results for lubricating compositions in Example 4. Oxidation and deposit control in severe L60-1 test improves with incorporation of Meridian viscosity modifier.
  • Fig, 9 depicts L-42 high speed shock testing results for lubricating compositions in Example 4.
  • Fig. 10 shows the results of 4-Ball Wear Scar (ASTM D4172) for the designated lubricant compositions (i.e., blends) of Example 1 .
  • FIG. 11 shows the results of 4-Baii EP (ASTM D2783) load wear index for the designated lubricant compositions (i.e., blends) of Example 2.
  • FIG. 12 shows the results of High Frequency Reciprocating Rig (HFRR) friction coefficient for the designated lubricant compositions (i.e., blends) of Example 2.
  • HFRR High Frequency Reciprocating Rig
  • a polymer is referred to as comprising homopolymers and copolymers, where copolymers include any polymer having two or more chemically distinct monomers.
  • polyalphaolefm or “PAO” includes homopolymers and copolymers of C or greater alphaoiefin monomers.
  • the lubricating compositions of this disclosure exhibit improved wear control (as determined by ASTM D4172), improved load carrying capacity (as determined by ASTM D2783) and/or improved traction reduction (as determined by Mini-Traction Machine (MTM) Ball-on-Dise apparatus) as compared to wear control, load carrying capacity and traction reduction achieved, at an equal or lower kinematic viscosity ( v(5 ) ] 00°C), with a lubricating composition containing a viscosity modifier other than a viscosity modifier comprising a copolymer having units derived from monomers of (i) an a ⁇ olefm and (ii) an ethylenically unsaturated carboxylic acid or derivatives thereof esterified with an
  • the lubricating compositions of this disclosure are also capable of providing at least one of improved oxidative stability, reduced mechanical device operating temperatures, increased mechanical device durability, improved shear stability, improved viscosity index, improved low temperature viscometrics and improved high temperature viscometrics.
  • this disclosure relates to a combination of a high viscosity synthetic base stock and an ester-containing viscosity modifier that enables improvement in wear control, load carrying capacity and traction and provides improved efficiency at equal or lower kinematic viscosity (Kv @100°C).
  • Current high performance commercial axle fluids are blended with low viscosity synthetic base stocks (such as ⁇ 10 cSt PAO) in combination with conventional viscosity modifiers.
  • higher viscosity fluids can result in lower fuel efficiency due to churning losses.
  • the internal friction of the fluid measured by its traction properties provides an indicator of its efficiency benefits in high pressure contact areas within axles.
  • the method of blending a high viscosity synthetic base stock and an ester-containing viscosity modifier in accordance with this disclosure provides lower traction and lower viscosity fluids.
  • This disclosure relates to lubricating driveline devices, e.g., gears and transmissions, using the lubricating oils to improve fuel efficiency without sacrificing driveline device durability.
  • rubricating Oil Base Stocks e.g., gears and transmissions
  • Lubricating oils that are useful in the present disclosure 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.
  • Groups I, II, III, IV, V and VI 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 stocks generally have a viscosity index of between 80 to 120 and contain greater than 0,03% sulfur and less than 90% saturates.
  • Group II base stocks generally have a viscosity index of between 80 to 120, and contain less than or equal to 0.03% sulfur and greater than or equal to 90% saturates.
  • Group III stock generally has a viscosity index greater than 120 and contains less than or equal to 0.03% sulfur and greater than 90% saturates.
  • Group IV includes polyalphaolefms (PAO).
  • Group V base stocks include base stocks not included in Groups I-IV. The table below summarizes properties of each of these six groups.
  • Group VI are polyinternal olefins ("PIO").
  • Polyintemal olefins are long- chain hydrocarbons, typically a linear backbone with some branching randomly attached; they are obtained by oligornerization of internal n-olefins.
  • the catalyst is usually a BF3 complex with a proton source that leads to a cationic polymerization, or promoted BF3 or A1C13 catalyst system.
  • the process to produce polyintemal olefins (PIO) consists of four steps: reaction, neutralization/washing, hydrogenation and distillation. These steps are somewhat similar to PAO process.
  • PIO are typically available in low viscosity grades, 4 cSt, 6 cSt and 8 cSt.
  • n-oiefins used as starting material are n-Ci 2 -C i8 internal olefins, more preferably, n-C i -C i6 olefins are used.
  • PIO can be made with VI and pour points very similar to PAO, only slightly inferior. They can be used in engine and industrial lubricant formulations. For more detailed discussion, see Chapter 2, Polyinternaioiefins in the book, "Synthetics, Mineral Oils, and Bio-Based Lubricants-Chemistry and Technology" Edited by Leslie R.
  • 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 disclosure. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight ran or cracked, hydrorefmed, or solvent extracted.
  • Group II and/or Group III hydroprocessed or hydrocracked base stocks, as well as synthetic oils such as polyalphaolefins, aikyl aromatics and synthetic esters, i.e.. Group IV and Group V oils are also well known base stock oils.
  • Synthetic oils include hydrocarbon oil such as polymerized and mterpolymerized olefins (polybutylenes, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethyiene-alphaolefin copolymers, for example).
  • Polyalphaolefm (PAO) oil base stocks the Group IV API base stocks, are a commonly used synthetic hydrocarbon oil.
  • PAOs derived from Cg, do, Ci2, C M olefins or mixtures thereof may be utilized. See U.S. Patent Nos.
  • Group IV oils that is, the PAG base stocks have viscosity indices preferably greater than 130, more preferably greater than 135, still more preferably greater than 140.
  • Esters in a minor amount may be useful in the lubricating oils of this disclosure. Additive solvency and seal compatibility characteristics may be secured by the use of esters such as the esters of dibasic acids with monoalkanois and the polyoi esters of mono car boxylie acids.
  • Esters of the former type include, for example, the esters of dicarboxylie acids such as phthalic acid, succinic acid, sebacic acid, fumaric acid, adipic acid, iinoleic acid dimer, maionic acid, alky] malonic acid, alkenyl malonic acid, etc., with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc.
  • dicarboxylie acids such as phthalic acid, succinic acid, sebacic acid, fumaric acid, adipic acid, iinoleic acid dimer, maionic acid, alky] malonic acid, alkenyl malonic acid, etc.
  • alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc.
  • esters include dibutyl adipate, di(2 ⁇ ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azeiate, dioctyl phthaiate, 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 neopeiityl polyols; e.g., neopentyl glycol, trimethylol ethane, 2 -methyl -2-propy 1-1, 3 -propanediol, trimethylol propane, pentaerythritol and dipentaerythritol with alkanoic acids containing at least 4 carbon atoms, preferably C5 to C30 acids such as saturated straight chain fatty acids including caprylic acid, capric acids, 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 aci d, or mixtures of any of these materials,
  • the hindered polyols such as the neopei
  • Esters should be used in an amount such that the improved wear and corrosion resistance provided by the lubricating oils of this disclosure are not adversely affected .
  • the esters preferably have a D5293 viscosity of less than 10,000 cP at -35°C.
  • Non-conventional or unconventional base stocks and/or base oils include one or a mixture of base stock(s) and/or base oil(s) derived from: (1) one or more Gas-to- Liquids (GTL) materials, as well as (2) hydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/or base oils derived from synthetic wax, natural wax or waxy feeds, mineral and/or non-mineral oil waxy feed stocks such as gas oils, slack waxes (derived from the solvent dewaxing of natural oils, mineral oils or synthetic oils; e.g., Fischer-Tropsch feed stocks), natural waxes, and waxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, foots oil or other mineral, mineral oil, or even non-petroleum oil derived waxy materials such as waxy materials recovered from coal liquefaction or shale oil,
  • GTL
  • GTL materials are materials that are derived via one or more synthesis, combination, transformation, rearrangement, and/or degradation/deconstructive processes from gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feed stocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes.
  • GTL base stocks and/or base oils are GTL materials of lubricating viscosity that are generally derived from hydrocarbons; for example, waxy synthesized hydrocarbons, that are themselves derived from simpler gaseous carbon- containing compounds, hydrogen-containing compounds and/or elements as feed stocks.
  • GTL base stock(s) and/or base oil(s) include oils boiling in the lube oil boiling range (1 ) separated/fractionated from synthesized GTL materials such as, for example, by distillation and subsequently subjected to a final wax processing step which involves either or both of a catalytic dewaxing process, or a solvent dewaxing process, to produce lube oils of reduced/low pour point;
  • synthesized wax isomerates comprising, for example, hydrodewaxed or hydroisomerized cat and/or solvent dewaxed synthesized wax or waxy hydrocarbons;
  • hydrodewaxed or hydroisomerized cat and/or solvent dewaxed Fischer-Tropsch (F-T) material i.e., hydrocarbons, waxy hydrocarbons, waxes and possible analogous oxygenates
  • F-T Fischer-Tropsch
  • GTL base stock(s) and/or base oii(s) derived from GTL materials are characterized typically as having kinematic viscosities at 100°C of from 2 mrn 2 /s to 50 mm /s (ASTM D445). They are further characterized typically as having pour points of -5°C to -40°C or lower (ASTM D97). They are also characterized typically as having viscosity indices of 80 to 140 or greater (ASTM D2270).
  • the GTL base stock(s) and/or base oil(s) are typically highly paraffmic (>90% saturates), and may contain mixtures of monocycloparaffins and multicycloparaffins in combination with non-cyclic isoparaffms.
  • the ratio of the naphthenic (i.e., cycloparaffm) content in such combinations varies with the catalyst and temperature used.
  • GTL base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content, generally containing less than 10 ppm, and more typically less than 5 ppm of each of these elements.
  • GTL base stock and/or base oil and/or wax isomerate base stock and/or base oil is to be understood as embracing individual fractions of such materials of wide viscosity range as recovered in the production process, mixtures of two or more of such fractions, as well as mixtures of one or two or more low viscosity fractions with one, two or more higher viscosity fractions to produce a blend wherein the blend exhibits a target kinematic viscosity
  • the GTL material, from which the GTL base stock(s) and/or base oil(s) is/are derived is preferably an F ⁇ T material (i.e., hydrocarbons, waxy hydrocarbons, wax).
  • Base oils for use in the formulated lubricating oils useful in the present disclosure are any of the variety of oils corresponding to API Group I, Group II, Group III, Group IV, Group V and Group VI oils and mixtures thereof, preferably API Group II, Group III, Group IV, Group V and Group VI oils and mixtures thereof, more preferably the Group III to Group VI base oils due to their exceptional volatility, stability, viscometric and cleanliness features.
  • Minor quantities of Group I stock such as the amount used to dilute additives for blending into formulated lube oil products, can be tolerated but should be kept to a minimum, i.e. amounts only associated with their use as diluent/carrier oil for additives used on an "as-received" basis.
  • Even in regard to the Group II stocks it is preferred that the Group II stock be in the higher quality range associated with that stock, i.e. a Group II stock having a viscosity index in the range 100 ⁇ VI ⁇ 120.
  • the GTL base stock(s) and/or base oil(s) are typically highly paraffinic (>90% saturates), and may contain mixtures of monocycloparaffins and multicycloparaffins in combination with non-cyclic isoparaffins.
  • the ratio of the naphthenic (i.e., cycloparaffin) content in such combinations varies with the catalyst and temperature used.
  • GTL base stock(s) and/or base oil(s) and hydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content, generally containing less than 10 ppm, and more typically less than 5 ppm of each of these elements.
  • the sulfur and nitrogen content of GTL base stock(s) and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially nil.
  • the absence of phosphorous and aromatics make this material especially suitable for the formulation of low sulfur, sulfated ash, and phosphorus (low SAP) products.
  • Polyalphaoiefms are preferred lubricating oil basestocks of this disclosure.
  • the PAOs can preferably comprise one or more C 8 to C 12 monomers.
  • the PAOs have a viscosity (KVJ OO) from 2 to 700 cSt at 1 G0°C, preferably from 3 to 155 cSt at 1 Q0°C, and more preferably from 4 to 150 cSt at 100°C; and a viscosity index (V I) from 130 to 207, preferably from 140 to 200, and more preferably from 150 to 197.
  • viscosity ( vioo ) is determined by ASTM D 445-01
  • viscosity index (VI) is determined by ASTM D 2270-93 (1998).
  • the PAOs useful in this disclosure can have a pour point (PP) less than -25°C; a molecular weight distribution (Mw/Mn) less than 2.0; and a glass transition temperature T g less than -60°C.
  • any PAO described herein may have a kinematic viscosity (Kv) at 100°C in any of the following ranges: from 65 to 1 ,000 cSt, from 100 to 950 cSt, from 250 cSt to 900 cSt, from 400 cSt to 800 cSt, wherein all values are measured by ASTM D445-01 .
  • Kv kinematic viscosity
  • the PAOs useful in this disclosure have a high viscosity index and a Kv 100 of 2 cSt or more, alternatively 3 cSt or more, alternatively 4 cSt or more, up to 700 cSt, with a VI of 1 30 or more, alternatively 140 or more, alternatively 1 50 or more.
  • base stock VI is a function of fluid viscosity. Usually, the higher the VI, the better it is for lube application. Base stock VI also depends on feed composition. Fluids made from single 1 -octene, 1 -nonene, 1 -decene, or 1-dodecene have excellent V I and good low pour point.
  • Fluids made from two or more olefins selected from C to C 1 2 alphaolefins generally have excellent high VI and superior low pour points if the average carbon chain length of feed LAOs is kept within 8 to 12 carbons.
  • a relatively much lower average chain l ength in the feed (much below 6 carbons) of the mixed LAO would result in lower VI.
  • Too high of a average chain length in the feed (much above 12 carbons) of the mixed LAO would result in very high pour point, around room temperature.
  • Viscosity Index is an empirical, unitless number which indicates the rate of change in the viscosity of an oil within a given temperature range and is related to kinematic viscosities measured at 40°C and 100°C (typically using ASTM Method D 445). Fluids exhibiting a relatively large change in viscosity with temperature are said to have a low viscosity index.
  • the low VI oil for example, will thin out at elevated temperatures faster than the high VI oil.
  • the high VI oil is more desirable because it has higher viscosity at higher temperature, which translates into better or thicker lubrication film and better protection of the contacting machine elements.
  • the viscosity of the hig VI oil will not increase as much as the viscosity of low VI oil. This is advantageous because the excessive high viscosity of the low VI oil will decrease the efficiency of the operating machine.
  • high VI oil has performance advantages in both high and low temperature operation.
  • the PAOs useful in this disclosure have low pour points (PP) less than -25°C, preferably less than -30°C, and more preferably less than -35°C. As used herein, pour point is determined by ASTM D97.
  • any PAO described herein may have a pour point of less than -25°C (as measured by ASTM D97), preferably less than -35°C, preferably less than -45°C, preferably less than -55°C, preferably less than -65°C, and preferably between -25°C and -75°C.
  • the PAOs useful in this disclosure have a narrow molecular weight distribution (Mw/Mn) less than 2.0, preferabl less than 1.95, and more preferably less than 1.9 as synthesized.
  • Mw/Mn molecular weight distribution
  • Mw/Mn is determined by GPC using a column for medium to low molecular weight polymers, tetrahydrofuran as solvent and polystyrene as calibration standard.
  • the PAOs useful in this disclosure have a Mw of 100,000 g ' mol or less, or between 2000 and 80,000 g/mol, or between 2500 and 60,000 g/mol, or between 2800 and 50,000 g / mol, or between 3360 and 40,000 g/mol.
  • Preferred Mw's include those from 840 to 55,100 g/mol, or from 900 to 45,000 g/mol, or 1000 to 40,000 g/mol, or 2,000 to 37,500 g/mol.
  • preferred Mw's include 2240 to 67900 g/mol and 2240 to 37200 g/mol.
  • the PAOs useful in this disclosure preferably have an Mn of 50,000 g moi or less, or 40,000 g/mol or less, or between 2000 and 40,000 g/mol, or between 2500 and 30,000 g/mol, preferably between 5000 and 20,000 g/mol.
  • Preferred Mn ranges include those from 2800 to 10,000 g/mo! or from 2800 to 8,000 g-'mol.
  • preferred Mn ranges are from 2000 to 20,900 g/mol, or 2800 to 20,000 g mol, or 2000 to 17000 g/mol, or 2000 to 12000 g mol, or 2800 to 29000 g/mo!, or 2800 to 17000 g/mol, or 2000 to 5000 g/mol.
  • Mw and Mn are measured by GP ' using a column for medium to low molecular weight polymers, tetrahydrofuran as solvent and polystyrene as calibration standard, correlated with the fluid viscosity according to a power equation,
  • the PAOs described herein have a narrow molecular weight distribution of greater than 1 and less than 2, alternatively less than 1.95, alternatively less than 1.90, alternatively less than 1.85.
  • the Mn and Mw are measured by gel permeation chromatography (GPC) using a column for medium to low molecular weight polymers, tetrahydrofuran as solvent and narrow molecular weight distribution polystyrene as calibration standard, correlated with the fluid viscosity according to a power equation.
  • the MWD of PAO is a function of fluid viscosity.
  • any of the polyalphaolefins described herein preferably have an Mw/Mn of between I and 2.0, alternatively between 1 and 1.95, depending on fluid viscosity.
  • the PAOs useful in this disclosure have low glass transition temperature T g less than -6G°C, preferably less than -70°C, and more preferably less than -80°C.
  • glass transition temperature T g is determined by differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the polyolefm products produced in accordance with the process of this disclosure have no crystallization peak as measured by differential scanning calorimetry and high thermal stability.
  • the PAOs useful in this disclosure can comprise a single alphaolefin monomer type, or may comprise two or more different alphaolefin monomers.
  • this disclosure relates to PAOs comprising a molar amount of Cg to C 12 alphaolefin monomers selected from the group consisting of 55 moi% or more, 60 mol% or more, 65 mol% or more, 70 rnoi % or more, 75 mol% or more, 80 moi % or more, 85 mol% or more, 90 mol% or more, 95 mol% or more, 100 mol%, all based on the total moles of monomers present in the poiyalphaoleim, as measured by " C NMR.
  • the PAOs comprise polymers of one or more alphaolefins (also known as 1 -olefins) with carbon numbers of Cg to C 12 .
  • at least one of the alphaolefins is a linear alphaolefin (LAO); more preferably, all the alphaolefins are LAOS.
  • LAOs include 1-octene, 1-nonene, 1-decene, l -tmdecene, and 1-dodecene, and blends thereof.
  • the PAO comprises polymers of two or more Cg to C 12 LAOs to make 'copolymer' or 'terpolymer' or higher-order copolymer combinations.
  • Other embodiments involve polymerization of a mixture of LAOs selected from Cg to C 12 LAOs with even carbon numbers, preferably a mixture of two or three LAOs selected from 1-octene, l-decene, and 1-dodecene.
  • the PAO comprises polymers of a single alphaolefin species having a total carbon count of 8 to 12. In other embodiments, the PAO comprises polymers of mixed (i.e., two or more) alphaolefin species, wherein each alphaolefin species has a carbon number of 8 to 12. In other embodiments, the PAO comprises polymers of mixed alphaolefin species wherein the molar-average carbon number (“CLAO") is 8 to 12 or 9 to 11.
  • CLAO molar-average carbon number
  • any PAO described herein may have a density of 0.75 to 0.96 g/cm J , preferably 0.80 to 0.94 g/cm 3 , alternatively from 0.76 to 0.855 g/cm'.
  • the high viscosity PAOs useful in this disclosure are desirable for use as lubricating oil base stocks and also blend stocks with API Groups I to V or gas-to-liquid (GTL) derived lube base stocks for use in industrial and automotive engine or gear oil, especially certain high v 100 grades of 65 to 155 cSt which are especiall desirable for use as lubricating oil base stocks or blend stocks with Groups I to V or GTL-derived lube base stocks for use in industrial and automotive engine or gear oil.
  • GTL gas-to-liquid
  • PAOs can be used as lubricating oil base stocks and also superior blend stocks. They can be blend stocks with any of the API Group I to V and GTL fluids to give the optimum viscometrics, solvency, high and low temperature lubricity, etc.
  • the PAOs can be further blended with proper additives, including antioxidants, antiwear additives, friction modifiers, dispersants, detergents, corrosion inhibitors, defoamants, extreme pressure additives, seal swell additives, and optionally viscosity modifiers, etc. Description of typical additives can be found in the book “Lubricant Additives: Chemistry and Applications," L.R. Rudnick, ed. Marcel Dekker Inc., New York, 2001.
  • the PAOs can be produced by conventional methods known in the art.
  • the preferred high viscosity PAOs used in this disclosure can be prepared from different feed olefins using metallocene catalysts.
  • the metallocene catalyst system, products, process and feeds are described, for example, in U.S. Application Publication No. 2011/0136714.
  • the basestock component of the present lubricating oils will typically be from 80 to 99 weight percent of the total composition (all proportions and percentages set out in this specification are by weight unless the contrary is stated) and more usually in the range of 90 to 99 weight percent.
  • the viscosity modifiers useful in the lubricating compositions of the disclosure include substantially linear polymers with a weight average molecular weight of 45,000 or less, or 35,000 or less, or 25,000 or less, or 8000 to 25,000, or 12,000 to 20,000.
  • the substantially linear polymers may be copolymers comprising units derived from monomers (i) an a-olefin and (ii) an ethylenicaliy unsaturated carboxylic acid or derivatives thereof esterified with an alcohol.
  • the substantially linear polymer may be a copolymer comprising units derived from monomers (i) one or more alpha olefins and (ii) one or more alkyl (meth) acryiate esters.
  • the ethylenicaliy unsaturated carboxylic acid may be esterified with alcohol before or after polymerization with the a-olefin. In one embodiment the ethylenicaliy unsaturated carboxylic acid may be esterified with alcohol before polymerization with the a-olefin. In one embodiment the ethylenicaliy unsaturated carboxylic acid may be esterified with alcohol after polymerization with the a-olefin,
  • a commercially available copolymer prepared by esterification before polymerization is available from Akzo Nobel sold under the tradename Ketjenlube®3700.
  • the alcohol may have 1 to 40, or 1 to 30, or 4 to 20, or 6 to 16 carbon atoms.
  • Examples of a suitable alcohol include 2-ethylhexanol, 2- butyloctanol, 2-hexyldecanol, 2-octyldodeeanol, 2-decyitetradecanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undeeanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanoi, heptadecanol, octadeeanol, eicosanol, or mixtures thereof.
  • a copolymer of this type is described in more detail in U.S. Patent Nos, 4,526,950, 6,419,714, 6,573,224, or 6,174,843.
  • the ethylenicaliy unsaturated carboxylic acid may be esterified with alcohol after polymerization with the a-olefin.
  • a copolymer of this type may be a substantially linear polymer that may in one embodiment be (a) a copolymer comprising units derived from monomers (i) an ⁇ -olefin and (ii) an ethylenicaliy unsaturated carboxylic acid or derivatives thereof esterified with a primary alcohol branched at the ⁇ - or higher position, wherein the copolymer typical ly has a reduced specific viscosity of up to 0.2, (b) a poiy(meth)acrylate, or mixtures thereof.
  • the substantially linear polymer may be present in the lubricating compositions described herein at 0.1 wt% to 50 wt%, or 2 wt% to 40 wt%, or 5 wt% to 30 wt%, or 8 wt% to 20 wt% of the lubricating composition.
  • the lubricating composition contains 65 to 99 wt % of synthetic base stock and 1 to 35 wt % of substantially linear polymer.
  • the lubricating composition contains 75 to 98 wt% of synthetic base stock and 2 to 25 wt% of substantially linear polymer.
  • the substantially linear polymer may be a copolymer comprising units derived from monomers (i) one or more alpha olefins and (ii) one or more alkyl (meth)acryiate esters.
  • the substantially linear polymer includes a mixtures of (a) a copolymer comprising units derived from monomers of (i) an a-olefin and (ii) an ethylenically unsaturated carboxylic acid or derivatives thereof esterified with a primary alcohol, and (b) a poly(meth)acrylate.
  • the poly(meth)acry!ate (typically a poiymethacrylate) can have units derived from a mixture of alkyl (rneth)acrylate ester monomers containing (a) 8 to 24, or 12 to 18, or to 15 carbon atoms in the alcohol-derived portion of the ester group and (b) 6 to 11, or 8 to 11, or 8 carbon atoms in the alcohol-derived portion of the ester group, and which have 2-(C 1 - 4 alkyl)-substituents, and optionally, at least one monomer selected from the group consisting of (meth)acryiic acid esters containing I to 7 carbon atoms in the alcohol-derived portion of the ester group and which are different from (meth)acrylic acid esters (a) and (b), vinyl aromatic compounds (or vinyl aromatic monomers); and nitrogen-containing vinyl monomers; provided that no more than 60% by weight, or no more than 50% by weight, or no more than 35% by weight of the esters contain not more than 10 carbon
  • the linear polymer of this type is described in more detail in US 6,124,249 or EP 0 937 769 Al.
  • the linear polymer may further contain a third monomer.
  • the third monomer may be styrene, or mixtures thereof.
  • the third monomer may be present in an amount 0% to 25% of the polymer composition, or from 1% to 15% of the composition, 2%o to 10% of the composition, or even from 1% to 3% of the composition.
  • the mole ratio of esters (a) to esters (b) in the copolymer ranges from 95:5 to 35:65, or 90: 10 to 60:40, or 80:20 to 50:50.
  • the esters are usually aliphatic esters, typically alkyl esters.
  • the ester of (a) may he a C 12 . 15 alkyl methacrylate and the ester of (b) may be 2-ethylhexyl methacrylate.
  • ester groups in ester (a) contain branched alkyl groups.
  • the ester groups may contain 2 to 65%, or 5 to 60% or greater of the ester groups having branched alkyl groups.
  • the C 1-4 alkyl substituents may be methyl, ethyl, and any isomers of propyl and butyl.
  • the weight average molecular weight of the poly(meth)acrylate may be 45,000 or less, or 35,000 or less, or 25,000 or less, or 8000 to 25,000, or 12,000 to 20,000.
  • the substantially linear polymer includes a copolymer comprising units derived from monomers (i) an ⁇ -olefm and (if) an ethylenically unsaturated carboxylie acid or derivatives thereof esterified with a primary alcohol branched at the ⁇ - or higher position, wherein the copolymer typically has a reduced specific viscosity of up to 0.2, or up to 0.15, or up to 0.10, or up to 0.08.
  • the reduced specific viscosity may be up to 0.08 (or 0.02 to 0.08 (or 0.02 to 0.07, 0.03 to 0.07 or 0.04 to 0.06).
  • a measurement correlating with molecular weight of the copolymer may be expressed in terms of the "reduced specific viscosity" of the copolymer which is a recognized means of expressing the molecular size of a polymeric substance.
  • the copolymer may be derived from monomers (i) an a-olefin and (ii) an ethylenically unsaturated carboxvlic acid or derivatives thereof, wherein 0.1 to 99.89% of the carboxvlic acid units are esterified with a primary alcohol branched at the ⁇ - or higher position, wherein 0.1 to 99.89% of the carboxvlic acid units are esterified with a linear alcohol or an alpha-branched alcohol (e.g., a secondary alcohol), wherein 0.01 to 10% of the carboxylic acid units has at least one of an amino-, amido- and/or imido- group, and wherein the copolymer has a reduced specific viscosity (prior to esterification) of up to 0.08.
  • monomers i) an a-olefin and (ii) an ethylenically unsaturated carboxvlic acid or derivatives thereof, wherein 0.1 to 99.89% of the carboxvlic acid units
  • the copolymer may be derived from monomers (i) an a-olefin and (ii) an ethylemcally unsaturated carboxylic acid or derivatives thereof, wherein 0.1 to 99.89% of the carboxylic acid units are esterified with a primary alcohol branched at the ⁇ - or higher position, wherein 0.1 to 99.9% of the carboxylic acid units are esterified with a linear alcohol or an alpha-branched alcohol, wherein 0 to 10% of the carboxylic acid units has at least one of an amino-, amido- and/or imido- group, and wherein the copolymer has a reduced specific viscosity of up to 0.08.
  • a linear alcohol may include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, oetadecanol, nonadecanol, eicosanol, or mixtures thereof.
  • the linear alcohol contains 6 to 30, or 8 to 20, or 8 to 15 carbon atoms (typically 8 to 15 carbon atoms).
  • the linear alcohol may include commercially available materials such as Oxo Alcohol® 791 1, Oxo Alcohol® 7900 and Oxo Alcohol® 1 100 of Monsanto; Alphanol® 79 of ICI; Nafol® 1620, Alibi ⁇ 610 and Alfol® 810 of Condea (now Sasol); Epal® 610 and Epal® 810 of Ethyl Corporation (now Afton); Linevol® 79, Linevol® 91 1 and Dobanol® 25 L of Shell AG; Lial® 125 of Condea Augusta, Milan; Dehydad® and Lorol® of Henkel GaA (now Cognis) as well as Linopol® 7-1 1 and Acropol® 91 of Ugine Kimlmami.
  • the copolymer may be derived from monomers of (i) an a-olefin and (ii) an ethylenically unsaturated carboxylic acid or derivatives thereof, wherein 5 to 15% of the carboxylic acid units are esterified with a primary alcohol branched at the ⁇ - or higher position, wherein 0.1 to 95% of the carboxylic acid units are esterified with a linear alcohol or an alpha-branched alcohol, wherein 0 to less than 2% of the carboxylic acid units has at least one of an amino-, amido- and/or imido- group, and wherein the copolymer has a reduced specific viscosity of up to 0.08.
  • the copolymer comprises units derived from monomers (i) an ⁇ -olefin and (ii) an ethylenically unsaturated carboxylic acid or derivatives thereof esterified with a primary alcohol branched at the ⁇ - or higher position.
  • the copolymer may be represented by the formula below. Ester or other groups with the primary alcohol-derived moiety branched at the ⁇ - or higher position may be represented within the ( ) w shown in the formula:
  • Formula (I) may comprise a copolymer backbone (BB), and one or more pendant groups as shown, wherein BB may be derived from a copolymer of (i) an a-olefin and (ii) an ethylenicaliy unsaturated carboxylic acid or derivatives thereof (typically fumaric acid, maleic anhydride, maleic acid, (meth)acrylic acid, itaconic anhydride or itacomc acid);
  • X may be a functional group which either (i) contains a carbon and at least one oxygen or nitrogen atom (such as an ester or amide, or imide linkage), or (ii) is an alkylene group with 1 to 5 carbon atoms (typically -CH 2 -), connecting the copolymer backbone and a branched hydrocarbyl group contained within ( ) y , (typically X may be a functional group which either (i) contains a carbon and at least one oxygen or nitrogen atom); w may be the number of pendant groups attached to the copolymer backbone, which may be in the range of 2 to 2000, or 2 to 500, or 5 to 250; y may be 0, 1, 2 or 3, provided that in at least I mol % of the pendant groups, y is not zero; and with the proviso that when y is 0, X is bonded to a terminal group in a manner sufficient to satisfy the valence of X, wherein the tenninal group is selected from hydrogen, alkyl,
  • R ' and R " may independently be linear or branched hydrocarbyl groups, and the combined total number of carbon atoms present in R' and R" may be at least 12 (or at least 16, or at least 18 or at least 20).
  • the copolymer with pendant groups may contain 0.10% to 100%, or 0.5% to 20%, or 0.75% to 10%, branched hydrocarbyl groups represented by a group within ( ) y of the formula (I) above, expressed as a percentage of the total number of pendant groups .
  • the pendant groups of formula (1) may also be used to define the ester groups as defined above by the phrase "esterified with a primary alcohol branched at the ⁇ - or higher position".
  • the functional groups defined by X on the formula above may comprise at least one of ⁇ C0 2 -, ⁇ C(0)N :::: or -(CH 2 )y-, wherein v is an integer in the range of 1 to 20, or 1 to 10, or 1 to 2,
  • X may be derived from an ethylenically unsaturated carboxylic acid or derivatives thereof.
  • a suitable carboxylic acid or derivatives thereof typically include maleic anhydride, maleic acid, (meth)acrylic acid, itaconic anhydride or itaconic acid.
  • the ethylenically unsaturated carboxylic acid or derivatives thereof may be at least one of maleic anhydride or maleic acid,
  • X is other than an alkylene group, connecting the copolymer backbone and the branched hydrocarbyl groups.
  • the pendant groups may be esterified, amidated or imidated functional groups.
  • the pendant groups may be derived from esterified and/or amidated functional groups.
  • the copolymer includes esterified pendant groups.
  • the pendant groups may be derived from Guerbet alcohols.
  • the Guerbet alcohols may contain 10 to 60, or 12 to 60, or 16 to 40 carbon atoms.
  • the primary alcohol branched at the ⁇ - or higher position described herein may be a Guerbet alcohol. Methods to prepare Guerbet alcohols are disclosed in U.S. Patent No. 4,767,815.
  • alkyl groups containing C ⁇ . ⁇ 6 polymeihylene groups such as 2-C MS alkyl-hexadecyl groups (e.g. 2-octylhexadecyl) and 2-alkyl-octadecyl groups (e.g., 2-ethyloctadecyi, 2-tetradecyi-octadecyi and 2-iiexadecyloctadecyl);
  • alkyl groups containing C .] 4 polymethylene groups such as 1-C 1-1 5 alkyl-tetradecyi groups (e.g., 2-hexyltetradecyl, 2-decyitetradecyl and 2-undecyltridecyl) and 2-C ]_i 5 alkyl-hexadecyl groups (e.g., 2-ethyl-hexadecyl and 2-dodecylhexadecyl);
  • alkyl groups containing C 10-12 polymethylene groups such as 2-Cj.is alkyl-dodecyl groups (e.g., 2-octyldodecyl) and 2-C 1-1 5 alkyl-dodecyl groups (2-hexyldodecyl and 2-octyldodecyl), 2-C M5 alkyl-tetradecyi groups (e.g., 2-hexyltetradecyl and 2-decyltetradecyl);
  • alkyl groups containing C 6- 9 polymethylene groups such as 2-C MS alkyl-decyl groups (e.g., 2-octyldecyl) and 2,4-di-C 1-15 alkyl-decyl groups (e.g., 2-ethyl-4-butyl- decyl group);
  • alkyl groups containing C 1 -5 polymethylene groups such as 2-(3-methylhexyl)-7-methyl-decyl and 2-(l,4-dimethylbutyl)-5,7,7-trimethyl-octyl groups;
  • the pendant groups may contain a total combined number of carbon atoms on R ' and R"in the range of 12 to 60, or 14 to 50, or 16 to 40, or 18 to 40, or 20 to 36.
  • Each of R' and R " may individually contain 5 to 25, or 8 to 32, or 10 to 18 methylene carbon atoms. In one embodiment the number of carbon atoms on each R' and R" group may be 10 to 24.
  • Examples of suitable primary alcohol branched at the ⁇ - or higher position include 2-ethyl.hexanol, 2 -propyl heptanol, 2-butyloctanol, 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol, or mixtures thereof
  • the ethylenically unsaturated carboxylic acid or derivatives thereof may be an acid or anhydride or derivatives thereof that may be wholly estenfied, partially esterified or mixtures thereof.
  • other functional groups include acids, salts or mixtures thereof.
  • Suitable salts include alkali metals, alkaline earth metals or mixtures thereof.
  • the salts include lithium, sodium, potassium, magnesium, calcium or mixtures thereof.
  • the unsaturated carboxylic acid or derivatives thereof includes acrylic acid, methyl acrylate, methacrylic acid, maleic acid or anhydride, tumaric acid, itaconic acid or anhydride or mixtures thereof, or substituted equivalents thereof.
  • Suitable examples of the ethylenically unsaturated carboxylic acid or derivatives thereof include itaconic anhydride, maleic anhydride, methyl maleic anhydride, ethyl maleic anhydride, dimethyl maleic anhydride or mixtures thereof.
  • the ethylenically unsaturated carboxylic acid or derivatives thereof includes maleic anhydride or derivatives thereof.
  • Examples of an alpha-olefm include 1-decene, 1-undecene, 1-dodecene, l-rridecene, 1-tetradecene, l-pentadecene, l-hexadecene, 1-hepta-decene 1-octadecene, or mixtures thereof.
  • An example of a useful alpha-olefm is 1 -dodecerie.
  • the alpha- olefin may be a branched alpha-olefm, or mixtures thereof.
  • the number of carbon atoms of the a-olefm may range from 4 to 32, or 6 to 20, or 8 to 16.
  • the copolymer of the disclosure further includes a nitrogen containing group such as those disclosed above.
  • the nitrogen containing group may be derived from a nitrogen containing compound capable of being incorporated during copolymerization.
  • the copolymer of the disclosure further includes a nitrogen containing group that may be capable of reacting with the functionalized copolymer backbone, typically for capping the copolymer backbone. The capping may result in the copolymer having ester, amide, imide or amine groups.
  • the nitrogen group is described in more detail in PCT Patent Application No. PCT/US09/052028.
  • the copolymer comprises units derived from monomers (i) an a-olefm and (ii) an ethylenicaliy unsaturated carboxylic acid or derivatives thereof may be further reacted with an amine to additionally provide oxidation control.
  • the copolymer with oxidation control contains an incorporated residue of an armne-containmg compound such as morphoiines, pyrrolidmones, imidazolidinones, acetamides, ⁇ -alanine alkyl esters, or mixtures thereof.
  • nitrogen- containing compounds examples include 3-raorpholm-4-yl-propylamme, 3-morpholin-4-yl- ethyiamine, [hetaj-alanine alkyl esters (typically alkyl esters have 1 to 30, or 6 to 20 carbon atoms), or mixtures thereof.
  • the compounds based on imidazolidinones, cyclic carbamates or pyrrolidinones may be derived from a compound of general structure:
  • Hy may be hydrogen, or a hydrocarbyl group (typically alkyl, or C 1-4- , or C 2 - alkyl);
  • Q >NH, >N , ⁇ >CHR, >CR 2 , or -O- (typically >NH, or >NR) and R may be C 4 alkyl.
  • the imidazoiidinone includes [-(2-amino-ethyi)- imidazolidin-2-one (may also be called ammoethylethyleneurea), l ⁇ (3 ⁇ amino ⁇ propyl)- imidazolidin-2-one, l-(2-hydroxy-ethy!-imidazo!idin-2-one, l-(3-amino-propyl)- pyrrolidin-2-one, l-(3-ammo-ethyl)-pyrrolidin-2-one, or mixtures thereof,
  • the copolymer may be reacted with an amine-containing compound selected from morpholines, imidazolidmories, and mixtures thereof.
  • the formulated lubricating oil useful in the present disclosure may additionally contain one or more of the other commonly used lubricating oil performance additives including but not limited to dispersants, other detergents, corrosion inhibitors, rust inhibitors, metal deactivators, other antiwear agents and/or extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improvers, fluid-loss additives, seal compatibility agents, other friction modifiers, lubricity agents, anti- staining agents, chromophoric agents, defoamants, demulsifiers, emul.sifi.ers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, and others.
  • dispersants including but not limited to dispersants, other detergents, corrosion inhibitors, rust inhibitors, metal deactivators, other antiwear agents and/or extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improvers, fluid-loss additives, seal compatibility
  • Typical antioxidant include phenolic antioxidants, aminic antioxidants and oil-soluble copper complexes,
  • the phenolic antioxidants include sulfurized and non-sulfurized phenolic antioxidants.
  • the terms "phenolic type” or “phenolic antioxidant” used herein includes compounds having one or more than one hydroxy! group bound to an aromatic ring which may itself be mononuclear, e.g., benzyl, or poly-nuclear, e.g., naphthyl and spiro aromatic compounds.
  • phenol type includes phenol per se, catechol, resorcinol, hydroquinone, naphthol, etc., as well as alkyl or alkenyl and sulfurized alkyl or alkenyl derivatives thereof, and bisphenol type compounds including such bi-phenol compounds linked by alkylene bridges sulfuric bridges or oxygen bridges.
  • Alkyl phenols include mono- and poly-alkyl or alkenyl phenols, the alkyl or alkenyl group containing from 3-100 carbons, preferably 4 to 50 carbons and sulfurized derivatives thereof, the number of alkyl or alkenyl groups present in the aromatic ring ranging from 1 to up to the available unsatisfied valences of the aromatic ring remaining after counting the number of hydroxy! groups bound to the aromatic ring.
  • the phenolic anti-oxidant may be represented by the general formula:
  • R is a C3 -C 100 alkyl or alkenyl group, a sulfur substituted alkyl or alkenyi group, preferably a C --C50 alkyl or alkenyl group or sulfur substituted alkyl or alkenyl group, more preferably CVC' ioo alkyl or sulfur substituted alkyl group, most preferably a C4-C50 alkyl group
  • R s is a C 1 -C 100 alkylene or sulfur substituted alkyl ene group, preferably a C2-C50 alkylene or sulfur substituted alkylene group, more preferably a C2-C2 alkylene or sulfur substituted alkylene group
  • y is at least 1 to up to the available valences of Ar
  • x ranges from 0 to up to the available valances of Ar-y
  • z ranges from 1 to 10
  • n ranges from 0 to 20
  • m is 0 to 4
  • p is 0 or 1, preferably
  • Preferred phenolic antioxidant compounds are the hindered phenolics and phenolic esters which contain a sterically hindered hydrox l group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxvl groups are in the o- or p-position to each other.
  • Typical phenolic anti-oxidants include the hindered phenols substituted with Cj + alkyl groups and the alkylene coupled derivatives of these hindered phenols.
  • phenolic materials of this type 2-t-butyl-4-heptyl phenol; 2-t-butyI-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t-b tyl ⁇ 4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl phenol; 2-methyl-6-t-butyl- 4-dodecyl phenol; 2,6-di-t-buryl-4 methyl phenol; 2,6-di-t-butyl-4-ethyl phenol; and 2,6-di-t-butyi 4 alkoxy phenol; and
  • Phenolic type antioxidants are well known in the lubricating industry and commercial examples such as Ethanox® 4710, Irganox ⁇ 1076, Irganox® L1035, Irganox® 1010, irganox® L109, Irganox® L118, Irganox® L135 and the like are familiar to those skilled in the art. The above is presented only by way of exemplification, not limitation on the type of phenolic anti-oxidants which can be used.
  • the phenolic antioxidant can be employed in an amount in the range of 0,1 to 3 wt%, preferably 0.25 to 2.5 wt%, more preferably 0.5 to 2 wt% on an active ingredient basis.
  • Aromatic amine antioxidants include phenyl-a-naphthyl amine which is described by the following molecular structure:
  • R z is hydrogen or a Cj to C 14 linear or C3 to C 14 branched alkyl group, preferably Cj to C 10 linear or C3 to C 10 branched alkyl group, more preferably linear or branched Ce, to Cg and n is an integer ranging from 1 to 5 preferably 1.
  • a particular example is Irganox L06.
  • aromatic amine antioxidants include other alkylated and non-al.kyl.ated aromatic amines such as aromatic monoamines of the formula R 8 R R ! °N where R 8 is an aliphatic, aromatic or substituted aromatic group, 9 is an aromatic or a substituted aromatic group, and R J l ' is H, alkyl, aryl or R n S(Q)xR 1 2 where R i ! is an al.kyl.ene, alkenylene, or araikyiene group, R is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2.
  • the aliphatic group R 8 may contain from 1 to 20 carbon atoms, and preferably contains from 6 to 12 carbon atoms.
  • the aliphatic group is a
  • 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 8 and R 9 may be joined together with other groups such as S.
  • Typical aromatic amines anti -oxidants have alkyl substituent groups of at least 6 carbon atoms.
  • Examples of aliphatic groups include hexyl, heptyl, octyl, noiiyl, and decyl.
  • the aliphatic groups wi ll not contain more than 14 carbon atoms.
  • the general types of such other additional amine antioxidants which may be present include diphenyl amines, phenothiazines, imidodibenzyls and di phenyl phenyl en e diamines. Mixtures of two or more of such other additional aromatic amines may also be present. Polymeric amine antioxidants can also be used.
  • antioxidants used in lubricating oil compositions and which may also be present are oil-soluble copper compounds. Any oil-soluble suitable copper compound may be blended into the lubricating oil. Examples of suitable copper antioxidants include copper dihydrocarbyl thio- or dithio-phosphates and copper salts of carboxylic acid (naturally occurring or synthetic). Other suitable copper salts include copper dith.iacarbam.ates, sulphonates, phenates, and acetyl.acetonat.es. Basic, neutral, or acidic copper Cu(I) and or Cu(II) salts derived from alkenyl succinic acids or anhydrides are known to be particularly useful . [00128] Such antioxidants may be used individually or as mixtures of one or more types of antioxidants, the total amount employed being an amount of 0.50 to 5 wt%, preferably 0.75 to 3 wt% (on an as-received basis).
  • alkali or alkaline earth metal salicylate detergent which is an optional component in the present disclosure
  • other detergents may also be present. While such other detergents can be present, it is preferred that the amount employed be such as to not interfere with the synergistic effect attributable to the presence of the salicylate. Therefore, most preferably such other detergents are not employed.
  • additional detergents can include alkali and alkaline earth metal phenates, sulfonates, carboxylates, phosphonates and mixtures thereof.
  • These supplemental detergents can have total base number (TBN) ranging from neutral to highly overbased, i.e. TBN of 0 to over 500, preferably 2 to 400, more preferably 5 to 300, and they can be present either individually or in combination with each other in an amount in the range of from 0 to 10 wt%, preferably 0.5 to 5 wt% (active ingredient) based on the total weight of the formulated lubricating oil.
  • TBN total base number
  • Such additional other detergents include by way of example and not limitation calcium phenates, calcium sulfonates, magnesium phenates, magnesium sulfonates and other related components (including borated detergents).
  • Dispersants help keep these byproducts in solution, thus diminishing their deposition 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 phosphorus.
  • Typical hydrocarbon ch ains contain 50 to 400 carbon atoms.
  • A. particularly useful class of dispersants are the alkenylsuccinic derivatives, typically produced by the reaction of a long chain substituted alkenyi 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 nomially a poiyisobutvlene group.
  • Many examples of this type of dispersant are well known commercially and in the literature. Exemplary U.S.
  • Hydrocarbyl-substituted succinic acid compounds are popular dispersants.
  • succminiide, 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 alkyiene amine are particularly useful.
  • Succinimides are formed by the condensation reaction between alkenyi succinic anhydrides and amines. Molar ratios can vary depending on the amine or polyamine. For example, the molar ratio of alkenyi succinic anhydride to TEPA can vary from 1 : 1 to 5 : 1.
  • 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 aikanol amines.
  • suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and po!yalkenylpolyamines such as polyethylene polyamines.
  • propoxylated hexamemylenediarnine is propoxylated hexamemylenediarnine .
  • the molecular weight of the alkenyl succinic anhydrides 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 0.1 to 5 moles of boron per mole of dispersant reaction product.
  • Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. 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 or more.
  • Typical high molecular weight aliphatic acid modified Mannich condensation products can be prepared from high molecular weight alkyl-substituted hydroxyaromafics or HN(R) 2 group-containing reactants.
  • Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenol, po!ybutyi phenol, and other polyalkylphenols. These polyaikyiphenois can be obtained by the alkylation, in the presence of an alkylating catalyst, such as BF 3 , of phenol with high molecular weight polypropylene, polybutyiene, and other polyalkylene compounds to give alkyl substituents on the benzene ring of phenol having an average 600-100,000 molecular weight.
  • Examples of HN(R)2 group-containing reactants are alkylene polyarnines, principally polyethylene polyarnines.
  • HN(R) 2 group suitable for use in the preparation of Mannich condensation products are well known and include the mono- and di -amino a!kanes and their substituted analogs, e.g., ethylamine and diethanol amine; aromatic diamines, e.g., phenyl en e diamine, di amino naphthalenes; heterocyclic amines, e.g., morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and their substituted analogs .
  • mono- and di -amino a!kanes and their substituted analogs e.g., ethylamine and diethanol amine
  • aromatic diamines e.g., phenyl en e diamine, di amino naphthalenes
  • heterocyclic amines e.g., morpholine, pyrrole, pyrrolidine, imid
  • alkylene poiyamine reactants include ethylenediamine, diethyl en e triamine, triethylene tetraamine, tetraethylene pentaamine, pentaethylene hexamine, hexaethylene heptaamine, heptaethylene octaamine, octaethyiene nonaamme, nonaethylene decamine, and decaethylene undecamine and mixture of such amines having nitrogen contents corresponding to the alkylene polyarnines, 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.
  • Corresponding propylene polyarnines such as propylene diamine and di-, tri ⁇ , terra-, pentapropylene tri-, terra-, penta- and bexaam es are also suitable reactants.
  • the alkylene polyarnines are usually obtained by the reaction of ammonia and dihalo alkanes, such as dichloro alkanes.
  • the alkylene polyarnines obtained from the reaction of 2 to 1 1 moles of ammonia with 1 to 10 moles of dichloroalkanes having 2 to 6 carbon atoms and the chlorines on different carbons are suitable alkylene poiyamine reactants.
  • Aldehyde reactants useful in the preparation of the high molecular products useful in this disclosure include the aliphatic aldehydes such as formaldehyde (also as paraformaldehyde and formalin), acetaldehyde and aldol ( ⁇ -hydroxybutyraldehyde). Formaldehyde or a formaldehyde-yielding reactant is preferred,
  • Preferred dispersants include berated and non-borated succmimides, including those derivatives from mono-succmimides, bis-succinimides, and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succmimide is derived from a hydrocarbylene group such as polyisobutylene having a n of from 500 to 5000 or more or a mixture of such hydrocarbylene groups.
  • Other preferred dispersants include succinic acid-esters and amides, alkylphenol-polyamine-coupled Manmch adducts, their capped derivatives, and other related components. Such additives may be used in an amount of 0.1 to 20 wt%, preferably 0.1 to 8 wt%, more preferably 1 to 6 wt% (on an as- received basis) based on the weight of the total lubricant.
  • pour point depressants also known as lube oil flow improvers
  • Pour point depressant may be added to lower the minimum temperature at which the fluid will flow or can be poured.
  • suitable pour point depressants include alkylated naphthalenes polym.ethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dia3ky3fumarates, vinyl esters of fatty acids and allyl vinyl ethers.
  • Such additives may be used in amount of 0.0 to 0.5 wt%, preferably 0 to 0.3 wt%, more preferably 0.001 to 0.1 wt% on an as-received basis.
  • Corrosion inhibitors are used to reduce the degradation of metallic parts that are in contact with the lubricating oil composition.
  • Suitable corrosion inhibitors include aryl thiazines, alky! substituted dimercapto thiodiazoles thiadiazoles and mixtures thereof.
  • Such additives may be used in an amount of 0.01 to 5 wt%, preferably 0.01 to 1 .5 wt%, more preferably 0.0.1 to 0.2 w ⁇ .%, still more preferably 0.01 to 0.1 wt.% (on an as-received basis) based on the total weight of the lubricating oil composition.
  • 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 poiybutenyl succinic anhydride and suifoiaiie-type seal swell agents such as Lubrizol 730-type seal .. 4() .
  • swell additives Such additives may be used in an amount of 0.01 to 3 wt%, preferably 0.01 to 2 wt% on an as-received basis.
  • 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, preferably 0.001 to 0.5 wt%, more preferably 0.001 to 0.2 wt%, still more preferably 0.0001 to 0.15 wt% (on an as-received basis) based on the total weight of the lubricating oil composition.
  • Antirust additives are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants.
  • One type of 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-oii emulsion so that only the oil touches the surface.
  • Yet another type of antirust additive chemically adheres to the metal to produce a non- reactive surface.
  • suitable additives include zinc dithiophosphates, metal phenol ates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of 0.01 to 5 wt%, preferably 0.01 to 1.5 wt% on an as-received basis.
  • organo molybdenum-nitrogen complexes embraces the organo molybdenum-nitrogen complexes described in U.S. Patent 4,889,647.
  • the complexes are reaction products of a fatty oil, dithanoiamine and a molybdenum source. Specific chemical structures have not been assigned to the complexes.
  • U.S. Patent 4,889,647 reports an infrared spectrum for a typical reaction product of that disclosure; the spectrum identifies an ester carbonyi band at 1740 cm "1 and an amide carbonyi band at 1620 cm "1 ,
  • the fatty oils are glyceryl esters of higher fatty acids containing at least 12 carbon atoms up to 22 carbon atoms or more.
  • the molybdenum source is an oxygen- containing compound such as ammonium molybdates, molybdenum oxides and mixtures.
  • organo molybdenum complexes which can be used in the present disclosure are tri-nuciear molybdenum-sulfur compounds described in EP 1 040 115 and WO 99/31113 and the molybdenum complexes described in U.S. Patent No. 4,978,464.
  • the lubricating composition may optionally further contain other known viscosity modifiers.
  • the viscosity modifiers may be hydrogenated styrene-butadiene rubbers, ethylene- propylene copolymers, hydrogenated styrene-isoprene polymers, hydrogenated diene polymers, polyalkyl styrenes, polyolefms, esters of raaleic anhydride-styrene copolymers, or mixtures thereof.
  • the lubricating compositions can include at least one antiwear agent.
  • suitable antiwear agents include oil soluble amine salts of phosphorus compounds, sulphurised olefins, metal dihydrocarbyldithio-phosphates (such as zinc dialkyldithiophosphates), thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulphides,
  • the oil soluble phosphorus amine salt antiwear agent mcludes an amine salt of a phosphoms acid ester or mixtures thereof.
  • the amine salt of a phosphorus acid ester includes phosphoric acid esters and amine salts thereof; dialkyldithiophosphoric acid esters and amine salts thereof; amine salts of phosphites; and amine salts of phosphorus-containing carboxyiic esters, ethers, and amides; and mixtures thereof.
  • the amine salt of a phosphorus acid ester may be used alone or in combination.
  • the oil soluble phosphorus amine salt includes partial amine salt-partial metal salt compounds or mixtures thereof.
  • the phosphorus compound further includes a sulphur atom in the molecule.
  • the amine salt of the phosphorus compound may be ashless, i.e., metal-free (prior to being mixed with other components).
  • the amines which may be suitable for use as the amine salt include primary amines, secondary amines, tertiary amines, and mixtures thereof.
  • the amines include those with at least one hydrocarbyl group, or, in certain embodiments, two or three hydrocarbyl groups.
  • the hydrocarbyl groups may contain 2 to 30 carbon atoms, or in other embodiments 8 to 26, or 10 to 20, or 13 to 19 carbon atoms.
  • Primary amines include ethylamine, propylamine, butylamine, 2-ethylhexylamine, octylamine, and dodecylamine, as well as such fatty amines as n-octylamme, n-deeylamme, n-dodecylamine, n-tetradecyl amine, n-hexadecylamine, n-octadecyl amine and oleyamine.
  • fatty amines include commercially available fatty amines such as "Armeen®” amines (products available from Akzo Chemicals, Chicago, Illinois), such as Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein the letter designation relates to the fatty group, such as coco, oleyl, tallow, or stearyi groups.
  • Examples of suitable secondary amines include ciimethyl amine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamme, diheptylamine, methylethylamine, ethylbutylamine and ethylamyl amine.
  • the secondary amines may be cyclic amines such as piperidine, piperazine and morpholine.
  • the amine may also be a tertiary-aliphatic primary amine.
  • the aliphatic group in this case may be an alkyl group containing 2 to 30, or 6 to 26, or 8 to 24 carbon atoms.
  • Tertiary alkyl amines include monoamines such as tert-butylamine, tert- hexyl amine, 1 -methyl- 1-amino-cyclohexane, tert-octylamine, tert-deeyl amine.
  • tertdodecyl amine tert-tetradecylamine, tert-hexadecyl amine, tert-octadecylamine, tert-tetracosanylamine, and tert-octacosanylamine.
  • the phosphorus acid amine salt includes an amine with C i i to C i 4 tertiary alkyl primary groups or mixtures thereof. In one embodiment the phosphorus acid amine salt includes an amine with C 14 to C jg tertiary alkyl primary amines or mixtures thereof. In one embodiment the phosphorus acid amine salt includes an amine with C j g to C22 tertiary alkyl primary amines or mixtures thereof.
  • amines may also be used in the disclosure.
  • a useful mixture of amines is "Primene ⁇ 81 R” and “Primene® JMT.”
  • Primene® 81R and Primene® JMT are mixtures of C n to C 14 tertiary alkyl primary amines and Cig to C22 tertiary alkyl primary amines, respectively.
  • oil soluble amine salts of phosphorus compounds include a sulphur-free amine salt of a phosphorus-containing compound may be obtained/obtainable by a process comprising: reacting an amine with either (i) a hydroxy-substituted di-ester of phosphoric acid, or (ii) a phosphorylated hydroxy- substituted di- or tri-ester of phosphoric acid.
  • a process comprising: reacting an amine with either (i) a hydroxy-substituted di-ester of phosphoric acid, or (ii) a phosphorylated hydroxy- substituted di- or tri-ester of phosphoric acid.
  • the hydrocarbyl amine salt of an alkylphosphoric acid ester is the reaction product of a C 14 to C jg alkylated phosphoric acid with Primene 81RTM (produced and sold by Rohm & Haas) which is a mixture of C n to C 14 tertiary alkyl primary amines.
  • hydrocarbyl amine salts of diaikyldithiophosphoric acid esters include the reaction product(s) of isopropyi, methyl-amyl (4-methyl-2-pentyI or mixtures thereof), 2-ethylhexyi, heptyl, octyl or nonyl dithiophosphoric acids with ethylene diamine, morpbolme, or Primene 81RTM, and mixtures thereof.
  • the dithiophosphoric acid may be reacted with an epoxide or a glycol. This reaction product is further reacted with a phosphorus acid, anhydride, or lower ester.
  • the epoxide includes an aliphatic epoxide or a styrene oxide. Examples of useful epoxides include ethylene oxide, propylene oxide, buteiie oxide, octene oxide, dodecene oxide, and styrene oxide. In one embodiment the epoxide may be propylene oxide.
  • the glycols may be aliphatic glycols having from 1 to 12, or from 2 to 6, or 2 to 3 carbon atoms.
  • dithiophosphoric acids glycols, epoxides, inorganic phosphorus reagents and methods of reacting the same are described in U.S. Patent Nos. 3,197,405 and 3,544,465.
  • the resulting acids may then be salted with amines.
  • An example of suitable dithiophosphoric acid is prepared by adding phosphorus pentoxide (64 grams) at 58°C over a period of 45 minutes to 514 grams of hydroxypropyl 0,0-di(4-methyl- 2-pentyl)phosphorodithioate (prepared by reacting di(4-rnethyl-2 ⁇ pentyl) ⁇ phosphorodithioic acid with 1.3 moles of propylene oxide at 25°C).
  • the mixture may be heated at 75°C for 2.5 hours, mixed with a diatom aceous earth and filtered at 70°C.
  • the filtrate contains 1 1.8% by weight phosphorus, 15.2% by weight sulphur, and an acid number of 87 (bromophenol blue).
  • the dithiocarbamate-containing compounds may be prepared by reacting a dithiocarbamate acid or salt with an unsaturated compound.
  • the dithiocarbamate containing compounds may also be prepared by simultaneously reacting an amine, carbon disulphide and an unsaturated compound. Generally, the reaction occurs at a temperature from 25°C to 125°C.
  • Suitable olefins that may be sulphurised to form an the sulphurised olefin include propylene, butyl ene, isobutylene, pentene, hexane, heptene, octane, nonene, decene, undecene, dodecene, undecyl, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, octadecenene, nonodecene, eicosene or mixtures thereof.
  • hexadecene, heptadecene, octadecene, octadecenene, nonodecene, eicosene or mixtures thereof and their dimers, trimers and tetramers are especially useful olefins.
  • the olefin may be a Diels-Alder adduct of a diene such as 1 ,3-butadiene and an unsaturated ester, such as, butylacrylate.
  • Another class of sulphurised olefin includes fatty acids and their esters.
  • the fatty acids are often obtained from vegetable oil or animal oil; and typically contain 4 to 22 carbon atoms.
  • suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof.
  • the fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof.
  • fatty acids and/or ester are mixed with olefins.
  • the ashless antiwear agent may be a monoester of a polyol and an aliphatic carboxylic acid, often an acid containing 12 to 24 carbon atoms.
  • the monoester of a polyol and an aliphatic carboxylic acid is in the form of a mixture with a sunflower oil or the like, which may be present in the friction modifier mixture from 5 to 95, in several embodiments from 10 to 90, or from 20 to 85, or 20 to 80 weight percent of said mixture.
  • the aliphatic carboxylic acids (especially a monocarboxylic acid) which form the esters are those acids typically containing 12 to 24, or from 14 to 20 carbon atoms. Examples of carboxylic acids include dodecanoic acid, stearic acid, lauric acid, behenic acid, and oleic acid,
  • Polyols include diols. trials, and alcohols with higher numbers of alcoholic OH groups.
  • Polyhydric alcohols include ethylene glycols, including di-, tri- and tetraethyiene glycols; propylene glycols, including di-, tri- and tetrapropylene glycols; glycerol; butane diol; hex an e diol; sorbitol; arabitol; manmtol; sucrose; fructose; glucose; cyclohexane diol; eiythritoi; and pentaerythritols, including di- and tripentaerythritol.
  • the polyol is di ethylene glycol, triethyiene glycol, glycerol, sorbitol, penta erythritol or dipentaerythritoi.
  • glycerol monooleate The commercially available monoester known as "glycerol monooleate” is believed to include 60 + 5 percent by weight of the chemical species glycerol monooleate, along with 35 + 5 percent glycerol dioleate, and less than 5 percent trioleate and oleic acid.
  • the amounts of the monoesters, described above, are calculated based on the actual, corrected, amount of polyol monoester present in any such mixture.
  • EP agents that are soluble in the oil include sulphur- and chlorosulphur-contaming EP agents, chlorinated hydrocarbon EP agents and phosphorus EP agents.
  • EP agents include chlorinated wax; sulphurised olefins (such as sulphurised isobutylene), organic sulphides and polysulphides such as dibenzyldisulphide, bis-(chlorobenzyl) disulphide, dibutyl tetrasulphide, sulphurised methyl ester of oleic acid, sulphurised aikylphenoi, sulphurised dipentene, sulphurised terpene, and sulphurised Diels-Alder adducts; phosphosulphurised hydrocarbons such as the reaction product of phosphorus sulphide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon
  • the method and lubricating compositions of this disclosure may be suitable for greases, gear oils, axle oils, drive shaft oils, traction oils, manual transmission oils, automatic transmission oils, metal working fluids, hydraulic oils, or internal combustion engine oils.
  • the method and lubricating composition of the disclosure may be suitable for at least one of gear oils, axle oils, drive shaft oils, traction oils, manual transmission oils or automatic transmission oils, in one embodiment the disclosure provides a method of lubricating a manual transmission.
  • An automatic transmission includes continuously variable transmissions (CVT), infinitely variable transmissions (IVT), toroidal transmissions, continuously slipping torque converter clutches (CSTCC), stepped automatic transmissions or dual clutch transmissions (DCT).
  • CVT continuously variable transmissions
  • IVT infinitely variable transmissions
  • CSTCC continuously slipping torque converter clutches
  • DCT dual clutch transmissions
  • the internal combustion engines may be 2-stroke or 4-stroke engines.
  • Suitable internal combustion engines include marine diesei engines, aviation piston engines, low-load diesei engines, and automobile and truck engines.
  • the term "(rneth) acrylic” and related terms includes both acrylic and methacrylic groups.
  • a primary alcohol branched at the ⁇ - or higher position relates to an alcohol with branching at the 2-position or a higher position (e.g., 3-, or 4-, or 5-, or 6-, or 7 -position, etc.).
  • the number of carbon atoms present in the ester groups of the polymers of the disclosure is counted to include only those carbon atoms of the alcohol- derived portion of the ester group. Specifically, the number of carbon atoms excludes the carbonyi carbon of the ester.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include: hydrocarbon substitueiits, including aliphatic, alicyclic, and aromatic substitueiits; substituted hydrocarbon substitueiits, that is, substitueiits containing non- hydrocarbon groups which, in the context of this disclosure, do not alter the predominantly hydrocarbon nature of the substituent; and hetero substitueiits, that is, substitueiits which similarly have a predominantly hydrocarbon character but contain other than carbon in a ring or chain,
  • Lubricant compositions i.e., axle oil blends
  • a poiyalphaolefm base stock e.g., mPAO 700, mPAO 450, mPAO 300 , mPAO 150, mPAO 65, mPAO 14, PAD 70, PAO 4, and PAO 6
  • HOEP hybrid olefin ester polymer
  • the MeridianTM viscosity modifier is available from Lubrizol Corporation.
  • the axle oil additive package used in Examples 1 and 2 is available from Lubrizol Corporation as AnglarnolTM 6043M.
  • the axle oil additive package used in Examples 3 and 4 is available from Afton Chemicals.
  • FIG. 1 shows 4-Ball Wear Scar (ASTM D4172) is reduced when using the MeridianTM viscosity modifier alone or in combination with mPAO 150 or mPAO 65, A surprising aspect of this disclosure is that base oil and viscosity modifiers are not expected to have significant impact on wear or load-carrying properties of the fluid.
  • Fig. 10 shows the results of 4-Ball Wear Scar (ASTM D4172) for the designated lubricant compositions (i.e., blends).
  • Fig. 4 shows on average 25-30% lower traction coefficients for lubricating compositions containing mPAO 150, mPAO 65, and/or MeridianTM compared to a conventional viscosity modifier. Lower traction indicates potential axle efficiency enhancement and therefore improved fuel economy.
  • Fig. 11 shows the results of 4-Ball EP (ASTM D2783) load wear index for the designated lubricant compositions (i.e., blends).
  • Fig. 12 shows the results of High Frequency Reciprocating Rig (HFRR) friction coefficient for the designated lubricant compositions (i.e., blends).
  • HFRR High Frequency Reciprocating Rig
  • Fig. 7 indicates a potential antiwear/antiscuffing advantage for a MeridianTM viscosity modifier in the FZG scuffing test even in a lower SAE 75W-80 viscosity formulation containing all MeridianTM as the viscosity modifier.
  • a trend reflecting lower Total Gear weight loss with increased concentration of MeridianTM was observed in the FZG test. All formulations showed excellent performance by delivering "> Stage 12" passing results, a requirement for premium high performance gear oils.
  • Fig. 8 shows surprisingly excellent sludge and varnish results for fluids evaluated in 100-hr L6Q-1 Thermal and Oxidative Stability test, which is double the standard duration (i.e., 50 hours) required for SAE J2360 high performance gear oil specification.
  • the results clearly demonstrate that incorporation of the MeridianTM viscosity modifier in the lubricating compositions of this disclosure provides improved stability and cleanliness even for already high performing technology. This further substantiates the potential to formulation even higher performing lower viscosity finished products by incorporating new synthetic base fluids and viscosity modifiers.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

L'invention porte sur une composition lubrifiante comprenant un premier composant huile de base comprenant : une ou plusieurs poly(alpha-oléfines) produites par catalyse avec un métallocène (mPAO), chaque mPAO ayant une viscosité cinématique (Kv100) de 40 cSt à 155 cSt et un indice de viscosité (IV) de 150 à 207; une seconde huile de base comprenant une ou plusieurs poly(alpha-oléfines) (PAO), chaque PAO ayant une viscosité cinématique (Kv100) inférieure à 10 cSt et un IV de 130 à 145; et un modificateur de viscosité comprenant un copolymère ayant des motifs issus de monomères de (i) une alpha-oléfine et (ii) un acide carboxylique à insaturation éthylénique ou des dérivés d'un acide carboxylique à insaturation éthylénique estérifiés avec un alcool. L'invention porte également sur un lubrifiant comprenant la composition lubrifiante ci-dessus. L'invention porte également sur un procédé permettant d'améliorer le rendement du carburant, tout en maintenant ou améliorant la limitation de l'usure, la capacité de charge et/ou la réduction de la traction dans un dispositif de chaîne cinématique, par exemple des engrenages et des transmissions, lubrifié par une huile de graissage, à l'aide du lubrifiant ci-dessus utilisé comme huile de graissage.
EP13773574.2A 2012-10-24 2013-09-27 Utilisation d'un modificateur de viscosité dans des combinaisons d'huiles de base à haut indice de viscosité Active EP2912151B1 (fr)

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US201261717947P 2012-10-24 2012-10-24
PCT/US2013/062147 WO2014065984A1 (fr) 2012-10-24 2013-09-27 Associations de modificateur de viscosité de réserve de base d'huile de graissage à haut indice de viscosité et huiles de graissage issues de celles-ci

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US20140113847A1 (en) 2014-04-24
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SG10201703150VA (en) 2017-06-29
WO2014065984A1 (fr) 2014-05-01

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